Biodegradable graft polymers

Abstract

To provide novel graft polymers, having beneficial properties in terms of biodegradability and their washing behavior.SOLUTION: The present invention relates to a novel graft polymer that includes a block copolymer backbone (A) as a graft base, having polymeric sidechains (B) grafted thereon. The polymeric sidechains (B) are obtainable by polymerization of at least one vinyl ester monomer (B1) and optionally an N-vinylpyrrolidone monomer (B2). In a most preferable form, the block copolymer backbone (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG). The present invention further relates to a process for obtaining such a graft polymer, wherein preferably, the process is carried out by free-radical polymerization. Furthermore, the present invention relates to the use of such a graft polymer within fabric and home care products. Another subject-matter of the present invention relates to fabric and home care products, containing such a graft polymer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to novel graft polymers comprising a block copolymer backbone (A) as a graft base having polymer side chains (B) grafted thereon. 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 also relates to a process for obtaining such graft polymers, which process is preferably carried out by free radical polymerization. Furthermore, the present invention relates to the use of such graft polymers in textiles and home care products. Another subject of the present invention is textiles and home care products containing such graft polymers. [Background technology]

[0002] Initiatives to ban microplastics, especially in cosmetic products, have already been introduced in various states. In addition to this ban on insoluble microplastics, there is intense discussion about future requirements for soluble polymers used in consumer products. Therefore, identifying new, well-biodegradable components for such applications is highly desirable. This problem is primarily acute for polymers produced by radical polymerization based on carbon-only backbones, since carbon-only backbones (those without heteroatoms such as oxygen) are particularly difficult to degrade by microorganisms. Even industrially important radical-generated graft polymers with polyethylene glycol backbones exhibit only limited biodegradability in wastewater. However, the polymers described in this invention, preferably produced by radical graft polymerization, offer enhanced biodegradability compared to the state of the art.

[0003] WO 2007 / 138053 discloses amphiphilic graft polymers based on a water-soluble polyalkylene oxide (A) as a graft base and side chains formed by polymerization of a vinyl ester component (B), the polymers having an average grafting site of less than 1 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 regarding the biodegradability of the respective graft polymers disclosed therein.

[0004] Y. Zhang et al., J. Coll. Inter. Sci. 2005, 285, 80, relates to the synthesis and characterization of specific grafted polymers based on Pluronic®-type backbones. Pluronic poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO) block copolymers are grafted with poly(vinylpyrrolidone) by free radical polymerization of vinylpyrrolidone in dioxane with simultaneous chain transfer to Pluronic. However, Y. Zhang does not disclose that the polymer side chains of each grafted polymer are based on vinyl ester monomers. Furthermore, Y. Zhang does not disclose any biodegradability of the grafted polymers disclosed therein. Y. Zhang also does not disclose any use of such grafted polymers in textiles and home care products.

[0005] WO 03 / 042262 relates to a graft polymer comprising (A) a polymeric graft backbone free of monoethylenically unsaturated units and (B) polymeric 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 amount of side chains (B) accounts for 35 to 55% by weight of the total polymer. However, the graft polymer according to WO 03 / 042262 is not based on vinyl ester monomers in each polymeric side chain grafted onto the backbone. Other than that, WO 03 / 042262 does not disclose any information related to the biodegradability of the graft polymers disclosed therein.

[0006] U.S. Patent No. 5,318,719 relates to a new class of biodegradable, water-soluble graft copolymers having builder, anti-filming, dispersibility, and threshold crystallization-inhibiting properties, comprising (a) an acid-functional monomer and, optionally, (b) another water-soluble, monoethylenically unsaturated monomer copolymerizable with (a), grafted to a biodegradable substrate comprising a polyalkylene oxide and / or a polyalkoxylated material. However, U.S. Patent No. 5,318,719 does not disclose the use of a block copolymer backbone within each graft polymer. Furthermore, each side chain of this graft polymer necessarily contains a large amount of an acid-functional monomer, such as acrylic acid or methacrylic acid. Such types of acid monomers are not useful in the context of the present invention. Summary of the Invention

[0007] The object of the present invention is to provide novel grafted polymers which, when used in compositions such as cleaning compositions, should further have beneficial properties in terms of biodegradability and their cleaning behavior. [Means for solving the problem]

[0008] The purpose of this is to (A) a block copolymer backbone as a graft base, said block copolymer backbone (A) being obtainable by polymerizing 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, said block copolymer backbone (A) having three or more alkylene oxide blocks; (B) polymeric side chains grafted onto the block copolymer backbone (A), said polymeric side chains (B) being obtainable by polymerization of at least one vinyl ester monomer (B1), the vinyl ester monomer (B1) comprises at least 50% vinyl acetate by weight of the B1 monomer; the polymer has an OG greater than 0; OG=a X EO+b X M n 2 -c X (M n ×SUB)-d X M n +e X SUB+h X and During the ceremony, "M n " is the number average molecular weight of the block copolymer backbone (A), "EO" is the molar ratio of ethylene oxide moieties to the total alkylene oxide moieties present in the backbone (A), and EO is in the range of 0 to less than 1.00; "SUB" is the weight ratio of the polymer side chain (B) to the weight of the polymer; "a X " is the coefficient and is equal to 7.06, "b X " is the coefficient, 5.63 x 10 -7 is equal to "c X " is a coefficient, 1.25 x 10 -3 is equal to "dX " is the coefficient, 7.03 x 10 -3 is equal to "e X " is the coefficient and is equal to 3.66, "h X " is a coefficient and is equal to 16.3.

[0009] Preferred graft polymers also have an FJ greater than 0, 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 and During the ceremony, "a Y " is the coefficient and is equal to 446, "b Y " is the coefficient, 4.02 x 10 -6 is equal to "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, "h Y " is a coefficient and is equal to 83.6.

[0010] In preferred versions of the foregoing embodiment, the number (x) of individual blocks in the block copolymer backbone (A) is an integer, where x is 3 to 10, preferably 3 to 5, and more preferably 3.

[0011] The grafted polymers according to the present invention can be used, for example, in cleaning compositions and / or fabric and home care products. They provide at least the same, and preferably even improved, anti-redeposition and cleaning performance in such compositions or products, for example, in terms of soil redeposition and stain removal, compared to corresponding polymers or grafted polymers according to the prior art. In addition, the grafted polymers according to the present invention, for example, in cleaning compositions and / or fabric and home care products, provide improved biodegradability when used in such compositions or products.

[0012] The biodegradable enhanced graft polymers according to the present invention can be advantageously used in laundry and cleaning compositions where they support the surfactant-mediated removal of a variety of hydrophobic and hydrophilic soils such as body soils, food and grease stains, particulate soils such as clay or carbon black, grass stains, makeup, motor oil, etc. from textiles or hard surfaces, thus improving the washing and cleaning performance of the formulation.

[0013] Furthermore, the grafted polymer also provides better dispersion of removed soils in the laundry or wash liquor, preventing redeposition of washed or cleaned materials onto surfaces. Herein, removed soils include all typical soils present during the laundry process, such as body soils, food and grease stains, particulate soils such as clay or carbon black, grass stains, makeup, motor oil, etc. Such anti-redeposition effects can be observed on various types of fabrics, including cotton, polycotton, polyester, polyester / polyurea copolymers (Spandex™), etc. Additionally, such anti-redeposition effects are also effective on fabrics that have a history of fabric improver use, i.e., even when the fabrics are washed in the presence of fabric improvers or other laundry additives, such as freshening beads or bleaching agents. DETAILED DESCRIPTION OF THE INVENTION

[0014] The term "block copolymer (backbone)" as used herein means that each polymer contains at least two (two or more) homopolymer subunits (blocks) linked by covalent bonds. A two-block copolymer has two different blocks (homopolymer subunits), while a triblock copolymer consequently has three different blocks (homopolymer subunits), and so on. The number of individual blocks in such a block copolymer is not limited to an "n-block copolymer," which consequently contains n different blocks (homopolymer subunits). Within an individual block (homopolymer subunit), the size / length of such a block may vary. The shortest / smallest block is based on two individual monomers (minimum). The understanding of the term "block copolymer" will be defined in more detail below, especially in conjunction with the definition of a "triblock copolymer" according to general formula (A1) or general formula (A2).

[0015] The present invention is specified in more detail as follows:

[0016] The first subject of the present invention is (A) a block copolymer backbone as a graft base, said block copolymer backbone (A) being obtainable by polymerizing 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, said block copolymer backbone (A) having three or more alkylene oxide blocks; (B) polymeric side chains grafted onto the block copolymer backbone (A), said polymeric side chains (B) being obtainable by polymerization of at least one vinyl ester monomer (B1), The vinyl ester monomer (B1) comprises at least 50% vinyl acetate by weight of the B1 monomer.

[0017] The ratio of block copolymer backbone (A) to polymer side chains (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 is understood that the graft polymer contains more than 1 wt. % 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 wt. % 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 wt. % of polymer side chains (B) relative to the total weight of the graft polymer (SUB=0.10).

[0018] In preferred versions of the foregoing embodiment, the number (x) of individual blocks in the block copolymer backbone (A) is an integer, where x is 3 to 10, preferably 3 to 5, and more preferably 3.

[0019] The graft polymer preferably comprises 20 to 95% by weight of the block copolymer backbone (A) and 5 to 80% by weight of the polymer side chains (B) (based on the total weight of the graft polymer).

[0020] Preferably, the graft polymer comprises 40 to 90 wt. %, more preferably 50 to 85 wt. %, even more preferably 55 to 80 wt. % of the block copolymer backbone (A) and preferably 10 to 60 wt. %, more preferably 15 to 50 wt. %, even more preferably 20 to 45 wt. % of the polymer side chains (B) (based on the total weight of the graft polymer).

[0021] The block copolymer backbone (A) itself, as well as methods for producing such a block copolymer backbone, are known to those 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 Pluronic PE6100, Pluronic PE6800, or Pluronic PE3100.

[0022] Suitable block copolymer backbones (A) for use in the present invention are described, for example, in EP 0 362 688. In the present invention, it is preferred that the monomers used to prepare the individual blocks of the block copolymer backbone (A) are added sequentially. However, in the transition of the feed from one monomer to another, it is possible to generate so-called "dirty structures," where at the edges / boundaries of each block, a small number of monomers from each adjacent block may be included in the individual block under consideration. However, it is preferred that the block copolymer backbone (A) according to the present invention does not contain so-called "dirty structures" or "dirty passages" at the boundaries of each block.

[0023] Regarding the block copolymer backbone (A) of the graft polymer according to the invention, the block copolymer backbone (A) is i) obtainable by polymerization of at least two monomers selected from the group 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 ii) one of the at least two monomers used is ethylene oxide, and preferably the second monomer used is 1,2-propylene oxide; and / or iii) It is preferred that the number (x) of individual alkylene oxide blocks in the block copolymer backbone (A) is an integer, with x having a value of 3 to 10, preferably x having a value of 3 to 5, and more preferably x being 3.

[0024] When x is an even number, the graft polymer typically includes an end-capping group. Suitable end-capping groups are described in detail below.

[0025] The graft polymer according to the present invention can have any molecular weight known to those skilled in the art. However, the graft polymer preferably has a weight average molecular weight M of 1,000 to 100,000 g / mol, preferably 2,000 to 45,000 g / mol, more preferably 3,000 to 30,000 g / mol. w It is preferred that the compound has the following structure:

[0026] The graft polymers according to the present invention preferably have low polydispersity. The graft polymers preferably have a polydispersity M of <3, preferably <2.5, more preferably <2.3, most preferably in the range of 1.0 to 2.2. w / M n It is preferred to have (M w = weight average molecular weight, M n = number average molecular weight, polydispersity is [ g / mol / g / mol ] (unit not included). M w and / or M n The respective values ​​of can be determined as described in the experimental section below.

[0027] The graft polymer of the present invention may contain polymer 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 typically 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 polymer in the graft polymer product of the present invention produced or producible by the process described in this invention.

[0028] The graft polymers of the present invention may contain non-grafted block copolymer backbone (A). The level of non-grafted block copolymer backbone (A) may be high or low, depending on the reaction conditions. Preferably, the level of non-grafted block copolymer backbone (A) is typically less than 50%. More preferably, the level of non-grafted block copolymer backbone (A) is less than 30%. More preferably, the level of non-grafted block copolymer backbone (A) is less than 10%. All based on the total weight of polymer in the graft polymer product of the present invention produced or producible by the process described in this invention.

[0029] The graft polymers of the present invention can be characterized by their degree of grafting (the number of grafting sites of polymer side chains (B) on the block copolymer backbone (A)). The degree of grafting can be high (more than one polymer side chain per 50 alkylene oxide units) or low (less than one polymer side chain per 50 alkylene oxide units), depending on the reaction conditions. It is possible to adjust the degree of grafting to achieve optimized performance in specific areas of interest. The degree of branching can be measured, for example, using C NMR spectroscopy from the integration of the signals of the grafting sites and the -CH- groups of the polyalkylene oxide.

[0030] The block copolymer backbone (A) contained in the graft polymer according to the present invention may be either capped or uncapped (uncapped) at each end group of the backbone. Consequently, in the present invention, the block copolymer backbone (A) can be optionally capped at one or both end groups, and preferably, the block copolymer backbone (A) is uncapped at both end groups, or, if the block copolymer backbone (A) is capped, the capping is at least one of C1 to C6. 25 This is done by alkyl groups.

[0031] In one embodiment of the present invention, the block copolymer backbone (A) is preferably a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG).

[0032] 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), Formula (A1) is defined as follows:

[0033] [ka] where: n is an integer ranging from 2 to 100, preferably from 3 to 80; m is an integer ranging from 2 to 100, preferably from 10 to 70, and more preferably from 14 to 54; Formula (A2) is defined as follows:

[0034] [ka] where: o is an integer ranging from 2 to 100, preferably from 5 to 50, and more preferably from 8 to 27; p is an integer ranging from 2 to 100, preferably from 5 to 50, and more preferably from 7 to 24.

[0035] The block copolymer (A) may contain different levels of hydrophilic ethylene glycol, which affects the overall properties of the graft polymer. The total EO content ("EO"), which describes the total amount of ethylene glycol units in the block copolymer, is defined as follows:

[0036] "EO" is the molar ratio of ethylene oxide moieties to the total alkylene oxide moieties present in the backbone (A), and EO is in the range of 0 to less than 1.00;

[0037] The block copolymers can be low, medium, or high "EO," which affects biodegradation properties and performance in laundry formulations. The ranges are defined as follows: - Low: 0.05~0.20 - Medium: 0.21~0.50 - High: 0.51~0.90

[0038] With regard to the polymer side chains (B) contained in the graft polymer according to the invention, it is preferred that the polymer side chains (B) are obtained by radical polymerization and / or that at least one vinyl ester monomer (B1) is vinyl acetate.

[0039] As the vinyl ester monomer (B1), any additional vinyl ester other than vinyl acetate known to those skilled in the art may be used, provided that the vinyl ester monomer (B1) contains at least 50% vinyl acetate by weight of the B1 monomer. Suitable other vinyl esters include vinyl propionate, vinyl valerate, vinyl pivalate, vinyl neononanoate, vinyl decanoate, vinyl benzoate, and vinyl laurate, more preferably vinyl propionate or vinyl laurate. When N-vinylpyrrolidone is optionally used as an additional monomer (B2) to prepare the polymer side chains (B) in the graft polymer according to the present invention, the ratio of the essential vinyl ester monomer (B1) to the additional monomer (B2) may have any value known to those skilled in the art. However, the amount of vinyl ester monomer (B1) is typically 1% by weight or more (based on the total of (B1) and (B2)). As a result, the polymeric side chain (B) is preferably obtainable by radical polymerization of 1 to 100% by weight of a monomer (B1), most preferably vinyl acetate, and 0 to 99% by weight of N-vinylpyrrolidone as an optional further monomer (B2).

