Biodegradable graft polymer useful for preventing dye migration

Abstract

The present application relates to a biodegradable graft polymer for use, for example, particularly as a dye transfer inhibitor in laundry applications. The graft polymer of the present invention comprises a polyalkylene oxide polymer as the polymer main chain of the graft polymer, and in the presence of the polymer main chain, a grafted side chain obtained by radical polymerization of at least one vinylimidazole monomer or its derivative, at least one vinyl lactam, and optionally further monomers. The graft polymer of the present invention exhibits, inter alia, dye transfer inhibition properties. Since these also have biodegradability, they are particularly useful polymers for preventing dye transfer in fabric care and home care, as well as in laundry applications. Furthermore, the present invention also relates to the production of such graft polymers. Furthermore, the present invention relates to the use of such graft polymers in fabric care and home care products, as well as in detergent compositions, and to the use of such graft polymers for preventing dye transfer in laundry applications, and to the compositions and products themselves containing such graft polymers.

Description

Technical Field

[0001] The present application relates in particular to biodegradable graft polymers for use as dye transfer inhibitors in laundry applications.

[0002] The graft polymer of the present invention comprises a polyalkylene oxide polymer as the polymer main chain of the graft polymer, and, in the presence of the polymer main chain, a grafted side chain obtained by radical polymerization of at least one vinylimidazole monomer or a derivative thereof and at least one vinyl lactam, and no vinyl ester monomer is used.

[0003] The graft polymers of the present invention exhibit dye transfer inhibition properties. Since they are also biodegradable, they are useful polymers for preventing dye transfer in laundry washing applications.

[0004] Furthermore, the present invention also relates to the production of such graft polymers.

[0005] Furthermore, the present invention relates to the use of such graft polymers in fabric care and home care products, and to the use of such graft polymers for preventing dye transfer in laundry applications.

[0006] The present invention also relates to fabric care and home care products themselves containing such graft polymers.

[0007] Such graft polymers for use in preventing dye transfer are not yet known.

Background Art

[0008] Due to climate change, one of the most important goals in the current detergent and cleaning (D&C) industry is to improve cold water conditions, for example, by improving cleaning efficiency at temperatures below 40, below 30, or below 20, or even lower, reducing the amount of chemicals used per wash, increasing the weight efficiency of cleaning technology, reducing the amount of water per wash, introducing bio-derived components, etc., so as to greatly reduce the CO2 emissions per wash. Therefore, one important goal of the D&C industry is to improve the sustainability of cleaning formulations by improving efficiency especially at low temperatures and reducing the amount of water required (especially in laundry and dishwashing formulations), and the need to avoid the accumulation of non-degradable compounds in the ecosystem. The desire to reduce such CO2 emissions or improve the "footprint" of any product is high, and in this industry and among consumers, whether it relates to its origin, such as being derived from natural or renewable resources, or whether it relates to its production in terms of production efficiency and thus reduction of energy usage, compared to conventional products in both cases, or whether it relates to its usage efficiency, such as having the same performance in a smaller amount or higher performance at the same usage level, or whether it relates to its persistence in the natural environment during and / or after use, such as biodegradability, there is an increasing interest.

[0009] As a result of these trends, there is a strong need for new biodegradable cleaning additives that provide at least equivalent cleaning properties and a reduction in the CO2 footprint due to being bio-derived, biodegradable, or both. This material preferably needs to exhibit good primary cleaning activity against oily / fatty and particulate stains, stain removal, and / or improve whiteness retention, and thus also minimize the amount of suspended and emulsified oily / fatty and particulate stains that redeposit on the fabric surface or hard surface.

[0010] Accordingly, there is a need to provide compounds that are biodegradable and yet have at least the same performance as known non-biodegradable compounds, such biodegradability being required by many users, particularly in the detergent art, and being a requirement under laws applicable in several countries and regions of the world in the future, as measured within 28 days under specified conditions.

[0011] When dye transfer occurs during laundering of a fabric, there may be a possibility that the dye in a part of the fabric is suspended in the washing liquid, and then there may occur problems such as the dye adhering to another part of the same fabric or to a completely different fabric. Such transfer of dyes (known as "fugitive dyes") can cause dye graying and color fading, particularly in light-colored or white fabrics.

[0012] Conventionally, to address the problem of dye transfer, certain polymers commonly known as dye transfer inhibitors / preventive polymers ("DTI" polymers, and "DTI" will also be used with respect to "dye transfer inhibition") have been used in laundry compositions. Examples of 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, typically containing a relatively large amount of 1-vinylpyrrolidone ("VP"). Such conventional DTI polymers are very effective in preventing the transfer of direct dyes, but they do not have biodegradability because they have a carbon-carbon backbone that cannot be effectively attacked by microorganisms.

[0013] Copolymers of 1-vinylimidazole and 1-vinylpyrrolidone (such as "Sokalan® HP 56" by BASF) and their use as highly efficient dye transfer inhibitors (DTIs) in laundry applications (liquid, gel, and solid color care detergents) are well known and are regarded as the "gold-standard". These polymers exhibit excellent dye transfer inhibition properties in very small amounts, but like all other known DTI polymers mentioned above, they also have a polymer backbone with carbon-carbon bonds and thus cannot be biodegraded in significant amounts.

[0014] However, a certain amount of consumer products containing this type of polymer is washed away after use. If these cannot be biodegraded or are not removed in sewage treatment plants, they may ultimately flow into rivers and oceans. Therefore, it is highly desirable for this type of polymer used in detergent applications to be biodegradable.

[0015] Therefore, there is a strong desire to identify components with higher biodegradability for use in this type of application.

[0016] The main chain consisting only of carbon is particularly difficult for microorganisms to decompose. Therefore, the problem of poor biodegradability is mainly exacerbated when the polymer is produced by radical polymerization based on a main chain consisting only of carbon (i.e., a main chain containing no heteroatoms such as oxygen or nitrogen). Even industrially important graft polymers produced using radicals with a polyethylene glycol main chain show only very limited biodegradability in wastewater.

[0017] Although it is known that low molecular weight polyethylene oxide with an Mw of 600 g / mol is easily biodegradable, polyethylene oxide with an Mw of 6000 g / mol shows only insufficient biodegradability. In the revised version 2.0 dated January 5, 2021 of the safety data sheet for BASF's Pluriol® E 600, it is confirmed that the DOC value (dissolved organic carbon) measured in accordance with OECD 301A for polyethylene glycol with Mw = 600 g / mol exceeds 70%. In contrast, for polyethylene glycol with Mw = 6000 g / mol, the revised version 2.0 dated August 10, 2018 of the safety data sheet for BASF's Pluriol® E 6000 Pellet states that the biodegradability is only insufficient, and the amount of CO2 generated in accordance with OECD 301B is only 10 - 20% of the theoretical value (60 d).

[0018] Various further attempts have already been made to obtain DTI polymers having performance comparable to that of the copolymer of 1 - vinylimidazole and 1 - vinylpyrrolidone, but comparable DTI performance and useful biodegradability have not been achieved.

[0019] International Publication No. WO 03 / 042262 pamphlet relates to a graft polymer comprising (A) a polymer graft main chain 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 - containing heterocyclic ring, wherein the proportion of the amount of the side chain (B) is 35 - 55% by weight of the total polymer.

[0020] However, the graft polymer according to International Publication No. WO 03 / 042262 uses a larger amount of vinylimidazole and vinylpyrrolidone monomers to produce each polymer side chain grafted onto the main chain. The performance of these polymers in DTI is acceptable but still does not reach the highest level at all. Biodegradability is not mentioned. Due to the increase in the amount of vinyl monomers, the production cost also becomes higher.

[0021] U.S. Patent Application Publication No. 5,318,719 relates to a class of biodegradable water-soluble graft copolymers having building properties, anti-film-forming properties, dispersibility, and threshold crystal inhibition properties, which comprise (a) an acid-functional monomer grafted onto a biodegradable substrate containing a polyalkylene oxide and / or a polyalkoxylated material, and optionally (b) other water-soluble monoethylenically unsaturated monomers copolymerizable with (a). However, in U.S. Patent Application Publication No. 5,318,719, it is surely necessary to use a large amount of an acid-functional monomer such as acrylic acid or methacrylic acid to form the side chains of the above graft polymer. This type of acid monomer is not useful for the present invention because it will interfere with the DTI action of the amine (imidazole) group and the lactam group.

[0022] U.S. Patent Application Publication No. 2019 / 0390142 relates to a fabric care composition comprising a graft copolymer that can be composed of (a) a polyalkylene oxide such as polyethylene oxide (PEG), (b) N-vinylpyrrolidone (VP), and (c) a vinyl ester such as vinyl acetate. However, U.S. Patent Application Publication No. 2019 / 0390142 does not disclose other nitrogen-containing monomers such as vinyl imidazole. Furthermore, the amounts of the main chain and monomers used and the intended uses are also different.

[0023] International Publication Pamphlet No. 2007 / 138053 discloses an amphiphilic graft polymer based on a water-soluble polyalkylene oxide (A) as a graft matrix and side chains formed by polymerizing a vinyl ester component (B). The above polymer has an average of less than 1 graft site per 50 units of alkylene oxide and an average molar mass M of 3000 to 100000. However, International Publication Pamphlet No. 2007 / 138053 does not include a disclosure regarding the biodegradability of each graft polymer disclosed in the pamphlet, nor does it disclose the use of a large amount of nitrogen-containing monomers.

[0024] International Publication No. WO 2021 / 160795 A1 pamphlet relates to a graft polymer containing a block copolymer main chain (A) as a graft substrate having a polymer side chain (B) grafted thereon. The polymer side chain (B) can be obtained by polymerizing at least one vinyl ester monomer (B1) and optionally further monomer (B2) as optional N-vinylpyrrolidone. Most preferably, the block copolymer main chain (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG). Further, the present invention also relates to the use of such graft polymers, for example, in fabric care and home care products. However, other monomers, specifically vinyl imidazole monomers, are not included except for vinyl pyrrolidone which is an "optionally" included monomer and the essential vinyl ester monomer. The use as a DTI is not described either.

[0025] WO 2020 / 005476 pamphlet discloses a fabric care composition comprising a graft copolymer and a so-called processing aid. The graft copolymer comprises a polyalkylene oxide, preferably polyethylene oxide, as the main chain based on ethylene oxide, propylene oxide or butylene oxide, and N-vinylpyrrolidone and vinyl ester as grafted side chains on the main chain. The main chain and both monomers are in specific ratios. Vinyl imidazole as a monomer is not disclosed. However, although the use targeted by the fabric care composition of the present invention is stated to be DTI, in addition to the possibility that the dye transfer inhibition performance may decrease when the molecular weight of the graft matrix, for example, polyethylene glycol, is relatively low, if the molecular weight is too high, the polymer may not remain suspended in the solution and / or may be likely to adhere to the treated fabric. Except that it is "considered" that way, it is not explicitly disclosed that this graft polymer itself is clearly used as a DTI polymer. The DTI performance seems to be not derived from the graft polymer itself alone, but from a specific combination of the claimed compounds. This seems to be even more so because the further "processing aid" described as a preferred component is the known DTI polymer described above as the general state of the art known to those skilled in the art.

[0026] WO 2020 / 264077 pamphlet discloses a cleaning composition comprising a combination of an enzyme and a polymer, and this scomposition is suitable for removing stains from contaminated materials.

[0027] This publication 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 contain vinyl imidazole as a monomer. Further, specifically claimed is not only this suspension graft polymer, but also typical well-known dye transfer inhibitor polymers (those described above as general prior art known to those skilled in the art) are included in the claimed fabric washing composition.

[0028] WO 00 / 18375 pamphlet discloses a pharmaceutical composition containing a graft polymer obtained by polymerizing a vinyl ester of at least one aliphatic C1-C24-carboxylic acid in the presence of a polyether, and the vinyl ester is preferably vinyl acetate. In the most preferred variant form, the graft polymer is prepared by grafting vinyl acetate onto PEG with Mw 6000 g / mol and then hydrolyzing vinyl acetate to alcohol (then this becomes similar to a polymer obtained from the virtual monomer "vinyl alcohol"). The main uses are the coating of solid pharmaceutical dosage forms such as tablets and the formation of films.

[0029] On the other hand, WO 00 / 18375 pamphlet also claims polymers obtained by polymerizing a vinyl ester of at least one aliphatic C1-C6-carboxylic acid in the presence of a polyether with at least one monomer selected from the group consisting of c1) C1-C6-alkyl esters of monoethylenically unsaturated C3-C8-carboxylic acids, c4) N-vinyl pyrrolidone, N-vinyl imidazole, N-vinyl caprolactam, c5) (meth)acrylic acid.

[0030] International Publication No. 0018375 pamphlet also claims polymers prepared by polymerizing 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, and c5) monoethylenically unsaturated C3-C8 carboxylic acids, in addition to vinyl esters.

[0031] Furthermore, International Publication No. 0018375 pamphlet also claims polymers prepared by polymerizing at least one other monomer selected from the group consisting of c1) C1-C6 alkyl esters of monoethylenically unsaturated C3-C8 carboxylic acids, c4) N-vinyl pyrrolidone, N-vinyl imidazole, N-vinyl caprolactam, and c5) (meth)acrylic acid, in addition to vinyl esters.

[0032] In International Publication No. 0018375 pamphlet, as the polymer main chain, a polyether having a number average molecular weight in the range of less than 500,000, preferably in the range of 300 to 100,000, particularly preferably in the range of 500 to 20,000, and particularly very preferably in the range of 800 to 15,000 g / mol is disclosed. Further, it is stated that it is advantageous to use a homopolymer of ethylene oxide or a copolymer having an ethylene oxide content of 40 to 99% by weight. Therefore, ethylene oxide units are used in the ethylene oxide polymer, preferably at a content of 40 to 100 mol%. It is said that propylene oxide, butylene oxide and / or isobutylene oxide are suitable as comonomers for these copolymers, and preferred examples thereof are 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 kind of butylene oxide. It is stated 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 in the range of 1 to 30 mol%. As the graft substrate used for grafting, it is said that not only linear but also branched homo- or copolymers can be used.

[0033] However, only PEG6000 and 9000, "polyethylene glycol / polypropylene glycol block copolymer" (average molecular weight "about 8000"), and "polyglycerol" (average molecular weight "2200") (all in g / mol units) are exemplified in International Publication No. 0018375 pamphlet. Five examples use only vinyl acetate as the monomer, and only one example uses vinyl acetate and methyl methacrylate as the monomers. No other monomers are exemplified. In all examples, as the final step, hydrolysis of the polymerized vinyl acetate monomer is carried out.

[0034] Accordingly, in WO 0018375, polymers that do not contain vinyl ester monomers but contain the further essential monomers claimed in the present invention have not been manufactured or characterized.

[0035] WO 0018375 also does not disclose using this type of polymer in detergents and cleaning or fabric care applications as disclosed herein, and specifically is not for use as a DTI polymer. This disclosure does not mention such uses or applications at all.

[0036] US 2008 / 255326 discloses a process for preparing a graft polymer comprising a polyalkylene oxide polymer, such as polyethylene glycol, as a graft matrix, both a vinyl ester, such as vinyl acetate, and a vinyl lactam, such as vinyl pyrrolidone, which are both grafted to the polyalkylene oxide backbone, and optionally a monomer from a third classification ("monomer c") in an amount of zero to a maximum of 10 weight percent based on the total amount of graft monomers, the total amount of graft monomers being 100 weight percent in total, and the amount of graft monomers being 10 to 95 weight percent based on the total weight of the resulting graft polymer. However, vinyl acetate or any other vinyl ester monomer is not used in the present invention.

[0037] U.S. Patent Application Publication No. 2019 / 390142A1 does not disclose a graft polymer containing vinyl imidazole as a monomer nor a graft polymer containing any other optional amine-containing monomer essential to the present invention. Similarly, the use of the graft polymer according to this disclosure for preventing dye transfer during washing is not disclosed. The only vinyl imidazole-containing polymer described as being used as a dye transfer inhibitor in this disclosed composition is a known copolymer of vinyl imidazole and vinyl pyrrolidone, such as Sokalan HP 56, i.e., a standard linear copolymer of these two monomers.

Summary of the Invention

Means for Solving the Problems

[0038] As used herein, the articles "a" and "an" when used in the claims or embodiments are understood to mean one or more of what is claimed or described. As used herein, the term "comprising" means non-limiting and thus includes more than the specific item(s) subsequently recited following that term.

[0039] The compositions of the present disclosure can "comprise" (i.e., contain other components), "consist essentially of" (primarily contain or contain substantially only the recited component(s) and contain only trace amounts of other components primarily as impurities), or "consist of" (i.e., contain only the recited component(s) and may contain only impurities unavoidable in the technical environment, preferably only the component(s)).

[0040] Similarly, the terms "substantially free of...", "substantially free from...", or "(containing / comprising) essentially no..." can be used in this specification; this means that the specified substance is not intentionally added thereto so as to constitute at least a part of the composition, or, preferably, does not exist at a detectable level by analysis. It means that it includes a composition in which the indicated material exists only as an impurity in one of the other intentionally included materials. The indicated material, if any, may be present at a level of less than 1% by weight of the composition, or further less than 0.1%, or even further less than 0.01%, or even 0%.

[0041] The term "about", as used herein, when referred to, for example, as "about X%", etc., includes the exact numerical value "X" and a small difference of X, which is minus 5 to plus 5%, preferably minus 2 to plus 2%, more preferably minus 1 to plus 1%, even more preferably minus 0.5 to plus 0.5% and smaller differences from X (assuming X is set to 100% for this calculation). Needless to say, when the given numerical value X itself is already "100%" (e.g., purity, etc.), what the term "about" can mean is clearly a deviation towards a value smaller than "100", and thus, it surely means only a deviation towards a value smaller than "100".

[0042] The term "fabric care composition" is meant to include compositions and formulations designed for treating fabrics. Such compositions include laundry washing compositions and detergents, fabric softening compositions, fabric functionalizing compositions, fabric cleaning compositions, laundry pre-treatments, laundry pre-spotters, laundry additives, spray products, dry cleaning agents or compositions, fabric rinsing additives, cleaning additives, post-rinse fabric treatment agents, ironing aids, unit dose formulations, delayed delivery formulations, detergents contained on or in a porous substrate or nonwoven sheet, and other suitable forms that may be apparent to one of ordinary skill in the art considering the teachings herein and those detailed below, but are not limited thereto. Such compositions may be used as a laundry pre-treatment, a laundry post-treatment, or added as further detailed below herein in the context of the rinsing or washing cycles of a laundry operation and the use and application of the graft polymers of the present invention and compositions containing such graft polymers.

[0043] Unless otherwise specified, all component or composition levels are with respect to the active portion of that component or composition, excluding impurities, such as residual solvents or by-products, that may be present in a commercial source of such component or composition.

[0044] All temperatures herein are in degrees Celsius (°C) unless otherwise indicated. Unless otherwise specified, all measurements herein are made at 20 °C and under atmospheric pressure. In all embodiments of the present disclosure, all percentages are by weight of the total composition unless otherwise specified. All ratios are weight ratios unless otherwise specified.

DETAILED DESCRIPTION OF THE INVENTION

[0045] Graft Polymer The present invention encompasses a graft polymer comprising a polymer backbone as a graft matrix as a first structural unit and polymer side chains as a second structural unit.

[0046] The first structural unit of the graft polymer is the polymer main chain used as the graft substrate of the graft polymer of the present invention. The above polymer main chain (A) can be obtained by polymerizing at least one alkylene oxide monomer selected from the group of C2-C10-alkylene oxides, preferably C2-C5-alkylene oxides, such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide; can it be obtained from 1,4-diol or its cyclic or oligomeric analogues, or is it based on a polymer ether of this kind of 1,4-diol; can it be obtained from 1,6-diol or its cyclic or oligomeric analogues, or is it based on a polymer ether of this kind of 1,6-diol; or can it be obtained by polymerizing any of these in any ratio as a block of a specific polymer unit or as a statistical polymer structure, or a polymer containing one or more homoblocks of a specific monomer and one or more statistical blocks containing two or more of this kind of monomer, and any combination of these, for example, a polymer having several different blocks of different monomers, or a polymer having blocks of two different monomers, a polymer having blocks of a statistical mixture of two or more monomers, etc.

