CN117795048A - Biodegradable graft polymers for dye transfer inhibition - Google Patents

Abstract

The present application relates to biodegradable graft polymers useful as dye transfer inhibitors, particularly in laundry applications. The graft polymers of the present invention comprise a polyalkylene oxide polymer as the polymer backbone of the graft polymer and grafted side chains obtained by free radical polymerization of at least one vinyl ester, at least one vinyl imidazole monomer or its derivative in an amount greater than 10 weight percent based on the total weight of the graft polymer, and optionally at least one vinyl lactam in the presence of the polymer backbone. The graft polymers of the present invention exhibit dye transfer inhibition properties; since they are also biodegradable, they are polymers that can be used in clothing cleaning applications to prevent dye transfer. The present invention further relates to the production of such graft polymers. In addition, the present invention relates to the use of such graft polymers in fabrics and home care products, and the use of such graft polymers for inhibiting dye transfer in laundry applications. The present invention also relates to fabrics and home care products themselves containing such graft polymers.

Description

Biodegradable graft polymers for dye transfer inhibition

The present application relates to biodegradable grafted polymers useful as dye transfer inhibiting agents, particularly in laundry applications.

The graft polymer of the present invention comprises a polyalkylene oxide polymer as the polymer backbone of the graft polymer and grafted side chains obtained from free radical polymerization of at least one vinyl ester, at least one vinyl imidazole monomer or derivative thereof, and optionally at least one vinyl lactam in the presence of the polymer backbone.

The grafted polymers of the present invention exhibit dye transfer inhibiting properties; since they are also biodegradable, they are polymers useful in laundry cleaning applications to prevent dye transfer.

The invention further relates to the production of such grafted polymers.

Furthermore, the present invention relates to the use of such grafted polymers in textile and home care products, and to the use of such grafted polymers for inhibiting dye transfer in laundry applications.

The invention also relates to textile and home care products themselves containing such grafted polymers.

Such grafted polymers for dye transfer inhibition are not known.

When washing fabrics, dye transfer can present challenges, as dyes from one portion of the fabric may become suspended in the wash liquor and may then be deposited on a different portion of the fabric, or on a different fabric entirely. Transfer of such dyes (referred to as "fading dyes") may result in graying of the dye and discoloration of fabrics, especially those of light or white colors.

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

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

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

Therefore, it is highly desirable to identify better biodegradable ingredients for such applications.

This problem of poor biodegradability is particularly serious for polymers produced by free radical polymerization based on a carbon backbone only (i.e. a backbone without heteroatoms such as oxygen or nitrogen), since the carbon backbone alone is particularly refractory to degradation by microorganisms. Even industrially important free radically produced graft polymers with a polyethylene glycol backbone show only limited biodegradation in wastewater.

It is known that low molecular weight polyethylene oxide with a Mw of 600 g/mol is readily biodegradable, whereas polyethylene oxide with a Mw of 6000 g/mol is only poorly biodegradable. E 600, BASF's safety data sheet (revised version 2.0, dated January 05, 2021) confirms a DOC value (dissolved organic carbon) of > 70% measured according to OECD 301A for polyethylene glycol with Mw = 600 g/mol. The safety data sheet for E 6000 Pellet, BASF (revised version 2.0, dated August 10, 2018), mentions that the biodegradability of polyethylene glycol with Mw = 6000 g/mol is only poor, showing only 10%-20% CO2 formation relative to the theoretical value (60d) according to OECD 301B.

Various further attempts have been made to provide DTI-polymers with similar properties to the copolymers of 1-vinylimidazole and 1-vinylpyrrolidone, but none have achieved similar DTI properties or a useful degree of biodegradability.

WO 03/042262 relates to so-called “graft polymers” comprising (A) a polymer graft backbone having no monoethylenically unsaturated units and (B) polymer side chains formed from copolymers of two different monoethylenically unsaturated monomers (B1) and (B2), each comprising a nitrogen-containing heterocycle, wherein the proportion of side chains (B) amounts to 35 to 55% by weight of the total polymer.

However, the grafted polymers according to WO 03/042262 do not use vinyl ester monomers to produce the corresponding polymer side chains grafted onto the main chain. The DTI performance of those polymers is acceptable, but still far from the gold standard. Biodegradation is not mentioned.

Those monomers polymerize free-radically in the presence of a "polymer backbone", but in the studies that led to this invention turned out not to possess a reactivity sufficient to achieve sufficient grafting and therefore sufficiently high performance at a given vinylimidazole concentration.

US A 5,318,719 relates to a class of biodegradable water-soluble graft copolymers with building, anti-filming, dispersion and threshold crystal inhibition properties, comprising (a) acid-functional monomers and optionally (b) other water-soluble monoethylenically unsaturated monomers (a) copolymerizable with a biodegradable substrate comprising polyalkylene oxide and/or polyalkoxylated materials. However, US-A 5,318,719 does require the use of large amounts of acid-functional monomers such as acrylic acid or methacrylic acid to produce the side chains of the graft polymer. Such type of acid monomers are not useful in the context of the present invention because they would disrupt the DTI action of the amine-(imidazole) group and the lactam group.

US2019/0390142 relates to a fabric care composition comprising a graft copolymer, which may be composed of: (a) polyalkylene oxide, such as polyethylene oxide (PEG); (b) N-vinyl pyrrolidone (VP); and (c) vinyl ester, such as vinyl acetate. However, US 2019/0390142 does not disclose additional nitrogen-containing monomers such as vinylimidazole. Moreover, the amount of the backbone and monomers used and the intended use are different.

WO 2007/138053 discloses amphiphilic graft polymers based on water-soluble polyalkylene oxides (A) as grafting base and side chains formed by polymerization of vinyl ester components (B), said polymers having on average less than one grafting site per 50 alkylene oxide units and an average molar mass M of 3 000 to 100 000. However, WO 2007/138053 does not contain any disclosure about the biodegradability of the corresponding graft polymers disclosed therein, nor does it disclose the use of vinylimidazoles instead of vinyllactams, nor the use of any significant amounts of nitrogen-containing monomers.

Unpublished patent application PCT/EP 2021/053446 relates to grafted polymers comprising a block copolymer backbone (A) as a grafting matrix, on which are grafted polymer side chains (B). These polymer side chains (B) can be obtained by polymerization of at least one vinyl ester monomer (B1) and optionally N-vinyl pyrrolidone as an optional additional monomer (B2). Most preferably, the block copolymer backbone (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG). The invention further relates to the use of such grafted polymers in, for example, fabrics and home care products. However, except for the monomers vinyl pyrrolidone and the required vinyl ester monomers, which are included only as "optional", no other monomers are included, specifically no vinyl imidazole monomers are included. There is also no mention of the application as DTI.

Y. Zhang et al., J. Coll. Inter. Sci [Journal of Colloid and Interface Science] 2005, 285, 80 relates to the synthesis and characterization of specific grafted polymers based on pluronic-type backbones. Pluronic poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO) block copolymers are grafted with poly(vinyl pyrrolidone) by free radical polymerization of vinyl pyrrolidone with simultaneous transfer to the pluronic chains in dioxane. However, Y. Zhang does not disclose that the polymer side chains of the corresponding grafted polymers are based on vinyl ester monomers rather than vinyl imidazole monomers. In addition, Y. Zhang does not have any disclosure about the biodegradability of the grafted polymers disclosed therein. Y. Zhang also does not contain any disclosure about the use of such grafted polymers in fabric and home care products.

WO 2020/005476 discloses fabric care compositions comprising graft copolymers and so-called treatment aids, the graft copolymers comprising as a main chain a polyalkylene oxide based on ethylene oxide, propylene oxide or butylene oxide, preferably polyethylene oxide, and as grafted side chains on the main chain N-vinyl pyrrolidone and vinyl esters, and wherein the main chain and the two monomers are in a specific ratio. Vinylimidazole is not disclosed as a monomer. However, as a target application of the fabric care composition of the present invention, DTI is mentioned; the use of the graft polymer itself as a DTI-polymer is not explicitly disclosed, except for the following "viewpoint": if the molecular weight of the grafting matrix, such as polyethylene glycol, is relatively low, there may be a decrease in the performance of dye transfer inhibition, and when the molecular weight is too high, the polymer may not remain suspended in solution and/or may deposit on the treated fabric. The DTI-properties appear to be due to the specific combination of claimed compounds rather than to the graft polymer alone itself, even more so, the further "processing aids" mentioned as preferred ingredients are the known DTI-polymers as mentioned above as general state of the art known to the skilled person.

WO 2020/264077 discloses cleaning compositions containing a combination of enzymes and polymers, such compositions being suitable for removing stains from soiled materials.

This publication discloses so-called "suspended graft copolymers" which are 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 therefore do not contain vinylimidazole as a monomer. Furthermore, it is specifically claimed that in addition to the suspended graft polymer, typical known dye transfer inhibitor polymers (those mentioned above as the general state of the art known to the skilled person) are also contained in the claimed fabric cleaning compositions.

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

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

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

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

As polymer backbones, polyethers are disclosed in WO 0018375, which have 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, very particularly preferably in the range of 800 to 15,000 g/mol. It is further mentioned that homopolymers of ethylene oxide or copolymers having an ethylene oxide content of 40 to 99% by weight are advantageously used and that ethylene oxide units are therefore preferably used in a content of 40 to 100 mol % in the ethylene oxide polymers. Suitable comonomers for these copolymers are said to be propylene oxide, butylene oxide and/or isobutylene oxide, wherein suitable examples are said to be copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide, and copolymers of ethylene oxide, propylene oxide and at least one butylene oxide. The ethylene oxide content in the copolymer is said to be preferably 40 to 99 mol %, the propylene oxide content is 1 to 60 mol % and the butylene oxide content in the copolymer is 1 to 30 mol %. Not only linear but also branched homopolymers or copolymers are said to be useful as grafting bases for grafting.

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

Thus, polymers containing non-hydrolyzed vinyl acetate and the further required monomers as claimed in the present invention are not produced and characterized in WO 0018375.

Moreover, WO 0018375 does not disclose nor claim specific grafted polymers made of polyalkylene oxide polymers as polymer backbone and - as grafted side chains monomers - vinyl esters and vinyl imidazoles and optionally vinyl pyrrolidone, although vinyl pyrrolidone and vinyl imidazole are mentioned in the list of at least 5 different monomers (one of which is the Markush group), they are not emphasized or exemplified in any way. The disclosure itself focuses on different compositions containing only PEG grafted with vinyl acetate and then hydrolyzed to vinyl alcohol for use as film-forming polymers in pharmaceutical applications.

The use of such polymers as disclosed herein for detergent and cleaning or fabric care applications and in particular not as DTI-polymers is also not disclosed in WO 0018375. Such applications or uses are not mentioned at all in this disclosure.

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

Similarly, WO 2020/264077 A1 does not disclose any graft polymers containing vinylimidazole or any other amine-containing monomers such as those required by the present invention. Moreover, the use of graft polymers composed of polyethylene glycol, vinyl acetate and vinylpyrrolidone (i.e., vinyl lactam) as dye transfer inhibitors is also not disclosed.

US2008/255326 discloses a method for preparing a graft polymer comprising a polyalkylene oxide polymer such as polyethylene glycol, a vinyl ester such as vinyl acetate and a vinyl lactam such as vinyl pyrrolidone as a grafting base (both grafted onto the polyalkylene oxide backbone), and optionally a monomer from a third class ("monomer c)") in an amount of 0 to up to 10 (ten) weight percent based on the total amount of grafted monomers (wherein the preferred range is 0 to 5 and more preferably 0 to 2 and most preferably "zero", i.e. not present at all), wherein the total amount of grafted monomers adds up to 100 weight percent, and the amount of all grafted monomers is 10 to 95 weight percent based on the total weight of the resulting grafted polymer. Among many other items, vinyl imidazole is also listed as an optional "monomer c)". However, vinyl imidazole is not preferred anywhere compared to other monomers c), but only one group in the list spanning eight paragraphs of potentially used monomers c). In the most preferred list of monomers c), vinylimidazole is included, but this list consists of 13 monomers with completely different chemical structures and functionalities (from amides, to sulfonic acids to acrylates). There is also no specific emphasis in any way on any particular properties that vinylimidazole can impart to the grafted polymer, nor is there any mention in the disclosure itself that the grafted polymer can be used for cleaning purposes, nor is there any mention that the grafted polymer can be specifically used as a dye transfer inhibitor. This application is not mentioned at all in this disclosure, as the disclosure is focused on the production process of grafted polymers and the use of such grafted polymers for gas hydrate inhibition, which is a technical application of such polymers in the field of offshore oil production, where those polymers are injected into pipes right at offshore oil rigs. This has nothing to do with cleaning and the interaction of polymers with dyes during cleaning.

DETAILED DESCRIPTION

As used herein, the articles "a/an" when used in a claim should be understood to mean one or more of what is claimed or described. As used herein, the terms "include" and "including" are intended to be non-limiting and thus encompass more than the specific items mentioned after these words.

The composition of the present disclosure may "comprise" (i.e. contain other ingredients) the components of the present disclosure, "essentially consist of the components of the present disclosure" (mainly or almost only contain the mentioned ingredients and only in very small amounts of other ingredients, mainly only as impurities) or "consist of the components of the present disclosure" (i.e. contain only the mentioned ingredients and may additionally contain only impurities that are unavoidable in the technical environment, preferably contain only these ingredients).

Similarly, the term "substantially free of" or "substantially free from" or "substantially does not (contain/comprise)..." may be used herein; this means that the indicated material is present in a very small amount not intentionally added to the composition to form a part thereof, or, preferably, is not present at an analytically detectable level. It is meant to include compositions in which the indicated material is present only as an impurity in one of the other materials intentionally included. If present, the indicated material may be present at a level of less than 1%, or even less than 0.1%, or even much less than 0.01%, or even 0% by weight of the composition.

As used herein, the term "about" encompasses the exact number "X" mentioned, such as "about X%", etc., as well as small variations of X, including deviations from X by -5% to +5% (for this calculation, X is set to 100%), preferably -2% to +2%, more preferably -1% to +1%, even more preferably -0.5% to +0.5% and smaller variations. Of course, if the given value X itself is already "100%" (such as for purity, etc.), the term "about" can clearly and therefore does only mean its deviation less than "100".

Unless otherwise indicated, all component or composition levels refer to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such component or composition.

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

Graft polymer

The present invention encompasses a graft polymer comprising a polymer main chain as a graft base as a first structural unit and a polymer side chain as a second structural unit.

The first structural unit of the graft polymer is a polymer backbone used as a grafting base for the graft polymer of the present invention, wherein the polymer backbone (A) is obtainable by polymerization of at least one alkylene oxide monomer selected from the group consisting of C2- to C10-alkylene oxides, preferably C2- to C5-alkylene oxides, such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide; selected from 1,4-diols or their cyclic or oligomeric analogs, or based on such 1,4- Polyethers of diols; selected from 1,6-diols or their cyclic or oligomeric analogs, or polymeric ethers based on such 1,6-diols; or any of their mixtures in any ratios, as blocks of certain polymer units, or as statistical polymer structures, or polymers comprising one or more homopolymeric blocks of a certain monomer and one or more statistical blocks comprising more than one such monomer and any combination thereof, such as polymers having several different blocks of different monomers, or blocks of two different monomers, blocks of statistical mixtures of two or more monomers, etc.

The term "block (co)polymer (main chain)" as used herein means that the corresponding polymer comprises at least two (i.e., two, three, four, five or more) homopolymer or copolymer subunits ("blocks") connected by covalent bonds. A "two-block" copolymer has two different blocks (homopolymer and/or copolymer subunits), while a "three-block" copolymer therefore has three different blocks (homopolymer and/or copolymer subunits), and so on. The number of individual blocks in such a block copolymer is not limited; therefore, an "n-block copolymer" comprises n different blocks (homopolymer and/or copolymer subunits). In a separate block, the size/length of such a block may vary independently of the other blocks. The minimum length/size of a block is based on two separate monomers (as a minimum), but may be as large as 50. The corresponding monomers for the individual blocks used to prepare the block copolymer main chain (A) can be added in sequence. However, it is also possible that there is a transition of the feed from one monomer to another to produce a so-called "dirty structure", in which at the edge/boundary of the respective block, a minority of monomers of the respective adjacent block may be contained in a separate block to be considered (so-called "dirty structure" or "dirty segment"). However, it is preferred that the block copolymer backbone (A) according to the present invention does not contain any dirty structure at the respective block boundary, although for commercial reasons (i.e., mainly the cost of efficient use of the reactor, etc.), a small amount of dirty structure may still be contained (although not intentionally).

Preferably, at least one monomer in the polymer backbone is derived from the use of ethylene oxide, and more preferably the polymer backbone is obtained from the use of ethylene oxide alone.

In another embodiment, more than one alkylene oxide monomer is included in the structure of the polymer backbone; in such case, the polymer backbone is a random copolymer, a block copolymer or a copolymer of a mixed structure comprising block units (where each block is a homoblock or a random block itself) and a statistical/random part consisting of two or more alkylene oxides, one of which is ethylene oxide. Preferably, in addition to ethylene oxide, the additional monomers are propylene oxide and/or 1,2-butylene oxide, preferably only 1,2-propylene oxide.

In other embodiments, the amount of ethylene oxide in the polymer backbone (A) is within 10-90 weight percent (relative to the total molar amount of ethylene oxide in the polymer backbone (A)).

More preferably, the monomers in the polymer backbone are derived from the use of ethylene oxide and propylene oxide, wherein the amount of ethylene oxide in the polymer backbone A is within 10 to 90, preferably at least 30, more preferably at least 50, even more preferably at least 70, most preferably at least 80 weight percent (relative to the total molar amount of alkylene oxide in the polymer backbone (A)).