[0040] However, in the context of the present invention, the polymer side chain (B) is (B1) 10 to 100% by weight, preferably 50 to 100% by weight, more preferably 75 to 100% by weight (based on the total of (B1) and (B2)) of at least one vinyl ester monomer (B1); (B2) is preferably obtained by free radical polymerization with 0 to 90% by weight, preferably 0 to 50% by weight, more preferably 0 to 25% by weight (based on the total of (B1) and (B2)) of N-vinylpyrrolidone as a further monomer (B2).

[0041] Within the context of the present invention, it is even more preferred that the polymeric side chains (B) are obtained by radical polymerization of 100% by weight (with respect to the total amount of monomers used) of at least one vinyl ester monomer (B1), preferably vinyl acetate or vinyl propionate, more preferably vinyl acetate.

[0042] 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 the graft polymer is obtained, which 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.

[0043] This complete or at least partial hydrolysis of the polymer side chain (B) of the graft polymer according to the present invention converts each side chain unit derived from at least one vinyl ester monomer (B1) from its respective ester functionality in the polymer side chain (B) to an alcohol functionality. It should be noted that the corresponding vinyl alcohol is not suitable for use as a monomer in the polymerization process of the polymer side chain (B) due to its stability. To obtain an alcohol functionality (hydroxy substituent) in the polymer side chain (B) of the graft polymer according to the present invention, the alcohol functionality is typically introduced by hydrolyzing the ester functionality of the side chain. From a theoretical point of view, each ester functional group of the polymer side chain (B) can be replaced by an alcohol functional group (hydroxy group). In such a case, the polymer side chain is completely hydrolyzed (saponified). It should be noted that when N-vinylpyrrolidone is used as an additional monomer, the units of the polymer side chain (B) derived from N-pyrrolidone used as the additional monomer (B) are typically not hydrolyzed.

[0044] Hydrolysis can be carried out by any method known to those skilled in the art, for example, hydrolysis can be induced by the addition of a suitable base such as sodium hydroxide or potassium hydroxide.

[0045] However, in this embodiment of the invention, it is preferred that the hydrolysis of the polymer side chains (B) is carried out only partially, for example to an extent of up to 20%, 40% or 60% by weight (relative to the total weight of the polymer side chains).

[0046] In this embodiment, the polymer side chains (B) may be completely 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) used in the polymerization, but preferably the polymer side chains (B) are not hydrolyzed after polymerization. In the context of the present invention, it is preferred that in each polymerization process to obtain the polymer side chain (B), no other monomers are used other than those defined above in connection with at least one vinyl ester monomer (B1), with N-vinylpyrrolidone optionally present as the optional further monomer (B2). However, if any further polymer monomers other than the monomers according to (B1) and optionally (B2) are present, such monomers (other than 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 chain (B). Preferably, the amount of such additional monomers is less than 0.5% by weight, even more preferably less than 0.01% by weight, and most preferably, no additional monomers other than the monomers (B1) and optionally (B2) are present at all.

[0047] It is particularly preferred in the present invention that no monomers containing acid functional groups are used, in particular the monomers used to obtain the polymer side chains (B) of the graft polymer according to the invention do not comprise any acid functional monomer selected from acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, vinylacetic acid or acryloxy-propionic acid.

[0048] The polymer of the present invention must have at least one, and preferably two or more of the following properties in order to be successfully used in various application fields. a) a particular level of biodegradability, such biodegradability being tested as defined elsewhere herein. To exhibit useful biodegradability, the biodegradation rate (at 28 days according to the methods disclosed herein) should preferably be at least 20 percent, more preferably at least 40%, even more preferably at least 50%, e.g., 25, 30, 32, 35, 45, 55, 60, 65, 75, 80, 85, or more up to 100%. b) The water solubility of the polymer should be to some extent so as to allow the polymer to be used in the aqueous environments typically present in the application fields generally targeted by the present invention. Preferably, the polymer of the present invention should exhibit moderate to good, more preferably very good, solubility in the environment of aqueous formulations such as those typically used in various types of formulations, for example, in the fields of dishwashing, automatic dishwashing, hard surface cleaning, fabric cleaning, fabric care, cosmetic formulations, etc. c) The viscosity of the polymer solution must be such that at a reasonably high solids concentration of the polymer as it is handled during and after production and provided to the user, it can be, for example, as a "pure" (and typically liquid) product dissolved in a solvent, typically an aqueous solution comprising water and an organic solvent, water alone, or an organic solvent alone, and the viscosity of such polymer or polymer solution must be in a range that allows typical technological processes such as pouring, pumping, dosing, etc. Thus, the viscosity is preferably less than about 4000 mPas, more preferably up to 3500 mPas, even more preferably up to 3000 mPas, for example up to 4500, 3750, 3250, 2750 or even 2600, for example 2500, 2000, 1750, 1500, 1250, 1000, 750, 500, 250, 200, 150 or 100 mPas, at a polymer concentration (based on the solids content of the polymer in the solution, defined as the weight percent of dry polymer in the total weight of the polymer solution) of preferably at least 10 wt%, more preferably at least 20 wt%, even more preferably at least 40 wt%, most preferably at least 50 wt%, for example at least 60, 70, 80 or even 90 wt%. The viscosity can be measured at 25°C or at an elevated temperature, for example 50°C or even 60°C. This allows for convenient handling of the polymer solution on a commercial scale. Of course, depending on the amount of solvent added, the viscosity will decrease as the amount of solvent increases, and vice versa, so it can be adjusted as desired. It is also clear that the measured viscosity will depend on the temperature at which it is measured; for example, the viscosity of a given polymer with a given solids content, e.g., 80% by weight, will be higher when measured at a lower temperature and lower when measured at a higher temperature. In a preferred embodiment, the polymer as prepared without additional solvent has a solids content of 70-90% by weight, more preferably 75-85% by weight. In a more preferred embodiment, the polymer as prepared without additional solvent has a solids content of 70-90% by weight, more preferably 75-85% by weight, and has a viscosity of less than 3000 mPas when measured at 60°C.

[0049] To achieve these requirements, the following guidance can be given on how to achieve such properties in the polymers of the present invention. Biodegradability is generally increased by at least one of the following conditions: 1) Lower molecular weight of the block copolymer backbone (A) compared to the high molecular weight; · 2) A lower weight percentage of polymer side chains (monomer B) is grafted onto the backbone compared to the high weight percentage. 3) Selecting the framework structure A2 over A1; 4) The molar ratio of ethylene oxide moieties to the total alkylene oxide moieties present in the skeleton (A) is within the range of about 0.10 to about 0.80.

[0050] The favorable properties of the polymers of the present invention are achieved by at least one of the following conditions: 1) The block copolymer backbone (A) of the graft polymer has an M of less than 3500 g / mol, more preferably less than 3200 g / mol n It has. 2) the weight ratio of the polymer side chains ("SUB") of the graft polymer is in the range of about 0.10 to about 0.60, more preferably about 0.20 to about 0.50; 3) The graft polymer has a backbone structure A2. 4) The molar ratio of ethylene oxide moieties to total alkylene oxide moieties present in backbone A ("EO") is within the range of about 0.10 to about 0.80.

[0051] More preferred properties of the polymers of the present invention are achieved by the combination of the following conditions ("A1", "B1", etc. are defined above): 1)+2), i.e., the block copolymer backbone (A) has an M of less than 3500 g / mol n wherein the weight ratio of the polymer side chains ("SUB") of the graft polymer is in the range of about 0.20 to about 0.50; 1)+3) 1)+2)+3) 1)+2)+3)+4)

[0052] Even more favorable properties of the polymers of the present invention are achieved by the combination of the following conditions: 1)+2) 1)+2)+3)

[0053] The most favorable properties of the polymers of the present invention are achieved by the combination of the following conditions: 1)+2)+3)

[0054] In one preferred embodiment of the present invention, the graft polymer has a number average molecular weight M of the triblock copolymer backbone (A). n is less than 6000 g / mol, preferably less than 5000 g / mol, more preferably less than 3650 g / mol, even more preferably less than 3000 g / mol, and the weight percentage of vinyl acetate (monomer B) grafted onto the backbone is between 10 and 80, preferably between 10 and less than 80, more preferably at least 20, most preferably at least 30, and preferably less than 70, more preferably less than 60, most preferably less than 50 (relative to the total weight of the grafted polymer).

[0055] In another preferred embodiment of the invention, the graft polymer has a number average molecular weight M n is less than 6000 g / mol, preferably less than 5000 g / mol, more preferably less than 3650 g / mol, even more preferably less than 3000 g / mol, and most preferably less than 2500 g / mol, the backbone having structure A2 and the weight percent of vinyl acetate (monomer B) grafted onto the backbone is between 10 and 80, preferably between more than 10 and less than 80, more preferably at least 20, 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).

[0056] As a further criterion, it is of course necessary to evaluate the individual performance of specific polymers, and therefore, it is necessary to rank each individual formulation in specific application fields.Although the wide usefulness of the polymers of the present invention makes it impossible to provide an exhaustive overview, this specification and examples provide guidance on how to prepare and select useful polymers with desired properties and how to adjust properties to desired needs.One such criterion for home care and especially for fabric care is, of course, washing performance, for example, subjecting specific materials that exhibit specific stains to defined washing procedures.

[0057] The examples provide some guidance for applications to clean fabrics, i.e., the general area of ​​fabric care.

[0058] Depending on the particular need for a polymer exhibiting defined degrees of biodegradability, water solubility, and viscosity (i.e., handling characteristics), the general and specific teachings herein will guide methods for obtaining such polymers, although they are not intended to be limited to the specific examples given.

[0059] Another subject of the present invention is a process for preparing the above-described inventive graft polymers, in which 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) to obtain at least one graft polymer according to the invention.

[0060] It should be noted that the grafting process, in which a polymer backbone, such as a block copolymer backbone, is grafted with polymer side chains, is itself known to those skilled in the art, and any process known to those skilled in the art in this regard can be used in the present invention.

[0061] In the process of the invention, it is preferred that the polymeric side chains (B) are obtained by radical polymerization.

[0062] Such radical polymerizations are also known to those skilled in the art. Those skilled in the art also know that the process of the present invention can be carried out in the presence of a radical-forming initiator (C) and / or at least one solvent (D). Those skilled in the art know the respective components themselves.

[0063] The term "radical polymerization" as used in the context of the present invention includes free radical polymerization as well as its variants, such as controlled radical polymerization. Suitable control mechanisms are RAFT, NMP, or ATRP, each of which includes a suitable control agent and is known to those skilled in the art.

[0064] The process according to the invention is carried out by a method comprising the polymerization of at least one monomer (B1) selected from vinyl acetate and a further vinyl ester other than vinyl acetate, with the proviso that the vinyl ester monomer (B1) comprises at least 50% by weight of the B1 monomer, vinyl acetate, and optionally N-vinylpyrrolidone as the optional further monomer (B2), to obtain polymeric side chains (B) 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 of at least one organic solvent (D), based on the sum of components (A), (B1), optionally (B2), and (C), at an average polymerization temperature at which the decomposition half-life of the initiator (C) is between 40 and 500 minutes, in such a way that the fraction of unconverted graft monomers (B1) and optionally (B2), and initiator (C) in the reaction mixture is always quantitatively deficient relative to the block copolymer backbone (A).

[0065] The amount of ((free) radical-forming) initiator (C) is preferably 0.1 to 5% by weight, in particular 0.3 to 3.5% by weight, based in each case on the polymer side chain (B).

[0066] In the process according to the invention, the steady-state concentration of radicals present at the average polymerization temperature is substantially constant, and the grafting monomer (B1) or (B2) is preferably always present in the reaction mixture only in low concentrations (for example, not more than 5% by weight), which allows the reaction to be controlled and graft polymers with the desired low polydispersity to be prepared in a controlled manner.

[0067] The term "average polymerization temperature" is intended here to mean that the process is substantially isothermal, but due to the exothermic nature of the reaction there may be temperature fluctuations that are preferably maintained within a range of + / - 10°C, more preferably within a range of + / - 5°C.

[0068] According to the present invention, the (radical-forming) initiator (C) at the average polymerization temperature should have a decomposition half-life of 40 to 500 minutes, preferably 50 to 400 minutes, more preferably 60 to 300 minutes.

[0069] According to the invention, the initiator (C) and the grafting monomers (B1) and / or (B2) are advantageously added so that a low and substantially 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 is preferably ≦15% by weight, in particular ≦10% by weight, based on the total amount of initiator metered during the monomer addition.

[0070] The average polymerization temperature is in the range of approximately 50 to 140°C, preferably 60 to 120°C, and more preferably 65 to 110°C.

[0071] Examples of suitable initiators (C) having a decomposition half-life of 20 to 500 minutes in the temperature range of 50 to 140°C include: - tert-C4~C 12 -Alkyl hydroperoxide and tert-(C9-C 12 -aralkyl)hydroperoxides of O-C2 to C 12-acylated derivatives, such as tert-butyl peroxyacetate, tert-butyl monoperoxymaleate, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, tert-amyl peroxyneo-decanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneo-decanoate, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate and di-tert-butyl diperoxyphthalate, - tert-C8~C 14 -Alkylenebisperoxide di-O-C4~C 12 - acylated derivatives, such as 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane and 1,3-di(2-neodecanoylperoxyisopropyl)benzene, - Ji (C2~C 12 -alkanoyl) and dibenzoyl peroxides, for example diacetyl peroxide, dipropionyl peroxide, disuccinyl peroxide, dicapryloyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, di(4-methylbenzoyl) peroxide, di(4-chlorobenzoyl) peroxide and di(2,4-dichlorobenzoyl) peroxide; - tert-C4~C5-Alkylperoxy (C4~C 12 -alkyl) carbonates, for example tert-amylperoxy(2-ethyl-hexyl) carbonate, - Ji (C2~C 12-alkyl)peroxydicarbonates, for example, di(n-butyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate.

[0072] Depending on the average polymerization temperature, examples of particularly suitable initiators (C) are:

[0073] - At an average polymerization temperature of 50 to 60°C, tert-butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-amyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneodecanoate, 1,3-di(2-neodecanoylperoxyisopropyl)benzene, di(n-butyl)peroxydicarbonate, and di(2-ethylhexyl)peroxydicarbonate, - At an average polymerization temperature of 60 to 70°C, tert-butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate and di(2,4-dichlorobenzoyl) peroxide, - At an average polymerization temperature of 70 to 80°C, tert-butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-amyl peroxypivalate, dipropionyl peroxide, dicapryloyl peroxide, didecanoyl peroxide, dilauroyl peroxide, di(2,4-dichlorobenzoyl) peroxide, and 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, - At an average polymerization temperature of 80 to 90°C, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, dipropionyl peroxide, dicapryloyl peroxide, didecanoyl peroxide, dilauroyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, dibenzoyl peroxide, and di(4-methylbenzoyl) peroxide, - At an average polymerization temperature of 90 to 100°C, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl monoperoxymaleate, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide and di(4-methylbenzoyl) peroxide, - At an average polymerization temperature of 100 to 110°C, tert-butyl monoperoxymaleate, tert-butyl peroxyisobutyrate and tert-amylperoxy(2-ethylhexyl)carbonate, - At an average polymerization temperature of 110 to 120°C, tert-butyl monoperoxymaleate, tert-butylperoxy-3,5,5-trimethylhexanoate and tert-amylperoxy(2-ethylhexyl)carbonate.

