Fabric and home care compositions

Abstract

The present invention relates to fabrics and home care compositions comprising specific graft polymers. The composition is particularly suitable for use as a laundry detergent composition.

Description

Technical Field

[0001] The present invention relates to fabrics and household care compositions comprising specific graft polymers. These graft polymers can be used in fabric and household care compositions, preferably in laundry detergent compositions. Background Art

[0002] Initiatives have been proposed in various countries to ban microplastics, especially in cosmetic products. In addition to the ban on insoluble microplastics, there is a strong dialogue about future requirements for soluble polymers used in consumer products. Therefore, it is highly desirable to identify new and better biodegradable components for such applications. This problem is particularly severe for polymers produced by free radical polymerization based on a carbon-only main chain (a main chain that does not contain heteroatoms such as oxygen), because a carbon-only main chain is particularly difficult for microorganisms to degrade. Even industrially important free radical-produced graft polymers with a polyethylene glycol main chain show only limited biodegradation in wastewater. However, the polymers described in the present invention are preferably produced by free radical graft polymerization and provide enhanced biodegradation performance compared to the prior art.

[0003] Polyalkylene oxides are important polymers with a wide range of applications. They have been widely used as a basis for the production of graft polymers, and such polymers are commonly used in various consumer formulated products, including household cleaning compositions and cleaning compositions for other uses.

[0004] Similarly, graft polymers in which vinyl esters are grafted onto polyalkylene oxide polymers (such as vinyl acetate-grafted-polyethylene glycol) are known polymers. Their use in the detergent field and many other application fields is also known. However, those polymers lack biodegradability or at least suffer from very limited biodegradability.

[0005] However, after use, a significant portion (and possibly all) of such consumer products will ultimately be rinsed away, and if they cannot be removed by biodegradation or other means in a sewage treatment plant, they may flow into rivers or the ocean.

[0006] Therefore, biodegradability is becoming a crucial property, not only in the detergent field, because biodegradable polymers can avoid the problem of continuous accumulation in the environment.

[0007] In some countries / regions, according to current legal regulations, such problems will no longer be permitted, and even if the relevant provisions have not yet come into force, it is expected that the legislative process will be completed in the near future.

[0008] On the other hand, the functional properties imparted by such polymers are equally crucial, as they not only enable efficient cleaning but also reduce the use of cleaning additives during a single cleaning process (which is just one of many advantages), thereby saving the materials used and thus avoiding environmental pollution. These special polymers can also achieve cleaning effects at low temperatures, in short time periods, and with low water consumption, and are thus key materials essential for environmentally friendly cleaning processes.

[0009] Therefore, it is crucial to provide biodegradable polymers for the detergent field, which can solve the environmental pollution problem without affecting the cleaning efficiency - because a reduction in cleaning efficiency would instead lead to a more serious environmental burden than the inevitable pollution.

[0010] A well-known such polymer is the graft polymer of vinyl acetate on PEG6000, with a weight ratio of 60% (VAc) to 40% (PEG), which is known for its beneficial cleaning and whitening effects and is widely used in liquid washing formulations (liquid detergents and gel detergents) and solid washing formulations (such as washing powders and laundry sheets).

[0011] Polyalkylene oxides have poor biodegradability, and their biodegradability gradually decreases as the molecular weight increases from several hundred grams per mole to up to several kilograms per mole. Even more so, the biodegradation performance of graft polymers based on such polyalkylene oxides is usually even worse, which may be due to the grafting effect.

[0012] Prior Art on Graft Polymers

[0013] US2019 / 0390142 relates to a fabric care composition comprising a graft copolymer, which can consist of: (a) a polyalkylene oxide, such as polyethylene oxide (PEG); (b) N-vinylpyrrolidone (VP); and (c) a vinyl ester, such as vinyl acetate. However, US 2019 / 0390142 does not disclose the graft polymer required currently.

[0014] WO2020 / 005476 discloses a fabric care composition comprising a graft copolymer and a so-called processing aid, the graft copolymer having a polyalkylene oxide composed of ethylene oxide, propylene oxide, or butylene oxide as the main chain (preferably polyethylene oxide), and N-vinylpyrrolidone and vinyl ester as side chains grafted onto the main chain, and the ratio of the main chain to the two monomers needs to meet specific requirements.

[0015] WO2020 / 264077 discloses a cleaning composition comprising a combination of an enzyme and a polymer, such compositions being suitable for removing stains from soiled materials.

[0016] The present disclosure discloses a so-called "suspension graft copolymer" selected from the group consisting of: poly(vinyl acetate)-g-poly(ethylene glycol), poly(vinylpyrrolidone)-poly(vinyl acetate)-g-poly(ethylene glycol), and combinations thereof. However, the graft polymers defined in the present invention are not disclosed.

[0017] US31816566 discloses so-called "lactone polyesters" graft polymers and their blends with PVC. The lactone polyester is a homopolymer of ε-caprolactone or a copolyester of ε-caprolactone and ε-alkyl-ε-caprolactone. No polymers prepared with a combination of lactone and alkylene oxide as the graft substrate as described in the present invention are disclosed in the prior art. The lactone polyesters described in US31816566 are grafted with ethylenically unsaturated monomers, and in a long list, "vinyl esters of aliphatic acids" are also mentioned, which lists vinyl formate, vinyl acetate, and vinyl propionate. Twenty-two examples demonstrate graft polymerization reactions using acrylic acid, butyl acrylate, methyl dimethylaminoacrylate, styrene, acrylonitrile, and methyl methacrylate as the only monomers actually used, and all examples use only a single monomer for grafting without using any monomer mixtures. Only one example (Example 12) uses vinyl acetate as the monomer and poly ε-caprolactone as the graft substrate (i.e., a graft substrate without any alkylene oxide), with 200 grams of the main chain and 30 grams of vinyl acetate, that is, the addition amount of vinyl acetate based on the graft substrate is 15% by weight, equivalent to 13% by weight of vinyl acetate based on the total polymer weight. US31816566 does not disclose any information on the biodegradability of such polymers; the only disclosed use is as a plasticizer in PVC polymers. The graft polymers of the type shown in the present invention are neither disclosed nor implied in the prior art.

[0018] WO2022 / 136409 of BASF discloses amphiphilic alkoxylated polyalkyleneimines or amines; no graft polymers are disclosed that have a polymer made from lactone and alkylene oxide as the graft backbone and graft ethylenically unsaturated monomers containing at least one vinyl ester by free radical polymerization. Therefore, except for the following two points, this patent publication is completely irrelevant to the present invention: First, it also relates to polymer structures in a similar technical field to the present invention; Second, the products contain lactone and alkylene oxide. The lactone and alkylene oxide are polymerized to produce lactone-alkylene oxide copolymers, which are then attached to the amino groups of the starting compound polyethylenimine or polyamine. No graft polymerization is carried out after the formation of these side chains. Therefore, such compounds are essentially different from the present invention in terms of structure, preparation process, properties, and thus application functions. The graft polymers of the type shown in the present invention are neither disclosed nor implied in the prior art.

[0019] The cleaning composition disclosed in US2022 / 0056380 has a specific enzyme as the core component, so it neither particularly focuses on a specific polymer itself nor involves its structure, preparation process or characteristics. Among the numerous components of such compositions, graft polymers are only mentioned as general components. However, graft polymers are conventionally known graft polymers (such as the preferably mentioned "BASF HP22"), and the main chains of such polymers do not contain lactones, so such main chains are only composed of alkylene oxides. These alkylene oxides (especially the preferred polymers with a main chain molecular weight of about 6000 g / mol) have almost no biodegradability, and as shown in the present invention, the graft polymers prepared with such polyalkylene oxide main chains have even worse biodegradability. The graft polymers of the type shown in the present invention are neither disclosed nor implied in the prior art.

[0020] Regarding the technical problem of improving the biodegradability of graft polymers based on main chains with polyalkylene oxide units, it has been solved in the unpublished patent application PCT / EP2022 / 065983 (now published as WO2022 / 263354). This patent discloses graft polymers based on main chains containing ester functional groups and polyalkylene oxide units as functional units. The preparation method of the main chain is: oxidizing the polyalkylene oxide in the initial reaction, and then esterifying the oxidized PEG mixture - either by self-esterification or by esterification with an additional polyalkylene oxide. Then the main chain is grafted with vinyl acetate. The polymers in this disclosure have the defect that the synthesis of the main chain requires two-step reactions: first, the oxidation process as the initial reaction step is costly and time-consuming; second, the composition obtained by oxidation is difficult to control because changes in the reaction time will cause changes in the mixture composition. Usually, the resulting mixture contains unoxidized starting materials, polyalkylene oxides with single-terminal hydroxyl groups oxidized to carboxyl functional groups, and polyalkylene oxides oxidized at both ends. Therefore, the flexibility in designing the backbone is highly restricted. This patent application also does not disclose the technical solution of preparing graft polymers using nitrogen-containing monomers.

[0021] Prior Art on the Main Chain

[0022] The present invention discloses the use of three main types of polymer main chains, which contain (oligo / poly) alkylene oxide moieties and (oligo / poly) lactone / hydroxy acid-derived moieties.

[0023] Such main chains are named (A1), (A2), (A3) and (A4) (definitions are given below), and are in principle prior art known:

[0024] (A1)

[0025] WO2002046268 (Cognis, now part of BASF) discloses biodegradable polymers as surfactants, emulsifiers, etc., obtained by reacting an organic initiator with: 1. an alkylene oxide, 2. a mixture of an alkylene oxide and a lactone. The "organic initiator" is defined on page 4 as a mono-functional or multi-functional alcohol or amine.

[0026] To obtain a copolymer from an alkylene oxide and caprolactone, a suitable starting material is reacted with a premixed combination of an alkylene oxide and caprolactone.

[0027] To obtain a main-chain copolymer of type (A1) from an alkylene oxide and a lactone (such as caprolactone), a suitable starting material is reacted with a premixed combination of an alkylene oxide and caprolactone.

[0028] Alcohols containing 2 hydroxyl groups (diols) are used as starting materials. Examples of such diols are: ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, block copolymers of ethylene oxide and propylene oxide, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.

[0029] The alkylene oxides used in combination with caprolactone are: ethylene oxide, 1,2-propylene oxide or 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentylene oxide, preferably ethylene oxide and propylene oxide.

[0030] The copolymerization reaction of an alkylene oxide and caprolactone is carried out under typical conditions of alkoxylation reaction. Basic catalysts such as potassium hydroxide, sodium hydroxide, sodium methoxide, potassium methoxide are used.

[0031] (A2)

[0032] The main-chain polymer of type (A2) can in principle be obtained by the alkoxylation reaction of a poly-lactone.

[0033] The poly-lactone can be obtained, for example, by polymerizing a lactone (such as caprolactone) onto a starting material having 2 hydroxyl groups, such as a diol, such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, block copolymers of ethylene oxide and propylene oxide, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.

[0034] The polymerization reaction of caprolactone is carried out in the presence of various catalysts, such as the transesterification catalyst tin(II) alkanoate.

[0035] The alkoxylation reaction of such polycaprolactone is carried out under typical alkoxylation conditions. Since alkoxylation needs to be carried out under basic reaction conditions, transesterification may occur at the ester bond in the polycaprolactone.

[0036] US4281172 describes acrylates from polyester-polyether copolymers. To obtain these structures, polycaprolactone esters derived from monoalcohols, diols, triols or tetraols are reacted with alkylene oxides.

[0037] The polycaprolactone esters are synthesized according to US3169945 by reacting a hydroxyl group-containing component with various catalysts including Ti or Sn catalysts, or alkali metal hydroxides.

[0038] The alkoxylation reaction is catalyzed by BF3-etherate or potassium hydroxide, etc.

[0039] JP07149883 describes a method for obtaining polyester polyols by first reacting a compound containing at least two active hydrogen atoms with a lactone and then reacting with an alkylene oxide. Both reactions are carried out with the same catalyst. The catalyst is an alkali metal hydroxide or an alkali metal alcoholate.

[0040] WO9636656 claims a biodegradable alkylene oxide-lactone copolymer. The polymer is synthesized by first copolymerizing a bifunctional or polyfunctional starter with an alkylene oxide and a lactone, and then end-capping with an alkylene oxide block. The catalyst is an alkali metal hydroxide or an alkaline earth metal hydroxide or a Lewis acid. This patent application describes that the claimed polymer has better biodegradability compared to polyalkylene oxides and is used as a surfactant, emulsifier, etc., but cannot be used as the main chain of a graft polymer.

[0041] (A3)

[0042] (A3)-type main-chain polymers can in principle be obtained by the polycondensation reaction of polyalkylene glycols with lactones, which produces (in short) triblock polymers.

[0043] Using caprolactone and alkylene oxide as raw materials, the synthesis method of a triblock copolymer with an intermediate polyalkylene oxide block includes: 1. reacting a diol or water with an alkylene oxide to form a polyalkoxylate; and 2. polymerizing and grafting caprolactone onto the polyalkoxylate.

[0044] These two reactions can be carried out respectively under the typical reaction conditions of the alkoxylation reaction (producing polyalkoxylate) and the typical reaction conditions of caprolactone polymerization (producing polycaprolactone blocks).

[0045] Such triblock copolymers with a middle polyethylene oxide block have been known since the 1990s. These polymers are used for drug release and solubilization purposes (Z. Zhu et al., Journal of Polymer Science, Part A: Polymer Chemistry 1997, 35(4), 709-714; M. Boffito et al., Journal of Biomedical Materials Research, Part A, 2015, 103A(3), 1276-1290).

[0046] (A4)

[0047] (A4)-type main chains are also known:

[0048] WO96 / 36656 discloses biodegradable alkylene oxide-lactone copolymers and copolyesters, which have been described above for (A3).

[0049] WO2002046268 (Cognis, now part of BASF) discloses alkylene oxide-lactone copolymers, which have been described for (A1).

[0050] However, there is currently no knowledge of a way to use such polymers as the backbone of a graft polymer, i.e., to introduce enhanced biodegradability properties into such graft polymers via this backbone.

[0051] Object of the Invention

[0052] It has been recognized that graft polymers based on conventional polyalkylene oxides (main chains without ester groups) exhibit unexpectedly low percentages of biodegradation, which are often much lower than the expected values calculated from the biodegradation data of pure polyalkylene oxides.

[0053] As the degree of modification of polyalkylene oxides by grafting polymerizable monomers onto such a main chain via free radicals (usually using polyalkylene oxides with two hydroxy end groups, and thus such polyalkylene oxides with hydroxy groups are commonly referred to as "polyalkylene glycols") increases (i.e., the number of side chains on the main chain increases), graft polymers based on such conventional polyalkylene oxides generally exhibit reduced biodegradation performance compared to unmodified polyalkylene oxides and unmodified polyalkylene glycols. This phenomenon is sometimes attributed to a blocking effect on the biodegradation mechanism, since the degradation process of polyalkylene oxide / diol seems to start at its corresponding end groups and then proceeds step by step along the polymer chain. Thus, any additional branched structures on the main chain carbon atoms (which are formed when polymer side chains are grafted onto such a main chain) will impede, and may even completely terminate, the degradation process. It can be inferred therefrom that the higher the grafting degree (i.e., the more side chains attached to the main chain), the lower the percentage of biodegradation of such a graft polymer. Unfortunately, it is also often observed that the higher the degree of branching, the more excellent the performance of the material in the desired application, because only when the number of side chains is high enough will the chemical structure of the main chain be sufficiently changed so that the new graft polymer exhibits specific properties different from a simple mixture of the unmodified main chain and the (unattached / ungrafted) homopolymer that will form the side chains of the graft polymer.

[0054] Therefore, when using polyalkylene oxides as the main chain, the technical problem of how to balance the contradictory characteristics of "a suitable graft polymer with excellent application performance" and "maintaining the percentage of biodegradation of the unmodified main chain (i.e., unmodified polyalkylene oxide / diol)" has not been solved yet.

[0055] Although the unpublished patent application PCT / EP2022 / 065983 first solved the problem of the lack of biodegradation performance of the polyalkylene oxide main chain, it was found that the actual application effect of this solution was still not satisfactory, mainly because: the two-step reaction process was long and costly, requiring two completely different types of chemical reactions (oxidation and polymerization), and the structure regulation was difficult because the oxidation process produced a mixture of compounds such as diols (i.e., the starting material polyalkylene glycol), monoalcohol monocarbonic acids (i.e., partially oxidized polyalkylene glycols), and dicarboxyl polyalkylene oxides (i.e., fully oxidized polyalkylene glycols). The specific structure adopted herein cannot be obtained by the method disclosed in this patent document. Similarly, nitrogen-containing monomers were not disclosed.

[0056] Therefore, it is necessary to improve the biodegradation performance of conventional graft polymers based on polyalkylene oxides by enhancing the biodegradation ability of the grafting substrate and maintaining the overall structure of the graft polymer, so as to maintain or even enhance its application performance; it is also necessary to optimize the cost and efficiency of the unpublished patent application PCT / EP2022 / 065983 by simplifying the production process to only one-step reaction (using only one type of reaction) while improving the controllability of the chemical structure.

[0057] Although (A1), (A2), and (A3) type polymers as defined herein are known, using such polymers as the main chain to prepare graft polymers has not been reported.

[0058] Accordingly, an object of the present invention is to provide novel graft polymers based on a polyalkylene oxide type graft main chain having an ester functional group imparting ability.

[0059] Furthermore, when used in compositions such as cleaning compositions, these novel graft polymers should have beneficial properties regarding biodegradability and / or their washing behavior. Summary of the Invention

[0060] The present invention provides a fabric and home care composition comprising:

[0061] (i) a graft polymer; and

[0062] (ii) one or more fabric and home care ingredients,

[0063] wherein the graft polymer consists of:

[0064] (A) 20% to 95%, preferably 30% to 90%, more preferably 40% to 85%, most preferably 50% to 80% of a polymer main chain that serves as a graft substrate,

[0065] which comprises at least one subunit (a1) and at least one subunit (a2), wherein

[0066] (a1) is a unit comprising, preferably consisting essentially of, a moiety derived from at least one alkylene oxide monomer and / or at least one polyalkylene oxide polymer having two hydroxyl end groups, the alkylene oxide monomer being selected from C2 to C 10 alkylene oxide, preferably the group of C2 to C5 alkylene oxides,

[0067] (a2) is a unit comprising, preferably consisting of, at least one lactone and / or at least one hydroxy acid, such a subunit (a2) being a moiety derived from a single lactone and / or hydroxy acid, or an oligomeric or polymeric unit consisting of at least one type of lactone and / or at least one type of hydroxy acid,

[0068] wherein preferably, the at least one lactone and / or hydroxy acid is selected from group (i) and / or group (ii), wherein

[0069] (i) Lactones, i.e., cyclic esters, starting from α-lactones (three ring atoms), followed by β-lactones (four ring atoms), γ-lactones (five ring atoms), and so on; such lactones are preferably β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, ε-caprolactone, δ-decalactone, γ-decalactone, ε-decalactone; caprolactone is preferred;

[0070] and

[0071] (ii) Hydroxy acids, which can be derived by hydrolysis from any lactone, particularly from any lactone within group (i) above, specifically α-hydroxy acids, β-hydroxy acids or γ-hydroxy acids derived by hydrolysis from the corresponding lactone, as well as lactic acid, glycolic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 12-hydroxystearic acid, citric acid;

[0072] Lactic acid or caprolactone is preferred, and caprolactone is more preferred,

[0073] wherein the polymer backbone is obtained by:

[0074] (A1) Copolymizing at least one subunit (a1) with at least one subunit (a2), wherein in this copolymerization of at least one subunit (a1) and at least one subunit (a2), optionally at least one oligomer or polymer prepared from at least one subunit (a1) or at least one subunit (a2) can also be used;

[0075] (A2) First oligomerizing / polymerizing subunit (a2), and then reacting the product with subunit (a1); or

[0076] (A3) First oligomerizing / polymerizing subunit (a1), and then copolymerizing the product with subunit (a2);

[0077] (A4) First providing an oligomeric or polymeric subunit (a1) with a capping group on one side, which is preferably etherified with an alcohol, more preferably etherified with a C1 to C4 short-chain alcohol, and this subunit then reacts as a starting block with at least one subunit (a2) and / or at least one subunit (a1), where subunit (a1) can be different from the subunit (a1) in the starting block or can be arranged in a different order compared to the subunit (a1) in the starting block, to attach a new block containing a portion of the subunits used in the (co)polymerization reaction to the uncapped side of the starting block, thereby obtaining a diblock structure, i.e., [capping group]-[subunit (a1)]-[subunit (a2)] or [capping group]-[subunit

[0078] (a1)]-[random-{subunit (a2)-subunit (a1)}];

[0079] Where, in the case that there are already more than one subunit (a1) and / or more than one subunit (a2) present in the oligomer or polymer employed, these subunits can be arranged in any order within such employed oligomer or polymer, and

[0080] where, in the case that there are more than one subunit (a1) and / or more than one subunit (a2) for this polymerization reaction, these subunits (and optionally the oligomer / polymer used if any) can be arranged in any order within the obtained main chain; and

[0081] (B) 5% to 80%, preferably 10% to 70%, more preferably 15% to 60%, most preferably 20% to 50% of polymer side chains (B) grafted onto the polymer main chain (A), where the polymer side chains (B) can be obtained by the (co)polymerization reaction of the following monomers: at least one vinyl ester monomer (B1), optionally vinyl pyrrolidone as monomer (B2), optionally other monomers (B3), and optionally other monomers,

[0082] where all percentages are expressed by weight percentage based on the total weight of the graft polymer.

[0083] The present invention also provides a fabric and home care composition, which comprises:

[0084] (i) a graft polymer; and

[0085] (ii) one or more fabric and home care ingredients,

[0086] where the graft polymer consists of:

[0087] (A) 20% to 95%, preferably 30% to 90%, more preferably 40% to 85%, most preferably 50% to 80% of a polymer main chain, which serves as a graft substrate,

[0088] which comprises at least one subunit (a1) and at least one subunit (a2), where

[0089] (a1) is a unit comprising the following moiety, preferably consisting essentially of the following moiety: a moiety derived from at least one alkylene oxide monomer and / or at least one polyalkylene oxide polymer having two hydroxyl end groups, and the alkylene oxide monomer is selected from C2 to C 10 alkylene oxide, preferably the group of C2 to C5 alkylene oxides,

[0090] (a2) is a unit comprising, preferably consisting of: at least one lactone and / or at least one hydroxy acid, such a subunit (a2) being a moiety derived from a single lactone and / or hydroxy acid, or an oligomeric or polymeric unit consisting of at least one type of lactone and / or at least one type of hydroxy acid,

[0091] wherein preferably, the at least one lactone and / or hydroxy acid is selected from group i) and / or group ii), wherein

[0092] i) lactones, i.e. cyclic esters, starting from α-lactones (three ring atoms), followed by β-lactones (four ring atoms), γ-lactones (five ring atoms), and so on; such lactones are preferably β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, ε-caprolactone, δ-decalactone, γ-decalactone, ε-decalactone; preferably caprolactone;

[0093] and

[0094] ii) hydroxy acids, which can be derived by hydrolysis from any lactone, in particular from any lactone within group i) above, specifically α-hydroxy acids, β-hydroxy acids or γ-hydroxy acids derived by hydrolysis from the corresponding lactone, as well as lactic acid, glycolic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 12-hydroxystearic acid, citric acid;

[0095] preferably lactic acid or caprolactone, more preferably caprolactone,

[0096] wherein the polymer backbone is selected from

[0097] (A1) a backbone consisting of monomeric, oligomeric and / or polymeric (a1) subunits and monomeric, oligomeric and / or polymeric (a2) subunits in a random arrangement order, wherein there are more than one subunit (a1) and / or more than one subunit (a2);

[0098] (A2) a backbone consisting of oligomeric or polymeric subunits (a2) as an inner block and two oligomeric and / or polymeric (a1) subunit outer blocks, defined as “-[(a1) block]-[(a2) block]-[(a1) block]-”, and may also include higher-order block polymers such as 5-block, 7-block, 9-block, etc., wherein (a1) and (a2) blocks are further connected outside the triblock structure, such as the pentablock structure “[(a1) block]-[(a2) block]-[(a1) block]-[(a2) block]-[(a1) block]-[(a2) block]-[(a1) block]”; and

[0099] (A3) A main chain composed of oligomeric and / or polymeric (a1) subunit inner segments and two oligomeric or polymeric subunit (a2) outer segments, in the form of at least a triblock polymer, defined as "-[(a2) block]-[(a1) block]-[(a2) block]-",

[0100] (A4) A main chain consisting of

[0101] A first block,

[0102] which has a capping group at one end - such a capping group is a C1 to C 18 alkyl group attached to the first block via an ether functional group, preferably a C1 to C4 alkyl group; and

[0103] carries an oligomeric or polymeric subunit (a1); and

[0104] A second block, which is attached to the first block at the opposite end of the first block via an ether or ester functional group ("opposite" is relative to the capping group of the first block), the second block being composed of at least one subunit (a2) and optionally at least one subunit (a1), where the optional subunit (a1) in the second block can be different from the subunit (a1) in the first block, or can be arranged in a different order compared to the subunit (a1) in the first block, and the subunits (A1) and (a2) can also be arranged in any order, including a random structure,

[0105] This diblock structure has the following idealized structure when only using subunit (a2): [capping group]-[subunit (a1)]-[subunit (a2)]

[0106] Or when using subunits (a1) and (a2):

[0107] [capping group]-[subunit (a1)]-[random-{subunit (a2)-subunit (a1)}];

[0108] And

[0109] (B) 5% to 80%, preferably 10% to 70%, more preferably 15% to 60%, most preferably 20% to 50% of polymer side chains (B) grafted onto the polymer main chain (A), where the polymer side chains (B) can be obtained by the (co)polymerization reaction of: at least one vinyl ester monomer (B1), optionally vinyl pyrrolidone as monomer (B2), optionally other monomers (B3), and optionally other monomers,

[0110] where all percentages are expressed as weight percentages based on the total weight of the graft polymer. Description of the Drawings

[0111] Figure 1 (a, b): Comparison of the ¹H NMR spectra (298 K, D₂O, 400 MHz) of a fresh sample, i.e., Comparative Graft Polymer 1 (lower figure), and a 9 wt% aqueous solution stored at 54 °C for two weeks (upper figure). a) Full spectrum, b) Enlarged view of the region from 4.0 ppm to 4.35 ppm. 1 ¹H NMR spectra (298 K, D₂O, 400 MHz) comparison. a) Full spectrum, b) Enlarged view of the region from 4.0 ppm to 4.35 ppm.

[0112] Figure 2 (a, b): Comparison of the ¹H NMR spectra (298 K, D₂O, 400 MHz) of a fresh graft polymer of the present invention, Graft Polymer 5 (Invention 5) (lower figure), and a 9 wt% aqueous solution stored at 54 °C for two weeks (upper figure). a) Full spectrum, b) Enlarged view of the region from 3.75 ppm to 4.35 ppm. 1 ¹H NMR spectra (298 K, D₂O, 400 MHz) comparison. a) Full spectrum, b) Enlarged view of the region from 3.75 ppm to 4.35 ppm. Detailed Description of the Invention

[0113] The fabric and home care composition comprises:

[0114] (i) A graft polymer; and

[0115] (ii) One or more fabric and home care ingredients.

[0116] Graft Polymer

[0117] The graft polymer of the present invention comprises a polymer main chain (first structural unit) as a graft substrate and a polymer side chain as a second structural unit.

[0118] First Structural Unit (Main Chain)

[0119] The first structural unit of the graft polymer is a polymer main chain that serves as the graft substrate of the graft polymer of the present invention, wherein the polymer main chain (A) can be obtained by the polymerization reaction of at least one subunit (a1) and at least one subunit (a2).

[0120] The subunit (a1) is made of: at least one alkylene oxide monomer and / or at least one polyalkylene oxide polymer having two hydroxyl end groups, and the alkylene oxide monomer is selected from C₂ to C 10A group of alkylene oxides, preferably C2 to C5 alkylene oxides such as ethylene oxide, 1,2-epoxypropane, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxypentane or 2,3-epoxypentane; 1,4-diols, or their cyclic or oligomeric analogs, or polyether polymers based on such 1,4-diols; 1,6-diols, or their cyclic or oligomeric analogs, or polyether polymers based on such 1,6-diols; or any mixture of any of the above in any proportion, presented as blocks of specific polymer units, statistical polymer structures, or polymers containing one or more homopolymer blocks of specific monomers and one or more statistical blocks containing more than one such monomer, and any combination thereof, such as polymers with several different blocks of two or more different monomers, polymers with blocks of two or more different monomers, or polymers with statistical mixture blocks of two or more monomers, etc.