[0047] As used herein, the term "block (co)polymer (main chain)" means that each polymer contains at least two (i.e., 2, 3, 4, 5 or more) homo- or copolymer subunits ("blocks") linked by covalent bonds. A "two-block" copolymer has two different blocks (homo- and / or copolymer subunits), and accordingly, a "triblock" copolymer has three different blocks (homo- and / or copolymer subunits), and so on. The number of individual blocks within this type of block copolymer is not limited, and thus, an "n-block copolymer" contains n different blocks (homo- and / or copolymer subunits). The size / length of this type of block within an individual block can vary independently of the other blocks. The minimum length / size of a block is based on two individual monomers (at least), but can be up to 50. Each monomer used in the preparation of the individual blocks of the block copolymer main chain (A) can be added sequentially. However, by transitioning from the supply of one type of monomer to the supply of another, there may also occur a so-called "dirty structure" in which a small amount of the monomers of each adjacent block is contained at the end / boundary of each block within the considered individual block (so-called "impure structure" or "impure passage"). The block copolymer main chain (A) according to the present invention preferably contains no impure structure at each boundary of the blocks, but still, even if not intentionally so, for commercial reasons (i.e., mainly from a cost perspective such as efficient use of the reactor), there may still be a small amount of impure structure contained.

[0048] Preferably, at least one monomer in the polymer main chain is produced by the use of ethylene oxide.

[0049] In a preferred embodiment, the main chain is made only from ethylene oxide.

[0050] In another embodiment, two or more alkylene oxide monomers are included within the structure of the polymer backbone, and in such cases, the polymer backbone is a random copolymer, a block copolymer, or a copolymer containing a structure in which block units (each block being a homoblock or itself being a random block) are mixed with a statistical / random portion composed of two or more alkylene oxides, and one of the monomers is ethylene oxide. Preferably, the other monomers other than ethylene oxide are propylene oxide and / or 1,2-butylene oxide, and preferably only 1,2-propylene oxide.

[0051] Furthermore, the preferred backbone is a backbone starting from what is hereinafter referred to as the "core" in this specification, which is an organic compound having at least two hydroxy groups and containing water, and these hydroxy groups are subsequently modified with any of the compounds for generating the first structural unit to generate the backbone polymer defined at the beginning of the description of the "first structural unit" above, and this deviates from the structure of the above-mentioned backbone only by additional "insertion" of the core into the structure defined above. Such suitable cores are glycerin, 2-methyl-1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, trimethylolpropane, water, pentaerythritol, sorbitol, sucrose, glucose, fructose, lactose, and similar compounds having similar chemical structures. Diamines such as ethylenediamine, propylenediamine, diethylenetriamine, dipropylenetriamine are also possible in principle, but these amines are not preferred from the viewpoint that they may cause problems regarding ecological toxicity, especially when they are released again from the polymer structure when the graft polymer of the present invention is biodegraded.

[0052] However, it is not preferred to use such cores for preparing the backbone for use as the first structural unit in the present invention.

[0053] In a further embodiment, the amount of ethylene oxide in the polymer backbone A is in the range of 10 to 100 weight percent (relative to the total molar amount of alkylene oxide in the polymer backbone (A)).

[0054] More preferably, the monomers in the polymer backbone are produced by the use of ethylene oxide and optionally at least one further monomer selected from 1,2 - propylene oxide (PO) and 1,2 - butylene oxide, preferably only PO. The amount of ethylene oxide in the polymer backbone A is in the range of 10 to 100 weight percent, preferably 10 to 90, more preferably at least 30, even more preferably at least 50, even more preferably at least 70, and most preferably at least 80 weight percent (relative to the total amount of alkylene oxide in the polymer backbone (A)).

[0055] Accordingly, preferred polymer backbones are selected from i) poly(ethylene oxide), and ii) polyalkylene oxides containing only ethylene oxide (EO) and propylene oxide (PO), preferably an EO / PO / EO triblock polymer, a PO / EO / PO triblock polymer, or a random EO / PO copolymer, more preferably an EO / PO / EO triblock polymer or a PO / EO / PO triblock polymer, and most preferably a PO / EO / PO triblock polymer, with random EO / PO > 100% EO > EO / PO / EO being preferred in descending order, and PO / EO / PO being more preferred overall than the others.

[0056] It should be noted that any of the alkylene oxides used to prepare the main chain of the first structural unit can be derived from a fossil carbon source or a non-fossil carbon source, or even a mixture thereof. Preferably, the amount of non-fossil carbon atoms in the alkylene oxide used is at least 10%, at least 20%, at least 40%, at least 70%, at least 95%, most preferably up to 100% based on the carbon atoms of non-fossil origin, and the same applies to the whole of the compounds of the present invention. Those skilled in the art are familiar with commercially available alkylene oxide products manufactured from non-fossil carbon sources (these products are often marketed as "sustainable", "renewable", or "bio-based"). For example, Croda International (Snaith, UK) sells bio-ethanol-based ethylene oxide and related products under the "ECO"-Range. Furthermore, methods for preparing bio-based propylene oxide are also known (see Abraham, D.S., "Production of propylene oxide from propylene glycol" Master's Thesis University of Missouri-Columbia (2007) (75 pages)).

[0057] This, of course, also applies to the starter molecules for use as the above-mentioned "core". These diol structures can, of course, be derived from natural renewable sources and can thus be obtained from bio-based raw materials. Such materials and processes are known. Preferably, the amount of non-fossil carbon atoms in the starter molecules used as the "core" is at least 10%, at least 20%, at least 40%, at least 70%, at least 95%, most preferably up to 100% based on the carbon atoms of non-fossil origin, and the same applies to the whole of the compounds of the present invention.

[0058] The molecular weight of the polymer main chain (A), expressed in g / mol as "Mn" (number average molecular weight), is in the range of 400 to 12,000, preferably 8,000 or less, more preferably 6,000 or less, even more preferably 4,000 or less, still even more preferably 3,000 or less, and at least 400, more preferably at least 500. It is understood that all ranges created by combining any of the numbers detailed above as the lower limit with any of the numbers detailed above as the upper limit are included within the scope of the present invention. A more preferred range of Mn is 400 to 4,000, and even more preferably 400 to 3,000.

[0059] One or both of the terminal groups of the polymer main chain (A) are optionally capped, and this capping is carried out using known techniques with a C1-C25-alkyl group, preferably a C1-C4 group.

[0060] In a preferred embodiment, the polymer main chain (A) is not capped and has a hydroxy group at the chain end.

[0061] The second structural unit of the graft polymer is a polymer side chain (B) grafted onto the polymer main chain (A). The above polymer side chain (B) can be obtained by copolymerizing at least one monomer of (B1) and at least one monomer of (B2). The monomer (B1) is preferably selected from at least one olefinically unsaturated amine-containing monomer, such as 1-vinylimidazole or a derivative thereof, for example an alkyl-substituted derivative of 1-vinylimidazole, such as 2-methyl-1-vinylimidazole, more preferably 1-vinylimidazole only. Monomer (B2) is selected from at least one nitrogen-containing monomer that is not monomer (B1), preferably a vinyl lactam monomer, more preferably selected from N-vinyl lactams such as N-vinyl pyrrolidone, N-vinyl piperidone, N-vinyl caprolactam, even more preferably selected from N-vinyl pyrrolidone, N-vinyl caprolactam, and most preferably selected from N-vinyl pyrrolidone. Additional monomers such as 1-vinyl oxazolidinone and other vinyl oxazolidinones, 4-vinyl pyridine-N-oxide, N-vinyl formamide (when hydrolyzed after polymerization, and its amine), N-vinyl acetamide, N-vinyl-N-methyl acetamide, acrylamide, methyl acrylamide, any one or more of N,N'-dialkyl (meth) acrylamides can be used as optional monomers.

[0062] However, neither monomer (B1) nor (B2) nor additional monomers contain vinyl ester monomers, that is, vinyl acetate, vinyl propionate, and vinyl laurate, and any other known vinyl ester monomers, etc. are not employed to obtain the graft polymer of the present invention.

[0063] The amount of additional monomers is 0 to 5, preferably at most 2, more preferably 0, but in all cases at most 50% of the amount of (B1) and less than the amount of (B2).

[0064] However, if there are any other monomers other than the monomers of (B1) and (B2) and optional further monomers, such other monomers are preferably present in an amount of less than 2% of the total amount of monomers used to obtain the polymer side chain (B), and are preferably not intentionally added to the polymerization and are present only as impurities. Preferably, the amount of the above other monomers is less than 1% by weight, more preferably less than 0.5% by weight, even more preferably less than 0.01% by weight, and most preferably, any other monomers other than the monomers (B1), (B2) and optional further monomers are basically absent or not present at all.

[0065] The graft polymer of the present invention detailed above with respect to its composition, its preferred, more preferred, etc., most preferred composition contains the first and second structural units in the following amounts in weight percent units based on the total weight of the graft polymer respectively: - The amount of the polymer main chain (A) is 70 - 95, preferably 73 - 90, more preferably 73 - 87, even more preferably 75 - 85, and most preferably 77 - 85. - The amount of the polymer side chain (B) is 5 - 30, preferably 10 - 27, more preferably 13 - 27, even more preferably 15 - 25, and most preferably 15 - 23. - The amount of (B1) is at least 4 and at most 29. - The amount of (B2) is at least 1 and at most 15. - The amount of (B2) relative to (B1) is 4 times or less, preferably 3 times or less, more preferably 2 times or less, even more preferably the same amount, in all cases, and preferably at least 5%, more preferably at least 10%, even more preferably at least 25%, even more preferably at least 50, even more preferably at least 75% of the amount of (B1). - The amount of the further monomer is 0 - 5, preferably at most 2, more preferably 0, but in all cases at most 50% of the amount of (B1) and less than or equal to the amount of (B2).

[0066] (A), (B), (B1), (B2), and the amounts of further monomers may be selected from the various detailed ranges indicated individually, i.e., lower and upper limits from two different indicated ranges may be combined to obtain a certain number of numerical ranges nt, but it should be understood that it is explicitly intended that such combined ranges for (A), (B), (B1), (B2), or such combined ranges for further monomers are encompassed by the present invention.

[0067] Also, in one embodiment of the present invention, a wide range and a very particularly preferred narrow range can be combined, and as long as the sum of all numerical values is "100% polymer", the selection of the range of one component is independent of the selection of the range of the other component. For example, the most preferred ranges of (A) and (B) can be selected and combined with the widest possible range shown for (B1) / (B2) and any other possible combinations.

[0068] In all possible selections for (A) / (B) and (B1) / (B2) / (further monomers), it is preferred to make the same selection, 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.

[0069] Therefore, in a more preferred embodiment, the following amounts are selected in weight percent units based on the total weight of the graft polymer, respectively: - The amount of polymer main chain (A) is 75 - 85, most preferably 77 - 85, - The amount of polymer side chain (B) is 15 - 25, most preferably 15 - 23, - The amount of (B1) is at least 6 and at most 24, more preferably at most 20, even more preferably at most 15, even more preferably at most 12, most preferably at least 7.5 and at most 10, - The amount of (B2) is at least 1 and at most 15, more preferably at most 13, even more preferably at most 12, even more preferably at most 11, and most preferably at least 7.5 and at most 10, - More preferably, the amount of (B2) relative to (B1) is the same amount, but does not exceed the total upper or lower limit of (B).

[0070] In another embodiment, the following amounts are selected in weight percent units based on the total weight of the graft polymer, respectively: - The amount of polymer main chain (A) is 75 - 85, most preferably 77 - 85, - The amount of polymer side chain (B) is 15 - 25, most preferably 15 - 23, - The amount of (B1) is at least 6 and at most 24, more preferably at most 20, even more preferably at most 15, even more preferably at most 12, and most preferably at least 7.5 and at most 10, - The amount of (B2) is at least 1 and at most 15, more preferably at most 13, even more preferably at most 12, even more preferably at most 11, and most preferably at least 7.5 and at most 10, - Preferably, the amount of (B2) relative to (B1) is, in all cases, at most 75% of the amount of (B1), even more preferably at most 50%, and most preferably at most 25%.

[0071] In a preferred embodiment, the graft polymers disclosed herein, specifically the graft polymers detailed in the above embodiments, are as follows: (A) The polymer main chain (A) is a triblock polymer EO / PO / EO, the molecular weight of the polymer main chain (A) is within 400 - 3000 as Mn in units of g / mol, and the relative amount of EO in the polymer main chain (A) is 10 - 90, preferably 10 - 60, more preferably 15 - 50 weight percent based on the total molar amount of alkylene oxide in the polymer main chain (A). Also, (B) The polymer side chain consists of the following monomers, - B1 is 1-vinylimidazole, - B2 is an N-vinyl lactam, preferably N-vinylpyrrolidone.

[0072] In a more preferred embodiment, the graft polymer detailed above is (A) a polymer main chain (A) which is a triblock polymer EO / PO / EO, wherein the molecular weight of the polymer main chain (A) is within 400 to 3000 as Mn in units of g / mol, and the relative amount of EO in the polymer main chain (A) is 10 to 90, preferably 10 to 60, more preferably 15 to 50 weight percent based on the total molar amount of alkylene oxide in the polymer main chain (A), the polymer main chain (A), and (B) a polymer side chain, consisting of the following monomers, - B1 is 1-vinylimidazole, - B2 is an N-vinyl lactam, preferably N-vinylpyrrolidone, a polymer containing a polymer side chain, each in weight percent units based on the total weight of the graft polymer, - the amount of the polymer main chain (A) is 70 to 95, preferably 73 to 90, more preferably 73 to 87, even more preferably 75 to 85, most preferably 77 to 85, - the amount of the polymer side chain (B) is 5 to 30, preferably 10 to 27, more preferably 13 to 27, even more preferably 15 to 25, most preferably 15 to 23, - the amount of (B1) is at least 4 and at most 29, - the amount of (B2) is at least 1 and at most 15, - the amount of (B2) relative to (B1) is 4 times or less, preferably 3 times or less, more preferably 2 times or less, even more preferably the same amount, in all cases, preferably at least 5%, more preferably at least 10%, even more preferably at least 25%, even more preferably at least 50, even more preferably at least 75% of the amount of (B1), - The amount of additional monomer is from 0 to 5, preferably at most 2, more preferably 0, but in all cases at most 50% of the amount of (B1) and less than or equal to the amount of (B2).

[0073] In an even more preferred embodiment, the preferred selection of the polymer composition detailed in the two immediately preceding paragraphs is combined with the preferred selection of the amounts detailed above.

[0074] In an even more preferred embodiment, the graft polymer detailed above is (A) a polymer backbone (A) which is a triblock polymer EO / PO / EO, wherein the molecular weight of the polymer backbone (A) is within 400 to 3000 as Mn in units of g / mol, and the relative amount of EO in the polymer backbone (A) is 10 to 90, preferably 10 to 60, more preferably 15 to 50 weight percent based on the total molar amount of alkylene oxide in the polymer backbone (A), the polymer backbone (A), and (B) a polymer side chain, which consists of the following monomers, - B1 is 1-vinylimidazole, - B2 is an N-vinyl lactam, preferably N-vinylpyrrolidone, a polymer containing the polymer side chain, each in weight percent units based on the total weight of the graft polymer, - The amount of the polymer backbone (A) is 70 to 95, preferably 73 to 90, more preferably 73 to 87, even more preferably 75 to 85, most preferably 77 to 85, - The amount of the polymer side chain (B) is 5 to 30, preferably 10 to 27, more preferably 13 to 27, even more preferably 15 to 25, most preferably 15 to 23, - The amount of (B1) is at least 4 and at most 29, - The amount of (B2) is at least 1 and at most 15, - The amount of (B2) relative to (B1) is, in all cases, 4 times or less, preferably 3 times or less, more preferably 2 times or less, even more preferably the same amount, and preferably at least 5%, more preferably at least 10%, even more preferably at least 25%, even more preferably at least 50, even more preferably at least 75% of the amount of (B1), and most preferably, the amount of (B2) relative to (B1) is the same amount, but does not exceed the upper or lower limit of the total of (B). - The amount of further monomers is 0 to 5, preferably at most 2, more preferably 0, but in all cases at most 50% of the amount of (B1) and not more than the amount of (B2).

[0075] In an even more preferred embodiment, preferred selections possible for the various variations of the polymer composition detailed in the immediately preceding paragraph are selected and combined.

[0076] In an even more preferred embodiment than the immediately preceding one, more preferred selections possible for the various variations of the polymer composition detailed in the pre-preceeding paragraph are selected and combined.

[0077] In an even more preferred embodiment than the immediately preceding one, the most preferred selections possible for the various variations of the polymer composition detailed in the pre-pre-preceding paragraph are selected and combined.

[0078] In another, less preferred embodiment, the following amounts are selected in weight percent units based on the total weight of the graft polymer, respectively: - The amount of polymer main chain (A) is 75 to 85, most preferably 77 to 85. - The amount of polymer side chain (B) is 15 to 25, most preferably 15 to 23. - The amount of (B1) is at least 6 and at most 24, more preferably at most 20, even more preferably at most 15, even more preferably at most 12, and most preferably at least 7.5 and at most 10. - The amount of (B2) is at least 1 and at most 15, more preferably at most 13, even more preferably at most 12, even more preferably at most 11, and most preferably at least 7.5 and at most 10, - Preferably, the amount of (B2) relative to (B1) is, in all cases, at most 75%, even more preferably at most 50%, and most preferably at most 25% of the amount of (B1).

[0079] The polydispersity (PDI) Mw / Mn of the graft polymer of the present invention detailed above is at most 3, preferably at most 2.5, and more preferably at most 2 (Mw = weight average molecular weight (g / mol unit), Mn = number average molecular weight (g / mol unit); PDI is unitless), and a smaller value is preferred, but it also varies depending on the Mn of the polymer main chain used (usually, the higher the Mn of (A), the higher the PDI), and the amount of (B) (usually, the higher the amount of (B) relative to the amount of (A), the higher the PDI).

[0080] M w and M n Each value of can be determined as described later in the experimental section.

[0081] The graft polymer of the present invention may contain a specific amount of ungrafted polymer (ungrafted side chain) made from monomers that have not reacted with the polymer main chain (i.e., are not grafted to the polymer main chain).

[0082] The amount of such ungrafted polymer can be high or low depending on the reaction conditions, but it is preferably reduced, and thus, a lower amount is more preferred. By performing such reduction, the amount of grafted side chains preferably increases. Such reduction can be achieved by suitable reaction conditions such as the administration of monomers and radical initiators, and their relative amounts, and the amount relative to the main chain present). Such adjustment is, in principle, known to those skilled in the art and is described in detail with respect to the present invention in the description of the process for obtaining the graft polymer of the present invention.

[0083] The graft polymers of the present invention as detailed above in this specification have been found to exhibit improved biodegradability, being at least 40, more preferably at least 45, such as 46, 47, 48, 49, 50, 55, 60, 65, etc., and any number in between, and up to 100% within 28 days when tested under OECD 301F.

[0084] Process The present invention also encompasses a process for obtaining a graft polymer according to any one of claims 1 to 7, wherein at least one monomer B1, at least one monomer B2, and optionally at least one further monomer are polymerized in the presence of at least one polymer backbone (A), and the polymer side chain (B) is obtained by radical polymerization using a radical-forming compound that initiates radical polymerization, and each of B, B1, B2, and A is as detailed above in this specification and exemplified in the following examples.

[0085] It should be noted that the "grafting process" itself in which a polymer backbone such as the polymer backbone (A) described above in this specification is grafted by a polymer side chain is known to those skilled in the art. Any process known to those skilled in the art in this regard can, in principle, be used in the present invention.

[0086] Radical polymerization is also known per se to those skilled in the art. Those skilled in the art also understand that the process of the present invention can be carried out in the presence of a radical-forming initiator (C) and / or at least one solvent (D). A person skilled in the art knows the respective components suitable as they are.

[0087] The term "radical polymerization" as used in connection with the present invention includes, in addition to free radical polymerization, its variant forms such as controlled radical polymerization. Suitable control mechanisms are RAFT, NMP or ATRP, which are known to those skilled in the art including the respective suitable control agents.