The polymer backbone may contain an additional starter block, which is present at the beginning of the preparation process of the polyalkylene oxide polymer. This starter block reacts with alkylene oxide, and those chains are further extended, thereby producing a polyalkylene oxide containing the starter block in the chain. Suitable starter blocks are those that can react with alkylene oxide and have two hydroxyl groups, such as glycols, alkylene glycols, and diols; preferably, those starter blocks are selected from glycerol, 2-methyl-1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, trimethylolpropane, water, pentaerythritol, sorbitol, sucrose, glucose, fructose, lactose, and similar compounds with similar chemical structures. In principle, diamines such as ethylenediamine, propylenediamine, diethylenetriamine, dipropylenetriamine etc. are also possible, but those amines are not preferred in view of potential ecotoxicity problems, especially when released again from the polymer structure after biodegradation of the graft polymers according to the invention.

In a more preferred embodiment, no such starting blocks are used in the polymer backbone of the present invention.

As the most preferred embodiment, the polymer backbone is obtained from using only ethylene oxide and no other alkylene oxide monomers.

The molecular weight (number average molecular weight) of the polymer backbone (A) in g/mol as given as "Mn" is within 500 to 12000, preferably not more than 9000, more preferably not more than 6000, even more preferably not more than 3500, further even more preferably not more than 3000, even further even more preferably not more than 2750 and at least 600, more preferably at least 1000, even more preferably at least 1500, and wherein all ranges formed by combining any number previously specified for the lower boundary with any number previously specified as the upper boundary are understood to be included as the scope of the present invention. As a more preferred range, the Mn is 600 to 3000, even more preferably 1000 to 2750, and most preferably 1500 to 2750.

The polymer backbone (A) is optionally terminated at one or both end groups, this being accomplished using known techniques by means of C1-C25-alkyl, preferably C1 to C4-groups.

In a preferred embodiment, the polymer backbone (A) is not terminated at the chain ends but carries hydroxyl groups.

The second structural unit of the grafted polymer is a polymer side chain (B), which is grafted onto the polymer main chain (A), wherein the polymer side chain (B) is obtainable by copolymerization of at least one monomer (B1) and at least one monomer (B2), wherein monomer (B2) is at least one monomer (B2a) and optionally at least one further monomer (B2b):

Monomer (B1) is selected from at least one vinyl ester monomer, preferably at least one monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate and any other known vinyl ester monomer, more preferably selected from vinyl acetate and vinyl laurate, and most preferably vinyl acetate. The remaining amount of vinyl ester monomer (B1) can be any other known vinyl ester monomer, such as vinyl valerate, vinyl neopentanoate, vinyl neodecanoate (such as VEOVA9 and VEOVA10), vinyl decanoate or vinyl benzoate.

Preferably, as vinyl ester only vinyl acetate and/or vinyl propionate, and more preferably at least 80 weight percent, even more preferably at least 90 weight percent, and most preferably substantially only (i.e. about 100 wt % or even 100 wt %) vinyl acetate is used as the vinyl ester.

Monomer (B2) is selected from at least one monomer from group (B2a) and optionally also at least one monomer from group (B2b).

At least one monomer (B2a) is to be used for preparing the polymer side chain (B) of the graft polymer of the present invention, wherein at least one monomer (B2a) is an ethylenically unsaturated amine-containing monomer, preferably 1-vinylimidazole and/or its derivatives such as alkyl-substituted derivatives of 1-vinylimidazole such as 2-methyl-1-vinylimidazole, more preferably only 1-vinylimidazole.

As an optional additional monomer (B2b), in addition to (B2a) and (B1), at least one monomer (B2b) can also be used to prepare the polymer side chain (B) of the graft polymer of the present invention, and this at least one monomer (B2b) is a 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 N-vinyl pyrrolidone, N-vinyl caprolactam, and most preferably N-vinyl pyrrolidone.

Additional - non-preferred - monomers (B2b) may be any one or more of the following: 1-vinyloxazolidinone and other vinyloxazolidinones, 4-vinylpyridine-N-oxide, N-vinylformamide (and its amines if hydrolyzed after polymerization), N-vinylacetamide, N-vinyl-N-methylacetamide, acrylamide, methacrylamide, N,N′-dialkyl(meth)acrylamides; such monomers are preferably used in an amount lower than the vinyllactam monomers, such as up to 50, preferably up to 30, more preferably up to 10 and even more preferably up to 5 weight percent, based on the weight of the vinyllactam used, and most preferably not used at all.

Therefore, in a more preferred embodiment of the present invention, the graft polymer as defined herein comprises no further monomers (B2b) besides the vinyllactam monomers as defined before.

In the context of the present invention, it is preferred that no further monomers are used in the respective polymerization process for obtaining the polymer side chains (B) apart from those defined above as (B1), (B2a) and optionally (B2b). However, if any further monomers are present apart from the monomers according to (B1), (B2a) and optionally (B2b), such further monomers are present in an amount of less than 3% of the total amount of monomers used to obtain the polymer side chains (B) and are preferably present only as impurities and not intentionally added for the polymerization. Preferably, the amount of said further monomers is less than 1% by weight, more preferably less than 0.5% by weight, even more preferably less than 0.01% by weight, most preferably apart from the monomers (B1), (B2a) and optionally (B2b), substantially no or even completely no further monomers are present.

As described in detail above, the graft polymer of the present invention contains the following amounts of the first and second structural units in its composition:

The amount of polymer backbone (A) by weight percent is 30 to less than 89, preferably 40 to 80, more preferably 45 to 75, even more preferably 50 to 70, and most preferably 50 to 65, based on the total weight of the grafted polymer; and

The amount of polymer side chains (B) by weight percent is greater than 11 to 70, preferably 20 to 60, more preferably 25 to 55, even more preferably 30 to 50 and most preferably 35 to 50, based on the total weight of the grafted polymer.

The amount of (B1) in weight percent is 1 to 30, preferably 3 to 25, more preferably 5 to 20, most preferably 5 to 15, based on the total weight of the graft polymer;

The amount of (B2) by weight percentage is greater than 10 to 60, preferably 20 to 60, more preferably 20 to 50, even more preferably 20 to 40, most preferably 25 to 35, based on the total weight of the graft polymer;

The amount of (B2a) in weight percent, based on the total amount of monomers (B2), is 10 to 100, preferably greater than 10 to 100, more preferably greater than 15 to 90, more preferably 20 to 90, more preferably at least 15, even more preferably at least 20, even more preferably at least 25, even more preferably at least 30 and even more preferably at least 35, and most preferably at least 40 and as an upper limit is at most 85, even more preferably at most 80, even more preferably at most 75, and most preferably at most 70, such as greater than 10 and up to 90, more preferably from 20 to 85, even more preferably from 25 to 80, even more preferably from 30 to 80, even more preferably from 35 to 75, and most preferably from 40 to 70, with the proviso that the amount by weight percentage of (B2a) is always at least greater than 10, preferably at least 12, more preferably at least 15, more preferably at least 17, even more preferably at least 20, and most preferably at least 25 and at most 60, more preferably at most 50, even more preferably at most 45, even more preferably at most 40, and most preferably at most 35, based on the total weight of the grafted polymer; and

The amount of (B2b) in weight percent is equal to [100% of the amount of (B2)] minus [the amount of (B2a)].

It is clear that all amounts of the desired part of the grafted polymer, i.e. the amount of polymer backbone (A) and all monomers (B1), (B2a) and (B2b) actually used, must add up to 100%/weight of the total grafted polymer. It is also clear that the total amount of all monomers (B), all monomers (B1), all monomers (B2) must each add up to "100%" of (B), (B1) and (B2), respectively.

Preferably, the amounts previously detailed for (B1), (B2a) and (B2b) are combined with the amounts of (A) and (B). It will be appreciated that the amounts of (A) and (B) may be selected from the respective detailed ranges given independently of the respective amounts and ranges given for (B1), (B2a) and (B2b): for example the most preferred ranges for (A) and (B) may be selected and combined with the widest possible range given for (B1)/(B2a)/(B2b), and any other possible combination. Preferably, for all selections that may be made for (A)/(B) and (B1)/(B2a)/(B2b), the same selection is made, for example all "preferred" ranges are selected, or - more preferably - all "more preferred" ranges are selected, or - most preferably - all "most preferred" ranges are selected.

Therefore, in a more preferred embodiment, the following amounts are selected:

The amount of polymer backbone (A) in weight percent based on the total weight of the grafted polymer is most preferably 50 to 70; and

The amount of the polymer side chains (B) is most preferably 30 to 50 weight percent based on the total weight of the grafted polymer; and

The amount by weight percent of (B1) is most preferably 5 to 15, or alternatively but less preferably 10 to 20, based on the total weight of the grafted polymer;

The amount of (B2) in weight percent based on the total weight of the graft polymer is most preferably 25 to 35; and

The amount of (B2a) in weight percent is most preferably 40 to 70 based on the total amount of monomer (B2); and

The amount of (B2b) in weight percent, based on the total amount of monomer (B2), is equal to [100% of the amount of (B2)] minus [the amount of (B2a)].

In a more preferred embodiment, the following amounts are selected:

The amount of the polymer backbone (A) is 40 to 70 weight percent based on the total weight of the grafted polymer; and

The amount of the polymer side chains (B) is 30 to 60 weight percent based on the total weight of the grafted polymer; and

The amount of (B1) is 5 to 15 weight percent based on the total weight of the graft polymer;

The amount of (B2) is 15 to 55 weight percent based on the total weight of the graft polymer; and

The amount of (B2a) is 15 to 35 weight percent based on the total weight of the graft polymer; and

The amount of (B2b) in weight percent is equal to [100% of the amount of (B2)] minus [the amount of (B2a)],

Wherein preferably the polymer backbone (A) is a polyalkylene oxide containing more than 70, preferably more than 80, even more preferably more than 90 weight percent of ethylene oxide based on the total alkylene oxide, and most preferably containing only ethylene oxide, and

(B1) is vinyl acetate, (B2a) is vinylimidazole, and (B2b) is a vinyllactam, preferably vinylpyrrolidone.

In an even more preferred embodiment, the following amounts are selected:

The amount of the polymer backbone (A) is 45 to 65 weight percent based on the total weight of the grafted polymer; and

The amount of the polymer side chains (B) is 40 to 55 weight percent based on the total weight of the grafted polymer; and

The amount of (B1) is 5 to 15 weight percent based on the total weight of the graft polymer;

The amount of (B2) is 25 to 50 weight percent based on the total weight of the graft polymer; and

The amount of (B2a) is 15 to 30, preferably 20 to 30, by weight percent based on the total weight of the graft polymer; and

The amount of (B2b) in weight percent is equal to [100% of the amount of (B2)] minus [the amount of (B2a)],

Wherein preferably the polymer backbone (A) is a polyalkylene oxide containing more than 70, preferably more than 80, even more preferably more than 90 weight percent of ethylene oxide based on the total alkylene oxide, and most preferably only containing ethylene oxide, and

(B1) is vinyl acetate, (B2a) is vinylimidazole, and (B2b) is a vinyllactam, preferably vinylpyrrolidone.

In a preferred embodiment, the grafted polymer as previously detailed is made of: a polymer backbone (A) which itself contains only ethylene oxide as monomer; and/or polymer side chains (B) which consist of vinyl acetate as the only monomer (B1), 1-vinylimidazole as the only monomer (B2a), and (B2b) which is an N-vinyllactam, preferably N-vinylpyrrolidone.

In another preferred embodiment, the graft polymer as previously detailed is made of: a polymer backbone (A), which itself contains only ethylene oxide as monomer; and polymer side chains (B), which consist of vinyl acetate as the only monomer (B1) and 1-vinylimidazole as the only monomer (B2a), wherein monomer (B2b) is absent.

In a more preferred embodiment, the grafted polymer as previously detailed is made of: a polymer backbone (A), which itself contains only ethylene oxide as monomer; and polymer side chains (B), which consist of vinyl acetate as the only monomer (B1), 1-vinylimidazole as the only monomer (B2a), and (B2b) which is an N-vinyllactam, preferably N-vinylpyrrolidone.

In even more preferred embodiments, the preferred choices of monomers as detailed previously and the preferred choices of amounts as detailed previously are combined.

In another embodiment, the grafted polymer is described in detail as follows:

The polymer backbone (A) is present in an amount of 50 to 70 weight percent based on the total weight of the graft polymer and comprises only ethylene oxide as a monomer; and

The amount of the polymer side chains (B) is 30 to 50 weight percent based on the total weight of the grafted polymer; and

In the case of vinyl acetate as the only monomer (B1), the amount of (B1) by weight percentage is 10 to 20, based on the total weight of the graft polymer; and

The amount of (B2) is 25 to 35 weight percent based on the total weight of the graft polymer; and

In case of 1-vinylimidazole as the only monomer (B2a), the amount by weight percentage of (B2a) is 40 to 70, based on the total amount of monomers (B2); and

Based on the total amount of monomers (B2), the amount of (B2b) in weight percentage is equal to [100% of the amount of (B2)] minus [the amount of (B2a)], wherein (B2b) is N-vinyllactam, preferably only N-vinylpyrrolidone.

As previously detailed the graft polymers of the present invention have a polydispersity (PDI) Mw/Mn (wherein Mw = weight average molecular weight in g/mol and Mn = number average molecular weight in g/mol; wherein PDI is unitless) of less than 7, preferably less than 5, more preferably less than 4, and most preferably in the range of 1 to 3, with lower values being preferred, but this depends on the Mn of the polymer backbone used (the higher the Mn of (A), the higher the PDI is also typically) and also the amount of (B) (the higher the amount of (B) relative to the amount of (A), the higher the PDI is typically).

The respective values of _Mw and _Mn can be determined as described in the experimental section below.

The grafted polymers of the invention may contain a certain amount of ungrafted polymers made of vinyl esters ("ungrafted side chains"), for example polyvinyl acetate, and/or - depending on the monomers used and their respective reactivity towards copolymerization - copolymers of vinyl esters with other monomers or even small amounts of copolymers of other monomers used. The amount of such ungrafted polymers may be high or low, depending on the reaction conditions, but is preferably reduced and therefore more preferably low. By this reduction, the amount of grafted side chains is preferably increased. Such a reduction can be achieved by suitable reaction conditions, such as the dosage of vinyl ester and free radical initiator and their relative amounts, and also in relation to the amount of main chain present. This is generally well known to the person skilled in the art.

In another embodiment of the present invention, the polymerized vinyl acetate in the polymer side chain (B) can be completely or partially hydrolyzed after obtaining the graft polymer itself. This means that the complete or at least partial hydrolysis of the polymer side chain (B) of the graft polymer is carried out after the polymerization process of the polymer side chain (B) is completed.

Due to this complete or partial hydrolysis, the corresponding side chain units originating from at least one vinyl ester monomer (B1) are changed from the corresponding ester functional groups to alcohol functional groups in the polymer side chains (B). It must be noted that the corresponding vinyl alcohols are not suitable for use as monomers in the polymerization process of the polymer side chains (B) due to the instability of "vinyl alcohol" itself. Therefore, in order to obtain alcohol functional groups (hydroxyl substituents) in the polymer side chains (B) of the graft polymer according to the present invention, the alcohol functional groups are typically introduced by hydrolyzing the ester functional groups of the side chains.

From a theoretical point of view, each ester function of the polymer side chain (B) can be replaced by an alcohol function (hydroxyl). In such a case, the polymer side chain is completely hydrolyzed (saponified) with respect to the amount of vinyl ester. It should be noted that, whether vinyl imidazole or, in certain cases, N-vinyl pyrrolidone is used as the additional monomer, typically no hydrolysis occurs at those units of the polymer side chain (B) which are derived from vinyl imidazole or N-pyrrolidone (used as the additional monomer).

The hydrolysis may be carried out by any method known to those skilled in the art. For example, the hydrolysis may be induced by the addition of a suitable base, such as sodium hydroxide or potassium hydroxide.

However, in this embodiment of the invention, it is preferred that the hydrolysis of the polymer side chains (B) is only partial in terms of the amount of vinyl ester, for example to an extent of up to 20 wt%, 40 wt% or 60 wt% (relative to the total weight of the polymer side chains).

In this embodiment, it is preferred that the polymer side chains (B) are completely hydrolyzed or partially hydrolyzed after the polymerization with respect to the amount of vinyl ester, preferably to an extent of up to 50% relative to the amount of at least one vinyl ester monomer (B1) used in the polymerization.

However, in a preferred embodiment of the present invention, the polymer side chains (B) of the graft polymer as fully detailed before are not hydrolyzed after the polymerization.

It has been found that the grafted polymers of the present invention as detailed above exhibit an improved biodegradability of at least 20%, preferably at least 30%, even more preferably at least 40% within 28 days when tested according to OECD 301F, and may be at least 45%, 50%, 55%, 60% or even 65%, and all values therebetween.

method

The present invention also encompasses a process for obtaining a grafted polymer as described above in detail, wherein the process comprises the steps of polymerizing monomers (B1), (B2a) and optionally (B2b) in the presence of at least one polymer backbone (A) as described above in detail, to obtain polymer side chains (B) grafted onto the polymer backbone (A) and therefore the "grafted polymer" of the present invention.

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

The present invention also covers a process for obtaining a grafted polymer as described above in detail, wherein the process comprises the steps of polymerizing at least one monomer (B1) as described above in detail, at least one monomer (B2a) as described above in detail, optionally at least one monomer (B2b) as described above in detail, in the presence of at least one polymer backbone (A) as described above in detail, to obtain polymer side chains (B) grafted onto the polymer backbone (A), preferably by free radical polymerization, more preferably using a free radical forming compound to initiate the free radical polymerization.

Free radical polymerization is also known per se to the skilled person. This person is also aware that the process according to the invention can be carried out in the presence of a free radical forming initiator (C) and/or at least one solvent (D). The skilled person is aware of the corresponding components per se.

The term "free radical polymerization" as used within the context of the present invention comprises besides free radical polymerization also variants thereof, such as controlled radical polymerization. Suitable control mechanisms are RAFT, NMP or ATRP, each known to the skilled person, including suitable control agents.

