Biodegradable graft polymers

Abstract

The present invention relates to novel graft polymers, the graft polymers comprising a block copolymer backbone (A) as a grafting base, onto which polymer side chains (B) are grafted. The polymer side chains (B) can be obtained by polymerization of at least one vinyl ester monomer (B1) and optional 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 present invention further relates to a method for obtaining such graft polymers, the method preferably being carried out by free radical polymerization. In addition, the present invention relates to the use of such graft polymers in, for example, fabrics and home care products. Another subject of the present invention is a fabric and home care product that itself contains such graft polymers.

Description

[0001] illustrate

[0002] The present invention relates to novel graft polymers, which comprise a block copolymer backbone (A) as a grafting base, onto which polymer side chains (B) are grafted. The polymer side chains (B) can be obtained by polymerization of at least one vinyl ester monomer (B1). Most preferably, the block copolymer backbone (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG). The present invention further relates to a method for obtaining such graft polymers, which method is preferably carried out by free radical polymerization. In addition, the present invention relates to the use of such graft polymers in fabrics and home care products. Another subject of the present invention is a fabric and home care product that itself contains such a graft polymer.

[0003] Various countries have proposed initiatives to ban microplastics, especially in cosmetic products. In addition to the ban on insoluble microplastics, there is an intense dialogue on the future requirements for soluble polymers used in consumer products. Therefore, it is highly desirable to identify new and better biodegradable ingredients for such applications. This problem is mainly serious for polymers produced by free radical polymerization based on carbon-containing backbones only (main chains that do not contain heteroatoms such as oxygen), because carbon-containing backbones alone are particularly difficult to degrade for microorganisms. Even industrially important free radical-generated graft polymers with polyethylene glycol backbones show only limited biodegradation in wastewater. However, the polymers described in the present invention are preferably produced by free radical graft polymerization and provide enhanced biodegradability compared to the prior art.

[0004] WO 2007 / 138053 discloses amphiphilic graft polymers based on water-soluble polyalkylene oxides (A) as graft base and side chains formed by polymerization of vinyl ester components (B), said polymers having an average of <1 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 describe any backbone materials based on block copolymers. Furthermore, WO 2007 / 138053 does not contain any disclosure about the biodegradability of the corresponding graft polymers disclosed therein.

[0005] Y. Zhang et al. J. Coll. Inter. Sci 2005, 285, 80 are concerned with the synthesis and characterization of specific grafted polymers based on a pluronic type backbone. Pluronic poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO–PPO–PEO) block copolymers were grafted with poly(vinyl pyrrolidone) by free radical polymerization of vinyl pyrrolidone with simultaneous chain transfer to the diblock copolymer. However, Y. Zhang does not disclose that the polymer side chains of the corresponding graft polymers are based on vinyl ester monomers. Furthermore, Y. Zhang does not have any disclosure about the biodegradability of the graft polymers disclosed therein. Y. Zhang also does not contain any disclosure about the use of such graft polymers in fabric and home care products.

[0006] WO 03 / 042262 relates to graft polymers comprising (A) a polymer graft backbone free of monoethylenically unsaturated units and (B) polymer side chains formed from a copolymer of two different monoethylenically unsaturated monomers (B1) and (B2), each of which contains a nitrogen-containing heterocycle, whereby the proportion of side chains (B) amounts to 35% to 55% by weight of the total polymer. However, the graft polymers according to WO 03 / 042262 are not based on vinyl ester monomers grafted onto the backbone in the corresponding polymer side chains. Apart from this, WO 03 / 042262 does not have any disclosure in connection with the biodegradability of the graft polymers disclosed therein.

[0007] US-A 5,318,719 relates to a novel class of biodegradable water-soluble graft copolymers with architectural, anti-filming, dispersing and threshold crystal inhibition properties, comprising (a) acid-functional monomers and optionally (b) other water-soluble monoethylenically unsaturated monomers copolymerizable with (a), grafted to a biodegradable substrate comprising polyalkylene oxide and / or polyalkoxylated materials. However, US-A 5,318,719 does not disclose the use of block copolymer backbones in the corresponding graft polymers. In addition, the corresponding side chains of the graft polymers must contain a large amount of acid-functional monomers, such as acrylic acid or methacrylic acid. Such type of acid monomers are not useful in the context of the present invention.

[0008] It is an object of the present invention to provide novel graft polymers. Furthermore, these novel graft polymers should have advantageous properties with regard to biodegradability and their washing behavior when used in compositions such as cleaning compositions.

[0009] This object is achieved by a graft polymer comprising

[0010] (A) a block copolymer backbone as a graft base, wherein the block copolymer backbone (A) is obtainable by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide, wherein the block copolymer backbone (A) has three or more alkylene oxide blocks;

[0011] (B) polymer side chains grafted onto the block copolymer backbone (A), wherein the polymer side chains (B) are obtainable by polymerization of at least one vinyl ester monomer (B1),

[0012] wherein the vinyl ester monomer (B1) comprises at least 50% by weight of the B1 monomer of vinyl acetate,

[0013] wherein the polymer has an OG greater than 0, wherein

[0014] OG=a X EO+b X M n 2 -c X (M n ×SUB)-d X M n +e X SUB+h X

[0015] in:

[0016] “M n " is the number average molecular weight of the block copolymer main chain (A);

[0017] "EO" is the molar ratio of ethylene oxide moieties to all alkylene oxide moieties present in the backbone (A), wherein EO is in the range of 0 to less than 1.00,

[0018] "SUB" is the weight percent of polymer side chains (B) based on the weight of the polymer;

[0019] “a X” ” is the coefficient and is equal to 7.06;

[0020] “b X " is the coefficient and is equal to 5.63×10 -7 ;

[0021] "c X " is the coefficient and is equal to 1.25×10 -3 ;

[0022] "d X ” is the coefficient and is equal to 7.03×10 -3 ;

[0023] “e X ” is the coefficient and is equal to 3.66; and

[0024] “h X ” is the coefficient and is equal to 16.3.

[0025] Preferred grafted polymers also have a FJ greater than 0, wherein

[0026] FJ=a Y EO-b Y M n 2 +d Y M n +e Y SUB-f Y SUB 2 -g Y (EO×SUB)-h Y

[0027] in:

[0028] “a Y ” is the coefficient and is equal to 446;

[0029] “b Y " is the coefficient and is equal to 4.02×10 -6 ;

[0030] "d Y ” is the coefficient and is equal to 0.0168;

[0031] “e Y ” is the coefficient and is equal to 281;

[0032] “f Y ” is the coefficient and is equal to 229;

[0033] "g Y ” is the coefficient and is equal to 1140; and

[0034] “h Y ” is the coefficient and is equal to 83.6.

[0035] In a preferred version of the previous embodiment, the number (x) of individual blocks within the block copolymer backbone (A) is an integer, wherein x is from 3 to 10, preferably from 3 to 5, more preferably 3.

[0036] The graft polymers according to the invention can be used, for example, in cleaning compositions and / or textile and home care products. Compared to corresponding polymers or graft polymers according to the prior art, they produce in such compositions or products at least comparable and preferably even improved anti-redeposition and cleaning properties, for example with respect to redeposition of soils and removal of stains. In addition, when used in such compositions or products, for example in cleaning compositions and / or textile and home care products, the graft polymers according to the invention lead to improved biodegradability.

[0037] The graft polymers with enhanced biodegradation according to the invention can be advantageously used in washing and cleaning compositions, where they support the removal of various hydrophobic and hydrophilic soils, such as body soils, food and greasy soils, particulate soils like clay or carbon black, grass soils, cosmetics, motor oils etc., from textiles or hard surfaces by surfactants and thus improve the washing and cleaning performance of the formulations.

[0038] In addition, the grafted polymer also makes the removed soils better dispersed in the washing or cleaning liquid and prevents them from being redeposited on the surface of the washed or cleaned materials. In this context, the removed soils include all typical soils present in the laundry washing process, such as body soils, food and grease soils, particulate soils such as clay or carbon black, grass soils, cosmetics, motor oil, etc. Such anti-redeposition effects can be observed on various fabric types, including cotton, polyester cotton, polyester, copolymers of polyether / polyurea (Spandex TM ) etc. In addition, such anti-redeposition effect is also effective on fabrics with a history of fabric enhancers, or when fabric washing is carried out in the presence of fabric enhancers or other laundry detergent additives such as freshening beads or bleaching agents.

[0039] As used herein, the term "block copolymer (main chain)" means that the corresponding polymer comprises at least two (two or more) homopolymer subunits (blocks) connected by covalent bonds. Two block copolymers have two different blocks (homopolymer subunits), and triblock copolymers therefore have three different blocks (homopolymer subunits), etc. The number of single blocks in such block copolymers is not limited, so "n-block copolymers" include n different blocks (homopolymer subunits). In a single block (homopolymer subunit), the size / length of such blocks can vary. The minimum length / size of a block is based on two separate monomers (as a minimum value). The understanding of the term "block copolymer" is further defined in detail below, particularly according to the definition of "triblock copolymers" of formula (A1) or formula (A2).

[0040] The present invention is described in more detail below.

[0041] The first subject of the present invention relates to a graft polymer comprising

[0042] (A) a block copolymer backbone as a graft base, wherein the block copolymer backbone (A) is obtainable by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide, wherein the block copolymer backbone (A) has three or more alkylene oxide blocks;

[0043] (B) polymer side chains grafted to the block copolymer backbone (A), wherein the polymer side chains (B) are obtainable by polymerization of at least one vinyl ester monomer (B1);

[0044] The vinyl ester monomer (B1) comprises at least 50% by weight of B1 monomer vinyl acetate.

[0045] The ratio of the block copolymer main chain (A) to the polymer side chain (B) in the graft polymer according to the present invention is not limited to a specific value. Any ratio known to those skilled in the art can be used. However, it should be understood that the graft polymer contains more than 1% by weight of polymer side chains (B) relative to the total weight of the graft polymer (SUB=0.01). Preferably, the graft polymer contains more than 5% by weight of polymer side chains (B) relative to the total weight of the graft polymer (SUB=0.05). More preferably, the graft polymer contains more than 10% by weight of polymer side chains (B) relative to the total weight of the graft polymer (SUB=0.10).

[0046] In a preferred version of the previous embodiment, the number (x) of individual blocks within the block copolymer backbone (A) is an integer, wherein x is from 3 to 10, preferably from 3 to 5, more preferably 3.

[0047] The grafted polymer preferably comprises 20 to 95 wt % of the block copolymer backbone (A) and 5 to 80 wt % of the polymer side chains (B) (relative to the total weight of the grafted polymer).

[0048] Preferably, the grafted polymer comprises 40% to 90% by weight, more preferably 50% to 85% by weight, even more preferably 55% to 80% by weight of the block copolymer backbone (A), and preferably 10% to 60% by weight, more preferably 15% to 50% by weight, even more preferably 20% to 45% by weight of polymer side chains (B) (relative to the total weight of the grafted polymer).

[0049] The block copolymer backbone (A) itself and methods for preparing such block copolymer backbones are known to the person skilled in the art. Various types of such block copolymer backbones are commercially available, for example, under the trademark series "Pluronic" (BASF SE, Ludwigshafen, Germany). Specific examples are PE 6100, Pluronic PE 6800 or Pluronic PE3100.

[0050] Suitable block copolymer backbones (A) for the present invention are described in, for example, EP-A 0 362 688. In the present invention, it is preferred that the corresponding monomers for preparing the individual blocks of the block copolymer backbone (A) are added sequentially. However, the feed can be changed from one monomer to another monomer to produce a so-called "dirty structure", in which a small amount of monomers of the corresponding adjacent blocks can be contained in the individual blocks to be considered at the edges / borders of the corresponding blocks. However, it is preferred that the block copolymer backbone (A) according to the present invention does not contain any so-called "dirty structure" or "dirty channel" at the corresponding boundaries of the blocks.

[0051] Regarding the block copolymer backbone (A) of the graft polymer according to the present invention, it is preferred that the block copolymer backbone (A) is obtainable by polymerization of:

[0052] i) at least two monomers selected from ethylene oxide, 1,2-propylene oxide or 1,2-butylene oxide, preferably by polymerization of ethylene oxide and 1,2-propylene oxide as monomers, and / or

[0053] ii) one of the at least two monomers used is ethylene oxide, preferably the second monomer used is 1,2-propylene oxide, and / or

[0054] iii) The number of individual alkylene oxide blocks (x) in the block copolymer backbone (A) is an integer, wherein the value of x is 3 to 10, preferably the value of x is 3 to 5, and more preferably x is 3.

[0055] In the case where x is an even number, the grafted polymer generally comprises an end-capping group. Suitable end-capping groups are described in detail below.

[0056] The graft polymer according to the invention may have any molecular weight known to the skilled person. However, it is preferred that the graft polymer has a weight average molecular weight M of 1 000 g / mol to 100 000 g / mol, preferably 2000 g / mol to 45 000 g / mol, and more preferably 3 000 g / mol to 30 000 g / mol. w .

[0057] The graft polymers according to the present invention preferably have a low polydispersity. Preferably, the graft polymer has a polydispersity M <3, preferably <2.5, more preferably <2.3, and most preferably in the range of 1.0 to 2.2. w / M n (where M w = weight average molecular weight and M n = number average molecular weight; polydispersity does not have the unit [g / mol / g / mol]). M w and / or M nThe corresponding value of can be determined as described in the experimental part below.

[0058] The grafted polymers of the present invention may contain polymeric side chains (B) in an ungrafted form. The level of ungrafted polymer side chains may be high or low, depending on the reaction conditions. Preferably, the level of ungrafted polymer side chains is generally less than 25%. More preferably, the level of ungrafted polymer side chains is less than 15%. More preferably, the level of ungrafted polymer side chains is less than 5%. All based on the total weight of the polymer in the grafted polymer product of the present invention produced or producible by the method described in the present invention.

[0059] The grafted polymers of the present invention may contain ungrafted block copolymer backbone (A). The level of ungrafted block copolymer backbone (A) may be high or low, depending on the reaction conditions. Preferably, the level of ungrafted block copolymer backbone (A) is generally less than 50%. More preferably, the level of ungrafted block copolymer backbone (A) is less than 30%. More preferably, the level of ungrafted block copolymer backbone (A) is less than 10%. All based on the total weight of the polymer in the grafted polymer product of the present invention as produced or producible by the method described in the present invention.

[0060] The grafted polymers of the present invention can be characterized by their degree of grafting (the number of grafting sites of the polymer side chains (B) on the block copolymer backbone (A)). The degree of grafting can be high (greater than 1 polymer side chain / 50 alkylene oxide units) or low (less than 1 polymer side chain / 50 alkylene oxide units), depending on the reaction conditions. The degree of grafting can be adjusted to achieve optimized performance in certain areas of interest. The degree of branching can be determined, for example, by the relationship between the grafting sites and the -CH 2 -group signal integration.

[0061] The block copolymer main chain (A) contained in the graft polymer according to the present invention may be terminated at the corresponding end groups of the main chain or may not be terminated (unterminated). Therefore, in the present invention, the block copolymer main chain (A) may be optionally terminated at one or both end groups, preferably the block copolymer main chain (A) is not terminated at both end groups, or if the block copolymer main chain (A) is terminated, the termination is carried out by C 1 -C 25 Alkyl groups.

[0062] In one embodiment of the present invention, it is preferred that the block copolymer backbone (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG).

[0063] In the context of the present invention, it is generally preferred that the graft polymer has a block copolymer backbone (A) having a structure according to formula (A1) or formula (A2), wherein

[0064] Formula (A1) is defined as follows:

[0065]

[0066] in

[0067] n is an integer in the range of 2 to 100, preferably 3 to 80, and

[0068] m is an integer ranging from 2 to 100, preferably from 10 to 70, more preferably from 14 to 54, or

[0069] Formula (A2) is defined as follows:

[0070]

[0071] in

[0072] o is an integer in the range of 2 to 100, preferably 5 to 50, more preferably 8 to 27, the inner cavity

[0073] p is an integer ranging from 2 to 100, preferably from 5 to 50, more preferably from 7 to 24.

[0074] The block copolymer (A) may contain different levels of hydrophilic ethylene glycol, which affects the overall properties of the grafted polymer. The total EO content ("EO"), which describes the total amount of ethylene glycol units in the block copolymer, is defined as:

[0075] "EO" is the molar ratio of ethylene oxide moieties to all alkylene oxide moieties present in the backbone (A), wherein EO is in the range of 0 to less than 1.00,

[0076] The block copolymers can be low, medium or high in the corresponding "EO", which has an impact on the biodegradation properties as well as performance in laundry detergent formulations. The ranges are defined as follows:

[0077] - Low: 0.05–0.20

[0078] -Medium: 0.21–0.50

[0079] - High: 0.51–0.90

[0080] With regard to the polymeric side chains (B) contained in the graft polymer according to the present invention, it is preferred that the polymeric side chains (B) are obtained by free radical polymerization and / or that the at least one vinyl ester monomer (B1) is vinyl acetate.

[0081] As vinyl ester monomer (B1), any other vinyl ester known to the person skilled in the art except vinyl acetate may be used, provided that the vinyl ester monomer (B1) comprises at least 50% of vinyl acetate by weight of the B1 monomers. Suitable other vinyl esters include vinyl propionate, vinyl valerate, vinyl pivalate, vinyl neononanoate, vinyl decanoate, vinyl benzoate, vinyl laurate, more preferably vinyl acetate or vinyl laurate. In case N-vinylpyrrolidone is used as an optional additional monomer (B2) for the preparation of the polymer side chains (B) in the graft polymer according to the present invention, the ratio of the mandatory vinyl ester monomer (B1) to the additional monomer (B2) may have any value known to the person skilled in the art. However, the amount of vinyl ester monomer (B1) is generally not less than 1% by weight (relative to the sum of (B1) and (B2)). Thus, the polymer side chains (B) can preferably be obtained by free radical polymerization of 1 to 100 wt. % of monomers (B1), most preferably vinyl acetate, and 0 to 99 wt. % of N-vinylpyrrolidone as optional additional monomer (B2).