[0088] In a preferred embodiment, the process for obtaining the graft polymers of the present invention detailed above in this specification is in the presence of at least one polymer backbone (A), i) at least one monomer (B1), ii) at least one monomer (B2), iii) optionally at least one further monomer and (B1, B2, the optional further monomer, and A are each in the respective ranges, amounts, and selections, including the respective "preferred", "more preferred", etc., "most preferred" ranges as detailed above, and combinations thereof, as detailed above and below in this specification), iv) a free radical forming initiator (C), v) optionally, in the presence of at least one solvent (D) present in an amount of up to 60% by weight, preferably up to 50% by weight, based on the total of components (A), (B1), (B2), the optional further monomer, and (C), preferably in the presence of a solvent (such a solvent preferably comprises water and up to 20 volume percent, more preferably up to 10, even more preferably up to 5, most preferably 3, 2, or even less than 1 volume percent of an organic solvent, based on the total volume of all solvents) (even more preferably, the solvent (D) used in the polymerization reaction is only water, and most preferably, the radical initiator is dissolved in such a small amount of organic solvent only as necessary for introducing the radical initiator C, and the solvent for such dissolution is disclosed below in this specification), polymerizing in a main polymerization reaction step at an average polymerization temperature, wherein the initiator (C) has a decomposition half-life of 40 to 500 minutes, and optionally, performing at least one further polymerization step ( "post-polymerization") to reduce the amount of unreacted monomer, and Optionally, in order to remove volatile components such as volatile solvents and unreacted monomers, all are carried out under atmospheric pressure or reduced pressure, by thermal distillation or vacuum distillation, or stripping with a gas such as steam or nitrogen, preferably stripping with steam prepared from water, and implementing at least one purification step selected therefrom; Optionally, carrying out a drying step; comprises.

[0089] Preferably, the immediately preceding embodiment is carried out as follows. - In Variant A) of this embodiment, the fraction of unconverted graft monomers (B1, B2, and any optional further monomers) and initiator (C) in the reaction mixture is always maintained in a quantitatively deficient state with respect to the polymer main chain (A), whereas in Variant B) of this embodiment, instead of maintaining the fraction of unconverted graft monomers (B1, B2, and any optional further monomers) in a quantitatively deficient state of monomers at the time of initiating the polymerization reaction, it is higher and as shown below. Preferably, in Variant B, the polymerization reaction is carried out such that the fraction of unconverted graft monomers B1, B2, and any optional further monomers is at least more than 5, preferably more than 20, even more preferably more than 50, even more preferably more than 75, even more preferably more than 90, and most preferably 100 percent at the time when it affects the polymerization reaction.

[0090] In Variant A, the grafting efficiency is higher, but the biodegradation performance and washing performance tested in the examples of this specification are equivalent.

[0091] In a more preferred embodiment, Variant A is more preferred than Variant B.

[0092] In another preferred embodiment of the present invention, and more preferably, in any preferred variation of the above process embodiments, the solvent is selected from at least one organic solvent and water (D), and such solvent is present in an amount of at most 60% by weight, preferably at most 50% by weight, based on the total of components (A), (B1), (B2), any optional further monomers, (C), and (D), and such solvent (D) preferably contains at most 20 percent, more preferably at most 10, even more preferably at most 5, most preferably 3, 2, or even less than 1 volume percent of an organic solvent, based on the total weight percent of the polymer consisting of {(A)+(B1)+(B2)+any optional further monomers}.

[0093] “Low concentration of graft monomer” (synonymous with “quantitative deficiency”) means, in the case of preferred embodiment A), a concentration of about 0.1 to at most 5% by weight, more preferably at most 3, even more preferably 1, even more preferably at most 0.5% by weight of the total amount of each monomer added, while in the case of embodiment B), the fraction of unconverted monomers (B1, B2, and any optional further monomers) is at least more than 5, preferably more than 20, even more preferably more than 50, even more preferably more than 75, even more preferably more than 90, most preferably at most 100 percent.

[0094] According to embodiment A) of the present invention, the polymerization is carried out in such a way that an excess of polymer (polymer main chain (A) and formed graft polymer (B)) is always present in the reactor.

[0095] “Per total weight of the graft polymer” means the total content of the polymer in the reaction mixture, regardless of whether the produced polymer is actually grafted or not.

[0096] ((Free) radical forming) The amount of initiator (C) is, in any case, preferably 0.1 to 5% by weight, specifically 0.3 to 3.5% by weight, and any number in between, based on the total weight of the graft polymer.

[0097] In the case of the process according to the invention, the steady-state concentration of radicals present at the average polymerization temperature is substantially constant, and the graft monomers (B1) and / or (B2) preferably are present only in a low concentration at all times in the reaction mixture in the above-described first preferred embodiment A). This makes it possible to control the reaction, and the graft polymer can be prepared in a controlled manner with the desired low polydispersity.

[0098] In the above-described preferred embodiment B), it is likewise preferred that the steady-state concentration of radicals present at the average polymerization temperature is substantially constant. In order to ensure safe temperature control while having a large amount or all of the monomers present from the start of the polymerization temperature, it is advisable and thus preferred to use additional efficient means for temperature control. This can be carried out by external or internal cooling, and such cooling can be effected by an internal or external cooler such as a heat exchanger, or by using a reflux condenser when operating at the boiling point of a solvent or solvent mixture.

[0099] Of course, the same means can equally well be used for the alternative preferred embodiment A), but in the case of A), this is usually not important since the temperature is at least partly controlled by the propagation of the polymerization reaction by controlling the concentration of radicals and the available amount of polymerizable monomers.

[0100] Of course, if the scale becomes large enough such that the ratio of the volume to the surface of the polymerization mixture becomes very high, in both variants A) and B), such additional cooling as described above may be required depending on the scale of the polymerization reaction.

[0101] However, this is generally known to those skilled in the art of commercial-scale polymerization and can thus be adapted to the needs.

[0102] The term "average polymerization temperature" is here intended to mean that, although the process is substantially isothermal, there may be temperature fluctuations which are preferably kept within a range of + / - 10 °C, more preferably within a range of + / - 5 °C, due to the exothermicity of the reaction.

[0103] According to the present invention, the initiator (C) (for radical formation) at the average polymerization temperature should have a decomposition half-life of 40 to 500 minutes, preferably 50 to 400 minutes, more preferably 60 to 300 minutes.

[0104] According to the present invention, the initiator (C) as well as the graft monomers (B1), (B2) and any optional further monomers are advantageously added such that the undegraded initiator as well as the graft monomers (B1), (B2) and any optional further monomers are present in the reaction mixture at a substantially constant low concentration.

[0105] The proportion of undegraded initiator in the overall reaction mixture is preferably 15% by weight or less, in particular 10% by weight or less, based on the total amount of initiator metered in during monomer addition. The average polymerization temperature is suitably in the range of 50 to 140 °C, preferably 60 to 120 °C, more preferably 65 to 110 °C.

[0106] Examples of suitable initiators (C) having a decomposition half-life of 20 to 500 minutes in the temperature range of 50 to 140 °C are - tert-C4~C 12 alkyl hydroperoxides and tert-(C9~C 12 aralkyl) hydroperoxides of O-C2~C 12Acylation derivatives, such as tert-butyl peracetate, tert-butyl monoperoxymaleate, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, tert-amyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneodecanoate, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate, and di-tert-butyl diperoxyphthalate, etc.; - tert-C8~C 14 Di-O-C4-C of alkylene bisperoxide 12 Acylation derivatives, such as 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, and 1,3-di(2-neodecanoylperoxyisopropyl)benzene, etc.; - Di(C2~C 12 Alkanoyl) and dibenzoyl peroxide, such as diacetyl peroxide, dipropionyl peroxide, disuccinic peroxide, didecanoyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, dibenzoyl peroxide, di(4-methylbenzoyl) peroxide, di(4-chlorobenzoyl) peroxide, and di(2,4-dichlorobenzoyl) peroxide, etc.; - Peroxy(C4~C 12 Alkyl) carbonate tert-C4~C5 alkyl, such as tert-amyl peroxy(2-ethylhexyl) carbonate, etc.; - Di(C2~C 12 Alkyl) diperoxy dicarbonate, such as di(n-butyl) diperoxy dicarbonate and di(2-ethylhexyl) diperoxy dicarbonate, etc.

[0107] Examples of particularly suitable initiators (C) according to the average polymerization temperature are - at an average polymerization temperature of -50 to 60 °C, tert-butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-amyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneodecanoate, 1,3-di(2-neodecanoylperoxyisopropyl)benzene, di(n-butyl) peroxydicarbonate and di(2-ethylhexyl) peroxydicarbonate; - at an average polymerization temperature of 60 to 70 °C, tert-butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate and di(2,4-dichlorobenzoyl) peroxide; - at an average polymerization temperature of 70 to 80 °C, tert-butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-amyl peroxypivalate, dipropionyl peroxide, didecanoyl peroxide, dilauroyl peroxide, di(2,4-dichlorobenzoyl) peroxide, and 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane; - at an average polymerization temperature of 80 to 90 °C, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, dipropionyl peroxide, didecanoyl peroxide, dilauroyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, dibenzoyl peroxide and di(4-methylbenzoyl) peroxide; - at an average polymerization temperature of 90 to 100 °C, tert-Butyl peroxydiisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl monoperoxymaleate, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide and di(4-methylbenzoyl) peroxide; - At an average polymerization temperature of 100 to 110 °C, tert-Butyl monoperoxymaleate, tert-butyl peroxydiisobutyrate and tert-amyl peroxy(2-ethylhexyl) carbonate; - At an average polymerization temperature of 110 to 120 °C, tert-Butyl monoperoxymaleate, tert-butyl peroxy-3,5,5-trimethylhexanoate and tert-amyl peroxy(2-ethylhexyl) carbonate.

[0108] Preferred initiator (C) is an O-C4-C of tert-C4-C5 alkyl hydroperoxide 12 acylated derivative, and tert-butyl peroxypivalate and tert-butyl peroxy-2-ethylhexanoate are particularly preferred.

[0109] Particularly advantageous polymerization conditions can be easily established by precise adjustment of initiator (C) and polymerization temperature. For example, the preferred average polymerization temperature when using tert-butyl peroxypivalate is 60 to 90 °C, and for tert-butyl peroxy-2-ethylhexanoate it is 80 to 100 °C.

[0110] Further examples of suitable initiators (C) are also azo initiators having an equivalent decomposition half-life of 20 to 500 minutes in the temperature range of 50 to 140 °C, for example, those available from company WAKO (i.e., Fujifilm Wako), for example, V-50 (2,2'-azobis(2-methylpropionamidine) dihydrochloride), V-59 (2,2'-azobis(2-methylbutyronitrile)), V-601 and V-601HP (dimethyl 2,2'-azobis(2-methylpropionate)), VA-086 (2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide]), V-501 (4,4'-azobis(4-cyanovaleric acid)), VA-057 (2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate), V-40 (1,1'-azobis(cyclohexane-1-carbonitrile)), AIBN and AIBN-HP (2,2'-azobis(isobutyronitrile)), V-65 and V-65HP (2,2'-azobis(2,4-dimethylvaleronitrile)), VAm-110 (2,2'-azobis(N-butyl-2-methylpropionamide)), VR-110 (2,2'-azobis(2,4,4-trimethylpentane)), VPE-0201 (see structure), and, of course, the same chemical compounds available from other sources.

[0111] Structure of VPE-0201:

Chemical formula

[0112] The most preferred initiators are tert-butyl peroxypivalate and (2,2'-azobis(2-methylpropionamidine) dihydrochloride).

[0113] In a preferred embodiment of the process of the present invention, the amount of the (free) radical-forming initiator (C) is in each case from 0.1 to 5% by weight, specifically from 0.3 to 3.5% by weight, based on the total weight of the graft polymer.

[0114] The polymerization reaction of the present invention can be carried out in the presence of a solvent (D). Naturally, it is also possible to use a mixture of different solvents (D) including a mixture of organic solvents, and a mixture of an organic solvent and water, or water alone. It is preferred to use a water-soluble or water-miscible solvent.

[0115] When the solvent (D) is used as a diluent, in each case generally from 1 to 40% by weight, preferably from 1 to 35% by weight, more preferably from 1.5 to 30% by weight, most preferably from 2 to 25% by weight, based on the total of the constituents (A), (B1), optionally (B2) and (C) is used.

[0116] Examples of suitable solvents (D) are - monohydric alcohols, preferably aliphatic C1-C 16 alcohols, more preferably aliphatic C2-C 12 alcohols, most preferably C2-C4 alcohols such as ethanol, propanol, isopropanol, butanol, sec-butanol and tert-butanol; - polyhydric alcohols, preferably C2-C 10 diols, more preferably C2-C6 diols, most preferably C2-C4 alkylene glycols such as ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol; - alkylene glycol ethers, preferably alkylene glycol mono (C1-C 12(C1-C6 alkyl) ethers and alkylene glycol di(C1-C6 alkyl) ethers, more preferably alkylene glycol mono- and di(C1-C2 alkyl) ethers, most preferably alkylene glycol mono(C1-C2 alkyl) ethers, such as ethylene glycol monomethyl and ethyl ethers and propylene glycol monomethyl and ethyl ethers, etc.; - Polyalkylene glycols, preferably poly(C2-C4 alkylene) glycols having 2 to 20 C2-C4 alkylene glycol units, more preferably polyethylene glycols having 2 to 20 ethylene glycol units and polypropylene glycols having 2 to 10 propylene glycol units, most preferably polyethylene glycols having 2 to 15 ethylene glycol units and polypropylene glycols having 2 to 4 propylene glycol units, such as diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol, etc.; - Polyalkylene glycol monoethers, preferably poly(C2-C4 alkylene) glycol mono(C1-C 25 alkyl) ethers having 2 to 20 alkylene glycol units, more preferably poly(C2-C4 alkylene) glycol mono(C1-C 20 alkyl) ethers having 2 to 20 alkylene glycol units, most preferably poly(C2-C3 alkylene) glycol mono(C1-C 16 alkyl) ethers having 3 to 20 alkylene glycol units; - 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, etc.; - Aliphatic ketones preferably having 3 to 10 carbon atoms, such as acetone, methyl ethyl ketone, diethyl ketone and cyclohexanone, etc.; - Cyclic ethers, especially tetrahydrofuran are mentioned.

[0117] The solvent (D) is preferably a solvent that is also used for formulating the graft polymers of the present invention for use (e.g., in cleaning and cleaning compositions), and thus can remain in the polymerization product.

[0118] Preferred examples of these solvents are polyethylene glycols having 2 to 15 ethylene glycol units, polypropylene glycols having 2 to 6 propylene glycol units, and in particular alkoxylation products of C6-C8 alcohols (alkylene glycol monoalkyl ethers and polyalkylene glycol monoalkyl ethers).

[0119] Here, alkoxylation products of C8-C 16 alcohols with a high degree of branching are particularly preferred, as they are free-flowing at 40-70 °C and enable the formulation of polymer mixtures with a very low polymer content and relatively low viscosity. The branching 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 to 15 moles of ethylene oxide, C 13 / C 15 oxo alcohol or C 12 / C 14 or C 16 / C 18 fatty alcohol, and 2-propylheptanol alkoxylated with 1 to 15 moles of ethylene oxide and 1 to 3 moles of propylene oxide is preferred.

[0120] In a preferred embodiment of the process of the present invention, at least one organic solvent and / or water (D) is present in an amount of up to 60% by weight, based on the sum of components (A), (B1), (B2), any optional further monomers, and (C) and (D).

[0121] In a preferred embodiment, the polymerization is carried out without using solvent (D), except for the solvent necessary for the introduction of the initiator.

[0122] In a more preferred embodiment, the solvent (D) used is water, and as disclosed below in the present specification, the radical initiator is dissolved in a small amount of an organic solvent. If the initiator is also water-soluble, then of course the organic solvent can be completely omitted.

[0123] A small amount of an organic solvent may be used, preferably for introducing a radical initiator and the graft monomers (B1) and / or (B2) which, for example, do not dissolve in water but can dissolve to a reasonable extent only in this type of organic solvent. Suitable organic solvents can be isopropanol, ethanol, 1,2-propanediol and / or tripropylene glycol and / or other suitable alcohols, or organic solvents such as 1-methoxy-2-propanol which are quite inexpensive and available for large-scale use, or solvents such as ethyl acetate, methyl ethyl ketone and the like of the same kind, and isopropanol, 1,2-propanediol, 1-methoxy-2-propanol, ethyl acetate and / or tripropylene glycol are preferred co-solvents, with ethyl acetate and tripropylene glycol being more preferred. Preferably, for the reaction, they are introduced in the smallest possible amount only as solvents for the radical initiator and / or the graft monomers (B1) and / or (B2), preferably only for the radical initiator.

[0124] Thus, when reducing the total amount of alcohol or other organic solvents compared to water, this type of organic solvent may remain in the final polymer, preferably less than 1 weight percent, preferably less than 0.5 weight percent, more preferably less than 0.1 weight percent, based on the total amount of the entire solvent.

[0125] In the case of solvents with a boiling point below about 110 - 120 °C at atmospheric pressure, such solvents can be removed in whole or in part, or essentially completely, either at atmospheric pressure or under reduced pressure, by high-temperature or vacuum distillation or stripping with a gas such as steam or nitrogen, preferably steam stripping, while solvents with a higher boiling point will generally remain in the resulting polymer product. Thus, solvents such as 1-methoxy-2-propanol, 1,2-propanediol, and tripropylene glycol will remain in the polymer product, and thus, the amounts of these need to be minimized as much as possible by using the radical initiator at the highest possible concentration.

[0126] The radical initiator (C) is preferably used in the form of a concentrated solution in one of the solvents mentioned above. The concentration, of course, depends on the solubility of the radical initiator. The concentration is preferably as high as possible to enable introduction of as little organic solvent as possible into the polymerization reaction.

[0127] The monomers are preferably used in pure form or, although less preferably, in the form of a 10 - 95 weight percent solution in one of the solvents described above. Again, this concentration is preferably as high as possible to minimize the amount of organic solvent introduced into the polymerization reaction.

[0128] In the process according to the invention, the polymer backbone (A), the graft monomers (B1), (B2), and any optional further monomers, the initiator (C), and, if appropriate, the solvent (D) are usually heated to the selected average polymerization temperature in the reactor.

[0129] The polymerization process according to the invention can in principle be carried out in various types of reactors.

[0130] In a preferred embodiment, the reactor used is preferably a stirred tank, and first all or part of the polymer main chain (A), optionally together with a specific total amount of graft monomers (B1), (B2), and optional further monomers, initiator (C), and solvent (D), generally up to 15% by weight, is charged, heated to the polymerization temperature, and the remaining amounts of (B1), (B2), and optional further monomers, (C), and optionally (D) are preferably metered in separately. The remaining amounts of (B1), (B2), and optional further monomers, (C), and optionally (D) are, in embodiment A), preferably for at least 1 hour, more preferably at least 2 hours, most preferably at least 3 hours, and preferably at most 15 hours, more preferably 12 hours or less, even more preferably 10 hours or less, even more preferably 8 hours or less, for example 7, 6, 5, or even 4 hours, most preferably in the range of about 3 to 7 hours (which also varies depending on the scale of the reaction) metered in, while in embodiment B), the monomers are added to the reaction zone in an amount of at least 50, more preferably at least 70, even more preferably at least 90, most preferably 100 percent of the total amount of each monomer (the total amounts of all the monomers used can be selected individually and independently of each other) before the addition of the radical initiator, and the remaining amounts of the monomers and the radical initiator are not added at the start of the polymerization reaction as added in embodiment A).

[0131] In both cases of embodiments A) and B), the period of adding the radical initiator is preferably longer than the period of adding the monomers, preferably by about 0.25 hour, preferably by about 0.5 hour, and at most 3 hours.

[0132] A post-polymerization process step can be added after the main polymerization reaction. To that end, a further amount of initiator (dissolved in a solvent) can be added over a period of from 0.5 hours to a maximum of 3 hours, preferably about 1 to 2 hours, more preferably about 1 hour, and the radical initiator and the solvent therefor are typically and preferably the same as the solvent of the main polymerization reaction. Needless to say, different radical initiators and / or different solvents can also be used.

[0133] A certain period can be waited between the post-polymerization and the main polymerization, where the main polymerization reaction is allowed to proceed and then the post-polymerization reaction is initiated by starting the addition of a further radical initiator.

[0134] The temperature of the post-polymerization process step can be the same as that in the main polymerization reaction (which is preferred in the present invention) or can be increased. When increasing, it can typically be about 5 to 40 °C, preferably 10 to 20 °C higher.

[0135] The procedure in the low-solvent process, which is a further particularly preferred variant, is as described above, except that the solvent (D) is metered in during the polymerization to limit the viscosity of the reaction mixture. It is also possible to start the metered addition of the solvent only at a later stage when the polymerization has progressed, or to add it in small portions.