In a preferred embodiment, the method for obtaining the grafted polymer of the present invention as detailed above comprises polymerizing at least one monomer (B1), at least one monomer (B2a), optionally at least one monomer (B2b) in at least one polymer backbone (A) (wherein B1, B2a, B2b and A as detailed above include the corresponding "preferred", "more preferred", "most preferred" ranges, amounts and selections and combinations thereof as described in detail above in their corresponding ranges), a free radical forming initiator (C) and (if necessary) up to 50% by weight of at least one organic solvent (D) based on the sum of components (A), (B1), (B2a), optionally (B2b), and (C) at an average polymerization temperature at which the initiator (C) has a decomposition half-life of 40 to 500 min in such a manner that the fraction of unconverted grafted monomers (B1 and B2) and initiator (C) in the reaction mixture is continuously kept in a quantitative deficit relative to the polymer backbone (A).

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

For the process according to the invention, it is preferred that the steady-state concentration of free radicals present at the average polymerization temperature is substantially constant and that the grafting monomers (B1) or (B2) are present only constantly in a low concentration (e.g. not more than 5% by weight) in the reaction mixture. This allows the reaction to be controlled and the grafted polymers to be prepared in a controlled manner with the desired low polydispersity.

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

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

According to the invention, the initiator (C) and the grafting monomers (B1), (B2a) and optionally (B2b) are advantageously added in such a way that a low and substantially constant concentration of undecomposed initiator and grafting monomers (B1), (B2a) and optionally (B2b) is present in the reaction mixture. The proportion of undecomposed initiator in the reaction mixture as a whole is preferably up to 15% by weight, in particular up to 10% by weight, based on the total amount of initiator metered during the monomer addition. For this purpose, "low concentration of grafting monomers" means a concentration of up to 20, preferably up to 15, more preferably up to 10, most preferably up to 5 weight percent of the total amount of each monomer to be added.

At the end of the polymerization, the amount of residual monomer is preferably very low, such as less than 0.5 weight percent, more preferably less than 0.1, even more preferably less than 0.05 and most preferably less than 0.01 or even 0.005 weight percent based on polymer solids. This can be achieved by a suitably long polymerization duration, the addition of additional free radical initiator at the end, an increase in the polymerization temperature, or any combination of those measures.

In preferred embodiments, the steady state concentration of free radicals present at the average polymerization temperature is substantially constant.

However, in order to ensure safe temperature control - especially when the polymerization is started in large quantities and/or with large amounts of monomers present from the outset - it is advisable and therefore preferred to use additional and effective measures to control the temperature. This can be done by external or internal cooling; such cooling can be done by internal and/or external coolers such as heat exchangers, and/or when working at the boiling temperature of the solvent or solvent mixture, using a reflux condenser.

The same measures can of course be used for embodiments in which the monomer is added over an extended period of time and therefore the monomer concentration in the reaction volume is continuously low over time, which is generally not a critical point since the temperature is also at least partly controlled by the progress of the polymerization reaction by controlling the free radical concentration and the available amount of polymerizable monomer.

Of course, this depends on the scale of the polymerization reaction, and when the scale becomes large enough that the volume to surface ratio of the polymerization mixture becomes very large, such additional cooling as described above may be necessary for both variants - batch or bulk reactions, which have a large amount of monomer present from the beginning, or semi-continuous or continuous polymerization reactions with typically constant low monomer concentrations.

However, this is well known to those skilled in the art of commercial scale polymerisation and can therefore be adapted to these requirements.

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

Examples of suitable initiators (C) whose decomposition half-life is 20 to 500 min in the temperature range of 50° C. to 140° C. are:

- _OC2 - _C12 -acylated derivatives of tert- _C4 - _C12 -alkyl hydroperoxides and tert-( _C9 - _C12 -aralkyl)hydroperoxides, such as tert-butyl peroxyacetate, tert-butyl monoperoxymaleate, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl 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;

- di-OC ₄ -C ₁₂ -acylated derivatives of tert-C ₈ -C ₁₄ -alkylene bisperoxides, 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;

- di(C ₂ -C ₁₂ -alkanoyl) and dibenzoyl peroxides, such as diacetyl peroxide, dipropionyl peroxide, disuccinyl peroxide, dioctanoyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, di(4-methylbenzoyl) peroxide, di(4-chlorobenzoyl) peroxide and di(2,4-dichlorobenzoyl) peroxide;

- tert-C ₄ -C ₅ -alkylperoxy(C ₄ -C ₁₂ -alkyl)carbonates, such as tert-amylperoxy(2-ethylhexyl)carbonate;

- di(C ₂ -C ₁₂ -alkyl) peroxydicarbonates, such as di(n-butyl) peroxydicarbonate and di(2-ethylhexyl) peroxydicarbonate.

Examples of particularly suitable initiators (C), depending on the average polymerization temperature, are:

-At an average polymerization temperature of 50°C 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°C 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°C to 80°C:

tert-Butyl peroxypivalate, tert-Butyl peroxyneoheptanoate, tert-Amyl peroxypivalate, dipropionyl peroxide, dioctanoyl 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°C to 90°C:

tert-Butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, dipropionyl peroxide, dioctanoyl 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°C to 100°C:

tert-Butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl monoperoxymaleate, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, and di(4-methylbenzoyl)peroxide;

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

tert-Butyl monoperoxymaleate, tert-butyl peroxyisobutyrate, and tert-amyl peroxy(2-ethylhexyl)carbonate;

-At an average polymerization temperature of 110°C to 120°C:

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

Preferred initiators (C) are OC ₄ -C ₁₂ -acylated derivatives of tert-C ₄ -C ₅ -alkyl hydroperoxides, tert-butyl peroxypivalate and tert-butyl peroxy-2-ethylhexanoate coming into consideration with particular preference.

Particularly favorable polymerization conditions can be easily established by precise adjustment of the initiator (C) and the polymerization temperature. For example, in the case of using tert-butyl peroxypivalate, the preferred average polymerization temperature is 60° C. to 80° C., and in the case of using tert-butyl peroxy-2-ethylhexanoate, it is 80° C. to 100° C.

The polymerization reaction according to the invention can be carried out in the presence of (preferably a small amount of) an organic solvent (D). Of course, mixtures of different solvents (D) can also be used. Preference is given to using water-soluble or water-miscible solvents.

When solvents (D) are used as diluents, generally 1 to 40% by weight, preferably 1 to 35% by weight, more preferably 1.5 to 30% by weight, most preferably 2 to 25% by weight, based in each case on the sum of components (A), (B1), optionally (B2) and (C) are used.

Examples of suitable solvents (D) include:

- monohydric alcohols, preferably aliphatic C ₁ -C ₁₆ -alcohols, more preferably aliphatic C ₂ -C ₁₂ -alcohols, most preferably C ₂ -C ₄ -alcohols, such as ethanol, propanol, isopropanol, butanol, sec-butanol and tert-butanol;

- polyols, preferably C ₂ -C ₁₀ -diols, more preferably C ₂ -C ₆ -diols, most preferably C ₂ -C ₄ -alkylene glycols, such as ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol;

- alkylene glycol ethers, preferably alkylene glycol mono- and di-(C ₁ -C ₆ -alkyl) ethers, more preferably alkylene glycol mono- and di-(C ₁ -C ₂ -alkyl) ethers, most preferably alkylene glycol _mono- ( _{C 1 -C 2} -alkyl) ethers, such as ethylene glycol monomethyl ether and -ethyl ether and propylene glycol monomethyl ether and -ethyl ether;

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

- polyalkylene glycol monoethers, preferably poly(C ₂ -C ₄ -alkylene) glycol mono(C ₁ -C 25 -alkyl) ethers having 2 to 20 alkylene glycol units, more preferably poly(C ₂ -C ₄ -alkylene) glycol mono(C ₁ -C ₂₀ -alkyl) ethers having 2 to 20 alkylene glycol units, most preferably poly(C ₂ -C ₃ -alkylene) glycol mono(C ₁ -C ₁₆ -alkyl) ethers having ₃ to 20 alkylene glycol units;

- carboxylic acid esters, preferably C ₁ -C ₈ -alkyl esters of C ₁ -C ₆ -carboxylic acids, more preferably C ₁ -C ₄ -alkyl esters of C ₁ -C ₃ -carboxylic acids, most preferably C ₂ -C ₄ -alkyl esters of C ₂ -C ₃ -carboxylic acids, such as ethyl acetate and ethyl propionate;

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

- cyclic ethers, in particular tetrahydrofuran.

Solvents (D) are advantageously those solvents which are also used for formulating the graft polymers according to the invention for use (for example in washing and cleaning compositions) and which can therefore remain in the polymerisation product.

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 C ₆ -C ₈ -alcohols (alkylene glycol monoalkyl ethers and polyalkylene glycol monoalkyl ethers).

Particularly preferred here are alkoxylation products of _C8 - _C16 -alcohols with a high degree of branching, which allow the formulation of polymer mixtures which flow freely at 40° C. to 70° C. and have a very low polymer content at a relatively low viscosity. The branches may be present in the alkyl chain of the alcohol and/or in the polyalkoxylate part (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 mol of ethylene oxide, _C13 / _C15 oxo alcohols or _C12 / _C14 or _C16 /C18 fatty alcohols alkoxylated with 1 to 15 mol of ethylene oxide and 1 to ₃ mol of propylene oxide, preferably 2-propylheptanol alkoxylated with 1 to 15 mol of ethylene oxide and 1 to 3 mol of propylene oxide.

In the process according to the invention, the polymer backbone (A), the grafting monomers (B1), (B2a) and optionally (B2b), the initiator (C) and, if appropriate, the solvent (D) are generally heated in a reactor to a selected average polymerization temperature.

In a preferred embodiment, the polymerization reaction is conducted substantially without the addition of solvent (D), except for the free radical initiator dissolved in a small amount of an organic solvent as disclosed below.

In the case of little or no added solvent, the reaction is carried out in the liquid state. This liquid state already exists - in the case when the backbone is liquid - or the reaction is carried out when the backbone is molten.

Liquid monomers may help achieve such a liquid state, depending on the amount of monomer present from the start of the polymerization reaction.

Small amounts of organic solvents can be used and are preferably used for the introduction of, for example, free radical initiators and grafting monomers (B1) and/or (B2), which may be soluble only in such organic solvents to a reasonable extent but not necessarily in water. Suitable organic solvents may be isopropanol, ethanol, 1,2-propylene glycol and/or tripropylene glycol, and/or other suitable alcohols or organic solvents like 1-methoxy-2-propanol, which is quite cheap and can be used for large-scale applications, or solvents such as ethyl acetate, methyl ethyl ketone, etc., wherein isopropanol, 1,2-propylene glycol, 1-methoxy-2-propanol, ethyl acetate and/or tripropylene glycol are preferred solvents, preferably introduced into the reaction only as a solvent for the free radical initiator and/or grafting monomers (B1) and/or (B2) in as low an amount as possible, more preferably only as a solvent for the free radical initiator. In the case where the free radical initiator is soluble in water, then of course water or a mixture of an organic solvent and water can be used as solvent for the introduction of the free radical initiator.

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

In such cases of low total amounts of solvent, such solvents may remain in the final polymer, preferably less than 1, preferably less than 0.5, more preferably less than 0.1 weight percent based on the total amount of total solvents. In the case of using water as one of the solvents, large amounts are of course acceptable - it depends on the intended use.

The monomers are preferably used in their pure form or - less preferred - in the form of a 10 to 95% by weight solution in one of the previously mentioned solvents. Here again, it is preferred that the concentration is as high as possible to allow as little organic solvent as possible to be introduced into the polymerization reaction.

For solvents having a boiling point of less than about 110° C.-120° C. at atmospheric pressure, such solvents can - as a purification step - be partially or substantially completely removed by thermal distillation or vacuum distillation, all at ambient pressure or reduced pressure, or stripping with a gas such as water vapor or nitrogen (e.g. stripping with water vapor made from water), preferably vacuum distillation, whereas higher boiling point solvents will generally remain in the polymer product obtained. When mercaptoethanol is used as a chain transfer regulator, steam distillation is the preferred purification step. Thus, higher boiling point solvents like 1-methoxy-2-propanol, 1,2-propylene glycol and tripropylene glycol will remain in the polymer product, and therefore when such solvents are used only for the introduction of initiators, their amount should be minimized as much as possible by using as high a concentration of free radical initiator as possible, unless such solvents also form part of the formulation in which the grafted polymer is to be used.

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

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

The reactor used is preferably a stirred tank into which the polymer backbone (A), if appropriate, together with the grafting monomers (B1), (B2a) and optionally (B2b), the initiator (C) and the solvent (D) are initially charged completely or partly, usually up to 15% by weight, of a specific total amount and heated to the polymerization temperature, and the remaining amounts of (B1), (B2a) and optionally (B2b), (C) and, if appropriate, (D) are metered in, preferably individually. The remaining amounts of (B1), (B2a) and optionally (B2b), (C) and, if appropriate, (D) are preferably metered in over a period of ≥2 h, more preferably ≥4 h and most preferably ≥5 h.

In the case of a particularly preferred, essentially solvent-free process variant, the entire amount of the polymer backbone (A) is initially charged as a melt (if it is solid at ambient temperature) or as a preheated liquid (in the case it is a viscous liquid with a high viscosity that is not suitable for handling), and the grafting monomers (B1), (B2a) and optionally (B2b), and also the initiator (C), preferably in the form of a 10 to 50% by weight solution in one of the solvents (D), are metered in, the temperature being controlled so that the selected polymerization temperature is maintained on average during the polymerization in a range of, in particular, +/-10°C, in particular +/-5°C.

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

The polymerization can be carried out at standard pressure or at reduced or elevated pressure. When the pressure is chosen to be above the boiling point of the monomers (B1), (B2a) and optionally (B2b) or any diluent (D) used, the polymerization is carried out with reflux cooling.

A post-polymerization process step may be added after the main polymerization reaction. For this purpose, additional amounts of initiator (dissolved in one or more solvents) may be added over a period of 0.5 hours and up to 3 hours, preferably about 1 to 2 hours, more preferably about 1 hour, wherein the free radical initiator and the one or more solvents for the initiator are typically - and preferably - the same as the initiator and solvent used for the main polymerization reaction. Of course, different free radical initiators and/or different solvents may also be used.

A certain period of time may be waited between the post-polymerization and the main polymerization, wherein the main polymerization reaction continues, and then the post-polymerization reaction is started by starting to add additional free radical initiator. Such a waiting period is typically about 0.1 hours and up to 3 hours, preferably about 0.2 to 2 hours, more preferably up to about 1 hour.

The temperature of the post-polymerization process step may be the same as that in the main polymerization reaction (which is preferred in the present invention), or may be increased. In the case of increase, the temperature may typically be higher by about 5°C to 40°C, preferably 10°C to 20°C. In an alternative embodiment, the post-polymerization temperature may be the same as that used in the main polymerization step.

The grafted polymer of the invention, ie the polymer solution obtained from the process, can also be subjected to concentration or drying means in order to remove a part or almost all of the remaining solvents (as long as they are removable due to their boiling point).

The grafted polymer solution obtained can be concentrated to increase the solid polymer concentration by removing a portion of one or more solvents. This can be achieved by a distillation process such as thermal distillation or vacuum distillation, preferably vacuum distillation, which is carried out until the desired solid content is obtained. Such a process can be combined with a purification step as disclosed before, wherein the grafted polymer solution obtained is purified by removing a portion or all of the volatile components such as volatile solvents and/or unreacted volatile monomers, by removing the desired amount of solvent.

The graft polymer solution can also be further concentrated or dried after the main polymerization and/or optional postpolymerization step and the optional purification step in the following manner: the graft polymer solution is subjected to a means of partially or completely removing volatiles, such as drying such as drum drying, spray-drying, vacuum drying or freeze-drying, preferably-mainly for cost reasons-spray-drying. Such a drying process can also be combined with an agglomeration or granulation process, such as spray-agglomeration, spray-granulation or drying in, for example, a fluidized bed dryer. All such methods are known in principle and are applicable in principle to the graft polymers of the present invention.

The grafted polymer obtained from the process of the present invention is similar to the grafted polymer as described in detail above, and the polymer structure is described in all its embodiments, variations, and preferred, more preferred, etc. embodiments, and also includes the detailed embodiments as further described in "Example 1/2/3, etc." listed at the end of the specification below.

use

In principle, the graft polymers of the invention can be used in any application to replace known graft polymers of similar composition (however not comprising vinylimidazole) (in terms of the relative amounts of polymer backbone and graft monomer, especially when the type and amount of graft monomer are comparable), such as the graft polymers cited in the prior art section of the present disclosure. Such applications are, for example:

Cosmetics, Personal Care: Such compositions and formulations include shampoos, lotions, gels, sprays, soaps, powders, lipsticks, hairsprays.

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

Lacquers, Paints and Stain Formulations: Such compositions and formulations include non-aqueous and - preferably - water-based lacquers and stains, paints, finishes.

Agricultural formulations: Such compositions and formulations include formulations and compositions containing agrochemical actives in a liquid, semisolid, mixed-liquid-solid or solid environment.

Aroma chemical formulations: Such compositions and formulations include formulations that dissolve or disperse aroma chemicals in liquid or solid compositions to uniformly disperse and/or maintain their stability so as to retain their aromatic properties over extended periods of time; compositions showing release of aroma chemicals over time, such as delayed release or sustained release formulations are also encompassed.

A further subject of the present invention is therefore the use of the graft polymers of the invention and/or obtained or obtainable by the process of the invention and/or as described in detail above in fabric care and home care products, in cosmetic and personal care formulations, as crude oil demulsifiers, in technical applications (including in pigment dispersions for inkjet inks), in formulations for electroplating, in cementitious compositions, in agrochemical formulations as, for example, dispersants, crystal growth inhibitors and/or solubilizers, in paint and colorant formulations, preferably in agrochemical compositions and cleaning compositions and in fabric and home care products, in particular in cleaning compositions for improved removal of oily and fatty stains, removal of solid soils such as clay, prevention of graying of fabric surfaces and/or antifouling agents, and in particular for inhibiting dye transfer, wherein the cleaning compositions are preferably laundry detergent formulations and/or dishwashing detergent formulations, more preferably liquid laundry detergent formulations and/or liquid hand dishwashing detergent formulations.