[0074] Preferred initiators (C) are tert-C4-C5-alkyl hydroperoxides O-C4-C 12 -acylated derivatives, particularly preferred are tert-butyl peroxypivalate and tert-butyl peroxy-2-ethylhexanoate.

[0075] By precisely adjusting the initiator (C) and the polymerization temperature, particularly advantageous polymerization conditions can be established. For example, the preferred average polymerization temperature when tert-butyl peroxypivalate is used is 60 to 80°C, and when tert-butyl peroxy-2-ethylhexanoate is used is 80 to 100°C.

[0076] The polymerization reaction of the present invention can be preferably carried out in the presence of a small amount of organic solvent (D). Of course, it is also possible to use a mixture of different solvents (D). It is preferable to use water-soluble or water-miscible solvents.

[0077] When solvent (D) is used as a diluent, it is generally used in an amount of 1 to 40% by weight, preferably 1 to 35% by weight, more preferably 1.5 to 30% by weight, and most preferably 2 to 25% by weight, in each case based on the total of components (A), (B1), optionally (B2), and (C).

[0078] Examples of suitable solvents (D) include: - monohydric alcohols, preferably aliphatic C1-C 16 -Alcohols, more preferably aliphatic C2-C 12 alcohols, most preferably C2-C4-alcohols, such as ethanol, propanol, isopropanol, butanol, sec-butanol and tert-butanol, - Polyhydric alcohols, preferably C2-C 10 -diols, more preferably C2-C6-diols, most preferably C2-C4-alkylene glycols, such as ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol, - alkylene glycol ethers, preferably alkylene glycol mono(C1-C 12 -alkyl) ethers and alkylene glycol di(C1-C6-alkyl) ethers, more preferably alkylene glycol mono- and di(C1-C2-alkyl) ethers, most preferably alkylene glycol mono(C1-C2-alkyl) ethers, for example ethylene glycol monomethyl and -ethyl ethers and propylene glycol monomethyl and -ethyl ethers, polyalkylene glycols, preferably poly(C2-C4-alkylene) glycols having 2 to 20 C2-C4-alkylene glycol units, more preferably polyethylene glycols having 2 to 20 ethylene glycol units and polypropylene glycols having 2 to 10 propylene glycol units, most preferably polyethylene glycols having 2 to 15 ethylene glycol units and polypropylene glycols having 2 to 4 propylene glycol units, such as diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol, - polyalkylene glycol monoethers, preferably poly(C2-C4-alkylene) glycol mono(C1-C) having 2 to 20 alkylene glycol units; 25 -alkyl) ethers, more preferably poly(C2-C4-alkylene) glycol mono(C1-C4) ethers having 2 to 20 alkylene glycol units. 20 -alkyl) ethers, most preferably poly(C2-C3-alkylene) glycol mono(C1-C2-alkylene) glycol mono(C1-C3-alkylene) ethers having 3 to 20 alkylene glycol units; 16 -alkyl) ethers, carboxy esters, preferably C1-C8-alkyl esters of C1-C6-carboxylic acids, more preferably C1-C4-alkyl esters of C1-C3-carboxylic acids, most preferably C2-C4-alkyl esters of C2-C3-carboxylic acids, such as ethyl acetate and ethyl propionate, aliphatic ketones, preferably having 3 to 10 carbon atoms, such as acetone, methyl ethyl ketone, diethyl ketone and cyclohexanone, - cyclic ethers, in particular tetrahydrofuran and dioxane;

[0079] Solvent (D) is advantageously also used to formulate the graft polymer of the present invention for use (e.g., in laundry and cleaning compositions) and may therefore remain in the polymerization product.

[0080] Preferred examples of these solvents are polyethylene glycols having 2 to 15 ethylene glycol units, polypropylene glycols having 2 to 6 propylene glycol units, and in particular alkoxylation products of C6-C8 alcohols (alkylene glycol monoalkyl ethers and polyalkylene glycol monoalkyl ethers).

[0081] Particularly preferred herein are highly branched C8-C 16 Alkoxylation products of alcohols, which allow the formulation of polymer mixtures with very low polymer contents at relatively low viscosities and free flowing at 40-70°C. Branching can be present in the alkyl chain of the alcohol and / or in the polyalkoxylate moiety (copolymerization of at least one propylene oxide, butylene oxide, or isobutylene oxide unit). Particularly suitable examples of these alkoxylation products are 2-ethylhexanol or 2-propylheptanol alkoxylated with 1-15 mol of ethylene oxide, C alkoxylated with 1-15 mol of ethylene oxide and 1-3 mol of propylene oxide. 13 / C 15 Oxo alcohol or C 12 / C 14 or C 16 / C 18 An aliphatic alcohol is preferably 2-propyl-heptanol alkoxylated with 1 to 15 mol of ethylene oxide and 1 to 3 mol of propylene oxide.

[0082] In the process according to the invention, the block copolymer backbone (A), the grafting monomer (B1), and, if appropriate, (B2), the initiator (C), and, if appropriate, the solvent (D), are typically heated in a reactor to the selected average polymerization temperature.

[0083] According to the invention, the polymerization is carried out so that an excess of polymer (block copolymer backbone (A) and formed graft polymer (B)) is always present in the reactor. The ratio of the amount of polymer to non-grafted monomer and initiator is generally ≧10:1, preferably ≧15:1, more preferably ≧20:1.

[0084] The polymerization process according to the invention can in principle be carried out in various reactor types.

[0085] The reactor used is preferably a stirred tank into which the block copolymer backbone (A), if appropriate, together with the graft monomer (B1) or (B2), the initiator (C) and part of the solvent (D), generally up to 15% by weight of the specified total amount, is first fully or partially charged and heated to the polymerization temperature, and the remaining amounts of (B), (C) and, if appropriate, (D) are preferably metered in separately. (B), (C) and, if appropriate, the remaining amounts of (D) are preferably metered in over a period of ≥ 2 hours, more preferably ≥ 4 hours, most preferably ≥ 5 hours. In the particularly preferred substantially solvent-free process variant, the total weight of the block copolymer backbone (A) is initially charged as a melt, and the grafting monomers (B1) and, if appropriate (B2), also the initiator (C), which is preferably present in the form of a 10 to 50% by weight solution in one of the solvents (D), are metered in, and the temperature is maintained on average during the polymerization within a range of, in particular + / - 10°C, in particular + / - 5°C, of ​​the selected polymerization temperature.

[0086] In a further particularly preferred low-solvent process variant, the procedure is as described above, except that solvent (D) is metered in during polymerization to limit the viscosity of the reaction mixture. It is also possible to start the metered addition of solvent only at a later time with advanced polymerization, or to add it partially.

[0087] The polymerization can be carried out under normal pressure or at low or high pressure. If the boiling point of the monomers (B1) or (B2) or the optional diluent (D) used is exceeded at the selected pressure, the polymerization is carried out with reflux cooling.

[0088] Another subject of the present invention is the use of at least one graft polymer as defined above in laundry detergents, cleaning compositions and / or fabric and home care products.

[0089] A further subject of the present invention is a fabric and home care product comprising the above-described graft polymer. The product may be a laundry detergent, a dish detergent, a cleaning composition, and / or a fabric and home care product containing at least one of the above-described graft polymers.

[0090] Such laundry detergents, cleaning compositions, and / or fabric and home care products are known to those skilled in the art. Any compositions, etc., known to those skilled in the art in connection with the respective uses can be used in the context of the present invention.

[0091] In preferred laundry detergents, cleaning compositions, and / or fabric and home care products according to the present invention, the at least one grafted polymer is present in an amount ranging from about 0.01% to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1% to about 10%, and most preferably from about 0.5% to about 5%, based on the total weight of such composition or product.

[0092] Laundry Detergent Compositions: Suitable laundry detergent compositions include laundry detergent powder compositions, laundry detergent liquid compositions, laundry detergent gel compositions, and aqueous laundry detergent compositions.

[0093] Dishwashing Detergent Compositions: Suitable dishwashing detergent compositions include hand dishwashing detergent compositions and automatic dishwashing detergent compositions.

[0094] Surfactant System: The composition comprises a surfactant system in an amount sufficient to impart the desired cleaning characteristics. In some embodiments, the composition comprises from about 1% to about 70% surfactant system, by weight of the composition. In other embodiments, the liquid composition comprises from about 2% to about 60% surfactant system, by weight of the composition. In further embodiments, the composition comprises from about 5% to about 30% surfactant system, by weight of the composition. The surfactant system may comprise a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and mixtures thereof. One skilled in the art will recognize that a detersive surfactant includes any surfactant or mixture of surfactants that provides cleaning, stain removal, or laundering benefits to soiled materials.

[0095] Anionic Surfactants: In some examples, the surfactant system of the composition may comprise from about 1% to about 70% by weight of the surfactant system of one or more anionic surfactants. In other examples, the surfactant system of the composition may comprise from about 2% to about 60% by weight of the surfactant system of one or more anionic surfactants. In further examples, the surfactant system of the composition may comprise from about 5% to about 30% by weight of the surfactant system of one or more anionic surfactants. In further examples, the surfactant system may consist essentially of, or consist additionally of, one or more anionic surfactants.

[0096] Specific non-limiting examples of suitable anionic surfactants include any conventional anionic surfactant, which may include, for example, sulfate detersive surfactants for alkoxylated and / or non-alkoxylated alkyl sulfate materials, and / or sulfonic acid detersive surfactants, such as alkyl benzene sulfonates.

[0097] Other useful anionic surfactants may include alkali metal salts of alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms in a linear (straight chain) or branched configuration.

[0098] Suitable alkylbenzene sulfonates (LAS) can be obtained by sulfonating commercially available linear alkylbenzenes (LABs). Suitable LABs include low 2-phenyl LABs, such as those supplied by Sasol under the trade name Isochem® or Petrelab® by Petresa; other suitable LABs include high 2-phenyl LABs, such as those supplied by Sasol under the trade name Hyblene®. 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 embodiment, magnesium salts of LAS are used.

[0099] The detersive surfactant may 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 alkyl benzene sulfonate, e.g., a mid-chain branched alkyl sulfate. In one aspect, the mid-chain branching is 1~4 The alkyl groups are typically methyl and / or ethyl groups.

[0100] Other anionic surfactants useful herein are the water-soluble salts of paraffin sulfonates 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 Ethers of alcohols (e.g., derived from animal fat and coconut oil). Mixtures of alkyl benzene sulfonates with the above-mentioned paraffin sulfonates, secondary alkane sulfonates, and alkyl glyceryl ether sulfonates are also useful. Further suitable anionic surfactants include methyl ester sulfonates and alkyl ether carboxylates.

[0101] Anionic surfactants may exist in acid form, and the acid form may be neutralized to form surfactant salts. Typical neutralizing agents include hydroxides, such as metal counterion bases, such as NaOH or KOH. Further suitable neutralizing agents for neutralizing these acid forms of anionic surfactants 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 may be complete or partial; for example, a portion of the anionic surfactant mixture may be neutralized with sodium or potassium, and a portion of the anionic surfactant mixture may be neutralized with amines or alkanolamines.

[0102] Nonionic surfactants: The surfactant system of the composition may include a nonionic surfactant. In some examples, the surfactant system includes up to about 25% by weight of the surfactant system of one or more nonionic surfactants, e.g., as co-surfactants. In some examples, the composition includes from about 0.1% to about 15% by weight of the surfactant system of one or more nonionic surfactants. In further examples, the composition includes from about 0.3% to about 10% by weight of the surfactant system of one or more nonionic surfactants.

[0103] Suitable nonionic surfactants useful herein can include any conventional nonionic surfactant, which can include, for example, alkoxylated fatty alcohols, and amine oxide surfactants.

[0104] Other non-limiting examples of nonionic surfactants useful herein include C8-C 18 Alkyl ethoxylates (NEODOL® nonionic surfactants (Shell), etc.); C6-C 12Alkylphenol alkoxylate (the alkoxylate units can be ethyleneoxy units, propyleneoxy units, or combinations thereof); C 12 ~C 18 C6-C with alcohol and ethylene oxide / propylene oxide block polymer 12 Alkylphenol condensates (such as Pluronic® (BASF)); C 14 ~C 22 Medium-chain branched alcohol (BA); C 14 ~C 22 Medium-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(oxyalkylated) alcohol surfactants.

[0105] Suitable nonionic detersive surfactants also include alkyl polyglucosides and alkyl alkoxylated alcohols. Suitable nonionic surfactants also include those sold by BASF under the trade name Lutensol®.

[0106] Anionic and 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 further examples, the weight ratio of anionic surfactant to nonionic surfactant is at least about 10:1.

[0107] Cationic Surfactants: The surfactant system may include a cationic surfactant. In some embodiments, the surfactant system includes from about 0% to about 7%, from about 0.1% to about 5%, or from about 1% to about 4% by weight of the surfactant system of a cationic surfactant, e.g., as a co-surfactant. In some embodiments, the compositions of the present invention are substantially free of cationic surfactants and surfactants that become cationic at a pH below 7 or below 6. Non-limiting examples of cationic surfactants include quaternary ammonium surfactants, which may have 26 or fewer carbon atoms, including alkoxylate quaternary ammonium (AQA) surfactants; dimethylhydroxyethyl quaternary ammonium; dimethylhydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants; cationic ester surfactants; and amino surfactants, such as amidopropyldimethylamine (APA).

[0108] Suitable cationic detersive surfactants also include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl tertiary sulfonium compounds, and mixtures thereof.

[0109] Zwitterionic surfactants: Examples of zwitterionic surfactants include secondary and tertiary amine derivatives, heterocyclic secondary and tertiary amine derivatives, or derivatives of quaternary ammonium compounds, quaternary phosphonium compounds, or tertiary sulfonium compounds. Betaines, including alkyl dimethyl betaine and cocodimethylamidopropyl betaine, C8-C 18 (For example, C 12 ~C 18 ) amine oxides, and sulfo- and hydroxybetaines such as N-alkyl-N,N-dimethylamino-1-propanesulfonates (wherein the alkyl group is C8-C 18 In particular embodiments, C 10 ~C 14 (It can be said that).

[0110] Amphoteric surfactants: Examples of amphoteric surfactants include aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines, where the aliphatic group can be linear or branched, and one of the aliphatic substituents contains at least about 8 carbon atoms, or from about 8 to about 18 carbon atoms, and at least one of the aliphatic substituents contains an anionic water-solubilizing group, e.g., carboxy, 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, disodium 3-(N-carboxymethyldodecylamino)propane-1-sulfonate, disodium octadecyl-iminodiacetate, sodium 1-carboxymethyl-2-undecylimidazole, and sodium N,N-bis(2-hydroxyethyl)-2-sulfato-3-dodecoxypropylamine. Suitable amphoteric surfactants also include sarcosinates, glycinates, taurinates, and mixtures thereof.

[0111] Branched Detersive Surfactants: Suitable branched detersive surfactants include branched sulfate or branched sulfonate surfactants, such as branched alkyl sulfates, branched alkyl alkoxylated sulfates, and branched alkyl benzene sulfonates, and may include one or more random alkyl branches, such as C 1~4 Included are anionic branched surfactants containing alkyl groups, typically methyl and / or ethyl groups.

[0112] The branched detersive surfactant may 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 alkyl benzene sulfonate. In some embodiments, the detersive surfactant is a mid-chain branched alkyl sulfate. In some embodiments, the mid-chain branching is C 1~4 The alkyl groups are typically methyl and / or ethyl groups.

[0113] Further suitable branched anionic detersive surfactants include surfactants derived from alcohols branched at the 2-alkyl position, such as those sold under the trade names Isalchem® 123, Isalchem® 125, Isalchem® 145, and Isalchem® 167, which are derived from the oxo process. Due to the oxo process, the branching is at the 2-alkyl position. These 2-alkyl branched alcohols typically range in length from C11 to C14 / C15, and all include structural isomers branched at the 2-alkyl position.