[0136] The polymerization can be affected under standard pressure or reduced pressure or high pressure. Under the selected pressure, if the boiling points of the monomers (B1), (B2), and any optional further monomers, or any solvent (D) used are exceeded, the polymerization is carried out with reflux cooling.

[0137] The graft polymer of the present invention can be subjected to concentration and / or drying means. The resulting graft polymer solution can be concentrated by removing a part of the solvent to increase the solid polymer concentration. This can be achieved by carrying out a distillation process such as thermal distillation or vacuum distillation, preferably thermal distillation or steam distillation, and even more preferably steam distillation, until the desired solid content is reached. This kind of process can be combined with a purification step. In that case, by removing a desired amount of the solvent from the resulting graft polymer solution, a part or all of the volatile components such as volatile solvents and / or unreacted volatile monomers are removed, and thus it is purified.

[0138] After the main polymerization and optional post-polymerization steps and optional purification step, the graft polymer solution can also be concentrated or dried by subjecting it to drying means, for example, rotary drum drying, spray drying, vacuum drying or freeze drying, preferably spray drying mainly for cost reasons. Such a drying process can also be combined with an agglomeration or granulation process, for example, drying by spray-agglomeration or a fluidized bed dryer.

[0139] Use In principle, the graft polymer of the present invention can be used for any application, especially when the types and amounts of the grafted monomers are equivalent to those of the graft polymers referred to in the prior art section of the present disclosure, by replacing it with a known graft polymer having a similar composition (excluding vinylimidazole) in terms of the relative amounts of the polymer backbone and the grafted monomers. Such applications are as follows, for example. - Cosmetics, personal care: Such compositions and formulations include shampoos, lotions, gels, sprays, soaps, makeup powders, lipsticks, hairsprays. - Technical uses: Such compositions and formulations include use as a dispersant in any type of dispersion system, such as in any type of adhesive, non-aqueous, and preferably aqueous liquid or solid formulations, typically dispersed in another liquid or solid, for example in oilfield applications, automotive applications, etc. - Lacquer, paint and colorant formulations: Such compositions and formulations include non-aqueous, and preferably aqueous lacquers and colorants, paints, finishing agents. - Agricultural formulations: Such compositions and formulations include formulations and compositions containing pesticidal active substances in liquid, semi-solid, mixed liquid-solid or solid environments. - Perfume formulations: Such compositions and formulations include formulations in which the perfume is dissolved or dispersed so as to be uniformly dispersed and / or its stability is maintained in a liquid or solid composition in order to maintain its scent profile over a long period of time; compositions that release the perfume over time, for example, formulations that release it over a long period of time or release it with a delay are also included.

[0140] Therefore, a) As an additive in cleaning compositions, preferably for liquid, solid, or semi-solid detergent formulations, particularly liquid detergent formulations, preferably concentrated liquid detergent formulations, or single-dose laundry detergent formulations or liquid manual dishwashing detergent formulations, or as an additive for solid automatic dishwashing formulations, b) In fabric care and home care products, c) In pesticide formulations, preferably as a dispersant, d) For example, as an aid for producing multilayer composite films by adapting not only different polymer layers but also metal foils, e) For example, as an adhesion promoter for adhesives used in combination with polyvinyl alcohol, butyrate, and acetate, and styrene copolymers, or as a flocculation promoter for label adhesives, f) As a primer for improving adhesion to substrates such as glass, wood, plastic, and metal in coating applications, g) For improving the wet adhesion in standard emulsion paints and, for example, for improving the immediate rain resistance of paints for road markings, h) As a complexing agent having a high binding ability particularly for heavy metals such as Hg, Pb, Cu, Ni, i) As a penetration aid for active metal salt formulations, for example, in wood protection, j) As a corrosion inhibitor, for example, for iron and non-ferrous metals and in the sectors of oil production and secondary oil production, k) For the immobilization of proteins and enzymes, microorganisms, or as an immobilization support for enzymes and microorganisms, l) As a fixing solution in the film manufacturing industry, m) As an additive, for example, in hair setting compositions and cosmetic formulations for hair rinses, n) As an emulsifier, o) As a surfactant in the industrial cleaning (IC) sector, p) For preparing a complexing agent (polycarboxylate), q) For producing an aid for ore mining and beneficiation, r) As a dispersant for pigments, ceramics, carbon black, carbon, carbon fibers, metal powders, for example, as an emulsifier or dispersant for inks, for example, for inkjet printing, s) As a crystallization inhibitor, for example, in pesticide formulations, for oilfield applications, t) As a rheology modifier, u) As an aid or as a component for an aid for extracting and treating oil, coal, and natural gas, v) As an additive in coolants, lubricants, and coolant-lubricants, or w) As a component of a zinc plating bath, The use of the above graft polymers is also the subject of the present invention.

[0141] Preferably, the graft polymer is used in a cleaning composition and / or in fabric care and home care products, specifically in a cleaning composition for improving the resistance to dye transfer, where the cleaning composition is preferably a laundry detergent formulation, more preferably a liquid laundry detergent formulation.

[0142] Preferred areas of application for using the graft polymer and products and compositions containing the graft polymer are in fabric care and home care products and in cleaning compositions, preferably in the field of cleaning compositions for industrial use and for consumer use in the home.

[0143] Accordingly, another subject of the present invention is a composition or product for the uses listed above in this section, each containing at least one graft polymer as defined above or obtained or obtainable by the process of the present invention and / or described in detail herein, specifically a cleaning composition, a fabric care and home care product, an industrial cleaning product, or a pesticide formulation, preferably a cleaning composition and / or a fabric care and home care product, more preferably a laundry detergent, even more preferably a liquid laundry detergent.

[0144] Accordingly, a preferred subject of the present invention is a cleaning composition, a fabric care and home care product, preferably a composition for laundry cleaning, a product for laundry treatment, or a product for laundry care, or a product for laundry washing, preferably a laundry detergent formulation or a liquid laundry detergent product, containing 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, and such a composition or product has improved resistance to dye transfer.

[0145] Such use of the present invention encompasses the use of graft polymers that are detailed herein and / or that can be obtained or have been obtained by the process of the present invention, such graft polymers being similar to those described for the polymer structure in all of the embodiments, variants, and preferred and more preferred embodiments detailed above, and also including the detailed embodiments further described in the "Embodiment 1 / 2 / 3 etc." recited herein.

[0146] In one embodiment, a cleaning composition, a fabric care and home care product, preferably a laundry cleaning composition, a laundry treatment product, or a laundry care product, or a laundry washing product, more preferably a liquid laundry detergent formulation or a liquid laundry detergent product (such compositions or products preferably having improved anti-dye transfer properties), comprising at least one graft polymer of the present invention and / or at least one graft polymer that can be obtained or has been obtained by the process of the present invention, preferably contains at least one enzyme selected from one or more of lipase, hydrolase, amylase, protease, cellulase, mannanase, hemicellulase, phospholipase, esterase, xylanase, DNase, dispersin, pectinase, oxidoreductase, cutinase, lactase, and peroxidase, and more preferably also contains at least two of the above types additionally.

[0147] At least one graft polymer described in this specification and / or at least one graft polymer obtained or obtainable by the process of the present invention detailed above is present in the above-described compositions and products of the present invention in an amount of from about 0.05% to about 20%, preferably from 0.05 to 10%, more preferably from about 0.1% to 8%, even more preferably from about 0.2% to about 6%, still more preferably from about 0.2% to about 4%, most preferably up to 2% (further including any range obtained by selecting any of the lower limits and any of the upper limits described herein, as well as any numerical value therebetween), by weight based on the total weight of such composition or product, and such composition or product can further contain a surfactant system in an amount of from about 1% to about 70% by weight of the composition or product, and preferably contains this, and the above-described compositions, formulations, washing compositions, and products are preferably used or useful as a dye transfer inhibitor and / or are used or useful for preventing the transfer of dyes.

[0148] Even more preferably, the at least one graft polymer of the present invention detailed above and / or at least one graft polymer obtained or obtainable by the process of the present invention detailed above is contained in the amount defined in the above paragraph, preferably for the use of the graft polymer for preventing the transfer of dyes, and optionally further contains at least one surfactant or surfactant system in an amount of from about 1% to about 70% by weight of the composition or product, and the composition or product of the present invention detailed above in this specification is for performing primary washing (i.e., removal of dirt) in laundry applications, and further, at least one enzyme selected from lipase, hydrolase, amylase, protease, cellulase, mannanase, hemicellulase, phospholipase, esterase, xylanase, DNase, dispersin, pectinase, oxidoreductase, cutinase, lactase, and peroxidase, more preferably, can contain at least two of the above-mentioned types.

[0149] In a preferred embodiment, the cleaning composition of the present invention is a liquid or solid laundry detergent composition, preferably a liquid laundry detergent composition.

[0150] In one embodiment, the graft polymer of the present invention can be used in a cleaning composition or product comprising a surfactant system including a 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.

[0151] In a further embodiment, the graft polymer of the present invention can be used in a cleaning composition or fabric care and home care product, preferably a laundry cleaning composition, a laundry care product or a laundry treatment product or a laundry washing product, preferably a liquid laundry detergent formulation or a liquid laundry detergent product, comprising a C8-C18 linear or branched alkyl ether sulfate 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.

[0152] In a further embodiment, the graft polymer of the present invention can be used in a cleaning composition or fabric care and home care product, preferably a laundry cleaning composition, a laundry care product or a laundry washing product, preferably a liquid laundry detergent formulation or a liquid laundry detergent product, comprising a C12-C18 alkyl ethoxylate surfactant containing 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.

[0153] In one embodiment of the present invention, the graft polymer is a component of a cleaning composition or a fabric care and home care product, each further comprising at least one surfactant, preferably at least one anionic surfactant, preferably a laundry detergent composition, a laundry care product or a laundry treatment product or a laundry washing product, preferably a liquid laundry detergent formulation or a liquid laundry detergent product.

[0154] In a further embodiment, the present invention relates to a composition, specifically a cleaning composition, more preferably a cleaning composition in liquid, solid or semi-solid form, preferably a concentrated liquid detergent formulation, a single single-dose laundry detergent formulation, a liquid manual dishwashing detergent formulation, or a solid automatic dishwashing formulation, more preferably a cleaning composition which is a laundry detergent formulation containing the graft polymer described above in the amounts detailed above, preferably a detergent composition, preferably selected from the group consisting of 2-phenoxyethanol, more preferably containing the antibacterial agent described below in the present specification in an amount in the range of 2 ppm to 5% based on the weight of the composition, and even more preferably containing 0.1 to 2% phenoxyethanol, and further includes a cleaning composition further containing an antibacterial agent.

[0155] In a further embodiment, the present invention further includes a method for protecting a cleaning composition, which is an aqueous composition, specifically a cleaning composition, more preferably in liquid, solid or semi-solid form, preferably a concentrated liquid detergent formulation, a single single-dose laundry detergent formulation, a liquid manual dishwashing detergent formulation, or a solid automatic dishwashing formulation, more preferably a laundry detergent formulation containing the graft polymer described above in the amounts detailed above, preferably a detergent composition, from microbial contamination or growth, such method including adding at least one antibacterial agent selected from the antibacterial agents of the present disclosure disclosed below in the present specification, such antibacterial agent preferably being 2-phenoxyethanol.

[0156] In a further embodiment, the present invention further includes 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. Such compositions each contain the graft polymer and / or polymer backbone in the amounts detailed above as described hereinabove, and such compositions further contain 4,4'-dichlorohydroxydiphenyl ether at a concentration of 0.001 to 3% by weight, preferably 0.002 to 1% by weight, more preferably 0.01 to 0.6% by weight, based on the weight of the composition respectively.

[0157] In a further embodiment, the present invention further includes a method of washing fabrics or cleaning hard surfaces, the method comprising treating the fabric or hard surface 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. Such compositions each contain the graft polymer and / or polymer backbone in the amounts detailed above as described hereinabove, and such compositions further contain 4,4'-dichlorohydroxydiphenyl ether.

[0158] The selection of additional surfactants and further components (both detailed in the "Cleaning Additives" section below) in these embodiments may depend on the application and the desired benefits.

[0159] Description of Cleaning Compositions, Formulations, and Their Components As used herein, the term "cleaning composition" includes compositions, formulations, and products designed for the cleaning of soiled materials. Such compositions, formulations, and products include those designed for cleaning any type of soiled material or soiled surface.

[0160] Examples of the composition for "industrial cleaning" include any type of composition designed for use in industrial cleaning, such as hard surface cleaners for any type of surface, including tiles, carpets, PVC surfaces, wood surfaces, metal surfaces, and lacquered surfaces, for cleaning any type of soiled material or surface.

[0161] Examples of the "fabric care and home care compositions" include, but are not limited to, compositions and detergents for laundry cleaning, fabric softening compositions, fabric strengthening compositions, fabric cooling compositions, detergents for pre-washing laundry, laundry pretreatment agents, laundry aids, spray products, dry cleaning agents or compositions, additives for rinsing laundry, additives for washing away, fabric treatment agents after rinsing, ironing aids, compositions for dishwashing, compositions for hard surface cleaning, unit-dose formulations, delayed delivery formulations, detergents contained on or inside porous substrates or non-woven sheets, and other suitable forms that may be apparent to those skilled in the art in view of the teachings herein. Such compositions may be used as laundry pretreatment agents or post-treatment agents, or may be added during the rinsing or wash-away cycle of the laundry operation, preferably during the wash-away cycle of the laundry or dishwashing operation.

[0162] The cleaning composition of the present invention can be in any form, namely, liquid form; solids such as powders, granules, aggregates, pastes, tablets, sachets, rods, gels; emulsions; those of the type delivered in containers having two or more compartments; single-phase or multi-phase unit-dose articles; spray or foam detergents; wet wipe sheets (i.e., a combination of the cleaning composition with a non-woven material such as those described in U.S. Patent No. 6,121,165 by Mackey et al.); dry wipe sheets that are activated by the user or consumer wetting with water (i.e., a combination of the cleaning composition with a non-woven material such as those described in U.S. Patent No. 5,980,931 by Fowler et al.); and other homogeneous, heterogeneous, or single-phase or multi-phase cleaning product forms.

[0163] The liquid cleaning composition of the present invention preferably has a viscosity of 50 to 10,000 mPa·s. The manual dish wash cleaning composition (also referred to as the manual “dish wash composition”) has a viscosity of preferably 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 of preferably 50 to 3,000 mPa·s, more preferably 100 to 1,500 mPa·s, and most preferably 200 to 1,000 mPa·s at 20 1 / s and 20 °C.

[0164] The liquid cleaning composition of the present invention can have any suitable pH value. Preferably, the pH of the composition is adjusted to 4 to 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 adjusting components known in the art, which is measured at 25 °C with the concentration of the product being 10% by weight in deionized water. For example, NaOH can be used, and the actual weight percentage of NaOH can be varied to adjust to the desired pH, for example, pH 8.0. In one embodiment of the present invention, the pH is adjusted to >7 by using an amine, preferably an alkanolamine, more preferably triethanolamine.

[0165] Cleaning compositions such as fabric care and home care products and industrial cleaning formulations, more specifically detergents for laundry and manual dishwashing, are known to those skilled in the art. Any composition known to those skilled in the art related to each use, especially when such a composition is used in its field of use, can be used in relation to the present invention by including at least one polymer of the present invention, preferably at least one polymer in an amount suitable for expressing specific properties within such a composition.

[0166] The use of the polymers of the present invention as detergent complexes, in particular liquid detergent complexes, preferably concentrated liquid detergent complexes, or as additives for single-dose use in laundry is also an aspect of the present invention.

[0167] Washing additive The cleaning compositions and formulations of the present invention may, preferably do, contain auxiliary cleaning additives (which may sometimes be abbreviated herein as "auxiliaries"), and such auxiliaries are preferably added to the surfactant systems defined above.

[0168] Suitable auxiliary cleaning additives include builders, cobuilders, structuring or thickening agents, clay soil removal / redeposition inhibitors, polymeric soil release agents, dispersants such as polymeric dispersants, polymeric oil cleaners, solubilizers, chelating agents, enzymes, enzyme stabilization systems, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, optical brighteners, malodor suppressants, pigments, dyes, opacifiers, color correctors, dye transfer inhibitors, chelating agents, foam boosters, foam suppressants (antifoaming agents), color speckles, silver product cleaners, anti-fogging and / or corrosion inhibitors, alkalizing agents, pH adjusters, pH buffers, hydrotropes, scrubbing particles, antibacterial agents, antioxidants, softeners, carriers, processing aids, perfume precursors and perfumes. All of these auxiliaries are described and exemplified in more detail in the sections below.

[0169] The liquid cleaning composition can, preferably does, additionally contain at least one of a rheology control / modifying agent, a skin softening agent, a moisturizing agent, a skin rejuvenating active and a solvent.

[0170] The solid composition can, preferably does, additionally contain at least one of a filler, a bleaching agent, a bleach activator and a catalyst material.

[0171] Suitable examples of this type of cleaning auxiliaries and amounts used are described in WO 99 / 05242 pamphlet, US Pat. Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1.

[0172] Those skilled in the art will understand that detergent surfactants include any surfactant or surfactant mixture that is beneficial for cleaning soiled materials, removing stains, or laundering.

[0173] Accordingly, the cleaning compositions of the present invention, such as fabric care and home care products and industrial cleaning formulations, more specifically detergents for laundry and dishwashing, preferably further comprise a surfactant system as described above and will be described in more detail later, and more preferably further auxiliary agents.

[0174] The surfactant system can be composed of one surfactant or a combination of surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. Those skilled in the art will understand that detergent surfactant systems include any surfactant or surfactant mixture that is beneficial for cleaning soiled materials, removing stains, or laundering.

[0175] The cleaning compositions of the present invention preferably contain a surfactant system in an amount sufficient to impart the desired detergency. In some embodiments, the cleaning composition contains a surfactant system of about 1% to about 70% by weight of the composition. In other embodiments, the liquid cleaning composition contains a surfactant system of about 2% to about 60% by weight of the composition. In further embodiments, the cleaning composition contains a surfactant system of about 5% to about 30% by weight of the composition. The surfactant system can include detergency surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and combinations thereof.

[0176] The selection of additional surfactants and further components in these embodiments can depend on the application and the desired benefits.

[0177] All such cleaning compositions, their components including (auxiliary) cleaning additives, their general compositions, and more specific compositions are known from, for example, documents 800542 and 800500 published by Protegas, Liechtenstein, as well as from International Publication Pamphlets No. 2022 / 136409 and No. 2022 / 136408, and in any of the past prior art documents, the general composition, and in addition to the above publications, any other publication disclosing the cleaning formulations and products considered herein, polymers (i.e., in particular graft polymers made from PEG and vinyl esters, and / or anti-dye transfer polymers, more specifically anti-dye transfer polymers) that serve the same purpose as the object of the present invention within each individualized composition disclosed can be partially or completely replaced by the compounds of the present invention. In particular, these documents mentioned above in this paragraph also disclose formulations for various types of cleaning compositions, and all such types of compositions are equally applicable to the general composition and even more so to each individual specific cleaning composition considered herein and to these cleaning compositions considered herein.

[0178] Accordingly, the present invention further encompasses any such prior art composition that contains a polymer that serves the same purpose as the object of the present invention, or any such compound that can be replaced by such a compound of the present invention, in addition to or instead of, the above-described disclosed compositions of the prior art disclosure, but further contains at least one of the compounds of the present invention. Such replacement is in principle known to those skilled in the art or will readily become apparent in view of the present invention. The content of the compounds of the present invention is in the concentration indicated at the beginning of this section, i.e., typically in units of weight % relative to the total weight of each such composition / product, from about 0.1% to about 50%, preferably from about 0.25% to 15%, more preferably from about 0.5% to about 10%, even more preferably from about 0.5% to about 5%, and most preferably up to 3% in the above formulations.

[0179] Laundry composition "Laundry composition" can be any composition, formulation, or product intended for use in laundry, including laundry care, laundry washing, etc. Therefore, this term is used below to mean any composition, formulation, or product.

[0180] In laundry compositions, anionic surfactants usually account for the largest proportion among the surfactants in such formulations. Therefore, preferably, the cleaning composition of the present invention for use in laundry comprises at least one anionic surfactant and, optionally, a further surfactant selected from any of the types of surfactants described herein, preferably a nonionic surfactant and / or an amphoteric surfactant and / or a zwitterionic surfactant and / or a cationic surfactant.

[0181] The cleaning composition can also contain, preferably contains, an anionic surfactant that can be used in combination with two or more other surfactants.