A further subject of the present invention is therefore also a cleaning composition, a fabric care and home care product, an industrial and institutional cleaning product, a cosmetic or personal care product, an oilfield formulation such as a crude oil demulsifier or dispersant or a gas hydrate inhibitor, a pigment dispersion for example for inkjet inks and inks containing grafted polymers, an electroplating product, an adhesive composition, a lacquer, agrochemical formulation, which preferably comprises in a laundry detergent, in a cleaning composition and/or in a fabric and home care product each at least one grafted polymer as defined above or obtained or obtainable by the process according to the invention and/or as described in detail herein.

Therefore, a preferred subject of the present invention is also the use of at least one graft polymer according to the invention and/or at least one graft polymer obtained or obtainable by the process according to the invention in fabric care and home care products, preferably in cleaning compositions and in laundry treatment, laundry care and laundry washing products, more preferably laundry detergent formulations, even more preferably liquid laundry detergent formulations. In particular, the graft polymers according to the invention are used in such compositions/products/formulations for improved dye transfer inhibition.

Such inventive use encompasses the use of grafted polymers as detailed herein and/or as obtainable or obtained from the inventive method, such grafted polymers being similar to the grafted polymers as detailed above, the polymer structures being described in all of their embodiments, variants, and preferred, more preferred, etc. embodiments, and also including the detailed embodiments as further described in "Examples 1/2/3, etc." listed at the end of the specification below.

Therefore, another subject of the present invention is 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, preferably a liquid laundry detergent formulation or a liquid laundry detergent product, which contains at least one graft polymer according to the invention and/or at least one graft polymer obtained or obtainable by the process according to the invention, such a composition or product exhibiting improved dye transfer inhibition.

Such a composition or product of the present invention encompasses at least one grafted polymer as detailed herein and/or as obtainable or obtained from the process of the present invention, such grafted polymer being similar to the grafted polymer as detailed above, with the polymer structure described in all its embodiments, variations, and preferred, more preferred, etc. embodiments, and also including the detailed embodiments as further described in "Examples 1/2/3, etc." listed at the end of the specification below.

In one embodiment, it is also preferred that 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 contains at least one graft polymer according to the present invention and/or at least one graft polymer obtained or obtainable by the process according to the present invention, such composition or product preferably exhibiting improved dye transfer inhibition properties, additionally comprises at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, xylanases, deoxyribonucleases, dispersins, pectinases, oxidoreductases, hemicellulases, phospholipases, esterases, pectinases, cutinases, lactases and peroxidases, and a combination of at least two of the aforementioned types, preferably at least one protease.

The phrase "fabric care composition" means to include compositions and formulations designed for treating fabrics. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric cleaning compositions, laundry pre-wash agents, laundry pre-treaters, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, washing additives, rinse-post fabric treatment agents, ironing aids, unit dose formulations, delayed delivery formulations, detergents on or included in porous substrates or nonwoven sheets, and other suitable forms that will be apparent to those skilled in the art and described in detail below in view of the teachings herein. Such compositions can be used as pre-wash treatment agents, post-wash treatment agents, or can be added during the rinse or wash cycle of a washing operation, and are further described below in detail when describing the uses and applications of the grafted polymers of the present invention and compositions comprising such grafted polymers.

At least one grafted polymer as described herein and/or at least one grafted polymer obtained or obtainable by the process of the invention as previously detailed is present in said compositions and products of the 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% and further more preferably from about 0.2% to about 4% and most preferably in a concentration of up to 2%, each in % by weight relative to the total weight of such composition or product, and further including all ranges resulting from the selection of any lower limit and any upper limit and all numbers between the mentioned upper and lower limits; such compositions or products may - and preferably do - further comprise from about 1% to about 70% of a surfactant system by weight of the composition or product; said compositions and products are to be used as dye transfer inhibiting agents and/or for inhibiting dye transfer.

Even more preferably, the compositions or products of the invention as detailed above, comprising at least one graft polymer of the invention as detailed before and/or at least one graft polymer obtained or obtainable by the process of the invention as detailed before, and optionally further comprising at least one surfactant or surfactant system in an amount of from about 1% to about 70% by weight of the composition or product, are those for primary cleaning (i.e. stain removal) in laundry applications, and may additionally comprise at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, xylanases, deoxyribonucleases, dispases, pectinases, oxidoreductases, hemicellulases, phospholipases, esterases, pectinases, cutinases, lactases and peroxidases, and a combination of at least two of the preceding types, preferably at least one protease.

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.

In one embodiment, the grafted polymers of the present invention can be used in a cleaning composition or product comprising a surfactant system comprising C10-C15 alkylbenzene sulfonate (LAS) as the primary surfactant and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

In a further embodiment, the graft polymers of the present invention can be used in cleaning compositions or fabric and home care products, preferably laundry cleaning compositions, laundry care products or laundry treatment products or laundry washing products, preferably liquid laundry detergent formulations or liquid laundry detergent products, comprising as the main surfactant a C8-C18 linear or branched alkyl ether sulfate having 1-5 ethoxy units and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

In a further embodiment, the graft polymers of the present invention can be used in cleaning compositions or fabric and home care products, preferably laundry cleaning compositions, laundry care products or laundry washing products, preferably liquid laundry detergent formulations or liquid laundry detergent products, comprising as the main surfactant a C12-C18 alkyl ethoxylate surfactant having 5-10 ethoxy units and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic or other nonionic surfactants, or mixtures thereof.

In one embodiment of the present invention, the grafted polymer is a component of a cleaning composition or a fabric 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, each additionally comprising at least one surfactant, preferably at least one anionic surfactant.

In a further embodiment, the present invention also encompasses a composition comprising a grafted polymer and/or a polymer backbone, each as described above, further comprising an antimicrobial agent as disclosed below (preferably selected from the group consisting of 2-phenoxyethanol), more preferably comprising an amount ranging from 2 ppm to 5% by weight of the composition of the antimicrobial agent; even more preferably comprising 0.1% to 2% phenoxyethanol.

In a further embodiment, the present invention also encompasses a method of preserving an aqueous composition to prevent microbial contamination or growth, such a composition comprising a grafted polymer and/or a polymer backbone as described above, such a composition is preferably a detergent composition, such a method comprising adding at least one antimicrobial agent selected from the disclosed antimicrobial agents as disclosed below, such an antimicrobial agent is preferably 2-phenoxyethanol.

In a further embodiment, the present invention also encompasses a composition, preferably a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dishwashing composition, even more preferably a liquid laundry detergent composition, or a liquid softener composition for use in laundry, such a composition comprising a grafted polymer and/or a polymer backbone, each as described above, such a composition further comprising 4,4'-dichloro-2-hydroxydiphenyl ether at a concentration of 0.001% to 3%, preferably 0.002% to 1%, more preferably 0.01% to 0.6%, each by weight of the composition.

In a further embodiment, the present invention also encompasses a method for washing fabrics or cleaning hard surfaces, the method comprising treating the fabrics or hard surfaces with a cleaning composition, more preferably a liquid laundry detergent composition or a liquid manual dishwashing composition, even more preferably a liquid laundry detergent composition, or a liquid softener composition for use in laundry, such a composition comprising a grafted polymer and/or a polymer backbone, each as described above, such a composition further comprising 4,4'-dichloro-2-hydroxydiphenyl ether.

The choice of additional surfactants in these embodiments may depend on the application and the desired benefit.

Description of cleaning compositions, formulations and ingredients thereof

As used herein, the phrase " cleaning composition " includes compositions and formulations designed for cleaning soiled materials. Such compositions and formulations include compositions and formulations designed for cleaning any type of soiled material or surface.

Compositions for " industrial and institutional cleaning " include cleaning compositions designed for industrial and institutional cleaning, such as those for cleaning any kind of soiled materials or surfaces, such as hard surface cleaners for any kind of surfaces including tiles, carpets, PVC-surfaces, wooden surfaces, metal surfaces, painted surfaces.

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

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

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

Non-limiting examples of "liquids"/"liquid compositions" include light-duty and heavy-duty liquid detergent compositions, fabric enhancers, detergent gels typically used for laundry, bleach and laundry additives. Liquids may contain gases, such as suspended bubbles, or solids, such as particles.

The liquid cleaning composition of the present invention preferably has a viscosity of 50 to 10000 mPa*s; at 20 1/s and 20°C, the liquid manual dishwashing cleaning composition (also referred to as liquid manual "dishwashing composition") has a viscosity of preferably 100 to 10000 mPa*s, more preferably 200 to 5000 mPa*s and most preferably 500 to 3000 mPa*s; at 20 1/s and 20°C, the liquid laundry cleaning composition has a viscosity of preferably 50 to 3000 mPa*s, more preferably 100 to 1500 mPa*s and most preferably 200 to 1000 mPa*s.

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

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

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

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

Suitable auxiliary cleaning additives include builders, co-builders, surfactant systems, fatty acids and/or salts thereof, structuring agents, thickeners and rheology modifiers, clay/soil removal/anti-redeposition agents, polymeric soil removal agents, dispersants such as polymeric dispersants, polymeric grease cleaners, solubilizers, amphiphilic copolymers (including those free of vinyl pyrrolidone), chelating agents, enzymes, enzyme stabilizing systems, encapsulated benefit agents such as encapsulated perfumes, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, catalytic materials, brighteners, malodor control agents, pigments, dyes, opacifiers, pearlescent agents, hues, dye transfer inhibitors, fabric softeners, carriers, foam boosters, foam suppressants (defoamers), color stain removers (color stain removers), and bleaching agents. speckle, silver care, anti-tarnish and/or anti-corrosion agents, alkalinity sources, pH adjusters, pH buffers, hydrotropes, detergent particles, antibacterial and antimicrobial agents, preservatives, antioxidants, softeners, carriers, fillers, solvents, processing aids, pro-perfumes, and perfumes.

Adjuvants may be present in the composition at levels suitable for the intended use of the composition. Typical usage levels range from as low as 0.001% by weight of the composition of an adjuvant such as an optical brightener to 50% by weight of the composition of a builder.

In addition to the surfactant system and the grafted polymer, the liquid cleansing composition additionally may comprise - and preferably does comprise - at least one of the following: a rheology control agent/modifier, an emollient, a humectant, a skin rejuvenating active, and a solvent.

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

Suitable examples of such cleaning adjuncts and usage levels can be found in WO 99/05242, US Pat. Nos. 5,576,282, 6,306,812 Bl and 6,326,348 Bl.

Those of ordinary skill in the art will appreciate that detersive surfactants encompass any surfactant or mixture of surfactants that provides cleaning, stain removal, or detersive benefits to soiled materials.

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

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. It will be understood by those of ordinary skill in the art that the surfactant system for detergents encompasses any surfactant or mixture of surfactants that provides cleaning, stain removal, or washing benefits to soiled materials.

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

Laundry composition

In laundry formulations, anionic surfactants usually contribute the largest share of surfactants in such formulations. Thus, preferably, the cleaning composition of the present invention for use in laundry comprises at least one anionic surfactant and optionally an additional surfactant selected from any class of surfactants described herein, preferably selected from nonionic surfactants and/or amphoteric surfactants and/or zwitterionic surfactants and/or cationic surfactants.

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

Preferred examples of suitable anionic surfactants are alkali metal and ammonium salts of _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 to 50 mol of ethylene oxide/mol), _C12 - _C18 -alkylsulfonic acids, _C12 - _C18 -sulfofatty acid alkyl esters, for example _C12 - _C18 -sulfofatty acid methyl esters, _C10 - _C18 -alkylarylsulfonic acids, preferably n- _C10 - _C18 -alkylbenzenesulfonic acids, _C10 - _C18 -alkylalkoxycarboxylates and soaps such as, for example, _C8 - _C24 -carboxylic acids. Alkali metal salts, particularly preferably sodium salts, of the aforementioned compounds are preferred.

In one embodiment of the present invention, the anionic surfactant is selected from _nC10 - _C18 -alkylbenzenesulfonic acids and alcohol polyether sulfates, which in the context of the present invention are in particular sulfuric acid half esters of ethoxylated _C12 - _C18 -alkanols, preferably _nC12 - _C18 -alkanols (ethoxylation: 1 to 50 mol of ethylene oxide/mol).

In one embodiment of the invention, it is also possible to employ alcohol polyether sulfates derived from branched (ie synthetic) C ₁₁ -C ₁₈ -alkanols (ethoxylation: 1 to 50 mol of ethylene oxide/mol).

Preferably, the alkoxylated groups of both types of alkoxylated alkyl sulfates based on _C12 - _C18 -fatty alcohols or based on branched (ie synthetic) _C11 - _C18 -alcohols are ethoxylated groups and the average degree of ethoxylation of any alkoxylated alkyl sulfate is 1 to 5, preferably 1 to 3.

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

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

Non-limiting examples of nonionic surfactants - which may also be used in combination with more than one other surfactant - include: C8-C18 alkyl ethoxylates, such as ETHOXYLATE from Shell Nonionic surfactants; as from BASF C14-C22 mid-chain branched alkyl alkoxylates, BAEx, wherein x is 1 to 30, as discussed in US 6,153,577, US 6,020,303 and US 6,093,856; alkyl polysaccharides, as discussed in US 4,565,647, issued January 26, 1986 to Llenado; specifically, alkyl polyglycosides, as discussed in US 4,483,780 and US 4,483,779; polyhydroxy fatty acid amides, as discussed in US 5,332,528; and ether-terminated poly(oxyalkylated) alcohol surfactants, as discussed in US 6,482,994 and WO 01/42408.

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

Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are compounds of the general formula (A)

The variables are defined as follows:

R1 is selected from the group consisting of linear C1-C10-alkyl, preferably ethyl and particularly preferably methyl,

R2 is selected from C8-C22-alkyl, for example n-C8H17, n-C10H21, n-C12H25, n-C14H29, n-C16H33 or n-C18H37,

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

m and n are in the range of zero to 300, wherein the sum of n and m is at least 1. Preferably, m is in the range of 1 to 100 and n is in the range of 0 to 30.

The compounds of the general formula (A) may be block copolymers or random copolymers, with block copolymers being preferred.

Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are compounds of the general formula (B)

The variables are defined as follows:

R ¹ are identical or different and are selected from linear C ₁ -C ₄ -alkyl, preferably are identical in each case and are ethyl, and particularly preferably are methyl,

R ⁴ is selected from C ₆ -C ₂₀ -alkyl, in particular nC ₈ H ₁₇ , nC ₁₀ H ₂₁ , nC ₁₂ H ₂₅ , nC ₁₄ H ₂₉ , nC ₁₆ H ₃₃ , nC ₁₈ H ₃₇ ,

a is a number in the range of zero to 6, preferably 1 to 6,

b is a number in the range of zero to 20, preferably 4 to 20,

d is a number in the range of 4 to 25.

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

The compounds of the general formula (B) can be block copolymers or random copolymers, with block copolymers being preferred.

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

Of course, mixtures of two or more different nonionic surfactants may also be present.

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

Non-limiting examples of amphoteric surfactants - which can also be used in combination with more than one other surfactant - include: water-soluble amine oxides containing an alkyl moiety of about 8 to about 18 carbon atoms and 2 parts selected from the group consisting of an alkyl moiety containing about 1 to about 3 carbon atoms and a hydroxyalkyl moiety; and water-soluble sulfoxides containing an alkyl moiety of about 10 to about 18 carbon atoms and a part selected from the group consisting of an alkyl moiety of about 1 to about 3 carbon atoms and a hydroxyalkyl moiety. See WO 01/32816, US 4,681,704 and US 4,133,779. Therefore, suitable surfactants include so-called amine oxides, such as lauryl dimethylamine oxide ("laurylamine oxide").

Preferred examples of amphoteric surfactants are amine oxides. Preferred amine oxides are alkyl dimethyl amine oxides or alkyl amidopropyl dimethyl amine oxides, more preferably alkyl dimethyl amine oxides and especially coconut oil dimethyl amine oxides. The amine oxides may have straight chain or intermediate branched alkyl moieties. 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 and C1-C3 hydroxyalkyl. Preferably, the amine oxide is characterized by the following formula

R1-N(R2)(R3)-O

Wherein R1 is C8-18 alkyl, and R2 and R3 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl and 3-hydroxypropyl. The linear amine oxide surfactant can particularly include linear C10-C18 alkyl dimethyl amine oxide and linear C8-C12 alkoxyethyl dihydroxyethyl amine oxide. Preferred amine oxides include linear C10, linear C10-C12 and linear C12-C14 alkyl dimethyl amine oxides. As used herein, "intermediate branching" means that the amine oxide has an alkyl portion with n1 carbon atoms, wherein there is an alkyl branch on the alkyl portion with n2 carbon atoms. The alkyl branch is located on the alpha carbon from the nitrogen on the alkyl portion. This type of branching of the amine oxide is also referred to as internal amine oxide in the art. The sum of n1 and n2 is 10 to 24 carbon atoms, preferably 12 to 20 and more preferably 10 to 16. The number of carbon atoms (n1) of the one alkyl portion should be approximately the same as the number of carbon atoms (n2) of the one alkyl branch, so that the one alkyl portion and the one alkyl branch are symmetrical. As used herein, "symmetrical" means that in at least 50 wt%, more preferably at least 75 wt% to 100 wt% of the intermediate branched amine oxides used herein, (n1-n2) is less than or equal to 5, preferably 4, most preferably 0 to 4 carbon atoms. The amine oxide further comprises two parts, which are independently selected from C1-C3 alkyl, C1-C3 hydroxyalkyl, or polyethylene oxide groups containing an average of about 1 to about 3 ethylene oxide groups. Preferably, the two parts are selected from C1-C3 alkyl, more preferably the two parts are both selected from C1 alkyl.

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.

The cleaning compositions may also contain zwitterionic surfactants - which may also be used in combinations of more than one other surfactant.