[0121] As used herein, the term "block (co)polymer" means that the corresponding polymer contains at least two (i.e., two, three, four, five or more) homopolymer or copolymer subunits ("blocks") connected by covalent bonds. A "diblock" copolymer has two independent blocks (homopolymer and / or copolymer subunits), while a "triblock" copolymer has three independent blocks (homopolymer and / or copolymer subunits), and so on. The number of independent blocks in such block copolymers is not limited; accordingly, an "n-block copolymer" contains n independent blocks (homopolymer and / or copolymer subunits). Within each block, the size / length of such block can vary independently of other blocks. The minimum block length / size is based on two individual monomers (as a minimum), but can be as large as 50, even 100 or 200, and any value between 2 and 200. The corresponding monomers used to prepare each block of the block copolymer backbone (a1) can be added sequentially. However, during the feed switch from one monomer to another, there may also be a transition phenomenon, resulting in a so-called "dirty structure", where at the edge / junction of the corresponding block, a small amount of monomers of the corresponding adjacent block may be contained within the individual block under consideration (the so-called "dirty structure" or "dirty channel"). However, preferably, the block copolymer subunits (a1) according to the present invention do not contain any dirty structures at the corresponding junctions of the blocks, but for commercial reasons (i.e., mainly factors such as the cost of efficient reactor utilization), although there may still be a small amount of dirty structures, these are not deliberately introduced products.

[0122] Preferably, at least one monomer in the polymer is derived from the use of ethylene oxide.

[0123] In another embodiment, the structure of the polymer subunit (A1) contains more than one alkylene oxide monomer; in this case, the polymer backbone is a random copolymer, a block copolymer, or a copolymer of a mixed structure comprising: block units (where each block is itself a homopolymer block or a random block), and a statistical / random portion consisting of two or more alkylene oxides, wherein at least one monomer is ethylene oxide. Preferably, the other monomers in addition to ethylene oxide are propylene oxide (PO) and / or 1,2-epoxybutane (BO), and preferably only 1,2-propylene oxide is used.

[0124] The subunit (a2) is made from at least one lactone and / or at least one hydroxy acid.

[0125] At least one lactone and / or hydroxy acid is selected from group i) and / or group ii), where

[0126] i) Lactones, i.e., cyclic esters, starting from α-lactones (three ring atoms), followed by β-lactones (four ring atoms), γ-lactones (five ring atoms), and so on; such lactones are preferably β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, ε-caprolactone, δ-decalactone, γ-decalactone, ε-decalactone; preferably caprolactone;

[0127] and

[0128] ii) Hydroxy acids, which can be derived by hydrolysis from any lactone, particularly from any lactone within group i) above, specifically α-hydroxy acids, β-hydroxy acids or γ-hydroxy acids derived by hydrolysis from the corresponding lactone, as well as lactic acid, glycolic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 12-hydroxystearic acid, citric acid; preferably lactic acid or caprolactone, more preferably caprolactone.

[0129] The subunits (a1) and (a2) can be combined in any order according to the application mode of the starting materials and their relative amounts. Thus, by selecting the desired subunits (a1) and (a2), specifically, for subunit (a1), by selecting the number of different alkylene oxides, their relative amounts, their reaction order, etc.; and of course also applicable to subunit (a2), by selecting specific compounds and their relative amounts, etc., the polymer backbone (A) obtained from the reaction of (a1) and (a2) can be defined within a very wide range, specifically achievable in the following three ways:

[0130] -1) First obtain a structurally defined subunit (a1), and then react it with subunit (a2),

[0131] -2) React the alkylene oxide in monomer form from subunit (a1) directly with subunit (a2) in monomer form; or

[0132] -3) Combine the above methods 1) and 2).

[0133] Therefore, three of the most important main chain structures can be defined and obtained:

[0134] (A1)：

[0135] The subunit (a2) can be added during the polymerization of the alkylene oxide (a1 unit) to form a random copolymer; in its variant method, a polyalkylene oxide having two hydroxyl groups can be added to this polymerization reaction to introduce a specific (a1) subunit block; this variant method has practical value when any of the following occurs: at least a part of the alkylene oxide used is different from the alkylene oxide used in the preparation of the polyalkylene oxide used simultaneously, or the structure of the polyalkylene oxide (i.e., the arrangement order of the alkylene oxide units) is different from the structure obtained by reacting at least one alkylene oxide used in the copolymerization reaction with the (a2) subunit and the polyalkylene oxide.

[0136] In a simplified method, the (A1) main chain can be described as a structure composed of (a1) subunits and (a2) subunits in a random arrangement order. According to the relative amounts and reactivities of (a1) and (a2), the block lengths of (a1) and (a2) change.

[0137] The following structures can be obtained by this method:

[0138] Poly[random-{lactone}-{alkylene oxide}]

[0139] Therefore, in a preferred embodiment, the polymer main chain is selected from

[0140] (A1) A main chain composed of monomeric, oligomeric, and / or polymeric (a1) subunits and monomeric, oligomeric, and / or polymeric (a2) subunits in a random arrangement order, where there are more than one subunit (a1) and / or more than one subunit (a2).

[0141] (A2)：

[0142] The subunit (a2) can first be oligomerized / polymerized and then copolymerized with at least one alkylene oxide to form a mixed random / block structure; according to the degree of oligomerization of the lactone / hydroxy acid and whether there is still lactone / hydroxy acid in monomer form when the alkylene oxide is added, the structure can be further adjusted by adjusting the number and length of the (a2) subunit chains in the (A2) main chain.

[0143] Similar to (A1), in another variant method, a polyalkylene oxide having two hydroxyl groups can also be added to such a polymerization reaction, thereby also introducing a specific (a1) subunit block; this variant method has practical value when any of the following situations occur: at least a part of the alkylene oxide used is different from the alkylene oxide used in the preparation of the polyalkylene oxide used simultaneously, or the structure of the polyalkylene oxide (i.e., the arrangement order of the alkylene oxide units) is different from the structure obtained by reacting at least one alkylene oxide used in the copolymerization reaction with the (a2) subunit and the polyalkylene oxide.

[0144] In a simplified method, the (A2) main chain can be described as a triblock polymer having an internal (a2) block and two external (a1) blocks. (Reversing the order generates structure (A3); see below.)

[0145] The following structure (in its simplest form) can be obtained by this method:

[0146] [PAG]-[oligomeric / polymeric lactone]-[PAG]

[0147] ("Lactone" used here refers to the (a2) subunit and is thus made from lactone / hydroxy acid, which can be either a single monomer unit or an oligomeric or polymeric unit made from monomers through an initial reaction step; "PAG" (i.e., polyalkylene glycol) here is used to represent the (a1) subunit)

[0148] In the case where the starting material of the (a2) subunit has not completely reacted, the structure will no longer be a true triblock structure but will additionally contain more shorter (a2) units in the chain, thus forming a multiblock structure and even turning into a mixture of block and random arrangement structures.

[0149] Therefore, in a preferred embodiment, the polymer main chain is selected from the (A2) main chain composed of an oligomeric or polymeric subunit (a2) as an internal block and two oligomeric and / or polymeric (a1) subunit external blocks, defined as "-[(a1) block]-[(a2) block]-[(a1) block]-", and may also include higher-order block polymers such as pentablock, heptablock, nonablock, etc., where (a1) and (a2) blocks are further connected outside the triblock structure, such as the pentablock structure "[(a1) block]-[(a2) block]-[(a1) block]-[(a2) block]-[(a1) block]-[(a2) block]-[(a1) block]" etc.

[0150] (A3)：

[0151] The subunit (a2) can be added after the alkylene oxide oligomerization reaction or after the (near-complete) polymerization reaction, thereby generating a block structure containing longer (a2) chains and longer (a1) chains; in the case where the complete polymerization of (a1) is completed before adding (a2), the resulting structure can be described as "(a2)-polyalkylene oxide-(a2)"; such a structure can also be obtained by the direct reaction of polyalkylene oxide with (a2). More complex structures can be obtained by the following two methods: first, only the alkylene oxide is oligomerized, and then the mixture containing the alkylene oxide oligomer and the monomeric alkylene oxide is reacted with (a2); or (a2) is polymerized with the alkylene oxide and the polyalkylene oxide.

[0152] In a simplified method, the (A3) main chain can be described as a triblock polymer having an internal (a1) block and two external (a2) blocks:

[0153] (Reversing the order generates the structure (A2); see above.)

[0154] [Oligo / polyester]-[PAG]-[Oligo / polyester]

[0155] ("Oligo / polyester" represents the (a2) subunit and is thus made from lactone / hydroxy acid; here "PAG" (i.e., polyalkylene glycol) is used to represent the (a1) subunit)

[0156] Thus, in a preferred embodiment, the polymer main chain is selected from the (A3) main chain consisting of an internal block of oligomeric and / or polymeric (a1) subunits and two external blocks of oligomeric or polymeric subunits (a2), in the form of at least a triblock polymer, defined as "-[(a2) block]-[(a1) block]-[(a2) block]-".

[0157] Similar to the case of (A2), in the case where the starting material of the (a2) subunit has not completely reacted, the structure will no longer be a true triblock structure, but will additionally contain more shorter (a1) units in the chain, thus forming a multi-block structure and even turning into a mixture of block and random arrangements.

[0158] Similarities of (A1), (A2), and (A3)

[0159] When adding the corresponding other subunit substances, the more unreacted (a2) substances (in the case of the (A2) main chain) or the more unreacted (a1) substances (in the case of the (A3) main chain), the smaller the difference between (A2) and (A3).

[0160] In the extreme case, the result of this operation will be the complete copolymerization reaction of the subunits (a1) and (a2), and thus its structure will also be similar to or even identical to (A1).

[0161] Thus, (A1), (A2), and (A3) are merely extreme examples in the general principle of copolymerizing alkylene oxides, polyalkylene glycols, and lactones / hydroxy acids in every conceivable order of arrangement, proportion, and variation of reaction time before adding other starting materials.

[0162] Thus, in a preferred embodiment, the polymer backbone is selected from backbones obtained according to the following general principle: alkylene oxides, polyalkylene glycols, and lactones / hydroxy acids are copolymerized in every conceivable order of arrangement, proportion, and variation of reaction time before adding other starting materials.

[0163] In a preferred embodiment, the polymer backbone serving as the graft substrate contains at least one subunit (a1) and at least one subunit (a2), wherein

[0164] (a1) is a unit containing, preferably consisting essentially of, a moiety derived from at least one alkylene oxide monomer and / or at least one polyalkylene oxide polymer having two hydroxyl end groups, and the alkylene oxide monomer is selected from C2 to C 10 alkylene oxides, preferably the group of C2 to C5 alkylene oxides,

[0165] (a2) is a unit containing, preferably consisting of, at least one lactone and / or at least one hydroxy acid, and such a subunit (a2) is a moiety derived from a single lactone and / or hydroxy acid or an oligomeric or polymeric unit composed of at least one type of lactone and / or at least one type of hydroxy acid,

[0166] wherein preferably, the at least one lactone and / or hydroxy acid is selected from group i) and / or group ii), wherein

[0167] i) lactones, i.e., cyclic esters, starting from α-lactones (three ring atoms), followed by β-lactones (four ring atoms), γ-lactones (five ring atoms), and so on; such lactones are preferably β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, ε-caprolactone, δ-decalactone, γ-decalactone, ε-decalactone; preferably caprolactone; and

[0168] ii) hydroxy acids, which can be derived by hydrolysis from any lactone, particularly from any lactone within group i) above, specifically α-hydroxy acids, β-hydroxy acids, or γ-hydroxy acids derived by hydrolysis from the corresponding lactones, as well as lactic acid, glycolic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 12-hydroxystearic acid, citric acid; preferably lactic acid or caprolactone, more preferably caprolactone, and the polymer backbone is obtained by the following:

[0169] (A1) copolymerize at least one subunit (a1) with at least one subunit (a2), wherein in this copolymerization of at least one subunit (a1) and at least one subunit (a2), optionally at least one oligomer or polymer prepared from at least one subunit (a1) or at least one subunit (a2) can also be used;

[0170] (A2) First carry out oligomerization / polymerization on subunit (a2), and then carry out polymerization on the product with subunit (a1); or

[0171] (A3) First carry out oligomerization / polymerization on subunit (a1), and then carry out copolymerization on the product with subunit (a2);

[0172] (A4) First provide a side-capped oligomeric or polymeric subunit (a1), which is preferably etherified with an alcohol, more preferably etherified with a C1 to C4 short-chain alcohol. This subunit then reacts as a starting block with at least one subunit (a2) and / or at least one subunit (a1), where the subunit (a1) can be different from the subunit (a1) in the starting block or can be arranged in a different order compared to the subunit (a1) in the starting block, to attach a new block containing a portion of the subunits used in the (co)polymerization reaction to the uncapped side of the starting block, thereby obtaining a diblock structure, i.e., [capping group]-[subunit (a1)]-[subunit (a2)] or [capping group]-[subunit (a1)]-[random-{subunit (a2)-subunit (a1)}];

[0173] where in the case where there are already more than one subunit (a1) and / or more than one subunit (a2) present in the oligomer or polymer used, these subunits can be arranged in any order within such used oligomer or polymer, and

[0174] where in the presence of more than one subunit (a1) and / or more than one subunit (a2)

[0175] for the case of this polymerization reaction, these subunits (and the optional oligomer / polymer if used) can be arranged in any order within the obtained main chain;

[0176] and where - optionally - the main chain structure contains at least one starting molecule.

[0177] The polymer main chain (A), especially (A1), (A2), and (A3), can optionally be capped at the end groups, and this capping treatment uses known techniques, through C1 to C 25The capping is carried out with an alkyl group (preferably a C1 to C4 group). This capping treatment will be carried out after the preparation of the main chain and preferably can be completed before grafting.

[0178] In the case of (A4), a capping treatment of one end group needs to be carried out before the polycondensation reaction with subunit (a1) and / or subunit (a2), because only in this way can the (A4) structure be obtained subsequently. In another more preferred method, the preparation of (A4) starts from a monoalcohol, and then it is reacted with an alkylene oxide to obtain a "mono-end-capped" oligomer / polymer of subunit (a1) (the end of the oligo / polyalkylene oxide chain carries a hydroxyl group), and then it is reacted with subunit (a2) to obtain the (A4) structure.

[0179] When preparing oligo / polyalkylene oxide as the starting block, a diol can be used as the starting molecule to prepare the oligo / polyalkylene oxide. Therefore, such an oligo / polymer of subunit (a1) can contain a part derived from such a diol in its structure. Diols for such uses and methods for preparing such oligo / polyalkylene oxides containing diols in their structure are known. Typical diols include ethylene glycol, propylene glycol, etc. In principle, all known diols can be used for this purpose.

[0180] In another preferred embodiment, the polymer main chain as the grafting substrate contains at least one subunit (a1) and at least one subunit (a2), where

[0181] (a1) is a unit containing the following part, preferably consisting essentially of the following part: a part derived from at least one alkylene oxide monomer and / or at least one polyalkylene oxide polymer having two hydroxyl end groups, and the alkylene oxide monomer is selected from C2 to C 10 alkylene oxide, preferably the C2 to C5 alkylene oxide group,

[0182] (a2) is a unit containing the following part, preferably consisting of the following part: at least one lactone and / or at least one hydroxy acid. Such a subunit (a2) is a part derived from a single lactone and / or hydroxy acid, or an oligomeric or polymeric unit composed of at least one type of lactone and / or at least one type of hydroxy acid,

[0183] where preferably, the at least one lactone and / or hydroxy acid is selected from group i) and / or group ii), where

[0184] i) Lactones, that is, cyclic esters, starting from α-lactones (three ring atoms), followed by β-lactones (four ring atoms), γ-lactones (five ring atoms), and so on; such lactones are preferably β-propiolactone, g-butyrolactone, δ-valerolactone, g-valerolactone, e-caprolactone, d-decalactone, g-decalactone, e-decalactone; preferably caprolactone; and

[0185] ii) Hydroxy acids, which can be derived by hydrolysis from any lactone, particularly from any lactone within group i) above, specifically α-hydroxy acids, β-hydroxy acids or γ-hydroxy acids derived by hydrolysis from the corresponding lactone, as well as lactic acid, glycolic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 12-hydroxystearic acid, citric acid;

[0186] Preferably lactic acid or caprolactone, more preferably caprolactone,

[0187] wherein the polymer backbone serves as the grafting substrate (A),

[0188] wherein the polymer backbone is selected from

[0189] (A1) A backbone composed of monomeric, oligomeric and / or polymeric (a1) subunits and monomeric, oligomeric and / or polymeric (a2) subunits in a random arrangement order, where there is more than one subunit (a1) and / or more than one subunit (a2);

[0190] (A2) A backbone composed of oligomeric or polymeric subunit (a2) as an inner block and two oligomeric and / or polymeric (a1) subunit outer blocks, defined as "-[(a1) block]-[(a2) block]-[(a1) block]-", and may also include higher-order block polymers such as 5-block, 7-block, 9-block, etc., where (a1) and (a2) blocks are further connected outside the triblock structure, such as the pentablock structure "[(a1) block]-[(a2) block]-[(a1) block]-[(a2) block]-[(a1) block]-[(a2) block]-[(a1) block]" etc.; and

[0191] (A3) A backbone composed of oligomeric and / or polymeric (a1) subunit inner block and two oligomeric or polymeric subunit (a2) outer blocks, in the form of at least a triblock polymer, defined as "-[(a2) block]-[(a1) block]-[(a2) block]-",

[0192] (A4) A backbone composed of

[0193] a first block,

[0194] (i) having a capping group at one end - such a capping group is a C1 to C 18 alkyl group attached to the first block via an ether functional group, preferably a C1 to C4 alkyl group; and

[0195] (ii) having oligomeric or polymeric subunit (a1); and

[0196] A second block, which is attached to the first block at the opposite end of the first block via an ether or ester functional group ("opposite" being relative to the capping group of the first block), the second block being composed of at least one subunit (a2) and optionally at least one subunit (a1), wherein the optional subunit (a1) in the second block may be different from the subunit (a1) in the first block or may be arranged in a different order compared to the subunit (a1) in the first block, and the subunits (A1) and (a2) can also be arranged in any order, including a random structure,

[0197] This diblock structure has the following idealized structure when only using subunit (a2): [capping group]-[subunit (a1)]-[subunit (a2)]

[0198] Or when using subunits (a1) and (a2):

[0199] [capping group]-[subunit (a1)]-[random-{subunit (a2)-subunit (a1)}];

[0200] And wherein - optionally - at least one starting molecule is included in this main chain structure.

[0201] In a preferred embodiment, the polymer main chain (A), in particular (A1),

[0202] (A2) and (A3), are not capped but carry hydroxyl groups at the chain ends.

[0203] Preferably, the polyalkoxylate-ester main chain contains moieties derived from

[0204] (i) alkylene oxide (AO), which includes at least one of ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO), preferably includes at least one of EO and PO,

[0205] wherein the amount of AO is 40 wt% to 95 wt%, preferably at most 90 wt%, preferably at least 50 wt%, more preferably at least 60 wt%, and even more preferably at least 70 wt%, and any value and range between the above values, each based on the total weight of the main chain,

[0206] Based on the total AO, the amount of EO is 0 wt% to 100 wt%, preferably at least 10 wt%, more preferably at least 20 wt%, even more preferably at least 30 wt%, even more preferably at least 40 wt%, such as at least 50 wt%, 60 wt%, 70 wt%, 80 wt% or even at least 90 wt%,

[0207] The total amount of PO and / or BO is from 0 wt% to 100 wt%, preferably at most 90 wt%, more preferably at most 80 wt%, even more preferably at most 70 wt%, even more preferably at most 60 wt%, and most preferably at most 50 wt%, and any value between the above values, such as at most 5 wt%, 10 wt%, 15 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 55 wt%, 65 wt%, 75 wt%, 85 wt% or at most 95 wt%, and more preferably at least 10 wt%, even more preferably at least 20 wt%, even further more preferably at least 30 wt%, such as at least 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt% or even at least 90 wt%, each based on the total weight of AO, wherein for the sum of PO and BO, the total amount of PO and BO totals 100 wt%,

[0208] wherein the total amount of AO totals 100 wt%;

[0209] (ii) lactone / hydroxy acid monomers, in an amount of at least 1 wt% and at most 60 wt%, preferably at most 50 wt%, more preferably at most 40 wt%, most preferably at most 30 wt%, and preferably at least 2 wt%, more preferably at least 3 wt%, even more preferably at least 4 wt% and most preferably at least 5 wt%, each based on the total weight of the main chain, preferably only caprolactone;

[0210] wherein the total weight of the subunits (a1) and (a2) in the main chain (A) totals 100 wt%.

[0211] More preferably, based on the total AO, the amount of EO is at least 80 wt%, preferably at least about 85 wt%, more preferably at least about 90 wt%, even more preferably at least about 95 wt%, and most preferably about 100 wt%; based on the total weight of AO, the amount of PO and / or BO is from about 0 wt% to 50 wt%, more preferably at most about 30 wt%, even more preferably at most about 20 wt%, even more preferably about 10 wt%, and most preferably about 0 wt%, each based on the total AO; in a more preferred embodiment, the amounts of PO and BO given previously in this paragraph are the sum of the total amounts of PO and BO. In an even more preferred embodiment, the main chain unit (a1) is made only of ethylene oxide.

[0212] In an alternative but preferred embodiment, at least two different alkylene oxides are used to prepare the main chain / present in the main chain.

[0213] Thus, in a more preferred embodiment, the polymer main chain consists of the following

[0214] (i) An alkylene oxide (AO) selected from ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO), preferably only EO and PO,

[0215] Based on the total AO, the amount of EO is from 10 wt% to 90 wt%, preferably from 20 wt% to 80 wt%, more preferably from 30 wt% to 70 wt%, and most preferably from 40 wt% to 60 wt%,

[0216] The total amount of PO and BO is from 10 wt% to 90 wt%, preferably from 20 wt% to 80 wt%, more preferably from 30 wt% to 70 wt%, and most preferably from 40 wt% to 60 wt%, each based on the total weight of AO, wherein for the sum of PO and BO, the total amount of PO and BO totals 100 wt%, and

[0217] wherein the total amount of AO totals 100 wt%;

[0218] (ii) A lactone / hydroxy acid monomer in an amount of at least 1 wt% and at most 60 wt%, preferably at most 40 wt%, more preferably at most 30 wt%, even more preferably at most 25 wt%, even further more preferably at most 20 wt%, most preferably at most 15 wt%, and preferably at least 2 wt%, more preferably at least 3 wt%, even more preferably at least 4 wt and most preferably at least 5 wt%, each based on the total weight of the main chain, preferably only caprolactone;

[0219] wherein the total weight of the subunits (a1) and (a2) in the main chain (A) totals 100 wt%.

[0220] Thus, in a more preferred alternative embodiment, the polymer main chain consists of the following

[0221] (i) An alkylene oxide (AO) selected from ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO), preferably only EO and PO, more preferably only EO,

[0222] Based on the total AO, the amount of EO is from 20 wt% to 100 wt%,

[0223] The total amount of PO and BO is from 0 wt% to 80 wt%, preferably at most 50 wt%, more preferably at most 30 wt%, even more preferably at most 20 wt%, even further preferably at most 10 wt%, and most preferably 0 wt%, such as 45 wt%, 45 wt%, 45 wt%, 25 wt%, 15 wt%, 7 wt% and 5 wt%, and any value between the above values, each based on the total weight of AO, wherein for the sum of PO and BO, the total amount of PO and BO totals 100 wt%,

[0224] wherein the total amount of AO totals 100 wt%;

[0225] (ii) lactone / hydroxy acid monomers, the amount of which is at least 5 wt% and at most 50 wt%, preferably at most 40 wt%, more preferably at most 35 wt%, even more preferably at most 30 wt%, and the lower limit is preferably at least 7 wt%, more preferably at least 10 wt%, even more preferably at least 12 wt%, most preferably at least 15 wt%, such as 6 wt%, 8 wt%, 9 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt% and 15 wt%, and any value between the above values as the lower limit, and such as 30 wt%, 33 wt%, 37 wt%, 45 wt% and any value between the above values as the upper limit, based on the total weight of the main chain, preferably only caprolactone;

[0226] wherein the total weight of the subunits (a1) and (a2) in the main chain (A) totals 100 wt%.

[0227] In an even more preferred embodiment, the main chain of any embodiment of the graft polymer of the present invention as defined herein is a structure selected from structures (A1), (A2), (A3) and / or (A4).

[0228] Second Structural Unit (Graft Side Chain)

[0229] The second structural unit of the graft polymer is a polymer side chain (B), which is grafted onto the polymer main chain (A), wherein the polymer side chain (B) can be obtained by the (co)polymerization reaction of at least one vinyl ester monomer (B1), optionally a nitrogen-containing monomer (B2), optionally other monomers (B3), and optionally other monomers in addition to (B1), (B2) and (B3).

[0230] As the vinyl ester monomer (B1), at least one of vinyl acetate, vinyl propionate and / or vinyl laurate is selected. In addition to these, other vinyl ester monomers (B1) known to those skilled in the art can also be used, such as vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl decanoate and / or vinyl benzoate.

[0231] As the optional monomer (B2), N-vinylpyrrolidone can be used.

[0232] Other monomers (B3) can be used as optional monomers. Such monomers are different from (B1) and (B2) and are present only in an amount preferably less than 10%, more preferably only as impurities and not deliberately added for the polymerization reaction, in the total amount of monomers used to obtain the polymer side chain (B). The (B3) monomer can be any monomer selected from the following: 1-vinyl oxazolidinone and other vinyl oxazolidinones, 4-vinylpyridine-N-oxide, N-vinylformamide and the amine formed by its hydrolysis after the polymerization reaction, N-vinylacetamide, N-vinyl-N-methylacetamide, (meth)acrylic acid alkyl esters, and their derivatives.

[0233] In addition to the monomers (B1), (B2) and (B3), at least one other monomer different from the foregoing monomers can be present for carrying out the (co)polymerization reaction to produce the side chain (B), wherein such other monomer is present only in an amount less than 2% in the total amount of monomers used to obtain the polymer side chain (B), and preferably only as an impurity and not deliberately added for the polymerization reaction.

[0234] In the case where the monomer (B2) is present, based on the total weight of the graft polymer, the monomer dosages are as follows:

[0235] (B) is 10% to 60%, preferably at most 50%, more preferably at most 40%, and preferably at least 20%;

[0236] (B1) Vinyl ester, based on the total weight of the graft polymer, has a weight percentage of 9% to 55%, preferably at most 50%, more preferably at most 40%, even more preferably at most 35%, and even more preferably at most 30%;

[0237] (B2) Monomer N-vinylpyrrolidone, based on the total weight of the graft polymer, has a weight percentage of 1% to 25%, more preferably 5% to 25%, even more preferably at most 15%, such as 1% to 15%, more preferably 5% to 15%, and further such as at most 10%, at most 20%, 10%, and each value between 1% and 25%, wherein preferably, the amount of (B2) is not higher than the amount of (B1);

[0238] (B3) Other monomers are from 0% to 10%, preferably at most 2%, more preferably at most 1%, even more preferably about 0%, but in all cases at most 10% of the amount of (B1), and not exceeding the amount of (B2). The amounts of other monomers other than (B1), (B2) and (B3) are as detailed above.

[0239] In the absence of monomer (B2), based on the total weight of the graft polymer, the monomer usage amounts are as follows:

[0240] (B) is from 5% to 60%, preferably at most 50%, and preferably at least 20%;

[0241] (B1) Vinyl ester, based on the total weight of the graft polymer, has a weight percentage that is the total amount of (B) minus the total amount of (B3);

[0242] (B2) Vinyl pyrrolidone is 0%;

[0243] (B3) Other monomers are from 0% to 10%, preferably at most 2%, more preferably at most 1%, even more preferably about 0%. The amounts of other monomers other than (B1), (B2) and (B3) are as detailed above.

[0244] In a preferred embodiment, the amount of vinyl ester monomer (B1) is generally not less than 10% by weight (relative to the sum of (B1) and (B2)).

[0245] Preferably, the optional other monomer (B3) is present only as an impurity and not deliberately added for the polymerization reaction. More preferably, based on the total weight of monomer (B1), this amount is less than 1% by weight, more preferably less than 0.5% by weight, even more preferably less than 0.01% by weight, most preferably there is substantially no such monomer (B3), and most preferably there are no other monomers at all even except for monomer (B1) and optional monomer (B2). This also applies to other monomers other than (B1), (B2) and (B3).

[0246] In a preferred embodiment, the graft polymer of the present invention comprises the following polymer side chain (B): which is obtained or obtainable by free radical polymerization of at least one vinyl ester monomer (B1) and optionally at least one other monomer (B2) and optionally at least one other monomer (B3) in the presence of a polymer backbone (A), wherein at least 10% by weight of the total amount of vinyl ester monomer (B1) of vinyl ester monomers is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably selected from vinyl acetate and vinyl laurate, and most preferably is vinyl acetate, and wherein the remaining amount of vinyl ester can be any other known vinyl ester, wherein preferably at least 80% by weight, more preferably at least 90% by weight and most preferably substantially only vinyl acetate is used as the vinyl ester (weight percentages are based on the total weight of the vinyl ester monomer B1 used).