[0182] Non-limiting examples of useful anionic surfactants that can also be used in combinations of two or more surfactants herein include C9-C20 linear alkylbenzene sulfonates (LAS), C10-C20 primary, branched-chain, 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 1 to 5 ethoxy units; internal branched-chain alkyl sulfates described in U.S. Patent No. 6,020,303 and U.S. Patent No. 6,060,443; internal branched-chain alkyl alkoxy sulfates described in U.S. Patent No. 6,008,181 and U.S. Patent No. 6,020,303; modified alkylbenzene sulfonates (MLAS) described in WO 99 / 05243, WO 99 / 05242, and WO 99 / 05244; methyl ester sulfonates (MES); and α-olefin sulfonates (AOS).

[0183] Preferred examples of suitable anionic surfactants are C8-C12 alkyl sulfates, C12-C18 fatty alcohol ether sulfates, C12-C18 fatty alcohol polyether sulfates, sulfuric acid half-esters of ethoxylated C4-C12 alkylphenols (ethoxylation: 3-50 moles of ethylene oxide per mole), C12-C18 alkyl sulfonic acids, C12-C18 sulfofatty acid alkyl esters, for example C12-C18 sulfofatty acid methyl esters, C10-C18 alkylaryl sulfonic acids, preferably n-C10-C18 alkylbenzene sulfonic acids, C10-C18 alkyl alkoxycarboxylic acid esters, and soaps, for example C8-C24 carboxylic acids, etc., alkali metal salts and ammonium salts. Alkali metal salts of the above-mentioned compounds are preferred, and sodium salts are particularly preferred.

[0184] In one embodiment of the present invention, the anionic surfactant is selected from n-C10-C18 alkylbenzene sulfonic acid and fatty alcohol polyether sulfate, which, in the context of the present invention, is particularly the sulfuric acid half-ester of ethoxylated C12-C18 alkanols (ethoxylation: 1-50 moles of ethylene oxide per mole), preferably n-C12-C18 alkanols.

[0185] In one embodiment of the present invention, alcohol polyether sulfates derived from branched-chain (i.e., synthetic) C11-C18 alkanols (ethoxylation: 1-50 moles of ethylene oxide per mole) can also be used.

[0186] Preferably, the alkoxylation group of the alkoxylated alkyl sulfate based on C12-C18 fatty alcohol or based on branched-chain (i.e., synthetic) C11-C18 alcohol is an ethoxylation group in both cases, and the average ethoxylation degree of any alkoxylated alkyl sulfate is 1-5, preferably 1-3.

[0187] Preferably, the detergent composition of the present invention contains at least 1% by weight to 50% by weight, preferably in the range of about 2% by weight or more to about 30% by weight or less, more preferably in the range of 3% by weight or more to 25% by weight or less, and most preferably in the range of 5% by weight or more to 25% by weight or less, based on the total of the one or more anionic surfactants described above and other components as well as water and / or solvents in the specific composition.

[0188] In a preferred embodiment of the present invention, the anionic surfactant is selected from C10 - C15 linear alkylbenzene sulfonates, C10 - C18 alkyl ether sulfates containing 1 - 5 ethoxy units, and C10 - C18 alkyl sulfates.

[0189] The cleaning composition may also contain a nonionic surfactant that can be used in combination with two or more other surfactants.

[0190] Non-limiting examples of nonionic surfactants that can be used in combination with two or more other surfactants include C8 - C18 alkyl ethoxylates, such as the nonionic surfactant NEODOL (registered trademark) from Shell; ethylene oxide / propylene oxide block alkoxylates such as PLURONIC (registered trademark) from BASF; C14 - C22 medium-chain branched alkyl alkoxylates BAEx (x is 1 - 30) described in U.S. Patent No. 6,153,577, U.S. Patent No. 6,020,303, and U.S. Patent No. 6,093,856; alkyl polysaccharides described in U.S. Patent No. 4,565,647 by Llenado issued on January 26, 1986; specifically, alkyl polyglycosides described in U.S. Patent No. 4,483,780 and U.S. Patent No. 4,483,779; polyhydroxy fatty acid amides described in U.S. Patent No. 5,332,528; and ether-terminated poly(oxyalkylated) alcohol surfactants described in U.S. Patent No. 6,482,994 and International Publication No. 01 / 42408 pamphlet.

[0191] Preferred examples of nonionic surfactants are, in particular, alkoxylated alcohols and alkoxylated fatty alcohols, binary and polyblock copolymers of ethylene oxide and propylene oxide, and reaction products of sorbitan with ethylene oxide or propylene oxide, and furthermore alkylphenol ethoxylates, alkyl glycosides, polyhydroxy fatty acid amides (glucamides). Examples of (additional) amphoteric surfactants are the so-called amine oxides.

[0192] Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (A)

Chemical formula

[0193] In the present specification, the compounds of general formula (A) may be block copolymers or random copolymers, with block copolymers being preferred.

[0194] Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of general formula (B) [Chemical Formula] wherein the variables are defined as follows: R1 is the same or different and is selected from straight-chain C1-C4 alkyl, preferably the same in each case, ethyl, particularly preferably methyl, R4 is selected from C6-C20 alkyl, particularly n-C8H17, n-C10H21, n-C12H25, n-C14H29, n-C16H33, n-C18H37, a is a number in the range from 0 to 6, preferably in the range from 1 to 6, b is a number in the range from 0 to 20, preferably in the range from 4 to 20, d is a number in the range from 4 to 25.

[0195] Preferably, at least one of a and b is greater than zero.

[0196] Here, the compound of general formula (B) can be a block copolymer or a random copolymer, with the block copolymer being preferred.

[0197] More 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 alkyl polyglycosides or polyhydroxy fatty acid amides (glucamides) are likewise suitable. An overview of suitable further nonionic surfactants can be found in European Patent Application Publication No. A0851023 and German Patent Application Publication No. A19819187.

[0198] Naturally, mixtures of two or more different nonionic surfactants can also exist.

[0199] In a preferred embodiment of the present invention, the nonionic surfactant is selected from C12 / 14 and C16 / 18 fatty alcohol alkoxylates, C13 / 15 oxo alcohol alkoxylates, C13-alcohol alkoxylates, and 2-propylheptyl alcohol alkoxylates, each of which has 3 to 15 ethoxy units, preferably 5 to 10 ethoxy units, or 1 to 3 propoxy units and 2 to 15 ethoxy units.

[0200] The cleaning composition may also contain zwitterionic surfactants that can be used in combination with two or more other surfactants.

[0201] Non-limiting examples of zwitterionic surfactants that can also be used in combination with two or more other surfactants include: water-soluble amine oxides containing one alkyl moiety having from about 8 to about 18 carbon atoms and two moieties selected from the group consisting of an alkyl moiety and a hydroxyalkyl moiety containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety containing from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of an alkyl moiety and a hydroxyalkyl moiety having from about 1 to about 3 carbon atoms. See WO 01 / 32816 pamphlet, US Patent No. 4,681,704, and US Patent No. 4,133,779. Accordingly, suitable surfactants include so-called amine oxides, for example, lauryldimethylamine oxide ("lauramine oxide").

[0202] Preferred examples of the amphoteric surfactant are amine oxides. Preferred amine oxides are alkyldimethylamine oxides or alkylamidopropyldimethylamine oxides, more preferably alkyldimethylamine oxides, especially coconut oil alkyldimethylamine oxide. The amine oxide can have a straight-chain or internally branched alkyl moiety. Typical straight-chain amine oxides include water-soluble amine oxides containing one R1 = C8-18 alkyl moiety and two R2 and R3 moieties selected from the group consisting of C1-C3 alkyl groups and C1-C3 hydroxyalkyl groups. Preferably, the amine oxide has the formula: R1-N(R2)(R3)-O (In the formula, R1 is C8 - C18 alkyl, and R2 and R3 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2 - hydroxyethyl, 2 - hydroxypropyl, and 3 - hydroxypropyl). As the linear amine oxide surfactant, in particular, linear C10 - C18 alkyldimethylamine oxide and linear C8 - C12 alkoxyethyldihydroxyethylamine oxide can be mentioned. 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 one alkyl moiety having n1 carbon atoms and one alkyl branch having n2 carbon atoms on this alkyl moiety. This alkyl branch is located on the α - carbon with respect to the nitrogen on the alkyl moiety. This type of branching of the amine oxide is also known in the art as an internal amine oxide. The total number of carbon atoms of n1 and n2 is 10 - 24, preferably 12 - 20, more preferably 10 - 16. The number of carbon atoms of one alkyl moiety (n1) needs to be approximately equal to the number of carbon atoms of one alkyl branch (n2) so that this one alkyl moiety and one alkyl branch are symmetric. As used herein, "symmetric" means that at least 50% by weight, more preferably at least 75% - 100% by weight of the (n1 - n2) carbon atoms of the mid - branched amine oxide used herein is 5 or less, preferably 4 or less, most preferably 0 - 4. The amine oxide further comprises two moieties independently selected from C1 - C3 alkyl, C1 - C3 hydroxyalkyl groups, or polyethylene oxide groups containing an average of about 1 to about 3 ethylene oxide groups. Preferably, these two moieties are selected from C1 - C3 alkyl, and more preferably, both are selected as C1 alkyl.

[0203] In a preferred embodiment of the present invention, the amphoteric surfactant is selected from C8 - C18 alkyl - dimethylamine oxide and C8 - C18 alkyl - di(hydroxyethyl)amine oxide.

[0204] The cleaning composition can also contain an amphoteric surfactant that can also be used in combination with two or more other surfactants.

[0205] Suitable zwitterionic surfactants include betaines such as alkyl betaines, alkylamide betaines, amidazolinium betaines, sulfobetaines (INCI: sultaines), and phosphobetaines. Examples of suitable betaines and sulfobetaines are shown below (shown according to INCI): Almond amidopropyl betaine, Apricotamidopropyl betaine, Avocadamidopropyl betaine, Babassuamidopropyl betaine, Behenamidopropyl betaine, Behenyl betaine, Canol amidopropyl betaine, Capryl / Capramidopropyl betaine, Carnitine, Cetyl betaine, Cocamidoethyl betaine, Cocamidopropyl betaine, Cocamidopropyl Hydroxysultaine, Coco betaine, Coco Hydroxysultaine, Coco / Oleamidopropyl betaine, Coco Sultaine, Decyl betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl StearylGlycinate), Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl of PG-betaine, Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow of betaine, Isostearamidopropyl betaine, Lauramidopropyl betaine, Lauryl of betaine, Lauryl Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl betaine, Minkamidopropyl of betaine, Myristamidopropyl betaine, Myristyl of betaine, Oleamidopropyl betaine, Oleamidopropyl Hydroxysultaine, Oleyl of betaine, Olivamidopropyl of betaine, Palmidopropyl betaine, Palmitamidopropyl betaine, Palmitoyl Carnitine, Palm Kernelamidopropyl betaine, Polytetrafluoroethylene Acetoxypropyl of betaine, Ricinoleam idopropylbetaine), Sesamidopropyl betaine, Soyamidopropyl betaine, Stearamidopropyl betaine, Stearyl of betaine, Tallowamidopropyl betaine, Tallowamidopropyl Hydroxysultaine, Tallow of betaine, Tallow Dihydroxyethyl of betaine, Undecylenamidopropyl betaine, and Wheat Germamidopropyl betaine.

[0206] Preferred betaines are, for example, C12-C18 alkyl betaines and sulfobetaines. The zwitterionic surfactant is preferably a betaine surfactant, more preferably a cocamidopropyl betaine surfactant.

[0207] Non-limiting examples of cationic surfactants that can also be used in combination with two or more other surfactants include: quaternary ammonium surfactants that can have up to 26 carbon atoms, such as the alkoxylated quaternary ammonium (AQA) surfactants described in U.S. Patent No. 6,136,769; dimethylhydroxyethyl quaternary ammonium described in U.S. Patent No. 6,004,922; dimethylhydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants described in WO 98 / 35002, WO 98 / 35003, WO 98 / 35004, WO 98 / 35005 and WO 98 / 35006; cationic ester surfactants described in U.S. Patent Nos. 4,228,042, 4,239,660, 4,260,529 and U.S. Patent No. 6,022,844; and amino surfactants described in U.S. Patent No. 6,221,825 and WO 00 / 47708, specifically amidopropyldimethylamine (APA).

[0208] The compositions according to the invention may contain at least one builder. In the context of the present invention, a builder is not distinguished from a component otherwise referred to elsewhere as a "cobuilder". Examples of builders are complexing agents, also referred to hereinbelow as sequestering agents, ion exchange compounds, and precipitating agents. Builders are selected from citrate, phosphate, silicate, carbonate, phosphonate, aminocarboxylate, and polycarboxylate.

[0209] In the context of the present invention, the term citrate includes the mono- and dialkali metal salts of citric acid, in particular the monosodium salt and preferably the trisodium salt, ammonium salts or substituted ammonium salts of citric acid, and also citric acid. Citrates can be used as anhydrous compounds or as hydrates, for example as sodium citrate dihydrate. The amount of citrate is calculated on the basis of trisodium citrate anhydride.

[0210] 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 do not contain phosphates and polyphosphates, which also includes hydrogen phosphates, for example, trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate are not included ( "phosphate-free"). "Not containing" with respect to phosphates and polyphosphates relevant to the present invention is to be understood to mean that the total content of phosphates and polyphosphates determined by gravimetric analysis is in the range of 10 ppm to 0.2% by weight of each composition.

[0211] The term carbonate includes alkali metal carbonates and alkali metal bicarbonates, with the sodium salts being preferred. Na2CO3 is particularly preferred.

[0212] Examples of phosphonates are hydroxyalkane phosphonates and aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly important as a builder. This is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Suitable aminoalkane phosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) in addition to their higher homologues. These are preferably used in the form of sodium salts that react neutrally, for example, as the hexasodium salt of EDTMP or as the hepta- and octasodium salts of DTPMP.

[0213] Examples of aminocarboxylates and polycarboxylates are nitrilotriacetate, ethylenediaminetetraacetate, diethylenetriaminepentaacetate, triethylenetetraminehexaacetate, propylenediaminetetraacetate, ethanol-diglycine, methylglycinediacetate, and glutaminediacetate. The terms aminocarboxylates and polycarboxylates also include their respective unsubstituted or substituted ammonium salts and alkali metal salts, such as sodium salts, and in particular, their fully neutralized compounds respectively.

[0214] In the context of the present invention, examples of silicates include in particular sodium disilicate and sodium metasilicate, aluminosilicates such as zeolites and layered silicates, in particular those of the formula α-Na2Si2O5, β-Na2Si2O5, and δ-Na2Si2O5.

[0215] The composition according to the present invention may contain one or more builders selected from materials not described above. Examples of builders are α-hydroxypropionic acid and oxidized starch.

[0216] In one embodiment of the present invention, the builder is selected from polycarboxylates. The term "polycarboxylate" includes non-polymeric polycarboxylates such as succinic acid, C2-C16 alkyldisuccinates, C2-C16 alkenyldisuccinates, ethylenediamine N,N'-disuccinic acid, tartaric acid diacetate, alkali metal malonates, tartaric acid monoacetate, propane tricarboxylic acid, butane tetracarboxylic acid, and cyclopentane tetracarboxylic acid.

[0217] Oligomeric or polymeric polycarboxylates are, for example, polyaspartic acid or specifically alkali metal salts of (meth)acrylic acid homopolymers or (meth)acrylic acid copolymers.

[0218] Suitable comonomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid, and citraconic acid. Suitable polymers are, specifically, preferably, polyacrylic acids having a weight average molecular weight Mw in the range of 2,000 to 40,000 g / mol, preferably 2,000 to 10,000 g / mol, particularly 3,000 to 8,000 g / mol. More suitable copolymeric polycarboxylates are, specifically, those of acrylic acid and methacrylic acid, and those of acrylic acid or methacrylic acid and maleic acid and / or fumaric acid.

[0219] It is also possible to use a copolymer of at least one monomer selected from the group consisting of monoethylenically unsaturated C3 - C10 mono- or C4 - C10 dicarboxylic acids or their anhydrides, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid, and citraconic acid, and at least one hydrophilic or hydrophobic modifying comonomer listed below.

[0220] Suitable hydrophobic comonomers are, for example, olefins having 10 or more carbon atoms or mixtures thereof, such as isobutene, diisobutene, butene, pentene, hexene, and styrene, for example 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene, and 1-hexacosene, a mixture of C22-α-olefin, C20 - C24-α-olefin and polyisobutene having an average of 12 to 100 carbon atoms per molecule.

[0221] Suitable hydrophilic comonomers are monomers having a sulfonate or phosphonate group, and nonionic monomers having a hydroxyl functional group or an alkylene oxide group. Examples include 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. In the present specification, the polyalkylene glycol may contain 3 to 50, specifically 5 to 40, particularly 10 to 30 alkylene oxide units per molecule.

[0222] Particularly preferred sulfonic acid group-containing monomers in the present specification are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethyl methacrylamide, and salts of the above acids, such as their sodium, potassium, or ammonium salts.

[0223] Particularly preferred phosphonic acid group-containing monomers are vinylphosphonic acid and its salts.

[0224] Furthermore, amphoteric polymers can also be used as builders.

[0225] The composition of the present invention may contain, particularly in the case of solid formulations, for example, a builder in a total amount of 0.1 to 70% by weight, preferably 10 to 50% by weight, preferably at most 20% by weight. The liquid formulation of the present invention preferably contains a builder in the range of 0.1 to 8% by weight.

[0226] The formulation according to the present invention can contain one or more alkali carriers. The alkali carrier ensures a pH of at least 9, for example, when an alkaline pH is desired. For example, in addition to the alkali metal carbonates, alkali metal hydrogen carbonates and alkali metal metasilicates mentioned above, alkali metal hydroxides are also suitable. In any case, the preferred alkali metal is potassium, and sodium is particularly preferred. In one embodiment of the present invention, an amine, preferably an alkanolamine, more preferably triethanolamine, is used to adjust the pH above 7.

[0227] In one embodiment of the present invention, the laundry formulation according to the present invention further contains at least one enzyme.

[0228] Useful enzymes are, for example, lipase, amylase, protease, cellulase, hemicellulase, phospholipase, esterase, pectinase, lactase and peroxidase and one or more hydrolases selected from combinations of at least two of the above-mentioned types.

[0229] In one embodiment, the composition according to the present invention further contains at least one enzyme.

[0230] Preferably, this at least one enzyme is a detergent enzyme.

[0231] In one embodiment, the enzyme is classified as an oxidoreductase (EC1), transferase (EC2), hydrolase (EC3), lyase (EC4), isomerase (EC5), or ligase (EC6) (the EC numbering is based on Enzyme Nomenclature, Recommendations (1992) of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology published from 1993 to 1999, including its appendix). Preferably, the enzyme is a hydrolase (EC3).

[0232] In a preferred embodiment, the enzyme is selected from the group consisting of protease, amylase, lipase, cellulase, mannanase, hemicellulase, phospholipase, esterase, pectinase, lactase, peroxidase, xylanase, cutinase, pectate lyase, keratinase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, beta-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, nuclease, DNase, phosphodiesterase, phytase, carbohydrase, galactanase, xanthanase, xyloglucanase, oxidoreductase, perhydrolase, aminopeptidase, asparaginase, carbohydrase, carboxypeptidase, catalase, chitinase, cyclodextrin glycosyltransferase, alpha-galactosidase, beta-galactosidase, glucoamylase, alpha-glucosidase, beta-glucosidase, invertase, ribonuclease, transglutaminase, and dispersin, and combinations of at least two of the above types. More preferably, the enzyme is selected from the group consisting of protease, amylase, lipase, cellulase, mannanase, xylanase, DNase, dispersin, pectinase, oxidoreductase, and cutinase, and combinations of at least two of the above types. Most preferably, the enzyme is protease, preferably serine protease, more preferably subtilisin protease.

[0233] Such an enzyme can be incorporated into the composition at a level sufficient to provide the composition with an effective amount to achieve beneficial effects, preferably a primary washing effect and / or a secondary washing effect such as anti-blackening stain prevention or anti-pilling effect (e.g., in the case of cellulase). Preferably, the enzyme is present in the composition at a level of about 0.00001% to about 5%, preferably about 0.00001% to about 2%, more preferably about 0.0001% to about 1% or even more preferably about 0.001% to about 0.5% of enzyme protein by weight of the composition.