[0082] However, in the context of the present invention, it is preferred that the polymer side chains (B) are obtained by free radical polymerization of:

[0083] (B1) 10 to 100% by weight (relative to the sum of (B1) and (B2)) of at least one vinyl ester monomer (B1), preferably 50 to 100% by weight, more preferably 75 to 100% by weight, and

[0084] (B2) 0 to 90% by weight (relative to the sum of (B1) and (B2)) of N-vinylpyrrolidone as further monomer (B2), preferably 0 to 50% by weight, more preferably 0 to 25% by weight.

[0085] In the context of the present invention, it is even more preferred that the polymer side chains (B) are obtained by free radical polymerization of 100 wt. % (relative to the total amount of monomers employed) of at least one vinyl ester monomer (B1), preferably vinyl acetate or vinyl propionate, more preferably vinyl acetate.

[0086] In another embodiment of the present invention, the polymer side chains (B) of the graft polymer according to the present invention are completely or at least partially hydrolyzed after obtaining such graft polymer. This means that the complete or at least partial hydrolysis of the polymer side chains (B) of the graft polymer is carried out after the polymerization process of the polymer side chains (B) is completed.

[0087] Due to this complete or at least partial hydrolysis of the polymeric side chains (B) of the graft polymers according to the invention, the corresponding side chain units originating from the at least one vinyl ester monomer (B1) are changed from the corresponding ester functions to alcohol functions in the polymeric side chains (B). It must be noted that the corresponding vinyl alcohols are not suitable for use as monomers in the polymerization of the polymeric side chains (B) for reasons of stability. In order to obtain alcohol functions (hydroxyl substituents) in the polymeric side chains (B) of the graft polymers according to the invention, the alcohol functions are usually introduced by hydrolyzing the ester functions of the side chains.

[0088] From a theoretical point of view, each ester function of the polymer side chain (B) can be replaced by an alcohol function (hydroxyl group). In this case, the polymer side chain is completely hydrolyzed (saponified). It should be noted that in the case where N-vinylpyrrolidone is used as an additional monomer, hydrolysis generally does not occur at those units of the polymer side chain (B) which are derived from N-pyrrolidone used as an additional monomer (B).

[0089] 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.

[0090] However, in this embodiment of the invention, it is preferred that the hydrolysis of the polymer side chains (B) is only partially carried out, for example partially to an extent of up to 20%, 40% or 60% by weight (relative to the total weight of the polymer side chains).

[0091] In this embodiment, the polymer side chains (B) may be fully or partially hydrolyzed after polymerization, preferably to an extent of up to 50% by weight relative to the amount of at least one vinyl ester monomer (B1) employed in the polymerization. Preferably, however, the polymer side chains (B) are not hydrolyzed after polymerization.

[0092] In the context of the present invention, it is preferred that no other monomers than those defined above with respect to at least one vinyl ester monomer (B1) and optionally N-vinyl pyrrolidone as optional further monomer (B2) are used in the corresponding polymerization process for obtaining the polymer side chains (B). However, if any further polymerizable monomers than the monomers according to (B1) and optionally (B2) are present, such monomers (except B1 and B2) are present in an amount of less than 1% by weight of the total amount of monomers used to obtain the polymer side chains (B). Preferably, the amount of the further monomers is less than 0.5% by weight, even more preferably less than 0.01% by weight, most preferably, no further monomers are present at all than the monomers (B1) and optionally (B2).

[0093] In the present invention, it is particularly preferred that no acid-functional monomers are used. In particular, the monomers for obtaining the polymer side chains (B) of the grafted polymer according to the invention do not include any acid-functional monomers selected from acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, vinylacetic acid or acryloxypropionic acid.

[0094] The polymer of the present invention needs to have at least one, preferably two or more, of the following properties in order to be successfully used in various application fields:

[0095] a) a level of biodegradation, the biodegradation being tested as defined elsewhere in this specification. To demonstrate useful biodegradation, the percentage of biodegradation (at 28 days according to the methods disclosed herein) should preferably be at least 20%, more preferably at least 40%, and even more preferably at least 50%, such as 25%, 30%, 32%, 35%, 45%, 55%, 60%, 65%, 75%, 80%, 85% or more up to 100%;

[0096] b) The water solubility of the polymer should exist to a certain extent in order to be able to employ the polymer in aqueous environments typically present in application fields such as those typically targeted by the present invention. Preferably, the polymer of the present invention should show moderate to good solubility, more preferably very good solubility in the environment of aqueous formulations typically used in the fields of various formulations such as dishwashing, automatic dishwashing, hard surface cleaning, fabric cleaning, fabric care, cosmetic formulations, etc.

[0097] c) The viscosity of the polymer solution should be such that the solids concentration of the polymer handled during and after production and supplied to the user is reasonably high, the polymer being for example a "pure" (then usually liquid) product dissolved in a solvent, which is usually an aqueous solution comprising water and an organic solvent, exclusively water or exclusively organic solvent, the viscosity of this polymer or polymer solution being in a range that allows typical technological process steps such as pouring, pumping, dosing, etc. Thus, the viscosity should preferably be in the range of about up to less than 4000 mPas, more preferably up to 3500 mPas, even more preferably up to 3000 mPas, such as up to 4500 mPas, 3750 mPas, 3250 mPas, 2750 mPas or even 2600 mPas or below such as 2500 mPas, 2000 mPas, 1750 mPas, 1500 mPas, 1250 mPas, 1000 mPas, 750 mPas, 800 mPas, 900 mPas, 1000 mPas, 1200 mPas, 1500 mPas, 1500 mPas, 1200 mPas, 1000 mPas, 15 ... The viscosity of the polymer solution can be measured at 25°C or at elevated temperatures, for example at 50°C or even 60°C. Thus, the polymer solution can be suitably treated on a commercial scale. Of course, it is obvious that, depending on the amount of solvent added, when the amount of solvent increases, the viscosity is lower, and vice versa, thereby allowing adjustment in the desired case. It is also obvious that the measured viscosity depends on the measured temperature, for example, when measured at a lower temperature, the viscosity of a given polymer with a given solid content of, for example, 80% by weight will be higher, while when measured at a higher temperature, the viscosity will be lower. In a preferred embodiment, the solid content is between 70% and 90% by weight, more preferably between 75% and 85% by weight, and no additional solvent is added besides the polymer produced. In a more preferred embodiment, the solid content is between 70% and 90% by weight, more preferably between 75% and 85% by weight, and no additional solvent is added besides the polymer produced, and the viscosity is below 3000 mPas when measured at 60°C.

[0098] In order to achieve these requirements, the following guidance can be given on how to achieve such properties of the polymers of the present invention:

[0099] Biodegradability generally increases with at least one of the following conditions:

[0100] 1) The molecular weight of the block copolymer backbone (A) is lower compared to the higher molecular weight;

[0101] • 2) A lower weight percentage of polymer side chains (monomer B) grafted onto the backbone compared to a higher weight percentage.

[0102] 3) Selecting the main chain structure A2 relative to A1;

[0103] · 4) The molar ratio of ethylene oxide moieties present in the main chain (A) to the total alkylene oxide moieties is in the range of about 0.10 to about 0.80.

[0104] Preferred properties of the polymers of the present invention are achieved with at least one of the following conditions:

[0105] 1) The block copolymer backbone (A) of the grafted polymer has an M of less than 3500 g / mol, more preferably less than 3200 g / mol. n .

[0106] 2) the weight percent of polymer side chains of the grafted polymer ("SUB") is in the range of about 0.10 to about 0.60, more preferably in the range of about 0.20 to about 0.50;

[0107] 3) The grafted polymer has a main chain structure A2;

[0108] • 4) The molar ratio of ethylene oxide moieties present in the backbone A ("EO") to the total alkylene oxide moieties is in the range of about 0.10 to about 0.80.

[0109] The more preferred properties of the polymers of the present invention are achieved using a combination of the following conditions: ("A1", "B1", etc. are as defined above)

[0110] 1)+2), i.e. the block copolymer main chain (A) has an M of less than 3500 g / mol n and the weight percent of polymer side chains of the grafted polymer ("SUB") is in the range of about 0.20 to about 0.50;

[0111] 1)+3)

[0112] 1)+2)+3)

[0113] 1)+2)+3)+4)

[0114] Even more preferred properties of the polymers of the present invention are achieved by a combination of the following conditions:

[0115] 1)+2)

[0116] 1)+2)+3)

[0117] The most preferred properties of the polymers of the present invention are achieved by a combination of the following conditions:

[0118] 1)+2)+3)

[0119] In a preferred embodiment of the present invention, the grafted polymer is a polymer in which the number average molecular weight M of the triblock copolymer backbone (A) is n Below 6000 g / mol, preferably below 5000 g / mol, more preferably below 3650 g / mol, and even more preferably below 3000 g / mol, and the weight percentage of vinyl acetate (monomer B) grafted onto the main chain is between 10 and 80, preferably greater than 10 and less than 80, more preferably at least 20, and most preferably at least 30, and preferably less than 70, more preferably less than 60, and most preferably less than 50 (relative to the total weight of the grafted polymer).

[0120] In another preferred embodiment of the present invention, the graft polymer is a polymer in which the number average molecular weight M of the triblock copolymer backbone (A) is n Below 6000 g / mol, preferably below 5000 g / mol, more preferably below 3650 g / mol, and even more preferably below 3000 g / mol, and most preferably below 2500 g / mol, and the main chain has structure A2, and the weight percentage of vinyl acetate (monomer B) grafted to the main chain is between 10 and 80, preferably greater than 10 and less than 80, more preferably at least 20, and most preferably at least 30, and preferably less than 70, more preferably less than 60, and most preferably less than 50 (relative to the total weight of the grafted polymer).

[0121] Of course, as a further criterion, it is necessary to evaluate the individual properties of specific polymers and thereby rank each individual formulation in a specific field of application. Due to the wide range of uses of the polymers according to the invention, an exhaustive overview is not possible, but the description and the examples give guidance on how to prepare and select useful polymers with the desired properties and how to adjust the properties to the desired requirements. One such criterion in the field of home care, in particular in the field of fabric care, is of course its performance in the wash, e.g. subjecting certain materials showing stains of certain materials to a prescribed washing program.

[0122] The examples provide some guidance for fabric laundering applications, ie the general area of ​​fabric care.

[0123] Depending on the individual need for a polymer exhibiting a defined degree of biodegradability, water solubility, and viscosity (ie, handling properties), the general and specific teachings herein (not intended to be limited to the specific examples given) will guide how to obtain such polymers.

[0124] Another subject of the present invention is a process for preparing the graft polymers according to the invention as described above. In this process for obtaining at least one graft polymer according to the invention, at least one monomer (B1) and optionally N-vinylpyrrolidone as optional monomer (B2) are polymerized in the presence of at least one block copolymer backbone (A).

[0125] It has to be noted that such grafting methods, wherein a polymer backbone, such as a block copolymer backbone, is grafted with polymer side chains, are known per se to those skilled in the art.Any method known to those skilled in the art may be employed in the present invention.

[0126] In the process of the present invention, it is preferred that the polymer side chains (B) are obtained by free radical polymerization.

[0127] Free radical polymerization itself is also known to the person skilled in the art. The person skilled in the art also knows that the process according to the invention can be carried out in the presence of free radical forming initiators (C) and / or at least one solvent (D). The person skilled in the art knows the corresponding components themselves.

[0128] The term "free radical polymerization" as used in the context of the present invention includes besides free radical polymerization its variants, such as controlled radical polymerization. Suitable control mechanisms are RAFT, NMP or ATRP, each of which is known to the person skilled in the art, including suitable control agents.

[0129] Even more preferably, the process according to the invention is carried out by a process which comprises polymerizing at least one monomer (B1) chosen from vinyl acetate and other vinyl esters other than vinyl acetate in the presence of at least one block copolymer backbone (A), a free-radical forming initiator (C) and, if desired, up to 50% by weight, based on the sum of components (A), (B1), optionally (B2) and (C), of at least one organic solvent (D), at an average polymerization temperature at which the decomposition half-life of the initiator (C) is from 40 minutes to 500 minutes, so as to obtain the polymer side chains (B), with the proviso that the vinyl ester monomers (B1) comprise at least 50% of vinyl acetate, based on the weight of the B1 monomers, and optionally N-vinylpyrrolidone as an optional additional monomer (B2), in such a way that the fractions of unconverted grafting monomers (B1) and optionally (B2) and of initiator (C) in the reaction mixture are kept constantly in a quantitative deficit relative to the block copolymer backbone (A).

[0130] The amount of ((free) radical forming) initiators (C) is preferably from 0.1 to 5% by weight, in particular from 0.3 to 3.5% by weight, based in each case on the polymer side chains (B).

[0131] 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 grafted polymers with the desired low polydispersity can be prepared in a controlled manner.

[0132] 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.

[0133] According to the present invention, the (free radical forming) initiator (C) should have a decomposition half-life at the average polymerization temperature of 40 to 500 minutes, preferably 50 to 400 minutes and more preferably 60 to 300 minutes.

[0134] According to the invention, initiator (C) and grafting monomers (B2) and / or (B2) are advantageously added in such a way that a low and essentially constant concentration of undecomposed initiator and grafting monomers (B1) and / or (B2) is present in the reaction mixture. The proportion of undecomposed initiator in the overall reaction mixture, based on the total amount of initiator metered during the monomer addition, is preferably ≤15% by weight, in particular ≤10% by weight.

[0135] The average polymerization temperature is suitably in the range of 50°C to 140°C, preferably 60°C to 120°C and more preferably 65°C to 110°C.

[0136] Examples of suitable initiators (C) whose decomposition half-life in the temperature range of 50° C. to 140° C. is 20 minutes to 500 minutes are:

[0137] -Uncle-C 4 -C 12 -alkyl hydroperoxides and tert-(C 9 -C 12 -aralkyl) hydroperoxide OC 2 -C 12 - acylated derivatives such as tert-butyl peroxyacetate, tert-butyl monopermaleate, 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;

[0138] -Uncle-C 8 -C 14 -alkylene bisperoxide di-OC 4 -C 12 - acylated derivatives such as 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoyl-peroxy)hexane and 1,3-di(2-neodecanoylperoxyisopropyl)benzene;

[0139] -2(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;

[0140] -Peroxide (C 4 -C 12 -alkyl) carbonate tert-C 4 -C 5 - alkyl esters, such as tert-amyl peroxy(2-ethyl-hexyl)carbonate;

[0141] -Peroxydicarbonate (C 2 -C 12 -alkyl esters), such as di(n-butyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate.

[0142] Examples of particularly suitable initiators (C) are, depending on the average polymerization temperature:

[0143] - At an average polymerization temperature of 50°C to 60°C:

[0144] 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;

[0145] - At an average polymerization temperature of 60°C to 70°C:

[0146] tert-Butyl peroxypivalate, tert-Butyl peroxyneoheptanoate, tert-Butyl peroxyneodecanoate, tert-Amyl peroxypivalate, and di(2,4-dichlorobenzoyl)peroxide;

[0147] - At an average polymerization temperature of 70°C to 80°C:

[0148] 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-ethylhexylperoxy)hexane;

[0149] - At an average polymerization temperature of 80°C to 90°C:

[0150] 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;

[0151] - At an average polymerization temperature of 90°C to 100°C:

[0152] tert-Butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl monopermaleate, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, and di(4-methylbenzoyl)peroxide;

[0153] - At an average polymerization temperature of 100°C to 110°C:

[0154] tert-Butyl monopermaleate, tert-butyl peroxyisobutyrate, and tert-amyl peroxy(2-ethylhexyl)carbonate;

[0155] - At an average polymerization temperature of 110°C to 120°C:

[0156] tert-Butyl monoperoxymaleate, tert-butyl peroxy-3,5,5-trimethylhexanoate and tert-amyl peroxy (2-ethylhexyl) carbonate.

[0157] Preferred initiators (C) are tert-C 4 -C 5 -OC of alkyl hydroperoxide 4 -C 12 -acylated derivatives, particularly preferably tert-butyl peroxypivalate and tert-butyl peroxy-2-ethylhexanoate.

[0158] Particularly favorable polymerization conditions can be easily established by precisely adjusting 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 tert-butyl peroxy-2-ethylhexanoate, the preferred average polymerization temperature is 80° C. to 100° C.

[0159] The polymerization reaction of the present invention can be carried out in the presence of a preferably small amount of an organic solvent (D). Of course, mixtures of different solvents (D) can also be used. Preferably, a water-soluble or water-miscible solvent is used.

[0160] When solvents (D) are used as diluents, generally from 1 to 40% by weight, preferably from 1 to 35% by weight, more preferably from 1.5 to 30% by weight and most preferably from 2 to 25% by weight, based in each case on the sum of components (A), (B1), optionally (B2) and (C).