[0247] In an even more preferred embodiment of the previous embodiment, substantially no other monomer (B3) is used.

[0248] In an even more preferred embodiment of the previous embodiment, substantially no other monomer (B2) or (B3) is used.

[0249] In a preferred embodiment, the graft polymer of the present invention consists of monomers, wherein

[0250] (B) these monomers are:

[0251] (B1) at least one vinyl ester selected from vinyl acetate, vinyl propionate and / or vinyl laurate, in an amount of 70% to 100% by weight of the total weight of the monomers grafted onto the backbone (A), preferably only vinyl acetate, and

[0252] (B2) optionally the monomer vinyl pyrrolidone, in an amount of 0% to 20% by weight of the total amount of monomers grafted onto the backbone (A),

[0253] wherein the vinyl ester monomer (B1) is optionally partially or completely hydrolyzed after the polymerization reaction.

[0254] In its preferred embodiment, the vinyl ester is not hydrolyzed.

[0255] In an alternative embodiment, in addition to at least one monomer (B1), vinyl pyrrolidone is present as monomer (B2), wherein monomer (B1) preferably comprises vinyl acetate, and even more preferably is only vinyl acetate. Even more preferably, vinyl acetate is the only monomer (B1), and vinyl pyrrolidone is the only monomer (B2).

[0256] In an alternative embodiment to the embodiment described in the immediately preceding paragraph, monomer (B1) can be partially or completely hydrolyzed after the polymerization reaction. In a preferred embodiment thereof, monomer (B1) is partially hydrolyzed, and the degree of hydrolysis is even more preferably at most 80 mol%, 70 mol%, 60 mol%, 50 mol%, 40 mol%, 30 mol%, 20 mol% or 10 mol% based on the total amount of monomer (B1).

[0257] Preferably, monomer (B1) is partially hydrolyzed, and the degree of hydrolysis is at least 20% and at most 50%. In a most preferred embodiment among the foregoing embodiments, vinyl acetate is used as monomer (B1), vinyl pyrrolidone is used as monomer (B2), and the polymer portion derived from vinyl acetate is partially hydrolyzed after the polymerization reaction. The amount of hydrolysis is preferably about 20 mol% to 50 mol%, more preferably about 30 mol% to 45 mol%, such as about 40 mol% based on the total amount of vinyl acetate.

[0258] In an alternative and even more preferred embodiment to the embodiments described in the immediately preceding two paragraphs, the vinyl ester is not hydrolyzed at all.

[0259] It should be understood that the amounts of (A), (B), (B1), (B2), (B3) and other monomers other than the foregoing monomers can each independently be selected from the various ranges given in detail, that is: the upper and lower limits can also form a numerical range not explicitly indicated by combining two different ranges given for a certain element (such as such a combined range for (A), (B), (B1), (B2) and (B3)), but the present invention clearly aims to cover such combined ranges.

[0260] In addition, in an embodiment of the present invention, a wide range and a very particularly preferred narrow range can be used in combination, where the range selection of one component is independent of the range selection of the other component, provided that the total amount of each component constitutes "100% polymer": for example, the most preferred ranges of (A) and (B) can be selected and combined with the widest possible range given for (B1) / (B2) / (B3), and any other possible combinations are covered.

[0261] Preferably, the same selection criteria should be adopted for all possible selections of (A) / (B) and (B1) / (B2) / (B3), for example, all select the "preferred" range, or more preferably all select the "more preferred" range, or most preferably all select the "most preferred" range.

[0262] The polydispersity (PDI) Mw / Mn of the graft polymer of the present invention as described in detail above is at most 10, preferably at most 5, more preferably at most 3, and most preferably in the range of 1.0 to 2.6; and is any value a as an upper or lower limit, and any range in between (such as 1.3 to 2.6, 1 to 3, etc.) (where Mw = weight average molecular weight, unit g / mol; Mn = number average molecular weight, unit g / mol; where PDI is a dimensionless quantity), the lower the value, the more preferred, but specifically depends on the Mn of the polymer backbone used ((A) the higher the Mn, the higher the PDI usually) and the amount of (B) ((B) the higher the amount relative to (A), the higher the PDI usually).

[0263] M w and M n The corresponding values of and can be determined using GPC standard methods (such as the methods mentioned in the experimental section). However, the molecular weights of the main chains used in the present invention can also be calculated because these reactions are basically complete. Therefore, it is also a feasible method to calculate the molecular weight based on the total molar amount of the components used in the preparation reaction. The graft polymer of the present invention may contain a certain amount of ungrafted polymer ("ungrafted side chain") made from monomers that did not react with the polymer backbone (i.e., were not grafted to the polymer backbone, or were not grafted onto the polymer backbone).

[0264] The content of such ungrafted polymer may be higher or lower (depending on the reaction conditions), but preferably the content is reduced, and thus a lower content is more preferred. By this reduction, the amount of grafted side chains is preferably increased. This reduction in content can be achieved by appropriate reaction conditions, such as controlling the feed amounts of the monomer and the free radical initiator and their relative amounts, as well as the ratio relationship with the amount of the main chain. This adjustment is generally known to those skilled in the art and will be elaborated in detail in the process description of obtaining the graft polymer of the present invention below.

[0265] It has been found that the graft polymer of the present invention as described in detail above shows an improved biodegradability of at least 35%, more preferably at least 40%, even more preferably at least 50%, such as 41%, 42%, 43%, 44%, 45%, etc., 51%, 52%, 53%, etc., 55%, 60%, 65%, etc., and any value between the above values and up to 100% within 28 days when tested according to OECD 301F.

[0266] The ratio of (A) to (B) in the embodiments described herein is as follows:

[0267] (A) 20% to 95%, preferably 30% to 90%, more preferably 40% to 85%, most preferably 50% to 80% of the polymer backbone, which serves as the grafting substrate, and

[0268] (B) 5% to 80%, preferably 10% to 70%, more preferably 15% to 60%, and most preferably 20% to 50% of the polymer side chain (B), which is grafted onto the polymer main chain (A),

[0269] where each percentage is based on the total weight of the graft polymer, and the sum of (a) and (B) is 100% by weight.

[0270] All of each subunit (a1), (a2), the polymer main chains (A), (A1), (A2), (A3), and (A4) serving as the graft substrate (as defined by its structure or preparation method), the monomers (B), (B1), (B2), (B3), and other monomers other than (B1), (B2), (B3) are as defined herein and specifically those defined in all of its embodiments, preferred embodiments, etc. and examples hereinbefore; any such embodiments regarding the subunit (a1), (a2), the polymer main chains (A), (A1), (A2), (A3), and (A4) serving as the graft substrate (as defined by its structure or preparation method), the monomers (B), (B1), (B2), (B3), and other monomers other than (B1), (B2), (B3) can be selected and combined separately provided that such selection is feasible herein and not excluded, that is: the total amount of each component needs to meet the requirements and the embodiments are mutually compatible (i.e., an embodiment requiring the presence of (B2) obviously cannot be combined with an embodiment requiring the absence of (B)).

[0271] In a more preferred embodiment, the present invention and / or the graft polymer as detailed above

[0272] consists of:

[0273] (A) at least one polymer main chain serving as the graft substrate, such a graft substrate being any of the polymer main chains defined previously in any embodiment, preferably any of (A1), (A2), (A3), and (A4) as defined previously,

[0274] the amount thereof being as defined in any embodiment herein

[0275] (including the specification, examples, and claims),

[0276] and

[0277] (B) a polymer side chain (B) grafted onto the polymer main chain (A), wherein the polymer side chain (B) can be obtained by the (co)polymerization reaction of the following monomers: at least one vinyl ester monomer (B1), optionally vinyl pyrrolidone (B2), optionally other monomers (B3), and optionally other monomers,

[0278] All such monomers are any monomers as defined in any embodiment herein, and the amounts thereof are as defined in any embodiment herein

[0279] (including the specification, examples and claims).

[0280] In one embodiment of the previous embodiment, the vinyl ester monomer comprises vinyl acetate as the only monomer (B1), and comprises vinyl pyrrolidone as the only monomer (B2), and most preferably there are no other monomers (B3) and no other monomers other than the aforementioned monomers.

[0281] In a preferred embodiment of the previous embodiment, the degree of hydrolysis of the vinyl ester is from about 20 mol% to 50 mol%, preferably from about 30 mol% to 45 mol%, and most preferably about 40 mol%.

[0282] In a specific embodiment, the graft polymer of the present invention consists of:

[0283] (A) 20% to 95%, preferably 30% to 90%, more preferably 40% to 85%, and most preferably 50% to 80% of a polymer backbone, which serves as a graft substrate, wherein the percentages are by weight based on the total weight of the graft polymer;

[0284] which comprises at least one subunit (a1) and at least one subunit (a2), wherein

[0285] (a1) is a unit comprising, preferably consisting essentially of, a moiety derived from at least one alkylene oxide monomer and / or at least one polyalkylene oxide polymer having two hydroxyl end groups, and the alkylene oxide monomer is selected from C2 to C 10 alkylene oxides, preferably the group of C2 to C5 alkylene oxides,

[0286] (a2) is a unit comprising, preferably consisting of, at least one lactone and / or at least one hydroxy acid, and such a subunit (a2) is a moiety derived from a single lactone and / or hydroxy acid, or is an oligomeric or polymeric unit composed of at least one type of lactone and / or at least one type of hydroxy acid,

[0287] wherein preferably, the at least one lactone and / or hydroxy acid is selected from group (i) and / or group (ii), wherein

[0288] i) Lactones, i.e., cyclic esters, starting from α-lactones (three ring atoms), followed by β-lactones (four ring atoms), γ-lactones (five ring atoms), and so on; such lactones are preferably β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, ε-caprolactone, δ-decalactone, γ-decalactone, ε-decalactone; caprolactone is preferred;

[0289] and

[0290] ii) Hydroxy acids, which can be derived from any lactone by hydrolysis, particularly from any lactone within group i) above, specifically α-hydroxy acids, β-hydroxy acids or γ-hydroxy acids derived from the corresponding lactone by hydrolysis, as well as lactic acid, glycolic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 12-hydroxystearic acid, citric acid;

[0291] Lactic acid or caprolactone is preferred, and caprolactone is more preferred,

[0292] wherein the manner of obtaining the polymer backbone

[0293] includes

[0294] (A1) Causing at least one subunit (a1) to copolymerize with at least one subunit (a2), wherein in this copolymerization of at least one subunit (a1) and at least one subunit (a2), optionally at least one oligomer or polymer prepared from at least one subunit (a1) or at least one subunit (a2) can also be used;

[0295] (A2) First oligomerizing / polymerizing subunit (a2), and then polymerizing the product with subunit (a1); or

[0296] (A3) First oligomerizing / polymerizing subunit (a1), and then copolymerizing the product with subunit (a2);

[0297] (A4) First providing an oligomeric or polymeric subunit (a1) with a capping group on one side, which is preferably etherified with an alcohol, more preferably etherified with a C1 to C4 short-chain alcohol, and this subunit then reacts as a starting block with at least one subunit (a2) and / or at least one subunit (a1), where subunit (a1) can be different from the subunit (a1) in the starting block or can be arranged in a different order compared to the subunit (a1) in the starting block, to attach a new block containing a portion of the subunits used in the (co)polymerization reaction to the uncapped side of the starting block, thereby obtaining a diblock structure, i.e., [capping group]-[subunit (a1)]-[subunit (a2)] or [capping group]-[subunit (a1)]-[random-{subunit (a2)-subunit (a1)}];

[0298] where, in the case where more than one subunit (a1) and / or more than one subunit (a2) are already present in the oligomer or polymer employed, these subunits can be arranged in any order within the oligomer or polymer so employed, and

[0299] where, in the case where more than one subunit (a1) and / or more than one subunit (a2) are present for the polymerization reaction, these subunits (and any optional oligomers / polymers used) can be arranged in any order within the resulting main chain;

[0300] or selected from

[0301] (A1) a main chain consisting of monomeric, oligomeric and / or polymeric (a1) subunits and monomeric, oligomeric and / or polymeric (a2) subunits in a random arrangement order, where more than one subunit (a1) and / or more than one subunit (a2) are present;

[0302] (A2) a main chain consisting of oligomeric or polymeric (a2) subunits as an inner block and two oligomeric and / or polymeric (a1) subunit outer blocks, defined as "-[(a1) block]-[(a2) block]-[(a1) block]-", and may also include higher-order block polymers, such as pentablock, heptablock, nonablock, etc., where (a1) and (a2) blocks are further connected outside the triblock structure, such as the pentablock structure "[(a1) block]-[(a2) block]-[(a1) block]-[(a2) block]-[(a1) block]-[(a2) block]-[(a1) block]"; and

[0303] (A3) a main chain consisting of an oligomeric and / or polymeric (a1) subunit inner block and two oligomeric or polymeric (a2) subunit outer blocks, in the form of at least a triblock polymer, defined as "-[(a2) block]-[(a1) block]-[(a2) block]-";

[0304] (A4) a main chain consisting of

[0305] a first block,

[0306] which has a capping group at one end - such a capping group is a C1 to C 18 alkyl group attached to the first block via an ether functional group, preferably a C1 to C4 alkyl group; and

[0307] carries an oligomeric or polymeric (a1) subunit; and

[0308] A second block attached to the first block at the opposite end of the first block via an ether or ester functional group ("opposite" is relative to the capping group of the first block), the second block being composed of at least one subunit (a2) and optionally at least one subunit (a1), wherein the optional subunit (a1) in the second block may be different from the subunit (a1) in the first block or may be arranged in a different order compared to the subunit (a1) in the first block, and the subunits (A1) and (a2) can also be arranged in any order, including a random structure.

[0309] This diblock structure has the following idealized structure when only using subunit (a2): [capping group]-[subunit (a1)]-[subunit (a2)]

[0310] Or when using subunits (a1) and (a2): [capping group]-[subunit (a1)]-[random-{subunit (a2)-subunit (a1)}]; where the amounts of subunits (a1) and (a2) are as defined previously herein;

[0311] And wherein - optionally - at least one initiator molecule is included in the main chain structure;

[0312] And

[0313] (B) 5% to 80%, preferably 10% to 70%, more preferably 15% to 60%, most preferably 20% to 50% of polymer side chains (B) grafted onto the polymer main chain (A), wherein the polymer side chains (B) can be obtained by the (co)polymerization reaction of the following monomers: at least one vinyl ester monomer (B1), optionally vinyl pyrrolidone (B2), optionally other monomers (B3), and optionally other monomers.

[0314] Where the percentages are expressed as weight percentages based on the total weight of the graft polymer.

[0315] Where these monomers are:

[0316] (B1) At least one vinyl ester selected from vinyl acetate, vinyl propionate, and / or vinyl laurate, and any other vinyl esters known to those skilled in the art, such as vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl decanoate, and / or vinyl benzoate;

[0317] Optionally

[0318] (B2) N-vinyl pyrrolidone;

[0319] Optionally

[0320] (B3) at least one other monomer, such as any one or more of 1-vinyl oxazolidinone and other vinyl oxazolidinones, 4-vinylpyridine-N-oxide, N-vinylformamide and the amine formed by hydrolysis after polymerization, N-vinylacetamide, N-vinyl-N-methylacetamide, (meth)acrylic acid alkyl esters; and

[0321] Optionally

[0322] at least one other monomer different from the aforementioned monomers, and this other monomer is present in the total amount of monomers used to obtain the polymer side chain (B) in an amount of less than 2%, and preferably only present as an impurity rather than deliberately added for the polymerization reaction;

[0323] wherein the usage amounts are preferably as follows:

[0324] – If (B2) is present –

[0325] (B) is 10% to 60%, preferably at most 50%, more preferably at most 40%, and preferably at least 20%;

[0326] (B1) The vinyl ester is 9% to 55% by weight based on the total weight of the graft polymer, preferably at most 50%, more preferably at most 40%, even more preferably at most 35%, and even more preferably at most 30%;

[0327] (B2) The vinylpyrrolidone is 1% to 41% by weight based on the total weight of the graft polymer, preferably at most 30%, more preferably at most 25%, such as 1% to 25%, more preferably 5% to 25%, even more preferably at most 15%, such as 1% to 15%, more preferably 5% to 15%, and further such as at most 10%, at most 40%, 35%, 20%, 10%, and each value between 1% and 41%. Preferably, the amount of (B2) is not higher than the amount of (B1)

[0328] And

[0329] – If (B2) is absent –

[0330] (B) is 5% to 60%, preferably at most 50%, and preferably at least 20%;

[0331] (B1) (The vinyl ester) is the total amount of (B) minus the total amount of (B3) by weight based on the total weight of the graft polymer,

[0332] (B2) The vinylpyrrolidone is 0%,

[0333] And it is further stipulated that in all the aforementioned cases

[0334] (B3) (other monomers) is 0% to 10%, preferably at most 2%, more preferably at most 1%, even more preferably about 0%, but in all cases at most 10% of the amount of (B1), and does not exceed the amount of (B2);

[0335] Wherein preferably at least 10% by weight of the total amount of vinyl ester monomer (B1) of vinyl ester monomers is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably selected from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester can be any other known vinyl ester, wherein preferably at least 80% by weight, more preferably at least 90% by weight and most preferably substantially only vinyl acetate is used as the vinyl ester (weight percentage based on the total weight of vinyl ester monomer B1 used).

[0336] And optionally, the vinyl ester is hydrolyzed after polymerization.

[0337] In one embodiment of the previous embodiment, the vinyl ester monomer comprises vinyl acetate as the sole monomer (B1), and more preferably comprises vinyl pyrrolidone as the sole monomer (B2), and most preferably no other monomers (B3) and other monomers other than the aforementioned monomers are present.

[0338] In a preferred embodiment of the previous embodiment, the degree of hydrolysis of the vinyl ester is about 20 mol% to 50 mol%, preferably about 30 mol% to 45 mol%, and most preferably about 40 mol%.

[0339] The polymer of the present invention preferably has at least one of the following additional properties, preferably has two or more of the following additional properties, for more successful application in various application fields targeted by the present invention:

[0340] i) The polymer backbone (A) can carry two hydroxyl groups as end groups, or can be capped at both ends with C1 to C 22 alkyl groups (preferably C1 to C4 alkyl groups);

[0341] ii) The polydispersity (PDI) Mw / Mn of the graft polymer is at most 10, preferably at most 5, more preferably at most 3, and most preferably in the range of 1.0 to 2.6; and is either value a as the upper limit or the lower limit, and any range in between (such as 1.3 to 2.6, 1 to 3, etc.) (where Mw = weight average molecular weight; Mn = number average molecular weight [g / mol / g / mol]);

[0342] iii) The biodegradability of the graft polymer is at least 35%, more preferably at least 40%, even more preferably at least 45%, and even further more preferably at least 50%, such as 46%, 47%, 48%, 49%, 50%, 55%, 60%, 65%, 70%, 75%, etc., and any value between the above values and up to 100% within 28 days when tested according to OECD 301F.

[0343] In addition, the graft polymer preferably has a certain degree of water solubility so that the polymer can be applied in an aqueous environment typically present in the application fields generally targeted by the present invention. Preferably, the polymer of the present invention should exhibit medium to good solubility in the environment of an aqueous formulation, more preferably good solubility, and such aqueous formulations are commonly used in various such fields of formulations, such as dishwashing, automatic dishwashing, hard surface cleaning, fabric cleaning, fabric care, cosmetic formulations, etc.

[0344] In addition, the graft polymer solution preferably has a suitable viscosity, which should be within a suitable range when at a reasonably high polymer solid concentration (to meet the processing requirements during and after production and to be provided in the form required by the user, for example, as a "pure" (usually liquid at this time) product, dissolved in a solvent (typically an aqueous solution (containing water and an organic solvent), water only, or an organic solvent only)), to allow typical technical process steps such as pouring, pumping, metering, etc. Therefore, the viscosity should preferably be in the range of at most about 4000 mPas, more preferably at most 3500 mPas, even more preferably at most 3000 mPas, such as at most 4500 mPas, 3750 mPas, 3250 mPas, 2750 mPas, or even 2600 mPas, or less than, for example, 2500 mPas, 2000 mPas, 1750 mPas, 1500 mPas, 1250 mPas, 1000 mPas, 750 mPas, 500 mPas, 250 mPas, 200 mPas, 150 mPas, or 100 mPas. The concentration of the polymer (defined as the weight percentage of the dry polymer in the total weight of the polymer solution, based on the total solid content of the polymer in the solution) is preferably at least 10 wt%, more preferably at least 20 wt%, and even more preferably at least 40 wt%, and most preferably at least 50 wt%, such as at least 60 wt%, 70 wt%, 80 wt%, or even 90 wt%. The viscosity can be measured at 25 °C or an elevated temperature, such as 50 °C or even 60 °C. Thereby, the polymer solution can be suitably processed on a commercial scale. Of course, it is obvious that depending on the amount of solvent added, when the amount of solvent increases, the viscosity is lower, and vice versa, thus allowing adjustment in the desired situation. It is also obvious that the measured viscosity depends on the temperature at which it is measured. For example, when measured at a lower temperature, the viscosity of a given polymer with a given solid content of, for example, 80 wt% will be higher, while when measured at a higher temperature, the viscosity will be lower. In a preferred embodiment, the solid content is between 70 wt% and 99 wt%, more preferably between 75 wt% and 85 wt%, and no additional solvent is added except for the polymer prepared.In a more preferred embodiment, the solids content is between 70% and 99% by weight, more preferably between 75% and 95% by weight, no additional solvent is added apart from the polymer being prepared, and the viscosity is below 3000 mPas, more preferably 3250 mPas, or even below 2750 mPas, 2600 mPas, 2500 mPas, 2000 mPas, 1750 mPas, 1500 mPas, 1250 mPas, 1000 mPas, 750 mPas, 500 mPas, or even 250 mPas when measured at 60 °C. The viscosity can be determined as is commonly known for such polymers, preferably as described in the experimental section below.

[0345] As a further criterion, of course, the specific properties of the particular polymer need to be evaluated and each specific formulation ranked accordingly in the particular field of application. Due to the wide range of uses of the polymers of the present invention, it is not possible to give an exhaustive overview or detailed guidance for each field of application, but the present specification and examples give guidance on how to prepare and select useful polymers with the desired properties and how to adjust these properties to meet the requirements. One such criterion in the field of home care, in particular in the field of fabric care, is of course its performance during washing, for example subjecting certain materials showing stains of certain materials to a defined washing program.

[0346] The examples provide some guidance for the application of washing fabrics, i.e. the general field of fabric care.

[0347] Depending on the individual need for polymers showing a defined degree of biodegradability, water solubility and viscosity (i.e. handling properties), the general and specific teachings herein (not intended to be limited to the specific examples given) will guide on how to obtain such polymers.

[0348] Process

[0349] The present invention also encompasses a method for obtaining a graft polymer according to any of the foregoing embodiments as defined herein, in particular any of the embodiments in the previous part, and any of the examples disclosed herein, wherein at least one vinyl ester monomer (B1), optionally vinylpyrrolidone monomer (B2), optionally other monomers (B3) and optionally other monomers (other than (B1), (B2) and (B3)) are polymerized in the presence of at least one polymer backbone (A) as defined herein, the polymer backbone (A) being preferably selected from the backbones (A1), (A2), (A3) and (A4) as defined herein, wherein the polymer side chain (B) is obtained by a radical polymerization reaction, preferably using a radical-forming compound to initiate the radical polymerization reaction, wherein B1, B2 and B3 (and other monomers other than (B1), (B2) and (B3)) and (A), (A1), (A2), (A3) and (A4) are each as defined above (including any embodiments exemplified in the claims and the following examples), each component being preferably selected from any of its preference levels, and each component should be selected as individually as possible according to its preference, but always subject to the general requirements of preferred compatibility (such as the sum not exceeding 100% etc.).

[0350] It must be noted that the "grafting method" in which a polymer backbone (such as the polymer backbone (A) described above) is grafted with polymer side chains is itself known to those skilled in the art. Any method known to those skilled in the art in this regard can in principle be employed in the present invention.

[0351] Radical polymerization itself is also known to those skilled in the art. Those skilled in the art also know that the method of the present invention can be carried out in the presence of a radical-forming initiator (C) and / or at least one solvent (D).

[0352] Those skilled in the art know the respective components suitable for such uses.

[0353] The term "radical polymerization" used in the context of the present invention includes, in addition to radical polymerization, its variants such as controlled radical polymerization. Suitable control mechanisms are RAFT, NMP or ATRP, each of which is known to those skilled in the art, including suitable control agents.

[0354] In a preferred embodiment, the process for producing the graft polymers of the invention and / or the process as detailed previously comprises: polymerizing at least one vinyl ester monomer (B1), optionally vinylpyrrolidone as monomer (B2), optionally at least one other monomer (B3) and optionally other monomers (which are preferably present only as impurities and more preferably are substantially absent) in the presence of at least one polymer backbone (A), a free-radical forming initiator (C) and, if desired, at least one solvent (D) up to a maximum of 50% by weight, based on the sum of components (A), (B) and (C), at an average polymerization temperature at which the decomposition half-life of the initiator (C) is from 40 minutes to 500 minutes, where the polymer backbone (A) is preferably selected from the backbones (A1), (A2), (A3) and (A4) as defined previously, in such a way that the content of unreacted graft monomers (B1), optionally (B2) and optionally (B3) (the other monomers are generally present only in very low and thus negligible amounts as impurities and therefore do not need to be monitored) and the initiator (C) in the reaction mixture is always substoichiometric with respect to the copolymer backbone (A). In a preferred embodiment, monomer (B2) is not used. In a more preferred embodiment, neither monomer (B2) nor monomer (B3) is used. In an even more preferred embodiment, only monomer (B1) is used. Generally, the amount of other monomers apart from (B1), (B2) and (B3) is minimized, preferably these other monomers are completely absent.

[0355] In a preferred embodiment of any of the embodiments of the process as detailed in the preceding paragraph, at least 10% by weight of the total amount of vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, and most preferably is vinyl acetate, and where the remaining amount of vinyl ester can be any other known vinyl ester, where preferably at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight, even more preferably at least 90% by weight and most preferably substantially only (i.e. about 100% by weight or even 100% by weight) vinyl acetate is used as the vinyl ester (weight percentages based on the total weight of the vinyl ester monomer B1 used).

[0356] Generally, apart from monomers (B1), (B2) and (B3), at least one other monomer different from the aforementioned monomers can be used for carrying out the (co)polymerization reaction to produce the side chain (B), where such other monomer is present in an amount of less than 2% in the total amount of monomers used to obtain the polymer side chain (B), and is preferably present only as an impurity which cannot be avoided in practice and not deliberately added for the polymerization reaction, most preferably is completely absent.

[0357] In a more preferred embodiment of the foregoing two paragraphs, with regard to the monomer amounts and ratios, the following additional provisions 1) (the case when (B2) is present) and 2) (the case when (B2) is absent) apply:

[0358] In the case of using monomer (B2), based on the total weight of the graft polymer, the monomer amounts are as follows:

[0359] (B) is 10% to 60%, preferably at most 50%, more preferably at most 40%, and preferably at least 20%;

[0360] (B1) Vinyl ester, based on the total weight of the graft polymer, is 9% to 55% by weight, preferably at most 50%, more preferably at most 40%, even more preferably at most 35%, and even more preferably at most 30%;

[0361] (B2) Vinylpyrrolidone, based on the total weight of the graft polymer, is 1% to 25% by weight, more preferably 5% to 20%, even more preferably at most 15%, such as 1% to 15%, more preferably 5% to 15%, and further such as at most 10%, at most 19%, 18%, 17%, 16%, 14%, 13%, 12%, 11%, 10%, and each value between 1% and 25%, wherein preferably, the amount of (B2) is not higher than the amount of (B1);

[0362] (B3) (Other monomers) is 0% to 10%, preferably at most 2%, more preferably at most 1%, even more preferably about 0%, but in all cases at most 10% of the amount of (B1), and does not exceed the amount of (B2).

[0363] The amounts of other monomers other than (B1), (B2), and (B3) are as detailed above, and monomers (B1), (B2), and (B3) are those monomers detailed in any of the foregoing disclosed embodiments.

[0364] In the case of not using monomer (B2), based on the total weight of the graft polymer, the monomer amounts are as follows:

[0365] B) is 5% to 60%, preferably at most 50%, and preferably at least 20%;

[0366] (B1) Vinyl ester, based on the total weight of the graft polymer, is the total amount of (B) minus the total amount of (B3),

[0367] (B2) Vinylpyrrolidone is 0%;

[0368] (B3) (Other monomers) is from 0% to 10%, preferably at most 2%, more preferably at most 1%, and even more preferably about 0%.