[0234] Preferably, the enzyme-containing composition further comprises an enzyme stabilization system.

[0235] Preferably, the enzyme-containing composition described herein comprises an enzyme stabilization system in an amount of about 0.001% to about 10%, about 0.005% to about 8%, or about 0.01% to about 6% by weight of the composition. The enzyme stabilization system can be any stabilization system compatible with the enzyme.

[0236] 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), salts (preferably CaCl2, MgCl2, or NaCl), short-chain (preferably C1-C6) carboxylic acids (preferably formic acid, formate (preferably sodium formate), acetic acid, acetate, or lactate), borates, boric acid, boronic acids (preferably 4-formylphenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde hydrogensulfite adducts. Preferably, the enzyme stabilization system comprises at least two combinations of compounds selected from the group consisting of salts, polyols, and short-chain carboxylic acids, preferably one or more of the compounds selected from the group consisting of borates, boric acid, boronic acids (preferably 4-formylphenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde hydrogensulfite adducts. In particular, when protease is present in the composition, preferably, a protease inhibitor selected from borates, boric acid, boronic acids (preferably 4-FPBA), peptide aldehydes (preferably peptide aldehydes such as Z-VAL-H or Z-GAY-H), peptide acetals, and peptide aldehyde hydrogensulfite adducts can be added. The composition according to the present invention can comprise one or more bleaching agents.

[0237] Preferred bleaching agents are selected from sodium perborate anhydrous or as, for example, the monohydrate or the tetrahydrate or the so-called dihydrate, sodium percarbonate anhydrous or as, for example, the monohydrate, and sodium persulfate, and in any case, the term "persulfate" includes the peracid H2SO5 and the salts of peroxodisulfuric acid.

[0238] In this context, the alkali metal salts can in any case also be alkali metal hydrogen carbonates, alkali metal hydrogen perborates, and alkali metal hydrogen persulfates. However, dialkali metal salts are preferred in any case.

[0239] The formulations according to the invention can contain one or more bleach catalysts. The bleach catalysts can 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. Complexes of nitrogen-containing tripod ligands with manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper, and cobalt-, iron-, copper- and ruthenium-amine complexes can also be used as bleach catalysts.

[0240] The formulations of the invention can contain one or more bleach activators, for example tetraacetylethylenediamine, tetraacetylmethylenediamine, tetraacetylglycoluril, tetraacetylhexylenediamine, acylated phenolsulfonates such as, for example, n-nonanoyl- or isononanoyloxybenzenesulfonates, N-methylmorpholinium acetonitrile salt ("MMA salt"), trimethylammonium acetonitrile salt, N-acylimides such as, for example, N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine ("DADHT") or nitrile quat (trimethylammonium acetonitrile salt).

[0241] The formulation according to the present invention can include one or more corrosion inhibitors. In the context of the present invention, this is understood to include compounds that inhibit the corrosion of metals. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazole, bisbenzotriazole, aminotriazole, alkylaminotriazole, and also phenolic derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.

[0242] In one embodiment of the present invention, the formulation according to the present invention includes corrosion inhibitors in a total range of 0.1 to 1.5% by weight.

[0243] The formulation of the present invention can also include further cleaning polymers and / or soil release polymers.

[0244] Examples of additional cleaning polymers include, but are not limited to, "polyfunctional polyethyleneimine" (e.g., Sokalan® HP20 from BASF) and / or "polyfunctional diamine" (e.g., Sokalan® HP96 from BASF). Such polyfunctional polyethyleneimines are typically ethoxylated polyethyleneimines with a weight average molecular weight Mw in the range of 3,000 to 250,000 g / mol, preferably 5,000 to 200,000 g / mol, more preferably 8,000 to 100,000 g / mol, more preferably 8,000 to 50,000 g / mol, more preferably 10,000 to 30,000 g / mol, and most preferably 10,000 to 20,000 g / mol. Suitable polyfunctional polyethyleneimines have ethylene oxide side chains in an amount 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% based on the total weight of the material. The ethoxylated polyethyleneimine is typically based on a polyethyleneimine core and a polyethylene oxide shell. Suitable polyethyleneimine core molecules are polyethyleneimines with a weight average molecular weight Mw in the range of 500 to 5,000 g / mol. Preferably, those with a molecular weight of 500 to 1,000 g / mol are used, and more preferably, Mw is 600 to 800 g / mol. In that case, the ethoxylated polymer has an average of 5 to 50, preferably 10 to 35, and even more preferably 20 to 35 ethylene oxide (EO) units per NH functional group.

[0245] Suitable polyfunctional diamines are further quaternized and optionally sulfated, typically ethoxylated C2-C12 alkylene diamines, preferably hexamethylene diamine. Typical polyfunctional diamines have a weight average molecular weight Mw in the range of 2000-10000 g / mol, more preferably 3000-8000 g / mol, and most preferably 4000-6000 g / mol. In a preferred embodiment of the present invention, it contains on average 10-50, preferably 15-40, and even more preferably 20-30 ethylene oxide (EO) groups per NH functional group, and preferably, a further quaternized and sulfated ethoxylated hexamethylene diamine having 2 cationic ammonium groups and 2 anionic sulfate groups can be used.

[0246] In a preferred embodiment of the present invention, the cleaning composition can contain at least one polyfunctional polyethyleneimine and / or at least one polyfunctional diamine in order to improve the cleaning performance of the laundry detergent, for example, preferably, to improve the stain removal ability, particularly the primary cleaning power of the stain of particles on polyester fabrics. The polyfunctional polyethyleneimine or polyfunctional diamine or a mixture thereof described above can generally be added in an amount of 0.05-15% by weight, preferably 0.1-10% by weight, more preferably 0.25-5% by weight, and even up to 2% by weight, based on the entire specific composition including other components as well as water and / or solvent in the laundry detergent and the cleaning composition.

[0247] Accordingly, one aspect of the present invention is a laundry detergent composition, particularly a liquid laundry detergent, containing (i) at least one polymer of the present invention and (ii) at least one compound selected from polyfunctional polyethyleneimine, polyfunctional diamine, and mixtures thereof.

[0248] In one embodiment of the present invention, the ratio of at least one polymer of the present invention to at least one compound selected from (ii) polyfunctional polyethyleneimine, polyfunctional diamine, and mixtures thereof is from 10:1 to 1:10, preferably from 5:1 to 1:5, more preferably from 3:1 to 1:3.

[0249] The cleaning composition, fabric care and home care products, and especially the laundry formulation, containing the polymer of the present invention may also contain at least one antibacterial agent (also referred to as "preservative").

[0250] An antibacterial agent is a compound that kills microorganisms or inhibits their growth or reproduction. The microorganisms can be bacteria, yeast or mold. A preservative is an antibacterial agent that can be added to aqueous products and compositions to maintain the original performance, properties and integrity of the products and compositions by killing or inhibiting the growth of contaminating microorganisms.

[0251] The composition / formulation may contain one or more antibacterial agents and / or preservatives as listed on pages 35 - 39 of WO 2021 / 115912 A1 ("Formulations comprising a hydrophobically modified polyethyleneimine and one or more enzymes").

[0252] Particularly high interest is paid to the following antibacterial agents and / or preservatives with respect to cleaning compositions, and fabric care and home care products, especially laundry formulations: 4,4'-Dichlor-2-hydroxy-diphenylether (also known as 5-chloro-2-(4-chlorophenoxy)phenol, dichlorosan, DCPP), Tinosan® HP100 (a commercially available product from BASF SE, containing 30% antibacterial active 4,4'-dichlor-2-hydroxy-diphenylether); 2-phenoxyethanol (also known as phenoxyethanol, methylphenylglycol, phenoxetyethanol, ethylene glycol phenyl ether, ethylene glycol monophenyl ether, 2-(phenoxy)ethanol, 2-phenoxy-1-ethanol); 2-bromo-2-nitropropane-1,3-diol (also known as 2-bromo-2-nitro-1,3-propanediol, bronopol); glutaraldehyde (also known as 1,5-pentanedial, pentane-1,5-dial, glutaral, glutar dialdehyde); glyoxal (also known as ethanedial, oxaldehyde, 1,2-ethanedial); 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; potassium (E,E)-hex-2,4-dienoate (potassium sorbate); lactic acid and its salts; L-(+)-lactic acid; in particular 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;Didecyldimethylammonium chloride ("DDAC"); N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine ("diamine"); peracetic acid; hydrogen peroxide;

[0253] At least one antibacterial or preservative agent can be added to the composition of the present invention at a concentration of 0.001 to 10% based on the total weight of the composition.

[0254] Preferably, the composition contains 2-phenoxyethanol at a concentration of 0.1 to 2% or 4,4'-dichlor-2-hydroxy diphenyl ether (DCPP) at a concentration of 0.005 to 0.6%.

[0255] The present invention also encompasses a method for protecting an aqueous composition according to the present invention from microbial contamination or growth, the method comprising adding at least one antibacterial or preservative agent, preferably 2-phenoxyethanol.

[0256] The present invention also encompasses a method for imparting an antibacterial effect to a textile product after treatment with a solid laundry detergent (e.g., powder, granule, capsule, tablet, stick, etc.), liquid laundry detergent, fabric softener or post-washing treatment agent containing 4,4'-dichlor-2-hydroxy diphenyl ether (DCPP).

[0257] The formulation according to the present invention can also include water and / or additional organic solvents, such as ethanol or propylene glycol.

[0258] Further optional components can be, but are not limited to, viscosity modifiers, cationic surfactants, foam boosters or defoamers, fragrances, dyes, optical brighteners and dye transfer inhibitors.

[0259] General cleaning compositions and formulations for laundry The liquid formulations disclosed in this chapter can contain, and preferably contain, 0 to 2%, preferably about 1% of 2-phenoxyethanol in addition to all other recited components.

[0260] The liquid formulations disclosed above and below can contain, and preferably contain, 0 to 0.2%, preferably about 0.15%, of 4,4'-dichloro 2-hydroxydiphenyl ether in addition to all other ingredients mentioned. The solid laundry compositions without bleach can contain, in addition to all other ingredients mentioned, 0 to 0.2%, preferably about 0.15%, of 4,4'-dichloro 2-hydroxydiphenylethe.

[0261] The formulations disclosed in this chapter may contain, and preferably contain, one or more enzymes selected from those disclosed above in this specification, more preferably protease and / or amylase, and even more preferably, the protease has at least 90% sequence identity to SEQ ID NO: 22 of European Patent No. 1921147B1 and has the amino acid substitution R101E (according to BPN' numbering), and the amylase has at least 90% sequence identity to SEQ ID NO: 54 of WO 2021 / 032881A1, and such enzymes are preferably present in the formulation at a level of about 0.00001 wt% to about 5 wt%, preferably about 0.00001 wt% to about 2 wt%, more preferably about 0.0001 wt% to about 1 wt%, or even more preferably about 0.001 wt% to about 0.5 wt% based on the weight of the composition.

[0262] The table in this chapter shows certain types of general laundry compositions corresponding to typical compositions correlated with typical washing conditions commonly employed in various regions and countries of the world. At least one polymer of the present invention can be added to such formulations in a suitable amount as outlined herein.

[0263] When the polymer of the present invention is not added, the shown formulation is the "formulation of the comparative example", and when the selected amount is within the general range disclosed in this specification, particularly within the range disclosed herein as the preferred amount for various components and the graft polymer of the present invention, the formulation is the formulation of the present invention. Components (other than the polymer of the present invention) listed with amounts including "0%" within the mentioned range may or may not be present in both the formulation of the present invention and the formulation of the comparative example. In this specification, each numerical value encompassed by a given range is intended to be included in the formulations shown in this chapter, and all possible deviations and permutations are similarly intended to be included.

[0264] In a preferred embodiment, the graft polymer according to the present invention is used in a laundry detergent.

[0265] The liquid laundry detergent according to the present invention comprises at least one polymer of the present invention in an amount of 0.05 to 10%, a surfactant in an amount of 1 to 50%, a builder, cobuilder, and / or chelating agent in an amount of 0.1 to 40%, other adjuvants in an amount of 0.1 to 50%, and water to make the total 100%.

[0266] The preferred liquid laundry detergent of the present invention comprises at least one polymer of the present invention in an amount of 0.2 to 4%, an anionic surfactant selected from C10 - C15 - LAS and C10 - C18 alkyl ether sulfates containing 1 to 5 ethoxy units in an amount of 5 to 40%, a nonionic surfactant selected from C10 - C18 alkyl ethoxylates containing 3 to 10 ethoxy units in an amount of 1.5 to 10%, a soluble organic builder / cobuilder selected from C10 - C18 fatty acids, di - and tricarboxylic acids, hydroxydi - and hydroxytricarboxylic acids, aminopolycarboxylates, and polycarboxylic acids in an amount of 2 to 20%, An enzyme system containing 0.05 to 5% of at least one enzyme suitable for detergent use and preferably further an enzyme stabilization system. 0.5 to 20% of a mono- or diol selected from ethanol, isopropanol, ethylene glycol or propylene glycol. 0.1 to 20% of other adjuvants. Water to make up 100%.

[0267] The solid laundry detergent (e.g., powder, granule, or tablet, etc.) of the present invention. 0.05 to 10% of at least one polymer of the present invention. 1 to 50% of a surfactant. 0.1 to 90% of a builder, cobuilder and / or chelating agent. 0 to 50% of a filler. 0 to 40% of a bleach active substance. 0.1 to 30% of other adjuvants and / or water. The total of the components is 100%.

[0268] A preferred solid laundry detergent according to the present invention. 0.2 to 2% of at least one polymer of the present invention. 5 to 30% of an anionic surfactant selected from C10 - C15 - LAS, C10 - C18 alkyl sulfates and C10 - C18 alkyl ether sulfates containing 1 to 5 ethoxy units. 1.5 to 7.5% of a nonionic surfactant selected from C10 - C18 alkyl ethoxylates containing 3 to 10 ethoxy units. 20 to 80% of an inorganic builder and filler selected from sodium carbonate, sodium bicarbonate, zeolite, soluble silicate, sodium sulfate. 0.5 to 15% of a cobuilder selected from C10 - C18 fatty acids, di- and tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids, aminopolycarboxylates and polycarboxylic acids. 0.1 to 5% of an enzyme system containing at least one enzyme suitable for detergent use and preferably further an enzyme stabilization system. 0.5 to 30% of a bleaching active substance, 0.1 to 20% of other adjuvants, and water to make up 100% in total.

[0269]

Table 1

[0270]

Table 2

[0271]

Table 3

[0272]

Table 4

[0273]

Table 5

[0274] Further typical liquid detergent formulations LD1, LD2 and LD3 are shown in the following three tables.

[0275]

Table 6

[0276]

Table 7

[0277]

Table 8

[0278] In all of the three tables above: *60 wt% vinyl acetate grafted onto polyethylene glycol with Mn of 6000 g / mol as the graft matrix (based on the total weight of the polymer; manufactured according to the general disclosure of WO 2007 / 138054 A1 pamphlet)

[0279] Throughout the present disclosure, the specific embodiments described are included in the present invention as part of the present invention. The various further options disclosed herein as "optional", "preferred", "more preferred", "even more preferred" or "most preferred" (or such as "preferably") for the specific embodiments are selected independently individually (provided that such independent selection is possible due to the nature of the feature, or such independent selection is not explicitly excluded), and can subsequently be combined in any of the other embodiments (although other such options and preferences can also be selected independently individually, provided that such independent selection is not possible due to the nature of the feature, or such independent selection is explicitly excluded). All such possible combinations are included as part of the present invention as individual embodiments.

[0280] The present invention will be further illustrated by the following examples, which do not limit the scope of the present invention.

Examples

[0281] Measurement of Polymer The K value is obtained by measuring the relative viscosity of a diluted polymer solution and serves as a relative measure of the weight-average molecular weight. As the weight-average molecular weight of a specific polymer increases, the K value also tends to increase. The K value is measured at 23 °C in a 3 wt% NaCl solution with a polymer concentration of 1% of the polymer according to the method of H. Fikentscher in “Cellulosechemie”, 1932, 13, 58.

[0282] The number-average molecular weight (M n )), weight-average molecular weight (M w ) and polydispersity M w / M nIt was measured by gel permeation chromatography in dimethylacetamide. The mobile phase (eluent) used was dimethylacetamide containing 0.5 wt% LiBr. The concentration of the graft polymer in tetrahydrofuran was 4.0 mg / mL. After filtration (pore size 0.2 μm), 100 μL of this solution was injected into the GPC system. Four columns (heated to 60 °C) were used for separation (PLgel precolumn, three PLgel MIXED-E columns). The GPC system was operated at a flow rate of 1 mL / min. A DRI Agilent 1100 was used as the detection system. For calibration, poly(ethylene glycol) (PEG) standards (PL) with molecular weights M n ranging from 106 to 1378000 g / mol were used.

[0283] Method for measuring the biodegradability of polymers Biodegradation in wastewater was tested in triplicate using the OECD 301F manometric respirometry method. A 30 mg / mL test substance was inoculated into wastewater collected from the Mannheim Wastewater Treatment Plant and incubated at 25 °C for 28 days in a sealed flask. The oxygen consumption during this time was measured as the change in pressure inside the flask using an OxiTop C (WTW). The CO2 generated was absorbed using a NaOH solution. The amount of oxygen consumed by the microbial population during the biodegradation of the test substance, after correction using a blank, is expressed as a percentage of the ThOD (theoretical oxygen demand).

[0284] Synthesis procedure In Examples 1 to 17, which are examples of the present invention, commercially available EO / PO polyether products and PEG polyethers were used as the main chain materials. These products are available, for example, from BASF under the trade names Pluriol®, Pluronic®, or Breox®.

[0285] The details of the structures of the comparative examples and the examples of the polymers of the present invention are listed in Tables 1 and 2.

[0286] Table 1 and 2 summarize the biodegradation data of the comparative examples and the polymers of the present invention after 28 days by the OECD 301F test.

[0287] Synthesis procedure of comparative examples: Comparative Example I: Copolymer of N-vinylpyrrolidone and 1-vinylimidazole, weight ratio 1:1; K value about 30; available, for example, as Sokalan HP 56 from BASF.

[0288] Comparative Example II: The polymer was prepared as described in Example 1 of WO 03 / 042264 pamphlet.

[0289] Comparative Example III: First, PEG (288.00 g) and water (629.00 g) were charged into a polymerization vessel equipped with a stir bar and a reflux condenser under a nitrogen atmosphere and heated to 80 °C. Feed 1 (96.00 g of vinylimidazole and 96.00 g of vinylpyrrolidone), Feed 2 (3.20 g of tert-butyl peroxypivalate dissolved in 71.81 g of isopropanol), and Feed 3 (1.92 g of 2-mercaptoethanol in 98.08 g of water) were started simultaneously and administered to the stirred vessel at a constant feed rate with Feed 1 (6:00 hours), Feed 2 (6:30 hours), and Feed 3 (6:00 hours). After the feed was completed, the mixture was stirred at 80 °C for 2:00 hours. Feed 4 (1.28 g of tert-butyl peroxypivalate dissolved in 28.70 g of isopropanol) was administered at 80 °C within 1:00 hour at a constant feed rate. After the addition of the feed was completed, the mixture was stirred at 80 °C for 1:00 hour. 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 hour to remove volatiles. 1213 g of a polymer solution was obtained.

[0290] Comparative Example IV: First, a polymerization vessel equipped with a stir bar and a reflux condenser was charged with a random EO / PO copolymer (288.00 g) and water (386.00 g) under a nitrogen atmosphere and heated to 80°C. Feed 1 (96.00 g of vinylimidazole and 96.00 g of vinylpyrrolidone), Feed 2 (3.20 g of tert-butyl peroxypivalate dissolved in 71.81 g of isopropanol), and Feed 3 (1.92 g of 2-mercaptoethanol in 98.08 g of water) were started simultaneously and administered to the stirred vessel at a constant feed rate over Feed 1 (6:00 hours), Feed 2 (6:30 hours), and Feed 3 (6:00 hours). After the feeding was complete, the mixture was stirred at 80°C for 2:00 hours. Feed 4 (1.28 g of tert-butyl peroxypivalate dissolved in 28.70 g of isopropanol) was administered at 80°C at a constant feed rate within 1:00 hour. After the addition of the feeds was complete, the mixture was stirred at 80°C for 1:00 hour. 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 hour to remove volatiles. 1813 g of a polymer solution was obtained.