[0161] Examples of suitable solvents (D) include:

[0162] -monohydric alcohol, preferably aliphatic C 1 -C 16 - alcohol, more preferably aliphatic C 2 -C 12 - alcohol, most preferably C 2 -C 4 - alcohols such as ethanol, propanol, isopropanol, butanol, sec-butanol and tert-butanol;

[0163] - polyol, preferably C 2 -C 10 -diol, more preferably C 2 -C 6 -diol, most preferably C 2 -C 4 - alkylene glycols such as ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol;

[0164] -alkylene glycol ethers, preferably alkylene glycol mono(C 1 -C 12 -alkyl) ether and alkylene glycol 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 ethylene glycol monoethyl ether and propylene glycol monomethyl ether and propylene glycol monoethyl ether;

[0165] -polyalkylene glycol, preferably having 2 to 20 C 2 -C 4 -alkylene glycol units of poly (C 2 -C 4-alkylene) glycol, more preferably polyethylene glycol having 2-20 ethylene glycol units and polypropylene glycol having 2-10 propylene glycol units, most preferably polyethylene glycol having 2-15 ethylene glycol units and polypropylene glycol having 2-4 propylene glycol units, such as diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol;

[0166] - polyalkylene glycol monoethers, preferably poly(C 2 -C 4 -alkylene) glycol mono(C 1 -C 25 -alkyl) ethers, more preferably poly(C 2 -C 4 -alkylene) glycol mono(C 1 -C 20 -alkyl) ethers, most preferably poly(C 2 -C 3 -alkylene) glycol mono(C 1 -C 16 -alkyl) ether;

[0167] - carboxylic acid ester, preferably C 1 -C 6 -Carboxylic acid C 1 -C 8 -alkyl ester, more preferably C 1 -C 3 -Carboxylic acid C 1 -C 4 -alkyl esters, most preferably C 2 -C 3 -Carboxylic acid C 2 -C 4 - alkyl esters, such as ethyl acetate and ethyl propionate;

[0168] - aliphatic ketones preferably having 3 to 10 carbon atoms, such as acetone, methyl ethyl ketone, diethyl ketone and cyclohexanone;

[0169] - Cyclic ethers, especially tetrahydrofuran and dihydrofuran alkyl.

[0170] The 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 polymer product.

[0171] Preferred examples of these solvents are polyethylene glycol having 2 to 15 ethylene glycol units, polypropylene glycol having 2 to 6 propylene glycol units, and in particular C 6 -C 8- Alkoxylation products of alcohols (alkylene glycol monoalkyl ethers and polyalkylene glycol monoalkyl ethers).

[0172] Particularly preferred here are C 8 -C 16 - alkoxylation products of alcohols, which allow the formulation of polymer mixtures which flow freely at 40° C. to 70° C. and have a very low polymer content at relatively low viscosities. Branching may be present in the alkyl chain of the alcohol and / or in the polyalkoxylate portion (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 mol to 15 mol of ethylene oxide, C 2-hydroxy-1-hydroxy-2-propanediol alkoxylated with 1 mol to 15 mol of ethylene oxide and 1 mol to 3 mol of propylene oxide. 13 / C 15 Oxo alcohol or C 12 / C 14 or C 16 / C 18 Fatty alcohols, preferably 2-propyl-heptanol, are alkoxylated with 1 mol to 15 mol of ethylene oxide and 1 mol to 3 mol of propylene oxide.

[0173] In the process according to the invention, the block copolymer backbone (A), the graft monomers (B1) and, if appropriate, (B2), the initiator (C) and, if appropriate, the solvent (D) are generally heated in a reactor to the chosen average polymerization temperature.

[0174] According to the invention, the polymerization is carried out in such a way that an excess of polymer (block copolymer backbone (A) and formed graft polymer (B)) is constantly present in the reactor. The quantitative ratio of polymer to ungrafted monomer and initiator is generally ≥10:1, preferably ≥15:1, and more preferably ≥20:1.

[0175] The polymerization process according to the invention can in principle be carried out in various reactor types.

[0176] The reactor used is preferably a stirred tank, in which the block copolymer backbone (A) together with, if appropriate, portions of usually up to 15% by weight of the specific total amount of grafting monomers (B1) or (B2), initiator (C) and solvent (D), if appropriate, are first charged completely or partly and heated to the polymerization temperature, and the remaining amounts of (B), (C) and, if appropriate, (D) are metered in, preferably separately. The remaining amounts of (B), (C) and, if appropriate, (D) are preferably metered in over a period of ≥2 h, more preferably ≥4 h and most preferably ≥5 h.

[0177] In the case of the particularly preferred essentially solvent-free process variant, the entire amount of block copolymer backbone (A) is initially charged as a melt, and the grafting monomers (B1) and, if appropriate, (B2) and the initiator (C), preferably in the form of a 10% to 50% by weight solution in a solvent (D), are metered in, the temperature being controlled such that during the polymerization the selected average polymerization temperature is maintained in a range of, in particular, + / -10° C., in particular + / -5° C.

[0178] 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 to limit the viscosity of the reaction mixture. It is also possible to start metering the solvent only when the polymerization is subsequently carried out, or to add it in portions.

[0179] The polymerization can be carried out at standard pressure or at reduced or elevated pressure. When the boiling point of the monomers (B1) or (B2) or any diluent (D) used is exceeded at the pressure chosen, the polymerization is carried out with reflux cooling.

[0180] A further subject of the present invention is the use of at least one graft polymer as described above in laundry detergents, cleaning compositions and / or textile and home care products.

[0181] A further subject of the present invention is a textile and home care product comprising the above-described graft polymers. The product may be a laundry detergent, a dishwashing detergent, a cleaning composition and / or a textile and home care product containing at least one of the above-described graft polymers.

[0182] Laundry detergents, cleaning compositions and / or fabric and home care products are known per se to the person skilled in the art. Any compositions etc. known to the person skilled in the art in connection with the respective uses can be used in the context of the present invention.

[0183] Laundry detergents, cleaning compositions and / or fabric and home care products according to the present invention are preferred, wherein the at least one grafted polymer is present in an amount of from about 0.01% to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1% to about 10%, and most preferably from about 0.5% to about 5%, relative to the total weight of such composition or product.

[0184] Laundry detergent compositions: Suitable laundry detergent compositions include laundry detergent powder compositions, laundry detergent liquid compositions, laundry detergent gel compositions and water-soluble laundry detergent compositions.

[0185] Dishwashing Detergent Compositions: Suitable dishwashing detergent compositions include manual dishwashing detergent compositions and automatic dishwashing detergent compositions.

[0186] Surfactant system: The composition comprises a surfactant system in an amount sufficient to provide the desired cleaning properties. In some embodiments, the composition comprises from about 1% to about 70% of the surfactant system by weight of the composition. In other embodiments, the liquid composition comprises from about 2% to about 60% of the surfactant system by weight of the composition. In further embodiments, the composition comprises from about 5% to about 30% of the surfactant system by weight of the composition. The surfactant system may comprise a detersive surfactant selected from the following: anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, amphoteric electrolyte surfactants, and mixtures thereof. It will be understood by those of ordinary skill in the art that detersive surfactants encompass any surfactant or mixture of surfactants that provide cleaning, stain removal, or laundry benefits to soiled materials.

[0187] Anionic surfactants: In some examples, the surfactant system of the composition may include from about 1% to about 70% of one or more anionic surfactants by weight of the surfactant system. In other examples, the surfactant system of the composition may include from about 2% to about 60% of one or more anionic surfactants by weight of the surfactant system. In further examples, the surfactant system of the composition may include from about 5% to about 30% of one or more anionic surfactants by weight of the surfactant system. In further examples, the surfactant system may consist essentially of or even consist of one or more anionic surfactants.

[0188] Specific non-limiting examples of suitable anionic surfactants include any conventional anionic surfactants. This may include sulfate detersive surfactants (eg, alkoxylated and / or non-alkoxylated alkyl sulfate materials) and / or sulfonic acid detersive surfactants (eg, alkyl benzene sulfonates).

[0189] Other useful anionic surfactants can include the alkali metal salts of alkylbenzene sulfonic acids in either a straight chain (linear) or branched configuration wherein the alkyl group contains from about 9 to about 15 carbon atoms.

[0190] Suitable alkylbenzene sulfonates (LAS) can be obtained by sulfonating commercially available linear alkylbenzenes (LAB); suitable LABs include lower 2-phenyl LABs such as those sold under the trade name Those supplied by Sasol, or under the trade name Other suitable LABs include those supplied by Petresa, higher 2-phenyl LABs such as those sold under the trade name Those supplied by Sasol. Suitable anionic detersive surfactants are alkylbenzene sulfonates obtained by the DETAL catalyzed process, although other synthetic routes such as HF may also be suitable. In one aspect, the magnesium salt of LAS is used.

[0191] The detersive surfactant can be a mid-chain branched detersive surfactant, in one aspect, a mid-chain branched anionic detersive surfactant, in one aspect, a mid-chain branched alkyl sulfate and / or a mid-chain branched alkylbenzene sulfonate, such as a mid-chain branched alkyl sulfate. In one aspect, the mid-chain branch is C 1-4 Alkyl groups, typically methyl and / or ethyl groups.

[0192] Other anionic surfactants useful herein are the water-soluble salts of paraffin and secondary alkane sulfonates containing from about 8 to about 24 (and in some instances from about 12 to 18) carbon atoms; alkyl glyceryl ether sulfonates, especially C 8-18 Those ethers of alcohols (such as those derived from tallow and coconut oil). Mixtures of alkylbenzene sulfonates with the above-mentioned paraffin sulfonates, secondary alkane sulfonates and alkyl glyceryl ether sulfonates are also useful. Additional suitable anionic surfactants include methyl ester sulfonates and alkyl ether carboxylates.

[0193] Anionic surfactants can exist in acid form, and the acid form can be neutralized to form surfactant salts. Typical reagents for neutralization include alkaline metal counterions such as hydroxides, such as NaOH or KOH. Other suitable reagents for neutralizing the anionic surfactants in their acid form include ammonia, amines or alkanolamines. Non-limiting examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine and other linear or branched alkanolamines known in the art; Suitable alkanolamines include 2-amino-1-propanol, 1-aminopropanol, monoisopropanolamine or 1-amino-3-propanol. Amine neutralization can be completed in whole or in part, for example, a part of anionic surfactant mixture can be neutralized with sodium or potassium and a part of anionic surfactant mixture can be neutralized with amines or alkanolamines.

[0194] Nonionic surfactants: The surfactant system of the composition can include a nonionic surfactant. In some examples, the surfactant system includes up to about 25% of one or more nonionic surfactants, for example as a co-surfactant, by weight of the surfactant system. In some examples, the composition includes from about 0.1% to about 15% of one or more nonionic surfactants, by weight of the surfactant system. In other examples, the composition includes from about 0.3% to about 10% of one or more nonionic surfactants, by weight of the surfactant system.

[0195] Suitable nonionic surfactants for use herein may include any conventional nonionic surfactants. These may include, for example, alkoxylated fatty alcohols and amine oxide surfactants.

[0196] Other non-limiting examples of nonionic surfactants useful herein include: 8 -C 18 Alkyl ethoxylates, such as those from Shell Nonionic surfactant; C 6 -C 12 Alkylphenol alkoxylates, wherein the alkoxylate units may be ethyleneoxy units, propyleneoxy units, or mixtures thereof; C 12 -C 18 Alcohol and C 6 -C 12 Condensates of alkylphenols with ethylene oxide / propylene oxide block polymers, such as BASF C 14 -C 22 Medium chain branched alcohol (BA); C 14 -C 22 Mid-chain branched alkyl alkoxylate (BAE x ) ， wherein x is 1 to 30; alkyl polysaccharides; specifically alkyl polyglycosides; polyhydroxy fatty acid amides; and ether-terminated poly(alkoxylated) alcohol surfactants.

[0197] Suitable nonionic detersive surfactants also include alkyl polyglucosides and alkyl alkoxylated alcohols. Suitable nonionic surfactants also include those sold under the trade name BASF The ones that are sold.

[0198] Anionic / nonionic combinations: The surfactant system may include a combination of anionic and nonionic surfactant materials. In some examples, the weight ratio of anionic surfactant to nonionic surfactant is at least about 2:1. In other examples, the weight ratio of anionic surfactant to nonionic surfactant is at least about 5:1. In other examples, the weight ratio of anionic surfactant to nonionic surfactant is at least about 10:1.

[0199] Cationic surfactant: The surfactant system may include a cationic surfactant. In some aspects, the surfactant system includes from about 0% to about 7%, or from about 0.1% to about 5%, or from about 1% to about 4% of a cationic surfactant, for example as a co-surfactant, by weight of the surfactant system. In some aspects, the composition of the present invention is substantially free of cationic surfactants and surfactants that become cationic at a pH below 7 or a pH below 6. Non-limiting examples of cationic surfactants include: quaternary ammonium surfactants, which may have up to 26 carbon atoms, including: alkoxylated quaternary ammonium (AQA) surfactants; dimethylhydroxyethyl quaternary ammonium; dimethylhydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants; ester cationic surfactants; and amino surfactants, specifically amidopropyl dimethylamine (APA).

[0200] Suitable cationic detersive surfactants also include alkyl pyridines Compounds, alkyl quaternary ammonium compounds, alkyl quaternary Compounds, alkyl ternary sulfonium compounds, and mixtures thereof.

[0201] Zwitterionic surfactants: Examples of zwitterionic surfactants include: derivatives of secondary and tertiary amines; derivatives of heterocyclic secondary and tertiary amines; or quaternary ammonium, quaternary Or derivatives of tertiary sulfonium compounds. Betaines, including alkyl dimethyl betaine and coconut dimethyl amidopropyl betaine, C 8 To C 18 (For example, C 12 To C 18 ) amine oxides and sulfonates and hydroxybetaines, such as N-alkyl-N,N-dimethylamino-1-propane sulfonates, in which the alkyl group may be C 8 To C 18 , and in certain embodiments C 10 To C 14 .

[0202] Amphoteric surfactants: Examples of amphoteric surfactants include aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines, wherein the aliphatic group may be straight or branched, and wherein one of the aliphatic substituents contains at least about 8 carbon atoms, typically about 8 to about 18 carbon atoms, and at least one of the aliphatic substituents contains a water-solubilizing anionic group, such as carboxyl, sulfonate, sulfate. Examples of compounds falling within this definition are sodium 3-(dodecylamino) propionate, sodium 3-(dodecylamino) propane-1-sulfonate, sodium 2-(dodecylamino) ethyl sulfate, sodium 2-(dimethylamino) octadecanoate, sodium 3-(N-carboxymethyldodecylamino) propane 1-sulfonate, sodium octadecyl-iminodiacetate, 1-carboxymethyl-2-undecylimidazole, and N,N-bis(2-hydroxyethyl)-2-sulfato-3-dodecyloxypropylamine. Suitable amphoteric surfactants also include sarcosinates, glycinates, taurates, and mixtures thereof.

[0203] Branched surfactants: Suitable branched detersive surfactants include anionic branched surfactants selected from branched sulfate or branched sulfonate surfactants, for example, branched alkyl sulfates, branched alkyl alkoxylated sulfates and branched alkylbenzene sulfonates containing one or more random alkyl branches, for example C 1-4 Alkyl groups, typically methyl and / or ethyl groups.

[0204] The branched detersive surfactant can be a mid-chain branched detersive surfactant, typically a mid-chain branched anionic detersive surfactant, such as a mid-chain branched alkyl sulfate and / or a mid-chain branched alkylbenzene sulfonate. In some aspects, the detersive surfactant is a mid-chain branched alkyl sulfate. In some aspects, the mid-chain branch is C 1-4 Alkyl groups, typically methyl and / or ethyl groups.

[0205] Further suitable branched anionic detersive surfactants include surfactants derived from alcohols branched at the 2-alkyl position, such as those sold under the trade name 123. 125. 145. The oxo process is derived from those sold as 167. Due to the oxo process, the branches are located at the 2-alkyl position. These 2-alkyl branched alcohols are generally in the range of C11 to C14 / C15 in length and include structural isomers that are all branched at the 2-alkyl position.

[0206] Adjunct cleaning additives: The compositions of the present invention may also contain adjunct cleaning additives. Suitable adjunct cleaning additives include builders, structurants or thickeners, clay soil removal / anti-redeposition agents, polymeric detergents, polymeric dispersants, polymeric grease cleaners, enzymes, enzyme stabilization systems, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, dyes, hueing agents, dye transfer inhibitors, chelating agents, suds suppressors, softeners and perfumes.

[0207] Enzymes: The compositions described herein may include one or more enzymes that provide cleaning performance and / or fabric care benefits. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, melanases, β-glucanases, arabinanases, hyaluronidases, chondroitinases, laccases, and amylases, or mixtures thereof. A typical combination is an enzyme mixture that may include, for example, a protease and a lipase combined with an amylase. When present in the composition, the aforementioned additional enzymes may be present in an amount of about 0.00001% to about 2%, about 0.0001% to about 1%, or even about 0.001% to about 0.5% enzyme protein by weight of the composition.

[0208] In one aspect, preferred enzymes will include proteases. Suitable proteases include metalloproteases and serine proteases, serine proteases including neutral or alkaline microbial serine proteases, such as subtilisin (EC3.4.21.62). Suitable proteases include those of animal origin, plant origin, or microbial origin. In one aspect, such suitable proteases may be of microbial origin. Suitable proteases include chemically modified or genetically modified mutants of the aforementioned suitable proteases. In one aspect, suitable proteases may be serine proteases, such as alkaline microbial proteases or / and trypsin-type proteases. Examples of suitable neutral or alkaline proteases include:

[0209] (a) Subtilisins (EC 3.4.21.62), including those derived from Bacillus, such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus, and Bacillus gibsonii.