[0369] The amounts of other monomers in addition to (B1), (B2) and (B3) are as detailed above, and the monomers (B1), (B2) and (B3) are those monomers detailed in any of the embodiments disclosed above.

[0370] In a preferred embodiment, the amount of vinyl ester monomer (B1) used is generally not less than 10% by weight (relative to the sum of (B1) and (B2)).

[0371] Preferably, the optional other monomer (B3) is also present only as an impurity and not deliberately added for the polymerization reaction. More preferably, based on the total weight of monomer (B1), this amount is less than 1%, more preferably less than 0.5%, even more preferably less than 0.01%, and most preferably there is substantially no such monomer (B3), and most preferably there is not even any other monomer except monomer (B1) and optional monomer (B2). This also applies to other monomers in addition to (B1), (B2) and (B3).

[0372] In a particularly preferred embodiment, based on the total weight of the graft polymer, the amounts of the monomers used are as follows:

[0373] (A) accounts for 40% to 90% of the polymer backbone as defined above, preferably at least 50%, more preferably at least 60%, and preferably at most 80%, and preferably at least one of (A1), (A2) and (A3) is used as the graft substrate.

[0374] (B) is 10% to 60%, preferably at most 50%, more preferably at most 40%, and preferably at least 20%;

[0375] (B1) Vinyl ester is 9% to 55%, preferably at most 50%, more preferably at most 40%, even more preferably at most 35%, and even more preferably at most 30%;

[0376] (B2) Vinylpyrrolidone is 1% to 25%, preferably at most 20%, more preferably at most 15%, even more preferably at most 10%, such as even only at most 5%, where the amount of (B2) is at most not more than the amount of (B1);

[0377] (B3) (Other monomers) is 0% to 2%, preferably at most 1%, more preferably 0%, but in all cases is at most 10% of the amount of (B1) and does not exceed the amount of (B2);

[0378] More preferably, any optional additional monomer (B3) and any other monomers other than (B1), (B2), and (B3) are preferably present only as impurities and not deliberately added for the polymerization reaction; more preferably, based on the total weight of monomer (B1), the amount is less than 1% by weight, more preferably less than 0.5% by weight, even more preferably less than 0.01% by weight, and most preferably there are substantially no such monomers (B3) nor any other monomers, and most preferably there are no other monomers at all even in addition to monomers (B1) and (B2).

[0379] The amount of vinyl ester monomer (B1) is generally not less than 10% by weight (relative to the sum of (B1) and (B2)).

[0380] In an alternatively particularly preferred embodiment, based on the total weight of the graft polymer, the amounts of the monomers used are as follows:

[0381] (A) accounts for 40% to 90% of the polymer backbone as defined above, preferably at least 50%, more preferably at least 80%, and preferably at least one of (A1), (A2), and (A3) is used as the graft substrate;

[0382] (B) is 10% to 60%, preferably at most 50%, and preferably at least 20%;

[0383] (B1) vinyl ester is the total amount of (B) minus the total amount of (B3);

[0384] (B2) is 0%;

[0385] (B3) (other monomers) is 0% to 2%, preferably at most 1%, more preferably 0%, but in all cases at most 10% of the amount of (B1) and does not exceed the amount of (B2);

[0386] The amount of vinyl ester monomer (B1) is generally not less than 10% by weight (relative to the sum of (B1) and (B2));

[0387] Any optional additional monomer (B3) and any other monomers other than (B1), (B2), and (B3) are preferably present only as impurities and not deliberately added for the polymerization reaction. More preferably, based on the total weight of monomer (B1), the amount is less than 1% by weight, more preferably less than 0.5% by weight, even more preferably less than 0.01% by weight, and most preferably there are substantially no such monomers (B3) nor any other monomers, and most preferably there are no other monomers at all even in addition to monomer (B1).

[0388] In each case based on the polymer side chain (B), the amount of the ((free) radical-forming) initiator (C) is preferably 0.1% to 5% by weight, particularly 0.3% to 3.5% by weight.

[0389] For the process according to the invention, it is preferred that the steady-state concentration of free radicals present at the average polymerization temperature remains substantially constant, and that the graft monomers (B), in particular (B1), more preferably (B1) and (B2), even more preferably (B1), (B2) and (B3), are always present in the reaction mixture only in low concentrations (for example, not more than 5% by total weight). This allows the reaction to be controlled and graft polymers with the desired low polydispersity to be prepared in a controlled manner.

[0390] To ensure safe temperature control (especially when the polymerization is initiated at high solid concentrations or in bulk and / or when a large amount of monomer is present initially), it is recommended and thus preferred to take additional effective temperature control measures. This can be done by external and / or internal cooling; such cooling can be achieved by internal and / or external coolers (such as heat exchangers), or when operating at the boiling point temperature of a solvent or solvent mixture under a given temperature / pressure combination, by using a reflux condenser.

[0391] Of course, the same measures can also be used for the preferred embodiments mentioned above, where the monomers are added continuously over a longer period of time so that the monomer concentration in the reaction system remains low over time.

[0392] However, under such conditions, temperature control is usually not a critical control point, since the temperature is at least partially also controlled by the course of the polymerization reaction achieved by regulating the free radical concentration and the available amount of polymerizable monomers. Of course, depending on the scale of the polymerization reaction, such additional cooling measures as described above may be necessary for both of the following process variants: batch or bulk reactions where a large amount of monomer is present initially, or semi-continuous or continuous polymerization reactions where the monomer concentration is usually continuously low - when the scale of the reaction becomes large enough that the volume-to-surface area ratio of the polymerization mixture increases significantly.

[0393] However, those skilled in the art in the field of commercial-scale polymerization are usually aware of this common technical knowledge and can thus make adaptations to meet the requirements.

[0394] According to the invention, the addition process of the initiator (C) and the graft monomers (B) (in particular (B1) and / or (B2) and / or (B3)) preferably employs a dual "and" connection structure and is achieved in the following advantageous manner: there is a substantially constant low concentration of undecomposed initiator and graft monomers (B) in the reaction mixture, where (B1) in particular remains at a constant low level, while (B2) in particular maintains an even lower concentration. Based on the total amount of initiator metered during monomer addition, the proportion of undecomposed initiator in the overall reaction mixture is preferably ≤ 15% by weight, especially ≤ 10% by weight.

[0395] In a more preferred embodiment, the method comprises polymerizing at least one vinyl ester monomer (B1), optionally at least one nitrogen-containing monomer (B2), optionally at least one other monomer (B3) and optionally at least one other monomer (more preferably only monomers (B1) and (B2)) in the presence of at least one polymer backbone (A) as defined herein (which is preferably selected from (A1), (A2) and (A3)), a radical-forming initiator (C) and, if desired, at least one solvent (D) up to a maximum of 50% by weight based on the sum of components (A), (B) and (C) at an average polymerization temperature at which the decomposition half-life of the initiator (C) is from 40 minutes to 500 minutes, in such a way that the content of unreacted graft monomers (B) and the initiator (C) in the reaction mixture is always substoichiometric with respect to the polymer backbone (A), wherein preferably at least 10% by weight of the total amount of vinyl ester monomer (B1) of vinyl ester monomers are selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester can be any other known vinyl ester, wherein preferably at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight, even more preferably at least 90% by weight and most preferably substantially only (i.e. about 100% by weight or even 100% by weight) vinyl acetate is used as the vinyl ester (weight percentages are based on the total weight of the vinyl ester monomer B1 used).

[0396] In an even more preferred embodiment of the foregoing embodiment, monomer (B2) is used substantially not in addition to monomer (B1), and (B1) preferably comprises vinyl acetate, more preferably consists essentially of vinyl acetate, all within the ranges and preferences given in the section "Graft polymers of the invention".

[0397] In an alternative embodiment of the foregoing embodiment, substantially only monomer (B2) is used in addition to monomer (B1), (B1) preferably comprises vinyl acetate, more preferably consists essentially of vinyl acetate, and preferably vinyl pyrrolidone is present as (B2), all within the ranges and preferences given in the section "Graft polymers of the invention".

[0398] The average polymerization temperature of the main polymerization reaction and the post-polymerization reaction is suitably in the range from 50 °C to 140 °C, preferably in the range from 60 °C to 120 °C, and more preferably in the range from 65 °C to 110 °C. Usually, the temperature of the post-polymerization reaction is 5 °C to 40 °C higher than that of the polymerization reaction.

[0399] The term "average polymerization temperature" is hereby intended to mean that, although the process is essentially isothermal, due to the exothermic nature of the reaction, there may be temperature variations which are preferably kept within the range of + / - 10 °C, more preferably within the range of + / - 5 °C.

[0400] According to the invention, the decomposition half-life of the initiator (C) (formation of free radicals) at the average polymerization temperature should be from 40 minutes to 500 minutes, preferably from 50 minutes to 400 minutes, and more preferably from 60 minutes to 300 minutes.

[0401] Examples of suitable initiators (C) having a decomposition half-life of from 20 min to 500 min in the temperature range from 50 °C to 140 °C are:

[0402] -tert-C4-C 12 -alkyl hydroperoxides and tert-(C9-C 12 -arylalkyl) hydroperoxides O-C2-C 12 -acylated derivatives such as tert-butyl peracetate, tert-butyl monoperoxymaleate, tert-butyl perisobutyrate, tert-butyl peroxypivalate, tert-butyl perneodecanoate, tert-butyl per-2-ethylhexanoate, tert-butyl per-3,5,5-trimethylhexanoate, tert-butyl perneodecanoate, tert-amyl peroxypivalate, tert-amyl per-2-ethylhexanoate, tert-amyl perneodecanoate, 1,1,3,3-tetramethylbutyl perneodecanoate, cumyl perneodecanoate, tert-butyl perbenzoate, tert-amyl perbenzoate and di-tert-butyl diperoxyphthalate;

[0403] -tert-C8-C 14 -alkylidene bisperoxides di-O-C4-C 12 -acylated derivatives such as 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 2,5-dimethyl-2,5-bis(benzoyl-peroxy)hexane and 1,3-bis(2-neodecanoylperoxyisopropyl)benzene;

[0404] -di(C2-C 12 -alkanoyl) and dibenzoyl peroxides such as diacetyl peroxide, dipropionyl peroxide, disuccinyl peroxide, dioctanoyl peroxide, bis(3,5,5-trimethylhexanoyl) peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis(4-methylbenzoyl) peroxide, bis(4-chlorobenzoyl) peroxide and bis(2,4-dichlorobenzoyl) peroxide;

[0405] -peroxy(C4-C 12 -alkyl) carbonic acid tert-C4-C5-alkyl esters such as tert-amyl peroxy(2-ethyl-hexyl) carbonate;

[0406] - Di(C2-C 12 - alkyl peroxydicarbonates), such as di(n-butyl) peroxydicarbonate and di(2-ethylhexyl) peroxydicarbonate.

[0407] Depending on the average polymerization temperature, examples of particularly suitable initiators (C) are:

[0408] - At an average polymerization temperature of 50 °C to 60 °C:

[0409] tert-Butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxyneopentanoate, tert-amyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneodecanoate, 1,3-bis(2-neodecanoylperoxyisopropyl)benzene, di(n-butyl) peroxydicarbonate and di(2-ethylhexyl) peroxydicarbonate;

[0410] - At an average polymerization temperature of 60 °C to 70 °C:

[0411] tert-Butyl peroxyneopentanoate, tert-butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxyneopentanoate and bis(2,4-dichlorobenzoyl) peroxide;

[0412] - At an average polymerization temperature of 70 °C to 80 °C:

[0413] tert-Butyl peroxyneopentanoate, tert-butyl peroxyneoheptanoate, tert-amyl peroxyneopentanoate, di(propionyl) peroxide, di(octanoyl) peroxide, di(decoyl) peroxide, dilauroyl peroxide, bis(2,4-dichlorobenzoyl) peroxide and 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexane;

[0414] - At an average polymerization temperature of 80 °C to 90 °C:

[0415] tert-Butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, di(propionyl) peroxide, di(octanoyl) peroxide, di(decoyl) peroxide, dilauroyl peroxide, bis(3,5,5-trimethylhexanoyl) peroxide, benzoyl peroxide and bis(4-methylbenzoyl) peroxide;

[0416] - At an average polymerization temperature of 90 °C to 100 °C:

[0417] tert-Butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl monoperoxymaleate, tert-amyl peroxy-2-ethylhexanoate, benzoyl peroxide and bis(4-methylbenzoyl) peroxide;

[0418] - At an average polymerization temperature of 100 °C to 110 °C:

[0419] tert-butyl monoperoxy maleate, tert-butyl peroxyisobutyrate and tert-amyl peroxy(2-ethylhexyl) carbonate;

[0420] - at an average polymerization temperature of from 110 °C to 120 °C:

[0421] tert-butyl monoperoxy maleate, tert-butyl peroxy-3,5,5-trimethylhexanoate and tert-amyl peroxy(2-ethylhexyl) carbonate.

[0422] Preferred initiator (C) is an O-C4-C of a tert-C4-C5-alkyl hydroperoxide 12 - acylated derivative, particularly preferably tert-butyl peroxypivalate and tert-butyl peroxy-2-ethylhexanoate.

[0423] Particularly advantageous polymerization conditions can be easily established by precisely adjusting the initiator (C) and the polymerization temperature. For example, in the case of using tert-butyl peroxypivalate, the preferred average polymerization temperature is from 60 °C to 80 °C, and in the case of tert-butyl peroxy-2-ethylhexanoate, the preferred average polymerization temperature is from 80 °C to 100 °C.

[0424] The polymerization reaction of the present invention can be carried out in the presence of a preferably small amount of solvent (D). Of course, a mixture of different solvents (D) can also be used. Water-soluble or water-miscible organic solvents are preferably used. However, water as the sole solvent is also possible in principle, but not preferred.

[0425] When the solvent (D) is used as a diluent, in each case based on the sum of components (A), (B1), optionally (B2), optionally (B3), any other monomers and (C), usually 1% to 40% by weight, preferably 1% to 35% by weight, more preferably 1.5% to 30% by weight, most preferably 2% to 25% by weight of the solvent (D) is used.

[0426] Examples of suitable solvents (D) include:

[0427] - 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;

[0428] - polyhydric alcohols, preferably C2-C 10 - diols, more preferably C2-C6-diols, most preferably C2-C4-alkylene diols such as ethylene glycol, 1,2-propanediol and 1,3-propanediol;

[0429] - alkylene glycol ethers, preferably alkylene glycol mono(C1-C 12-alkyl) ethers and alkylene glycol di(C1-C6-alkyl) ethers, more preferably alkylene glycol mono- and di(C1-C2-alkyl) ethers, most preferably alkylene glycol mono(C1-C2-alkyl) ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether and propylene glycol monomethyl ether and propylene glycol monoethyl ether;

[0430] -polyalkylene glycols, preferably poly(C2-C4-alkylene) glycols having 2-20 C2-C4-alkylene glycol units, more preferably polyethylene glycols having 2-20 ethylene glycol units and polypropylene glycols having 2-10 propylene glycol units, most preferably polyethylene glycols having 2-15 ethylene glycol units and polypropylene glycols having 2-4 propylene glycol units such as diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol;

[0431] -polyalkylene glycol monoethers, preferably poly(C2-C4-alkylene) glycol mono(C1-C 25 -alkyl) ethers, more preferably poly(C2-C4-alkylene) glycol mono(C1-C 20 -alkyl) ethers, most preferably poly(C2-C3-alkylene) glycol mono(C1-C 16 -alkyl) ethers;

[0432] -carboxylic acid esters, preferably C1-C8-alkyl esters of C1-C6-carboxylic acids, more preferably C1-C4-alkyl esters of C1-C3-carboxylic acids, most preferably C2-C4-alkyl esters of C2-C3-carboxylic acids such as ethyl acetate and ethyl propionate;

[0433] -aliphatic ketones preferably having 3 to 10 carbon atoms such as acetone, methyl ethyl ketone, diethyl ketone and cyclohexanone;

[0434] -cyclic ethers, especially tetrahydrofuran.

[0435] The solvent (D) is advantageously one of those solvents which are also used for formulating the graft polymers of the invention for use (e.g. in washing and cleaning compositions) and which can thus be retained in the polymerization product.

[0436] Preferred examples of these solvents are polyethylene glycols having 2 to 15 ethylene glycol units, polypropylene glycols having 2 to 6 propylene glycol units, especially the alkoxylation products of C6-C8 alcohols (alkylene glycol monoalkyl ethers and polyalkylene glycol monoalkyl ethers). Particularly preferred here are C8-C 16Alkoxylated alcohols, such substances being capable of formulating a free-flowing polymer mixture at 40 °C to 70 °C, the polymer mixture having a very low polymer content while maintaining a low viscosity. 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 alkoxylated products are 2-ethylhexanol or 2-propylheptanol alkoxylated with 1 mol to 15 mol of ethylene oxide, C 13 / C 15 oxo alcohols or C 12 / C 14 or C 16 / C 18 fatty alcohols, preferably 2-propylheptanol alkoxylated with 1 mol to 15 mol of ethylene oxide and 1 mol to 3 mol of propylene oxide.

[0437] In an alternative embodiment, the polymerization reaction is carried out using a mixture of at least one organic solvent and water.

[0438] In a preferred embodiment, the amount of water during the polymerization reaction is low, preferably at most 10% by weight, more preferably at most 5% by weight, even more preferably at most 1% by weight, based on the total amount of solvent.

[0439] In another alternative embodiment, water is used as the solvent (D) for the polymerization reaction. However, water as the sole solvent is not preferred.

[0440] The free radical initiator (C) is preferably used in the form of a concentrated solution in one of the aforementioned solvents. The concentration of course depends on the solubility of the free radical initiator. Preferably, the concentration is as high as possible to allow the introduction of as little organic solvent as possible into the polymerization reaction. In the case where the initiator is soluble in water and thus water is used as the solvent for introducing the initiator, the concentration does not need to be strictly controlled from the perspective of the residual amount of water.

[0441] Preferably, based on the total weight of the graft polymer (at the end of the polymerization reaction) or based on the total weight of (A) and (B) (at the start of the polymerization reaction), the amount of water during the polymerization reaction is at most 10% by weight, preferably at most 5% by weight, more preferably at most 1% by weight.

[0442] In the process according to the invention, the polymer backbone (A), the graft monomer (B), the initiator (C) and, if applicable, the solvent (D) are generally heated in a reactor to a selected average polymerization temperature.

[0443] According to the present invention, the polymerization is carried out in such a way that an excess of polymer (polymer backbone (A) and the formed graft polymer) is always present in the reactor. The quantitative ratio of the polymer to the ungrafted monomers and the initiator is generally ≥10:1, preferably ≥15:1, and more preferably ≥20:1.

[0444] The polymerization process according to the present invention can in principle be carried out in various reactor types. Such reactor types are well known in the art and include not only any stirred reactor (such as a reaction kettle), but also tubular reactors, cascade reactors composed of reaction kettles or various tubular devices, etc.

[0445] The reactor used is preferably a stirred tank, in which the polymer backbone (A) (if applicable), together with a part of the graft monomers (B), initiator (C) and solvent (D) usually up to 15% by weight of the specific total amount, is first completely or partially filled and then heated to the polymerization temperature, and the remaining amounts of (B), (C) and (if applicable) (D) are metered in, preferably metered in separately. The remaining amounts of (B), (C) and (if applicable) (D) are preferably metered in over a period of ≥2 h, more preferably ≥4 h and most preferably ≥5 h.

[0446] In the case of a particularly preferred, substantially solvent-free process variant, the entire amount of the polymer backbone (A) is first charged as a melt, and then the graft monomers (B1) and (if applicable) (B2) and / or (B3), and preferably the initiator (C) in the form of a 10% to 50% by weight solution prepared with one of the solvents (D) are metered in, and the temperature is controlled such that the average polymerization temperature selected during the polymerization reaction is maintained within a range of especially + / -10 °C, particularly + / -5 °C.

[0447] In another particularly preferred low-solvent process variant, except that the solvent (D) is metered in during the polymerization process to limit the viscosity of the reaction mixture, the procedure is as described above. It is also possible to start metering the addition of the solvent only during subsequent polymerization, or to add it in batches.

[0448] The polymerization can be carried out at standard pressure or at reduced or elevated pressures. When the boiling points of the monomers (B1) and / or (B2) (if (B3) is used, it also includes the monomer (B3)) and / or any solvent (D) used are exceeded at the selected pressure, the polymerization reaction needs to be carried out under reflux cooling.

[0449] After the main polymerization reaction, a post-polymerization process step can be added. To this end, a further amount of initiator (dissolved in a solvent) can be added for a period of 0.5 hours and generally up to 3 hours, preferably about 1 hour to 2 hours, more preferably about 1 hour (but this duration also depends on the reactor scale), and the free radical initiator and the solvent for this initiator are generally and preferably the same as those used in the main polymerization reaction. Of course, different free radical initiators and / or different solvents can also be used.

[0450] The temperature of the post-polymerization process step can be the same as that of the main polymerization reaction (which is preferred in the present invention), or it can be increased. In the case of increasing the temperature, it can generally be increased by about 5°C to 40°C, preferably 10°C to 20°C.

[0451] Between the post-polymerization reaction and the main polymerization reaction, a certain period of time can be waited (during which the main polymerization reaction maintains the system conditions and continues), and the post-polymerization reaction is initiated only when the additional free radical initiator starts to be added.

[0452] For solvents with a boiling point of about less than 110°C to 120°C at atmospheric pressure, such solvents can be partially or substantially completely removed (all operations are carried out at atmospheric or reduced pressure, preferably by vacuum distillation) by thermal distillation, vacuum distillation, or stripping with a gas such as steam or nitrogen (such as stripping with water vapor generated by water), while the higher boiling point solvents will generally remain in the resulting polymer product.

[0453] When mercaptoethanol is used as a chain transfer regulator, steam distillation is the preferred purification step. Therefore, when high boiling point solvents such as 1-methoxy-2-propanol, 1,2-propanediol, and tripropylene glycol are used and such solvents are only used to introduce the initiator, such solvents will remain in the polymer product, so their usage should be minimized as much as possible by using the highest possible concentration of free radical initiator; unless such solvents also constitute components of the formulation in which the graft polymer will be used, this reduction treatment is not required.

[0454] The graft polymers of the present invention prepared by the methods defined herein may contain an amount of ungrafted polymer (the "ungrafted side chains") made from vinyl esters, such as polyvinyl acetate made when only vinyl acetate is used, and / or when other monomers are used, homopolymers and copolymers made from vinyl esters and other monomers. The amount of such ungrafted vinyl ester homopolymers and copolymers may be high or low, depending on the reaction conditions, but is preferably reduced and thus low. By this reduction, the amount of the graft side chains is preferably increased. Such reduction can be obtained by suitable reaction conditions, such as the dosage of vinyl esters and free radical initiators and their relative amounts and relative to the amount of the main chain present. Such reaction control and the necessary process steps are common general knowledge to those skilled in the art and specific guidance has been given herein.

[0455] This adjustment of the graft degree and this amount of ungrafted polymer can be used to optimize the properties in areas of particular interest, such as certain (e.g., detergent) formulations, application areas or desired properties such as cleaning.

[0456] It is believed that the conditions considered to be advantageous herein promote (presumably have) a higher graft degree. This higher graft degree is associated with more excellent properties. However, this presumably higher graft degree does not impair the biodegradability performance (which is attributed to the ester bonds in the main chain that can "compensate" for the lower biodegradability performance of the graft polymer with a higher graft degree), a phenomenon that can be seen in "conventional graft polymers" based on polyalkylene oxides as the main chain.

[0457] The disadvantage is that it is extremely difficult (if not completely impossible) to actually verify this graft degree on the polymer, especially when the molecular weight of the polymer increases, because the total amount of graft sites in the polymer is usually very low compared to its molecular weight; therefore, the signal-to-noise ratio of the polymer is low in terms of existing analytical tools.

[0458] In another alternative embodiment of the present invention, the polymer side chains (B) of the graft polymer according to the present invention are completely or partially hydrolyzed after the polymerization reaction, and thus after obtaining the graft polymer itself, preferably partially hydrolyzed, based on the total molar amount of (B1) used, more preferably at most 50 mol%, preferably at least 20 mol%, more preferably 20 mol% to 50 mol%, even more preferably 30 mol% to 45 mol%, such as about 40 mol%. This means that the complete or at least partial hydrolysis of the polymer side chains (B) of the graft polymer is carried out in a further process step after the completion of the polymerization process of the polymer side chains (B) (including after this step if an optional post-polymerization step is employed).

[0459] In another alternative embodiment, after the completion of the polymerization process of the polymer side chains (B), the graft polymer is not subjected to hydrolysis treatment.

[0460] Due to this complete or at least partial hydrolysis of the polymer side chain (B) of the graft polymer according to the invention, the corresponding side chain units derived from at least one vinyl ester monomer (B1) change from the corresponding ester functional groups to alcohol functional groups within the polymer side chain (B). It must be noted that due to the stability problem of the "vinyl alcohol" monomer, the corresponding vinyl alcohol is not suitable as a monomer used in the polymerization process of the polymer side chain (B). In order to obtain alcohol functional groups (hydroxyl substituents) within the polymer side chain (B) of the graft polymer according to the invention, the alcohol functional groups are generally introduced by hydrolyzing the ester functional groups of the side chain.

[0461] From a theoretical perspective, each ester functional group of the polymer side chain (B) can be partially or completely replaced by an alcohol functional group (hydroxyl group). In this case, the polymer side chain is completely hydrolyzed ("saponified").

[0462] The hydrolysis can be carried out by any method known to those skilled in the art. For example, hydrolysis can be induced by adding a suitable base such as sodium hydroxide or potassium hydroxide. This hydrolysis method is known in the prior art.

[0463] In a preferred embodiment among the foregoing embodiments, vinyl acetate is used as the monomer (B1), vinyl pyrrolidone is used as the monomer (B2), and no other monomers are used except (B1) and (B2). The polymer portion derived from vinyl acetate is partially hydrolyzed after the polymerization reaction. Based on the total number of moles of (B1) used, the amount of hydrolysis is preferably 20 mol% to 50 mol%, more preferably 30 mol% to 45 mol%, such as most preferably about 40 mol%.

[0464] The graft polymer of the present invention (i.e., the polymer solution obtained by this process) can also be subjected to means of concentration and / or drying.

[0465] The obtained graft polymer solution can be concentrated by subjecting the polymer solution to means of removing part of the volatile substances (especially the solvent) to increase the solid polymer concentration. This can be achieved by a distillation process (such as thermal distillation or vacuum distillation), or by a stripping method using a gas such as steam or an inert gas (such as nitrogen or argon) until the desired solid content is reached. This process can be combined with the purification step as disclosed before, in which the obtained graft polymer solution is purified by removing part or all of the volatile components (such as volatile solvents and / or unreacted volatile monomers) and removing the required amount of solvent.

[0466] After the graft polymer solution has been subjected to the main polymerization and / or optional post-polymerization step and an optional purification step, it can be further concentrated or dried by the following means: subjecting the graft polymer solution to means for partially or completely removing volatile substances (such as using a distillation process for concentration, such as thermal distillation or vacuum distillation, or stripping with a gas such as steam or an inert gas (such as nitrogen or argon) until the desired solids content is reached), and / or drying, such as drum drying, spray drying, vacuum drying or freeze drying, preferably spray drying (mainly for cost considerations). This drying process can also be used in combination with an agglomeration or granulation process (such as spray agglomeration, granulation or drying in a fluidized bed dryer).

[0467] Therefore, the process of the present invention preferably encompasses at least one additional process step selected from i) to iv), including: i) post-polymerization; ii) purification; iii) concentration; and iv) drying.

[0468] More preferably, the process as detailed in any of the embodiments defined herein includes at least one additional process step selected from the following:

[0469] i) A post-polymerization process step carried out after the main polymerization reaction, in which preferably an additional amount of initiator (optionally dissolved in a solvent) is added over a period of 0.5 hours to a maximum of 3 hours, preferably about 1 hour to 2 hours, more preferably about 1 hour, where the free radical initiator and the solvent for the initiator are generally and preferably the same as those used for the main polymerization reaction; and where after the polymerization reaction is completed and before the post-polymerization reaction is started, preferably a waiting period is allowed for the main polymerization reaction to continue, and then the post-polymerization reaction is initiated by starting to add additional free radical initiator, this waiting period being preferably 10 minutes to a maximum of 4 hours, preferably at most 2 hours, even more preferably at most 1 hour, and most preferably at most 30 minutes; and where the temperature of the post-polymerization process step is preferably the same as or higher than the temperature of the main polymerization reaction, this temperature increase being preferably about 5°C to 40°C higher than the main polymerization reaction temperature, preferably 10°C to 20°C higher.