Suitable zwitterionic surfactants include betaines, such as alkyl betaines, alkyl amido betaines, imidazolinium betaines, sulfobetaines (INCI sulfobetaines) and betaine phosphates. Examples of suitable betaines and sulfobetaines are as follows (according to INCI nomenclature): Almond amidopropyl of betaine, Apricotamidopropyl betaine, Avocado oleamidopropyl betaine, Babassu oleamidopropyl betaine, Behenamidopropyl betaine, Behenyl betaine, Low erucic acid amidopropyl betaine, Capryloyl / Capryloyl propyl betaine, Carnitine, Cetyl betaine, Cocamide ethyl betaine, Cocamide propyl betaine, Cocoyl Aminopropyl Hydroxysultaine, Coco Betaine, Coco Hydroxysultaine, Coco/Oleamidopropyl Betaine, Coco Sultaine, Decyl Betaine, Dihydroxyethyl Oleyl Glycine, Dihydroxyethyl Soy Glycine, Dihydroxyethyl Stearyl Glycine, Dihydroxyethyl Tallow Glycine, Propyl PG-Betaine, Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow Betaine, Isostearamidopropyl Betaine, Lauramidopropyl betaine, lauryl betaine, lauryl hydroxysultaine, lauryl sultaine, milkamidopropyl betaine, mink oleamidopropyl betaine, myristamidopropyl betaine, myristyl betaine, oleamidopropyl betaine, oleamidopropyl hydroxysultaine, oleyl betaine, oliveamidopropyl betaine, palmitoleamidopropyl betaine, palmitamidopropyl betaine, palmitoyl carnitine, Palm kernel oleamidopropyl betaine, PTFE acetoxypropyl betaine, ricinoleamidopropyl betaine, sesame oleamidopropyl betaine, soy oleamidopropyl betaine, stearamidopropyl betaine, stearyl betaine, tallowamidopropyl betaine, tallowamidopropyl hydroxysultaine, tallow betaine, tallow dihydroxyethyl betaine, undecylenamidopropyl betaine and wheat germ oleamidopropyl betaine.

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

Non-limiting examples of cationic surfactants - which may also be used in combination with more than one other surfactant - include: quaternary ammonium surfactants, which may have up to 26 carbon atoms, including: alkoxylated quaternary ammonium (AQA) surfactants as discussed in US 6,136,769; dimethyl hydroxyethyl quaternary ammonium as discussed in US 6,004,922; dimethyl hydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants as discussed in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005 and WO 98/35006; cationic ester surfactants as discussed in US Pat. Nos. 4,228,042, 4,239,660, 4,260,529 and US 6,022,844; and Amino surfactants, specifically amidopropyldimethylamine (APA), are discussed in WO 6,221,825 and WO 00/47708.

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

In the context of the present invention, the term citrate includes mono- and di-alkali metal citrates, and in particular the monosodium and preferably the trisodium salt of citric acid, the ammonium or substituted ammonium salts of citric acid, and citric acid. Citrate can be used as an anhydrous compound or as a hydrate, for example as sodium citrate dihydrate. The amount of citrate is calculated with reference to anhydrous trisodium citrate.

The term phosphate includes sodium metaphosphate, sodium orthophosphate, sodium hydrogenphosphate, sodium pyrophosphate and polyphosphates such as sodium tripolyphosphate. Preferably, however, the composition according to the invention is free of phosphates and polyphosphates, wherein hydrogenphosphate is comprised, for example free of trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate ("phosphate-free"). With regard to phosphates and polyphosphates, "free" in the context of the present invention is understood to mean that the content of phosphates and polyphosphates is in total in the range of 10 ppm to 0.2% by weight of the respective composition, determined gravimetrically.

The term carbonate includes alkali metal carbonates and alkali metal hydrogen carbonates, preferably the sodium _salt . Particularly preferred is _Na2CO3 .

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

Examples of aminocarboxylates and polycarboxylates are nitrilotriacetate, ethylenediaminetetraacetate, diethylenetriaminepentaacetate, triethylenetetraaminehexaacetate, propylenediaminetetraacetate, ethanol-diglycinate, methylglycine diacetate and glutamine diacetate. The terms aminocarboxylates and polycarboxylates also include their respective unsubstituted or substituted ammonium and alkali metal salts, such as sodium salts, in particular the sodium salts of the respective fully neutralized compounds.

In the context of the present invention, silicates include in particular sodium disilicate and metasilicate, aluminosilicates such as, for example, zeolites and layered silicates, in particular those of the formula α-Na ₂ Si ₂ O ₅ , β-Na ₂ Si ₂ O ₅ and δ-Na ₂ Si ₂ O ₅ .

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

In one embodiment of the present invention, the builder is selected from polycarboxylates. The term "polycarboxylates" includes non-polymeric polycarboxylates such as succinic acid, _C2 - _C16 -alkyl disuccinates, _C2 - _C16 -alkenyl disuccinates, ethylenediamine N,N'-disuccinic acid, tartrate diacetate, alkali metal malonates, tartrate monoacetate, propanetricarboxylic acid, butanetetracarboxylic acid and cyclopentanetetracarboxylic acid.

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

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

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

It is also possible to use copolymers of at least one monomer 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 hydrophilically or hydrophobically modified comonomer as listed below.

Suitable hydrophobic comonomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins having ten or more carbon atoms or mixtures thereof, such as, for example, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene and 1-hexacosene, _C22 -α-olefins, _C20 - _C24 -α-olefins and mixtures of polyisobutenes having an average of 12 to 100 carbon atoms per molecule.

Suitable hydrophilic comonomers are monomers with sulfonate or phosphonate groups, and also nonionic monomers with hydroxyl functions or alkylene oxide groups. By way of example, mention may be made of: allyl alcohol, prenyl alcohol, 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. The polyalkylene glycols may contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.

Particularly preferred monomers containing sulfonic acid groups 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, sulfomethylmethacrylamide and the salts of the acids, such as the sodium, potassium or ammonium salts thereof.

Particularly preferred monomers containing phosphonate groups are vinylphosphonic acid and its salts.

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

Furthermore, amphoteric polymers can also be used as builders.

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

The formulation according to the invention may contain one or more alkaline carriers. For example, if an alkaline pH is desired, the alkaline carrier ensures a pH of at least 9. Suitable are, for example, the alkali metal carbonates, alkali metal hydrogen carbonates and alkali metal metasilicates mentioned above, and, additionally, alkali metal hydroxides. In each case, the preferred alkali metal is potassium, sodium being particularly preferred. In one embodiment of the invention, pH>7 is adjusted by using an amine, preferably an alkanolamine, more preferably triethanolamine.

In one embodiment of the present invention, the laundry formulation or composition according to the invention additionally comprises at least one enzyme.

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

In one embodiment, the composition according to the invention additionally comprises at least one enzyme.

Preferably, the at least one enzyme is a detergent enzyme.

In one embodiment, the enzyme is classified as an oxidoreductase (EC 1), a transferase (EC 2), a hydrolase (EC 3), a lyase (EC 4), an isomerase (EC 5), or a ligase (EC 6). EC numbering is according to the Enzyme Nomenclature Recommendations of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology (1992), including its supplements published from 1993 to 1999. Preferably, the enzyme is a hydrolase (EC 3).

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, phenoloxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, nuclease, deoxyribonuclease, diphosphodiesterase Preferably, the enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, mannanases, xylanases, deoxyribonucleases, dispersases, pectinases, oxidoreductases, perhydrolases, aminopeptidases, asparaginases, carbohydrases, carboxypeptidases, catalases, chitinases, cyclodextrin glycosyltransferases, α-galactosidases, β-galactosidases, glucoamylases, α-glucosidases, β-glucosidases, invertases, ribonucleases, transglutaminases and dispersins, and combinations of at least two of the foregoing types. More preferably, the enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, mannanases, xylanases, deoxyribonucleases, dispersases, pectinases, oxidoreductases and cutinases, and combinations of at least two of the foregoing types. Most preferably, the enzyme is a protease, preferably a serine protease, more preferably a subtilisin.

Preferably, the protease is a protease having at least 90% sequence identity with SEQ ID NO: 22 of EP 1921147B1 and having the amino acid substitution R101E (according to the numbering of BPN). Preferably, the amylase is an amylase having at least 90% sequence identity with SEQ ID NO: 54 of WO 2021032881A1.

The composition of the invention may comprise one type of enzyme or more than one enzyme of different types, e.g. an amylase and a protease, or more than one enzyme of the same type, e.g. two or more different proteases, or a mixture thereof, e.g. an amylase and two different proteases.

The enzymes may be incorporated into the composition at levels sufficient to provide an effective amount for achieving a beneficial effect, preferably for a primary cleaning effect and/or a secondary cleaning effect, such as an anti-ashing or anti-linting effect (e.g., in the case of cellulases). Preferably, the enzymes are present in the composition at a level of from about 0.00001% to about 5%, preferably from about 0.00001% to about 2%, more preferably from about 0.0001% to about 1%, or even more preferably from about 0.001% to about 0.5% enzyme protein by weight of the composition.

Preferably, the enzyme-containing composition further comprises an enzyme stabilizing system.

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

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

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

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

The formulations according to the invention may contain one or more corrosion inhibitors. In the present case, this is to be understood as including those compounds which inhibit the corrosion of metals. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, and phenol derivatives, such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.

In one embodiment of the present invention, the formulation according to the present invention comprises a total of 0.1 to 1.5% by weight of corrosion inhibitors.

The formulations according to the invention may also further comprise cleaning polymers and/or soil release polymers and/or antigreying polymers.

Additional cleaning polymers may include, but are not limited to, "polyfunctional polyethyleneimines" (e.g., HP20) and/or "polyfunctional diamines" (e.g. HP96). Such multifunctional polyethyleneimines are typically ethoxylated polyethyleneimines with a weight average molecular weight M in the range of 3000 to 250000, preferably 5000 to 200000, more preferably 8000 to 100000, more preferably 8000 to 50000, more preferably 10000 to 30000 and most preferably 10000 to 20000 g/mol. Based on the gross weight of the material, suitable multifunctional polyethyleneimines have _80wt % to 99wt%, preferably 85wt% to 99wt%, more preferably 90wt% to 98wt%, most preferably 93wt% to 97wt% or 94wt% to 96wt% of ethylene oxide side chains. Ethoxylated polyethyleneimines are typically based on polyethyleneimine core and polyethylene oxide shell. Suitable polyethyleneimine core molecules are polyethyleneimines with a weight average molecular weight _M in the range of 500 to 5000 g/mol. Preferably employed are molecular weights of 500 to 1000 g/mol, even more preferably M _w of 600 to 800 g/mol. The ethoxylated polymers then have on average 5 to 50, preferably 10 to 35 and even more preferably 20 to 35 ethylene oxide (EO) units per NH-functional group.

Suitable polyfunctional diamines are typically ethoxylated C2 to C12 alkylenediamines, preferably hexamethylenediamine, which are further quaternized and optionally sulfated. Typical polyfunctional diamines have a weight average molecular weight _Mw in the range of 2000 to 10000, more preferably 3000 to 8000 and most preferably 4000 to 6000 g/mol. In a preferred embodiment of the present invention, further quaternized and sulfated ethoxylated hexamethylenediamines can be used, which contain on average 10 to 50, preferably 15 to 40 and even more preferably 20 to 30 ethylene oxide (EO) groups/NH-functional groups, and which preferably carry two cationic ammonium groups and two anionic sulfate groups.

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

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

Therefore, one aspect of the present invention is a laundry detergent composition, in particular a liquid laundry detergent, comprising (i) at least one polymer of the present invention and (ii) at least one compound selected from any of polyfunctional polyethyleneimines, polyfunctional diamines and/or oligoamines and mixtures thereof, and in particular those claimed in WO 2022/136408A1, WO 2022/136409A1 and WO 2021/165468.

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

Suitable antigreying polymers include copolymers of acrylic acid or maleic acid and styrene, graft polymers of acrylic acid on maltodextrin or carboxymethylated cellulose and alkali metal salts thereof, especially sodium salts thereof.

Laundry formulations comprising the polymers of the present invention may also comprise at least one complexing agent.

Preferred complexing agents are methylglycine diacetic acid (MGDA) and glutamic acid diacetic acid (GLDA) and their salts. Particularly preferred complexing agents are methylglycine diacetic acid and its salts. According to the invention, 1 to 50%, preferably 1 to 20%, by weight of complexing agent is preferred.

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

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

MGDA or GLDA is preferably used as salt. Preferred salts are ammonium salts and alkali metal salts, particularly preferably potassium salts and in particular sodium salts. These may, for example, have the following general formula (CA I) or (CA II):

[CH ₃ -CH(COO)-N(CH ₂ -COO) ₂ ]Na _3-xy K _x H _y (CA I)

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

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

[OOC-(CH ₂ ) ₂ -CH(COO)-N(CH ₂ -COO) ₂ ]Na _4-xy K _x H _y (CA II)

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

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

Very particular preference is given to the trisodium salt of MGDA and the tetrasodium salt of GLDA.

Laundry formulations comprising the polymers of the present invention may also comprise at least one antimicrobial agent (also called "preservative").

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

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

Of particular interest for cleaning compositions as well as fabric and home care products and in particular in laundry formulations are any of the following antimicrobial agents and/or preservatives:

4,4'-Dichloro-2-hydroxydiphenyl ether (other names: 5-chloro-2-(4-chlorophenoxy)phenol, hydroxydichlorodiphenyl ether (Diclosan), DCPP), HP 100 (30 wt% DCPP in 1,2-propylene glycol); 2-phenoxyethanol (other names: phenoxyethanol, methylphenyl glycol, phenoxyethanol, ethylene glycol phenyl ether, ethylene glycol monophenyl ether, 2-(phenoxy)ethanol, 2-phenoxy-1-ethanol); 2-bromo-2-nitropropane-1,3-diol (other names: 2-bromo-2-nitro-1,3-propanediol, bronopol); Glutaraldehyde (other names: 1-5-glutaraldehyde, pentane-1,5-dialdehyde, glutaral, glutardialdehyde); Glyoxal (other names: ethandial, oxylaldehyde, 1,2-ethandial); 5-bromo-5-nitro-1,3-dioxane (other names: 5-bromo-5-nitro-m-dioxane, ); phenoxypropanol (other names: propylene glycol phenyl ether, phenoxyisopropanol, 1-phenoxy-2-propanol, 2-phenoxy-1-propanol); glucoprotamine (chemical description: reaction product of glutamic acid and alkylpropylenediamine, other name: glucoprotamine 50); cyclohexylhydroxydiazenium-1-oxide, potassium salt (other names: N-cyclohexyl-diazenium dioxide, potassium HDO, Xyligene); formic acid (other names: methanoic acid, FM, FM 75, FM 85, FM 99, FM) and its salts, such as sodium formate); tetrahydro-3,5-dimethyl-1,3,5-thiadiazine-2-thione (other names: 3,5-dimethyl-1,3-5-thiadiazine-2-thione, dazomet; 2,4-dichlorobenzyl alcohol (other names: dichlorobenzyl alcohol, 2,4-dichloro-benzyl alcohol, (2,4-dichloro-phenyl)-methanol, DCBA); 1-propanol (other names: n-propanol, propan-1-ol, n-propyl alcohol; 1,3,5-tris-(2-hydroxyethyl)-hexahydro- -1,3,5-triazine (other names: hexahydrotriazine, tris(hydroxyethyl)-hexahydrotriazine, hexahydro-1,3-5-tris(2-hydroxyethyl)-s-triazine, 2,2′,2″-(hexahydro-1,3,5-triazine-1,3,5-triyl)triethanol); 2-butyl-benzo[d]isothiazol-3-one (“BBIT”); 2-methyl-2H-isothiazol-3-one (“MIT”); 2-octyl-2H-isothiazol-3-one (“OIT”); 5-chloro-2-methyl-2H-isothiazol-3-one -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") (a mixture of CMIT/MIT); 1,2-benzisothiazol-3(2H)-one ("BIT"); hexa-2,4-dienoic acid (commonly known as "sorbic acid") and its salts, such as calcium sorbate, sodium sorbate; (E,E)-hexa-2,4-dienoic acid potassium (potassium sorbate); lactic acid and its salts; L-( +)-lactic acid; in particular sodium lactate; benzoic acid and salts of benzoic acid, for example sodium benzoate, ammonium benzoate, calcium benzoate, magnesium benzoate, MEA benzoate, potassium benzoate; salicylic acid and salts thereof, for example 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.

At least one antimicrobial agent or preservative may be added to the composition of the invention in a concentration ranging from 0.001% to 10% relative to the total weight of the composition.

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

The formulations, compositions and products according to the invention, and in particular cleaning compositions and fabric and home care products, may also comprise water and/or additional organic solvents, such as ethanol or propylene glycol, and/or fillers such as sodium sulfate.

Additional optional ingredients may be, but are not limited to, viscosity modifiers, cationic surfactants, foam boosters or depressants, perfumes, dyes, optical brighteners and dye transfer inhibitors.

Universal cleaning compositions and formulations

Since the polymers of the invention are biodegradable, and in particular cleaning formulations typically have a pH of about 7 or higher, and additionally often also contain enzymes - which are included in such cleaning formulations to degrade biodegradable substances such as grease, proteins, polysaccharides, etc., present in stains and dirt that should be removed by the cleaning composition - some factors need to be considered to formulate those biodegradable polymers of the invention. Such suitable formulations are known in principle, and include formulations that are solid - in which the enzyme and polymer can be separated by a coating or added to separate particles that are mixed - and formulations that are liquid and semi-liquid, in which the polymer and enzyme can be separated by formulating them in different compartments (such as different compartments of a multi-chamber pouch or bottle with different chambers), wherein the liquid is poured out of the compartments simultaneously in predetermined amounts to ensure that each component in each chamber is applied in an appropriate amount at each individual point of use. Such multi-compartment pouches and bottles, etc. are also known to the skilled person.