[0210] (b) Trypsin- or chymotrypsin-type proteases, such as trypsin (eg, of porcine or bovine origin), including the Fusarium protease and chymotrypsin derived from Cellumonas.

[0211] (c) Metalloproteases, including those derived from Bacillus amyloliquefaciens.

[0212] Preferred proteases include those derived from Bacillus gibberellus or Bacillus lentus.

[0213] Suitable commercially available proteases include those sold under the trade names Liquanase and Those sold by Novozymes A / S (Denmark) under the trade name Purafect Purafect and Purafect Those sold by Genencor International under the trade names and Those sold by Solvay Enzymes, those purchased from Henkel / Kemira, namely BLAP (having the following mutations S99D+S101 R+S103A+V104I+G159S, hereinafter referred to as BLAP), BLAP R (BLAP having S3T+V4I+V199M+V205I+L217D), BLAP X (BLAP having S3T+V4I+V205I) and BLAP F49 (BLAP having S3T+V4I+A194P+V199M+V205I+L217D) - all from Henkel / Kemira; and KAP (alkalophilic Bacillus subtilisin having mutations A230V+S256G+S259N) from Kao.

[0214] Suitable alpha-amylases include those derived from bacteria or fungi. Include chemically modified or genetically modified mutants (variants). Preferred alkaline alpha-amylases are derived from strains of the genus Bacillus, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis or other Bacillus, such as Bacillus NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375, DSM 12368, DSMZ No. 12649, KSM AP1378, KSM K36 or KSM K38.

[0215] Suitable commercially available α-amylases include TERMAMYL STAINZYME and (Novozymes A / S, Bagsvaerd, Denmark), AT 9000Biozym Biotech Trading GmbHWehlistrasse 27b A-1200Wien Austria, OPTISIZE HT and PURASTAR (Genencor International Inc., Palo Alto, California) and (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku Tokyo 103-8210, Japan). In one aspect, suitable amylases include and STAINZYME and mixtures thereof.

[0216] In one aspect, such enzymes can be selected from the group consisting of: lipases, including "first cycle lipases". In one aspect, the lipase is a first wash lipase, preferably a variant of a wild-type lipase from Thermomyces lanuginosus comprising one or more of the T231R and N233R mutations. The wild-type sequence is 269 amino acids (amino acids 23-291) with Swissprot accession number Swiss-Prot O59952 (derived from Thermomyces lanuginosus (Humicola lanuginosa)). Preferred lipases will include those sold under the trade name and Those that are sold.

[0217] In one aspect, other preferred enzymes include endoglucanases derived from microorganisms exhibiting endo-β-1,4-glucanase activity (EC 3.2.1.4) and mixtures thereof. Suitable endoglucanases are sold under the trade name and (Novozymes A / S, Bagsvaerd, Denmark).

[0218] Other preferred enzymes include those sold under the trade name Pectate lyases sold under the trade names (both from Novozymes A / S, Bagsvaerd, Denmark) and Mannanase sold by Genencor International Inc., Palo Alto, California.

[0219] Enzyme stabilization system: The enzyme-containing compositions described herein may optionally contain from about 0.001% to about 10%, in some examples from about 0.005% to about 8%, and in other examples from about 0.01% to about 6% of an enzyme stabilization system by weight of the composition. The enzyme stabilization system may be any stabilization system compatible with the detersive enzyme. In the case where the aqueous detergent composition contains a protease, a reversible protease inhibitor such as a boron compound (including borate esters), 4-formylphenylboronic acid, phenylboronic acid and their derivatives, or compounds such as calcium formate, sodium formate and 1,2-propylene glycol may be added to further improve stability.

[0220] Builder: The compositions of the present invention may optionally contain a builder. Building compositions typically contain at least about 1% builder, based on the total weight of the composition. Liquid compositions may contain up to about 10% builder, and in some examples up to about 8% builder, by weight of the composition. Granular compositions may contain up to about 30% builder, and in some examples up to about 5% builder, by weight of the composition.

[0221] Builders selected from aluminosilicates (e.g., zeolite builders, such as zeolite A, zeolite P, and zeolite MAP) and silicates help control mineral hardness in the wash water, especially calcium and / or magnesium, or help remove particulate dirt from the surface. Suitable builders can be selected from the group consisting of phosphates, such as polyphosphates (e.g., sodium tripolyphosphate), especially sodium salts thereof; carbonates, bicarbonates, sesquicarbonates, and carbonate minerals other than sodium carbonate or sodium sesquicarbonate; organic monocarboxylates, dicarboxylates, tricarboxylates, and tetracarboxylates, especially water-soluble non-surfactant carboxylates in the form of acid, sodium, potassium, or alkanolammonium salts, and oligomeric or water-soluble low molecular weight polymer carboxylates, including aliphatic and aromatic types; and phytic acid. These can be supplemented by borates (e.g., for pH buffering purposes) or by sulfates, especially sodium sulfate, and any other fillers or carriers (which may be important for engineering stable surfactants and / or builder-containing compositions). Other suitable builders can be selected from citric acid, lactic acid, fatty acids, polycarboxylate builders, such as copolymers of acrylic acid, copolymers of acrylic acid and maleic acid, and copolymers of acrylic acid and / or maleic acid with other suitable olefinic monomers having various types of additional functional groups. Also suitable for use as builders herein are synthetic crystalline ion exchange materials having a chain structure or their hydrates and compositions represented by the following general anhydride form: 2 O)·ySiO 2 zM'O, wherein M is Na and / or K, M' is Ca and / or Mg; y / x is 0.5 to 2.0; and z / x is 0.005 to 1.0.

[0222] Alternatively, the composition may be substantially free of builder.

[0223] Structuring agents / thickeners: Suitable structurants / thickeners include:

[0224] i. Dibenzylidene polyol acetal derivatives

[0225] ii. Bacterial cellulose

[0226] iii. Coated bacterial cellulose

[0227] iv. Non-BC-derived cellulose fibers

[0228] v. Non-polymeric crystalline hydroxyl functional materials

[0229] vi. Polymer structurants

[0230] vii. Diamide-based gelling agent

[0231] viii. Any combination of the above.

[0232] Polymeric dispersants: The composition may include one or more polymeric dispersants. Examples are carboxymethylcellulose, poly(vinyl pyrrolidone), poly(ethylene glycol), poly(vinyl alcohol), poly(vinyl pyridine-N-oxide), poly(vinylimidazole), polycarboxylates such as polyacrylates, maleic acid / acrylic acid copolymers, and lauryl methacrylate / acrylic acid copolymers.

[0233] The composition may include one or more amphiphilic cleaning polymers, such as compounds having the following general structure: Bis((C 2 H 5 O)(C 2 H 4 O)n)(CH 3 )-N + -C x H 2x -N + -(CH 3 )-bis((C 2 H 5 O)(C 2 H 4 O) n), wherein n = 20 to 30, and x = 3 to 8, or a sulfated or sulfonated variant thereof.

[0234] The compositions may comprise amphiphilic alkoxylated grease cleaning polymers having balanced hydrophilic and hydrophobic properties such that they remove grease particles from fabrics and surfaces. Specific embodiments of the amphiphilic alkoxylated grease cleaning polymers of the present invention comprise a core structure and a plurality of alkoxylate groups attached to the core structure. These may comprise alkoxylated polyalkyleneimines, such as polyalkyleneimines having polyethylene oxide inner blocks and polypropylene oxide outer blocks.

[0235] Alkoxylated polyamines can be used for grease and particle removal. Such compounds may include, but are not limited to, ethoxylated polyethyleneimine, ethoxylated hexamethylenediamine, and sulfated forms thereof. Polypropoxylated derivatives may also be included. Various amines and polyalkyleneimines may be alkoxylated to various degrees. A useful example is a 600 g / mol polyethyleneimine core, each NH of which is ethoxylated to 20 EO groups and is available from BASF.

[0236] The composition may include a random graft polymer having a hydrophilic backbone comprising monomers, for example, unsaturated C 1 -C 6 carboxylic acids, ethers, alcohols, aldehydes, ketones, esters, sugar units, alkoxy units, maleic anhydride, saturated polyols such as glycerol, and mixtures thereof; and one or more hydrophobic side chains, such as one or more C 4 -C 25 Alkyl groups, polypropylene, polybutylene, saturated C 1 -C 6 Vinyl esters of monocarboxylic acids, acrylic acid or methacrylic acid 1 -C 6 Alkyl esters, and mixtures thereof. Specific examples of such graft polymers are based on polyalkylene oxides and vinyl esters, in particular vinyl acetate. These polymers are usually prepared by polymerizing vinyl esters in the presence of polyalkylene oxides, the initiator used being dibenzoyl peroxide, dilauroyl peroxide or diacetyl peroxide.

[0237] The composition may include blocks of ethylene oxide and propylene oxide. Examples of such block polymers include ethylene oxide-propylene oxide-ethylene oxide (EO / PO / EO) triblock copolymers, wherein the copolymer comprises a first EO block, a second EO block, and a PO block, wherein the first EO block and the second EO block are connected to the PO block. Blocks of ethylene oxide, propylene oxide, and butylene oxide may also be arranged in other ways, such as (EO / PO) diblock copolymers, (PO / EO / PO) triblock copolymers. Block polymers may also contain additional butylene oxide (BO) blocks.

[0238] Carboxylate polymers - The compositions of the present invention may also include one or more carboxylate polymers, such as maleate / acrylate random copolymers or polyacrylate homopolymers. In one aspect, the carboxylate polymer is a polyacrylate homopolymer having a molecular weight of 4,000Da to 9,000Da, or 6,000Da to 9,000Da.

[0239] "Soil release polymer": The compositions described herein may comprise from about 0.01% to about 10.0%, typically from about 0.1% to about 5%, in some aspects from about 0.2% to about 3.0%, by weight of the composition, of a soil release polymer (also known as a polymeric soil release agent or "SRA").

[0240] Soil release polymers typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers (such as polyester and nylon) and have hydrophobic segments to deposit on the hydrophobic fibers and remain attached to them until the wash and rinse cycles are complete, thereby acting as an anchor for the hydrophilic segments. This can make stains that appear after treatment with a detergent easier to clean in a later wash cycle. It is also believed that promoting the release of soil helps improve or maintain the wicking properties of the fabric.

[0241] The structure and charge distribution of soil release polymers can be tailored for application to different fiber or textile types and for formulating different detergent or detergent additive products. Soil release polymers can be linear, branched or star-shaped.

[0242] Soil release polymers may also include various charged units (e.g., anionic or cationic units) and / or non-charged (e.g., nonionic) monomer units. In general, when SRPs are used in combination with cationic fabric conditioning actives such as quaternary ammonium ester compounds, nonionic SRPs may be particularly preferred in order to avoid potential negative interactions between the SRPs and the cationic actives.

[0243] The soil release polymers may contain end-capping moieties which are particularly effective in controlling the molecular weight of the polymer or altering the physical or surface active properties of the polymer.

[0244] One preferred class of suitable soil release polymers includes terephthalate derived polyester polymers comprising structural units (I) and / or (II):

[0245] (I)-[(OCHR 1 -CHR 2 ) a -O-OC-Ar-CO-] d

[0246] (II)-[(OCHR 3 -CHR 4 ) b -O-OC-sAr-CO-] e

[0247] in:

[0248] a, b are 1 to 200;

[0249] d, e are 1 to 50;

[0250] Ar is 1,4-substituted phenylene;

[0251] sAr is SO at position 5 3 M substituted 1,3-substituted phenylene;

[0252] M is a counterion selected from the group consisting of Na, Li, K, Mg / 2, Ca / 2, Al / 3, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium, or tetraalkylammonium, wherein the alkyl group is C 1 -C 18 Alkyl or C 2 -C 10 Hydroxyalkyl or mixtures thereof;

[0253] R 1 , R 2 , R 3 , R 4 Independently selected from H or C 1 -C 18 n-alkyl or isoalkyl;

[0254] Optionally, the polymer further comprises one or more terminal groups (III) derived from polyalkylene glycol monoalkyl ethers, preferably selected from the group consisting of structure (IV-a)

[0255] -O-[C 2 H 4 -O] c -[C 3 H 6 -O] d -[C 4 H 8 -O] e -R 7 (IV-a)

[0256] in:

[0257] R 7 C is a straight chain or branched chain 1-30 Alkyl, C 2 -C 30 alkenyl, or a cycloalkyl group having 5 to 9 carbon atoms, or C 8 -C 30 Aryl group, or C 6 -C 30 Arylalkyl group; preferably C 1-4 alkyl, more preferably methyl; and

[0258] c, d and e are numbers independently selected from 0 to 200 on a molar average basis, wherein the sum of c+d+e is 2 to 500,

[0259] The terminal group (IV-a) [C 2 H 4 -O]、[C 3 H 6 -O] and [C 4 H 8The [C-O] groups may be arranged in blocks, alternating, periodically and / or statistically, preferably in blocks and / or statistically. 2 H 4 -O]、[C 3 H 6 -O] and [C 4 H 8 Any of the -O] groups may be attached to the -R 7 and / or -O.

[0260] Optionally, the polymer further comprises one or more anionic end units (IV) and / or (V) as described in EP3222647, wherein M is a counterion selected from the group consisting of Na, Li, K, Mg / 2, Ca / 2, Al / 3, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium, wherein the alkyl group is C1-C18 alkyl or C2-C10 hydroxyalkyl or a mixture thereof.

[0261]

[0262] Optionally, the polymer may comprise cross-linked multifunctional structural units having at least three functional groups capable of undergoing esterification reactions. The functional groups may be, for example, acid-, alcohol-, ester-, anhydride- or epoxy groups.

[0263] Optionally, the polymer may contain other dicarboxylic acids or polycarboxylic acids or salts or (di)alkyl esters thereof which can be used in the polyester of the present invention, such as naphthalene-1,4-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, tetrahydrophthalic acid, trimellitic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, 2,5-furandicarboxylic acid, adipic acid, sebacic acid, decane-1,10-dicarboxylic acid, fumaric acid, succinic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexanediacetic acid, glutaric acid, azelaic acid or salts or (di)alkyl esters thereof, more preferably (C 1 -C 4 )-(di)alkyl esters, and more preferably (di)methyl esters thereof or mixtures thereof.

[0264] Preferably, suitable terephthalate derived soil release polymers are nonionic and do not comprise structure (II) above. Also particularly preferred nonionic terephthalate derived soil release polymers have a structure according to the formula:

[0265]

[0266] in:

[0267] R 5 and R 6 Independently selected from H or CH 3More preferably, R 5 and R 6 One of them is H and the other is CH 3 .

[0268] c, d are numbers independently selected from 0 to 200 based on the molar average, wherein the sum of c+d is 2 to 400,

[0269] More preferably, d is 0 to 50, c is 1 to 200,

[0270] More preferably, d is 1 to 10, c is 5 to 150,

[0271] R 7 C 1-4 alkyl, and more preferably methyl,

[0272] n is 1 to 50 based on the molar average value.

[0273] An example of a most preferred suitable terephthalate derived soil release polymer has R 5 and R 6 One of them is H and the other is CH 3 ; d is 0; c is 5-100 and R 7 It is methyl.

[0274] Suitable terephthalate derived soil release polymers may also be described as sulfonated and unsulfonated PET / POET (polyethylene terephthalate / polyoxyethylene terephthalate) polymers, both end-capped and un-end-capped. Examples of suitable soil release polymers include Polymers, including those supplied by Clariant SRA-100, SRA-300, SRN-100, SRN-170, SRN-240, SRN-260, SRN-300 and SRN-325.

[0275] Other suitable terephthalate derived soil release polymers are described in patents WO2014019903, WO2014019658 and WO2014019659.

[0276] Another class of soil release polymers also includes modified cellulose. Suitable modified cellulose may include nonionic modified cellulose derivatives such as cellulose alkyl ethers and cellulose hydroxyalkyl ethers. Examples of such cellulose alkyl ethers and cellulose hydroxyalkyl ethers include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose. In some embodiments, the modified cellulose may include C 4 or higher hydrocarbons, the preferred length of the alkyl group may be C 4, C 6 , C 8 , C 10 , C 12 , C 14 , C 16 , C 18 ; Examples of suitable modified celluloses are described in WO2019111948 and WO2019111949. In some embodiments, the modified cellulose may comprise additional cationic modifications, and examples of suitable modified celluloses with additional cationic modifications are described in WO2019111946 and WO2019111947.

[0277] Other examples of commercial soil release polymers are REPEL-O- series of polymers, including REPEL-O- SF, SF-2 and SRP6. Other suitable soil release polymers are Polymers, such as those supplied by Sasol SL, HSCB, L235MB and G82. Further suitable soil release polymers of different types include the commercially available materials ZELCON 5126 (from DuPont) and MILEASE T (from ICI), Sorez 100 (from ISP).

[0278] "Cellulosic polymer": The compositions described herein may comprise from about 0.1% to about 10%, typically from about 0.5% to about 7%, in some aspects from about 3% to about 5%, by weight of the composition, of a cellulosic polymer.

[0279] Suitable cellulose polymers include alkyl celluloses, alkyl alkoxyalkyl celluloses, carboxyalkyl celluloses and alkyl carboxyalkyl celluloses. In some aspects, the cellulose polymer is selected from carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose or mixtures thereof. In some aspects, the cellulose polymer is a carboxymethyl cellulose having a carboxymethyl degree of substitution of about 0.5 to about 0.9 and a molecular weight of about 100,000Da to about 300,000Da.