[0114] Auxiliary Cleaning Additives: The compositions of the present invention may also contain auxiliary cleaning additives. Suitable auxiliary cleaning additives include builders, structurants or thickeners, mud soil removal / anti-redeposition agents, polymeric soil release agents, polymeric dispersants, polymeric grease cleaners, enzymes, enzyme stabilizing systems, bleaching compounds, bleaches, bleach activators, bleach catalysts, brighteners, dyes, hueing agents, dye transfer inhibitors, chelating agents, suds suppressors, softeners, and fragrances.

[0115] Enzymes: The compositions described herein may contain one or more enzymes that provide cleaning performance and / or fabric care benefits. Examples of suitable enzymes include, but are not limited to, hemicellulase, peroxidase, protease, cellulase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, mannanase, pectate lyase, keratinase, reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, and amylase, or mixtures thereof. A typical combination is an enzyme cocktail, which may include, for example, protease and lipase together with amylase. When present in the composition, the additional enzymes may be present at an enzyme protein concentration of from about 0.00001% to about 2%, from about 0.0001% to about 1%, or even from about 0.001% to about 0.5% by weight of the composition.

[0116] In one aspect, preferred enzymes may include proteases. Suitable proteases include metalloproteases and serine proteases, including, for example, neutral or alkaline microbial serine proteases such as subtilisin (EC 3.4.21.62). Suitable proteases include those of animal, plant, or microbial origin. In one aspect, such suitable proteases may be of microbial origin. Suitable proteases include chemically or genetically modified variants of the aforementioned suitable proteases. In one aspect, suitable proteases may be serine proteases, such as alkaline microbial proteases and / or trypsin-type proteases. Examples of suitable neutral or alkaline proteases include: (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). (b) trypsin-type or chymotrypsin-type proteases, such as trypsin (e.g., of porcine or bovine origin), including Fusarium protease and chymotrypsin protease derived from Cellumonas. (c) Metalloproteases, including those derived from Bacillus amyloliquefaciens.

[0117] Preferred proteases include those derived from Bacillus gibsonii or Bacillus lentus.

[0118] Suitable commercially available protease enzymes include those sold under the trade names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®, Ovozyme®, Neutrase®, Everlase® and Esperase® by Novozymes A / S (Denmark); those sold under the trade names Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excellase® and Purafect OXP® by Genencor International; Enzymes under the trade names Opticlean® and Optimase®, those available from Henkel / Kemira, namely BLAP (having the following mutations S99D+S101R+S103A+V104I+G159S, hereafter 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 available from Henkel / Kemira), and Kao's KAP (a subtilisin derived from Bacillus alkalophilus with the mutations A230V+S256G+S259N).

[0119] Suitable α-amylases include those of bacterial or fungal origin, including chemically or genetically modified variants. Preferred alkaline α-amylases are derived from Bacillus species, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus species, e.g., Bacillus species, strains such as NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375, DSM 12368, DSMZ no. 12649, KSM AP1378, KSM K36, or KSM K38.

[0120] Suitable commercially available α-amylases include DURAMYL®, LIQUEZYME®, TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®, STAINZYME®, STAINZYME PLUS®, FUNGAMYL®, and BAN® (Novozymes A / S, Bagsvaerd, Denmark), KEMZYM® AT 9000 (Biozym Biotech Trading GmbH, Wehlistrasse 27b A-1200 Wien, Austria), RAPIDASE®, PURASTAR®, ENZYSIZE®, OPTISIZE HT PLUS®, POWERASE®, and PURASTAR OXAM® (Genencor International Inc., Palo Alto, CA). Alto, California), and KAM® (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku, Tokyo 103-8210, Japan). In one aspect, suitable amylases include NATALASE®, STAINZYME®, and STAINZYME PLUS®, and mixtures thereof.

[0121] In one aspect, such enzymes may 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 the wild-type lipase from Thermomyces lanuginosus, containing one or more of the T231R and N233R mutations. The wild-type sequence is Swiss-Prot Accession No. Swiss-Prot O59952 (269 amino acids (amino acids 23-291) from Thermomyces lanuginosus (Humicola lanuginosa)). Preferred lipases include those sold under the trade names Lipex® and Lipolex®.

[0122] In one aspect, other preferred enzymes include endoglucanases derived from microorganisms exhibiting endo-beta-1,4-glucanase activity (EC 3.2.1.4) and mixtures thereof. Suitable endoglucanases are sold under the trade names Celluclean® and Whitezyme® (Novozymes A / S, Bagsvaerd, Denmark).

[0123] Other preferred enzymes include pectate lyases sold under the trade names Pectawash®, Pectaway®, Xpect®, and mannases sold under the trade names Mannaway® (all from Novozymes A / S, Bagsvaerd, Denmark), and Purabrite® (from Genencor International Inc., Palo Alto, California).

[0124] Enzyme-Containing Compositions: The enzyme-containing compositions described herein may optionally comprise 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%, by weight of the composition, of an enzyme stabilizing system. The enzyme stabilizing system may be any stabilizing system compatible with the detersive enzyme. In the case of aqueous detergent compositions containing proteases, reversible protease inhibitors such as boron compounds, including borate, 4-formylphenylboronic acid, phenylboronic acid, and derivatives thereof, or compounds such as calcium formate, sodium formate, and 1,2-propanediol may be added to further improve stability.

[0125] Builder: The compositions of the present invention may optionally contain a builder. Built compositions typically contain at least about 1% by weight of builder, based on the total weight of the composition. Liquid compositions may contain up to about 10%, and in some instances, up to 8%, of builder by total weight of the composition. Granular compositions may contain up to about 30%, and in some instances, up to 5% of builder by weight of the composition.

[0126] Builders selected from aluminosilicates (e.g., zeolite builders such as zeolite A, zeolite P, and zeolite MAP) and silicates assist in controlling mineral hardness, especially calcium and / or magnesium, in wash water or in removing particulate soils from surfaces. Suitable builders may be selected from the group consisting of phosphates, such as polyphosphates (e.g., sodium tri-polyphosphate), especially its sodium salt; carbonates, bicarbonates, sesquicarbonates, and carbonate minerals other than sodium carbonate or sesquicarbonates; organic mono-, di-, tri-, and tetracarboxylates, especially water-soluble non-surfactant carboxylates in the form of acid, sodium, potassium, or alkanolammonium salts, as well as oligomeric or water-soluble low-molecular-weight polymeric carboxylates, including aliphatic and aromatic species, and phytic acid. These may be supplemented, for example, by borates for pH buffering purposes, or by sulfates, especially sodium sulfate, and any other fillers or carriers that may be important in engineering stable surfactant- and / or builder-containing compositions. Additional suitable builders may 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 and other suitable ethylenic monomers with various types of additional functional groups. Also suitable for use as builders herein are synthetic crystalline ion exchange materials or hydrates thereof having a chain structure and a composition represented by the following general anhydrous form: x(MO)·ySiO·zMO, where 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.

[0127] Alternatively, the composition may be substantially free of builders.

[0128] Structurants / Thickeners: Suitable structurants / thickeners include: i. Dibenzylidene polyol acetal derivatives ii. Bacterial cellulose iii. Coated bacterial cellulose iv. Cellulose fibers derived from non-bacterial cellulose v. Non-polymeric crystalline hydroxy-functional materials vi. Polymeric structuring agents vii. Diamide gelling agent viii. Any combination of the above.

[0129] Polymeric Dispersants: The composition may include one or more polymeric dispersants. Examples are carboxymethylcellulose, poly(vinyl-pyrrolidone), poly(ethylene glycol), poly(vinyl alcohol), poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylates such as polyacrylates, maleic acid / acrylic acid copolymers, and lauryl methacrylate / acrylic acid copolymers.

[0130] The composition has the following general structure: bis((C2H5O)(C2H4O)n)(CH3)-N + -C x H 2x -N + It may include one or more amphiphilic cleaning polymers such as a compound having the formula -(CH3)-bis((C2H5O)(C2H4O)n) where n=20-30 and x=3-8, or sulfated or sulfonated variants thereof.

[0131] The compositions may include amphiphilic alkoxylated grease cleaning polymers that have balanced hydrophilic and hydrophobic properties to remove grease particles from fabrics and surfaces. Specific embodiments of the amphiphilic alkoxylated grease cleaning polymers of the present invention include a core structure and a plurality of alkoxylate groups attached to the core structure. These may include, for example, alkoxylated polyalkyleneimines having an inner polyethylene oxide block and an outer polypropylene oxide block.

[0132] Alkoxylated polyamines can be used for grease and particulate removal. Such compounds include, but are not limited to, ethoxylated polyethyleneimine, ethoxylated hexamethylenediamine, and their sulfated derivatives. Polypropoxylated derivatives can also be included. A wide variety of amines and polyalkyleneimines can be alkoxylated to various degrees. A useful example is a 600 g / mole polyethyleneimine core ethoxylated to 20 EO groups per NH, available from BASF.

[0133] The composition may comprise a hydrophilic backbone comprising monomers such as, for example, unsaturated C1-C6 carboxylic acids, ethers, alcohols, aldehydes, ketones, esters, sugar units, alkoxy units, maleic anhydride, saturated polyalcohols such as glycerol, and mixtures thereof, and one or more C4-C6 carboxylic acids, for example, unsaturated C1-C6 carboxylic acids, ethers, alcohols, aldehydes, ketones, esters, sugar units, alkoxy units, maleic anhydride, saturated polyalcohols such as glycerol, and mixtures thereof. 25 Examples of such graft polymers include random graft polymers containing hydrophobic side chains such as alkyl groups, polypropylene, polybutylene, vinyl esters of saturated C1-C6 monocarboxylic acids, C1-C6 alkyl esters of acrylic or methacrylic acid, and mixtures thereof. Specific examples of such graft polymers are based on polyalkylene oxides and vinyl esters, particularly vinyl acetate. These polymers are typically prepared by polymerizing vinyl esters in the presence of polyalkylene oxides, with initiators such as dibenzoyl peroxide, dilauroyl peroxide, or diacetyl peroxide.

[0134] The composition may contain blocks of ethylene oxide and propylene oxide. Examples of such block polymers include ethylene oxide-propylene oxide-ethylene oxide (EO / PO / EO) triblock copolymers, in which the copolymer contains a first EO block, a second EO block, and a PO block, with the first EO block and the second EO block connected to the PO block. The ethylene oxide, propylene oxide, and butylene oxide blocks may also be arranged in other ways, such as (EO / PO) diblock copolymers and (PO / EO / PO) triblock copolymers. The block polymer may also contain an additional butylene oxide (BO) block.

[0135] 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 embodiment, the carboxylate polymer is a polyacrylate homopolymer having a molecular weight of 4,000 Da to 9,000 Da or 6,000 Da to 9,000 Da.

[0136] 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%, and in some embodiments, 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").

[0137] Soil release polymers typically have a hydrophilic segment for hydrophilizing the surface of hydrophobic fibers such as polyester and nylon, and a hydrophobic segment that deposits on the hydrophobic fibers and remains attached there until the completion of the washing and rinsing cycle, thereby serving as an anchor for the hydrophilic segment. This can make the soil that is lifted after treatment with the soil release agent more easily washable in the subsequent washing procedure. It is also believed that promoting soil release helps improve or maintain the wicking properties of fabrics.

[0138] The structure and charge distribution of the soil release polymer may be tailored for application to different types of fibers or fabrics and for formulation in different detergent or detergent additive products. The soil release polymer may be linear, branched, or star-shaped.

[0139] The soil release polymer may also comprise various charged units (e.g., anionic or cationic units) and / or uncharged (e.g., nonionic) monomer units. Typically, when the SRP is used in combination with a cationic fabric conditioning active, such as a quaternary ammonium ester compound, a nonionic SRP may be particularly preferred to avoid potentially negative interactions between the SRP and the cationic active.

[0140] The soil release polymer may include end-capping moieties that are particularly effective in controlling the molecular weight of the polymer or altering the physical or surface active properties of the polymer.

[0141] One preferred class of suitable soil release polymers includes terephthalate-derived polyester polymers comprising structural units (I) and / or (II): (I) -[(OCHR 1 -CHR 2 ) a -O-OC-Ar-CO-] d (II) -[(OCHR 3 -CHR 4 ) b -O-OC-sAr-CO-] e During the ceremony, a and b are 1 to 200; d and e are 1 to 50; Ar is 1,4-substituted phenylene; sAr is a 1,3-substituted phenylene substituted at the 5-position with SO3M; M is Na, Li, K, Mg / 2, Ca / 2, Al / 3, ammonium, mono-, di-, tri-, or tetra-alkylammonium (the alkyl groups are C1-C 18Alkyl or C2-C 10 hydroxyalkyl), or mixtures thereof; R 1 , R 2 , R 3 , R 4 are independently H or C1 to C 18 selected from n-alkyl or iso-alkyl, Optionally, the polymer further comprises one or more end groups (III) derived from a polyalkylene glycol monoalkyl ether, preferably selected from structure (IV-a):

[0142] [ka] During the ceremony, R7 is a linear or branched C 1~30 Alkyl, C2-C 30 Alkenyl or cycloalkyl groups having 5 to 9 carbon atoms, or C8 to C 30 Aryl group or C6-C 30 Aryl alkyl groups, preferably C 1~4 alkyl, more preferably methyl; c, d, and e are numbers independently selected from 0 to 200 on a molar average basis, and the sum of c+d+e is 2 to 500; The [C2H4-O], [C3H6-O] and [C4H8-O] groups of the terminal group (IV-a) may be arranged blockwise, alternatingly, periodically and / or statistically, preferably blockwise and / or statistically, and any of the [C2H4-O], [C3H6-O] and [C4H8-O] groups of the terminal group (IV-a) may be linked to -R7 and / or -O.

[0143] Optionally, the polymer further comprises one or more anionic terminal units (IV) and / or (V), as described in EP 3222647. M is a counterion selected from Na, Li, K, Mg / 2, Ca / 2, Al / 3, ammonium, mono-, di-, tri-, or tetra-alkylammonium, and the alkyl group is C1-C18 alkyl or C2-C10 hydroxyalkyl, or mixtures thereof.

[0144] [ka]

[0145] Optionally, the polymer may contain crosslinked multifunctional structural units having at least three functional groups capable of esterification reactions, such as acid, alcohol, ester, anhydride, or epoxy groups.

[0146] Optionally, the polymer may contain other di- or polycarboxylic acids, 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 thereof or (di)alkyl esters thereof, preferably (C1-C4)-(di)alkyl esters thereof, more preferably (di)methyl esters thereof, or mixtures thereof, or salts thereof or (di)alkyl esters thereof can be used in the polyesters of the present invention.

[0147] Preferably, suitable terephthalate-derived soil release polymers are non-ionic and do not include structure (II) above. Further, certain preferred non-ionic terephthalate-derived soil release polymers have a structure according to the following formula:

[0148] [ka] During the ceremony, R5 and R6 are independently selected from H or CH3. More preferably, one of R5 and R6 is H and the other is CH3. c and d are numbers independently selected from 0 to 200 on a molar average basis, and the sum of c and d is 2 to 400; More preferably, d is 0 to 50, and c is 1 to 200. More preferably, d is 1 to 10 and c is 5 to 150. R7 is C 1~4 alkyl, more preferably methyl; n is 1 to 50 on a molar average basis.

[0149] One example of the most preferred terephthalate-derived soil release polymer is one in which one of R5 and R6 is H and the other is CH3, d is 0, c is 5 to 100, and R7 is methyl.