[0470] ii) Subjecting the graft polymer obtained from the main polymerization process or (if carried out) the post-polymerization process to means for purification, concentration and / or drying to remove some or almost all of the residual solvent (the part that can be removed according to its boiling point) and / or volatile substances (such as residual monomers), where

[0471] a. Concentration is carried out by removing part of the solvent and optionally also removing volatile substances (thus, this step also serves as a purification means) to increase the solid polymer concentration (and optionally also achieve purification). Preferably, a distillation process such as thermal distillation or vacuum distillation (preferably vacuum distillation) is applied, and / or a stripping method using a gas such as steam or an inert gas (such as nitrogen, preferably steam) is applied. This process continues until the desired solid content is reached and optionally also the desired purity is achieved (preferably until the expected part or all of the volatile components (such as volatile solvents and / or unreacted volatile monomers) are removed);

[0472] b. Drying is carried out by subjecting the graft polymer containing at least a residual amount of volatile substances (such as residual solvents and / or unreacted monomers, etc.) to means for removing volatile substances, such as drum drying, spray drying, vacuum drying or freeze drying, preferably (mainly for cost reasons) spray drying; and optionally combining such a drying process step with agglomeration or granulation means to obtain agglomerated or granular graft polymer particles. Such a process is preferably selected from spray agglomeration, granulation or drying in a fluidized bed dryer, a spray granulation device and similar devices.

[0473] Use of the graft polymer.

[0474] In principle, the graft polymers of the present invention can be used in any application to replace conventional graft polymers of the same or very similar compositions (in terms of the relative amounts of the polymer backbone and graft monomers, especially when the type and amount of the graft monomers are similar or equivalent). Such applications include, for example: achieving soil redeposition inhibition and stain removal, preventing or reducing secondary pollution or ash formation or solid deposition or dye redeposition, enhancing the dispersion stability of active substances in a formulation, surface hydrophobization treatment, reducing surface microbial growth, and / or odor control, etc., compared with corresponding polymers or graft polymers according to the prior art.

[0475] The graft polymers of the present invention as defined herein (which can be obtained by the methods as defined herein, or by the methods as defined herein) can increase the total biodegradation rate of such formulations, compositions and products by replacing non-biodegradable polymers with similar structures or properties. Therefore, such graft polymers can be advantageously applied - the application effect also partly depends on the type of monomer B used for grafting, and the performance is adjusted accordingly to meet the specific requirements of a particular application; this monomer substitution pattern may also be deduced from the prior art of similar graft polymers of simple PEG and polyalkylene glycols.

[0476] Specifically, in addition to the performance advantages in specific types of applications, compared with previously known graft polymers, the graft polymers according to the present invention exhibit an improved biodegradation ability when applied to such compositions or products.

[0477] Accordingly, another subject of the present invention is the use of the graft polymers of the present invention and / or graft polymers obtainable or obtained by the method of the present invention and / or graft polymers as detailed above in cleaning compositions, fabrics and home care products, in particular for enhancing the removal of oily and lipid stains, removing solid dirt (such as clay), preventing graying or discoloration of the fabric surface, and / or a cleaning composition as a scale inhibitor, wherein the cleaning composition is preferably a laundry detergent formulation and / or a dishwashing detergent formulation, more preferably a liquid laundry detergent formulation and / or a liquid hand dishwashing detergent formulation.

[0478] Preferably, these graft polymers are used in cleaning compositions, fabric treatment agents, fabric care products and laundry products, more preferably in laundry detergent formulations, and even more preferably in liquid laundry detergent formulations. In particular, the graft polymers of the present invention are used in such compositions / products / formulations to improve the dye transfer inhibition effect.

[0479] Laundry detergents, cleaning compositions and / or fabrics and home care products themselves are known to those skilled in the art. Any compositions and the like known to those skilled in the art related to the corresponding uses can be used in the context of the present invention.

[0480] In a preferred embodiment, this is a cleaning composition and / or a fabric and home care product comprising at least one graft polymer as defined above. In particular, this is a cleaning composition for improving cleaning performance and / or (preferably "and") enhancing the anti-redeposition performance (e.g., in terms of the redeposition of dirt and dyes) and removing stains, preferably a laundry detergent formulation and / or a hand dishwashing detergent formulation, more preferably a liquid laundry detergent formulation and / or a liquid hand dishwashing detergent formulation.

[0481] These graft polymers support the removal of various hydrophobic and hydrophilic dirt from textiles or hard surfaces by surfactants, such as body soil, food and grease stains, particulate dirt (such as clay or carbon black), grass stains, cosmetics, engine oil, etc., thus improving the washing and cleaning performance of the formulation.

[0482] Furthermore, these graft polymers also better disperse the removed dirt in the washing or cleaning liquid and prevent it from redepositing onto the surface of the washed or cleaned material. Herein, the removed dirt includes all typical dirt present during the laundry process, such as body soil, food and grease stains, particulate dirt (such as clay or carbon black), grass stains, cosmetics, engine oil, etc. Such anti-redeposition effects can be observed on various fabric types, including cotton, polyester-cotton, polyester, copolymers of polyether / polyurea (Spandex TM) etc. In addition, this anti-redeposition effect is also effective for fabrics with a history of fabric softeners, or when fabric washing is carried out in the presence of fabric softeners or other laundry additives (such as freshness beads or bleaches).

[0483] In one embodiment, it is further preferred in the present invention that the cleaning composition (in addition to containing at least one graft polymer as described above) further contains at least one enzyme, which is preferably selected from one or more of the following, and optionally further contains at least one enzyme, preferably selected from one or more of lipase, hydrolase, amylase, protease, cellulase, hemicellulase, phospholipase, esterase, pectinase, lactase, pectate lyase, cutinase, β-glucanase, DNAse, xylanase, oxidoreductase, dispersins, mannanase, peroxidase, and combinations of at least two of the foregoing types. Preferably, at least one enzyme is selected from lipase.

[0484] At least one graft polymer as described herein is present in the cleaning composition of the present invention 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; such cleaning compositions may - and preferably do - further contain from 1% to about 70% by weight of a surfactant system.

[0485] Preferably, the cleaning composition of the present invention is a fabric and household care product, preferably a laundry detergent or a hand dishwashing detergent, which contains at least one graft polymer of the present invention, and optionally further contains at least one surfactant or surfactant system, thereby providing improved soil removal, dispersion, and / or emulsification performance, and / or achieving modification of the treated surface, and / or maintaining the whiteness of the treated surface.

[0486] Even more preferably, the cleaning composition of the present invention comprises at least one graft polymer of the present invention and optionally further comprises at least one surfactant or surfactant system (as detailed above). These cleaning compositions are suitable for cleaning and anti-redeposition performance in laundry and dishwashing applications. Even more specifically, they are used to improve the cleaning and anti-redeposition performance on substrates such as fabrics and tableware (such mechanisms of action have been detailed above). And it may additionally comprise at least one enzyme selected from the following list (which includes optionally further comprising at least one enzyme), and the enzyme is preferably selected from one or more of the following. Optionally further comprising at least one enzyme, preferably selected from one or more of lipase, hydrolase, amylase, protease, cellulase, hemicellulase, phospholipase, esterase, pectinase, lactase, pectate lyase, cutinase, β-glucanase, DNase, xylanase, oxidoreductase, dispersin, mannanase, peroxidase, and combinations of at least two of the foregoing types. Preferably selected from one or more of lipase, hydrolase, amylase, protease, cellulase, and combinations of at least two of the foregoing types. More preferably, at least one enzyme is selected from lipase.

[0487] In one embodiment of the present invention, the graft polymer of the present invention can be used to improve cleaning and anti-redeposition performance (such mechanisms of action have been detailed above), for example, for basic washing and / or removing particulate stains and / or oily and fatty stains, and / or additionally for maintaining whiteness, preferably in the field of laundry care applications. In another preferred embodiment, the graft polymer of the present invention can be used to reduce fabric graying (anti-graying), preferably having at least two of the multiple functions mentioned above, namely: improving cleaning effect, anti-redeposition performance, basic washing ability, ability to remove particulate stains and / or oily and fatty stains, whiteness maintenance, and / or anti-graying. The graft polymer of the present invention can exhibit multiple such characteristics simultaneously.

[0488] In another embodiment, the graft polymer of the present invention can be used to improve the dye transfer inhibition effect, that is, to prevent dyes from transferring from one fabric to another fabric by direct contact or via the wash liquor. For this application, preferably, the graft polymer comprises vinylpyrrolidone as monomer (B2) as defined herein for such cases. Such graft polymers containing this (B2), their suitable compositions and preparation processes have been defined herein and can be obtained by said compositions and processes.

[0489] In a preferred embodiment, the cleaning composition of the present invention is a liquid or solid laundry detergent composition.

[0490] In another preferred embodiment, the cleaning composition of the present invention is a liquid or solid (such as powder or tablet / unit dose) detergent composition for manual or automatic dishwashing, preferably a liquid manual dishwashing detergent composition. Such compositions are known to those skilled in the art.

[0491] In another embodiment, the cleaning composition of the present invention is a hard surface cleaning composition that can be used to clean various surfaces such as hardwood, tile, ceramic, plastic, leather, metal, and glass.

[0492] In another embodiment, the fabric care composition is in the form of a solid additive, sheet, tablet-like granule or bead, fiber product, solid product, tablet, lump, flake or a mixture thereof, for treating fabrics (optionally used in the presence of water).

[0493] Fabric and Home Care Compositions:

[0494] Any fabric and home care composition is suitable. The composition may or may not include a surfactant. Preferred compositions are detergent and cleaning compositions. Particularly preferred are fabric treatment compositions, and even more preferred are laundry detergent compositions.

[0495] Fabric and home care compositions are generally suitable for: (a) the care of finished textile fabrics, the cleaning of finished textile fabrics, the hygienic treatment of finished textile fabrics, the disinfection of finished textile fabrics, detergents, stain removers, softeners, fabric enhancers, stain removal or treatment of finished textile fabrics, pre-washing and post-washing treatments, washing machine cleaning and maintenance, where finished textile fabrics are intended to include clothing and articles made of cloth; (b) the care of dishes, glasses, pottery, cooking pots, pans, utensils, cutlery, etc. in automatic, in-machine washing, including detergents for dishwashers, the water used and its contents, products for pre-treatment and machine cleaning and maintenance; or (c) manual dishwashing detergents.

[0496] Preferably, the composition may contain 0.01% to 20.0% by weight, preferably 0.02% to 10.0% by weight, preferably 0.05% to 5% by weight, more preferably 0.1% to 3.0% by weight of a graft polymer.

[0497] The composition may contain 1.0% to 70% by weight of a stain-removing surfactant.

[0498] Fabric and home care compositions include but are not limited to:

[0499] Laundry detergent compositions: Suitable laundry detergent compositions include laundry detergent powder compositions, laundry detergent beads, laundry detergent liquid compositions, laundry detergent gel compositions, laundry detergent sheets, fibrous articles, and water-soluble unit-dose laundry detergent compositions.

[0500] Fabric softeners: Suitable fabric softeners are liquid fabric softeners including concentrated liquid fabric softeners and solid fabric softeners including fabric softener beads and sheets.

[0501] Dishwashing detergent compositions: Suitable dishwashing detergent compositions include manual dishwashing detergent compositions and automatic dishwashing detergent compositions, such as automatic dishwashing powders, tablets, and sachets.

[0502] Hard surface cleaner compositions: Suitable hard surface cleaner compositions include products that can be applied directly, for example by spraying, onto hard surfaces, and products that can be diluted in water before being applied onto hard surfaces.

[0503] Fabric and Home Care Ingredients

[0504] Suitable fabric and household care ingredients are described in more detail below.

[0505] Surfactant System:

[0506] The composition contains a surfactant system in an amount sufficient to provide the desired cleaning properties. In some embodiments, the composition contains from about 1% to about 70% by weight of the surfactant system, based on the weight of the composition. In other embodiments, the composition contains from about 2% to about 60% by weight of the surfactant system. In additional embodiments, the composition contains from about 5% to about 30% by weight of the surfactant system. The surfactant system can comprise a detersive surfactant selected from the group consisting of: anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and mixtures thereof. One of ordinary skill in the art will understand that a detersive surfactant encompasses any surfactant or mixture of surfactants that provides a cleaning, detergency, or laundry benefit to a soiled material.

[0507] Suitable surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. Suitable surfactants can be linear or branched, substituted or unsubstituted, and can be derived from petrochemical or biological materials. Preferred surfactant systems comprise an anionic surfactant and a nonionic surfactant, preferably in a weight ratio of from 90:1 to 1:90. In some cases, a weight ratio of anionic surfactant to nonionic surfactant of at least 1:1 is preferred. However, a ratio below 10:1 can be preferred. When present, the total surfactant level is preferably from 0.1% to 60%, 1% to 50%, or even 5% to 40% by weight of the subject composition.

[0508] Anionic surfactants: Anionic surfactants include, but are not limited to, those surface-active compounds containing an organic hydrophobic group that typically contains from 8 to 22 carbon atoms or typically contains from 8 to 18 carbon atoms in its molecular structure and at least one water-soluble group preferably selected from sulfonates, sulfates, and carboxylates to form a water-soluble compound. Generally, the hydrophobic group will comprise a C8-C 22 alkyl or acyl group. Such surfactants are used in the form of water-soluble salts, and the cation forming the salt is typically selected from sodium, potassium, ammonium, magnesium, and mono-, with the sodium cation being the one typically selected.

[0509] The anionic surfactants and co-anionic auxiliary surfactants of the present invention can exist in acid form, and the acid form can be neutralized to form surfactant salts suitable for the detergent compositions of the present invention. Typical reagents for neutralization include basic metal counterions such as hydroxides, for example, NaOH or KOH. Other preferred reagents for neutralizing the acid form of the anionic surfactants and co-anionic or auxiliary surfactants of the present invention include ammonia, amines, oligoamines, or alkanolamines. Alkanolamines are preferred. Suitable non-limiting examples include monoethanolamine, diethanolamine, triethanolamine, and other linear or branched alkanolamines known in the art; for example, highly preferred alkanolamines include 2-amino-1-propanol, 1-aminopropanol, monoisopropanolamine, or 1-amino-3-propanol. Amine neutralization can be accomplished in whole or in part, for example, a portion of the anionic surfactant mixture can be neutralized with sodium or potassium and a portion of the anionic surfactant mixture can be neutralized with an amine or alkanolamine.

[0510] Suitable sulfonate surfactants include methyl sulfonate, α-olefin sulfonates, alkyl benzene sulfonates, especially alkyl benzene sulfonates, preferably C 10- C 13Alkylbenzene sulfonates. Suitable alkylbenzene sulfonates (LAS) are available, preferably obtained by sulfonating commercially available linear alkylbenzenes (LAB). Suitable LABs include lower 2-phenyl LABs, such as those available under the trade name provided by Sasol, or those available under the trade name provided by Petresa. Other suitable LABs include higher 2-phenyl LABs, such as those available under the trade name provided by Sasol. Suitable anionic surfactants are alkylbenzene sulfonates obtained by the DETAL catalytic process, but other synthetic routes such as HF may also be suitable. In one aspect, the magnesium salt of LAS is used.

[0511] Preferably, the composition may contain from about 0.5% to about 30% by weight of the laundry detergent composition of an HLAS surfactant selected from alkylbenzene sulfonic acid, C 10 -C 16 alkali metal salts or amine salts of alkylbenzene sulfonic acid, wherein the HLAS surfactant contains more than 50% of C 12 preferably more than 60%, preferably more than 70% of C 12 , more preferably more than 75%

[0512] Suitable sulfate surfactants include alkyl sulfates, preferably C 8-18 alkyl sulfates, or predominantly C 12 alkyl sulfates.

[0513] Preferred sulfate surfactants are alkyl alkoxylated sulfates, preferably alkyl ethoxylated sulfates, preferably C8-C 18 alkyl alkoxylated sulfates, preferably C8-C 18 alkyl ethoxylated sulfates, preferably the alkyl alkoxylated sulfates have an average degree of alkoxylation of 0.5 to 20, preferably 0.5 to 10, preferably the alkyl alkoxylated sulfates are C8-C 18 alkyl ethoxylated sulfates having an average degree of ethoxylation of 0.5 to 10, preferably 0.5 to 5, more preferably 0.5 to 3 or about 1.5 to 3 or about 1.8 to 2.5. The alkyl alkoxylated sulfates can have a broad alkoxylate distribution or a peak alkoxylate distribution. The alkyl portion of AES can on average contain from 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 an alkyl portion having 14 or more carbon atoms, preferably 14 to 18 or 14 to 17 or 14 to 16 or 14 to 15 carbon atoms.

[0514] Alkyl sulfates, alkyl ethoxylated sulfates, and alkyl benzene sulfonates can be straight-chain or branched-chain, including 2-alkyl-substituted or mid-chain branched types, substituted or unsubstituted, and can be derived from petrochemical materials or biological materials. Preferably, the branching group is an alkyl group. Generally, the alkyl group is selected from methyl, ethyl, propyl, butyl, pentyl, cyclic alkyl groups, and mixtures thereof. One or more alkyl side chains can be present on the main hydrocarbon chain of one or more starting alcohols of the sulfated anionic surfactant used to prepare the detergents of the present invention. Most preferably, the branched sulfated anionic surfactants are selected from alkyl sulfates, alkyl ethoxysulfates, and mixtures thereof.

[0515] Alkyl sulfates and alkyl ethoxysulfates are commercially available with various chain lengths, degrees of ethoxylation, and degrees of branching. Commercially available sulfates include those based on Neodol alcohols of Shell company, Lial-Isalchem and Safol of Sasol company, and natural alcohols of Procter&Gamble Chemicals company.

[0516] Other suitable anionic surfactants include alkyl ether carboxylates, which contain C 10 -C 26 straight-chain or branched-chain, preferably C 10 -C 20 straight-chain, most preferably C 16 -C 18 straight-chain alkyl alcohols, and 2 to 20, preferably 7 to 13, more preferably 8 to 12, most preferably 9.5 to 10.5 ethoxylates. The acid form or salt form, such as sodium salt or ammonium salt, can be used, and the alkyl chain can contain one cis or trans double bond. Alkyl ether carboxylic acids are purchased from Kao Huntsman and Clariant

[0517] Other suitable anionic surfactants are rhamnolipids. Rhamnolipids can have a single rhamnose sugar ring or two rhamnose sugar rings.

[0518] Nonionic surfactants: Suitable nonionic surfactants are selected from: C8-C 18 alkyl ethoxylates, such as those obtained from Shell nonionic surfactants; C6-C 12 alkylphenol alkoxylates, where preferably the alkoxylate units are ethyleneoxy units, propyleneoxy units, or mixtures thereof; C 12 -C 18 alcohols and C6-C 12Condensates of alkylphenols with ethylene oxide / propylene oxide block polymers, such as those available from BASF alkyl polysaccharides, preferably alkyl polyglycosides; methyl ester ethoxylates; polyhydroxy fatty acid amides; ether-capped poly(alkoxylated) alcohol surfactants; and mixtures thereof.

[0519] Suitable nonionic surfactants are alkyl polyglucosides and / or alkyl alkoxylated alcohols.

[0520] Suitable nonionic surfactants include alkyl alkoxylated alcohols, preferably C8-C 18 alkyl alkoxylated alcohols, preferably C8-C 18 alkyl ethoxylated alcohols, preferably having an average degree of alkoxylation of 1 to 50, preferably 1 to 30, or 1 to 20, or 1 to 10, preferably the alkyl alkoxylated alcohol being C8-C 18 alkyl ethoxylated alcohols having an average degree of ethoxylation of 1 to 10, preferably 1 to 7, more preferably 1 to 5, and most preferably 3 to 7. In one aspect, the alkyl alkoxylated alcohol is C with an average degree of ethoxylation of 7 to 10 12- C 15 alkyl ethoxylated alcohols. The alkyl alkoxylated alcohols can be straight-chain or branched, and substituted or unsubstituted. Suitable nonionic surfactants include those available under the trade name from BASF. The alkyl alkoxylated sulfates can have a broad alkoxy distribution, such as Alfonic 1214-9 ethoxylate, or a peaked alkoxy distribution, such as Novel 1214-9 available commercially from Sasol

[0521] Cationic surfactants: Suitable cationic surfactants include alkylpyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl tertiary sulfonium compounds, and mixtures thereof.

[0522] Preferred cationic surfactants are quaternary ammonium compounds having the following general formula:

[0523] (R)(R1)(R2)(R3)N + X -

[0524] wherein R is a straight-chain or branched, substituted or unsubstituted C 6-18 alkyl or alkenyl moiety, R1 and R2 are independently selected from methyl or ethyl moieties, R3 is a hydroxy, hydroxymethyl or hydroxyethyl moiety, and X is an anion providing electrical neutrality, preferred anions including: halide ions, preferably chloride; sulfate; and sulfonate.

[0525] The fabric care composition of the present invention may contain up to about 30%, or about 0.01% to about 20%, or about 0.1% to about 20% by weight of the composition of a cationic surfactant. For the purposes of the present invention, cationic surfactants include those which can deliver fabric care benefits. Non-limiting examples of useful cationic surfactants include: fatty amines, imidazoline quaternary ammonium salt materials and quaternary ammonium surfactants, preferably N,N-bis(stearoyl-oxy-ethyl)N,N-dimethyl ammonium chloride, N,N-bis(tallowoyl-oxy-ethyl)N,N-dimethyl ammonium chloride, N,N-bis(stearoyl-oxy-ethyl)N-(2-hydroxyethyl)N-methyl ammonium methyl sulfate; N,N-bis(stearoyl-isopropoxy)N,N-dimethyl methyl sulfate ammonium, N,N-bis(tallowoyl-isopropoxy)N,N-dimethyl methyl sulfate ammonium, 1,2-bis(stearoyl-oxy)-3-trimethyl propane ammonium chloride; dialkyldimethyl ammonium salts such as dirapeseed dimethyl ammonium chloride, di(tallow)dimethyl ammonium chloride, dirapeseed dimethyl methyl sulfate ammonium; 1-methyl-1-stearoylaminoethyl-2-stearoyl imidazoline methyl sulfate; 1-tallowylaminoethyl-2-tallowyl imidazoline; N,N"-dialkyldiethylenetriamine; the reaction product of N-(2-hydroxyethyl)-1,2-ethylenediamine or N-(2-hydroxyisopropyl)-1,2-ethylenediamine esterified with a fatty acid and glycolic acid, wherein the fatty acid is (hydrogenated) tallow fatty acid, palm fatty acid, hydrogenated palm fatty acid, oleic acid, rapeseed fatty acid, hydrogenated rapeseed fatty acid; polyglycerol esters (PGE), oily sugar derivatives and wax emulsions and mixtures of the foregoing.

[0526] It should be understood that the combinations of softening agent active materials disclosed above are applicable herein

[0527] Amphoteric or zwitterionic surfactants: Suitable amphoteric or zwitterionic surfactants include amine oxides and / or betaines. Preferred amine oxides are alkyldimethylamine oxides or alkylamidopropyldimethylamine oxides, more preferably alkyldimethylamine oxides, and especially coco dimethylamine oxide. The amine oxide may have a straight-chain or mid-branched alkyl moiety. Typical straight-chain amine oxides include water-soluble amine oxides which contain one R 1 C8-C 18 alkyl moiety and two R 2 and R 3 moieties selected from the group consisting of C1-C3 alkyl groups and C1-C3 hydroxyalkyl groups. Preferably, the amine oxide can be characterized by the formula R 1 –N(R 2 )(R 3 )O, wherein R 1 is C8-C 18 alkyl, and R 2and R 3 is selected from the group consisting of: methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl and 3-hydroxypropyl. Specifically, the linear amine oxide surfactant may include linear C 10 -C 18 alkyl dimethyl amine oxide and linear C8-C 12 alkoxyethyl dihydroxyethyl amine oxide.

[0528] Other suitable surfactants include betaines such as alkyl betaines, alkylamide betaines, amidazolinium betaines, sulfobetaines (INCI sulfobetaines), and phosphobetaines.

[0529] Other Fabric and Home Care Ingredients.

[0530] The compositions of the present invention may also contain other fabric and home care additives. Suitable fabric and home care additives include enzymes, enzyme stabilizers, builders, dispersants, structurants or thickeners, polymers, additional amines, catalytic materials, bleaches, bleach catalysts, bleach activators, polymer dispersants, soil release / anti-redeposition agents, polymeric grease cleaners, amphiphilic copolymers, optical brighteners, fabric toners, chelating agents, encapsulating agents, fragrances, pre-fragrances, malodor reducing materials, conditioners, probiotics, organic acids, antioxidants, antimicrobials and / or preservatives, neutralizing agents and / or pH regulators, processing aids, rheology modifiers, corrosion and / or rust inhibitors, sanitizers, pearlescent agents, pigments, opacifiers, solvents, carriers, hydrotropes, defoamers, and mixtures thereof.

[0531] Enzymes:

[0532] Preferably, the composition comprises one or more enzymes. Preferred enzymes 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, galactanase, pectate lyase, keratinase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, melanase, β-glucanase, arabinase, hyaluronidase, chondroitinase, laccase, and amylase, or mixtures thereof. A typical combination is an enzyme mixture that may comprise, for example, protease and lipase in combination with amylase. When present in the composition, the foregoing additional enzymes may be present at a level of about 0.00001% to about 2%, about 0.0001% to about 1%, or even about 0.001% to about 0.5% of enzyme protein, based on the weight of the composition.

[0533] Protease. Preferably, the composition comprises one or more proteases. Suitable proteases include metalloproteases and serine proteases, and the serine proteases include 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 modified or genetically modified mutants of the aforementioned suitable proteases. In one aspect, the suitable protease may be a serine protease such as an alkaline microbial protease or / and a trypsin-type protease. Examples of suitable neutral or alkaline proteases include:

[0534] (a) Subtilisin (EC 3.4.21.62), in particular those derived from Bacillus (such as Bacillus sp., Bacillus genus, Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus gibsonii, Bacillus akibaii, Bacillus clausii, and Bacillus clarkii) as described in WO2004067737, WO2015091989, WO2015091990, WO2015024739, WO2015143360, US6,312,936B1, US5,679,630, US4,760,025, DE102006022216A1, DE102006022224A1, WO2015089447, WO2015089441, WO2016066756, WO2016066757, WO2016069557, WO2016069563, WO2016069569, WO2017 / 089093, WO2020 / 156419.

[0535] (b) Trypsin-type or chymotrypsin-type proteases such as trypsin (e.g., trypsin derived from pig or bovine), including the Fusarium protease described in WO 89 / 06270 and the chymotrypsin derived from Cellumonas described in WO 05 / 052161 and WO 05 / 052146.

[0536] (c) Metalloproteinases, in particular those derived from Bacillus amyloliquefaciens as described in WO07 / 044993A2, those derived from Bacillus, Brevibacillus, Thermoactinomyces, Geobacillus, Paenibacillus, Lysinibacillus or Streptomyces spp. as described in WO2014194032, WO2014194054 and WO2014194117, those derived from Kribella alluminosa as described in WO2015193488, and those derived from Streptomyces and Lysobacter as described in WO2016075078.

[0537] (d) A protease having at least 90% identity with the subtilisin from Bacillus sp. TY145, NCIMB40339 as described in WO92 / 17577 (Novozymes A / S), including variants of the subtilisin from Bacillus sp. TY145 as described in WO2015024739 and WO2016066757.

[0538] Suitable commercially available proteases include those sold by Novozymes A / S (Denmark) under the following trade names: Liquanase Savinase Blaze Exceed, Pro, Uno, Excel, Key, and Het Under the trade names Purafect Purafect and Purafect sold by Dupont; under the trade names and those sold by Solvay Enzymes; and those available from Henkel / Kemira, namely BLAP (the sequence is shown in Figure 29 of US 5,352,604, having the following mutations S99D+S101R+S103A+V104I+G159S, hereinafter referred to as BLAP), BLAP R (BLAP having S3T+V4I+V199M+V205I+L217D), BLAP X (BLAP having S3T+V4I+V205I), and BLAP F49 (BLAP having S3T+V4I+A194P+V199M+V205I+L217D); and KAP from Kao (Bacillus subtilis protease having mutations A230V+S256G+S259N) and Pro, C Bright.

[0539] Amylase. Preferably, the composition may comprise amylase. Suitable α-amylases include those of bacterial or fungal origin. Include chemically modified or genetically modified mutants (variants). Preferred alkaline α-amylases are derived from strains of Bacillus, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus sp., such as Bacillus sp. NCIB12289, NCIB 12512, NCIB 12513, DSM 9375 (USP 7,153,818), DSM12368, DSMZ no.12649, KSM AP1378 (WO 97 / 00324), KSM K36 or KSM K38 (EP 1,022,334). Preferred amylases include:

[0540] (a) variants described in WO 94 / 02597, WO 94 / 18314, WO96 / 23874 and WO 97 / 43424, especially variants having substitutions at one or more of the following positions relative to the enzyme listed in SEQ ID No.2 in WO 96 / 23874: 15, 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243, 264, 304, 305, 391, 408 and 444.