[0280] Carboxymethyl cellulose polymers include GDA (sold by CP Kelko), hydrophobically modified carboxymethyl cellulose, for example, sold under the trade name Alkyl ketene dimer derivative of carboxymethyl cellulose sold as SH1 (CP Kelko), or under the trade name A segmented carboxymethyl cellulose sold as Segmented Carboxymethyl Cellulose V (sold by CP Kelko).

[0281] Additional amines: Additional amines can be used in the compositions described herein to increase the removal of grease and particulates from soiled materials. The compositions described herein can contain from about 0.1% to about 10%, in some examples from about 0.1% to about 4%, and in other examples from about 0.1% to about 2% of the additional amine by weight of the composition. Non-limiting examples of additional amines can include, but are not limited to, polyamines, oligoamines, triamines, diamines, pentamines, tetraamines, or combinations thereof. Specific examples of suitable additional amines include tetraethylenepentamine, triethylenetetramine, diethylenetriamine, or mixtures thereof.

[0282] For example, alkoxylated polyamines can be used for grease and particle removal. Such compounds may include, but are not limited to, ethoxylated polyethyleneimine, ethoxylated hexamethylenediamine, and their sulfated forms. Polypropoxylated derivatives may also be included. Various amines and polyalkyleneimines may be alkoxylated to various degrees. A useful example is a 600 g / mol polyethyleneimine core, each NH of which is ethoxylated to 20 EO groups and is available from BASF. Compositions described herein may include about 0.1% to about 10% by weight of the composition, and about 0.1% to about 8% in some examples, and about 0.1% to about 6% of alkoxylated polyamines in other examples.

[0283] Alkoxylated polycarboxylates can also be used in the compositions herein to provide grease removal. Chemically, these materials comprise polyacrylates having one ethoxy side chain for every 7-8 acrylate units. The side chains have the formula -(CH 2 CH 2 O) m (CH 2 ) n CH 3 , wherein m is 2 to 3, and n is 6 to 12. The side chain esters are attached to the polyacrylate "backbone" to provide a "comb-type" polymer structure. The molecular weight may vary, but may range from about 2000 to about 50,000. The compositions described herein may contain from about 0.1% to about 10%, and in some examples from about 0.25% to about 5%, and in other examples from about 0.3% to about 2%, of the alkoxylated polycarboxylate, by weight of the composition.

[0284] Bleaching compounds, bleaching agents, bleach activators and bleach catalysts: The compositions described herein may contain a bleaching agent or a bleaching composition containing a bleaching agent and one or more bleach activators. The bleaching agent may be present at a level of about 1% to about 30%, and in some examples about 5% to about 20%, based on the total weight of the composition. If present, the amount of the bleach activator may be from about 0.1% to about 60%, and in some examples about 0.5% to about 40%, of the bleaching composition, which contains the bleaching agent plus the bleach activator.

[0285] Examples of bleaching agents include oxygen bleaches, perborate bleaches, percarboxylic acid bleaches and their salts, peroxygen bleaches, persulfate bleaches, percarbonate bleaches, and mixtures thereof.

[0286] In some examples, the composition may further include a transition metal bleach catalyst.

[0287] Bleaching agents other than oxygen bleaching agents are also known in the art and can be used in the composition. They include, for example, photoactivated bleaching agents, or preformed organic peracids such as peroxycarboxylic acids or salts thereof, or peroxysulfonic acids or salts thereof. A suitable organic peracid is phthalimidoperoxycaproic acid. If used, the compositions described herein will typically contain from about 0.025% to about 1.25% of such bleaching agents by weight of the composition, and in some examples include sulfonated zinc phthalocyanine.

[0288] Brighteners: Optical brighteners or other brighteners or whitening agents may be incorporated into the compositions described herein at a level of from about 0.01% to about 1.2% by weight of the composition. Commercial brighteners useful herein can be classified into subclasses which include, but are not necessarily limited to, stilbenes, pyrazolines, coumarins, benzophenones, Azoles, carboxylic acids, methine anthocyanins, 5,5-dibenzothiophene dioxide, oxazoles, derivatives of 5- and 6-membered heterocycles, and other miscellaneous reagents.

[0289] In some examples, the fluorescent brightener is selected from the group consisting of: disodium 4,4'-bis{[4-phenylamino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbene disulfonate (brightener 15, commercially available under the trade name Tinopal AMS-GX from Ciba Geigy Corporation), disodium 4,4'-bis{[4-phenylamino-6-(N-2-bis-hydroxyethyl)-s-triazin-2-yl]-amino}-2,2'-stilbene disulfonate (commercially available under the trade name Tinopal UNPA-GX from Ciba-Geigy Corporation), disodium 4,4'-bis{[4-phenylamino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl]-amino}-2,2'-stilbene disulfonate (commercially available under the trade name Tinopal 4-Phenylethyl)-s-triazin-2-yl 5BM-GX is commercially available from Ciba-Geigy Corporation). More preferably, the fluorescent whitening agent is disodium 4,4'-bis{[4-phenylamino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbene disulfonate.

[0290] The brightener may be added in granular form or as a premix with a suitable solvent (eg nonionic surfactant, monoethanolamine, propylene glycol).

[0291] Fabric hueing agent: The composition may include a fabric hueing agent (sometimes referred to as a coloring agent, bluing agent or whitening agent). Hueing agents typically provide a blue or purple hue to the fabric. Hueing agents can be used alone or in combination to produce a specific hue shade and / or to shade different fabric types. This can be provided, for example, by mixing red and cyan dyes to produce a blue or purple hue. Hueing agents can be selected from dyes of any known chemical class, including but not limited to acridines, anthraquinones (including polycyclic quinones), azine, azo (e.g., monoazo, disazo, triazo, tetrakis azo, polyazo), including premetallated azo, benzodifurans and benzodifuranones, carotenoids, coumarins, cyanines, diaza hemicyanines, diphenylmethanes, formazans, hemicyanines, indigos, methanes, naphthylimides, naphthoquinones, nitro and nitroso, oxadiazine, phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthene and mixtures thereof.

[0292] Dye transfer inhibitors: The composition may also include one or more materials effective to inhibit the transfer of dyes from one fabric to another during the cleaning process. Generally, such dye transfer inhibitors may include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinyl pyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase, and mixtures thereof. If used, these agents may be used at a concentration of about 0.0001% to about 10% by weight of the composition, in some examples about 0.01% to about 5% by weight of the composition, and in other examples about 0.05% to about 2% by weight of the composition.

[0293] Chelating agents: The compositions described herein may also include one or more metal ion chelating agents. Suitable molecules include copper, iron and / or manganese chelating agents, and mixtures thereof. Such chelating agents may be selected from the group consisting of phosphonates, aminocarboxylates, aminophosphonates, succinates, polyfunctionally substituted aromatic chelating agents, 2-hydroxypyridine-N-oxide compounds, hydroxamic acids, carboxymethyl inulin, and mixtures thereof. Chelating agents may exist in acid or salt form, including alkali metal salts, ammonium salts, and substituted ammonium salts thereof, and mixtures thereof.

[0294] The chelating agent may be present in the compositions disclosed herein at about 0.005 wt % to about 15 wt %, about 0.01 wt % to about 5 wt %, about 0.1 wt % to about 3.0 wt %, or about 0.2 wt % to about 0.7 wt %, or about 0.3 wt % to about 0.6 wt %, by weight of the composition.

[0295] Aminocarboxylates useful as chelating agents include, but are not limited to, ethylenediaminetetraacetate (EDTA); N-(hydroxyethyl)ethylenediaminetriacetate (HEDTA); nitrilotriacetate (NTA); ethylenediaminetetrapropionate; triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate (DTPA); methylglycine diacetic acid (MGDA); glutamic acid diacetic acid (GLDA); ethanol diglycine; triethylenetetraaminehexaacetic acid (TTHA); N-hydroxyethyliminodiacetic acid (HEIDA); dihydroxyethylglycine (DHEG); ethylenediaminetetrapropionic acid (EDTP) and derivatives thereof.

[0296] Encapsulate: The composition can comprise an encapsulate. In some aspects, the encapsulate comprises a core, a shell having an inner surface and an outer surface, wherein the shell encapsulates the core.

[0297] In some aspects, the encapsulate comprises a core and a shell, wherein the core comprises a material selected from: spices; whitening agents; dyes; insect repellents; silicones; waxes; flavors; vitamins; fabric softeners; skin care agents, such as alkanes; enzymes; antimicrobials; bleaching agents; sensory agents; or mixtures thereof; and wherein the shell comprises a material selected from: polyethylene; polyamides; polyvinyl alcohol, optionally including other comonomers; polystyrene; polyisoprene; polycarbonates; polyesters; polyacrylates; polyolefins; polysaccharides, such as alginate and / or chitosan; gelatin; shellac; epoxy resins; vinyl polymers; water-insoluble inorganics; silicones; aminoplasts, or mixtures thereof. In some aspects, in the case where the shell comprises aminoplasts, the aminoplasts comprise polyureas, polyurethanes and / or polyureaurethanes. Polyureas may include polyoxymethylene ureas and / or melamine formaldehyde.

[0298] Fabric and home care products are generally intended for: (a) the care of finished textiles, cleaning of finished textiles, sanitization of finished textiles, disinfection of finished textiles, detergents, stain removers, softeners, fabric enhancers, stain removal or finished textile treatment, pre- and post-wash treatment, washing machine cleaning and maintenance, where finished textiles are intended to include garments and articles made of fabric; (b) the care of dishes, glasses, crockery, cooking pots, pans, utensils, cutlery etc. in automatic, in-machine washing, including detergents for dishwashers, the water used and its contents, post-primary treatment and machine cleaning and maintenance products; or (c) detergents for hand dishwashing.

[0299] Fabric and home care products typically contain additional fabric and home care ingredients, such as those described in more detail above.

[0300] Liquid laundry detergent composition. The fabric and home care product can be a laundry detergent composition, such as a liquid laundry detergent composition. Suitable liquid laundry detergent compositions can contain a non-soap surfactant, wherein the non-soap surfactant includes an anionic non-soap surfactant and a non-ionic surfactant. The laundry detergent composition can contain 10% to 60%, or 20% to 55% of a non-soap surfactant by weight of the laundry detergent composition. The non-soap anionic surfactant to non-ionic surfactant is 1:1 to 20:1, 1.5:1 to 17.5:1, 2:1 to 15:1, or 2.5:1 to 13:1. Suitable non-soap anionic surfactants include linear alkylbenzene sulfonates, alkyl sulfates, or mixtures thereof. The weight ratio of linear alkylbenzene sulfonates to alkyl sulfates can be 1:2 to 9:1, 1:1 to 7:1, 1:1 to 5:1, or 1:1 to 4:1. Suitable linear alkylbenzene sulfonates are C 10 -C 16 Alkylbenzene sulfonic acid, or C 11 -C 14 Alkylbenzene sulfonic acid. Suitable alkyl sulfate anionic surfactants include alkoxylated alkyl sulfates, non-alkoxylated alkyl sulfates, and mixtures thereof. Preferably, the HLAS surfactant comprises greater than 50% C 12 , preferably greater than 60%, preferably greater than 70% C 12 , more preferably greater than 75% C 12 . Suitable alkoxylated alkyl sulfate anionic surfactants include ethoxylated alkyl sulfate anionic surfactants. Suitable alkyl sulfate anionic surfactants include ethoxylated alkyl sulfate anionic surfactants, the molar average ethoxylation degree of the ethoxylated alkyl sulfate anionic surfactant is 1 to 5, 1 to 3 or 2 to 3. Alkyl alkoxylated sulfates can have a broad alkoxy distribution or a peak alkoxy distribution. The alkyl portion of AES may include an average of 13.7 to about 16 or 13.9 to 14.6 carbon atoms. At least about 50% or at least about 60% of the AES molecules may include an alkyl portion having 14 or more carbon atoms, preferably 14 to 18, or 14 to 17, or 14 to 16, or 14 to 15 carbon atoms. The alkyl sulfate anionic surfactant may include non-ethoxylated alkyl sulfates and ethoxylated alkyl sulfates, wherein the molar average ethoxylation degree of the ethoxylated alkyl sulfate is 1 to 5, 1 to 3 or 2 to 3. The alkyl portion of the alkyl sulfate anionic surfactant may be derived from a fatty alcohol, an oxo alcohol, a Guerbet alcohol or a mixture thereof. Preferred alkyl sulfates include optionally ethoxylated alcohol sulfates including 2-alkyl branched primary alcohol sulfates, especially 2-branched C 12-15 Primary alcohol sulfates, linear primary alcohol sulfates, especially linear C 12-14Primary alcohol sulfates, and mixtures thereof.The laundry detergent composition may comprise from 10% to 50%, or from 15% to 45%, or from 20% to 40%, or from 30% to 40%, by weight of the laundry detergent composition, of a non-soap anionic surfactant.

[0301] Suitable nonionic surfactants may be selected from broad or narrow range alcohol alkoxylates, oxo alcohol alkoxylates, Guerbet alcohol alkoxylates, alkylphenol alcohol alkoxylates or mixtures thereof. The laundry detergent composition may comprise from 0.01% to 10%, from 0.01% to 8%, from 0.1% to 6%, or from 0.15% to 5% of a nonionic surfactant by weight of the liquid laundry detergent composition.

[0302] The laundry detergent composition comprises from 1.5% to 20%, or from 2% to 15%, or from 3% to 10%, or from 4% to 8% soap, such as a fatty acid salt, by weight of the laundry detergent composition. Such soaps may be amine neutralized, for example using an alkanolamine such as monoethanolamine.

[0303] The laundry detergent composition may comprise adjunct ingredients selected from the group comprising: builders including citrates, enzymes, bleaches, bleach catalysts, dyes, hueing dyes, leuco dyes, brighteners, cleaning polymers including alkoxylated polyamines and polyethyleneimines, amphiphilic copolymers, soil release polymers, surfactants, solvents, dye transfer inhibitors, chelating agents, diamines, perfumes, encapsulated perfumes, polycarboxylates, structurants, pH modifiers, antioxidants, antibacterial agents, antimicrobial agents, preservatives and mixtures thereof.

[0304] The laundry detergent composition may have a pH of from 2 to 11, or from 6.5 to 8.9, or from 7 to 8, wherein the pH of the laundry detergent composition is measured at a product concentration of 10% in deionized water at 20°C.

[0305] Liquid laundry detergent compositions may be Newtonian or non-Newtonian, preferably non-Newtonian.

[0306] For liquid laundry detergent compositions, the composition may comprise from 5% to 99%, or from 15% to 90%, or from 25% to 80% water by weight of the liquid detergent composition.

[0307] The detergent composition according to the present invention may be a liquid laundry detergent composition. The following are exemplary liquid laundry detergent formulations. Preferably, the liquid laundry detergent composition comprises between 0.1% and 4.0%, preferably between 0.5% and 3%, more preferably between 1% and 2.5% of the sulfated esteramine according to the present invention based on the weight of the laundry treatment composition.

[0308] Table 1

[0309]

[0310]

[0311] Description of superscript number:

[0312] 1 C12-15EO2.5S alkyl ethoxy sulfate, wherein the alkyl portion of AES contains from about 13.9 to 14.6 carbon atoms.

[0313] 2PE-20, commercially available from BASF

[0314] 3 nuclease as claimed in co-pending European patent application 19219568.3

[0315] 4 Antioxidant 1 is 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid, methyl ester [6386-38-5]

[0316] 5 Antioxidant 2 is Tinogard TS commercially available from BASF

[0317] 6 Sanitizer is Tinosan HP 100 agent commercially available from BASF

[0318] 7 Defoamer blend provided by Dow Corning 80%-92% ethylmethyl, methyl (2-phenylpropyl) siloxane; 5%-14% MQ resin in octyl stearate, 3%-7% modified silica.

[0319] 8. The fluorescent whitening agent is disodium 4,4'-bis{[4-anilino-6-morpholino-s-triazine-2-yl]-amino}-2,2'-stilbene disulfonate or disodium 2,2'-([1,1'-biphenyl]-4,4'-diyldi-2,1-ethylenediyl)bisbenzenesulfonate.

[0320] Water-soluble unit dose products .