[0150] Suitable terephthalate-derived soil release polymers can also be described as sulfonated and non-sulfonated PET / POET (polyethylene terephthalate / polyoxyethylene terephthalate) polymers, both end-capped and non-end-capped. Examples of suitable soil release polymers include TexCare® polymers supplied by Clariant, including TexCare® SRA-100, SRA-300, SRN-100, SRN-170, SRN-240, SRN-260, SRN-300, and SRN-325.

[0151] Other suitable terephthalate-derived soil release polymers are described in WO 2014019903, WO 2014019658, and WO 2014019659.

[0152] Another class of soil release polymers also includes modified celluloses.Suitable modified celluloses 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, hydroxypropylmethyl cellulose, and hydroxybutylmethyl cellulose.In some embodiments, the modified celluloses can include hydrocarbons of C4 or more, and the preferred length of the alkyl group is C4, C6, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33, C34, C35, C36, C37, C38, C39, C40, C41, C42, C43, C44, C45, C46, ​​C47, C48, C49, C50, C51, C52, C53, C54, C55, C56, C57, C58, C59, C60, C61, C62, C63, C64, C65, C66, C67, C68, C69, C70, C71, C72, C73, C74, C75, C76, C77, C78, ​​C79, C79, C80, C81, C82, C83, C84, C85, C86, C87, C88, C89, C90, C91, C92, C93, C94, C95, C96, C97, C98, C99, C99 10 , C 12 , C 14 , C 16 , C 18 Examples of suitable modified celluloses are described in WO 2019111948 and WO 2019111949. In some embodiments, the modified cellulose can include an additional cationic modification, examples of suitable modified celluloses with additional cationic modifications are described in WO 2019111946 and WO 2019111947.

[0153] Another example of a commercially available soil release polymer is the REPEel O-TEX® line of polymers supplied by RHODIA, such as REPEel O-TEX® SF, SF-2, and SRP6. Other suitable soil release polymers are the Marloquest® polymers supplied by Sasol, such as Marloquest® SL, HSCB, L235M, B, G82, etc. Further suitable soil release polymers of a different type include the commercially available materials ZELCON 5126 (DuPont), MILEASE T (ICI), and Sorez 100 (ISP).

[0154] Cellulosic polymer: The compositions herein may comprise from about 0.1% to about 10%, typically from about 0.5% to about 7%, and in some embodiments, from about 3% to about 5%, by weight of the composition, of a cellulosic polymer.

[0155] Suitable cellulosic polymers include alkyl celluloses, alkyl alkoxyalkyl celluloses, carboxyalkyl celluloses, and alkyl carboxyalkyl celluloses. In some embodiments, the cellulosic polymer is selected from carboxymethyl cellulose, methyl cellulose, methylhydroxyethyl cellulose, methylcarboxymethyl cellulose, and mixtures thereof. In some embodiments, the cellulosic polymer is carboxymethyl cellulose having a degree of carboxymethyl substitution of about 0.5 to about 0.9 and a molecular weight of about 100,000 Da to about 300,000 Da.

[0156] Carboxymethylcellulose polymers include hydrophobically modified carboxymethylcelluloses such as Finnfix® GDA (sold by CP Kelko), an alkyl ketene dimer derivative of carboxymethylcellulose sold, for example, under the trade name Finnfix® SH1 (CP Kelko), or block-based carboxymethylcelluloses sold under the trade name Finnfix® V (sold by CP Kelko).

[0157] Additional Amines: Various amines may be used in the compositions described herein to enhance the removal of grease and particles from soiled materials. The compositions described herein may comprise 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% by weight of the composition of an additional amine. Non-limiting examples of additional amines may include, but are not limited to, polyamines, oligoamines, triamines, diamines, pentamines, tetraamines, or combinations thereof. Specific examples of suitable additional amines include tetraethylenepentamine, triethylenetetraamine, diethylenetriamine, or mixtures thereof.

[0158] For example, alkoxylated polyamines can be used for grease and particulate removal. Such compounds can include, but are not limited to, ethoxylated polyethyleneimine, ethoxylated hexamethylenediamine, and sulfated versions thereof. Polypropoxylated derivatives can also be included. A wide variety of amines and polyalkyleneimines can be alkoxylated to various degrees. A useful example is a 600 g / mole polyethyleneimine core ethoxylated to 20 EO groups per NH, available from BASF. The compositions described herein may comprise from about 0.1% to about 10% by weight of the composition of alkoxylated polyamine, in some examples from about 0.1% to about 8% by weight, and in other examples from about 0.1% to about 6% by weight.

[0159] Alkoxylated polycarboxylates may also be used in the compositions herein to remove grease. Chemically, these materials comprise polyacrylates with one ethoxy side chain for every 7 to 8 acrylate units. The side chains have the formula -(CH2CHO) m (CH2) nCH3, where m is 2-3 and n is 6-12. The side chains are ester-linked to the polyacrylate "backbone" to provide a "comb" polymer type structure. The molecular weight can vary but may be in the range of about 2000 to about 50,000. The compositions described herein may comprise from about 0.1% to about 10%, in some instances from about 0.25% to about 5%, and in other instances from about 0.3% to about 2%, by weight of the composition, of an alkoxylated polycarboxylate.

[0160] Bleaching Compounds, Bleaching Agents, Bleach Activators: 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 in a concentration of about 1% to about 30% by weight, and in some examples, about 5% to about 20% by weight, based on the total weight of the composition. When present, the amount of bleach activator may be about 0.1% to about 60% by weight, and in some examples, about 0.5% to about 40% by weight of the bleaching composition including the bleaching agent plus bleach activators.

[0161] Examples of bleaching agents include oxygen bleaches, perborate bleaches, percarboxylic acid bleaches and their salts, peroxygen bleaches, persulfate bleaches, percarbonate bleaches, and mixtures thereof.

[0162] In some examples, the composition may also include a transition metal bleach catalyst.

[0163] Bleaching agents other than oxygen bleaches are also known in the art and can be used in the compositions. These include, for example, photoactivated bleaches, or preformed organic peracids such as peroxycarboxylic acids or their salts, or peroxysulfonic acids or their salts. A suitable organic peracid is phthaloylimoperoxycaproic acid. When used, the compositions described herein may typically contain such bleaching agents, and in some instances, zinc phthalocyanine sulfonate, in amounts of from about 0.025% to about 1.25% by weight of the composition.

[0164] Brightening Agents: Optical brighteners or other brightening or whitening agents may be incorporated into the compositions described herein at a concentration of about 0.01% to about 1.2% by weight of the composition. Commercially available optical brighteners that may be used herein can be divided into subgroups that include, but are not necessarily limited to, derivatives of stilbenes, pyrazolines, coumarins, benzoxazoles, carboxylic acids, methine cyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered heterocycles, and various other agents.

[0165] In some examples, the optical brightener is disodium 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate (brightener 15, commercially available under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation), disodium 4,4'-bis{[4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate (brightener 15, commercially available under the trade name Tinopal UNPA-GX by Ciba-Geigy Corporation), disodium 4,4'-bis{[4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate (brightener 15, commercially available under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation), disodium 4,4'-bis{[4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate (brightener 15, commercially available under the trade name Tinopal UNPA-GX by Ciba-Geigy Corporation), or disodium 4,4'-bis{[4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate (brightener 15, commercially available under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation). More preferably, the optical brightener is disodium 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate.

[0166] The whitening agent may be added in particulate form or as a premix with a suitable solvent, such as a non-ionic surfactant, monoethanolamine, propanediol.

[0167] Fabric hueing agents: The present compositions may include fabric hueing agents (sometimes called shading agents, bluing agents, or whitening agents). Typically, hueing agents impart a blue or blue-purple hue to fabrics. Hueing agents can be used either alone or in combination to create specific hue shades and / or tint different types of fabrics. This can be achieved, for example, by mixing red and green-blue dyes to produce a blue or purple hue. The hueing agent may be selected from any known chemical class of dyes, including, but not limited to, acridines, anthraquinones (including polycyclic quinones), azines, azos including premetallized azos (e.g., monoazos, diazos, trisazos, tetrakisazos, polyazos), benzodifurans and benzodifuranones, carotenoids, coumarins, cyanines, diazahemicyanines, diphenylmethanes, formasans, hemicyanines, indigoids, methanes, naphthalimides, naphthoquinones, nitro and nitroso, oxazines, phthalocyanines, pyrazoles, stilbenes, styryls, triarylmethanes, triphenylmethanes, xanthenes, and mixtures thereof.

[0168] Dye Transfer Inhibitors: The compositions may also include one or more substances effective in preventing the transfer of dyes from one fabric to another during the washing process. Generally, such dye transfer inhibitors can include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase, and mixtures thereof. When used, these agents may be used at a concentration of from about 0.0001% to about 10% by weight of the composition, in some instances from about 0.01% to about 5% by weight of the composition, and in other instances from about 0.05% to about 2% by weight of the composition.

[0169] Chelating Agents: The compositions described herein may also contain 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-pyridinol-N-oxide compounds, hydroxamic acids, carboxymethyl inulin, and mixtures thereof. The chelating agents may be present in the acid form or in the salt form, including alkali metal salts, ammonium salts, and substituted ammonium salts thereof, and mixtures thereof.

[0170] The chelating agent may be present in the compositions disclosed herein from about 0.005% to about 15%, from about 0.01% to about 5%, from about 0.1% to about 3.0%, or from about 0.2% to about 0.7%, or from about 0.3% to about 0.6% by weight of the composition.

[0171] Aminocarboxylates useful as chelating agents include, but are not limited to, ethylenediaminetetracetate (EDTA); N-(hydroxyethyl)ethylenediaminetriacetate (HEDTA); nitrilotriacetate (NTA); ethylenediaminetetraproprionate; triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate (DTPA); methylglycinediacetic acid (MGDA); glutamic acid diacetic acid (GLDA); ethanoldiglycine; triethylenetetraaminehexaacetic acid (TTHA); N-hydroxyethyliminodiacetic acid (HEIDA); dihydroxyethylglycine (DHEG); ethylenediaminetetrapropionic acid (EDTP), and derivatives thereof.

[0172] Encapsulating Agent: The composition may comprise an encapsulating agent. In some embodiments, the encapsulating agent comprises a core, a shell having an inner surface and an outer surface, the shell encapsulating the core.

[0173] In certain embodiments, the encapsulating agent comprises a core and a shell, wherein the core comprises a material selected from fragrances, brighteners, dyes, insect repellents, silicones, waxes, fragrances, vitamins, fabric softeners, skin care agents such as paraffin, enzymes, antibacterial agents, bleaching agents, sensates, or mixtures thereof, and the shell comprises a material selected from polyethylene, polyamides, polyvinyl alcohols, optionally containing other comonomers, polystyrene, polyisoprene, polycarbonates, polyesters, polyacrylates, polyolefins, polysaccharides such as alginates and / or chitosan, gelatin, shellac, epoxy resins, vinyl polymers, water-insoluble inorganic materials, silicones, amino resins, or mixtures thereof. In some embodiments where the shell comprises an aminoplast, the aminoplast comprises polyurea, polyurethane, and / or polyureaurethane. The polyurea may comprise polyoxymethylene urea and / or melamine formaldehyde.

[0174] The fabric and home care products are typically suitable for (a) finished textile care, finished textile laundering, finished textile sanitizing, finished textile disinfecting, detergents, stain removers, softeners, fabric enhancers, stain removal or finished textile treatment, pre-wash and post-wash treatment, washing machine cleaning and maintenance (finished textile is intended to include clothing and fabric products), (b) care of dishes, glasses, china, pots, pans, utensils, cutlery, and the like in automatic dishwashers, such as dishwasher detergents, detergents for both the water used and its contents, pre- and post-treatment and equipment cleaning and maintenance products, or (c) hand dishwashing detergents.

[0175] Fabric and home care products typically include additional fabric and home care ingredients such as those described in more detail above.

[0176] Liquid laundry detergent composition. Fabric and home care products can be laundry detergent compositions, such as liquid laundry detergent compositions. Suitable liquid laundry detergent compositions include non-soap surfactants, which may include anionic non-soap surfactants and nonionic surfactants. The laundry detergent composition may contain 10% to 60%, or 20% to 55%, by weight of the laundry detergent composition. The ratio of non-soap anionic surfactants to nonionic surfactants 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 sulfonate to alkyl sulfate may be 1:2 to 9:1, 1:1 to 7:1, or 1:1 to 5:1, most preferably 1:1 to 4:1. Suitable linear alkylbenzene sulfonates include C 10 ~C 16 Alkylbenzene sulfonic acid or C 11 ~C 14 The alkyl benzene sulfonic acid. Suitable alkyl sulfate anionic surfactants include alkoxylated alkyl sulfates, non-alkoxylated alkyl sulfates, and mixtures thereof. Preferably, the HLAS surfactant has a C of greater than 50%. 12 , preferably more than 60%, preferably more than 70% C 12 , more preferably more than 75% C 12Suitable alkoxylated alkyl sulfate anionic surfactants include ethoxylated alkyl sulfate anionic surfactants. Suitable alkyl sulfate anionic surfactants include ethoxylated alkyl sulfate anionic surfactants having a molar average degree of ethoxylation of 1 to 5, 1 to 3, or 2 to 3. The alkyl alkoxylated sulfates can have a broad alkoxy distribution or a peaked alkoxy distribution. The alkyl moieties of the AES can contain, on average, 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 can contain alkyl moieties 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, and the alkyl sulfate anionic surfactants have a molar average degree of ethoxylation of 1 to 5, 1 to 3, or 2 to 3. The alkyl fraction of the alkyl sulfate anionic surfactant may be derived from an aliphatic alcohol, an oxo-synthetic alcohol, a Guerbet alcohol, or a mixture thereof. Preferred alkyl sulfates include optionally 2-alkyl branched primary alcohol sulfates, particularly 2-branched C alkyl sulfates. 12~15 Primary alcohol sulfates, linear primary alcohol sulfates, especially linear C 12~14 and ethoxylated alcohol sulfates, including primary 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% of the non-soap anionic surfactant, by weight of the laundry detergent composition.

[0177] Suitable nonionic surfactants may be selected from broad or narrow range alkoxylated alcohols, oxo-synthetic alcohol alkoxylates, Guerbet alcohol alkoxylates, alkylphenol alcohol alkoxylates, or mixtures thereof. The laundry detergent composition may comprise from 0.01% to 10%, 0.01% to 8%, 0.1% to 6%, or 0.15% to 5% of nonionic surfactant by weight of the liquid laundry detergent composition.

[0178] 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%, by weight of the laundry detergent composition, of a soap, such as a fatty acid salt. Such soaps may be amine-neutralized, for example, using an alkanolamine, such as monoethanolamine.

[0179] 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 adjusters, antioxidants, antibacterial agents, antimicrobial agents, preservatives, and mixtures thereof.

[0180] 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, the pH of the laundry detergent composition being measured at a 10% product concentration in demineralized water at 20°C.

[0181] Liquid laundry detergent compositions may be Newtonian or non-Newtonian, preferably non-Newtonian.

[0182] In 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.

[0183] The detergent composition according to the present invention may be a liquid laundry detergent composition. The following is an exemplary liquid laundry detergent formulation. Preferably, the liquid laundry detergent composition comprises 0.1% to 4.0%, preferably 0.5% to 3%, more preferably 1% to 2.5% by weight of the detergent composition according to the present invention of sulfated esteramine chloride.