[0541] (b) Variants as described in USP 5,856,164 and WO99 / 23211, WO 96 / 23873, WO00 / 60060 and WO 06 / 002643, in particular variants having one or more substitutions at the following positions relative to the AA560 enzyme as listed in SEQ ID No.12 in WO 06 / 002643:

[0542] 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484, preferably also variants comprising the D183* and G184* deletions.

[0543] (c) Variants showing at least 90% identity to SEQ ID No.4 in WO06 / 002643, the wild-type enzyme from Bacillus sp. SP722, in particular variants having deletions at positions 183 and 184, and the variants described in WO 00 / 60060, the said documents being incorporated herein by reference.

[0544] (d) Variants showing at least 95% identity to the wild-type enzyme from Bacillus sp. 707 (SEQ ID NO:7 in US 6,093,562), in particular those comprising one or more of the following mutations: M202, M208, S255, R172 and / or M261. Preferably, the amylase comprises one or more of M202L, M202V, M202S, M202T, M202I, M202Q, M202W, S255N and / or R172Q. Particularly preferred are those comprising the M202L or M202T mutations.

[0545] (e) Variants described in WO 09 / 149130, preferably those showing at least 90% identity to SEQ ID NO:1 or SEQ ID NO:2 in WO 09 / 149130, the wild-type enzyme from Bacillus stearothermophilus or a truncated form thereof.

[0546] (f) Variants that exhibit at least 89% identity with SEQ ID NO:1 in WO2016091688, especially those containing a deletion at positions H183 + G184 and also one or more mutations at positions 405, 421, 422, and / or 428.

[0547] (g) Variants that exhibit at least 60% amino acid sequence identity with "PcuAmylα - amylase" (SEQ ID NO:3 in WO2014099523) from Paenibacillus curdlanolyticus YK9.

[0548] (h) Variants that exhibit at least 60% amino acid sequence identity with "CspAmy2 amylase" (SEQ ID NO:1 in WO2014164777) from Cytophaga sp.

[0549] (i) Variants that exhibit at least 85% identity with AmyE from Bacillus subtilis (SEQ ID NO:1 in WO2009149271).

[0550] (j) Variants that exhibit at least 90% identity with the wild - type amylase from Bacillus sp. KSM - K38 (accession number AB051102).

[0551] Suitable commercially available α - amylases include TERMAMYL STAINZYME and (Novozymes A / S, Bagsvaerd, Denmark)、 AT 9000 Biozym Biotech Trading GmbH Wehlistrasse 27b A - 1200 Wien Austria、 OPTISIZE HT and PURASTAR (Genencor International Inc., Palo Alto, California) and (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku Tokyo 103-8210, Japan). In one aspect, suitable amylases include and STAINZYME and mixtures thereof.

[0552] Lipase. Preferably, the composition comprises one or more lipases, including "first cycle lipases", such as those described in U.S. Patent No. 6,939,702 B1 and US PA 2009 / 0217464. The preferred lipase is a first wash lipase. In one embodiment of the present invention, the composition comprises a first wash lipase.

[0553] The first wash lipase includes a lipase that is a polypeptide having an amino acid sequence that: (a) has at least 90% identity with the wild-type lipase derived from Humicola lanuginosa strain DSM 4109; (b) compared to the wild-type lipase, includes a substitution of a positively charged amino acid for a neutral or negatively charged amino acid at the surface of the three-dimensional structure within 15 Å of E1 or Q249; and (c) includes an additional peptide segment at the C-terminus; and / or (d) includes an additional peptide segment at the N-terminus; and / or (e) satisfies the following limitations: i) includes a negatively charged amino acid at position E210 of the wild-type lipase; ii) contains a negatively charged amino acid in the region corresponding to positions 90-101 of the wild-type lipase; and iii) includes a neutral or negatively charged amino acid at the position corresponding to N94 of the wild-type lipase and / or has a net negative or neutral charge in the region corresponding to positions 90-101 of the wild-type lipase.

[0554] Preferably, variants of wild-type lipases from Thermomyces lanuginosus containing one or more of the T231R and N233R mutations are included. The wild-type sequence is 269 amino acids (amino acids 23–291) of Swiss-Prot accession number Swiss-Prot O59952 (from Thermomyces lanuginosus (Humicola lanuginosa)). Other suitable lipases include: Liprl 139, as described, for example, in WO2013 / 171241; TfuLip2, as described, for example, in WO2011 / 084412 and WO2013 / 033318; Pseudomonas stutzeri lipase, as described, for example, in WO2018228880; Microbulbifer thermotolerans lipase, as described, for example, in WO2018228881; Sulfobacillus acidocaldarius lipase, as described, for example, in EP3299457; LIP062 lipase, as described, for example, in WO2018209026; PinLip lipase, as described, for example, in WO2017036901, and Absidia sp. lipase, as described in WO2017005798.

[0555] Preferred lipases will include those sold under the trade names and and those sold under.

[0556] Cellulase. Suitable enzymes include cellulases of bacterial or fungal origin. Including mutants that have been chemically modified or protein engineered. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, for example, fungal cellulases prepared from Humicola insolens, Myceliophthora thermophila, and Fusarium oxysporum as disclosed in US 4,435,307, US 5,648,263, US 5,691,178, US 5,776,757, and US 5,691,178. Suitable cellulases include alkaline or neutral cellulases that have beneficial color care effects. Commercially available cellulases include and CAREZYME PREMIUM (Novozymes A / S), and PURADAX (Genencor International Inc.), and (Kao Corporation).

[0557] The bacterial detergent cellulase can be a glycosyl hydrolase having enzymatic activity against amorphous cellulose substrates, wherein the glycosyl hydrolase is selected from the GH families 5, 7, 12, 16, 44 or 74. Suitable glycosyl hydrolases can also be selected from the group consisting of: a GH family 44 glycosyl hydrolase from Paenibacillus polyxyma (wild type), such as XYG1006 or its variants described in US 7,361,736. A GH family 12 glycosyl hydrolase from Bacillus licheniformis (wild type), such as SEQ ID NO:1 or its variants described in US 6,268,197; a GH family 5 glycosyl hydrolase or its variants from Bacillus agaradhaerens (wild type); a GH family 5 glycosyl hydrolase from Paenibacillus (wild type), such as XYG1034 and XYG 1022 or its variants described in US 6,630,340; a GH family 74 glycosyl hydrolase from Jonesia sp. (wild type), such as XYG1020 or its variants described in WO 2002 / 077242; and a GH family 74 glycosyl hydrolase from Trichoderma Reesei (wild type), such as the enzyme or its variants more specifically described in sequence ID NO.2 of US 7,172,891. Suitable bacterial detergent cellulases are sold under the trade names and (Novozymes A / S, Bagsvaerd, Denmark).

[0558] The composition can comprise a fungal detergent cellulase having a molecular weight of 17 kDa to 30 kDa belonging to the glycosyl hydrolase family 45, for example, an endoglucanase sold under the trade names NCD, DCC and DCL (AB Enzymes, Darmstadt, Germany).

[0559] Pectate lyase. Other preferred enzymes include a pectate lyase sold under the trade name and a pectate lyase sold under the trade name (all obtained from Novozymes A / S, Bagsvaerd, Denmark) and mannanases sold by (Genencor International Inc., Palo Alto, California).

[0560] Nucleases. The composition may comprise nucleases. A nuclease is an enzyme capable of cleaving the phosphodiester bonds between the nucleotide subunits of a nucleic acid. The nuclease herein is preferably a deoxyribonuclease or ribonuclease or a functional fragment thereof. The so-called functional fragment or moiety refers to the part of the nuclease that catalyzes the cleavage of the phosphodiester bond in the DNA backbone and is thus the region of the nuclease protein that retains catalytic activity. Thus, it includes truncated but functional forms in which the functionality of the enzyme and / or variant and / or derivative and / or homolog is maintained. Suitable DNases include the wild-type and variants described in detail in WO2017162836 and WO2018108865, as well as variants of the Bacillus cibi DNase, including those described in WO2018011277.

[0561] RNases: Suitable RNases include the wild-type and variants of the DNases described in WO2018178061 and WO2020074499.

[0562] Preferably, the nuclease is a deoxyribonuclease, preferably selected from any of the following classes: E.C.3.1.21.x, where x = 1, 2, 3, 4, 5, 6, 7, 8 or 9, E.C.3.1.22.y, where y = 1, 2, 4 or 5, E.C.3.1.30.z, where z = 1 or 2, E.C.3.1.31.1 and mixtures thereof.

[0563] Hexosaminidase. The composition may comprise one or more hexosaminidases. The term hexosaminidase includes "dispase" and the abbreviation "Dsp", which refers to a polypeptide having hexosaminidase activity, EC 3.2.1.- which enzyme catalyzes the hydrolysis of β-1,6-glycosidic bonds of N-acetyl-glucosamine polymers present in microbially derived stains. The term hexosaminidase includes polypeptides having N-acetylglucosaminidase activity and β-N-acetylglucosaminidase activity. Hexosaminidase activity can be determined according to Assay II described in WO2018184873. Suitable hexosaminidases include those disclosed in WO2017186936, WO2017186937, WO2017186943, WO2017207770, WO2018184873, WO2019086520, WO2019086528, WO2019086530, WO2019086532, WO2019086521, WO2019086526, WO2020002604, WO2020002608, WO2020007863, WO2020007875, WO2020008024, WO2020070063, WO2020070249, WO2020088957, WO2020088958 and WO2020207944. Variants of the Geobacillus saccharophilus hexosaminidase defined by SEQ ID NO:1 of WO2020207944 may be preferred, particularly variants with improved thermal stability disclosed in that publication.

[0564] Mannanase. The composition may comprise extracellular polymeric substance degrading enzymes, which include mannanase. The term "mannanase" refers to a polypeptide having endo-1,4-β-mannanase activity (EC 3.2.1.78) from glycoside hydrolase family 26, which catalyzes the hydrolysis of 1,4-β-D-mannosidic bonds in mannan, galactomannan and glucomannan. Other names for endo-1,4-β-mannanase are 1,4-β-D-mannan hydrolase; endo-1,4-β-mannanase; endo-β-1,4-mannanase; β-mannanase B; β-1,4-mannan-4-mannanohydrolase; endo-β-mannanase; and β-D-mannanase. For the purposes of the present disclosure, the reducing end assay described in the experimental section of WO2015040159 can be used to determine mannanase activity. Suitable examples from class EC 3.2.1.78 are described in WO2015040159, such as the mature polypeptide SEQ ID NO:1 described therein.

[0565] Galactanase. The composition may comprise an extracellular polymer degrading enzyme, which extracellular polymer degrading enzyme comprises an endo-β-1,6-galactanase. The term "endo-β-1,6-galactanase" or "polypeptide having endo-β-1,6-galactanase activity" refers to an endo-β-1,6-galactanase activity (EC 3.2.1.164) from glycoside hydrolase family 30 that catalyzes the hydrolytic cleavage of 1,6-β-D-galactooligosaccharides with a degree of polymerization (DP) higher than 3, and acidic derivatives thereof having a 4-O-methylglucuronic acid or glucuronate group at the non-reducing end. For the purposes of the present disclosure, the endo-β-1,6-galactanase activity is determined according to the method described in Assay I in WO 2015185689. Suitable examples from EC 3.2.1.164 are described in WO 2015185689, such as the mature polypeptide SEQ ID NO:2.

[0566] Enzyme Stabilization System.

[0567] The composition may optionally comprise an enzyme stabilization system in an amount of from about 0.001% to about 10% by weight of the composition, in some examples from about 0.005% to about 8%, and in other examples from about 0.01% to about 6%. The enzyme stabilization system can be any stabilization system compatible with the detergent enzyme. In the case where the aqueous detergent composition contains a protease, a reversible protease inhibitor such as a boron compound (including borate esters), 4-formylphenylboronic acid, phenylboronic acid and their derivatives, or a compound such as calcium formate, sodium formate and 1,2-propanediol can be added to further improve the stability.

[0568] Builders:

[0569] The composition may optionally comprise a builder. The composition generally comprises at least about 1% builder based on the total weight of the composition. The liquid composition may comprise up to about 10% builder based on the total weight of the composition, and in some examples up to about 8%. The granular composition may comprise up to about 30% builder by weight of the composition, and in some examples up to about 5%.

[0570] Builders selected from aluminosilicates (such as zeolite builders, such as zeolite A, zeolite P, and zeolite MAP) and silicates help control the mineral hardness in wash water, especially calcium and / or magnesium, or help remove particulate soil from surfaces. Suitable builders may be selected from the group consisting of: phosphates, such as polyphosphates (e.g., sodium tripolyphosphate), especially their sodium salts; carbonates, bicarbonates, sesquicarbonates, and carbonate minerals other than sodium carbonate or sesquicarbonate of soda; organic mono-carboxylates, di-carboxylates, tri-carboxylates, and tetra-carboxylates, especially water-soluble non-surfactant carboxylates in the form of acids, sodium, potassium, or alkanolammonium salts, and oligomeric or water-soluble low molecular weight polymeric carboxylates, including aliphatic and aromatic types; and phytic acid. These may be supplemented with borates, e.g., for pH buffering purposes, or with sulfates, especially sodium sulfate and any other fillers or carriers, which may be important for engineering stable surfactants and / or builder-containing compositions. Additional suitable builders may be selected from citric acid, lactic acid, fatty acids, and their salts.

[0571] Suitable builders may include polycarboxylates and their salts, such as copolymers of acrylic acid, copolymers of acrylic acid and maleic acid, and homopolymers of acrylic acid and / or maleic acid with other suitable vinyl monomers having various types of additional functional groups. More suitable polycarboxylates are described in the polycarboxylate polymer section of this patent.

[0572] Also suitable for use as a builder herein are synthetic crystalline ion exchange materials having a chain structure or their hydrates and compositions represented by the following general anhydride form: x(M2O)·ySiO2·zM'O, where M is Na and / or K, M' is Ca and / or Mg; y / x is from 0.5 to 2.0; and z / x is from 0.005 to 1.0.

[0573] Alternatively, the composition may be substantially free of builders.

[0574] Structurants / thickeners: Suitable structurants / thickeners include:

[0575] - dibenzylidene polyol acetal derivatives

[0576] - bacterial cellulose

[0577] - coated bacterial cellulose

[0578] - cellulose fibers not derived from bacterial cellulose

[0579] - non-polymeric crystalline hydroxy-functional materials

[0580] - polymeric structurants

[0581] - diamide gelling agents

[0582] - Any combination of the above substances.

[0583] Polymers:

[0584] The composition may include one or more polymers. Generally, the content of the polymer is about 0.01% to about 10.0% by weight of the composition, preferably about 0.1% to about 5%, and more preferably about 0.2% to about 3.0% by weight of the composition. In some cases where the composition is in concentrated form, such as any form of concentrated fabric and home care products designed for consumers to dilute at home and then use according to their regular dosing habits, the content of the polymer may be higher than 10.0% or higher than 5.0% by weight of the composition.

[0585] Depending on the structure of the polymer, the polymer can provide various beneficial effects to the composition, including but not limited to hydrophobic and hydrophilic stain removal, surfactant enhancement, dirt suspension, whiteness retention, detergency, malodor control, dye transfer inhibition, enhanced softness, enhanced freshness, etc. The polymer is generally multifunctional, which means that a specific given type of polymer can provide more than one type of beneficial effect as described above. For example, a specific detergency polymer can provide a detergency beneficial effect as the main beneficial effect, while also providing other beneficial effects such as whiteness retention, malodor control, dirt suspension, and dye transfer inhibition.

[0586] Suitable polymers include but are not limited to the following:

[0587] Graft Polymers Based on Polyalkylene Oxides.

[0588] The composition may contain a graft polymer, which comprises a polyalkylene oxide backbone (A) as the graft base and a polymer side chain (B) grafted thereon. The polymer side chain (B) can be obtained by polymerization of at least one vinyl ester monomer. The polyalkylene oxide backbone (A) can be obtained by polymerization of at least one monomer selected from the group consisting of ethylene oxide, 1,2 - propylene oxide, 1,2 - butylene oxide, 2,3 - butylene oxide, 1,2 - pentylene oxide, or 2,3 - pentylene oxide. Such graft polymers are known to be effective dirt suspension polymers for hydrophobic and hydrophilic stains, surfactant promoters, and sometimes as dye transfer inhibitors.

[0589] Suitable graft polymers include amphiphilic graft copolymers, which comprise a polyethylene glycol backbone (A) as the graft base and at least one side - group type side chain (B) selected from polyvinyl acetate, polyvinyl alcohol, and mixtures thereof. A preferred graft polymer of this type is Sokalan HP22 purchased from BASF.

[0590] Suitable graft polymers are also described in WO2007 / 138053 as amphiphilic graft polymers based on a water-soluble polyalkylene oxide (A) as the graft base and side chains formed by the polymerization of a vinyl ester component (B), said polymers having on average < one graft site per 50 alkylene oxide units and an average molar mass M of 3,000 to 100,000. A particularly preferred graft polymer of this type is a polyvinyl acetate-grafted polyethylene oxide copolymer, which has polyethylene oxide as the graft base and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide main chain is about 6,000, and the weight ratio of polyethylene oxide to polyvinyl acetate is about 40 to 60, and there is no more than 1 graft point per 50 ethylene oxide units. The most preferred polymer of this type is available from BASF under the name Sokalan PG101.

[0591] Suitable graft polymers also include block copolymer main chains (A) of graft polymers that include, as the graft base, the block copolymer main chain (A) of a graft polymer that can be obtained by the polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-epoxypropane, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxypentane, or 2,3-epoxypentane, where the number (x) of individual blocks within the block copolymer main chain (A) is an integer, where x is from 2 to 10, and preferably from 3 to 5; and (B) polymer side chains grafted onto the block copolymer main chain, where the polymer side chains (B) can be obtained by the polymerization of at least one vinyl ester monomer. Suitable graft polymers of this type are described in WO2021 / 160795 and WO2021 / 160851, and these polymers have improved biodegradation characteristics.

[0592] Suitable graft polymers also include graft polymers that include: a polyalkylene oxide main chain (A) having a number average molecular weight of about 1,000 daltons to about 20,000 daltons and based on ethylene oxide, propylene oxide, or butylene oxide; side chains (B) derived from N-vinylpyrrolidone; and side chains (C) derived from vinyl esters, which are derived from saturated monocarboxylic acids containing 1 to 6 carbon atoms and / or methyl or ethyl esters of acrylic acid or methacrylic acid. Such graft polymers are described in WO2020005476 and can be used as dye transfer inhibitors.

[0593] Modified Polyamine Dispersants.

[0594] The composition may include one or more modified polyamine dispersants. The modified polyamine dispersant includes a polyamine core structure and multiple alkoxylate groups attached to the core structure. The polyamine core structure includes a polyalkyleneimine and a linear or branched oligomeric amine.

[0595] The polyamine core structure and alkoxylate groups attached to the core structure can be further derivatized. For example, the polyamine core structure can be further reacted with C1-C 30 linear or branched alkyl groups, more preferably C1-C 10 or even C1-C5 linear or branched alkyl groups, most preferably methyl groups, to be partially or completely quaternized. The alkoxylate groups can be further sulfated, sulfonated, and / or substituted with amino functional groups.

[0596] Suitable modified polyamine dispersants include ethoxylated polyethyleneimine (EPEI). EPEI is an effective dispersant for hydrophilic stains, especially hydrophilic particulate stains such as clay.

[0597] In one embodiment, EPEI has a polyethyleneimine backbone with a weight-average molecular weight between 100 g / mol and 2000 g / mol, preferably between 200 g / mol and 1500 g / mol, more preferably between 300 g / mol and 1000 g / mol, even more preferably between 400 g / mol and 800 g / mol, most preferably between 500 g / mol and 700 g / mol, and preferably about 600 g / mol. The ethoxylated chains in EPEI can have a weight-average molecular weight of 200 g / mol to 2000 g / mol per ethoxylated chain, preferably 400 g / mol to 1500 g / mol, more preferably 600 g / mol to 1000 g / mol, and most preferably about 880 g / mol. The ethoxylated chains in EPEI have an average of 5 to 40, preferably 10 to 30, more preferably 15 to 25, even more preferably 18 to 22, and most preferably about 20 ethoxy units per ethoxylated chain. The total weight-average molecular weight of EPEI can be 5000 g / mol to 20000 g / mol, preferably 7500 g / mol to 17500 g / mol, more preferably 10000 g / mol to 15000 g / mol, even more preferably 12000 g / mol to 13000 g / mol, and most preferably about 12700 g / mol. A preferred example is a polyethyleneimine core ethoxylated to 20 EO groups per NH (average molecular weight of about 600 g / mol). Suitable EPEIs of this type include Sokalan HP20 from BASF and Lutensol FP620 from BASF. Examples of available polyethyleneimine ethoxylates also include those prepared by reacting ethylene oxide with Epomine SP-006 manufactured by Nippon Shokubai.

[0598] In another embodiment, the EPEI comprises a polyethyleneimine having an average molecular weight (Mw) in the range of 1800 g / mol to 5000 g / mol (before ethoxylation), and the polyoxyethylene side chains have an average of 25 to 40 ethoxy units per side chain bonded to the polyethyleneimine backbone. Such EPEI is described in WO2020 / 030760 and WO2020 / 030469.

[0599] Suitable modified polyamine dispersants include amphiphilic alkoxylated polyalkyleneimine polymers. These polymers have a balanced hydrophilicity and hydrophobicity such that they remove oil and body soil particles from fabrics and surfaces and keep the particles suspended in the wash liquid. Suitable amphiphilic water-soluble alkoxylated polyalkyleneimine polymers are described in WO2009 / 061990 and WO2006 / 108857, which comprise a polyalkyleneimine, preferably a polyethyleneimine core, and the following alkoxide groups attached to the core

[0600] *-[A 2 -O] m -[CH2-CH2-O] n -[A 3 -O] p -R

[0601] (V)

[0602] wherein

[0603] "*" represents in each case half of the bond to the nitrogen atom of the core.

[0604] In each case, A 2 is independently selected from 1,2-propylene, 1,2-butylene and 1,2-isobutylene;

[0605] A 3 is 1,2-propylene;

[0606] In each case, R is independently selected from hydrogen and C1-C4-alkyl, preferably hydrogen;

[0607] The average value of m is in the range of 0 to 2, preferably 0;

[0608] The average value of n is in the range of 5 to 50; and

[0609] The average value of p is in the range of 3 to 50;

[0610] The polymer has a degree of quaternization in the range of 0 to 50, preferably 0 to 20, and more preferably 0 to 10.

[0611] Preferred alkoxylated polyalkyleneimine polymers are modified polyethyleneimines (MW = 600) in which each -NH has 24 ethoxylated groups and each -NH has 16 propoxylated groups. Another preferred alkoxylated polyalkyleneimine polymer is modified polyethyleneimine (MW = 600) in which each -NH has 10 ethoxylated groups and each -NH has 7 propoxylated groups.

[0612] Another suitable alkoxylated polyalkyleneimine polymer of this type includes Sokalan HP20 Booster purchased from BASF.

[0613] Another suitable modified polyamine dispersant is described in WO2021061774.

[0614] Suitable modified polyamine dispersants also include zwitterionic polyamines. The zwitterionic polyamines are selected from zwitterionic polyamines according to the following formula:

[0615]

[0616] R is each independently a C3-C 20 linear or branched alkylene;

[0617] R 1 is a polyalkoxy unit capped with an anionic unit of the following formula: -(R 2 O) x R 3 ,

[0618] where

[0619] R 2 is a C2-C4 linear or branched alkylene, preferably C2 (ethylene);

[0620] R 3 is hydrogen, an anionic unit, and mixtures thereof, where not all R 3 groups are hydrogen, preferably where R 3 The anionic unit is selected from -(CH2) p CO2M; -(CH2) q SO3M; -(CH2) q OSO3M; -(CH2) q CH(SO3M)-CH2SO3M; -(CH2) q CH(OSO3M)CH2OSO3M; -(CH2) q CH(SO3M)CH2SO3M; -(CH2) pPO3M; -PO3M; -SO3M and mixtures thereof; where M is hydrogen or a water-soluble cation, preferably selected from sodium, potassium, ammonium and mixtures thereof, and in an amount sufficient to satisfy charge balance;

[0621] x is from 5 to 50, preferably from 10 to 40, even more preferably from 15 to 30, and most preferably from 20 to 25;

[0622] Q is a quaternized unit selected from the group consisting of: C1-C 30 linear or branched alkyl, C6-C 30 cycloalkyl, C7-C 30 substituted or unsubstituted alkylene aryl and mixtures thereof, preferably C1-C 30 linear or branched alkyl, even more preferably C1-C 10 or even C1-C5 linear or branched alkyl, most preferably methyl; the degree of quaternization is preferably more than 50%, more preferably more than 70%, even more preferably more than 90%, and most preferably about 100%;.

[0623] X - is present in an amount sufficient to provide electrical neutrality as an anion, preferably a water-soluble anion selected from the group consisting of chloride ion, bromide ion, iodide ion, methyl sulfate ion and mixtures thereof, more preferably chloride ion;

[0624] n is from 0 to 8, preferably from 0 to 4, preferably from 0 to 2, and most preferably 0.

[0625] Suitable zwitterionic polyamines have the following general formula structure: bis((C2H5O)(C2H4O)n)(CH3)-N + -C x H 2x -N + -(CH3)-bis((C2H5O)(C2H4O)n), where n = 20 to 30 and x = 3 to 8, or their sulfated or sulfonated variants.

[0626] Particularly preferred zwitterionic polyamines are commercially available from BASF under the trade name Lutensit Z96 polymer (zwitterionic hexamethylenediamine according to the following formula: 100% quaternized and approximately 40% of the polyethoxy (EO 24 ) groups are sulfonated).

[0627]

[0628] Another preferred zwitterionic polyamine is Sokalan HP96 available from BASF.

[0629] Another suitable zwitterionic polyamine is an amphoterically modified low molecular weight polypropylenimine ethoxylate as described in WO2021239547.

[0630] Polyester Detergency Polymers.

[0631] The composition can comprise one or more soil release polymers (SRPs).

[0632] Polyester SRPs typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit on and adhere to the hydrophobic fibers until the wash and rinse cycles are complete, thereby acting as an anchor for the hydrophilic segments. This can make stains that appear after treatment with a detergent easier to clean in a later washing process. It is also believed that facilitating soil release helps to improve or maintain the wicking properties of the fabric.

[0633] The structure of the polyester SRP can be tailored to be suitable for different detergent or detergent additive products. The soil release polymer can be linear, branched, or star-shaped. The soil release polymer can also comprise a variety of charged units. Generally, when the SRP is used in combination with a detergent containing an anionic surfactant, a nonionic SRP or an anionic SRP can be particularly preferred to avoid potential negative interactions between the SRP and the anionic surfactant. The soil release polymer can comprise end-capping moieties that are particularly effective in controlling the molecular weight of the polymer or altering the physical or surface adsorption properties of the polymer.

[0634] Preferred polyester SRP soil release polymers include terephthalate-derived polyester polymers comprising structural units (I) and / or (II):

[0635] (I) - [(OCHR 1 -CHR 2 ) a -O-OC-Ar-CO-] d

[0636] (II) - [(OCHR 3 -CHR 4 ) b -O-OC-sAr-CO-] e

[0637] Wherein:

[0638] a, b are from 1 to 200;

[0639] d, e are from 1 to 50;

[0640] Ar is independently selected from 1,4-substituted phenylene and 1,3-substituted phenylene

[0641] sAr is a 1,3-disubstituted phenylene group substituted by -SO3M at position 5; wherein M is a counterion selected from Na, Li, K, Mg / 2, Ca / 2, Al / 3, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium, wherein the alkyl group is C1-C 18 alkyl or C2-C 10 hydroxyalkyl or mixtures thereof;

[0642] R 1 、R 2 、R 3 、R 4 are independently selected from H or C1-C 18 n-alkyl or iso-alkyl; preferably selected from H or C1 alkyl.