[0321] Fabric and home care products can be water-soluble unit dose articles. The water-soluble unit dose article comprises at least one water-soluble film oriented to produce at least one unit dose internal compartment, wherein the at least one unit dose internal compartment comprises a detergent composition. The water-soluble film preferably comprises a polyvinyl alcohol homopolymer or a polyvinyl alcohol copolymer, such as a blend of a polyvinyl alcohol homopolymer and / or a polyvinyl alcohol copolymer, such as a copolymer selected from sulfonated and carboxylated anionic polyvinyl alcohol copolymers, particularly carboxylated anionic polyvinyl alcohol copolymers, such as a blend of a polyvinyl alcohol homopolymer and a carboxylated anionic polyvinyl alcohol copolymer. In some examples, the water-soluble film is those supplied by Monosol with trade references M8630, M8900, M8779, M8310. The detergent product comprises a detergent composition, more preferably a laundry detergent composition. Preferably, the laundry detergent composition encapsulated in the water-soluble unit dose article comprises 0.1% to 8%, preferably 0.5% to 7%, more preferably 1.0% to 6.0% of the sulfated esteramine of the present invention, by weight of the detergent composition. Preferably, the soluble unit dose laundry detergent composition comprises a non-soap surfactant, wherein the non-soap surfactant includes an anionic non-soap surfactant and a non-ionic surfactant. Preferably, the laundry detergent composition comprises between 10% and 60% or between 20% and 55% of a non-soap surfactant by weight of the laundry detergent composition. The weight ratio of the non-soap anionic surfactant to the non-ionic surfactant is preferably 1:1 to 20:1, 1.5:1 to 17.5:1, 2:1 to 15:1, or 2.5:1 to 13:1. The non-soap anionic surfactant preferably comprises a linear alkylbenzene sulfonate, an alkyl sulfate, or a mixture thereof. The weight ratio of the linear alkylbenzene sulfonate to the alkyl sulfate is preferably 1:2 to 9:1, 1:1 to 7:1, 1:1 to 5:1, or 1:1 to 4:1. Exemplary linear alkylbenzene sulfonates are C 10 -C 16 Alkylbenzene sulfonic acid, or C 11 -C 14Alkylbenzene sulfonic acid. By "linear" herein is meant that the alkyl group is linear. Exemplary alkyl sulfate anionic surfactants may comprise alkoxylated alkyl sulfates or non-alkoxylated alkyl sulfates or mixtures thereof. Exemplary alkoxylated alkyl sulfate anionic surfactants include ethoxylated alkyl sulfate anionic surfactants. Exemplary alkyl sulfate anionic surfactants may comprise ethoxylated alkyl sulfate anionic surfactants having a molar average ethoxylation degree of 1 to 5, 1 to 3, or 2 to 3. Exemplary alkyl sulfate anionic surfactants may comprise non-ethoxylated alkyl sulfates and ethoxylated alkyl sulfates, wherein the molar average ethoxylation degree of the ethoxylated alkyl sulfates is 1 to 5, 1 to 3, or 2 to 3. The alkyl fraction of the exemplary alkyl sulfate anionic surfactant is derived from a fatty alcohol, an oxo alcohol, a Guerbet alcohol, or a mixture thereof. Preferably, the laundry detergent composition comprises between 10% and 50%, between 15% and 45%, between 20% and 40%, or between 30% and 40% of a non-soap anionic surfactant by weight of the laundry detergent composition. In some examples, the non-ionic surfactant is selected from an alcohol alkoxylate, an oxo alcohol alkoxylate, a Guerbet alcohol alkoxylate, an alkylphenol alcohol alkoxylate, or a mixture thereof. Preferably, the laundry detergent composition comprises between 0.01% and 10%, or between 0.01% and 8%, or between 0.1% and 6%, or between 0.15% and 5% of a non-ionic surfactant by weight of the liquid laundry detergent composition. In some examples, the laundry detergent composition comprises between 1.5% and 20%, between 2% and 15%, between 3% and 10%, or between 4% and 8% soap, in some examples a fatty acid salt, in some examples an amine-neutralized fatty acid salt, wherein in some examples the amine is an alkanolamine, preferably monoethanolamine. Preferably, the liquid laundry detergent composition comprises less than 15% or less than 12% water by weight of the liquid laundry detergent composition. Preferably, the laundry detergent composition comprises 10% to 40%, or 15% to 30% of a non-aqueous solvent selected from 1,2-propylene glycol, dipropylene glycol, tripropylene glycol, glycerol, sorbitol, polyethylene glycol, or a mixture thereof, by weight of the liquid laundry detergent composition. Preferably, the liquid laundry detergent composition comprises from 0.1% to 10%, preferably from 0.5% to 8%, by weight of the detergent composition, of an additional soil release polymer, preferably selected from the group consisting of: nonionic and / or anionic modified polyester terephthalate soil release polymers, such as those available from Clariant under the Texcare trademark; amphiphilic graft polymers, such as those based on polyalkylene oxides and vinyl esters; polyalkoxylated polyethyleneimines; and mixtures thereof.Preferably, the liquid detergent composition also comprises 0.1% to 10%, preferably 1% to 5% of a chelating agent. In some examples, the laundry detergent composition comprises an auxiliary ingredient selected from the group comprising the following: a builder including citrate, an enzyme, a bleach, a bleach catalyst, a dye, a hueing dye, a brightener, a cleaning polymer including (zwitterionic) alkoxylated polyamines, a surfactant, a solvent, a dye transfer inhibitor, a perfume, an encapsulated perfume, a polycarboxylate, a structurant, a pH trimmer, and a mixture thereof. Preferably, the laundry detergent composition has a pH between 6 and 10, between 6.5 and 8.9, or between 7 and 8, wherein the pH of the laundry detergent composition is measured at a product concentration of 10% in deionized water at 20°C. When the laundry detergent composition is liquid, the laundry detergent composition can be Newtonian or non-Newtonian, preferably non-Newtonian.

[0322] The following is an exemplary water-soluble unit dose formulation. The composition may be part of a single compartment water-soluble unit dose product, or may be separated over multiple compartments to obtain a complete product composition that is less than the "average across compartments." The composition is encapsulated in a water-soluble material based on polyvinyl alcohol, which comprises a blend of a polyvinyl alcohol homopolymer and an anion (e.g., a carboxylated polyvinyl alcohol copolymer).

[0323] Table 2

[0324] <![CDATA[ Element ]]> Comparative 4 (weight %) <![CDATA[Fatty alcohol ethoxylate nonionic surfactant, C 12-14 with an average ethoxylation degree of 7]]> 3.8 Lutensol XL100 0.5 <![CDATA[Linear C 11-14 alkylbenzenesulfonate]]> 24.6 AE3S ethoxylated alkyl sulfate, average degree of ethoxylation 3 12.5 Citric acid 0.7 Palm Kernel Fatty Acid 5.3 Nuclease* (Active protein wt%) 0.01 Protease (Active Protein Weight %) 0.07 Amylase (Active Protein Weight %) 0.005 Xyloglucanase (active protein weight %) 0.005 Mannanase (Active Protein wt%) 0.003 Ethoxylated polyethyleneimine (Lutensol FP620-PEI600EO20) 1.4 Amphiphilic graft copolymers** 1.6 Zwitterionic polyamine (Lutensit Z96) 1.5 Anionic polyester terephthalate (Texcare SRA300) 0.6 The graft polymer of the present invention 3.0 HEDP 2.2 Brightener 49 0.4 Silicone defoamer 0.3 Color dye 0.05 1,2-Propanediol 11.0 glycerin 4.7 DPG (Dipropylene Glycol) 1.7 TPG (Tripropylene glycol) 0.1 Sorbitol 0.1 Monoethanolamine 10.2 <![CDATA[K 2 SO 3 ]]> 0.4 <![CDATA[MgCl 2 ]]> 0.3 water 10.5 Hydrogenated castor oil 0.1 spices 2.1 Aesthetic dyes and trace components Remaining to 100 pH (10% product concentration in deionized water at 20°C) 7.4

[0325] Description of superscript:

[0326] *Nuclease as claimed in co-pending European patent application 19219568.3 **Polyethylene glycol grafted polymers comprising a polyethylene glycol backbone (Pluriol E6000) and hydrophobic vinyl acetate side chains, a polymer system comprising 40 wt% of the polyethylene glycol backbone polymer and 60 wt% of the grafted vinyl acetate side chains

[0327] Hand dishwashing liquid composition .

[0328] The fabric and home care product may be a dishwashing detergent composition, such as a hand dishwashing detergent composition, more preferably a liquid hand dishwashing detergent composition. Preferably, the liquid hand dishwashing detergent composition comprises from 0.1% to 5.0%, preferably from 0.5% to 4%, more preferably from 1.0% to 3.0% of the sulfated esteramine of the present invention by weight of the detergent composition. The liquid hand dishwashing detergent composition is preferably an aqueous composition comprising from 50% to 90%, preferably from 60% to 75% water by weight of the total composition. Preferably, the pH of the detergent composition of the present invention (measured as 10% product concentration in demineralized water at 20°C) is adjusted to between 3 and 14, more preferably between 4 and 13, more preferably between 6 and 12, and most preferably between 8 and 10. The composition of the present invention may be Newtonian or non-Newtonian, preferably Newtonian. Preferably, the composition has a viscosity of 10 to 10,000 mPa s, preferably 100 to 5,000 mPa s, more preferably 300 to 2,000 mPa s, or most preferably 500 to 1,500 mPa s, or a combination thereof. The viscosity is measured at 20°C using a Brookfield RT viscometer using a No. 31 spindle, wherein the RPM of the viscometer is adjusted to achieve a torque between 40% and 60%.

[0329] The composition comprises from 5% to 50%, preferably from 8% to 45%, more preferably from 15% to 40% of the surfactant system by weight of the total composition. The surfactant system preferably comprises from 60% to 90%, more preferably from 70% to 80% of anionic surfactant by weight of the surfactant system. Alkyl sulfated anionic surfactants are preferred, in particular those selected from the group consisting of alkyl sulfates, alkyl alkoxy sulfates, preferably alkyl ethoxy sulfates and mixtures thereof. The alkyl sulfated anionic surfactants preferably have an average alkyl chain length of 8 to 18, preferably 10 to 14, more preferably 12 to 14, most preferably 12 to 13 carbon atoms. The alkyl sulfated anionic surfactants preferably have an average degree of alkoxylation, preferably ethoxylation, of less than 5, preferably less than 3, more preferably from 0.5 to 2.0, most preferably from 0.5 to 0.9. The alkyl sulfate anionic surfactants preferably have a weight average branching degree of more than 10%, preferably more than 20%, more preferably more than 30%, even more preferably between 30% and 60%, most preferably between 30% and 50%. Suitable counterions include alkali metal cations, alkaline earth metal cations, alkanolammonium or ammonium or substituted ammonium, but sodium is preferred. Suitable examples of commercially available alkyl sulfate anionic surfactants include those marketed by Shell under the trade name Those derived from alcohols sold by Sasol under the trade name and Those sold by , or some natural alcohols produced by The Procter & Gamble Chemicals company.

[0330] The surfactant system preferably comprises 0.1% to 20%, more preferably 0.5% to 15%, and especially 2% to 10% of a co-surfactant by weight of the liquid hand dishwashing detergent composition. Preferred co-surfactants are selected from the group consisting of amphoteric surfactants, zwitterionic surfactants and mixtures thereof. The weight ratio of anionic surfactant to co-surfactant may be from 1:1 to 8:1, preferably from 2:1 to 5:1, more preferably from 2.5:1 to 4:1. Co-surfactants are preferably amphoteric surfactants, more preferably amine oxide surfactants. Preferably, the amine oxide surfactant is selected from the group consisting of alkyl dimethyl amine oxides, alkyl amidopropyl dimethyl amine oxides and mixtures thereof, most preferably C12-C14 alkyl dimethyl amine oxides. Suitable zwitterionic surfactants include betaine surfactants, preferably cocamidopropyl betaine.

[0331] Preferably, the surfactant system of the composition of the present invention further comprises from 1% to 25%, preferably from 1.25% to 20%, more preferably from 1.5% to 15%, most preferably from 1.5% to 5% of a nonionic surfactant by weight of the surfactant system. Suitable nonionic surfactants may be selected from the group consisting of alkoxylated nonionic surfactants, alkyl polyglucoside ("APG") surfactants and mixtures thereof. Suitable alkoxylated nonionic surfactants may be linear or branched, primary alkyl alkoxylated or secondary alkyl alkoxylated, preferably alkyl ethoxylated nonionic surfactants, containing an average of 9 to 15, preferably 10 to 14 carbon atoms in their alkyl chain and an average of 5 to 12, preferably 6 to 10, most preferably 7 to 8 ethylene oxide units per mole of alcohol. Most preferably, the alkyl polyglucoside surfactant has an average alkyl carbon chain length of 10 to 16, preferably between 10 and 14, most preferably between 12 and 14, with an average degree of polymerization of between 0.5 and 2.5, preferably between 1 and 2, most preferably between 1.2 and 1.6. C8-C16 alkyl polyglucosides are commercially available from several suppliers (e.g., surfactants; and from BASF Corporation 600 CSUP, 650 EC, 600 CSUP / MB and 650 EC / MB).

[0332] The liquid hand dishwashing detergent compositions herein may optionally contain a number of other adjunct ingredients such as builders (e.g., preferably citrates), chelants (e.g., preferably GLDA), conditioning polymers, cleaning polymers including polyalkoxylated polyalkyleneimines, surface modifying polymers, soil flocculating polymers, foaming polymers including EO-PO-EO triblock copolymers, grease cleaning amines including cyclic polyamines, structurants, emollients, humectants, skin rejuvenation actives, enzymes, carboxylic acids, abrasive particles, bleaching agents and bleach activators. , fragrances, malodor control agents, pigments, dyes, opacifiers, beads, pearlescent agent particles, microcapsules, organic solvents, inorganic cations such as alkaline earth metals (such as Ca / Mg-ions), antimicrobial agents, preservatives, viscosity modifiers (e.g. salts such as NaCl, and other monovalent, divalent and trivalent salts) and pH adjusters and buffers (e.g. carboxylic acids such as citric acid, HCl, NaOH, KOH, alkanolamines, phosphoric and sulfonic acids, carbonates such as sodium carbonate, bicarbonates, sesquicarbonates, borates, silicates, phosphates, imidazoles, etc.).

[0333] The following is an exemplary liquid hand dishwashing detergent formulation. The formulation can be prepared by standard mixing of the individual components.

[0334] Table 3

[0335]

[0336] Free-flowing solid granular laundry detergent composition .

[0337] The fabric and home care product may be a free-flowing solid granular laundry detergent composition. The following is an exemplary free-flowing solid granular laundry detergent composition.

[0338] Table 4

[0339]

[0340]

[0341] Additional embodiments

[0342] Another subject of the present invention is the use of at least one grafted polymer in laundry detergents, cleaning compositions and / or fabric and home care products, wherein the grafted polymer comprises

[0343] (A) a block copolymer backbone as a graft base, wherein the block copolymer backbone (A) is obtainable by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide, and

[0344] (B) polymer side chains grafted onto the block copolymer backbone, wherein the polymer side chains (B) are obtainable by polymerization of at least one vinyl ester monomer (B1) selected from vinyl acetate or vinyl propionate and, as an optional additional monomer (B2), optionally N-vinyl pyrrolidone.

[0345] Within this particular subject of the invention, it is preferred that the number (x) of individual blocks within the block copolymer backbone (A) is an integer, wherein x has a value of 2 to 10, preferably x has a value of 2 to 5, more preferably x is 2 or 3, most preferably x is 3.

[0346] Additionally, within this particular subject matter, it is preferred that the vinyl ester monomers (B1) comprise at least 50% vinyl acetate by weight of the B1 monomers.

[0347] Furthermore, this specific subject matter also comprises all preferred, more preferred etc. The same applies to the definitions / features as mentioned above in conjunction with the definition of the graft polymer, with the proviso that the at least one vinyl ester monomer (B1 ) is selected from vinyl acetate or vinyl propionate.

[0348] Therefore, a further subject matter of the present invention is a laundry detergent, cleaning composition and / or a fabric and home care product comprising at least one graft polymer comprising:

[0349] (A) a block copolymer backbone as a graft base, wherein the block copolymer backbone (A) is obtainable by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide, and

[0350] (B) polymer side chains grafted onto the block copolymer backbone, wherein the polymer side chains (B) are obtainable by polymerization of at least one vinyl ester monomer (B1) selected from vinyl acetate or vinyl propionate and, as an optional additional monomer (B2), optionally N-vinyl pyrrolidone.

[0351] Within this particular subject of the invention, it is preferred that the number (x) of individual blocks within the block copolymer backbone (A) is an integer, wherein x has a value of 2 to 10, preferably x has a value of 2 to 5, more preferably x is 2 or 3, most preferably x is 3.

[0352] Additionally, within this particular subject matter, it is preferred that the vinyl ester monomers (B1) comprise at least 50% vinyl acetate by weight of the B1 monomers.

[0353] Preferably, in corresponding laundry detergents, cleaning compositions and / or fabric and home care products, at least one grafted polymer is present in an amount of about 0.01% to about 20%, preferably about 0.05% to 15%, more preferably about 0.1% to about 10%, and most preferably about 0.5% to about 5%, relative to the total weight of such compositions or products.

[0354] Another embodiment of the present invention is directed to a grafted polymer comprising:

[0355] (A) a block copolymer backbone as a graft base, wherein the block copolymer backbone (A) is obtainable by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide, and

[0356] (B) polymer side chains grafted onto the block copolymer backbone, wherein the polymer side chains (B) are obtainable by polymerization of at least one vinyl ester monomer (B1) and optionally N-vinylpyrrolidone as optional additional monomer (B2).

[0357] Within this particular subject of the invention, it is preferred that the number (x) of individual blocks within the block copolymer backbone (A) is an integer, wherein x has a value of 2 to 10, preferably x has a value of 2 to 5, more preferably x is 2 or 3, most preferably x is 3.

[0358] Additionally, within this particular subject matter, it is preferred that the vinyl ester monomers (B1) comprise at least 50% vinyl acetate by weight of the B1 monomers.

[0359] Furthermore, this specific subject matter also includes all preferred, more preferred, etc. The same applies to the definitions / features as mentioned above in conjunction with other embodiments of the present invention.