[0184] [Table 1] Explanation of superscript numbers: 1. C12-15 EO2.5S alkyl ethoxy sulfate, in which the alkyl portion of the AES contains from about 13.9 to about 14.6 carbon atoms. 2 PE-20 available from BASF 3 The nuclease enzyme is as claimed in co-pending European patent application 19219568.3 4. Antioxidant 1 is 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, methyl ester [6386-38-5] 5 Antioxidant 2 is Tinogard TS, commercially available from BASF 6 The sanitizer is Tinosan HP100, commercially available from BASF. 7 Defoamer blend supplied by Dow Corning, 80-92% ethylmethyl, methyl(2-phenylpropyl)siloxane, 5-14% MQ resin in octyl stearate, 3-7% modified silica. 8 The optical brightener is disodium 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate or 2,2'-([1,1'-biphenyl]-4,4'-diyldi-2,1-ethenediyl)bis-benzenesulfonic acid disodium salt.

[0185] Water-soluble unit dose article. The fabric and home care product may be a water-soluble unit-dose article. The water-soluble unit-dose article comprises at least one water-soluble film oriented to create at least one unit-dose internal compartment, the at least one unit-dose internal compartment containing a detergent composition. The water-soluble film preferably comprises a polyvinyl alcohol homopolymer or a polyvinyl alcohol copolymer, such as a blend of polyvinyl alcohol homopolymer and / or polyvinyl alcohol copolymer, for example, a copolymer selected from sulfonated and carboxylated anionic polyvinyl alcohol copolymers, particularly carboxylated anionic polyvinyl alcohol copolymers, such as a blend of polyvinyl alcohol homopolymer and carboxylated anionic polyvinyl alcohol copolymer. In some examples, the water-soluble film may be one supplied by Monosol under product reference numbers M8630, M8900, M8779, or M8310. The detergent product comprises a detergent composition, more preferably a laundry detergent composition. Preferably, the laundry detergent composition packaged in the water-soluble unit dose article comprises 0.1% to 8%, preferably 0.5% to 7%, more preferably 1.0% to 6.0% by weight of the detergent composition of the present invention of sulfated esteramine chloride. Preferably, the soluble unit dose laundry detergent composition comprises a non-soap surfactant, which comprises an anionic non-soap surfactant and a nonionic surfactant. More preferably, the laundry detergent composition comprises 10% to 60%, or 20% to 55% by weight of the laundry detergent composition of non-soap surfactant. The weight ratio of non-soap anionic surfactant to nonionic 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 alkyl benzene sulfonate, an alkyl sulfate, or a mixture thereof. The weight ratio of linear alkylbenzene sulfonate to 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 include C 10 ~C 16 Alkylbenzene sulfonic acid or C11 ~C 14It is an alkyl benzene sulfonic acid. "Linear" as used herein means that the alkyl group is straight-chained. Exemplary alkyl sulfate anionic surfactants may include alkoxylated alkyl sulfates, 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 include ethoxylated alkyl sulfate anionic surfactants having a molar average degree of ethoxylation of 1 to 5, 1 to 3, or 2 to 3. Exemplary alkyl sulfate anionic surfactants may include non-ethoxylated alkyl sulfates and ethoxylated alkyl sulfates, where the molar average degree of ethoxylation of the alkyl sulfate anionic surfactants is 1 to 5, 1 to 3, or 2 to 3. Exemplary alkyl fractions of alkyl sulfate anionic surfactants are derived from fatty alcohols, oxosynthetic alcohols, Guerbet alcohols, or mixtures thereof. Preferably, the laundry detergent composition comprises 10% to 50%, 15% to 45%, 20% to 40%, or 30% to 40% of the non-soap anionic surfactant by weight of the laundry detergent composition. In some examples, the nonionic surfactant is selected from alcohol alkoxylates, oxosynthetic alcohol alkoxylates, Guerbet alcohol alkoxylates, alkylphenol alcohol alkoxylates, or mixtures thereof. Preferably, the laundry detergent composition comprises 0.01% to 10%, 0.01% to 8%, 0.1% to 6%, or 0.15% to 5% of the nonionic surfactant by weight of the liquid laundry detergent composition. Preferably, the laundry detergent composition comprises from 1.5% to 20%, from 2% to 15%, from 3% to 10%, or from 4% to 8%, by weight of the laundry detergent composition, of soap, in some instances a fatty acid salt, in some instances an amine-neutralized fatty acid salt, in some instances the amine is an alkanolamine, preferably monoethanolamine. Preferably, the liquid laundry detergent composition comprises less than 15%, or less than 12%, by weight of the liquid laundry detergent composition of water.Preferably, the laundry detergent composition comprises 10% to 40%, or 15% to 30%, by weight of the liquid laundry detergent composition, of a non-aqueous solvent selected from 1,2-propanediol, dipropylene glycol, tripropylene glycol, glycerol, sorbitol, polyethylene glycol, or mixtures thereof. Preferably, the liquid laundry detergent composition comprises 0.1% to 10%, preferably 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 commercially available from Clariant under the Texcare brand, amphiphilic graft polymers such as those based on polyalkylene oxides and vinyl esters, polyalkoxylated polyethyleneimines, and mixtures thereof. Preferably, the liquid detergent composition further comprises 0.1% to 10%, preferably 1% to 5%, of a chelating agent. In some examples, the laundry detergent composition comprises adjunct ingredients selected from the group including citrates, enzymes, bleaches, bleach catalysts, dyes, hueing dyes, brighteners, cleaning polymers including (zwitterionic) alkoxylated polyamines, surfactants, solvents, dye transfer inhibitors, perfumes, encapsulated perfumes, polycarboxylates, structurants, pH adjusters, and builders including mixtures thereof. Preferably, the liquid laundry detergent composition has a pH of 6-10, 6.5-8.9, or 7-8, where the pH of the liquid laundry detergent composition is measured as a 10% product concentration in demineralized water at 20°C. If liquid, the laundry detergent composition may be Newtonian or non-Newtonian, preferably non-Newtonian.

[0186] The following is an exemplary water-soluble unit dose formulation: The composition may be part of a single-chamber water-soluble unit dose article or may be divided across multiple compartments, resulting in the following "compartment-averaged" total article composition: The composition is encapsulated with a polyvinyl alcohol-based water-soluble body, where the polyvinyl alcohol comprises a blend of a polyvinyl alcohol homopolymer and an anionic, e.g., carboxylated, polyvinyl alcohol copolymer.

[0187] [Table 2] Superscript explanation: * The nuclease enzyme is as claimed in co-pending European patent application 19219568.3. ** A polyethylene glycol graft polymer comprising a polyethylene glycol backbone (Pluriol E6000) and hydrophobic vinyl acetate side chains, the polyethylene glycol graft polymer comprising 40% by weight of the polymer system of the polyethylene glycol backbone polymer and 60% by weight of the polymer system of the grafted vinyl acetate side chains.

[0188] A liquid composition for hand dishwashing. The fabric and home care product may be a dish detergent composition, such as a hand dish detergent composition, more preferably a liquid hand dish detergent composition. Preferably, the liquid hand dish detergent composition comprises 0.1% to 5.0%, preferably 0.5% to 4%, more preferably 1.0% to 3.0% by weight of the detergent composition of the present invention of sulfated esteramine chloride. The liquid hand dish detergent composition is preferably an aqueous composition comprising 50% to 90%, preferably 60% to 75% by weight of the total composition of water. Preferably, the pH of the detergent composition of the present invention, measured as a 10% product concentration in demineralized water at 20°C, is adjusted to 3 to 14, more preferably 4 to 13, more preferably 6 to 12, and most preferably 8 to 10. The composition of the present invention may be a Newtonian or non-Newtonian fluid, but is preferably a Newtonian fluid. Preferably, the composition has a viscosity of 10 mPa·s to 10,000 mPa·s, preferably 100 mPa·s to 5,000 mPa·s, more preferably 300 mPa·s to 2,000 mPa·s, or most preferably 500 mPa·s to 1,500 mPa·s, or a combination thereof. Viscosity is measured at 20°C using a Brookfield RT viscometer using spindle 31 with the viscometer RPM adjusted to achieve 40% to 60% torque.

[0189] The composition comprises a surfactant system in an amount of 5% to 50% by weight, preferably 8% to 45% by weight, and more preferably 15% to 40% by weight of the total composition. The surfactant system preferably comprises an anionic surfactant in an amount of 60% to 90% by weight, more preferably 70% to 80% by weight of the surfactant system. Alkyl sulfate anionic surfactants are preferred, particularly those selected from the group consisting of alkyl sulfates, alkyl alkoxy sulfates, preferably alkyl ethoxy sulfates, and mixtures thereof. The alkyl sulfate anionic surfactant preferably has an average alkyl chain length of 8 to 18, preferably 10 to 14, more preferably 12 to 14, and most preferably 12 to 13 carbon atoms. The alkyl sulfate anionic surfactant has an average degree of alkoxylation, preferably an ethoxylation degree, of less than 5, preferably less than 3, more preferably 0.5 to 2.0, and most preferably 0.5 to 0.9. The alkyl sulfate anionic surfactant preferably has a weight average degree of branching greater than 10%, preferably greater than 20%, more preferably greater than 30%, even more preferably 30% to 60%, and most preferably 30% to 50%. Suitable counterions include alkali metal cations, alkaline earth metal cations, alkanolammonium, or ammonium or substituted ammonium, preferably sodium. Suitable examples of commercially available alkyl sulfate anionic surfactants include those derived from alcohols sold by Shell under the brand name Neodol® or by Sasol under the brand names Lial®, Isalchem®, and Safol®, or some of the natural alcohols produced by Procter & Gamble Chemicals.

[0190] The surfactant system preferably comprises 0.1% to 20% by weight, more preferably 0.5% to 15% by weight, and especially 2% to 10% by weight of the liquid hand dishwashing detergent composition of a co-surfactant. Preferred co-surfactants are selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof. The weight ratio of the anionic surfactant to the co-surfactant may be 1:1 to 8:1, preferably 2:1 to 5:1, and more preferably 2.5:1 to 4:1. The co-surfactant is preferably an amphoteric surfactant, more preferably an amine oxide surfactant. Preferably, the amine oxide surfactant is selected from the group consisting of alkyl dimethyl amine oxide, alkylamidopropyl dimethyl amine oxide, and mixtures thereof, most preferably C12-C14 alkyl dimethyl amine oxide. Suitable zwitterionic surfactants include betaine surfactants, preferably cocamidopropyl betaine.

[0191] Preferably, the surfactant system of the present compositions further comprises from 1% to 25%, preferably from 1.25% to 20%, more preferably from 1.5% to 15%, and most preferably from 1.5% to 5% by weight of the surfactant system of a nonionic surfactant. 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 are linear or branched, primary or secondary alkyl alkoxylated, preferably alkyl ethoxylated, nonionic surfactants containing an average of 9 to 15, preferably 10 to 14, carbon atoms in the alkyl chain, and containing an average of 5 to 12, preferably 6 to 10, and most preferably 7 to 8, ethylene oxide units per mole of alcohol. Most preferably, the alkyl polyglycoside surfactants have an average alkyl carbon chain length of 10 to 16, preferably 10 to 14, most preferably 12 to 14, and an average degree of polymerization of 0.5 to 2.5, preferably 1 to 2, most preferably 1.2 to 1.6. C8 to C16 alkyl polyglycosides are commercially available from several sources (e.g., Simusol® surfactants from Seppic Corporation; and Glucopon® 600 CSUP, Glucopon® 650 EC, Glucopon® 600 CSUP / MB, and Glucopon® 650 EC / MB from BASF Corporation).

[0192] The liquid hand dish detergent compositions herein may contain a builder (e.g., preferably citrate), a chelating agent (e.g., preferably GLDA), a conditioning polymer, a cleaning polymer including a polyalkoxylated polyalkyleneimine, a surface modifying polymer, a soil flocculating polymer, a foaming polymer including an EO-PO-EO triblock copolymer, a grease cleaning polymer including a cyclic polyamine, a structurant, an emollient, a humectant, a skin rejuvenating active, an enzyme, a carboxylic acid, a scrubbing particle, a bleach and bleach activator, a fragrance, a malodor control agent, a pigment, a dye, a milk Many other auxiliary ingredients may optionally be included, such as whitening agents, beads, pearlescent 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 mono-, di-, and trivalent salts), and pH adjusters and buffering means (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.).

[0193] Below is an exemplary liquid hand dish detergent formulation, which can be made by standard mixing of the individual ingredients.

[0194] [Table 3]

[0195] A solid, free-flowing particulate laundry detergent composition. The fabric and home care product may be a solid, free-flowing particulate laundry detergent composition. The following is an exemplary solid, free-flowing particulate laundry detergent composition:

[0196] [Table 4]

[0197] Further embodiments Another subject of the present invention is the use of at least one graft polymer in laundry detergents, cleaning compositions and / or fabric and home care products, the graft polymer comprising (A) a block copolymer backbone as a graft base, said block copolymer backbone (A) being obtainable by polymerizing 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; (B) grafted onto the block copolymer backbone, said polymeric side chains (B) comprising polymeric side chains obtainable by polymerization of at least one vinyl ester monomer (B1) selected from vinyl acetate or vinyl propionate and, optionally, N-vinylpyrrolidone as optional further monomer (B2).

[0198] In this particular subject matter of the invention, it is preferred that the number (x) of individual blocks in the block copolymer backbone (A) is an integer, with x having a value of 2 to 10, preferably x having a value of 2 to 5, more preferably x is 2 or 3, and most preferably x is 3.

[0199] Also, in this particular subject matter, it is preferred that the vinyl ester monomer (B1) comprises at least 50% vinyl acetate by weight of the B1 monomer.

[0200] Furthermore, this particular subject matter also includes all preferred, more preferred etc. definitions / characteristics as described above in connection with the definition of such graft polymers, provided that at least one vinyl ester monomer (B1) is selected from vinyl acetate or vinyl propionate.

[0201] A further subject of the present invention is therefore laundry detergents, cleaning compositions and / or fabric and home care products containing at least one graft polymer, the graft polymer being (A) a block copolymer backbone as a graft base, said block copolymer backbone (A) being obtainable by polymerizing 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; (B) grafted onto the block copolymer backbone, said polymeric side chains (B) comprising polymeric side chains obtainable by polymerization of at least one vinyl ester monomer (B1) selected from vinyl acetate or vinyl propionate and, optionally, N-vinylpyrrolidone as optional further monomer (B2).

[0202] In this particular subject matter of the invention, it is preferred that the number (x) of individual blocks in the block copolymer backbone (A) is an integer, with x having a value of 2 to 10, preferably x having a value of 2 to 5, more preferably x is 2 or 3, and most preferably x is 3.

[0203] Also, in this particular subject matter, it is preferred that the vinyl ester monomer (B1) comprises at least 50% vinyl acetate by weight of the B1 monomer.

[0204] In each of these laundry detergent, cleaning compositions, and / or fabric and home care products, the at least one grafted polymer is present in an amount ranging from about 0.01% to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1% to about 10%, and most preferably from about 0.5% to about 5%, based on the total weight of such composition or product.

[0205] A further embodiment of the present invention relates to a graft polymer, the graft polymer comprising: (A) a block copolymer backbone as a graft base, said block copolymer backbone (A) being obtainable by polymerizing 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; (B) A polymeric side chain grafted onto the block copolymer backbone, said polymeric side chain (B) comprising a polymeric side chain obtainable by polymerization of at least one vinyl ester monomer (B1) and, optionally, N-vinylpyrrolidone as optional further monomer (B2).

[0206] In this particular subject matter of the invention, it is preferred that the number (x) of individual blocks in the block copolymer backbone (A) is an integer, with x having a value of 2 to 10, preferably x having a value of 2 to 5, more preferably x is 2 or 3, and most preferably x is 3.