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

The liquid formulations disclosed above and below may contain 0-0.2%, preferably about 0.15%, of 4,4'-dichloro-2-hydroxydiphenyl ether, as well as all the other mentioned ingredients. The bleach-free solid laundry compositions may contain 0-0.2%, preferably about 0.15%, of 4,4'-dichloro-2-hydroxydiphenyl ether, as well as all the other mentioned ingredients.

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

The following compositions shown below (including those in the table) disclose certain types of general cleaning compositions that correspond to typical compositions associated with typical washing conditions as typically used in regions and countries around the world. The at least one polymer of the present invention may be added to this one or more formulations in an appropriate amount as outlined herein.

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

In a preferred embodiment, the graft polymers according to the invention are used in laundry detergents.

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

0.05-10% of at least one polymer of the present invention

1-50% surfactant

0.1-40% of builders, co-builders and/or chelating agents

0.1-50% other auxiliary agents

Water, totaling 100%.

Preferred liquid laundry detergents according to the present invention consist of:

0.2-4% of at least one polymer of the invention

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

1.5-10% of nonionic surfactants selected from C10-C18-alkyl ethoxylates containing 3-10 ethoxy units

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

0.05-5% of an enzyme system comprising at least one enzyme suitable for detergent use and preferably also an enzyme stabilizing system

0.5-20% of a mono- or di-ol selected from ethanol, isopropanol, ethylene glycol, or propylene glycol

0.1-20% other auxiliary agents

Water, totaling 100%.

A solid laundry detergent according to the invention (such as, for example, a powder, granules or tablets) consists of:

0.05-10% of at least one polymer of the present invention

1-50% surfactant

0.1-90% of builder, co-builder and/or chelating agent

0-50% filler

0-40% bleach actives

0.1-30% other adjuvants and/or water

The sum of these components adds up to 100%.

Preferred solid laundry detergents according to the present invention consist of:

0.2-2% of at least one polymer of the invention

5-30% anionic surfactant selected from C10-C15-LAS, C10-C18 alkyl sulfates and C10-C18 alkyl ether sulfates containing 1-5 ethoxy units

1.5-7.5% of nonionic surfactants selected from C10-C18-alkyl ethoxylates containing 3-10 ethoxy units

20-80% of inorganic builders and fillers selected from sodium carbonate, sodium bicarbonate, zeolite, soluble silicates, sodium sulfate

0.5-15% of a co-builder selected from C10-C18 fatty acids, di- and tricarboxylic acids, hydroxydi- and tricarboxylic acids, aminopolycarboxylates and polycarboxylic acids

0.1-5% of an enzyme system comprising at least one enzyme suitable for detergent use and preferably also an enzyme stabilizing system

0.5-30% bleach active

0.1-20% other auxiliary agents

Water, totaling 100%

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

Liquid laundry frame preparation according to the invention:

Liquid Garment Frame Preparation According to the Invention - Continued:

The clothing powder frame formulation according to the present invention:

Clothing powder frame formulation according to the present invention - continued:

The following three tables show further typical liquid detergent formulations LD1, LD2 and LD3:

Liquid Detergent 1-LD1

Liquid detergent formulations Sodium Alkylbenzene Sulfonate (C ₁₀ -C ₁₃ ) LAS 9.5% Reaction of C ₁₃ /C ₁₅ -oxoalkanol with 7 mol of EO 4.5% 1,2-Propanediol 6% Ethanol 2% Potassium Coconut Soap 2.4% NaOH 2.2% Lauryl Ether Sulfate (Texapon) 5.0% Sodium Citrate 3% Sokalan HP 20 2% The polymer of the present invention or the comparative 0.2-2% Grafted polymer* 2% water to 100%

Liquid detergent 2-LD2

Liquid detergent 3-LD3

Liquid detergent formulations MGDA 5.5% APG, branched C13 glucoside 3.5% 1,2-Propanediol 6% Ethanol 2% Potassium Coconut Soap 4.4% NaOH 2.2% Lauryl Ether Sulfate 9.5% Sodium Citrate 3% The polymer of the present invention or the comparative 0.1-1.2% Grafted polymer* 2% water to 100%

All three previous tables: * Polyethylene glycol with Mn 6000 g/mol as graft base, grafted with 60 wt. % vinyl acetate (based on the total polymer weight; produced according to the general disclosure of WO 2007138054A1)

Preferably, in the corresponding laundry detergents, cleaning compositions and/or fabric and home care products, at least one grafted polymer is present in an amount of about 0.05% to about 10%, preferably about 0.1% to 8%, more preferably about 0.2% to about 6%, and even more preferably about 0.2% to about 4%, each in weight %, relative to the total weight of such compositions or products, and most preferably up to 2%, between and including all values of all ranges obtained by selecting any lower limit and combining with any upper limit.

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

Chapter on Most Preferred Embodiments

The following specific most preferred embodiments also form part of the invention, wherein all combinations are defined in the individual embodiments and wherein all combinations therein explicitly form part of the invention:

In a first most preferred embodiment, the grafted polymer of the present invention comprises:

(A) a polymer backbone as a grafting matrix,

wherein the polymer backbone (A) is obtainable by polymerization of at least one monomer selected from the group of C2- to C10-alkylene oxides, preferably C2- to C5-alkylene oxides, such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide, preferably at least one monomer is ethylene oxide, and more preferably the polymer backbone is obtained only from ethylene oxide,

wherein in the case of containing more than one alkylene oxide monomer, the structure of the polymer backbone is a random polymer, a block polymer or a polymer comprising a mixed structure of block units (wherein each block is a homoblock or a random block itself) and a statistical/random part composed of two or more alkylene oxides,

as well as

(B) a polymer side chain grafted onto the polymer backbone (A), wherein the polymer side chain (B) is obtainable by copolymerization of at least one monomer (B1) and at least one monomer (B2)

These monomers

(B1) is at least one vinyl ester monomer,

which is preferably selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably selected from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester may be any other known vinyl ester, wherein preferably at least 80 weight percent, even more preferably at least 90 weight percent, and most preferably substantially only (i.e. about 100 wt % or even 100 wt %) vinyl acetate is used as vinyl ester based on the total weight of monomer B1,

as well as

(B2) Yes

(B2a) at least one ethylenically unsaturated amine-containing monomer, which is preferably 1-vinylimidazole or a derivative thereof such as an alkyl-substituted derivative of 1-vinylimidazole such as 2-methyl-1-vinylimidazole, more preferably 1-vinylimidazole,

as well as

(B2b) optionally at least one additional nitrogen-containing monomer, which is preferably a vinyllactam monomer, preferably selected from N-vinyllactams such as N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, more preferably N-vinylpyrrolidone, N-vinylcaprolactam, and most preferably N-vinylpyrrolidone.

In a further most preferred embodiment, the graft polymer of the previous most preferred embodiments in this section comprises a polymer backbone (A) having a molecular weight as Mn in g/mol within the range of 500 to 12000, preferably not more than 9000, more preferably not more than 6000, even more preferably not more than 3500, further even more preferably not more than 3000, even further even more preferably not more than 2750 and at least 600, more preferably at least 1000, even more preferably at least 1500, and wherein all ranges are constituted by combining any number previously specified for the lower boundary with any number previously specified as the upper boundary, specifically as a more preferred range, the Mn is 600 to 3000, even more preferably 1000 to 2750, and most preferably 1500 to 2750, wherein the polymer backbone (A) has a molecular weight as Mn in the range of 500 to 12000, preferably not more than 9000, more preferably not more than 6000, even more preferably not more than 3000, even further even more preferably not more than 2750 and at least 600, more preferably at least 1000, even more preferably at least 1500 The polymer backbone (A) is preferably obtainable by polymerization of ethylene oxide and i) at least one monomer selected from 1,2-propylene oxide and 1,2-butylene oxide, preferably only 1,2-propylene oxide, and/or ii) the relative amount of EO in the polymer backbone A is within 10-90 weight percent (relative to the total molar amount of alkylene oxide in the polymer backbone (A)), or iii) the polymer backbone does not contain other monomers; and the amount of the polymer backbone (A) in weight percent is 30 to less than 89, preferably 40 to 80, more preferably 45 to 75, even more preferably 50 to 70, and most preferably 50 to 65, based on the total weight of the grafted polymer; and the amount of the polymer side chains (B) in weight percent is greater than 11 to 70, preferably 20 to 60, more preferably 25 to and the amount by weight percentage, based on the total weight of the grafted polymer, of (B1) is 1 to 30, preferably 3 to 25, more preferably 5 to 20, most preferably 10 to 20; and the amount by weight percentage, based on the total weight of the grafted polymer, of (B2) is greater than 10 to 60, preferably 20 to 60, more preferably 20 to 50, even more preferably 20 to 40, most preferably 25 to 35; and the amount by weight percentage, based on the total weight of the monomers (B2), of (B2a) is 10 to 100, preferably greater than 10 to 100, more preferably greater than 15 to 90, more preferably 20 to 90, more preferably at least 15, even more preferably at least 20, even more preferably at least 25, even more preferably at least 30 and even more preferably at least 35, and most preferably at least 35 Preferably at least 40 and as an upper limit up to 85, even more preferably up to 80, even more preferably up to 75, and most preferably up to 70, such as greater than 10 and up to 90, more preferably 20 to 85, even more preferably 25 to 80, even more preferably 30 to 80, even more preferably 35 to 75, and most preferably 40 to 70, with the proviso that the amount of (B2a) as a percentage by weight is always at least greater than 10, preferably at least 15, more preferably at least 17, even more preferably at least 20, and most preferably at least 25 and at most 60, more preferably at most 50, even more preferably at most 45, even more preferably at most 40, and most preferably at most 35, based on the total weight of the grafted polymer; and the amount of (B2b) as a percentage by weight is equal to [100% of the amount of (B2)] minus [the amount of (B2a)].

In a further most preferred embodiment, the graft polymer of any of the previous most preferred embodiments and specifically any of the previous most preferred embodiments in this section has a polydispersity Mw/Mn (wherein Mw = weight average molecular weight and Mn = number average molecular weight [g/mol/g/mol]) of <7, preferably <5, more preferably <4, and most preferably in the range of 1 to 3, and is based on a polymer backbone (A), which i) is optionally terminated at one or both end groups, preferably the polymer backbone (A) is not terminated at both end groups, Alternatively, if the polymer backbone (A) is end-capped, the end-capping is accomplished by C1-C25-alkyl, preferably C1 to C4-groups, ii) is a polymer comprising only EO and optionally PO, more preferably only ethylene oxide, and/or iii) has a biodegradability within 28 days of at least 30%, preferably at least 35%, even more preferably at least 40%, such as 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or even at least 90% when tested according to OECD 301F.

In a further most preferred embodiment, the graft polymer of any of the previous most preferred embodiments and specifically any of the previous most preferred embodiments in this section comprises a polymer backbone (A) having a molecular weight as Mn in g/mol within the range of 500 to 12000, preferably not more than 9000, more preferably not more than 6000, even more preferably not more than 3500, further even more preferably not more than 3000, even further even more preferably not more than 2750 and at least 600, more preferably at least 1000, even more preferably at least 1500, and wherein all ranges are obtained by converting the previous descriptions for Any number detailed as a lower boundary is combined with any number previously detailed as an upper boundary, specifically as a more preferred range, the Mn is 600 to 3000, even more preferably 1000 to 2750, and most preferably 1500 to 2750, wherein the polymer backbone (A) is preferably obtainable by polymerization of ethylene oxide and i) at least one monomer selected from 1,2-propylene oxide and 1,2-butylene oxide, preferably only 1,2-propylene oxide, and/or ii) the relative amount of EO in the polymer backbone A is within 10-90 weight percent (relative to the total amount of alkylene oxide in the polymer backbone (A) molar amount), or iii) the polymer backbone does not contain other monomers, preferably the polymer backbone (A) consists only of ethylene oxide as a monomer; and the amount of the polymer backbone (A) by weight percentage is 40 to 70 based on the total weight of the grafted polymer; and the amount of the polymer side chain (B) by weight percentage is 30 to 60 based on the total weight of the grafted polymer; and the amount of (B1) by weight percentage is 5 to 15 based on the total weight of the grafted polymer; the amount of (B2) by weight percentage is 15 to 55 based on the total weight of the grafted polymer; and the amount of (B1) by weight percentage is 5 to 15 based on the total weight of the grafted polymer; and the amount of (B2) by weight percentage is 15 to 55 based on the total weight of the grafted polymer. The amount of (B2a) in terms of weight percentage is 15 to 35 based on the total weight of the grafted polymer; and the amount of (B2b) in terms of weight percentage is equal to [100% of the amount of (B2)] minus [the amount of (B2a)] based on the total weight of the grafted polymer, wherein preferably the polymer backbone (A) is a polyalkylene oxide containing more than 70, preferably more than 80, even more preferably more than 90 weight percent of ethylene oxide based on the total alkylene oxide, and most preferably only containing ethylene oxide, and (B1) is vinyl acetate, (B2a) is vinylimidazole, and (B2b) is a vinyllactam, preferably vinylpyrrolidone.

In another most preferred embodiment, the graft polymer comprises i) a polymer backbone (A) which is a polyalkylene oxide comprising more than 70, preferably more than 80, even more preferably more than 90 weight percent ethylene oxide based on the total alkylene oxide, and most preferably only ethylene oxide, and having a molecular weight within the range of 500 to 12000, preferably not more than 9000, more preferably not more than 6000, even more preferably not more than 3500, further even more preferably not more than 3000, even further even more preferably not more than 2750 and at least 600, more preferably at least 1000, even more preferably at least 1500 ii) 40 to 55 weight percent of polymer side chains (B) based on the total weight of the graft polymer; wherein (B) comprises (B1) and (B2a) and optionally (B2b), wherein the amount of (B1) is 5 to 15 weight percent based on the total weight of the grafted polymer; and the amount of (B2) is 25 to 50 weight percent based on the total weight of the grafted polymer; and the amount of (B2a) is 15 to 30, preferably 20 to 30, based on the total weight of the grafted polymer; and the amount of (B2b) is equal to [100% of the amount of (B2)] minus [the amount of (B2a)], wherein (B1) is vinyl acetate, (B2a) is vinyl imidazole, and (B2b) is vinyl lactam, preferably vinyl lactam and the grafted polymer preferably has a polydispersity Mw/Mn (wherein Mw=weight average molecular weight and Mn=number average molecular weight [g/mol/g/mol]) of <7, preferably <5, more preferably <4, and most preferably in the range of 1 to 3; and more preferably, in addition to all the above characteristics, has a biodegradability of at least 25%, preferably at least 30%, even more preferably at least 35%, and most preferably at least 40%, such as 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90% within 28 days when tested according to OECD 301F.

In another most preferred embodiment, a method for obtaining a grafted polymer as detailed in any embodiment of the present disclosure, and specifically any previous most preferred embodiment of this section, is contemplated, the method comprising polymerizing at least one monomer B1, at least one monomer B2a, optionally at least one monomer B2b in the presence of at least one polymer backbone (A), wherein the polymer side chains (B) are obtained by grafting polymerization of monomers B1, B2a and optionally B2b onto the polymer backbone (A), using a free radical forming compound to initiate the free radical polymerization.

In an even more preferred embodiment of the process as detailed herein (including the even more preferred embodiments of the preceding paragraphs in this section), the process comprises polymerizing at least one monomer (B1), at least one monomer (B2a), optionally at least one monomer (B2b) in the presence of at least one polymer backbone (A), a free radical forming initiator (C) and optionally but preferably up to 50% by weight, based on the sum of components (A), (B1), (B2a), optionally (B2b) and (C), of at least one organic solvent (D) at an average polymerization temperature at which the initiator (C) has a decomposition half-life of 40 to 500 min in such a way that the fraction of unconverted grafting monomers (B1 and B2) and initiator (C) in the reaction mixture is continuously kept in a quantitative deficiency relative to the polymer backbone (A), preferably to A graft polymer is obtained comprising i) a polymer backbone (A) which is a polyalkylene oxide comprising more than 70, preferably more than 80, even more preferably more than 90 weight percent of ethylene oxide, and most preferably only ethylene oxide, based on the total alkylene oxide, and having a molecular weight as Mn in g/mol within the range of 500 to 12000, preferably not more than 9000, more preferably not more than 6000, even more preferably not more than 3500, further even more preferably not more than 3000, even further even more preferably not more than 2750 and at least 600, more preferably at least 1000, even more preferably at least 1500, and wherein all ranges are constituted by combining any number previously specified for the lower boundary with any number previously specified as the upper boundary, specifically as a more preferred range, the Mn is 600 to 3 000, even more preferably 1000 to 2750, and most preferably 1500 to 2750, and the polymer backbone (A) is present in the graft polymer in an amount of 45 to 65 weight percent based on the total weight of the graft polymer; and ii) 40 to 55 weight percent of polymer side chains (B) based on the total weight of the graft polymer; wherein (B) comprises (B1) and (B2a) and optionally (B2b), wherein the amount of (B1) is 5 to 15 weight percent based on the total weight of the graft polymer; and the amount of (B2) by weight percent is 25 to 50 based on the total weight of the graft polymer; and the amount of (B2a) by weight percent is 15 to 30, preferably 20 to 30, based on the total weight of the graft polymer; and the amount of (B2b) by weight percent is equal to [100% of [the amount of (B2)] minus [the amount of (B2a)], wherein (B1) is preferably vinyl acetate, (B2a) is preferably vinylimidazole, and (B2b) is vinyllactam, preferably vinylpyrrolidone; and the grafted polymer preferably has a polydispersity Mw/Mn (wherein Mw = weight average molecular weight and Mn = number average molecular weight [g/mol/g/mol]) of <7, preferably <5, more preferably <4, and most preferably in the range of 1 to 3; and more preferably, in addition to all the above characteristics, has a biodegradability of at least 25%, preferably at least 30%, even more preferably at least 35%, and most preferably at least 40%, such as 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90% within 28 days when tested according to OECD 301F.