[0291] Comparative Example V: First, PEG (312.00 g) and water (312.00 g) were charged into a polymerization vessel equipped with a stir bar 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 minutes 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 administered to the stirred vessel at a constant feed rate over Feed 1 (6:00 hours), Feed 2 (6:40 hours), and Feed 3 (6:00 hours). After the feed was completed, the mixture was stirred at 80°C for 2:00 hours. Feed 4 (5.12 g of tert-butyl peroxypivalate dissolved in 11.69 g of tripropylene glycol) was administered at 80°C at a constant feed rate within 1:00 hour. After the addition of the feed was completed, the mixture was stirred at 80°C for 1:00 hour. 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 hour to remove volatiles. 1232 g of a polymer solution was obtained.

[0292] Comparative Example VI: First, an EO / PO random copolymer (240.00 g) and water (240.00 g) were charged into a polymerization vessel equipped with a stir bar and a reflux condenser and heated to 80°C under a nitrogen atmosphere. Feed 2 (9.60 g of tert-butyl peroxypivalate dissolved in 21.91 g of tripropylene glycol) was initiated, and 10 minutes 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 simultaneously initiated. All feeds were administered to the stirred vessel at a constant feed rate over Feed 1 (6:00 hours), Feed 2 (6:40 hours), and Feed 3 (6:00 hours). After the feed was completed, the mixture was stirred at 80°C for 2:00 hours. Feed 4 (5.12 g of tert-butyl peroxypivalate dissolved in 11.69 g of tripropylene glycol) was administered at 80°C within 1:00 hour at a constant feed rate. After the addition of the feed was completed, the mixture was stirred at 80°C for 1:00 hour. 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 hour to remove volatiles. 1232 g of a polymer solution was obtained.

[0293] Synthesis procedures of Examples 1 to 17, which are examples of the present invention Example 1: First, PEG (336.00 g) and water (297.84 g) were charged into a polymerization vessel equipped with a stir bar and a reflux condenser under a nitrogen atmosphere and heated to 80 °C. Feed 1 (96.00 g of vinylimidazole and 48.00 g of vinylpyrrolidone), Feed 2 (3.20 g of tert-butyl peroxypivalate dissolved in 71.81 g of isopropanol), and Feed 3 (1.92 g of 2-mercaptoethanol in 98.06 g of water) were started simultaneously and administered to the stirred vessel at a constant feed rate over Feed 1 (6:00 hours), Feed 2 (6:30 hours), and Feed 3 (6:00 hours). After the feed was completed, the mixture was stirred at 80 °C for 2:00 hours. Feed 4 (1.28 g of tert-butyl peroxypivalate dissolved in 28.70 g of isopropanol) was administered at 80 °C at a constant feed rate within 1:00 hour. After the addition of the feed was completed, the mixture was stirred at 80 °C for 1:00 hour. 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 hour to remove volatiles. A 1132 g polymer solution was obtained.

[0294] Example 2: First, an EO / PO block copolymer (336.00 g) and water (297.84 g) were charged into a polymerization vessel equipped with a stir bar and a reflux condenser under a nitrogen atmosphere and heated to 80 °C. Feed 1 (72.00 g of vinylimidazole and 72.00 g of vinylpyrrolidone), Feed 2 (6.40 g of tert-butyl peroxypivalate dissolved in 71.81 g of isopropanol), and Feed 3 (1.92 g of 2-mercaptoethanol in 98.06 g of water) were started simultaneously and administered to the stirred vessel at a constant feed rate over Feed 1 (6:00 hours), Feed 2 (6:30 hours), and Feed 3 (6:00 hours). After the feeding was complete, water (333.75 g) was added and the mixture was stirred at 80 °C for 2:00 hours. Feed 4 (2.56 g of tert-butyl peroxypivalate dissolved in 28.70 g of isopropanol) was administered at 80 °C at a constant feed rate within 1:00 hour. After the addition of the feeds was complete, the mixture was stirred at 80 °C for 1:00 hour. The polymerization mixture was heated to 100 °C. Steam distillation was carried out at 100 °C for 1:00 hour to remove volatiles. A 1356 g polymer solution was obtained.

[0295] Example 3: First, an EO / PO block copolymer (360.00 g) and water (297.84 g) were charged into a polymerization vessel equipped with a stir bar and a reflux condenser under a nitrogen atmosphere and heated to 80°C. Feed 1 (60.00 g of vinylimidazole and 60.00 g of vinylpyrrolidone), Feed 2 (6.40 g of tert-butyl peroxypivalate dissolved in 71.81 g of isopropanol), and Feed 3 (1.92 g of 2-mercaptoethanol in 98.06 g of water) were started simultaneously and administered to the stirred vessel at a constant feed rate over Feed 1 (6:00 hours), Feed 2 (6:30 hours), and Feed 3 (6:00 hours). After the feed was completed, water (333.75 g) was added and the mixture was stirred at 80°C for 2:00 hours. Feed 4 (2.56 g of tert-butyl peroxypivalate dissolved in 28.70 g of isopropanol) was administered at 80°C at a constant feed rate within 1:00 hour. After the addition of the feed was completed, the mixture was stirred at 80°C for 1:00 hour. The polymerization mixture was heated to 100°C. Steam distillation was carried out at 100°C for 1:00 hour to remove volatiles. A 1242 g polymer solution was obtained.

[0296] Example 4: First, an EO / PO block copolymer (384.00 g) and water (340.32 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 1 (48.00 g of vinylimidazole and 48.00 g of vinylpyrrolidone), Feed 2 (6.40 g of tert-butyl peroxypivalate dissolved in 71.81 g of isopropanol), and Feed 3 (1.92 g of 2-mercaptoethanol in 98.06 g of water) were started simultaneously and administered to the stirred vessel at a constant feed rate over Feed 1 (6:00 hours), Feed 2 (6:30 hours), and Feed 3 (6:00 hours). After the supply was completed, water (300.00 g) was added and the mixture was stirred at 80°C for 2:00 hours. Feed 4 (2.56 g of tert-butyl peroxypivalate dissolved in 28.70 g of isopropanol) was administered at 80°C at a constant feed rate within 1:00 hour. After the addition of the feeds was completed, the mixture was stirred at 80°C for 1:00 hour. The polymerization mixture was heated to 100°C. Steam distillation was carried out at 100°C for 1:00 hour to remove volatiles. 1428 g of a polymer solution was obtained.

[0297] Example 5: First, an EO / PO block copolymer (400.00 g) and water (361.92 g) were charged into a polymerization vessel equipped with a stir bar and a reflux condenser and heated to 80°C under a nitrogen atmosphere. Feed 1 (36.00 g of vinylimidazole and 36.00 g of vinylpyrrolidone), Feed 2 (6.40 g of tert-butyl peroxypivalate dissolved in 71.81 g of isopropanol), and Feed 3 (1.92 g of 2-mercaptoethanol in 98.06 g of water) were started simultaneously and administered to the stirred vessel at a constant feed rate over Feed 1 (6:00 hours), Feed 2 (6:30 hours), and Feed 3 (6:00 hours). After the feed was completed, water (280.00 g) was added and the mixture was stirred at 80°C for 2:00 hours. Feed 4 (2.56 g of tert-butyl peroxypivalate dissolved in 28.70 g of isopropanol) was administered at 80°C at a constant feed rate within 1:00 hour. After the addition of the feed was completed, the mixture was stirred at 80°C for 1:00 hour. The polymerization mixture was heated to 100°C. Steam distillation was carried out at 100°C for 1:00 hour to remove volatiles. 1323 g of a polymer solution was obtained.

[0298] Example 6: First, an EO / PO block copolymer (336.00 g) and water (347.52 g) were charged into a polymerization vessel equipped with a stir bar and a reflux condenser under a nitrogen atmosphere and heated to 80°C. Feed 1 (96.00 g of vinyl imidazole and 48.00 g of vinyl pyrrolidone), Feed 2 (6.40 g of tert-butyl peroxypivalate dissolved in 24.00 g of tripropylene glycol), and Feed 3 (1.92 g of 2-mercaptoethanol in 98.06 g of water) were simultaneously started and administered to the stirred vessel at a constant feed rate over Feed 1 (6:00 hours), Feed 2 (6:30 hours), and Feed 3 (6:00 hours). After the feed was completed, the mixture was stirred at 80°C for 2:00 hours. Feed 4 (2.56 g of tert-butyl peroxypivalate dissolved in 9.60 g of tripropylene glycol) was administered at 80°C at a constant feed rate within 1:00 hour. After the addition of the feed was completed, the mixture was stirred at 80°C for 1:00 hour. Water (254.00 g) was added and the polymerization mixture was heated to 100°C. Steam distillation was carried out at 100°C for 1:00 hour to remove volatiles. A 1252 g polymer solution was obtained.

[0299] Example 7: First, PEG (360.00 g) and water (347.52 g) were charged into a polymerization vessel equipped with a stir bar and a reflux condenser under a nitrogen atmosphere and heated to 80 °C. Feed 1 (84.00 g of vinylimidazole and 36.00 g of vinylpyrrolidone), Feed 2 (12.80 g of tert-butyl peroxypivalate dissolved in 28.00 g of tripropylene glycol), and Feed 3 (1.92 g of 2-mercaptoethanol in 98.06 g of water) were simultaneously started and administered to the stirred vessel at a constant feed rate over Feed 1 (6:00 hours), Feed 2 (6:30 hours), and Feed 3 (6:00 hours). After the feed was completed, the mixture was stirred at 80 °C for 2:00 hours. Feed 4 (2.56 g of tert-butyl peroxypivalate dissolved in 5.60 g of tripropylene glycol) was administered at 80 °C at a constant feed rate within 1:00 hour. After the addition of the feed was completed, the mixture was stirred at 80 °C for 1:00 hour. Water (257.00 g) was added and the polymerization mixture was heated to 100 °C. Steam distillation was carried out at 100 °C for 1:00 hour to remove volatiles. 1313 g of a polymer solution was obtained.

[0300] Example 8: First, PEG (360.00 g) and water (347.52 g) were charged into a polymerization vessel equipped with a stir bar 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 minutes after the start of Feed 2, Feed 1 (96.00 g of vinylimidazole and 24.00 g of vinylpyrrolidone) and Feed 3 (1.92 g of 2-mercaptoethanol in 98.06 g of water) were started simultaneously. All feeds were administered to the stirred vessel at a constant feed rate over Feed 1 (6:00 hours), Feed 2 (6:40 hours), and Feed 3 (6:00 hours). After the feed was completed, the mixture was stirred at 80°C for 2:00 hours. Feed 4 (5.12 g of tert-butyl peroxypivalate dissolved in 11.69 g of tripropylene glycol) was administered at 80°C at a constant feed rate within 1:00 hour. After the addition of the feed was completed, the mixture was stirred at 80°C for 1:00 hour. Water (257.00 g) was added and the polymerization mixture was heated to 100°C. Steam distillation was carried out at 100°C for 1:00 hour to remove volatiles. 1246 g of a polymer solution was obtained.

[0301] Example 9: First, PEG (360.00 g) and water (347.52 g) were charged into a polymerization vessel equipped with a stir bar and a reflux condenser under a nitrogen atmosphere and heated to 80°C. Feed 2 (12.80 g of tert-butyl peroxypivalate dissolved in 24.00 g of tripropylene glycol) was started, and 10 minutes after the start of Feed 2, Feed 1 (72.00 g of vinylimidazole and 48.00 g of vinylpyrrolidone) and Feed 3 (1.92 g of 2-mercaptoethanol in 98.06 g of water) were simultaneously started. All feeds were administered to the stirred vessel at a constant feed rate over Feed 1 (6:00 hours), Feed 2 (6:40 hours), and Feed 3 (6:00 hours). After the feed was completed, the mixture was stirred at 80°C for 2:00 hours. Feed 4 (5.12 g of tert-butyl peroxypivalate dissolved in 9.60 g of tripropylene glycol) was administered at 80°C at a constant feed rate within 1:00 hour. After the addition of the feed was completed, the mixture was stirred at 80°C for 1:00 hour. Water (257.00 g) was added and the polymerization mixture was heated to 100°C. Steam distillation was carried out at 100°C for 1:00 hour to remove volatiles. 1252 g of a polymer solution was obtained.

[0302] Example 10: First, PEG (384.00 g) and water (384.00 g) were charged into a polymerization vessel equipped with a stir bar 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 minutes after the start of Feed 2, Feed 1 (60.00 g of vinylimidazole and 36.00 g of vinylpyrrolidone) and Feed 3 (1.92 g of 2-mercaptoethanol in 122.06 g of water) were started simultaneously. All feeds were administered to the stirred vessel at a constant feed rate over Feed 1 (6:00 hours), Feed 2 (6:40 hours), and Feed 3 (6:00 hours). After the feed was completed, the mixture was stirred at 80°C for 2:00 hours. Feed 4 (5.12 g of tert-butyl peroxypivalate dissolved in 11.69 g of tripropylene glycol) was administered at 80°C at a constant feed rate within 1:00 hour. After the addition of the feed was completed, the mixture was stirred at 80°C for 1:00 hour. Water (196.10 g) was added and the polymerization mixture was heated to 100°C. Steam distillation was carried out at 100°C for 1:00 hour to remove volatiles. 1232 g of a polymer solution was obtained.

[0303] Example 11: First, an EO / PO copolymer (336.00 g) and water (336.00 g) were charged into a polymerization vessel equipped with a stir bar 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 initiated, and 10 minutes after the start of Feed 2, Feed 1 (84.00 g of vinylimidazole and 60.00 g of vinylpyrrolidone) and Feed 3 (1.92 g of 2-mercaptoethanol in 122.06 g of water) were simultaneously initiated. All feeds were administered to the stirred vessel at a constant feed rate over Feed 1 (6:00 hours), Feed 2 (6:40 hours), and Feed 3 (6:00 hours). After the feed was completed, the mixture was stirred at 80°C for 2:00 hours. Feed 4 (5.12 g of tert-butyl peroxypivalate dissolved in 11.69 g of tripropylene glycol) was administered at 80°C at a constant feed rate within 1:00 hour. After the addition of the feed was completed, the mixture was stirred at 80°C for 1:00 hour. Water (244.10 g) was added and the polymerization mixture was heated to 100°C. Steam distillation was carried out at 100°C for 1:00 hour to remove volatiles. A 1232 g polymer solution was obtained.

[0304] Example 12: First, an EO / PO copolymer (360.00 g) and water (360.00 g) were charged into a polymerization vessel equipped with a stir bar 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 initiated, and 10 minutes after the start of Feed 2, Feed 1 (96.00 g of vinylimidazole and 24.00 g of vinylpyrrolidone) and Feed 3 (1.92 g of 2-mercaptoethanol in 122.06 g of water) were simultaneously initiated. All feeds were administered to the stirred vessel at a constant feed rate over Feed 1 (6:00 hours), Feed 2 (6:40 hours), and Feed 3 (6:00 hours). After the feed was completed, the mixture was stirred at 80°C for 2:00 hours. Feed 4 (5.12 g of tert-butyl peroxypivalate dissolved in 11.69 g of tripropylene glycol) was administered at 80°C at a constant feed rate within 1:00 hour. After the addition of the feed was completed, the mixture was stirred at 80°C for 1:00 hour. Water (220.10 g) was added and the polymerization mixture was heated to 100°C. Steam distillation was carried out at 100°C for 1:00 hour to remove volatiles. A 1232 g polymer solution was obtained.

[0305] Example 13: First, an EO / PO random copolymer (384.00 g) and water (384.00 g) were charged into a polymerization vessel equipped with a stir bar 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 initiated, and 10 minutes after the start of Feed 2, Feed 1 (24.00 g of vinylimidazole and 72.00 g of vinylpyrrolidone) and Feed 3 (1.92 g of 2-mercaptoethanol in 122.06 g of water) were simultaneously initiated. All feeds were administered to the stirred vessel at a constant feed rate over Feed 1 (6:00 hours), Feed 2 (6:40 hours), and Feed 3 (6:00 hours). After the feed was completed, the mixture was stirred at 80°C for 2:00 hours. Feed 4 (5.12 g of tert-butyl peroxypivalate dissolved in 11.69 g of tripropylene glycol) was administered at 80°C at a constant feed rate within 1:00 hour. After the addition of the feed was completed, the mixture was stirred at 80°C for 1:00 hour. Water (220.10 g) was added and the polymerization mixture was heated to 100°C. Steam distillation was carried out at 100°C for 1:00 hour to remove volatiles. A 1256 g polymer solution was obtained.

[0306] Example 14: First, PEG (408.00 g) and water (408.00 g) were charged into a polymerization vessel equipped with a stir bar 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 minutes after the start of Feed 2, Feed 1 (48.00 g of vinylimidazole and 24.00 g of vinylpyrrolidone) and Feed 3 (1.92 g of 2-mercaptoethanol in 122.06 g of water) were started simultaneously. All feeds were administered to the stirred vessel at a constant feed rate over Feed 1 (6:00 hours), Feed 2 (6:40 hours), and Feed 3 (6:00 hours). After the feed was completed, the mixture was stirred at 80°C for 2:00 hours. Feed 4 (5.12 g of tert-butyl peroxypivalate dissolved in 11.69 g of tripropylene glycol) was administered at 80°C at a constant feed rate within 1:00 hour. After the addition of the feed was completed, the mixture was stirred at 80°C for 1:00 hour. Water (172.10 g) was added and the polymerization mixture was heated to 100°C. Steam distillation was carried out at 100°C for 1:00 hour to remove volatiles. A 1232 g polymer solution was obtained.

[0307] Example 15: First, PEG (396.00 g) and water (396.00 g) were charged into a polymerization vessel equipped with a stir bar 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 minutes after the start of Feed 2, Feed 1 (48.00 g of vinylimidazole and 36.00 g of vinylpyrrolidone) and Feed 3 (1.92 g of 2-mercaptoethanol in 122.06 g of water) were started simultaneously. All feeds were administered to the stirred vessel at a constant feed rate over Feed 1 (6:00 hours), Feed 2 (6:40 hours), and Feed 3 (6:00 hours). After the feed was completed, the mixture was stirred at 80°C for 2:00 hours. Feed 4 (5.12 g of tert-butyl peroxypivalate dissolved in 11.69 g of tripropylene glycol) was administered at 80°C at a constant feed rate within 1:00 hour. After the addition of the feed was completed, the mixture was stirred at 80°C for 1:00 hour. Water (184.10 g) was added and the polymerization mixture was heated to 100°C. Steam distillation was carried out at 100°C for 1:00 hour to remove volatiles. 1232 g of a polymer solution was obtained.

[0308] Example 16: First, PEG (408.00 g) and water (361.00 g) were charged into a polymerization vessel equipped with a stirrer bar and a reflux condenser under a nitrogen atmosphere and heated to 80°C. Feed 2 (6.40 g of tert-butyl peroxypivalate dissolved in 71.91 g of isopropanol) was initiated, and 10 minutes after the start of Feed 2, Feed 1 (36.00 g of vinylimidazole and 36.00 g of vinylpyrrolidone) and Feed 3 (1.92 g of 2-mercaptoethanol in 98.06 g of water) were simultaneously initiated. All feeds were administered to the stirred vessel at a constant feed rate over Feed 1 (6:00 hours), Feed 2 (6:40 hours), and Feed 3 (6:00 hours). After the feed was completed, the mixture was stirred at 80°C for 2:00 hours. Feed 4 (2.56 g of tert-butyl peroxypivalate dissolved in 28.70 g of isopropanol) was administered at 80°C at a constant feed rate within 1:00 hour. After the addition of the feed was completed, the mixture was stirred at 80°C for 1:00 hour. Water (271.00 g) was added and the polymerization mixture was heated to 100°C. Steam distillation was carried out at 100°C for 1:00 hour to remove volatiles. 1221 g of a polymer solution was obtained.

[0309] Example 17: First, into a polymerization vessel equipped with a stir bar and a reflux condenser, PEG (408.00 g), water (361.92 g), vinylimidazole (36.00 g), and vinylpyrrolidone (36.00 g) were charged under a nitrogen atmosphere and heated to 80 °C. Feed 1 (6.40 g of tert-butyl peroxypivalate dissolved in 24.00 g of tripropylene glycol), and Feed 2 (1.92 g of 2-mercaptoethanol in 98.06 g of water) were started simultaneously. All feeds were administered to the stirred vessel at a constant feed rate over Feed 1 (3:30 hours) and Feed 2 (2:00 hours). After the feed was completed, the mixture was stirred at 80 °C for 2:00 hours. Feed 3 (2.56 g of tert-butyl peroxypivalate dissolved in 9.60 g of tripropylene glycol) was administered at 80 °C at a constant feed rate within 1:00 hour. After the addition of the feed was completed, the mixture was stirred at 80 °C for 1:00 hour. Water (237.00 g) was added and the polymerization mixture was heated to 100 °C. Steam distillation was carried out at 100 °C for 1:00 hour to remove volatiles. 1221 g of a polymer solution was obtained.