[0207] Also, in this particular subject matter, it is preferred that the vinyl ester monomer (B1) comprises at least 50% vinyl acetate by weight of the B1 monomer.

[0208] Moreover, this particular subject matter also includes all preferred, more preferred, etc. definitions / features as discussed above in connection with other embodiments of the present invention.

[0209] Embodiments of the present invention further include the following. 1. A graft polymer, (a) a block copolymer backbone as a graft base, said block copolymer backbone (A) being obtainable by polymerizing 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, said block copolymer backbone (A) having three or more alkylene oxide blocks; (B) polymeric side chains grafted onto the block copolymer backbone (A), said polymeric side chains (B) being obtainable by polymerization of at least one vinyl ester monomer (B1), the vinyl ester monomer (B1) comprises at least 50% vinyl acetate by weight of the B1 monomer; the polymer has an OG greater than 0; OG=a X EO+b X M n 2 -c X (M n ×SUB)-d X M n +e X SUB+h X and During the ceremony, "M n " is the number average molecular weight of the block copolymer backbone (A), "EO" is the molar ratio of ethylene oxide moieties to the total alkylene oxide moieties present in the backbone (A), and EO is in the range of 0 to less than 1.00; "SUB" is the weight ratio of the polymer side chain (B) to the weight of the polymer; "a X " is the coefficient and is equal to 7.06, "b X " is the coefficient, 5.63 x 10 -7 is equal to "c X " is a coefficient, 1.25 x 10 -3 is equal to "d X" is the coefficient, 7.03 x 10 -3 is equal to "e X " is the coefficient and is equal to 3.66, "h X " is the coefficient and is equal to 16.3 for the graft polymer.

[0210] 2. The graft polymer also has an FJ greater than 0; 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 and During the ceremony, "a Y " is the coefficient and is equal to 446, "b Y " is the coefficient, 4.02 x 10 -6 is equal to "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, "h Y " is a coefficient equal to 83.6.

[0211] 3. The graft polymer according to any of the preceding embodiments, wherein the polymeric side chains (B) are obtainable by polymerization of at least one vinyl ester monomer (B1) and at least one N-vinylpyrrolidone monomer (B2).

[0212] 4. The graft polymer of any one of embodiments 1 to 3, wherein "SUB" is the weight ratio of vinyl ester monomer side chains (B1) to the weight of the polymer.

[0213] 5. The graft polymer of any one of embodiments 1 to 4, wherein the graft polymer comprises 20% to 95% by weight of the block copolymer backbone (A) and 5% to 80% by weight of the polymer side chains (B) (based on the total weight of the graft polymer).

[0214] 6. The block copolymer backbone (A) is (i) obtainable by polymerization of 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 graft polymer of any one of embodiments 1 to 5, wherein the number (x) of individual alkylene oxide blocks in the block copolymer backbone (A) is an integer, and x has a value from 3 to 10.

[0215] 7. The graft polymer of embodiment 6, wherein the block copolymer backbone (A) comprises ethylene oxide.

[0216] 8. The graft polymer of embodiment 6, wherein the number (x) of individual alkylene oxide blocks in the block copolymer backbone (A) is an integer, and x has a value from 3 to 5.

[0217] 9. (i) The graft polymer has a weight average molecular weight M of 800 to 10,000 g / mol. w and / or (ii) the graft polymer has a polydispersity M of less than 3.0 w / M n wherein "M w " = weight average molecular weight [g / mol], "M n” = number average molecular weight [g / mol], and / or (iii) the block copolymer backbone (A) is capped with one or both end groups; and / or (iv) The graft polymer according to any one of embodiments 1 to 8, wherein the block copolymer backbone (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG).

[0218] 10. The block copolymer backbone (A) has a structure according to formula (A1) and / or formula (A2), Formula (A1) is defined as follows:

[0219] [ka] During the ceremony, "n" is an integer ranging from 2 to 100, "m" is an integer ranging from 2 to 100, Formula (A2) is defined as follows:

[0220] [ka] During the ceremony, "o" is an integer ranging from 2 to 100; The graft polymer of any one of embodiments 1 to 9, wherein "p" is an integer ranging from 2 to 100.

[0221] 11. The polymer side chain (B) is (B1) 50 to 100% by weight (based on the total of (B1) and (B2)) of at least one vinyl ester monomer (B1); (B2) obtainable by radical polymerization with 0 to 50% by weight (based on the sum of (B1) and (B2)) of N-vinylpyrrolidone as further monomer (B2), 11. The graft polymer according to any one of embodiments 1 to 10, wherein the polymer side chains (B) are optionally fully or partially hydrolyzed after polymerization.

[0222] 12. A process for obtaining at least one graft polymer according to any one of the preceding embodiments, wherein at least one monomer (B1) is polymerized in the presence of at least one block copolymer backbone (A), The process comprises the polymerization of 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) to obtain polymer side chains (B), at an average polymerization temperature at which the decomposition half-life of the initiator (C) is between 40 and 500 minutes, in such a way that the fraction of unconverted grafting monomer (B1) and initiator (C) in the reaction mixture is always maintained in a quantitatively deficient state relative to the block copolymer backbone (A), Optionally, the polymeric side chains (B) are obtained by radical polymerization, a process.

[0223] 13. A fabric and home care product comprising at least one grafted polymer according to any one of embodiments 1 to 11.

[0224] 14. The product of embodiment 13, wherein the product is a composition in the form of a liquid, gel, powder, hydrocolloid, aqueous solution, granules, tablet, capsule, single-compartment sachet, pad, multi-compartment sachet, single-compartment pouch, or multi-compartment pouch.

[0225] 15. The product of any of embodiments 13 or 14, wherein the product is a composition further comprising an ingredient selected from surfactants, enzymes, detergent builders, complexing agents, polymers, soil release polymers, surfactant-enhancing polymers, bleaching agents, bleach activators, bleach catalysts, fabric conditioners, clays, suds boosters, suds suppressors, corrosion inhibitors, soil suspending agents, soil anti-redeposition agents, dyes, disinfectants, anti-hazing agents, optical brighteners, fragrances, saturated or unsaturated fatty acids, dye transfer inhibitors, chelating agents, hueing dyes, calcium cations, magnesium cations, visual signaling components, defoamers, structuring agents, thickeners, anti-caking agents, starches, sands, gelling agents, or any combination thereof.

[0226] How to use The present invention includes a method for cleaning a target surface. As used herein, "target surface" may include such surfaces as cloths, dishes, glasses, and other cooking surfaces, hard surfaces, hair, or skin. As used herein, "hard surface" includes hard surfaces found in a typical household, such as hardwood, tile, ceramic, plastic, leather, metal, and glass. Such a method includes contacting a composition containing a modified polyol compound, either undiluted or diluted in a cleaning solution, with at least a portion of the target surface, and then optionally rinsing the target surface. Preferably, the target surface is subjected to a cleaning step before the optional rinsing step. For purposes of the present invention, cleaning includes, but is not limited to, scrubbing, wiping, and mechanical agitation.

[0227] 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.

[0228] The pH of the composition solution is selected to be most complementary to the target surface being cleaned over a wide pH range of about 3 to about 11. In personal care applications such as skin and hair cleaning, the pH of such compositions preferably ranges from about 5 to about 8, with laundry cleaning compositions having a pH of about 5 to about 11. The compositions are preferably used at concentrations of about 200 ppm to about 10,000 ppm in solution. Water temperatures preferably range from about 5°C to about 100°C.

[0229] For use in laundry cleaning compositions, the compositions are preferably employed at a concentration of from about 200 ppm to about 10,000 ppm in solution (or wash liquor). Water temperatures preferably range from about 5° C. to about 60° C. The water to fabric ratio is preferably from about 1:1 to about 20:1.

[0230] The method may include contacting a nonwoven substrate impregnated with an embodiment of the composition of the present invention. As used herein, "nonwoven substrate" may include any conventional nonwoven sheet or web having suitable basis weight, caliper (thickness), absorbency, and strength characteristics. Examples of suitable commercially available nonwoven substrates include those sold by DuPont under the trade name SONTARA® and by James River Corp. under the trade name POLYWEB®.

[0231] 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 compositions. A method for using the liquid dishwashing compositions of the present invention comprises contacting soiled dishes with an effective amount, typically about 0.5 mL to about 20 mL (per 25 dishes to be treated), of the liquid dishwashing composition of the present invention diluted with water.

[0232] The present invention also includes methods for using such grafted polymers for improved soil suspension, soil release, stain removal, anti-redeposition, and / or malodor control performance.

[0233] The following examples are intended to further illustrate the invention without limiting its scope.

[0234] Polymer Measurements 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 at a polymer concentration of 1% polymer in a 3% by weight NaCl solution at 23°C according to the method of H. Fikentscher in "Cellulosechemie", 1932, 13, 58.

[0235] The number average molecular weight (M n ), weight average molecular weight (M w ), and polydispersity M w / M nThe molecular weights were determined by gel permeation chromatography in tetrahydrofuran. The mobile phase (eluent) used was tetrahydrofuran containing 0.035 mol / L diethanolamine. The concentration of the grafted polymer in tetrahydrofuran was 2.0 mg per 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 the separation: SDV precolumn, SDV1000A, SDV100000A, and SDV1000000A. The GPC system was operated at a flow rate of 1 mL per minute. A DRI Agilent 1100 was used as the detection system. Molecular weights M ranged from 106 to 1,378,000 g / mol. n Poly(ethylene glycol) (PEG) standards (PL) with the following formula were used for calibration. [Example]

[0236] Synthesis example: Comparative polymer procedures: Graft polymerization of vinyl acetate onto poly(ethylene glycol) (Comparative Polymer 9) In a polymerization vessel equipped with a stirrer and a reflux condenser, 600 g of poly(ethylene glycol) was first charged under a nitrogen atmosphere and melted at 90°C. Feed 1, containing 4.8 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 23.6 g of tripropylene glycol, was charged to a stirred vessel at 90°C over 6 hours and 10 minutes. 5.56% of Feed 1 was charged in the first 10 minutes, and the remainder was charged at a constant rate over 6 hours. 10 minutes after the start of Feed 1, Feed 2 (400 g of vinyl acetate) was started and charged at a constant rate over 6 hours at 90°C. Upon completion of Feeds 1 and 2, 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 charged at a constant rate over 56 minutes at 95°C. After complete addition of the feeds, the mixture was stirred at 95°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0237] General procedure for comparison polymers without grafts (Comparative polymers 10-13) 1098.90 g of the triblock copolymer, 1.10 g of vinyl acetate and 58.30 g of 1,2-propanediol were mixed in a polymerization vessel at 90° C. and stirred for 3 hours.

[0238] General procedure for graft polymerization of vinyl acetate with poly(alkylene oxide) / VAc (40 / 60) ratio. (Polymers 1 and 3 of the present invention; Comparative polymers 6 and 7) 440 g of the triblock copolymer was first placed in a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere and melted at 90°C. Feed 1, containing 7.97 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 35.09 g of 1,2-propanediol, was charged to a stirred vessel over 6 hours and 10 minutes at 90°C. 5.56% of Feed 1 was charged in the first 10 minutes, with the remainder being charged at a constant rate over 6 hours. 10 minutes after the start of Feed 1, Feed 2 (660 g of vinyl acetate) was started and charged to the reactor at 90°C at a constant rate over 6 hours. Upon completion of the feeds, Feed 3, consisting of 5.28 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 23.21 g of 1,2-propanediol, was charged at a constant rate over 56 minutes at 90°C. After complete addition of the feeds, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0239] General procedure for graft polymerization of vinyl acetate with poly(alkylene oxide) / VAc (50 / 50) ratio. (Polymer 2 of the invention; Comparative polymer 4) 500 g of the triblock copolymer was first placed in a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere and melted at 90°C. Feed 1, containing 12.24 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 50.30 g of tripropylene glycol, was charged to the stirred vessel over 6 hours and 10 minutes at 90°C. 5.56% of Feed 1 was charged in the first 10 minutes, with the remainder being charged at a constant rate over 6 hours. 10 minutes after the start of Feed 1, Feed 2 (200 g of vinyl acetate) was started and charged to the reactor at 90°C at a constant rate over 6 hours. Upon completion of the feeds, Feed 3, consisting of 4.80 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 19.70 g of tripropylene glycol, was charged at a constant rate over 56 minutes at 90°C. After complete addition of the feeds, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0240] General procedure for graft polymerization of vinyl acetate with poly(alkylene oxide) / VAc (60 / 40) ratio 1 (Polymers 4, 5, 7-9, 13-15 of the present invention; Comparative Polymers 1, 2, 5, 8) First, 600 g of the triblock copolymer was placed in a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere, and melted at 90°C. Feed 1, containing 4.8 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 23.6 g of tripropylene glycol, was charged to a stirred vessel at 90°C over 6 hours and 10 minutes. 5.56% of Feed 1 was charged in the first 10 minutes, and the remainder was charged at a constant rate over 6 hours. 10 minutes after the start of Feed 1, Feed 2 (400 g of vinyl acetate) was started and charged at a constant rate over 6 hours at 90°C. Upon completion of Feeds 1 and 2, 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 charged at a constant rate over 56 minutes at 95°C. After complete addition of the feeds, the mixture was stirred at 95°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour. The resulting graft polymer (Example 7) had an average molecular weight M of 5190 g / mol. w and had a polydispersity of 1.5.

[0241] General procedure for graft polymerization of vinyl acetate with poly(alkylene oxide) / VAc (70 / 30) ratio. (Polymer 11 of the invention; Comparative polymer 3) 770 g of the triblock copolymer was first charged into a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere, and melted at 90°C. Feed 1, containing 7.97 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 35.09 g of 1,2-propanediol, was charged to a stirred vessel over 6 hours and 10 minutes at 90°C. 5.56% of Feed 1 was charged in the first 10 minutes, with the remainder being charged at a constant rate over 6 hours. 10 minutes after the start of Feed 1, Feed 2 (330 g of vinyl acetate) was started and charged to the reactor at 90°C at a constant rate over 6 hours. Upon completion of the feeds, Feed 3, consisting of 5.28 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 23.21 g of 1,2-propanediol, was charged at a constant rate over 56 minutes at 90°C. After complete addition of the feeds, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0242] General procedure for graft polymerization of vinyl acetate with poly(alkylene oxide) / VAc (80 / 20) ratio. (Polymers 6, 10, and 12 of the present invention) First, 800 g of the triblock copolymer was placed in a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere, and melted at 90°C. Feed 1, containing 10.20 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 47.61 g of tripropylene glycol, was charged to the stirred vessel over 6 hours and 10 minutes at 90°C. 5.56% of Feed 1 was charged in the first 10 minutes, with the remainder being charged at a constant rate over 6 hours. 10 minutes after the start of Feed 1, Feed 2 (200 g of vinyl acetate) was started and charged to the reactor at 90°C at a constant rate over 6 hours. Upon completion of the feeds, Feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.39 g of tripropylene glycol, was charged at a constant rate over 56 minutes at 90°C. After complete addition of the feeds, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0243] Procedure for the graft polymerization of vinyl acetate and vinylpyrrolidone in 1,2-propanediol (Polymer 16 of the present invention) In a polymerization vessel equipped with a stirrer and a reflux condenser, 376.3 g of the triblock copolymer was first charged under a nitrogen atmosphere and melted at 90°C. Feed 1, containing 7.12 g of tert-butyl perpivalate dissolved in 17.01 g of 1,2-propanediol, was charged to a stirred vessel over 6 hours and 10 minutes at 90°C. 5.56% of Feed 1 was charged in the first 10 minutes, with the remainder charged at a constant rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (225.78 g of vinyl acetate) and Feed 3 (150.25 g of vinylpyrrolidone) were started simultaneously and charged to the reactor at a constant rate over 6 hours at 90°C. Three hours after the start of Feeds 2 and 3, Feed 4 (142.31 g of 1,2-propanediol) was started and charged to the reactor at a constant rate over 3 hours. At the completion of the feeds, 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-propanediol, was charged at a constant flow rate over 56 minutes at 95° C. After complete addition of the feed, the mixture was stirred at 95° C. for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour. Water (76.84 g) was added.