[0643] Optionally, the polymer further comprises one or more end groups (III) derived from polyalkylene glycol monoalkyl ethers, preferably selected from the structure (III-a)

[0644] □-O-[C2H4-O] c -[C3H6-O] d -[C4H8-O] e -R7 (III-a)

[0645] wherein:

[0646] R7 is a straight-chain or branched C 1-30 alkyl, C2-C 30 alkenyl, or a cycloalkyl group having 5 to 9 carbon atoms, or a C8-C 30 aryl group, or a C6-C 30 arylalkyl group; preferably C 1-4 alkyl, more preferably methyl; and

[0647] c, d and e are numbers independently selected from 0 to 200 based on the molar average, wherein the sum of c + d + e is 2 to 500,

[0648] wherein the [C2H4-O], [C3H6-O] and [C4H8-O] groups of the end group (IV-a) can be block, alternating, periodic and / or statistical arrangements, preferably block and / or statistical arrangements, and any of the [C2H4-O], [C3H6-O] and [C4H8-O] groups of the end group (IV-a) can be connected to -R7 and / or -O. Preferably, the [C3H6-O] group is connected to -O, and -O is further connected to -OC-Ar-CO- or -OC-sAr-CO-.

[0649] Optionally, the polymer further comprises one or more of the anionic end units (IV) and / or (V) as described in EP3222647, wherein M is selected from Na + , Li + , K + , 1 / 2Mg 2+ , 1 / 2Ca 2+ , 1 / 3Al 3+ , ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium counterions, wherein the alkyl groups are C1-C 18 alkyl or C2-C 10 hydroxyalkyl or mixtures thereof.

[0650] -O-CH2CH2-SO3M (IV)

[0651]

[0652] Optionally, the polymer may comprise crosslinked polyfunctional structural units having at least three functional groups capable of undergoing an esterification reaction. The functional groups may be, for example, acid-, alcohol-, ester-, anhydride- or epoxy groups, etc.

[0653] Optionally, other dicarboxylic acids or polycarboxylic acids or their salts or their (di)alkyl esters can be used in the polyester, 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 their salts or their (di)alkyl esters, preferably their (C1-C4)-(di)alkyl esters, and more preferably their (di)methyl esters or mixtures thereof.

[0654] One type of preferred polyester SRP is a nonionic polyester SRP that does not contain the above structural unit (II). A particularly preferred nonionic terephthalate-derived detergent polymer has a structure according to the following formula:

[0655]

[0656] Wherein:

[0657] R5 and R6 are independently selected from H or CH3. More preferably, one of R5 and R6 is H and the other is CH3.

[0658] c, d are independently numbers selected from 0 to 200 based on a molar average, wherein the sum of c + d is 2 to 400, more preferably, d is 0 to 50, c is 1 to 200, more preferably, d is 1 to 10, c is 5 to 150,

[0659] R7 is C 1- a C4 alkyl group, and more preferably a methyl group,

[0660] n has a molar average value of from 1 to 50.

[0661] In one example of the most preferred suitable terephthalate-derived nonionic SRP, one of R5 and R6 is H and the other is CH3; d is 0; c is from 5 to 100, and R7 is a methyl group, and n is from 3 to 10.

[0662] Other suitable terephthalate-derived polyester SRPs are described in patents WO2014019903, WO2014019658 and WO2014019659. The end groups of these SRPs are selected from

[0663] X-(OC2H4) n -(OC3H6) m -

[0664] wherein X is a C1-C4 alkyl group and preferably a methyl group, the -(OC2H4) groups and the -(OC3H6) groups are arranged in blocks, and the block consisting of the -(OC3H6) groups is bonded to the COO group, n is a number having a molar average value of from 40 to 50, and m is a number having a molar average value of from 1 to 10 and preferably from 1 to 7.

[0665] The polyester detergent polymer can be available or converted into different forms, including powders, granules, liquids, waxes or premixes. In some embodiments, other materials (e.g., water, alcohols, other solvents, salts, surfactants, etc.) are required to convert the polyester detergent polymer into the above different forms, and the wt% of the active detergent polymer in the powder, granule, liquid, wax or premix ranges from 10% to 100%, such as 15%, 20%, 40%, 60%, 70%, 80%, 90%, 95%, 100%. Examples of useful detergent polymer premixes are described in EP351759 and WO2022100876. When the detergent polymer is in liquid or premix form, the premix can be transparent or opaque, white or slightly yellow. Opaque premixes can be used to provide an opaque appearance to the final product or a part of the final product.

[0666] The polyester may or may not be biodegradable, and the preferred detergent polymers are readily biodegradable.

[0667] Examples of suitable detergent polymers include those supplied by Clariant series, including nonionic detergent polymers SRN 100, SRN 170, SRN 170C, SRN 170Terra, SRN 172, SRN 240, SRN 260, SRN 260life, SRN 260SG Terra, SRN UL50, SRN 300, SRN 325; and anionic detergent polymers SRA 100, SRA 300, SRA300 F. Examples of suitable detergent polymers also include those supplied by Rhodia / Solvay series of polymers, including nonionic detergent polymers Crystal, Crystal PLUS, Crystal NAT, SRP6; and anionic detergent polymers SF-2. Other examples of commercial detergent polymers also include those supplied by WeylChem series of detergent polymers, including nonionic detergent polymers PLN1, PLN2; and anionic detergent polymers PSA1. Other examples of commercial detergent polymers are polymers such as those supplied by Sasol SL, HSCB, L235M B and G82. Other suitable commercial detergent polymers include Sorez 100 (obtained from ISP or Ashland).

[0668] Polysaccharide-Based Polymers.

[0669] A variety of polysaccharides have been shown to be useful starting materials for making polymers for fabric and home care products, including cellulose, starch, guar gum, dextran, polydextrose, chitin, gellan gum, xylan, inulin, pullulan, locust bean gum, cinnamon gum, tamarind gum (xyloglucan), xanthan gum, amylose, amylopectin, scleroglucan, and mixtures thereof.

[0670] The most common type of modified polysaccharide is modified cellulose.

[0671] Modified cellulose polymers include anionic modified cellulose polymers modified with functional groups containing negative charges. Suitable anionic modified cellulose polymers include carboxyalkyl celluloses, such as carboxymethyl cellulose. In a preferred embodiment, the carboxymethyl cellulose has a degree of carboxymethyl substitution of about 0.5 to about 0.9 and a molecular weight of about 80,000 Da to about 300,000 Da. Suitable carboxymethyl celluloses are described in WO2011 / 031599 and WO2009 / 154933. Suitable carboxymethyl celluloses include those sold by CP Kelco or Nouryon series, which includes GDA; hydrophobically modified carboxymethyl cellulose, such as the alkyl ketene dimer derivative of carboxymethyl cellulose sold under the trade name SH1 or the bulk carboxymethyl cellulose sold under the trade name V. Other suitable anionically modified cellulose polymers include the sulfoalkyl groups described in WO2006117056 and the sulfethyl cellulose described in WO2014124872.

[0672] The modified cellulose polymers also include non-ionic modified cellulose polymers that have been modified with functional groups that do not carry any charge. Suitable non-ionic modified cellulose polymers include alkyl celluloses, hydroxyalkyl celluloses, hydroxyalkyl alkyl celluloses, alkyl alkoxyalkyl celluloses. Suitable non-ionic modified cellulose polymers also include the non-ionic cellulose carbamate described in WO2015 / 044061; the non-ionic 6-deoxy-6-amino-cellulose derivatives described in US20180346846. Examples of alkyl celluloses include methyl cellulose (MC), ethyl cellulose (EC), etc. Suitable ethyl cellulose is sold by Dow Chemicals, DuPont or IFF under the trade name Ethocel TM for sale. Examples of hydroxyalkyl celluloses include hydroxyethyl cellulose (HEC) and hydroxypropyl cellulose (HPC). Suitable HEC is sold by Ashland under the trade name Natrosol TM hydroxyethyl cellulose, such as Natrosol with different grades TM 250, which has a total molar substitution (MS) of 2.5. Suitable HEC is also sold by Dow Chemicals under the trade name CELLOSIZE TM hydroxyethyl cellulose for sale. Suitable HPC is sold by Ashland under the trade name Klucel TM for sale. Examples of hydroxyalkyl alkyl celluloses include hydroxypropyl methyl cellulose (HPMC), suitable HPMC is sold in different grades by Dow Chemicals, DuPont or IFF under the trade name Methocel TM for sale, and by Ashland under the trade name Benecel TM for sale.

[0673] The modified cellulose polymers also include cationic modified cellulose polymers that have been modified with functional groups containing a cationic charge. Suitable cationic modified celluloses include quaternized hydroxyethyl cellulose (Polyquaternium-10), which is available from Dow Chemical under the trade name Ucare, such as Ucare LR400, Ucare LR30M, Ucare JR125, Ucare JR400, etc. Suitable cationic modified cellulose polymers also include quaternized hydroxyethyl cellulose (HEC) polymers (Polyquaternium-67) with trimethylammonium and dimethyldodecylammonium cation substitutions, which are available from Dow Chemical under the trade name SoftCAT, such as SoftCAT SK, SoftCAT SK-MH, SoftCAT SX, SoftCAT SL. Other suitable cationic modified celluloses include those sold by Dow Chemical under the trade name SupraCare TM such as SupraCare TM 150, SupraCare TM 133, SupraCare TM 212.

[0674] Suitable cationic modified cellulose polymers also include those modified with cationic groups and / or hydrophobic groups and described as detergency polymers in WO2019111948, WO2019111949, WO2019111946, and WO2019111947; suitable polymers are also disclosed in WO2022060754, WO2021242942, and WO2020 / 091988.

[0675] Another common type of modified polysaccharide is modified guar gum. Similar to modified cellulose, modified guar gum can be non-ionic modified and anionic modified. Suitable non-ionic modified guar gums include hydroxypropyl guar gum, such as N-Hance TM HP40 and HP40S guar gum. Suitable examples of modified guar gum also include anionic and non-ionic modified carboxymethylhydroxypropyl guar gum (CMHPG), such as Galactasol TM . Other non-ionic and / or anionic modified guar gums include, for example HP 105 (hydroxypropyl guar gum), SOFT and HP-120COS (carboxymethylhydroxypropyl guar gum).

[0676] Suitable modified polysaccharide polymers also include modified starches. Examples of modified starches include carboxylate esters of starch as described in WO2015144438, esterification products of starch with, for example, C6-C 24 alk(en)yl succinic anhydrides as described in EP0703243; starch maleates (reaction of starch with maleic anhydride) as described in US 6063914. Examples of modified starches also include, but are not limited to, acetylated starch, acetylated distarch adipate, distarch phosphate, hydroxypropyl starch, hydroxypropyl distarch phosphate, phosphorylated distarch phosphate, acetylated distarch phosphate, sodium starch octenyl succinate.

[0677] Suitable modified polysaccharide polymers also include polymers based on other polysaccharides, such as the cationic dextran polymers described in WO2021194808, which can be commercially obtained from Meito Sangyo under the trade names CDC, CDC-L, CDC-H.

[0678] Suitable modified polysaccharide polymers also include polymers based on polydextrose. Suitable modified polydextrose is based on α1,3-polydextrose and / or 1,6-polydextrose. In one embodiment, the modified polydextrose can be cationically modified, such as the cationically modified α1,3-polydextrose described in WO2021225837; such as the cationically modified α1,6-polydextrose described in WO2021257793, WO2021257932, and WO2021 / 257786. In another embodiment, the modified polydextrose can be hydrophobically and / or hydrophilically modified, such as those described in WO2018112187, WO2019246228, WO2019246171, WO2021252558, WO2021252560, WO2021252561, EP3922704, WO2021252569, WO2021252562, WO2021252559, WO2021252575, WO2021252563. In addition to hydrophobically and / or hydrophilically modified polydextrose, the polydextrose esters described in WO2021252562, WO2021252559, WO2021252575, WO2021252563 are particularly preferred due to their performance and biodegradability characteristics.

[0679] Other suitable polysaccharide polymers also include those based on inulin. Examples of modified inulin include carboxymethyl group modified inulin (CMI), and suitable CMI is the Carboxyline series sold by Cosun Beet Company, including Carboxyline 25–40D, Carboxyline 25D powder, Carboxyline 20LSD powder, Carboxyline 25, Carboxyline 25–30UP. Examples of modified inulin also include cationically modified inulin, such as those described in US20190274943 and US20180119055, and suitable cationically modified inulin is the Quatin series sold by Cosun Beet Company, including Quatin 350, Quatin 380 and Quatin 1280, which are characterized by different degrees of substitution (DS), cation density (meq / g) and molecular weight (g / mol).

[0680] Suitable modified polysaccharide polymers also include polymers based on other polysaccharides, such as xylan carbamate, as described in US20210115358; carboxy- or sulfo-alkylated amylose, as described in WO2019243072; carboxy- or sulfo-alkylated chitosan, as described in WO2019 / 243108 and WO2021156093.

[0681] Polycarboxylate Polymers.

[0682] The composition may also include one or more polycarboxylate polymers, which include at least one monomer containing a carboxyl group. Monomers containing a carboxyl group are selected from acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and their salts and their acid anhydrides.

[0683] Suitable polycarboxylate polymers include polyacrylate homopolymers having a molecular weight of 4,000 Da to 9,000 Da or 6,000 Da to 9,000 Da. Other suitable carboxylate polymers include copolymers of acrylic acid (and / or methacrylic acid) and maleic acid having a molecular weight of 50,000 Da to 120,000 Da or 60,000 Da to 80,000 Da. The polyacrylate homopolymers and the copolymers of acrylic acid (and / or methacrylic acid) and maleic acid are commercially available as Acusol 445 and 445N, Acusol 531, Acusol 463, Acusol 448, Acusol 460, Acusol 465, Acusol 497, Acusol 490 from Dow Chemicals, and as Sokalan CP 5, Sokalan CP 7, Sokalan CP 45 and Sokalan CP 12S from BASF. Suitable polycarboxylate polymers also include polyitaconate homopolymers, such as DSP 2K TM and Amaze SP purchased from Nouryon.

[0684] Suitable polycarboxylate polymers also include copolymers comprising a carboxyl-containing monomer and one or more sulfonate- or sulfonic acid group-containing monomers. The sulfonate- or sulfonic acid group-containing monomers are selected from 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy-propane sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, 3-allyloxy-2-hydroxy-1-propane sulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethyl methacrylamide, sulfomethyl methyl methacrylamide, and their water-soluble salts. In one embodiment, suitable polymers include maleic acid, acrylic acid, and 3-allyloxy-2-hydroxy-1-propane sulfonic acid, such polymers as described in US8450261 and US8389458. In another embodiment, suitable polymers include acrylic acid and 2-acrylamido-2-methyl-propane sulfonate, such as those sold by Dow Chemicals under the trade name Acusol 588, those sold by BASF under the trade name Sokalan CP 50, those sold by Nouryon under the trade names Aquatreat AR-545, Versaflex 310 and Versaflex 310-37. In another embodiment, suitable polymers also include sodium poly(itaconic acid-co-AMPS), such as those purchased from Itaconix TSITM 322 and CHT TM 122.

[0685] Suitable polymers also include those comprising other structural units in addition to monomers containing sulfonate or sulfonic acid groups and monomers containing carboxyl groups. Examples of suitable polymers are described in WO2010024468 and WO2014 / 032267, and the additional monomers herein are ether bond-containing monomers represented by the following formulas (1) and (2):

[0686]

[0687] wherein in formula (1)

[0688] R0 represents a hydrogen atom or a CH3 group,

[0689] R represents a CH2 group, a CH2CH2 group or a single bond,

[0690] x represents a number from 0 to 50, preferably from 0 to 20, more preferably from 0 to 5 (provided that when R is a single bond, x represents a number from 1 to 5), and

[0691] R1 is a hydrogen atom or a C1 to C 20 organic group

[0692] wherein in formula (2),

[0693] R0 represents a hydrogen atom or a CH3 group,

[0694] R represents a CH2 group, a CH2CH2 group or a single bond,

[0695] x represents a number from 0 to 5, and

[0696] R1 is a hydrogen atom or a C1 to C 20 organic group.

[0697] Particularly preferred polymers of this type comprise structural units derived from 1% to 49% by weight of 1-(allyloxy)-3-butoxypropan-2-ol, 50% to 98% by weight of acrylic acid or methacrylic acid, and 1% to 49% by weight of 3-allyloxy-2-hydroxy-1-propanesulfonic acid, and have a weight-average molecular weight of from about 20,000 to about 60,000. Particularly preferred polymers of this type comprise structural units derived from 1% to 10% by weight of 1-(allyloxy)-3-butoxypropan-2-ol, 70% to 89% by weight of acrylic acid or methacrylic acid, and 10% to 20% by weight of 3-allyloxy-2-hydroxy-1-propanesulfonic acid, and have a weight-average molecular weight of from about 30,000 to about 60,000. As used herein, 1-(allyloxy)-3-butoxypropan-2-ol is the preferred monomer represented by formula (2) when R0 is H, R is CH2, x is 0 and R1 is n-butyl (C4-alkyl).

[0698] Suitable polycarboxylate polymers also include copolymers comprising carboxyl-containing monomers and other suitable monomers. Other suitable monomers herein are selected from esters and / or amides of carboxyl-containing monomers, such as C1-C 20 alkyl esters of acrylic acid; alkylene; vinyl ethers, such as methyl vinyl ether, styrene, and any mixtures thereof. A particularly preferred family of polymers of this type is sold by Ashland under the trade name Gantrez, which includes Gantrez An (alternating copolymer of methyl vinyl ether and maleic anhydride), Gantrez S (alternating copolymer of methyl vinyl ether and maleic acid), Gantrez ES (alternating copolymer of methyl vinyl ether and maleate), Gantrez MS (alternating copolymer of methyl vinyl ether and maleate).

[0699] Suitable polycarboxylate polymers also include polyepoxysuccinic acid polymers (PESA). The most preferred polyepoxysuccinic acid polymers can be identified using CAS No.: 51274-37-4 or 109578-44-1. Suitable polyepoxysuccinic acid polymers are commercially available from various suppliers, such as Aquapharm Chemicals Pvt. Ltd (trade name: Maxinol 600); Shandong Taihe Water Treatment Technologies Co., Ltd (trade name: PESA) and Sirius International (trade name: Briteframe PESA).

[0700] Suitable polycarboxylate polymers also include polymers comprising monomers having at least one aspartic acid group or a salt thereof, the polymer comprising at least 25 mol%, 40 mol% or 50 mol% of said monomers. A preferred example is sodium poly(aspartate) with a molecular weight of 2000 g / mol to 3000 g / mol, which is commercially available under the trade name DS100 from Lanxess.

[0701] Other Polymers.

[0702] The composition may include block polymers of ethylene oxide, propylene oxide and butylene oxide. Examples of such block polymers include ethylene oxide - propylene oxide - ethylene oxide (EO / PO / EO) triblock copolymers, wherein the copolymer comprises a first EO block, a second EO block and a PO block, and wherein the first EO block and the second EO block are attached to the PO block. The blocks of ethylene oxide, propylene oxide and butylene oxide may also be arranged in other ways, such as (EO / PO) diblock copolymers, (PO / EO / PO) triblock copolymers. The block polymers may also contain additional butylene oxide (BO) blocks. Suitable block polymers are, for example, the Pluronic PE series from BASF, including Pluronic PE3100, PE4300, PE6100, PE6200, PE6400, PE6800, PE8100, PE9200, PE9400, PE10100, PE10500, PE10400. Suitable block polymers are also available from Dow Chemicals under the Tergitol L series, such as Tergitol L-61, L-62, L-64, L-81, L-101. Due to their hydrophobic and hydrophilic properties, such block polymers are sometimes also considered nonionic surfactants in the literature.

[0703] The composition may include a dye transfer inhibition reagent (also known as a dye transfer inhibitor or a dye fixative), which includes but is not limited to polyvinylpyrrolidone polymers (PVP), poly(vinylpyridine-N-oxide) polymers (PVNO), poly(vinylimidazole), polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyl oxazolidone and polyvinylimidazole or mixtures thereof. The dye transfer inhibition reagent may be selected from the group consisting of reaction products of: i) polyamines with cyanamides and organic and / or inorganic acids, ii) cyanamides with aldehydes and ammonium salts, iii) cyanamides with aldehydes and amines, or iv) amines with epichlorohydrin.

[0704] The composition may include one or more other polymer dispersants. Examples are poly(ethylene glycol), poly(vinyl alcohol).

[0705] Suitable polymers may also include monomers obtainable from renewable raw materials. Such monomers are described in US20200277548, US20200277549, WO2019096590.

[0706] Additional Amines:

[0707] Additional amines can be used in the compositions described herein to increase the removal of oils and particles from soiled materials. The compositions described herein may contain from about 0.1% to about 10%, in some examples from about 0.1% to about 4%, and in other examples from about 0.1% to about 2% of additional amines, by weight of the composition. Non-limiting examples of additional amines can include, but are not limited to, polyamines, oligamines, triamines, diamines, pentamines, tetraamines, or combinations thereof. Specific examples of suitable additional amines include tetraethylenepentamine, triethylenetetramine, diethylenetriamine, or mixtures thereof.

[0708] Bleaching Agents.

[0709] The composition may preferably contain one or more bleaching agents. Suitable bleaching agents other than bleaching catalysts include optical bleaches, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids, and mixtures thereof. Generally speaking, when a bleaching agent is used, the compositions of the present invention may contain from about 0.1% to about 50%, or even from about 0.1% to about 25% of a bleaching agent or a mixture of bleaching agents, by weight of the subject composition. Examples of suitable bleaching agents include:

[0710] (1) Optical bleaches: such as zinc sulfonated phthalocyanine, aluminum sulfonated phthalocyanine, xanthene dyes, thioxanthones, and mixtures thereof;

[0711] (2) Preformed peracids: Suitable preformed peracids include, but are not limited to, compounds selected from: preformed peroxyacids or their salts, typically percarboxylic acids and their salts, percarbonic acids and their salts, perimido acids and their salts, permonosulfuric acid and its salts (e.g. ) and mixtures thereof.

[0712] Particularly preferred peroxyacids are phthalimido peroxyalkanoic acids, specifically ε-phthalimido peroxycaproic acid (PAP). The peroxyacid or its salt preferably has a melting point in the range of 30 °C to 60 °C.

[0713] (3) Hydrogen peroxide source: For example, inorganic hydrogen peroxide compound salts, which include alkali metal salts such as sodium perborate salts (usually monohydrate or tetrahydrate), sodium percarbonate salts, sodium persulfate salts, sodium metaphosphate salts, sodium metasilicate salts, and mixtures thereof. When using inorganic hydrogen peroxide compound salts, the inorganic hydrogen peroxide compound salts are usually present in an amount of 0.05% to 40% by weight or 1% to 30% by weight of the total fabric and home care products, and are usually incorporated into such fabric and home care products in the form of crystalline solids that can be coated. Suitable coatings include: inorganic salts such as alkali metal silicates, carbonates or borates, or mixtures thereof, or organic materials such as water-soluble or water-dispersible polymers, waxes, oils or fatty soaps; and

[0714] (4) Bleaching activators having R-(C=O)-L, where R is an optionally branched alkyl group, which has 6 to 14 carbon atoms or 8 to 12 carbon atoms when the bleaching activator is hydrophobic, and has less than 6 carbon atoms or even less than 4 carbon atoms when the bleaching activator is hydrophilic; and L is a leaving group. Examples of suitable leaving groups are benzoic acid and its derivatives, especially benzenesulfonates. Suitable bleaching activators include dodecanoyl hydroxyphenylsulfonate, decanoyl hydroxyphenylsulfonate, decanoyl hydroxybenzoic acid or its salts, 3,5,5-trimethylhexanoyl hydroxyphenylsulfonate, tetraacetylethylenediamine (TAED), and nonanoyl hydroxyphenylsulfonate (NOBS).

[0715] (5) Bleaching catalysts. The compositions of the present invention may further comprise one or more bleaching catalysts, which are capable of accepting oxygen atoms from peroxyacids and / or their salts and transferring the oxygen atoms to oxidizable substrates. Suitable bleaching catalysts include, but are not limited to: iminium cations and polyions; iminium zwitterions; modified amines; modified amine oxides; N-sulfonylimines; N-phosphonylimines; N-acylimines; thiadiazole dioxides; perfluoroimines; cyclic glyoxals and α-aminoketones, and mixtures thereof. A particularly preferred catalyst is acylhydrazones, such as 4-(2-(2-((2-hydroxybenzylidene)hydrazino)-2-oxoethyl)-4-methyl chloride.

[0716] (6) The composition may preferably comprise catalytic metal complexes. A preferred type of metal-containing bleaching catalyst is a catalyst system that contains transition metal cations having defined bleaching catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese cations.

[0717] If desired, the compositions herein can be catalyzed by means of manganese compounds. These compounds and amounts are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. 5,576,282. In some embodiments, there is no additional source of oxidant present in the composition and molecular oxygen from air provides the oxidizing source.

[0718] Cobalt bleaching catalysts useful herein are known and are described, for example, in U.S. 5,597,936; U.S. 5,595,967.

[0719] Fluorescent Whitening Agents:

[0720] Commercially available fluorescent brightening agents suitable for the present disclosure can be divided into subclasses, which include but are not limited to stilbenes, pyrazolines, coumarins, benzoxazoles, carboxylic acids, polymethine cyanines, 5,5'-sulfoxide fluorene, oxazoles, derivatives of 5- and 6-membered heterocycles, and a variety of other reagents.

[0721] The fluorescent brightening agent can be selected from the group consisting of sodium 4,4'-bis{[4-phenylamino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate (brightening agent 15, commercially available under the trade name Tinopal AMS-GX (BASF)), sodium 4,4'-bis{[4-phenylamino-6-(N-2-bis-hydroxyethyl)-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate (commercially available from BASF under the trade name Tinopal UNPA-GX), sodium 4,4'-bis{[4-phenylamino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate (commercially available from BASF Corporation under the trade name Tinopal 5BM-GX). More preferably, the fluorescent brightening agent is sodium 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate or disodium 2,2'-([1,1'-biphenyl]-4,4'-diylbis(ethene-2,1-diyl))dibenzenesulfonate. The brightening agent can be added in particulate form or as a premix with a suitable solvent, such as a nonionic surfactant, propylene glycol.

[0722] Fabric toner: The composition may include a fabric toner (sometimes referred to as a colorant, bluing agent, or whitening agent). The toner typically provides a blue or purple hue to the fabric. The toners can be used alone or in combination to produce a specific toning hue and / or tone different fabric types. This can be provided, for example, by mixing red and blue-green dyes to produce a blue or purple hue. The toner can be selected from dyes of any known chemical class, including but not limited to acridine, anthraquinone (including polycyclic quinones), azine, azo (e.g., monoazo, bisazo, trisazo, tetrakisazo, polyazo), including pre-metallized azo, benzodifuran and benzodifurone, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane, merocyanine, hemicyanine, indigo type, methane, naphthalimide, naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, pyrazole, stilbene, styryl, triarylmethane, triphenylmethane, xanthene, and mixtures thereof.

[0723] Chelating Agents.

[0724] Preferably, the composition contains a chelating agent and / or a crystal growth inhibitor. Suitable molecules include copper, iron, and / or manganese chelating agents, and mixtures thereof. Suitable molecules include hydroxamic acids, aminocarboxylates, aminophosphonates, succinates, their salts, and mixtures thereof. Non-limiting examples of suitable chelating agents for use herein include ethylenediaminetetraacetate, N-(2-hydroxyethyl)-ethylenediamine-triacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetramine-hexaacetate, diethylenetriamine-pentaacetate, ethanol diglycine, ethylenediaminetetra(methylenephosphonate), diethylenetriaminepenta(methylenephosphonic acid) (DTPMP), ethylenediaminedisuccinate (EDDS), hydroxyethanedimethylene phosphonic acid (HEDP), methylglycine diacetic acid (MGDA), diethylenetriaminepentaacetic acid (DTPA), N,N-dicarboxymethylglutamic acid (GLDA) and its salts, and mixtures thereof. Other non-limiting examples of chelating agents for use in the present invention are found in U.S. Patents 7445644, 7585376, and 2009 / 0176684A1. Other chelating agents suitable for use herein are commercially available in the DEQUEST series, as well as chelating agents from Monsanto, DuPont, and Nalco, Inc. Other suitable chelating agents include pyridyl N-oxide types.

[0725] Encapsulates:

[0726] The composition may contain an encapsulant. In some aspects, the encapsulant includes a core, a shell having an inner surface and an outer surface, wherein the shell encapsulates the core.

[0727] In some aspects, the encapsulant comprises a core and a shell, wherein the core comprises a material selected from the group consisting of: perfumes; optical brighteners; dyes; insect repellents; siloxanes; waxes; flavorants; vitamins; fabric softeners; skin care agents such as alkanes; enzymes; antibacterial agents; bleaches; sensates; or mixtures thereof; and wherein the shell comprises a material selected from the group consisting of: polyethylene; polyamide; polyvinyl alcohol, optionally containing other comonomers; polystyrene; polyisoprene; polycarbonate; polyester; polyacrylate; polyolefin; polysaccharides such as alginates and / or chitosan; gelatin; shellac; epoxy resins; vinyl polymers; water-insoluble inorganic substances; siloxanes; aminoplastics, or mixtures thereof. In some aspects, where the shell comprises an aminoplastic, the aminoplastic comprises a polyurea, a polyurethane, and / or a polyureaurethane. The polyurea may include polyformaldehyde urea and / or melamine formaldehyde.