[0310] Example 18: First, into a polymerization vessel equipped with a stir bar and a reflux condenser, PEG (289.00 g), water (340 g), vinylimidazole (25.50 g), and vinylpyrrolidone (25.50 g) were charged under a nitrogen atmosphere and heated to 80 °C. Feed 1 (3.40 g of Wako V50 dissolved in 52.7 g of water), and Feed 2 (0.68 g of 2-mercaptoethanol in 29.9 g of water) were started simultaneously. All feeds were administered to the stirred vessel at a constant feed rate over Feed 1 (3:30 hours) and Feed 2 (2:00 hours). After the feed was completed, the mixture was stirred at 80 °C for 2:00 hours. Feed 3 (1.36 g of Wako V50 dissolved in 21.1 g of water) was administered at 80 °C at a constant feed rate within 1:00 hour. After the addition of the feed was completed, the mixture was stirred at 85 °C for 1:00 hour. Water (71.40 g) was added and the polymerization mixture was heated to 100 °C. Steam distillation was carried out at 100 °C for 1:00 hour to remove volatiles. 859 g of a polymer solution was obtained.

[0311]

Table 9

[0312]

Table 10

[0313] Evaluation of DTI Performance (Washing Experiment) Washing Results: The selected colored fabrics (EMPA 130 and EMPA 133 as dye donors) were washed at 60 °C with the addition of a dye transfer inhibitor in the presence of white test fabrics and polyester ballast fabrics. The liquid detergent was based on a mixture of anionic and non-ionic surfactants (LAS; AES, AEO). After the washing cycle, the fabrics were rinsed, dehydrated, and dried. To determine the dye transfer inhibition effect, the contamination of the white test fabrics was confirmed by photometry. The reflectance at 520 nm (EMPA 130) or 600 nm (EMPA 133) was measured using a Datacolor photometer (Elrepho 2000).

[0314]

Table 11

[0315]

Table 12

[0316] Explanation of the Abbreviations in the Table Above: wfk 10 A: Cotton fabric, reflectance 83.4% (520 nm), 84.5% (600 nm) wfk 20 A: Polyester / cotton fabric, reflectance 83.8% (520 nm), 83.3% (600 nm) EMPA 130: Cotton fabric dyed with Direct Red 83.1 EMPA 133: Cotton fabric dyed with Direct Blue 71 Manufacturer / Supplier: wfk Testgewebe GmbH, Bruggen, Germany; EMPA Testmaterialien AG, Sankt Gallen, Switzerland

[0317] Washing results of EMPA 130 and EMPA 133 colored fabrics (evaluation of reflectance %)

[0318]

Table 13

[0319] Examples of novel polymer combinations containing 2-phenoxyethanol and DCPP (Tinosan HP 100) based on a standard liquid laundry detergent formulation Prepare a liquid laundry detergent formulation containing 2% by weight of the polymer of the present invention of Example 5, and / or 0.3% of the biocide Tinosan® HP 100 (manufactured by BASF), and / or 1% of phenoxyethanol (Protectol® PE, BASF). First, prepare a premix containing surfactants, solvents, fatty acids, citric acid, and NaOH as shown in the table, water to make up to 90%, and prepare the formulation by adding all the components to an appropriate amount of water and stirring at room temperature. Subsequently, set the pH to pH = 8.5 using NaOH. Subsequently, at room temperature, stir 90% of this premix, the polymer of the present invention at an appropriate concentration, and / or Tinosan® HP 100 (a commercial product of BASF SE containing 30% antibacterial activity 4,4'-dichlorohydroxydiphenyl ether (CAS 3380-30-1)), and / or 2-phenoxyethanol (CAS 122-99-6), and water to make up to 100% by weight to prepare the final formulation. For comparison, prepare a standard liquid laundry detergent formulation containing neither the polymer nor the biocide of the present invention. Determine the turbidity using a 25 mm circular cuvette made of special optical glass and measuring the nephelometric turbidity unit (NTU) with a nephelometer (Hanna Instruments, HI-88703-02) at 23°C. The iodine color measurement is performed using a polystyrene cuvette with a path length of 1 cm and a photometer (Hack Lange, Lico 150) at 23°C.

[0320] The composition and results are shown in the following table.

[0321]

Table 14

[0322] Abbreviations used: AEO: C12 / C14 fatty alcohol (7EO) Lutensol AO7 (BASF) (CAS 68002-97-1) AES: Alcohol ethoxysulfate: Texapon N 70 (BASF) (CAS 68891-38-3) LAS: Linear alkylbenzene sulfonate Maranil DBS / LC (BASF) (CAS 85536-14-7) Coconut fatty acid: Edenor K12-18 (Emery Oleochemicals) (CAS 90990-15-1) 1,2-Propanediol: racemic mixture (CAS 57-55-6)

[0323] In the above table, the concentrations of surfactant commercial products are indicated.

[0324] It is clear from the above table that it is possible to combine the polymer of the present invention according to Example 5 with Tinosan HP 100 or phenoxyethanol in a liquid laundry formulation without any instability or significant turbidity.

Claims

1. A graft polymer, comprising: (A) a polymer main chain as a graft matrix, wherein the polymer main chain (A) can be obtained by polymerizing at least one monomer selected from the group consisting of C2-C10 alkylene oxides; when more than one kind of alkylene oxide monomer is included, the structure of the polymer main chain is a polymer including a structure in which a random polymer, a block polymer, or a block unit (each block is a homoblock or itself is a random block) and a statistical / random part composed of two or more kinds of alkylene oxides are mixed; the molecular weight of the polymer main chain (A) is 400 to 12,000, preferably at most 8000, more preferably at most 4000, and most preferably at most 3000 in terms of Mn in units of g / mol; a polymer main chain, and (B) a polymer side chain grafted to the polymer main chain (A), wherein the polymer side chain (B) can be obtained by copolymerizing at least one monomer of (B1) and at least one monomer of (B2); the monomer (B1) is at least one olefinically unsaturated amine-containing monomer, preferably 1-vinylimidazole or a derivative thereof, such as an alkyl-substituted derivative of 1-vinylimidazole, such as 2-methyl-1-vinylimidazole, more preferably only 1-vinylimidazole; (B2) is at least one further nitrogen-containing monomer, preferably a vinyl lactam monomer, more preferably selected from N-vinyl lactams, such as N-vinyl pyrrolidone, N-vinyl piperidone, N-vinyl caprolactam, even more preferably selected from N-vinyl pyrrolidone, N-vinyl caprolactam, and most preferably selected from N-vinyl pyrrolidone; optionally, further monomers other than (B1) and (B2) are any one or more of 1-vinyloxazolidinone and other vinyloxazolidinones, 4-vinylpyridine-N-oxide, N-vinylformamide (when hydrolyzed after polymerization, and its amine), N-vinylacetamide, N-vinyl-N-methylacetamide, acrylamide, methylacrylamide, N,N'-dialkyl(meth)acrylamide; (B) essentially does not contain vinyl ester monomers, a polymer side chain, and contains each, in weight percent units based on the total weight of the graft polymer, the amount of the polymer main chain (A) is 70 to 95, preferably 73 to 90, more preferably 73 to 87, even more preferably 75 to 85, and most preferably 77 to 85, the amount of the polymer side chain (B) is 5 to 30, preferably 10 to 27, more preferably 13 to 27, even more preferably 15 to 25, and most preferably 15 to 23, the amount of (B1) is at least 4 and at most 29, the amount of (B2) is at least 1 and at most 15, the amount of (B2) relative to (B1) is, in all cases, 4 times or less, preferably 3 times or less, more preferably 2 times or less, even more preferably the same amount, preferably at least 5% of the amount of (B1), more preferably at least 10%, even more preferably at least 25%, even more preferably at least 50, and even more preferably at least 75%, the amount of further monomers is 0 to 5, preferably at most 2, more preferably 0, but in all cases at most 50% of the amount of (B1) and less than or equal to the amount of (B2), a graft polymer.

2. The polymer main chain (A) can be obtained by polymerization of ethylene oxide (EO) and, optionally, at least one further monomer selected from 1,2 - propylene oxide (PO) and 1,2 - butylene oxide, preferably only PO. The relative amount of EO in the polymer main chain (A) is within 10 to 100 weight percent with respect to the total molar amount of alkylene oxides in the polymer main chain (A). The graft polymer according to Claim 1.

3. The main chain is i) poly(ethylene oxide), and ii) a polyalkylene oxide containing only ethylene oxide (EO) and propylene oxide (PO), preferably an EO / PO / EO triblock polymer, a PO / EO / PO triblock polymer, or a random EO / PO copolymer, more preferably an EO / PO / EO triblock polymer or a PO / EO / PO triblock polymer, and most preferably a PO / EO / PO triblock polymer, More preferably, 100% EO is preferred to EO / POP / EO in the main chain, random EO / PO is preferred to 100% EO, and PO / EO / PO is preferred to random EO / PO. The graft polymer according to claim 2.

4. i) The graft polymer has a polydispersity Mw / Mn of at most 3, more preferably at most 2.5, and most preferably at most 2, where Mw is the weight average molecular weight in g / mol and Mn is the number average molecular weight in g / mol. and / or ii) One or both of the terminal groups of the polymer main chain (A) are optionally capped, and when the polymer main chain (A) is capped, the capping is carried out by a C1-C25-alkyl group. and / or iii) The biodegradability of the graft polymer is at least 40, more preferably at least 45, such as 46, 47, 48, 49, 50, etc., and any number up to 100, when tested under OECD 301F within 28 days. The graft polymer according to any one of claims 1 to 3.

5. (A) The polymer main chain (A) contains only ethylene oxide as a monomer, and the molecular weight of the polymer main chain (A) is within 400 to 3000 as Mn in g / mol. (B) The polymer side chain consists of the following monomers. B1 is 1-vinylimidazole. B2 is N-vinyl lactam, preferably N-vinyl pyrrolidone. The graft polymer according to any one of claims 1 to 4.

6. (A) The polymer main chain (A) is a triblock polymer EO / PO / EO, the molecular weight of the polymer main chain (A) is within 400 to 3000 as Mn in g / mol, and the relative amount of EO in the polymer main chain (A) is 10 to 90, preferably 10 to 60, more preferably 15 to 50 weight percent based on the total molar amount of alkylene oxide in the polymer main chain (A). (B) The polymer side chain consists of the following monomers. B1 is 1-vinylimidazole. B2 is N-vinyl lactam, preferably N-vinyl pyrrolidone. The graft polymer according to any one of claims 1 to 4.

7. Each in weight percent units based on the total weight of the graft polymer. The amount of the polymer main chain (A) is 75 to 85, most preferably 77 to 85, The amount of the polymer side chain (B) is 15 to 25, most preferably 15 to 23, The amount of (B1) is at least 6 and at most 24, most preferably at least 7.5 and at most 10, The amount of (B2) is at least 1 and at most 15, most preferably at least 7.5 and at most 10, Optionally, the amount of (B2) relative to (B1) is the same amount, but does not exceed the total upper or lower limit of (B), The graft polymer according to any one of claims 1 to 6.

8. The at least one monomer B1, the at least one monomer B2, the optional at least one further monomer are polymerized in the presence of the at least one polymer main chain (A), and the polymer side chain (B) is obtained by radical polymerization using a radical-forming compound that initiates radical polymerization. A process for obtaining the graft polymer according to any one of claims 1 to 7.

9. In the main polymerization reaction step, at the average polymerization temperature, the at least one monomer (B1), the at least one monomer (B2), and the optional at least one further monomer are combined with the at least one polymer main chain (A), a free radical-forming initiator (C), and, if present, components (A), (B1), (B2), the optional further monomer, and (C) in total. Polymerization is carried out in the presence of up to 60% by weight of at least one solvent (D), wherein the initiator (C) has a decomposition half-life of 40 to 500 minutes at the average polymerization temperature, and optionally, at least one further polymerization step ("post-polymerization") is carried out to reduce the amount of unreacted monomer, Optionally, in order to remove volatile components such as volatile solvents and unreacted monomers, at least one purification step selected from thermal distillation or vacuum distillation, or stripping with a gas such as steam or nitrogen, preferably stripping with steam prepared from water, is carried out at atmospheric pressure or reduced pressure, Optionally, a drying step is carried out, The process according to claim 8, comprising

10. At least one solvent (D) consisting of at least one organic solvent and / or water is present in an amount of at most 60% by weight, based on the sum of components (A), (B1), (B2), any optional further monomers, (C), and (D), and such solvent (D) preferably contains, based on the total weight percentage of the polymer consisting of water and {(A) + (B1) + (B2) + any optional further monomers}, less than 20 percent, more preferably at most 10, even more preferably at most 5, and most preferably 3, 2, or even less than 1 volume percent of organic solvent, the process according to claim 8 or 9.

11. The polymerization reaction is carried out such that the fractions of the unconverted graft monomers B1, B2, and any optional further monomers, and the initiator (C) in the reaction mixture are always maintained in a quantitatively deficient state with respect to the polymer backbone (A), the process according to any one of claims 8 to 10.

12. The polymerization reaction is carried out such that the fraction of the unconverted graft monomers B1, B2, and any optional further monomers is at least more than 5, preferably more than 20, even more preferably more than 50, even more preferably more than 75, even more preferably more than 90, and most preferably at most 100 percent at the point in time when it affects the polymerization reaction, the process according to any one of claims 8 to 10.

13. The amount of the ((free) radical-forming) initiator (C) is in each case 0.1 to 5% by weight, specifically 0.3 to 3.5% by weight, based on the total weight of the graft polymer, the process according to any one of claims 8 to 12.

14. The solvent (D) used in the polymerization reaction is only water, and the radical initiator is dissolved in a small amount of organic solvent as disclosed below, the process according to any one of claims 8 to 13.

15. The main polymerization is carried out without using the solvent (D) and using only the solvent necessary for the introduction of the radical initiator, the process according to any one of claims 8 to 13.

16. A graft polymer obtainable by the process according to any one of claims 8 to 15.

17. a) as an additive in a cleaning composition, preferably for a liquid, solid, or semi-solid detergent formulation, particularly for a liquid detergent formulation, preferably a concentrated liquid detergent formulation, or a single-dose laundry detergent formulation or a liquid manual dishwashing detergent formulation, or for a solid automatic dishwashing formulation; b) in fabric care and home care products; c) in pesticide formulations, preferably as a dispersant; d) as an aid for producing multi-layer composite films by adapting, for example, not only different polymer layers but also metal foils; e) as an adhesion promoter for adhesives used in combination with, for example, polyvinyl alcohol, butyrate, and acetate, and styrene copolymers, or as a coagulation promoter for label adhesives; f) as a primer for improving adhesion to substrates such as glass, wood, plastics, and metals in coating applications; g) for improving wet adhesion in standard emulsion paints and, for example, for improving the immediate rain resistance of paints for road markings; h) as a complexing agent having a high binding capacity particularly for heavy metals such as Hg, Pb, Cu, Ni, etc.; i) as a penetration aid for active metal salt formulations, for example, in wood protection; j) as a corrosion inhibitor for, for example, iron and non-ferrous metals, and in the sectors of petroleum production and secondary petroleum production; k) for the immobilization of proteins and enzymes, microorganisms, or as an immobilization support for enzymes and microorganisms; l) as a fixing solution in the motion picture film manufacturing industry; m) as an additive in cosmetic formulations, for example, for hair setting compositions and hair rinses; n) as an emulsifier; o) as a surfactant in the industrial cleaning (IC) sector; p) for preparing a complexing agent (polycarboxylate); q) for producing aids for ore mining and beneficiation; r) as a dispersant for pigments, ceramics, carbon black, carbon, carbon fibers, metal powders, for example, as an emulsifier or dispersant for inks, for example, for inkjet printing; s) as a crystallization inhibitor in, for example, pesticide formulations, oilfield applications; t) as a rheology modifier; u) as an aid or as a component for an aid for extracting and processing oil, coal, and natural gas; v) as an additive in coolants, lubricants, and cooling lubricants, or w) as a component of a zinc plating bath; Use of at least one graft polymer according to any one of claims 1 to 7 or 16, or at least one graft polymer obtained by the process according to claim 8 or 15.

18. Use according to claim 17 in a cleaning composition, a fabric care product and a home care product, an industrial cleaning product, a cosmetic or personal care product, or a pesticide formulation.

19. Use according to claim 18, wherein the composition is a liquid, solid, or semi-solid cleaning composition or formulation, preferably a concentrated liquid detergent formulation, a single-dose laundry detergent formulation, a liquid manual dishwashing detergent formulation, or a solid automatic dishwashing formulation.

20. Use according to claim 19, wherein the composition comprises at least one enzyme, preferably one or more enzymes selected from lipase, hydrolase, amylase, protease, cellulase, mannanase, hemicellulase, phospholipase, esterase, xylanase, DNase, dispersin, pectinase, oxidoreductase, cutinase, lactase, and peroxidase, more preferably additionally comprising at least two of the above-mentioned species.

21. Use according to claim 19 or 20, wherein the graft polymer is used to prevent dye transfer.

22. The at least one graft polymer is present in an amount in the range of about 0.05 wt% to about 20 wt%, preferably 0.05 to 10 wt%, more preferably about 0.1 wt% to 8 wt%, even more preferably about 0.2 wt% to about 6 wt%, still more preferably about 0.2 wt% to about 4 wt%, most preferably up to 2 wt%, by weight of the total weight of such composition or product, and any numerical value therebetween, and any range obtained by selecting any one of the lower limit values and combining it with any one of the upper limit values, and such cleaning composition further comprises a surfactant system of 1 wt% to 70 wt%, use according to any one of claims 19 to 21.

23. In liquid, solid, or semi-solid form, preferably a concentrated liquid detergent formulation, a single single-dose laundry detergent formulation, a liquid manual dishwashing detergent formulation, or a solid automatic dishwashing formulation, more preferably at least one graft polymer according to any one of claims 1 to 7 or 16 or at least one graft polymer obtained by the process according to claim 8 or 15 A cleaning composition that is a laundry detergent formulation containing, wherein the at least one graft polymer is, in weight percent based on the total weight of such composition or product, about 0.05 wt% to about 20 wt%, preferably 0.05 to 10 wt%, more preferably about 0.1 wt% to 8 wt%, even more preferably about 0.2 wt% to about 6 wt%, still more preferably about 0.2 wt% to about 4 wt%, most preferably up to 2 wt% range of amounts, and any numerical value between these, and any range obtained by selecting any of the lower limit values and combining with any of the upper limit values, and is present in an amount including, Such a composition is, About 1 wt% to about 70 wt% of at least one surfactant, preferably a surfactant system, and Optionally, preferably at least one enzyme selected from lipase, hydrolase, amylase, protease, cellulase, mannanase, hemicellulase, phospholipase, esterase, xylanase, DNase, dispersin, pectinase, oxidoreductase, cutinase, lactase, and peroxidase, more preferably at least two of the above species, more preferably protease and Further comprises, Optionally, further comprising at least one antibacterial agent, preferably 2-phenoxyethanol, in an amount of 2 ppm to 5%, more preferably 0.1 to 2% based on the weight of the composition, Optionally, containing 4,4'-dichlorohydroxydiphenyl ether at a concentration of 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6% based on the weight of the composition, respectively, A cleaning composition.

24. The composition according to claim 23, wherein the graft polymer is used to prevent dye transfer.

25. The composition according to claim 23 or 24, which is a laundry detergent, preferably a liquid laundry composition, more preferably a concentrated liquid detergent formulation or a single single-dose laundry detergent formulation.

26. A method for protecting the composition according to any one of claims 23 to 25 from microbial contamination or growth, comprising adding an antibacterial agent selected from the group consisting of 2-phenoxyethanol to the composition, which is an aqueous composition containing water as a solvent.

27. A method for washing a fabric or cleaning a hard surface, comprising treating the fabric or hard surface with the composition according to any one of claims 23 to 25, wherein the composition contains 4,4'-dichlorodihydroxy diphenyl ether, preferably 4,4'-dichlorodihydroxy diphenyl ether at a concentration of 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6% based on the weight of the composition respectively.

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