In a further most preferred embodiment of the method as described above and in particular in any of the previous most preferred embodiments concerning such a method, the method comprises at least one further method step selected from:

i) a post-polymerization process step, which is carried out after the main polymerization, wherein a further amount of initiator (optionally dissolved in the solvent) is added, preferably within a time period of 0.5 hours and up to 3 hours, preferably about 1 to 2 hours, more preferably about 1 hour, wherein the free radical initiator and the solvent for the initiator are typically - and preferably - the same as those used for the main polymerization; and wherein after the polymerization and before the post-polymerization, preferably a period of waiting is observed, while the main polymerization is allowed to proceed, before the post-polymerization is started by starting to add the further free radical initiator, such period of time being preferably 10 minutes and up to 4 hours, preferably up to 2 hours, even more preferably up to 1 hour, and most preferably up to 30 minutes; and wherein the temperature of the post-polymerization process step is - preferably - the same as in the main polymerization, or increased, such increase being preferably about 5°C to 40°C, preferably 10°C to 20°C higher than the temperature of the main polymerization;

ii) subjecting the graft polymer as obtained from the main polymerization or - if carried out - a post-polymerization process - to a step of concentration and/or drying means in order to remove a part or substantially all of the remaining solvents (as long as they are removable due to their boiling point) and/or volatiles such as residual monomers, wherein

a. the concentration is carried out by removing a portion of the solvent and optionally also volatiles to increase the solid polymer concentration by preferably applying a distillation process such as thermal distillation or vacuum distillation, preferably vacuum distillation, the distillation process is carried out until the desired solid content is obtained, preferably the distillation process is carried out until the desired part or all of the volatile components such as volatile solvents and/or unreacted volatile monomers are removed;

b. The drying is carried out by subjecting the grafted polymer, which contains at least residual amounts of volatiles such as remaining solvents and/or unreacted monomers, etc., to means for removing the volatiles, such as drying using rollers, a spray dryer, vacuum drying or freeze drying, preferably - primarily for cost reasons - spray drying; and optionally combining such a drying method step with means of agglomeration or granulation to obtain agglomerated or granulated grafted polymer particles, such a process is preferably selected from spray-agglomeration, granulation or drying in a fluidized bed dryer, spray-granulation device, etc.

In another most preferred embodiment, the grafted polymer of any previous most preferred embodiment in this section or obtained by any previous most preferred embodiment in this section is used as a component in a composition or product (which is a fabric and home care product, a cleaning composition, an industrial and institutional cleaning product, a cosmetic or personal care product, an oilfield formulation such as a crude oil demulsifier, a pigment dispersion for, for example, an ink such as an inkjet ink, an electroplating product, an adhesive composition, a paint, a varnish or an agrochemical formulation), preferably in a fabric and home care composition or product, a cleaning composition, or an industrial and institutional cleaning product, more preferably in a cleaning composition, and most preferably in a laundry detergent formulation, wherein such fabric and home care product, cleaning composition, industrial and institutional cleaning product preferably further comprises at least one enzyme, which is preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, and a combination of at least two of the foregoing types.

In another most preferred embodiment, the grafted polymer of any of the previous most preferred embodiments in this section or obtained by any of the previous most preferred embodiments in this section is used as a component in a composition or product (which is a fabric and home care product, a cleaning composition, an industrial and institutional cleaning product), more preferably in a cleaning composition, and most preferably a laundry detergent formulation (which preferably further comprises at least one enzyme, the at least one enzyme is preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, and at least two of the foregoing types ) for inhibiting dye transfer, wherein at least one grafted polymer is present in such a composition or product in an amount of 0.05% to about 20%, preferably 0.05% to 10%, more preferably about 0.1% to 8%, even more preferably about 0.2% to about 6%, and further more preferably about 0.2% to about 4%, each by weight % relative to the total weight of such a composition or product, and most preferably up to 2%, and all values therebetween and including all ranges obtained by selecting any lower limit and combining with any upper limit (each percentage is calculated as a weight % relative to the total weight of such a composition or product).

In another most preferred embodiment, the grafted polymer of any of the previous most preferred embodiments in this section or obtained by any of the previous most preferred embodiments in this section is used as a component in a composition or product (which is a fabric and home care product, a cleaning composition, an industrial and institutional cleaning product), more preferably in a cleaning composition, and most preferably a laundry detergent formulation (which preferably further comprises at least one enzyme, the at least one enzyme is preferably selected from one or more proteases, amylases, lipases, cellulases, mannanases, xylanases, deoxyribonucleases, dispases, pectinases, oxidoreductases, and cutinases, and at least one of the foregoing types The invention relates to a method for inhibiting dye transfer in a composition or product comprising: injecting at least one grafted polymer into a ...

In another most preferred embodiment, the grafted polymer as detailed in the preceding paragraph is used in such a product or composition further comprising from about 1% to about 70% by weight of a surfactant system.

In another most preferred embodiment, the laundry detergent, cleaning composition, or fabric and home care product comprises at least one grafted polymer as detailed in any previous most preferred embodiment in this section or obtained by a method as detailed in any such embodiment disclosed herein (including specifically any previous most preferred embodiment disclosing such a method in this section).

In such laundry detergents, cleaning compositions or fabric and home care products as detailed in any embodiment of the present invention and in particular in the preceding paragraphs, at least one grafted polymer - as detailed in any such embodiment disclosed herein (including in particular any of the previous most preferred embodiments disclosing such grafted polymers and more particularly those in this section) - is present in an amount of about 0.05% to about 10%, preferably about 0.1% to 8%, more preferably about 0.2% to about 6%, and even more preferably about 0.2% to about 4%, each in weight % relative to the total weight of such composition or product, and most preferably up to 2%, between and including all values of all ranges obtained by selecting any lower limit and combining with any upper limit (each in weight % relative to the total weight of such composition or product), and optionally Further comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, and combinations of at least two of the foregoing types, and further optionally comprising an antimicrobial agent selected from the group consisting of 2-phenoxyethanol; preferably comprising said antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition, more preferably comprising 0.1 to 2% of phenoxyethanol, and optionally further comprising 4,4'-dichloro-2-hydroxydiphenyl ether at a concentration of 0.001% to 3%, preferably 0.002% to 1%, more preferably 0.01% to 0.6% each by weight of the composition, and further comprising from about 1% to about 70% of a surfactant system by weight of such detergent, composition or product.

In a further embodiment, the present invention also encompasses a composition comprising a grafted polymer and/or a polymer backbone, each as described above, further comprising an antimicrobial agent as disclosed below (preferably selected from the group consisting of 2-phenoxyethanol), more preferably comprising an amount ranging from 2 ppm to 5% by weight of the composition of the antimicrobial agent; even more preferably comprising 0.1% to 2% phenoxyethanol.

In a further embodiment, the present invention also encompasses a method of preserving an aqueous composition to prevent microbial contamination or growth, such a composition comprising a grafted polymer and/or a polymer backbone as described above, such a composition is preferably a detergent composition, such a method comprising adding at least one antimicrobial agent selected from the disclosed antimicrobial agents as disclosed below, such an antimicrobial agent is preferably 2-phenoxyethanol.

In a further embodiment, the present invention also encompasses a composition, preferably a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dishwashing composition, even more preferably a liquid laundry detergent composition, or a liquid softener composition for use in laundry, such a composition comprising a grafted polymer and/or a polymer backbone, each as described above, such a composition further comprising 4,4'-dichloro-2-hydroxydiphenyl ether at a concentration of 0.001% to 3%, preferably 0.002% to 1%, more preferably 0.01% to 0.6%, each by weight of the composition.

In a further embodiment, the present invention also encompasses a method for washing fabrics or cleaning hard surfaces, the method comprising treating the fabrics or hard surfaces with a cleaning composition, more preferably a liquid laundry detergent composition or a liquid manual dishwashing composition, even more preferably a liquid laundry detergent composition, or a liquid softener composition for use in laundry, such a composition comprising a grafted polymer and/or a polymer backbone, each as described above, such a composition further comprising 4,4'-dichloro-2-hydroxydiphenyl ether.

The following examples shall further illustrate the present invention without limiting the scope of the present invention.

Polymer Measurement

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

The number average molecular weight ( _Mn ), weight average molecular weight ( _Mw ) and polydispersity _Mw / _Mn of the grafted polymers of the present invention were determined by gel permeation chromatography in tetrahydrofuran. The mobile phase (eluent) used was tetrahydrofuran containing 0.035 mol/L diethanolamine. The concentration of the grafted polymer in tetrahydrofuran was 2.0 mg/mL. After filtration (pore size 0.2 μm), 100 μL of the solution was injected into the GPC system. Four different columns (heated to 60°C) were used for separation (SDV pre-column, SDV 1000A, SDV 100000A, SDV 1000000A). The GPC system was operated at a flow rate of 1 mL/min. DRI Agilent 1100 was used as the detection system. Poly(ethylene glycol) (PEG) standards (PL) with molecular weights _Mn ranging from 106 to 1 378 000 g/mol were used for calibration.

Methods for measuring the biodegradability of polymers

Use OECD 301F manometric respirometry, the biodegradation in wastewater is tested in triplicate.30mg/mL test substance is inoculated in the wastewater extracted from Mannheim wastewater treatment plant, and incubated 28 days at 25 ℃ in closed flask.During this time, oxygen consumption is measured as the change of pressure in the flask using OxiTop C (WTW).NaOH solution is used to absorb the CO2 that escapes.After using blank correction, the amount of oxygen consumed by microbial population during the biodegradation of test substance is expressed as % of ThOD (theoretical oxygen demand).

Synthesis procedure of comparative example:

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

Comparative Example II: Graft Polymerization of Vinyl Acetate (30 wt%) and Vinyl Pyrrolidone (20 wt%) on PEG (M _n 6000 g/mol; 50 wt%)

The experimental procedure was performed according to Example 1K of US 2019/0390142 A1.

Comparative Example III: "Graft" polymerization of vinylimidazole (40 wt%) and vinylpyrrolidone (40 wt%) in the presence of PEG (M _n 600 g/mol; 20 wt%)

The experimental procedure was carried out according to Example 6 in WO 03/042264 A2.

Comparative Example IV: (Graft polymerization using the process according to the invention but with too low an amount of B2a and too low an amount of B2)

Graft polymerization of vinyl acetate (20 wt%), vinyl imidazole (2 wt%) and vinyl pyrrolidone (13 wt%) onto EO/PO backbone (MW 1950 g/mol; 50% EO; 65 wt%)

A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 435.5 g of the EO/PO block copolymer under a nitrogen atmosphere and heated to 90°C.

Feed 1, containing 8.20 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 33.70 g of tripropylene glycol, was metered into the stirred vessel at 90° C. over 6:10 h. 5.56% of feed 1 was metered in the first 10 min and the remainder was metered at a constant feed rate for 6:00 h. 10 min after the start of feed 1, feed 2 (134 g of vinyl acetate), feed 3 (13.40 g of vinylimidazole) and feed 4 (87.10 g of vinylpyrrolidone) were started and metered into the reaction vessel at a constant feed rate and 90° C. over 6:00 h. After these feeds were completed, feed 5, consisting of 3.21 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 13.20 g of tripropylene glycol, was metered at a constant flow rate at 90° C. over 56 min. After complete addition of the feed, the mixture was stirred at 90°C for one hour.

Residual amounts of monomers were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

Synthesis procedures of Examples Ex.1-Ex.9 of the present invention

Example 1: Graft polymerization of vinyl acetate (10 wt%), vinylimidazole (25 wt%) and vinylpyrrolidone (15 wt%) onto an EO/PO backbone (MW 2650 g/mol; 40% EO; 50 wt%)

A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 376 g of the EO/PO block copolymer under a nitrogen atmosphere and heated to 90°C.

Feed 1, containing 5.45 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 25.52 g of tripropylene glycol, was metered into the stirred vessel at 90° C. over 6:10 h. 5.56% of feed 1 was metered in the first 10 min and the remainder was metered at a constant feed rate for 6:00 h. 10 min after the start of feed 1, feed 2 (75.2 g of vinyl acetate), feed 3 (188 g of vinylimidazole) and feed 4 (112.8 g of vinylpyrrolidone) were started and metered into the reaction vessel at a constant feed rate and 90° C. over 6:00 h. After these feeds were completed, feed 5, consisting of 3.61 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 16.89 g of tripropylene glycol, was metered at 90° C. at a constant flow rate over 56 min. After complete addition of the feed, the mixture was stirred at 90°C for one hour.

Residual amounts of monomers were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

Example 2: Graft polymerization of vinyl acetate (10 wt%), vinylimidazole (25 wt%) and vinylpyrrolidone (15 wt%) onto an EO/PO backbone (MW 2900 g/mol; 40% EO; 50 wt%)

A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 550 g of the EO/PO block copolymer under a nitrogen atmosphere and heated to 90°C.

Feed 1, containing 7.97 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 37.33 g of 1,2-propanediol, was metered into the stirred vessel at 90° C. over 6:10 h. 5.56% of feed 1 was metered in the first 10 min and the remainder was metered at a constant feed rate for 6:00 h. 10 min after the start of feed 1, feed 2 (110 g of vinyl acetate), feed 3 (275 g of vinylimidazole) and feed 4 (165 g of vinylpyrrolidone) were started and metered into the reaction vessel at a constant feed rate and 90° C. over 6:00 h. After these feeds were completed, feed 5, consisting of 5.28 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 24.70 g of 1,2-propanediol, was metered at a constant flow rate at 90° C. over 56 min. After complete addition of the feed, the mixture was stirred at 90°C for one hour.

Residual amounts of monomers were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

Example 3: Graft polymerization of vinyl acetate (10 wt%), vinylimidazole (25 wt%) and vinylpyrrolidone (15 wt%) onto an EO/PO backbone (MW 1750 g/mol; 30% EO; 50 wt%)

A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 430 g of the EO/PO block copolymer under a nitrogen atmosphere and heated to 90°C.

Feed 1, containing 6.23 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 29.19 g of tripropylene glycol, was metered into the stirred vessel at 90° C. over 6:10 h. 5.56% of feed 1 was metered in the first 10 min and the remainder was metered at a constant feed rate for 6:00 h. 10 min after the start of feed 1, feed 2 (86 g of vinyl acetate), feed 3 (215 g of vinylimidazole) and feed 4 (129 g of vinylpyrrolidone) were started and metered into the reaction vessel at a constant feed rate and 90° C. over 6:00 h. After these feeds were completed, feed 5, consisting of 4.12 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 19.32 g of tripropylene glycol, was metered at a constant flow rate at 90° C. over 56 min. After complete addition of the feeds, the mixture was stirred at 90° C. for one hour.

Residual amounts of monomers were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

Example 4: Graft polymerization of vinyl acetate (10 wt%), vinylimidazole (25 wt%) and vinylpyrrolidone (15 wt%) onto an EO/PO backbone (MW 2450 g/mol; 20% EO; 50 wt%)

A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 500 g of the EO/PO block copolymer under a nitrogen atmosphere and heated to 90°C.

Feed 1, containing 7.24 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 33.94 g of tripropylene glycol, was metered into the stirred vessel at 90° C. over 6:10 h. 5.56% of feed 1 was metered in the first 10 min and the remainder was metered at a constant feed rate for 6:00 h. 10 min after the start of feed 1, feed 2 (100 g of vinyl acetate), feed 3 (250 g of vinylimidazole) and feed 4 (150 g of vinylpyrrolidone) were started and metered into the reaction vessel at a constant feed rate and 90° C. over 6:00 h. After these feeds were completed, feed 5, consisting of 4.80 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.46 g of tripropylene glycol, was metered at a constant flow rate at 90° C. over 56 min. After complete addition of the feeds, the mixture was stirred at 90° C. for one hour.

Residual amounts of monomers were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

Example 5: Graft polymerization of vinyl acetate (10 wt%), vinyl imidazole (25 wt%) and vinyl pyrrolidone (15 wt%) on a PEG backbone (MW 1500 g/mol; 100% EO; 50 wt%)

A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 250 g of PEG backbone under nitrogen atmosphere and heated to 90°C.

Feed 1, containing 3.62 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 33.75 g of tripropylene glycol, was metered into the stirred vessel at 90° C. over 6:10 h. 5.56% of feed 1 was metered in the first 10 min and the remainder was metered at a constant feed rate for 6:00 h. 10 min after the start of feed 1, feed 2 (50 g of vinyl acetate), feed 3 (125 g of vinylimidazole) and feed 4 (75 g of vinylpyrrolidone) were started and metered into the reaction vessel at a constant feed rate and 90° C. over 6:00 h. After these feeds were completed, feed 5, consisting of 2.40 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.35 g of tripropylene glycol, was metered at a constant flow rate at 90° C. over 56 min. After complete addition of the feeds, the mixture was stirred at 90° C. for one hour.

Residual amounts of monomers were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

Example 6: Graft polymerization of vinyl acetate (5 wt%), vinylimidazole (20 wt%) and vinylpyrrolidone (20 wt%) onto a PEG backbone (MW 4000 g/mol; 100% EO; 55 wt%)

A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 341 g of PEG backbone under a nitrogen atmosphere and heated to 90°C.

Feed 1, containing 4.49 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 21.02 g of tripropylene glycol, was metered into the stirred vessel at 90° C. over 6:10 h. 5.56% of feed 1 was metered in the first 10 min and the remainder was metered at a constant feed rate for 6:00 h. 10 min after the start of feed 1, feed 2 (31 g of vinyl acetate), feed 3 (124 g of vinylimidazole) and feed 4 (124 g of vinylpyrrolidone) were started and metered into the reaction vessel at a constant feed rate and 90° C. over 6:00 h. After these feeds were completed, feed 5, consisting of 2.97 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 13.91 g of tripropylene glycol, was metered at a constant flow rate at 90° C. over 56 min. After complete addition of the feeds, the mixture was stirred at 90° C. for one hour.