[0244] Structural details of more comparative and inventive polymer examples are listed in Table 5.

[0245] [Table 5] VAc = vinyl acetate, VP = vinylpyrrolidone, A1: EO / PO / EO triblock structure, A2: PO / EO / PO triblock structure, C: PEG "M n " is the number average molecular weight of the block copolymer backbone (A) "EO" is the molar ratio of ethylene oxide moieties to the total alkylene oxide moieties present in the backbone (A). "SUB" is the weight ratio of the polymer side chain (B) to the weight of the polymer

[0246] Methods for determining the biodegradability of polymers Biodegradability in wastewater was tested in triplicate using the manometric respirometry method of OECD 301F. 30 mg / mL of test substance was inoculated into wastewater collected from the Mannheim Wastewater Treatment Plant and incubated in closed flasks at 25°C for 28 days. Oxygen consumption during this period was measured as the change in pressure inside the flask using an OxiTop C (WTW). The evolved CO2 was absorbed using a NaOH solution. The amount of oxygen consumed by the microbial community during the biodegradation of the test substance, after correction using a blank, was expressed as % of ThOD (theoretical oxygen demand).

[0247] Biodegradation data for comparative and inventive polymers at 28 days in the OECD 301F test are summarized in Table 5.

[0248] As shown in Table 5, compared to comparative polymers 1-10, graft polymers 1-17 of the present invention exhibit a higher percentage of biodegradability at 28 days in the OECD 301F test.

[0249] The graft polymer of the present invention has an OG greater than 0, OG=a X EO+b X M n 2 -c X (M n ×SUB)-d X M n +e X SUB+h X and During the ceremony, "M n " is the number average molecular weight of the block copolymer backbone (A), "EO" is the molar ratio of ethylene oxide moieties to the total alkylene oxide moieties present in the backbone (A), and EO is in the range of 0 to less than 1.00; "SUB" is the weight ratio of the polymer side chain (B) to the weight of the polymer; "a X " is the coefficient and is equal to 7.06, "b X " is the coefficient, 5.63 x 10 -7 is equal to "c X " is a coefficient, 1.25 x 10 -3 is equal to "d X " is the coefficient, 7.03 x 10 -3 is equal to "e X " is the coefficient and is equal to 3.66, "h X " is a coefficient and is equal to 16.3.

[0250] Within the scope of the graft polymers of the present invention as defined by OG, it is more preferred that the graft polymers of the present invention have an FJ greater than 0, FJ=a Y EO-b Y M n2 +d Y M n +e Y SUB-f Y SUB 2 -g Y (EO×SUB)-h Y and During the ceremony, "a Y " is the coefficient and is equal to 446, "b Y " is the coefficient, 4.02 x 10 -6 is equal to "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, "h Y " is a coefficient and is equal to 83.6.

[0251] Method for assessing foam persistence of hand dishwashing compositions The purpose of the Foam Persistence Index test is to compare the development over time of foam volume generated for different test formulations at specified water hardness, solution temperature, and formulation concentration while subjected to periodic soil injections. The data is compared and expressed as a Foam Persistence Index relative to a reference composition (the reference composition has a Foam Persistence Index of 100). The steps of the method are as follows: 1) A defined amount of test composition corresponding to the target composition concentration (0.12 wt%) is dispensed through a plastic pipette at a flow rate of 0.67 mL / sec into a stream of water (water hardness: 15 gpg, water temperature: 35°C) filling a sink to 4 L at a constant pressure of 4 bar, at a height of 37 cm above the bottom of the sink (dimensions: diameter 300 mm and height 288 mm). 2) Initial foam volume generated (measured as average foam height x sink surface area, cm 3 (represented by ) is recorded immediately after filling is completed. 3) A fixed volume (6 mL) of soil is immediately injected into the center of the sink. 4) Mix the resulting solution using a metal blade (10 cm x 5 cm) positioned in the center of the sink at the air-liquid interface at a 45 degree angle, rotating 20 times at 85 RPM. 5) Another measurement of total lather volume is recorded immediately after the blade rotation has finished. 6) The measured total foam volume is 400 cm 3 Repeat steps 3 to 5 until the minimum level of 400 cm is reached. 3 The amount of soil added required to reach a level of suds is considered the suds persistence of the test composition. 7) Each test composition is tested four times per test condition (i.e., water temperature, composition concentration, water hardness, soil type). 8) Calculate the average foam persistence as the average of four replicates per sample. 9) Calculate the Lather Persistence Index by comparing the average persistence of the test composition samples to the reference composition samples. The calculation is as follows:

[0252]

number

[0253] A stain composition is produced through a standard mix of the ingredients set forth in Table 6.

[0254] [Table 6]

[0255] Methods for assessing the whiteness effect of polymers Whiteness maintenance, also known as whiteness retention, is the ability of a detergent to prevent white items from losing their whiteness when washed in the presence of soil. White clothing can appear dirty / dull over time as soil is removed from soiled clothing and suspended in the wash water, and these soils can then be redeposited on the clothing, causing the clothing to lose its whiteness each time it is washed.

[0256] The whiteness benefit of the polymers of the present disclosure is evaluated using an automated tergotometer with 10 pots for laundry formulation testing.

[0257] To simulate consumer soiling levels (a mixture of body soil, food, grime, etc.), SBL2004 test soil strips supplied by WFK Testgewebe GmbH are used. On average, 8 g of soil is loaded per SBL2004 strip. The SBL2004 test soil strips are cut into 5 x 5 cm squares for use in the test.

[0258] The white fabric swatches in Table 7 below, purchased from WFK Testgewebe GmbH, are used as whiteness tracers. Prior to the wash test, the L, a, B values ​​of all whiteness tracers are measured using a Konica Minolta CM-3610D spectrophotometer.

[0259] [Table 7]

[0260] Additional ballast (background fabric swatches) are also used to simulate fabric loads and provide mechanical energy during the actual washing process. The ballast loads consist of 5x5cm swatches of cotton and polycotton knits.

[0261] Four wash cycles are required to complete the test. Cycle 1: The desired amount of detergent is completely dissolved by mixing with 1 L of water (defined hardness) in each tergotometer port. 60 grams of cloth (four types, measured in quadruplicate) containing whiteness tracer, twenty-one 5x5 cm SBL2004 cloths, and ballast are washed and rinsed in the tergotometer pot under defined conditions. For testing of the water-soluble unit dose composition, the wash concentration is 2000 ppm. An additional 47 ppm of PVOH film is also added to the tergotometer pot. The wash temperature is 30°C and the water hardness is 20 gpg. Cycle 2: Then, after the process of Cycle 1, the whiteness tracer and ballast of each pot are washed and rinsed again with a new set of SBL2004 (5 x 5 cm, 21 pieces). All other conditions remain the same as in Cycle 1. Cycle 3: After the process of Cycle 1, the whiteness tracer and ballast of each pot are then washed and rinsed again with a new set of SBL2004 (5x5cm, 21 pieces). All other conditions remain the same as in Cycle 1. Cycle 4: Then, after the process of Cycle 1, the whiteness tracer and ballast of each port are washed and rinsed again with a new set of SBL2004 (5 x 5 cm, 21 pieces). All other conditions remain the same as Cycle 1.

[0262] After cycle 4, all brightness tracer and ballast are tumble dried at 60-65°C until dry, and then the tracer is measured again using a Konica Minolta CM-3610D spectrophotometer. The change in brightness index (ΔWI(CIE)) is calculated based on the L, a, and b measurements before and after washing. ΔWI(CIE) = WI(CIE) (after cleaning) - WI(CIE) (before cleaning).

[0263] Polymer Performance in Hand Dishwashing Detergents The following hand dish detergent compositions are prepared by conventional means known to those skilled in the art by mixing the listed ingredients. The effect of the polymer of the present invention on foam persistence is evaluated in Table 8 by comparing the foam persistence of Formulas A (reference) and B (reference containing the polymer of the present invention). The foam persistence performance was evaluated using the method for evaluating foam persistence of hand dishwashing compositions described herein, and the foam persistence index is reported in Table 9.

[0264] [Table 8] * An amphiphilic alkoxylated polyethyleneimine (total MW: approximately 28,000 g / mol) comprising a polyethyleneimine backbone of MW 600 and alkoxylated chains each containing 24 internal EO units and 16 terminal PO units.

[0265] As shown in Table 9, the polymers of the present invention are capable of delivering high foam persistence benefits.

[0266] [Table 9]

[0267] Polymer Brightness Performance in Liquid Detergents The following water-soluble unit dose detergent compositions E and F are prepared by conventional means known to those skilled in the art by mixing the listed ingredients (Table 10).

[0268] The whiteness maintenance of the inventive and comparative polymers is evaluated according to the Method for Evaluating Whiteness Performance of Polymers by directly comparing the whiteness performance of Reference Composition E and Test Composition F. The ΔWI(CIE) of Composition F versus Composition E is reported in Table 11 as an indicator of polymer whiteness performance effectiveness.

[0269] [Table 10]

[0270] As shown in Table 11, the polymers of the present invention provide significant whiteness benefits.

[0271] Although high biodegradability can be observed for Comparative Polymers 10, 12, and 13, they are unable to provide meaningful whiteness benefits because, as can be seen in Table 5, Comparative Polymers 10, 12, and 13 have very low levels of grafting (Sub(wt%)=0.001) and are unable to deliver sufficient whiteness performance benefits at such low grafting levels.

[0272] [Table 11]

[0273] Dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

Claims

1. A graft polymer, (A) a block copolymer backbone as a graft base, said block copolymer backbone (A) being obtainable by polymerizing two monomers consisting of ethylene oxide and 1,2-propylene oxide, said block copolymer backbone (A) having three or more alkylene oxide blocks; (B) polymeric side chains grafted onto the block copolymer backbone (A), the polymeric side chains (B) being obtainable by polymerization of 50 to 100% by weight, based on the sum of (B1) and (B2), of at least one vinyl ester monomer (B1) and 0 to 50% by weight, based on the sum of (B1) and (B2), of an N-vinylpyrrolidone monomer (B2); the vinyl ester monomer (B1) comprises at least 50% vinyl acetate by weight of the B1 monomer; the polymer has an OG greater than 0; 970. Ｘ E+b Ｘ 7. ｎ ２ -c Ｘ (* ｎ ×353)-d Ｘ 7. ｎ +e Ｘ 353+h Ｘ であり、 During the ceremony, "M ｎ " is the number average molecular weight of the block copolymer skeleton (A), "EO" is the molar ratio of ethylene oxide moieties to total alkylene oxide moieties present in backbone (A), EO ranging from 0 to less than 1.00; "SUB" is the weight ratio of the polymer side chain (B) to the weight of the polymer and is greater than 0.01; "a Ｘ " is a coefficient equal to 7.06, "b Ｘ " is a coefficient, 5.63 x 10 －７ is equal to "c Ｘ " is a coefficient, 1.25 x 10 －３ is equal to "d Ｘ " is a coefficient, 7.03 x 10 －３ is equal to "e Ｘ " is a coefficient equal to 3.66, "h Ｘ " is a coefficient, equal to 16.3, of the graft polymer.

2. the graft polymer also has a FJ greater than 0; 040. Ｙ E9b Ｙ 7. ｎ ２ +d Ｙ 7. ｎ +e Ｙ 353-1 Ｙ 353 ２ g Ｙ (59×353)-- Ｙ であり、 During the ceremony, "M ｎ " is the number average molecular weight of the block copolymer skeleton (A), "EO" is the molar ratio of ethylene oxide moieties to total alkylene oxide moieties present in backbone (A), EO ranging from 0 to less than 1.00; "SUB" is the weight ratio of the polymer side chain (B) to the weight of the polymer and is greater than 0.01; "a Ｙ " is a coefficient equal to 446, "b Ｙ " is a coefficient, 4.02 x 10 －６ is equal to "d Ｙ " is a coefficient and is equal to 0.0168, "e Ｙ " is a coefficient and is equal to 281, "f Ｙ " is a coefficient and is equal to 229, "g Ｙ " is a coefficient equal to 1140, "h Ｙ 2. The graft polymer of claim 1, wherein " is a coefficient equal to 83.

6.

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

4. 3. The graft polymer according to claim 1 or 2, wherein "SUB" is the weight ratio of the vinyl ester monomer side chains (B1) to the weight of the polymer.

5. 3. The graft polymer according to claim 1, wherein the graft polymer comprises 20% by weight to 95% by weight of the block copolymer backbone (A) and 5% by weight to 80% by weight of the polymer side chains (B), based on the total weight of the graft polymer.

6. The block copolymer skeleton (A) is (iii) The graft polymer of claim 1 or 2, wherein the number (x) of individual alkylene oxide blocks in the block copolymer backbone (A) is an integer, with x having a value of 3 to 10.

7. 7. The graft polymer of claim 6, wherein the number (x) of individual alkylene oxide blocks in the block copolymer backbone (A) is an integer, with x having a value of 3 to 5.

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

9. the block copolymer backbone (A) has a structure according to formula (A1) and / or formula (A2), Formula (A1) is defined as follows: 【Chemical 1】 During the ceremony, "n" is an integer ranging from 2 to 100; "m" is an integer ranging from 2 to 100; Formula (A2) is defined as follows: 【Chemistry 2】 During the ceremony, "o" is an integer ranging from 2 to 100; 3. The graft polymer of claim 1, wherein "p" is an integer ranging from 2 to 100.

10. 3. The graft polymer according to claim 1, wherein the polymeric side chain (B) is obtainable by polymerization of 100% by weight of said polymeric side chain (B) of at least one vinyl ester monomer (B1).

11. A process for obtaining at least one graft polymer according to one of claims 1 to 10, wherein at least one monomer (B1) is polymerized in the presence of at least one block copolymer backbone (A), The process comprises the polymerization of 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) to obtain polymer side chains (B), at an average polymerization temperature at which the decomposition half-life of the initiator (C) is between 40 and 500 minutes, in such a way that the fraction of unconverted graft monomer (B1) and initiator (C) in the reaction mixture is always maintained in a quantitative deficiency relative to the block copolymer backbone (A), Optionally, said polymeric side chains (B) are obtained by radical polymerization.

12. A textile or home care product comprising at least one grafted polymer according to any one of claims 1 to 10.

13. 13. The product of claim 12, wherein the product is a composition in the form of a liquid, gel, powder, hydrocolloid, aqueous solution, granules, tablet, capsule, single-compartment sachet, pad, multi-compartment sachet, single-compartment pouch, or multi-compartment pouch.

14. 14. The product of claim 12 or 13, wherein the product is a composition further comprising an ingredient selected from surfactants, enzymes, detergent builders, complexing agents, soil release polymers, surfactant-enhancing polymers, bleaching agents, bleach activators, bleach catalysts, fabric conditioners, clays, suds boosters, suds suppressors, corrosion inhibitors, soil suspending agents, soil anti-redeposition agents, dyes, disinfectants, anti-tarnish agents, optical brighteners, fragrances, saturated or unsaturated fatty acids, dye transfer inhibitors, chelating agents, hueing dyes, calcium cations, magnesium cations, defoamers, structuring agents, thickeners, anti-caking agents, starches, sands, gelling agents, or any combination thereof.

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