[0360] Embodiments of the present invention also include:

[0361] 1. A grafted polymer, comprising:

[0362] (a) a block copolymer backbone as a graft base, wherein the block copolymer backbone (A) is obtainable by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide, wherein the block copolymer backbone (A) has three or more alkylene oxide blocks;

[0363] (B) polymer side chains grafted onto the block copolymer backbone (A), wherein the polymer side chains (B) are obtainable by polymerization of at least one vinyl ester monomer (B1),

[0364] wherein the vinyl ester monomer (B1) comprises at least 50% by weight of the B1 monomer of vinyl acetate,

[0365] wherein the polymer has an OG greater than 0, wherein

[0366] OG=a X EO+b X M n 2 -c X (M n ×SUB)-d X M n +e X SUB+h X

[0367] in:

[0368] “M n " is the number average molecular weight of the block copolymer main chain (A);

[0369] "EO" is the molar ratio of ethylene oxide moieties to all alkylene oxide moieties present in the backbone (A), wherein EO is in the range of 0 to less than 1.00,

[0370] "SUB" is the weight percent of polymer side chains (B) based on the weight of the polymer;

[0371] “a X” ” is the coefficient and is equal to 7.06;

[0372] “b X " is the coefficient and is equal to 5.63×10 -7 ;

[0373] "c X " is the coefficient and is equal to 1.25×10 -3 ;

[0374] "d X ” is the coefficient and is equal to 7.03×10 -3 ;

[0375] “e X ” is the coefficient and is equal to 3.66; and

[0376] “h X ” is the coefficient and is equal to 16.3.

[0377] 2. The grafted polymer according to embodiment 1, wherein the grafted polymer also has a FJ greater than 0, wherein

[0378] FJ=a Y EO-b Y M n 2 +d Y M n +e Y SUB-f Y SUB 2 -g Y (EO×SUB)-h Y

[0379] in:

[0380] “a Y ” is the coefficient and is equal to 446;

[0381] “b Y " is the coefficient and is equal to 4.02×10 -6 ;

[0382] "d Y ” is the coefficient and is equal to 0.0168;

[0383] “e Y ” is the coefficient and is equal to 281;

[0384] “f Y ” is the coefficient and is equal to 229;

[0385] "g Y ” is the coefficient and is equal to 1140; and

[0386] “h Y ” is the coefficient and is equal to 83.6.

[0387] 3. The graft polymer according to any preceding embodiment, wherein the polymer side chain (B) is obtainable by polymerization of at least one vinyl ester monomer (B1) and at least one N-vinyl pyrrolidone monomer (B2).

[0388] 4. The grafted polymer according to any preceding embodiment, wherein "SUB" is the weight percent of vinyl ester monomer side chains (B1) based on the weight of the polymer.

[0389] 5. The graft polymer according to any preceding embodiment, wherein the graft polymer comprises 20 to 95 wt% of the block copolymer backbone (A) and 5 to 80 wt% of the polymer side chains (B) (relative to the total weight of the graft polymer).

[0390] 6. The graft polymer according to any preceding embodiment, wherein the block copolymer backbone (A) is obtainable by polymerization of:

[0391] (i) at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide or 1,2-butylene oxide; and / or

[0392] (ii) one of the at least two monomers is ethylene oxide; and / or

[0393] (iii) the number of individual alkylene oxide blocks (x) within the block copolymer backbone (A) is an integer, wherein the value of x is from 3 to 10.

[0394] 7. The graft polymer according to embodiment 6, wherein the block copolymer backbone (A) comprises ethylene oxide.

[0395] 8. The graft polymer according to embodiment 6, wherein the number of individual alkylene oxide blocks (x) within the block copolymer backbone (A) is an integer, wherein the value of x is 3 to 5.

[0396] 9. The grafted polymer according to any preceding embodiment, wherein

[0397] (i) the graft polymer has a weight average molecular weight M of 800 g / mol to 10,000 g / mol w ; and / or

[0398] (ii) the grafted polymer has a polydispersity M of less than 3.0 w / M n ,in:

[0399] “M w ” = weight average molecular weight [g / mol]; and

[0400] “M n " = number average molecular weight [g / mol]; and / or

[0401] (iii) the block copolymer backbone (A) is terminated at one or both end groups, and / or

[0402] (iv) The main chain of the block copolymer (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG).

[0403] 10. The graft polymer according to any preceding embodiment, wherein the block copolymer backbone (A) has a structure according to formula (A1) and / or formula (A2),

[0404] Wherein formula (A1) is defined as follows:

[0405]

[0406] in:

[0407] "n" is an integer in the range of 2 to 100, and

[0408] "m" is an integer ranging from 2 to 100; and

[0409] Wherein formula (A2) is defined as follows:

[0410]

[0411] in:

[0412] "o" is an integer in the range of 2 to 100, and

[0413] "p" is an integer ranging from 2 to 100.

[0414] 11. The grafted polymer according to any preceding embodiment, wherein the polymer side chain (B) is obtained by free radical polymerization of:

[0415] (B1) 50 to 100 wt. % (relative to the sum of (B1) and (B2)) of at least one vinyl ester monomer (B1), and

[0416] (B2) 0 to 50 wt. % (relative to the sum of (B1) and (B2)) of N-vinylpyrrolidone as further monomer (B2),

[0417] The polymer side chains (B) are optionally fully or partially hydrolyzed after polymerization.

[0418] 12 A method for obtaining at least one graft polymer according to any one of embodiments 1 to 11, wherein at least one monomer (B1) is polymerized in the presence of at least one block copolymer backbone (A),

[0419] wherein the process comprises polymerizing at least one monomer (B1) selected from vinyl acetate or vinyl propionate in the presence of at least one block copolymer backbone (A), a free radical forming initiator (C) and at least one organic solvent (D), at an average polymerization temperature at which the decomposition half-life of the initiator (C) is between 40 minutes and 500 minutes, so as to obtain the polymer side chains (B), in such a way that the fractions of unconverted grafting monomer (B1) and initiator (C) in the reaction mixture remain constantly in quantitative deficiency relative to the block copolymer backbone (A),

[0420] And optionally, wherein the polymer side chain (B) is obtained by free radical polymerization.

[0421] 13. A fabric and home care product comprising at least one grafted polymer according to any one of embodiments 1 to 11.

[0422] 14. The product of embodiment 13, wherein the product is a composition in the form of a liquid, a gel, a powder, a hydrocolloid, an aqueous solution, granules, a tablet, a capsule, a single compartment packet, a pad, a multi-compartment packet, a single compartment pouch, or a multi-compartment pouch.

[0423] 15. The product according to any one of embodiments 13 to 14, wherein the product is a composition further comprising an ingredient selected from the group consisting of surfactants, enzymes, detergent builders, complexing agents, polymers, soil release polymers, surfactant enhancing polymers, bleaches, bleach activators, bleach catalysts, fabric conditioners, clays, foam boosters, foam suppressors, corrosion inhibitors, soil suspension agents, anti-soil redeposition agents, dyes, bactericides, tarnish inhibitors, optical brighteners, perfumes, saturated or unsaturated fatty acids, dye transfer inhibitors, chelating agents, hueing dyes, calcium cations, magnesium cations, visual signal ingredients, defoamers, structurants, thickeners, anti-caking agents, starch, sand, gelling agents, or any combination thereof.

[0424] How to use

[0425] The present invention includes a method for cleaning a target surface. As used herein, a "target surface" may include such surfaces as fabrics, dishes, glass, and other cooking surfaces, hard surfaces, hair, or skin. As used herein, a "hard surface" includes hard surfaces found in a typical home, such as hardwood, tile, ceramic, plastic, leather, metal, glass. Such a method comprises the steps of contacting a composition comprising a modified polyol compound in a pure form or in a diluted form in a washing liquid with at least a portion of the target surface, and then optionally rinsing the target surface. Preferably, a washing step is performed on the target surface prior to the aforementioned optional rinsing step. For purposes of the present invention, washing includes, but is not limited to, scrubbing, wiping, and mechanical stirring.

[0426] As will be appreciated by those skilled in the art, the cleaning compositions of the present invention are ideally suited for use in home care (hard surface cleaning compositions) and / or laundry applications.

[0427] The composition solution pH is selected to be best suited to the target surface to be cleaned in a wide range of pH spanning from about 3 to about 11. For personal care such as skin and hair cleaning, the pH of such compositions preferably has a pH of about 5 to about 8, and for laundry cleaning compositions, preferably has a pH of about 5 to about 11. The composition is preferably used at a concentration of about 200 ppm to about 10,000 ppm in solution. The water temperature is preferably in the range of about 5°C to about 100°C.

[0428] For use in laundry cleaning compositions, the compositions are preferably used at concentrations of from about 200 ppm to about 10,000 ppm in solution (or wash liquor). The water temperature is preferably in the range of from about 5°C to about 60°C. The water to fabric ratio is preferably from about 1:1 to about 20:1.

[0429] The method may include the step of contacting a nonwoven substrate impregnated with an embodiment of the composition of the present invention. As used herein, a "nonwoven substrate" may include any conventionally styled nonwoven sheet or web having suitable basis weight, thickness (thickness), absorbency, and strength characteristics. Examples of suitable commercially available nonwoven substrates include those manufactured by DuPont under the trade name Sold and marketed by James River Corp. under the trade name Those that are sold.

[0430] As will be appreciated by those skilled in the art, the cleaning compositions of the present invention are ideally suited for use in liquid dishwashing cleaning compositions. The method for using the liquid dishwashing compositions of the present invention comprises the steps of contacting soiled dishes with an effective amount (typically from about 0.5 ml to about 20 ml) (per 25 treated dishes) of the liquid dishwashing cleaning composition of the present invention diluted in water.

[0431] The present invention also includes methods of using such grafted polymers to improve soil suspension, soil removal, soil release, anti-redeposition and / or malodor control performance.

[0432] The following examples will further illustrate the present invention without limiting the scope of the present invention.

[0433] Polymer Measurement

[0434] 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 in 3 wt% NaCl solution at 23°C and a polymer concentration of 1% polymer according to the method of H. Fikentscher in "Cellulosechemie", 1932, 13, 58.

[0435] The number average molecular weight (M) of the grafted polymer of the present invention is n ), weight average molecular weight (M w ) and polydispersity M w / M n Determined by gel permeation chromatography in tetrahydrofuran. The mobile phase (eluent) used was tetrahydrofuran containing 0.035 mol / L diethanolamine. The concentration of the grafted polymer in tetrahydrofuran was 2.0 mg / mL. After filtration (pore size 0.2 μm), 100 μL of this solution was injected into the GPC system. Four different columns (heated to 60°C) were used for separation (SDV pre-column, SDV1000A, 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. Molecular weight M n Poly(ethylene glycol) (PEG) standards (PL) ranging from 106 g / mol to 1378000 g / mol were used for calibration. Example

[0436] Synthesis Example :

[0437] Procedure for Comparing Polymers: Graft Polymerization of Vinyl Acetate onto Poly(ethylene Glycol)

[0438] (Comparative polymer 9)

[0439] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 600 g of poly(ethylene glycol) under a nitrogen atmosphere and melted at 90°C.

[0440] Feed 1, containing 4.8 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 23.6 g of tripropylene glycol, was metered into the stirred vessel at 90° C. over 6:10 h. 5.56% of feed 1 was metered in over the first 10 minutes and the remainder was metered in at a constant feed rate for 6:00 h. 10 minutes after the start of feed 1, feed 2 (400 g of vinyl acetate) was started and metered in at a constant feed rate and at 90° C. over 6:00 h. After feed 1 and feed 2 were completed, the temperature was increased to 95° C. and feed 3, consisting of 3.16 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 15.70 g of tripropylene glycol, was metered in at 95° C. over 56 minutes at a constant flow rate. After complete addition of the feeds, the mixture was stirred at 95° C. for one hour.

[0441] Residual amounts of monomers were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0442] General procedure for ungrafted comparative polymers

[0443] (Compare polymers 10-13)

[0444] 1098.90 g of the triblock copolymer, 1.10 g of vinyl acetate and 58.30 g of 1,2-propylene glycol were mixed in a polymerization vessel at 90° C. and stirred for 3 hours.

[0445] General procedure for graft polymerization of vinyl acetate with polyalkylene oxide / VAc (40 / 60) ratio

[0446] (Polymers 1 and 3 of the present invention; comparative polymers 6 and 7)

[0447] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 440 g of the triblock copolymer under a nitrogen atmosphere and melted at 90°C.

[0448] Feed 1, containing 7.97 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 35.09 g of 1,2-propylene glycol, was metered into the stirred vessel at 90° C. over 6:10 h. 5.56% of feed 1 was metered in over the first 10 minutes and the remainder was metered in at a constant feed rate for 6:00 h. 10 minutes after the start of feed 1, feed 2 (660 g of vinyl acetate) was started and metered into the reaction vessel at a constant feed rate and at 90° C. over 6:00 h. After the feeds were complete, feed 3, consisting of 5.28 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 23.21 g of 1,2-propylene glycol, was metered in over 56 minutes at 90° C. at a constant flow rate. After complete addition of the feeds, the mixture was stirred at 90° C. for one hour.

[0449] Residual amounts of monomers were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0450] General procedure for graft polymerization of vinyl acetate with a polyalkylene oxide / VAc (50 / 50) ratio

[0451] (Inventive polymer 2; Comparative polymer 4)

[0452] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 500 g of the triblock copolymer under a nitrogen atmosphere and melted at 90°C.

[0453] Feed 1, containing 12.24 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 50.30 g of tripropylene glycol, was metered into the stirred vessel at 90° C. over 6:10 h. 5.56% of feed 1 was metered in over the first 10 minutes and the remainder was metered in at a constant feed rate for 6:00 h. 10 minutes after the start of feed 1, feed 2 (200 g of vinyl acetate) was started and metered into the reaction vessel at a constant feed rate and at 90° C. over 6:00 h. After the feeds were complete, feed 3, consisting of 4.80 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 19.70 g of tripropylene glycol, was metered in over 56 minutes at 90° C. at a constant flow rate. After complete addition of the feeds, the mixture was stirred at 90° C. for one hour.

[0454] Residual amounts of monomers were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0455] General procedure for graft polymerization of vinyl acetate with polyalkylene oxide / VAc (60 / 40) ratio 1

[0456] (Inventive polymers 4, 5, 7-9, 13-15; Comparative polymers 1, 2, 5, 8)

[0457] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 600 g of the triblock copolymer under a nitrogen atmosphere and melted at 90°C.

[0458] Feed 1, containing 4.8 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 23.6 g of tripropylene glycol, was metered into the stirred vessel at 90° C. over 6:10 h. 5.56% of feed 1 was metered in over the first 10 minutes and the remainder was metered in at a constant feed rate for 6:00 h. 10 minutes after the start of feed 1, feed 2 (400 g of vinyl acetate) was started and metered in at a constant feed rate and at 90° C. over 6:00 h. After feed 1 and feed 2 were completed, the temperature was increased to 95° C. and feed 3, consisting of 3.16 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 15.70 g of tripropylene glycol, was metered in at 95° C. over 56 minutes at a constant flow rate. After complete addition of the feeds, the mixture was stirred at 95° C. for one hour.

[0459] Residual amounts of monomers were removed by vacuum distillation at 95° C. and 500 mbar for 1 h. The resulting graft polymer (Example 7) had an average molecular weight M of 5 190 g / mol. w and a polydispersity of 1.5.

[0460] General procedure for graft polymerization of vinyl acetate with polyalkylene oxide / VAc (70 / 30) ratio

[0461] (Inventive polymer 11; Comparative polymer 3)

[0462] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 770 g of the triblock copolymer under a nitrogen atmosphere and melted at 90°C.

[0463] Feed 1, containing 7.97 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 35.09 g of 1,2-propylene glycol, was metered into the stirred vessel at 90° C. over 6:10 h. 5.56% of feed 1 was metered in over the first 10 minutes and the remainder was metered in at a constant feed rate for 6:00 h. 10 minutes after the start of feed 1, feed 2 (330 g of vinyl acetate) was started and metered into the reaction vessel at a constant feed rate and at 90° C. over 6:00 h. After the feeds were complete, feed 3, consisting of 5.28 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 23.21 g of 1,2-propylene glycol, was metered in over 56 minutes at 90° C. at a constant flow rate. After complete addition of the feeds, the mixture was stirred at 90° C. for one hour.

[0464] Residual amounts of monomers were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0465] General procedure for graft polymerization of vinyl acetate with polyalkylene oxide / VAc (80 / 20) ratio

[0466] (Polymers 6, 10, 12 of the present invention)

[0467] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 800 g of the triblock copolymer under a nitrogen atmosphere and melted at 90°C.

[0468] Feed 1, containing 10.20 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 47.61 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 over the first 10 minutes and the remainder was metered in at a constant feed rate for 6:00 h. 10 minutes after the start of feed 1, feed 2 (200 g of vinyl acetate) was started and metered into the reaction vessel at a constant feed rate and at 90° C. over 6:00 h. After the feeds were complete, feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.39 g of tripropylene glycol, was metered in over 56 minutes at 90° C. at a constant flow rate. After complete addition of the feeds, the mixture was stirred at 90° C. for one hour.

[0469] Residual amounts of monomers were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0470] Procedure for the Graft Polymerization of Vinyl Acetate and Vinyl Pyrrolidone in 1,2-Propanediol

[0471] (Polymer 16 of the present invention)

[0472] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 376.3 g of the triblock copolymer under a nitrogen atmosphere and melted at 90°C.

[0473] Feed 1, which contained 7.12 g of tert-butyl perpivalate dissolved in 17.01 g of 1,2-propylene glycol, was metered into the stirred vessel at 90° C. over 6:10 h. 5.56% of feed 1 was metered in over the first 10 minutes and the remainder was metered in at a constant feed rate for 6:00 h. 10 minutes after the start of feed 1, feed 2 (225.78 g of vinyl acetate) and feed 3 (150.25 g of vinyl pyrrolidone) were started simultaneously and metered into the reaction vessel at a constant feed rate and at 90° C. over 6:00 h. 3 h after the start of feed 2 and feed 3, feed 4 (142.31 g of 1,2-propylene glycol) was started and metered into the reaction vessel over 3 h at a constant feed rate. After the feeds were complete, the temperature was increased to 95° C. and feed 3 consisting of 4.72 g of tert-butyl perpivalate dissolved in 11.25 g of 1,2-propylene glycol was metered in over 56 minutes at 95° C. at a constant flow rate. After complete addition of the feeds, the mixture was stirred at 95° C. for one hour.