Residual amounts of monomers were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

Example 7: Graft polymerization of vinyl acetate (15 wt%), vinylimidazole (13 wt%) and vinylpyrrolidone (7 wt%) onto EO/PO backbone (MW 2650 g/mol; 40% EO; 65 wt%)

A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 435.5 g of the EO/PO block copolymer under a nitrogen atmosphere and heated to 90°C.

Feed 1, containing 8.20 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 33.70 g of tripropylene glycol, was metered into the stirred vessel at 90° C. over 6:10 h. 5.56% of feed 1 was metered in the first 10 min and the remainder was metered at a constant feed rate for 6:00 h. 10 min after the start of feed 1, feed 2 (100.50 g of vinyl acetate), feed 3 (87.10 g of vinylimidazole) and feed 4 (46.90 g of vinylpyrrolidone) were started and metered into the reaction vessel at a constant feed rate and 90° C. over 6:00 h. After these feeds were completed, feed 5, consisting of 3.21 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 13.20 g of tripropylene glycol, was metered at a constant flow rate at 90° C. over 56 min. After complete addition of the feed, the mixture was stirred at 90°C for one hour.

Residual amounts of monomers were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

Example 8: Graft polymerization of vinyl acetate (10 wt%), vinyl imidazole (15 wt%) and vinyl pyrrolidone (15 wt%) onto a PEG backbone (MW 1500 g/mol; 100% EO; 60 wt%)

A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 390 g of PEG backbone under nitrogen atmosphere and heated to 90°C.

Feed 1, containing 7.96 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 32.12 g of tripropylene glycol, was metered into the stirred vessel at 90° C. over 6:10 h. 5.56% of feed 1 was metered in the first 10 min and the remainder was metered at a constant feed rate for 6:00 h. 10 min after the start of feed 1, feed 2 (65 g of vinyl acetate), feed 3 (97.5 g of vinylimidazole) and feed 4 (97.5 g of vinylpyrrolidone) were started and metered into the reaction vessel at a constant feed rate and 90° C. over 6:00 h. After these feeds were completed, feed 5, consisting of 3.32 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 13.39 g of tripropylene glycol, was metered at a constant flow rate at 90° C. over 56 min. After complete addition of the feeds, the mixture was stirred at 90° C. for one hour.

Residual amounts of monomers were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

Example 9: Graft polymerization of vinyl acetate (5 wt%), vinyl imidazole (15 wt%) and vinyl pyrrolidone (15 wt%) onto a PEG backbone (MW 1500 g/mol; 100% EO; 65 wt%)

A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 402 g of PEG backbone under a nitrogen atmosphere and heated to 90°C.

Feed 1, containing 8.20 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 33.70 g of tripropylene glycol, was metered into the stirred vessel at 90° C. over 6:10 h. 5.56% of feed 1 was metered in the first 10 min and the remainder was metered at a constant feed rate for 6:00 h. 10 min after the start of feed 1, feed 2 (67 g of vinyl acetate), feed 3 (100.5 g of vinylimidazole) and feed 4 (100.5 g of vinylpyrrolidone) were started and metered into the reaction vessel at a constant feed rate and 90° C. over 6:00 h. After these feeds were completed, feed 5, consisting of 3.21 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 13.20 g of tripropylene glycol, was metered at 90° C. at a constant flow rate over 56 min. After complete addition of the feed, the mixture was stirred at 90°C for one hour.

Residual amounts of monomers were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

For the inventive examples Ex.1 to Ex.11, commercially available EO/PO polyether products and PEG polyethers were used as backbone materials. These products are available, for example, from BASF under the trade name or Available.

The structural details of more comparative polymer examples and inventive polymer examples are listed in Tables 1 and 2.

The biodegradation data of the comparative polymers and the inventive polymers at day 28 in the OECD 301F test are summarized in Tables 1 and 2.

These data show in particular that the total amount of B2 is related to the performance with respect to red, while for the performance with respect to blue, the amount of B2a is the relevant parameter: the more B2, the better the performance with respect to red, and the more B2a, the better the performance with respect to blue.

Evaluation of DTI performance (laundry test)

Washing results:

Selected colored fabrics (EMPA 130 and EMPA 133 as dye donors) were washed at 60°C in the presence of white test fabrics and polyester ballast fabrics with the addition of dye transfer inhibitors. The liquid detergents were based on a mixture of anionic and nonionic surfactants (LAS; AES, AEO). After the wash cycle, the fabrics were rinsed, spun and dried. In order to determine the dye transfer inhibition effect, the dyeing of the white test fabrics was determined photometrically. The reflectance was determined at 540 nm (EMPA 130) or at 600 nm (EMPA 133) using a Datacolor photometer (Elrepho 2000).

Liquid detergent composition

Washing conditions

Explanation of the abbreviations in the previous table:

wfk 10 A: cotton fabric, reflectivity 83.9 (540nm), 84.5 (600nm)

wfk 20 A: polyester-cotton fabric, reflectivity 83.8% (540nm), 83.9 (600nm)

EMPA 130: Cotton fabrics dyed with Direct Red 83.1

EMPA 133: Cotton fabrics dyed with Direct Blue 71

Manufacturer/supplier: wfk Testgewebe GmbH, Bruggen, Germany; EMPA Testmaterialien AG, St. Gallen, Switzerland,

Washing results of EMPA 130 colored fabric (red) (assessment of % reflectance)

Washing results of EMPA 133 colored fabric (blue) (assessment of % reflectance)

Claims (25)

1. A graft polymer comprising: (A) The polymer backbone as the grafting matrix, wherein said polymer backbone (A) is obtainable by polymerization of at least one monomer selected from the group of C2- to C10-alkylene oxides, wherein in the case of containing more than one alkylene oxide monomer, the structure of the polymer backbone is a random polymer, a block polymer or a polymer comprising a mixed structure of block units (wherein each block is a homoblock or a random block itself) and a statistical/random part composed of two or more alkylene oxides, as well as (B) a polymer side chain grafted onto the polymer backbone (A), wherein the polymer side chain (B) is obtainable by copolymerization of at least one monomer (B1) and at least one monomer (B2) Among these monomers (B1) is at least one vinyl ester monomer, which is preferably selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably selected from vinyl acetate and vinyl laurate, and even more preferably vinyl acetate, and most preferably only vinyl acetate, and wherein the remaining amount of the vinyl ester may be any other known vinyl ester and (B2) Yes (B2a) At least one ethylenically unsaturated amine-containing monomer, which is preferably 1-vinylimidazole or a derivative thereof such as an alkyl-substituted derivative of 1-vinylimidazole such as 2-methyl-1- Vinylimidazole, more preferably 1-vinylimidazole as well as (B2b) optionally at least one further nitrogen-containing monomer, which is preferably a vinyllactam monomer, preferably selected from N-vinyllactams, such as N-vinylpyrrolidone, N-vinylpiper ridinone, N-vinylcaprolactam, more preferably N-vinylpyrrolidone, N-vinylcaprolactam, and most preferably N-vinylpyrrolidone, in - the molecular weight in g/mol of the polymer backbone (A) as Mn is within the range from 500 to 12000 and is at least 1000, - the amount in weight percent of the polymer backbone (A), based on the total weight of the graft polymer, is from 30 to less than 89; and - the amount of polymer side chains (B) in weight percent, based on the total weight of the grafted polymer, is greater than 11 to 70; and - the amount in weight percent of (B1), based on the total weight of the graft polymer, is from 1 to 30; and - the amount in weight percent of (B2) based on the total weight of the graft polymer is greater than 10 to 60; and - the amount in weight percent of (B2a), based on the total amount of monomers (B2), is greater than 10 to 100, but at least 10, preferably at least 12, more preferably at least 15, by weight, based on the total weight of the graft polymer percentage; and - The amount in weight percent of (B2b) is equal to [100% of the amount of (B2)] minus [the amount of (B2a)]. 2. The graft polymer according to claim 1, Wherein, the polymer backbone (A) can be obtained by polymerization of ethylene oxide (EO) and optionally at least one other C3-C22-alkylene oxide, and the polymer backbone further complies with i), ii) , iii), iv), i)+iii) or ii)+iii), preferably iv), i)+iii) or ii)+iii), more preferably iv), or ii)+iii), wherein: i) the at least one further C3-C22-epoxyalkane is selected from the group consisting of 1,2-propylene oxide (PO) and 1,2-butylene oxide, ii) the polymer backbone (A) is a polymer containing only EO and optionally PO, iii) the relative amount of EO in the polymer backbone A is within 10-90 weight percent (relative to the total molar amount of alkylene oxide in the polymer backbone (A)), iv) Apart from EO, no other C3-C22-alkylene oxides are contained in the polymer backbone. 3. The graft polymer according to any one of claims 1 to 2, wherein the graft polymer meets at least one of the following i), ii) and/or iii): i) the graft polymer has a polydispersity Mw/Mn (wherein Mw=weight average molecular weight and Mn=number average molecular weight [g/mol/g/mol]) of <7, ii) The polymer backbone (A) is optionally terminated at one or both end groups, and if the polymer backbone (A) is terminated, the endcapping is accomplished by a C1-C25-alkyl group , iii) The graft polymer is biodegradable by at least 25% within 28 days when tested according to OECD 301F. 4. The graft polymer according to any one of claims 1 to 3, wherein, (A) the polymer backbone (A) contains only ethylene oxide as monomer, and/or, preferably "and", the molecular weight of the polymer backbone (A) as Mn in g/mol is within 600 to 3000, and/or, preferably "and", (B) These polymer side chains are composed of the following monomers: -B1 is vinyl acetate, - B2a is 1-vinylimidazole, and -B2b is N-vinyllactam, preferably N-vinylpyrrolidone. 5. The graft polymer according to any one of claims 1 to 4, comprising (A) a polymer backbone (A), the polymer backbone being a polyalkylene oxide, the polyalkylene oxide comprising more than 70, preferably more than 80, even more preferably more than 90 weight percent of ethylene oxide based on the total alkylene oxide, and most preferably comprising only ethylene oxide, and having a molecular weight within the range of 500 to 12000, preferably not more than 9000, more preferably not more than 6000, even more preferably not more than 3500, further even more preferably not more than 3000, even further even more preferably not more than 2750 and at least 600, more preferably at least 100 0, even more preferably a molecular weight in g/mol as Mn of at least 1500, and wherein all ranges are constituted by combining any number previously specified for the lower boundary with any number previously specified as the upper boundary, specifically as a more preferred range, the Mn is 600 to 3000, even more preferably 1000 to 2750, and most preferably 1500 to 2750, and the polymer backbone (A) is present in the graft polymer in an amount of 45 to 65 weight percent based on the total weight of the graft polymer; and (B) 40 to 55 weight percent of polymer side chains (B) based on the total weight of the graft polymer; wherein (B) comprises (B1) and (B2a) and optionally (B2b), wherein The amount of (B1) is 5 to 15 weight percent based on the total weight of the graft polymer; and The amount of (B2) is 25 to 50 weight percent based on the total weight of the graft polymer; The amount of (B2a) is 15 to 30 weight percent based on the total weight of the graft polymer; and The amount of (B2b) in terms of weight percent is equal to [100% of the amount of (B2)] minus [the amount of (B2a)]. 6. The graft polymer according to any one of claims 1 to 5, wherein (B1) is vinyl acetate, (B2a) is vinylimidazole, and (B2b) is vinyllactam, preferably ethylene pyrrolidone. 7. The graft polymer according to any one of claims 1 to 6, which has a polydispersity Mw/Mn of <7 (where Mw = weight average molecular weight and Mn = number average molecular weight [g/mol/g /mol]). 8. The graft polymer of any one of claims 1 to 7, which exhibits a biodegradability of at least 25% by weight within 28 days when tested according to OECD 301F. 9. A method for obtaining a graft polymer according to any one of claims 1 to 8, wherein the at least one monomer B1, the at least one monomer B2a, the optional at least One monomer B2b is polymerized in the presence of at least one polymer backbone (A), wherein the polymer side chains (B) are obtained by free-radical polymerization using free-radical forming compounds to initiate the free-radical polymerization. 10. Process according to claim 9, comprising at least one monomer (B1), at least one monomer (B2a), optionally at least one monomer (B2b) in at least one polymer backbone (A), radical-forming initiator (C) and optionally but preferably based on components (A), (B1), (B2a), optionally (B2b), (C), and solvent (D) are polymerized in the presence of at least one solvent (D) in an amount of up to 50% by weight at an average polymerization temperature of the initiator (C) having a decomposition half-life of 40 to 500 min in such a way that The fractions of unconverted graft monomers (B1 and B2) and initiator (C) in the reaction mixture remain consistently insufficient relative to the polymer backbone (A). 11. The method of any one of claims 9 to 10, wherein a solvent is used only to introduce the free radical initiator into the reaction mixture and no further solvent is added. 12. The method according to any one of claims 9 to 11, wherein the method comprises at least one further method step selected from i) to iv): i) post-polymerization; ii) purification; iii) Concentration; and iv) Drying. 13. The method of claim 12, wherein the method includes at least one further method step selected from: a post-polymerization process step (i.e. step i)), which is carried out after the main polymerization, wherein a further amount of initiator (optionally dissolved in the solvent) is added, preferably within a time period of 0.5 hours and up to 3 hours, preferably about 1 to 2 hours, more preferably about 1 hour, wherein the free radical initiator and the solvent for the initiator are typically - and preferably - the same as those used for the main polymerization; and wherein after the polymerization and before the post-polymerization, preferably a waiting period is carried out, while the main polymerization is allowed to proceed, before the post-polymerization is started by starting to add the further free radical initiator, such a period being preferably 10 minutes and up to 4 hours, preferably up to 2 hours, even more preferably up to 1 hour, and most preferably up to 30 minutes; and wherein the temperature of the post-polymerization process step is - preferably - the same as in the main polymerization, or increased, such increase being preferably about 5°C to 40°C, preferably 10°C to 20°C higher than the temperature of the main polymerization; a step of subjecting the graft polymer as obtained from the main polymerization or - if carried out - the postpolymerization process - to a step of removing a part or almost all of the remaining solvents (as long as they are removable due to their boiling point) and/or volatiles such as residual monomers by means of ii) purification, iii) concentration and/or iv) drying or a combination of such process steps, wherein a. the concentration (step iii)) is carried out by removing a portion of the solvent and optionally also volatiles to increase the solid polymer concentration by preferably applying a distillation process such as thermal distillation or vacuum distillation, preferably vacuum distillation, the distillation process being carried out until the desired solid content is obtained, preferably the distillation process is carried out until the desired part or all of the volatile components such as volatile solvents and/or unreacted volatile monomers are removed; b. The drying (step iv)) is carried out by subjecting the graft polymer, which contains at least residual amounts of volatiles such as remaining solvents and/or unreacted monomers etc., to means for removing the volatiles, such as using Drying of rollers, spray dryers, vacuum drying or freeze drying, preferably - mainly for cost reasons - spray drying; and optionally combining such drying process steps with means of agglomeration or granulation to obtain agglomerated or Granulated graft polymer particles, such a process preferably being selected from spray-agglomeration, granulation or drying in a fluidized bed dryer, spray-granulation unit or the like; and / or c. Such previous steps (i.e. steps iii) and/or iv)) also serve as purification means (step ii)). 14. At least one graft polymer according to any one of claims 1 to 8 or obtained or obtainable by a method according to any one of claims 9 or 13 in a composition, i.e. Fabric and home care products, cleaning compositions, or industrial and institutional cleaning products, cosmetic or personal care products, oil field preparations such as crude oil demulsifiers, pigment dispersions for e.g. inks such as inkjet inks, electroplating products, adhesives Use in compositions, lacquers, paints, agrochemical preparations. 15. Use according to claim 14 in compositions for fabric and home care, cleaning compositions, or industrial and institutional cleaning products. 16. Use according to claim 14 or 15, wherein the composition additionally comprises at least one enzyme. 17. Use according to any one of claims 14 to 16 for inhibiting dye transfer. 18. Use according to any one of claims 14 to 17, wherein the at least one graft polymer is present in an amount of from about 0.05% to about 10% by weight relative to the total weight of such composition or product. % concentration exists. 19. Use according to any one of claims 14 to 18, such product or composition further comprising from about 1% to about 70% by weight of a surfactant system, and optionally further comprising at least one Antimicrobials. 20. A laundry detergent, cleaning composition or fabric and home care product containing at least one agent according to any one of claims 1 to 8 or by means of any one of claims 9 or 14 The at least one graft polymer preferably exhibits dye transfer inhibiting properties. 21. The laundry detergent, cleaning composition or fabric and home care product according to claim 20, wherein the at least one grafted polymer is present in a concentration of about 0.05% to about 10% by weight relative to the total weight of such composition or product, the composition or product further comprising about 1% to about 70% by weight of a surfactant system, optionally comprising at least one antimicrobial agent and/or at least one enzyme. 22. A laundry detergent, cleaning composition or fabric and home care product according to claim 20 or 21, further comprising preferably in the range of 2 ppm to 5%, more preferably in the range of 0.1% to 2% - all in The amount of 2-phenoxyethanol, by weight of the composition, acts as an antimicrobial agent. 23. Laundry detergent, cleaning composition or fabric and home care product according to claims 20 to 22, comprising 0.001% to 3%, preferably 0.002% to 1%, more preferably 0.01% to 0.6% - each A concentration of 4,4'-dichloro 2-hydroxydiphenyl ether based on the weight of the composition. 24. A method of preserving a laundry detergent, cleaning composition or fabric and home care product according to any one of claims 20 to 23 against microbial contamination or growth, the method comprising adding 2-benzene to the composition Oxyethanol acts as an antimicrobial agent and the composition is an aqueous composition containing water as a solvent. 25. A method of laundering fabrics or cleaning hard surfaces, the method comprising treating fabrics or hard surfaces with a composition according to any one of claims 20 to 24, the composition comprising 4,4'-dichloro2 - Hydroxydiphenyl ether, preferably comprising 4,4'- in a concentration of 0.001% to 3%, preferably 0.002% to 1%, more preferably 0.01% to 0.6%, each by weight of the composition Dichloro 2-hydroxydiphenyl ether.