[0474] Residual amounts of monomers were removed by vacuum distillation at 95° C. and 500 mbar for 1 h. Water (76.84 g) was added.

[0475] Further structural details of comparative and inventive polymer examples are listed in Table 5.

[0476]

[0477]

[0478] Methods for measuring the biodegradability of polymers

[0479] Biodegradation in wastewater was tested in triplicate using the OECD 301F manometric respirometry method. 30 mg / mL of the test substance was inoculated into wastewater taken from the Mannheim wastewater treatment plant and incubated in closed flasks at 25°C for 28 days. OxiTop C (WTW) was used to measure the oxygen consumption during this period as the change in pressure in the flask. The released CO was absorbed using a NaOH solution. 2 The amount of oxygen consumed by the microbial population during the biodegradation of the test substance is expressed as % of ThOD (theoretical oxygen demand) after correction using a blank.

[0480] The 28-day biodegradation data of the comparative polymers and the inventive polymers in the OECD 301F test are summarized in Table 5.

[0481] As shown in Table 5, compared with Comparative Polymer 1 to Comparative Polymer 10, Inventive Graft Polymer 1 to Inventive Graft Polymer 17 showed higher biodegradation percentages at 28 days in the OECD 301F test.

[0482] The grafted polymers of the present invention have an OG greater than 0, wherein

[0483] OG=a X EO+b X M n 2 -c X (M n ×SUB)-d X M n +e X SUB+h X

[0484] in:

[0485] “M n " is the number average molecular weight of the block copolymer main chain (A);

[0486] "EO" is the molar ratio of ethylene oxide moieties to all alkylene oxide moieties present in the backbone (A), wherein EO is in the range of 0 to less than 1.00,

[0487] "SUB" is the weight percent of polymer side chains (B) based on the weight of the polymer;

[0488] “a X” ” is the coefficient and is equal to 7.06;

[0489] “b X " is the coefficient and is equal to 5.63×10 -7 ;

[0490] "c X " is the coefficient and is equal to 1.25×10 -3 ;

[0491] "d X ” is the coefficient and is equal to 7.03×10 -3 ;

[0492] “e X ” is the coefficient and is equal to 3.66; and

[0493] “h X ” is the coefficient and is equal to 16.3.

[0494] Within the scope of the grafted polymer of the present invention as defined by OG, it is more preferred that the grafted polymer of the present invention has a FJ greater than 0, wherein

[0495] FJ=a Y EO-b Y M n 2 +d Y M n +e Y SUB-f Y SUB 2 -g Y (EO×SUB)-h Y

[0496] in:

[0497] “a Y ” is the coefficient and is equal to 446;

[0498] “b Y " is the coefficient and is equal to 4.02×10 -6 ;

[0499] "d Y ” is the coefficient and is equal to 0.0168;

[0500] “e Y ” is the coefficient and is equal to 281;

[0501] “f Y ” is the coefficient and is equal to 229;

[0502] "g Y ” is the coefficient and is equal to 1140; and

[0503] “h Y ” is the coefficient and is equal to 83.6.

[0504] Method for evaluating the foam mileage of hand dishwashing compositions

[0505] The purpose of the Foam Mileage Index test is to compare the foam volume produced by different test formulations over time at specified water hardness, solution temperature and formulation concentration while under the influence of periodic soil injection. The data are compared with a reference composition and expressed as a Foam Mileage Index (the Foam Mileage Index of the reference composition is 100). The steps of this method are as follows:

[0506] 1) According to the target composition concentration (0.12 wt%), a determined amount of the test composition was dispensed by a plastic pipette into a water stream (water hardness: 15 gpg, water temperature: 35°C) at a height of 37 cm above the bottom of a water tank (dimensions: diameter 300 mm and height 288 mm) at a flow rate of 0.67 mL / sec, which filled the water tank to 4 L at a constant pressure of 4 bar.

[0507] 2) Immediately after filling is complete, record the initial foam volume produced (measured as average foam height x tank surface area and in cm 3 is expressed as a unit).

[0508] 3) Immediately inject a fixed amount (6 mL) of dirt into the middle of the tank.

[0509] 4) The resulting solution was mixed with a metal blade (10 cm x 5 cm) located in the middle of the water tank at the air-liquid interface and rotated at 85 RPM for 20 revolutions at an angle of 45 degrees.

[0510] 5) Record another measurement of the total foam volume immediately after the blade rotation is completed.

[0511] 6) Repeat steps 3-5 until the total foam volume measured reaches 400 cm 3 The lowest level. Reach 400cm 3 The amount of added soil required to level is considered the foam mileage of the test composition.

[0512] 7) Each test composition was tested 4 times under each test condition (ie water temperature, composition concentration, water hardness, soil type).

[0513] 8) The average foam mileage was calculated as the average of 4 replicates for each sample.

[0514] 9) Calculate the Foam Mileage Index by comparing the average mileage of the test composition samples with the reference composition samples. The calculation is as follows:

[0515]

[0516] The soil compositions were produced by standard mixing of the components described in Table 6.

[0517] Table 6: Grease and dirt

[0518] Element weight% Crisco Oil 12.730 Crisco shortening 27.752 lard 7.638 Refined edible butter 51.684 Oleic acid 90% (Techn) 0.139 Palmitic acid, 99+% 0.036 Stearic acid, 99+% 0.021

[0519] Method for evaluating the whiteness benefit of polymers

[0520] Whiteness retention (also called whiteness maintenance) is the ability of a detergent to prevent loss of whiteness of white items when they are washed in the presence of soil. When soil is removed from dirty fabrics and suspended in the wash water, it can then be redeposited onto clothes, making them less white each time they are washed, and white clothes can become very dirty / dingy looking over time.

[0521] The whiteness benefits of the polymers of the present disclosure were evaluated using an automated Tergotometer with 10 jars for laundry detergent formulation testing.

[0522] SBL2004 test soil bars supplied by WFK Testgewebe GmbH were used to simulate consumer soil levels (mixture of body soil, food, dust etc.). On average, each SBL2004 bar was loaded with 8 g of soil. The SBL2004 test soil bars were cut into 5 x 5 cm squares for testing.

[0523] White fabric samples from Table 7 below purchased from WFK Testgewebe GmbH were used as whiteness tracers. Before the wash test, the L, a, b values ​​of all whiteness tracers were measured using a Konica Minolta CM-3610D spectrophotometer.

[0524] Table 7

[0525] Code Fiber Content % Fiber Content Fabric construction size WFK Code CK cotton 100 Weft Knitting (5×5cm) 19502_5x5_stamped PC Polyester / Cotton 65 / 35 Braid (5×5cm) 19503_5x5_stamped PE Polyester 100 Weft Knitting (5×5cm) 19508_5x5_stamped PS <![CDATA[Polyester / Spandex TM > 95 / 5 Weft Knitting (5×5cm) 19507_5x5_stamped

[0526] Additional ballast (background fabric swatches) were also used to simulate fabric loading and provide mechanical energy during actual laundry washing. The ballast load consisted of 5x5 cm sized cotton and polycotton knitted swatches.

[0527] 4 wash cycles are required to complete the test:

[0528] Cycle 1: Completely dissolve the required amount of detergent by mixing with 1 L of water (at defined hardness) in each oscillating detergent tank. 60 grams of fabric, including whiteness tracers (4 types with 4 repetitions each), 21 pieces of 5x5 cm SBL2004 and ballast were washed and rinsed in the oscillating detergent tank under defined conditions.

[0529] In the test of water soluble unit dose composition, the wash concentration was 2000 ppm. An additional 47 ppm of PVOH film was also added to the oscillating scrubber tank. The wash temperature was 30°C and the water hardness was 20 gpg.

[0530] Cycle 2: The whiteness tracer and ballast from each tank were then washed and rinsed again with a new set of SBL2004 (5x5cm, 21 sheets) after the course of cycle 1. All other conditions remained the same as cycle 1.

[0531] Cycle 3: The whiteness tracer and ballast from each tank were then washed and rinsed again with a new set of SBL2004 (5x5cm, 21 sheets) after the course of cycle 1. All other conditions remained the same as cycle 1.

[0532] Cycle 4: The whiteness tracer and ballast from each tank were then washed and rinsed again with a new set of SBL2004 (5x5cm, 21 sheets) after the course of cycle 1. All other conditions remained the same as cycle 1.

[0533] After cycle 4, all whiteness tracers and ballast were tumble dried between 60°C and 65°C until dry, and then the tracers were measured again using a Konica Minolta CM-3610D spectrophotometer. The whiteness index change (ΔWI(CIE)) was calculated based on the L, a, b measurements before and after washing.

[0534] ΔWI(CIE)=WI(CIE)(after washing)−WI(CIE)(before washing).

[0535] Performance of polymers in hand dishwashing detergents

[0536] The following hand dishwashing detergent compositions were prepared by conventional methods known to those of ordinary skill in the art by mixing the listed ingredients. The effect of the polymers of the present invention on foam mileage was evaluated by comparing the foam mileage of Formulation A (reference) and Formulation B (reference with the polymer of the present invention) in Table 8. The foam mileage performance was evaluated using the method for evaluating the foam mileage of hand dishwashing compositions described herein, and the foam mileage index is reported in Table 9.

[0537] Table 8

[0538]

[0539] * Amphiphilic alkoxylated polyethyleneimine (total MW: about 28000 g / mol) with a polyethyleneimine backbone of MW 600 and alkoxylated chains, each chain containing 24 internal EO units and 16 terminal PO units.

[0540] As shown in Table 9, the polymers of the present invention can provide strong foam mileage benefits.

[0541] Table 9

[0542] Polymers of the present invention Bubble Mileage Index and A (reference) 3 106 6 108 7 105 9 107 10 107 11 104 12 104 13 105 14 107 15 108

[0543] Whiteness performance of polymers in liquid detergents

[0544] The following water-soluble unit dose detergent compositions E and F are prepared by conventional methods known to those of ordinary skill in the art by mixing the listed ingredients (Table 10).

[0545] According to the method for evaluating whiteness performance of polymers, the whiteness retention of the inventive and comparative polymers was evaluated by directly comparing the whiteness performance of Reference Composition E and Test Composition F. The ΔWI(CIE) of Composition F relative to Composition E is reported in Table 11 as an indication of the whiteness performance benefit of the polymer.

[0546] Table 10

[0547]

[0548] As shown in Table 11, the polymers of the present invention provide significant whiteness benefits.

[0549] Although high biodegradability was observed for Comparative Polymers 10, 12, and 13, they failed to provide meaningful whiteness benefits. This is because Comparative Polymers 10, 12, and 13 had very low grafting levels: Sub (wt%) = 0.001, as shown in Table 5, and the polymers failed to provide sufficient whiteness performance benefits at such low grafting levels.

[0550] Table 11

[0551]

[0552] The dimensions and values ​​disclosed herein are not to be understood as being strictly limited to the exact numerical values ​​cited. Instead, unless otherwise indicated, each such dimension is intended to represent the stated value and a functionally equivalent range around that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

Claims

1. A grafted polymer, comprising: (A) a block copolymer backbone as a graft base, wherein the block copolymer backbone (A) is obtainable by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide, wherein the block copolymer backbone (A) has three or more alkylene oxide blocks; (B) polymer side chains grafted onto the block copolymer backbone (A), wherein the polymer side chains (B) are obtainable by polymerization of at least one vinyl ester monomer (B1), wherein the vinyl ester monomer (B1) comprises at least 50% by weight of the B1 monomer of vinyl acetate, wherein the polymer has an OG greater than 0, wherein OG = a X EO + b X M n 2 - c X (M n × SUB) - d X M n + from X SUB + h X in: "M n " is the number average molecular weight of the block copolymer main chain (A); "EO" is the molar ratio of ethylene oxide moieties to all alkylene oxide moieties present in the backbone (A), wherein EO is in the range of 0 to less than 1.00, "SUB" is a weight ratio of the polymer side chains (B) to the grafted polymer greater than 0.01; "a X” ” is the coefficient and is equal to 7.06; "b X " is the coefficient and is equal to 5.63×10 -7 ; "c X " is the coefficient and is equal to 1.25×10 -3 ; "d X ” is the coefficient and is equal to 7.03×10 -3 ; "e X ” is the coefficient and is equal to 3.66; and "h X ” is the coefficient and is equal to 16.

3.

2. The grafted polymer of claim 1, wherein the grafted polymer also has a FJ greater than 0, wherein FJ = a Y EO - b Y M n 2 + d Y M n + and Y SUB - f Y SUB 2 - g Y (EO × SUB) - h Y in: "a Y ” is the coefficient and is equal to 446; "b Y ” is the coefficient and is equal to 4.02×10 -6 ; "d Y ” is the coefficient and is equal to 0.0168; "e Y ” is the coefficient and is equal to 281; "f Y ” is the coefficient and is equal to 229; "g Y " is the coefficient and is equal to 1140; and "h Y ” is the coefficient and is equal to 83.

6.

3. The graft polymer according to claim 1 or 2, wherein the polymer side chains (B) are obtainable by polymerization of at least one vinyl ester monomer (B1) and at least one N-vinyl pyrrolidone monomer (B2).

4. The grafted polymer according to claim 1 or 2, wherein "SUB" is the weight percentage of vinyl ester monomer side chains (B1) based on the weight of the polymer.

5. The graft polymer according to claim 1 or 2, wherein the graft polymer comprises 20 to 95 wt% of the block copolymer main chain (A) and 5 to 80 wt% of the polymer side chain (B), relative to the total weight of the graft polymer.

6. The graft polymer according to claim 1 or 2, wherein the block copolymer backbone (A) is obtainable by the following polymerization: (i) at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide or 1,2-butylene oxide; and / or (ii) one of the at least two monomers used is ethylene oxide; and / or (iii) the number of individual alkylene oxide blocks (x) within the block copolymer backbone (A) is an integer, wherein the value of x is from 3 to 10.

7. The graft polymer according to claim 6, wherein the block copolymer backbone (A) comprises ethylene oxide.

8. The graft polymer according to claim 6, wherein the number of individual alkylene oxide blocks (x) within the block copolymer backbone (A) is an integer, wherein the value of x is 3 to 5.

9. The graft polymer according to claim 1 or 2, wherein (i) the graft polymer has a weight average molecular weight M of 800 g / mol to 10,000 g / mol w ; and / or (ii) the grafted polymer has a polydispersity M of less than 3.0 w / M n ,in: "M w ” = weight average molecular weight in g / mol; and "M n " = number average molecular weight in g / mol; and / or (iii) the block copolymer backbone (A) is terminated at one or both end groups, and / or (iv) The block copolymer main chain (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG).

10. The graft polymer according to claim 1 or 2, wherein the block copolymer main chain (A) has a structure according to formula (A1) and / or formula (A2), Wherein formula (A1) is defined as follows: in: "n" is an integer in the range of 2 to 100, and "m" is an integer in the range of 2 to 100; and Wherein formula (A2) is defined as follows: in: "o" is an integer in the range of 2 to 100, and "p" is an integer in the range of 2 to 100.

11. The graft polymer according to claim 1 or 2, wherein the polymer side chain (B) is obtained by the following free radical polymerization: (B1) 50% to 100% by weight, relative to the sum of (B1) and (B2), of at least one vinyl ester monomer (B1), and (B2) 0 to 50% by weight, relative to the sum of (B1) and (B2), of N-vinylpyrrolidone as a further monomer (B2), The polymer side chains (B) are optionally fully or partially hydrolyzed after polymerization.

12. A process for obtaining at least one graft polymer according to any one of claims 1 to 11, wherein at least one monomer (B1) is polymerized in the presence of at least one block copolymer backbone (A), wherein the process comprises polymerizing at least one monomer (B1) selected from vinyl acetate or vinyl propionate in the presence of at least one block copolymer backbone (A), a free radical forming initiator (C) and at least one organic solvent (D), at an average polymerization temperature at which the decomposition half-life of the initiator (C) is between 40 minutes and 500 minutes, in such a way that the fractions of unconverted grafting monomers (B1) and initiator (C) in the reaction mixture remain constantly in quantitative deficiency relative to the block copolymer backbone (A) in order to obtain the polymer side chains (B), And optionally, wherein the polymer side chain (B) is obtained by free radical polymerization.

13. A fabric and home care product comprising at least one grafted polymer according to any one of claims 1 to 11.

14. The product according to claim 13, wherein the product is a composition in the form of a liquid, a gel, a powder, a hydrocolloid, an aqueous solution, granules, a tablet, a capsule, a single compartment packet, a pad, a multi-compartment packet, a single compartment pouch or a multi-compartment pouch.

15. The product according to claims 13 to 14, wherein the product is a composition further comprising an ingredient selected from the group consisting of surfactants, enzymes, detergent builders, complexing agents, soil release polymers, surfactant enhancing polymers, bleaches, bleach activators, bleach catalysts, fabric conditioners, clays, foam boosters, foam suppressors, corrosion inhibitors, soil suspension agents, anti-soil redeposition agents, dyes, bactericides, tarnish inhibitors, optical brighteners, perfumes, saturated or unsaturated fatty acids, dye transfer inhibitors, chelating agents, hueing dyes, calcium cations, magnesium cations, defoamers, structurants, thickeners, anti-caking agents, starch, sand, gelling agents, or any combination thereof.

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