[0728] Fragrances.

[0729] Preferred compositions of the present invention contain a perfume. Generally, the composition contains a perfume which comprises one or more perfume ingredients selected from those described in WO08 / 87497. However, any perfume that can be used in a laundry care composition can be used. A preferred method of incorporating the perfume into the composition of the present invention is via encapsulated perfume particles which contain a water-soluble hydroxy compound or melamine-formaldehyde or modified polyvinyl alcohol.

[0730] Odor Reduction Materials.

[0731] The cleaning compositions of the present disclosure may contain malodor reducing materials. Such materials are capable of reducing or even eliminating the perception of one or more malodors. These materials are characterized by a calculated malodor reduction value ("MORV") which is calculated according to the test method shown in WO2016 / 049389.

[0732] As used herein, "MORV" is the calculated malodor reduction value of the material in question. The MORV of a material represents the ability of such material to reduce or even eliminate the perception of one or more malodors.

[0733] The cleaning compositions of the present disclosure may contain one or more malodor reducing materials in amounts totaling from about 0.00025% to about 0.5%, preferably from about 0.0025% to about 0.1%, more preferably from about 0.005% to about 0.075%, and most preferably from about 0.01% to about 0.05% by weight of the composition. The cleaning composition may contain from about 1 to about 20 malodor reducing materials, more preferably 1 to about 15 malodor reducing materials, and most preferably 1 to about 10 malodor reducing materials.

[0734] One, some or each of the malodor reduction materials may have a MORV of at least 0.5, preferably 0.5 to 10, more preferably 1 to 10, most preferably 1 to 5. One, some or each of the malodor reduction materials may have a common MORV, defined as all MORV values ​​of malodors tested as described herein > 0.5. The sum of the malodor reduction materials may have a blocking index of less than 3, more preferably less than about 2.5, even more preferably less than about 2, and still more preferably less than about 1, and most preferably about 0. The sum of the malodor reduction materials may have a blocking index average of about 3 to about 0.001.

[0735] In the cleaning compositions of the present disclosure, the malodor reduction material may have a Fragrance Fidelity Index of less than 3, preferably less than 2, more preferably less than 1, and most preferably about 0, and / or an average Fragrance Fidelity Index of 3 to about 0.001 Fragrance Fidelity Index. As the Fragrance Fidelity Index decreases, the one or more malodor reduction materials provide less and less odor impact while continuing to combat malodor.

[0736] The cleaning compositions of the present disclosure may include fragrances. The weight ratio of the malodor reduction composition to the fragrance may be from about 1:20,000 to about 3000:1, preferably from about 1:10,000 to about 1,000:1, more preferably from about 5,000:1 to about 500:1, and most preferably from about 1:15 to about 1:1. As the ratio of the malodor reduction composition to the fragrance decreases, the one or more malodor reduction materials provide less and less odor impact while continuing to combat malodor.

[0737] Conditioners.

[0738] Suitable conditioning agents include high melting point fatty compounds. High melting point fatty compounds useful herein have a melting point of 25°C or higher and are selected from fatty alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives, and mixtures thereof. Suitable conditioning agents also include nonionic polymers and conditioning oils, such as hydrocarbon oils, polyolefins, and fatty esters.

[0739] Suitable conditioning agents include those generally characterized as silicones (e.g., silicone oils, poly-oils, silicone gums, high refractive silicones and silicone resins), organic conditioning oils (e.g., hydrocarbon oils, polyolefins and fatty esters), or combinations thereof, or those conditioning agents that otherwise form liquid dispersed particles in the aqueous surfactant matrix herein. The compositions of the present invention may also contain from about 0.05% to about 3% of at least one organic conditioning oil as a conditioning agent, which may be used alone or in combination with other conditioning agents (such as the silicones described above). Suitable conditioning oils include hydrocarbon oils, polyolefins and fatty acid esters.

[0740] Probiotics.

[0741] The composition may comprise probiotics such as those described in WO2009 / 043709.

[0742] Organic Acids.

[0743] The detergent comprises one or more organic acids selected from the group consisting of acetic acid, adipic acid, aspartic acid, carboxymethyloxy malonic acid, carboxymethyloxy succinic acid, citric acid, formic acid, glutaric acid, hydroxyethyliminodiacetic acid, iminodiacetic acid, lactic acid, maleic acid, malic acid, malonic acid, oxydiacetic acid, oxydisuccinic acid, succinic acid, sulfamic acid, tartaric acid, tartaric acid - disuccinic acid, tartaric acid - monosuccinic acid or mixtures thereof. Preferably, the detergent composition may comprise organic acids selected from the group consisting of acetic acid, lactic acid and citric acid.

[0744] Antioxidants.

[0745] The composition may optionally comprise an antioxidant which is present in the composition in an amount of from about 0.001 wt% to about 2 wt%. Preferably, the antioxidant is present at a concentration in the range of 0.01 wt% to 0.08 wt%. Mixtures of antioxidants may be used.

[0746] Sanitizers:

[0747] The composition of the present invention may further comprise components for delivering hygiene and / or malodor beneficial effects such as zinc ricinoleate, thymol, quaternary ammonium salts (such as ), polyethyleneimine (such as ) obtained from BASF and zinc complexes thereof, silver and silver compounds (especially those designed for slow release of Ag+ or silver nano - dispersions), one or more of them.

[0748] The cleaning composition of the present invention may also comprise an antimicrobial agent. Preferably, the antimicrobial agent is selected from 4,4'-dichloro - 2 - hydroxy diphenyl ether ("triclosan"), 2,4,4'-trichloro - 2'-hydroxy diphenyl ether ("triclocarban"), and combinations thereof. Most preferably, the antimicrobial agent is 4,4'-dichloro - 2 - hydroxy diphenyl ether, which is commercially available from BASF under the trade name HP100.

[0749] Pearlescents:

[0750] Non - limiting examples of pearlescent agents include: mica; titanium dioxide - coated mica; bismuth oxychloride; fish scales; mono - or diesters of alkylene glycols. The pearlescent agent may be ethylene glycol distearate (EGDS).

[0751] Light Blockers:

[0752] In one embodiment, the composition may further comprise an opacifier. As used herein, the term "opacifier" is a substance added to a material to ensure that the system is opaque. In a preferred embodiment, the opacifier is Acusol, which is available from Dow Chemicals. The Acusol opacifier is provided in liquid form at a specific solids %. As provided, the pH of the Acusol opacifier is in the range of 2.0 to 5.0, and the particle size is in the range of 0.17 to 0.45 μm. In a preferred embodiment, Acusol OP303B and 301 may be used.

[0753] In another embodiment, the opacifier may be an inorganic opacifier. Preferably, the inorganic opacifier may be TiO2, ZnO, talc, CaCO3, and combinations thereof. Composite opacifier-microsphere materials are easily formed with a preselected specific gravity such that the tendency for material separation is small.

[0754] Solvents.

[0755] The solvent system in the composition of the present invention may be a solvent system containing only water or a mixture of organic solvents with or preferably without water. The composition may optionally contain an organic solvent. Suitable organic solvents include C4-C 14 ethers and diethers, glycols, alkoxylated glycols, C6-C 16 glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated straight-chain C1-C5 alcohols, straight-chain C1-C5 alcohols, amines, C8-C 14 alkyl and cycloalkyl hydrocarbons and halogenated hydrocarbons, and mixtures thereof. Preferred organic solvents include 1,2-propanediol, 2,3-butanediol, ethanol, glycerol, ethoxylated glycerol, dipropylene glycol, methylpropanediol, and mixtures thereof 2-ethylhexanol, 3,5,5-trimethyl-1-hexanol, and 2-propylheptanol. The solvent may be a polyethylene ether of glycerol or a polypropylene ether of glycerol. Other lower alcohols, C1-C4 alkanolamines such as monoethanolamine and triethanolamine may also be used. For example, the solvent system of the anhydrous solid embodiment of the present invention may be absent, but more typically it is present at a level in the range of about 0.1 wt% to about 98%, preferably at least about 1% to about 50%, more typically about 5 wt% to about 25%, or about 1% to about 10% of the liquid detergent composition of the organic solvent. These organic solvents may be used in combination with water, or they may be used without water

[0756] Hydrotropes.

[0757] The composition may optionally contain an effective amount of a hydrotrope, i.e., from about 0% to 15%, or from about 1% to 10%, or from about 3% to about 6%, such that the composition is compatible in water. Hydrotropes suitable for use herein include anionic hydrotropes, especially sodium xylene sulfonate, potassium xylene sulfonate, and ammonium xylene sulfonate, sodium toluene sulfonate, potassium toluene sulfonate, and ammonium toluene sulfonate, sodium isopropyl benzene sulfonate, potassium isopropyl benzene sulfonate, and ammonium isopropyl benzene sulfonate, and mixtures thereof, as disclosed in U.S. Patent 3,915,903.

[0758] Defoamers.

[0759] Compounds for reducing or suppressing foam formation may be incorporated into the water-soluble unit dose article. Foam suppression may be particularly important in so-called "high concentration cleaning processes" and in front-loading washing machines. Examples of foam suppressants include monocarboxylic fatty acids and their soluble salts, high molecular weight hydrocarbons such as paraffin wax, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C 18 -C 40 -ketones (e.g., stearone), N-alkylated aminotriazines, waxy hydrocarbons preferably having a melting point below about 100 °C, silicone defoamers, and secondary alcohols. Preferred fatty acid blends may be mixtures or fatty acid mixtures rich in 2-alkyl fatty acids, preferably 2-methyl octanoic acid

[0760] Other suitable defoamers are those derived from polysiloxanes substituted with phenylpropylmethyl.

[0761] The detergent composition may contain a defoamer and a major filler that is modified silica, the defoamer being selected from a combination of an organically modified silicone polymer having aryl or alkylaryl substituents and a silicone resin. The detergent composition may contain from about 0.001% to about 4.0% by weight of the composition of such a defoamer.

[0762] The detergent composition contains a defoamer selected from: a) a mixture of about 80% to about 92% ethylmethyl(2-phenylpropyl)methylsiloxane; about 5% to about 14% of an MQ resin in octyl stearate; and about 3% to about 7% of modified silica; b) a mixture of about 78% to about 92% ethylmethyl(2-phenylpropyl)methylsiloxane; about 3% to about 10% of an MQ resin in octyl stearate; about 4% to about 12% of modified silica; or c) a mixture thereof, where the percentages are by weight of the antifoam.

[0763] Liquid Laundry Detergent Composition.

[0764] Fabric and home care products can be laundry detergent compositions, such as liquid laundry detergent compositions. Suitable liquid laundry detergent compositions can contain non-soap surfactants, where the non-soap surfactants include anionic non-soap surfactants and nonionic surfactants. The laundry detergent composition can contain 10% to 60% or 20% to 55% by weight of the non-soap surfactant based on the weight of the laundry detergent composition. The ratio of non-soap anionic surfactant to nonionic surfactant is from 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 can be from 1:2 to 9:1, 1:1 to 7:1, 1:1 to 5:1, or 1:1 to 4:1. Suitable linear alkylbenzene sulfonates are C 10 -C 16 alkylbenzenesulfonic acid, or C 11 -C 14 alkylbenzenesulfonic acid. Suitable alkyl sulfate anionic surfactants include alkoxylated alkyl sulfates, non-alkoxylated alkyl sulfates, and mixtures thereof. Preferably, the HLAS surfactant contains greater than 50% of C 12 , preferably greater than 60%, preferably greater than 70% of C 12 , more preferably greater than 75% of C 12 . Suitable alkoxylated alkyl sulfate anionic surfactants include ethoxylated alkyl sulfate anionic surfactants. Suitable alkyl sulfate anionic surfactants include ethoxylated alkyl sulfate anionic surfactants having a molar average degree of ethoxylation of 1 to 5, 1 to 3, or 2 to 3. The alkyl alkoxylated sulfate can have a broad alkoxy distribution or a peaked alkoxy distribution. The alkyl portion of AES can on average contain from 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 an alkyl portion having 14 or more carbon atoms, preferably 14 to 18 or 14 to 17 or 14 to 16 or 14 to 15 carbon atoms. The alkyl sulfate anionic surfactant can contain non-ethoxylated alkyl sulfates and ethoxylated alkyl sulfates, where the molar average degree of ethoxylation of the ethoxylated alkyl sulfate is 1 to 5, 1 to 3, or 2 to 3. The alkyl fraction of the alkyl sulfate anionic surfactant can be derived from fatty alcohols, oxo alcohols, Guerbet alcohols, or mixtures thereof. Preferred alkyl sulfates include optionally ethoxylated alcohol sulfates, which include 2-alkyl branched primary alcohol sulfates, especially 2-branched C 12-15 primary alcohol sulfates, linear primary alcohol sulfates, especially linear C 12-14Primary alcohol sulfates, and mixtures thereof. The laundry detergent composition may comprise from 10% to 50% or from 15% to 45% or from 20% to 40% or from 30% to 40% by weight of the laundry detergent composition of a non-soap anionic surfactant.

[0765] Suitable nonionic surfactants may be selected from a wide or narrow range of alcohol alkoxylates, oxo alcohol alkoxylates, Guerbet alcohol alkoxylates, alkylphenol alcohol alkoxylates or mixtures thereof. The laundry detergent composition may comprise from 0.01% to 10%, from 0.01% to 8%, from 0.1% to 6% or from 0.15% to 5% by weight of the liquid laundry detergent composition of a nonionic surfactant.

[0766] 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.

[0767] The laundry detergent composition may comprise builder components selected from the group consisting of: builders including citrates, enzymes, bleaches, bleach catalysts, dyes, color modifying dyes, colorless dyes, optical brighteners, cleaning polymers including alkoxylated polyamines and polyethyleneimines, amphiphilic copolymers, soil release polymers, surfactants, solvents, dye transfer inhibitors, chelating agents, diamines, fragrances, encapsulated fragrances, polycarboxylates, structurants, pH modifiers, antioxidants, antibacterial agents, antimicrobials, preservatives and mixtures thereof.

[0768] The laundry detergent composition may have a pH of from 2 to 11 or from 6.5 to 8.9 or from 7 to 8, wherein the pH of the laundry detergent composition is measured at 20 °C at a product concentration of 10% in deionized water.

[0769] The liquid laundry detergent composition may be Newtonian or non-Newtonian, preferably non-Newtonian.

[0770] For the liquid laundry detergent composition, the composition may comprise from 5% to 99% or from 15% to 90% or from 25% to 80% by weight of the liquid detergent composition of water.

[0771] The detergent composition according to the invention may be a liquid laundry detergent composition. The following is an exemplary liquid laundry detergent formulation (Table 1). Preferably, the liquid laundry detergent composition comprises from 0.1% to 20.0% by weight of the washing treatment composition, preferably from 0.2% to 10%, preferably from 0.3% and 5.0%, preferably from 0.5% and 3%, more preferably from 1% and 2.5% of the graft polymer according to the invention.

[0772] Table 1.

[0773]

[0774]

[0775] Description of superscript numbers:

[0776] 1C12 - 15EO2.5S alkyl ethoxysulfate, wherein the alkyl part of AES contains about 13.9 to 14.6 carbon atoms.

[0777] 2PE - 20 commercially available from BASF

[0778] 3Nucleases as claimed in co - pending European patent application 19219568.3

[0779] 4Antioxidant 1 is methyl 3,5 - bis(1,1 - dimethylethyl) - 4 - hydroxycinnamate [6386 - 38 - 5]

[0780] 5Antioxidant 2 is Tinogard TS commercially available from BASF

[0781] 6Sanitizer is Tinosan HP 100 reagent commercially available from BASF

[0782] 7Antifoam blend provided by Dow Corning: 80% - 92% ethyl methyl, methyl(2 - phenylpropyl)siloxane; 5% - 14% stearic acid octyl ester solution of MQ resin; 3% - 7% modified silica.

[0783] 8Fluorescent brightener is disodium 4,4' - bis{[4 - anilino - 6 - morpholino - s - triazin - 2 - yl] - amino} - 2,2' - stilbenedisulfonate or disodium 2,2' - ([1,1' - biphenyl] - 4,4' - diylbis - 2,1 - ethenediyl)bisbenzenesulfonate.

[0784] Water-Soluble Unit Dose Products.

[0785] Fabric and home care products can be water-soluble unit dose articles. The water-soluble unit dose articles include at least one water-soluble film that is oriented to produce at least one unit dose internal compartment, wherein the at least one unit dose internal compartment contains a detergent composition. The water-soluble film preferably comprises a polyvinyl alcohol homopolymer or a polyvinyl alcohol copolymer, such as a blend of a polyvinyl alcohol homopolymer and / or a polyvinyl alcohol copolymer, such as a copolymer selected from sulfonated and carboxylated anionic polyvinyl alcohol copolymers, particularly a carboxylated anionic polyvinyl alcohol copolymer, such as a blend of a polyvinyl alcohol homopolymer and a carboxylated anionic polyvinyl alcohol copolymer. In some examples, the water-soluble film is those supplied by Monosol under trade references M8630, M8900, M8779, M8310. The detergent product includes a detergent composition, more preferably a laundry detergent composition. Preferably, the laundry detergent composition encapsulated in the water-soluble unit dose article contains from 0.1% to 8%, preferably from 0.5% to 7%, more preferably from 1.0% to 6.0% by weight of the graft polymer of the present invention based on the weight of the detergent composition. Preferably, the soluble unit dose laundry detergent composition contains a non-soap surfactant, wherein the non-soap surfactant includes an anionic non-soap surfactant and a non-ionic surfactant. More preferably, the laundry detergent composition contains from 10% to 60% or from 20% to 55% by weight of the non-soap surfactant based on the weight of the laundry detergent composition. The weight ratio of the non-soap anionic surfactant to the non-ionic surfactant is preferably from 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 linear alkylbenzene sulfonate, alkyl sulfate, or a mixture thereof. The weight ratio of the linear alkylbenzene sulfonate to the alkyl sulfate is preferably from 1:2 to 9:1, 1:1 to 7:1, 1:1 to 5:1, or 1:1 to 4:1. Example linear alkylbenzene sulfonates are C 10 -C 16 alkylbenzenesulfonic acid, or C 11 -C 14Alkylbenzene sulfonic acid. As used herein, "linear" means that the alkyl group is a straight chain. Exemplary alkyl sulfate anionic surfactants can include alkoxylated alkyl sulfates or non-alkoxylated alkyl sulfates or mixtures thereof. Exemplary alkoxylated alkyl sulfate anionic surfactants include ethoxylated alkyl sulfate anionic surfactants. Exemplary alkyl sulfate anionic surfactants can 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 can include non-ethoxylated alkyl sulfates and ethoxylated alkyl sulfates, wherein the molar average degree of ethoxylation of the ethoxylated alkyl sulfate is 1 to 5, 1 to 3, or 2 to 3. The alkyl fraction of the exemplary alkyl sulfate anionic surfactants is derived from fatty alcohols, oxo alcohols, Guerbet alcohols, or mixtures thereof. Preferably, the laundry detergent composition contains from 10% to 50%, from 15% to 45%, from 20% to 40%, or from 30% to 40% by weight of the laundry detergent composition of a non-soap anionic surfactant. In some examples, the nonionic surfactant is selected from alcohol alkoxylates, oxo alcohol alkoxylates, Guerbet alcohol alkoxylates, alkylphenol alcohol alkoxylates, or mixtures thereof. Preferably, the laundry detergent composition contains from 0.01% to 10%, or from 0.01% to 8%, or from 0.1% to 6%, or from 0.15% to 5% by weight of the liquid laundry detergent composition of a nonionic surfactant. In some examples, the laundry detergent composition contains 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 a soap, in some examples a fatty acid salt, in some examples an amine-neutralized fatty acid salt, wherein in some examples the amine is an alkanolamine, preferably monoethanolamine. Preferably, the liquid laundry detergent composition contains less than 15% or less than 12% water by weight of the liquid laundry detergent composition. Preferably, the laundry detergent composition contains from 10% to 40%, or from 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 contains from 0.1% to 10%, preferably from 0.5% to 8% by weight of the detergent composition of an additional detergency polymer, preferably selected from the group consisting of: nonionic and / or anionic modified polyethylene terephthalate detergency polymers, such as those sold under the Texcare trademark by Clariant; 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 builder components selected from the group consisting of: builders including citrate, enzymes, bleaches, bleach catalysts, dyes, colorant dyes, optical brighteners, cleaning polymers including (zwitterionic) alkoxylated polyureas, surfactants, solvents, dye transfer inhibitors, fragrances, encapsulated fragrances, polycarboxylates, structurants, pH modifiers, and mixtures thereof. Preferably, the laundry detergent composition has a pH between 6 and 10, between 6.5 and 8.9, or between 7 and 8, wherein the pH of the laundry detergent composition is measured at a product concentration of 10% in deionized water at 20 °C. When in liquid form, the laundry detergent composition can be Newtonian or non-Newtonian, preferably non-Newtonian.

[0786] The following are exemplary water-soluble unit dose formulations (Table 2). The composition can be part of a single chamber water-soluble unit dose article, or can be separated over multiple compartments to obtain a full article composition that is below the "average across compartments". The composition is encapsulated in a water-soluble material based on polyvinyl alcohol, which comprises a blend of a polyvinyl alcohol homopolymer and an anion (e.g., a carboxylated polyvinyl alcohol copolymer).

[0787] Table 2.

[0788]

[0789]

[0790] Description of superscripts:

[0791] *Nuclease as claimed in co-pending European patent application 19219568.3

[0792] **Polyethylene glycol graft polymer, comprising a polyethylene glycol backbone (Pluriol E6000) and a hydrophobic vinyl acetate side chain, a polymer system comprising 40 wt% of the polyethylene glycol backbone polymer and a polymer system of 60 wt% of the grafted vinyl acetate side chain

[0793] Hand Dishwashing Liquid Composition.

[0794] Fabric and home care products can be dishwashing detergent compositions, such as hand dishwashing detergent compositions, more preferably liquid hand dishwashing detergent compositions. Preferably, the liquid hand dishwashing detergent composition comprises from 0.1% to 5.0%, preferably from 0.5% to 4%, more preferably from 1.0% to 3.0% of the graft polymer of the present invention, based on the weight of the detergent composition. The liquid hand dishwashing detergent composition is preferably an aqueous composition, which comprises from 50% to 90%, preferably from 60% to 75% water, based on the weight of the total composition. Preferably, the pH of the detergent composition of the present invention (measured at a 10% product concentration in deionized water at 20 °C) is adjusted to be between 3 and 14, more preferably between 4 and 13, more preferably between 6 and 12, and most preferably between 8 and 10. The compositions of the present invention can be Newtonian or non-Newtonian, preferably Newtonian. Preferably, the viscosity of the composition is from 10 mPa·s to 10,000 mPa·s, preferably from 100 mPa·s to 5,000 mPa·s, more preferably from 300 mPa·s to 2,000 mPa·s, or most preferably from 500 mPa·s to 1,500 mPa·s, or a combination thereof. The viscosity is measured at 20 °C using a Brookfield RT viscometer with rotor 31, where the RPM of the viscometer is adjusted to achieve a torque between 40% and 60%.

[0795] The composition comprises from 5% to 50%, preferably from 8% to 45%, more preferably from 15% to 40% of a surfactant system, based on the weight of the total composition. The surfactant system preferably comprises from 60% to 90%, more preferably from 70% to 80% of an anionic surfactant, based on the weight of the surfactant system. Alkylsulfated anionic surfactants are preferred, especially those selected from the group consisting of alkyl sulfates, alkyl alkoxysulfates, preferably alkyl ethoxysulfates, and mixtures thereof. The alkylsulfated anionic surfactant preferably has an average alkyl chain length of from 8 to 18, preferably from 10 to 14, more preferably from 12 to 14, most preferably from 12 to 13 carbon atoms. The alkylsulfated anionic surfactant preferably has an average degree of alkoxylation, preferably ethoxylation, of less than 5, preferably less than 3, more preferably from 0.5 to 2.0, most preferably from 0.5 to 0.9. The alkyl sulfate anionic surfactant preferably has a weight-average degree of branching of more than 10%, preferably more than 20%, more preferably more than 30%, even more preferably between 30% and 60%, most preferably between 30% and 50%. Suitable counterions include alkali metal cations, alkaline earth metal cations, alkanolammonium or ammonium or substituted ammonium, but preferably sodium. Suitable examples of commercially available alkyl sulfate anionic surfactants include those derived from alcohols sold by Shell under the trade name or those sold by Sasol under the trade names and Those sold or some natural alcohols produced by The Procter&Gamble Chemicals company.

[0796] The surfactant system preferably comprises from 0.1% to 20%, more preferably from 0.5% to 15%, and especially from 2% to 10% of a co-surfactant, by weight of the liquid dishwashing detergent composition. Preferred co-surfactants are selected from zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. The weight ratio of the anionic surfactant to the co-surfactant can be from 1:1 to 8:1, preferably from 2:1 to 5:1, more preferably from 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 C 12 -C 14 alkyl dimethyl amine oxide. Suitable zwitterionic surfactants include betaine surfactants, preferably cocamidopropyl betaine.

[0797] Preferably, the surfactant system of the composition of the present invention further comprises from 1% to 25%, preferably from 1.25% to 20%, more preferably from 1.5% to 15%, and most preferably from 1.5% to 5% of a non-ionic surfactant, by weight of the surfactant system. Suitable non-ionic surfactants can be selected from the group consisting of alkoxylated non-ionic surfactants, alkyl polyglucoside ("APG") surfactants, and mixtures thereof. Suitable alkoxylated non-ionic surfactants can be linear or branched, primary alkyl alkoxylated or secondary alkyl alkoxylated, preferably alkyl ethoxylated non-ionic surfactants, containing on average from 9 to 15, preferably from 10 to 14 carbon atoms in their alkyl chain, and containing on average from 5 to 12, preferably from 6 to 10, and most preferably from 7 to 8 ethylene oxide units per mole of alcohol. Most preferably, the alkyl polyglucoside surfactant has an average alkyl carbon chain length between 10 and 16, preferably between 10 and 14, and most preferably between 12 and 14, and an average degree of polymerization between 0.5 and 2.5, preferably between 1 and 2, and most preferably between 1.2 and 1.6. C8-C 16 alkyl polyglucoside can be commercially obtained from several suppliers (e.g., from Seppic Corporation surfactants; and from BASF Corporation 600CSUP, 650EC, 600CSUP / MB and 650EC / MB).

[0798] The liquid hand dishwashing detergent composition of the present invention may optionally contain many other auxiliary components, such as builders (e.g., preferably citrates), chelating agents (e.g., preferably GLDA), conditioning polymers, cleaning polymers including polyalkoxylated polyalkyleneimines, surface-modified polymers, soil flocculating polymers, foaming polymers including EO-PO-EO triblock copolymers, oil and grease cleaning amines including cyclic polyamines, structurants, emollients, wetting agents, skin-renewing actives, enzymes, carboxylic acids, scrubbing particles, bleaches and bleach activators, fragrances, odor control agents, pigments, dyes, opacifiers, beads, pearlescent particles, microcapsules, organic solvents, inorganic cations such as alkaline earth metals (such as Ca / Mg-ions), antibacterial agents, preservatives, viscosity regulators (e.g., salts such as NaCl, and other monovalent, divalent and trivalent salts), and pH regulators and buffers (e.g., carboxylic acids such as citric acid, HCl, NaOH, KOH, alkanolamines, phosphoric acid and sulfonic acids, carbonates such as sodium carbonate, bicarbonates, sesquicarbonates, borates, silicates, phosphates, imidazoles, etc.).

[0799] The following is an exemplary liquid hand dishwashing detergent formulation (Table 3). The formulation can be prepared by standard mixing of the individual components.

[0800] Table 3.

[0801]

[0802] Free-Flowing Solid Granular Laundry Detergent Composition.

[0803] The fabric and home care product can be a free-flowing solid granular laundry detergent composition. The following is an exemplary free-flowing solid granular laundry detergent composition (Table 4).

[0804] Table 4.

[0805]

[0806]

[0807]

[0808] Fibrous Water-Soluble Unit Dose Products.

[0809] As used herein, the phrases "water-soluble unit dose article", "water-soluble fibrous structure", and "water-soluble fibrous element" mean that the unit dose article, fibrous structure, and fibrous element are miscible with water. In other words, the unit dose article, fibrous structure, or fibrous element is capable of forming a homogeneous solution with water under ambient conditions. "Ambient conditions" as used herein refers to 23°C ± 1.0°C and 50% ± 2% relative humidity. The water-soluble unit dose article may contain insoluble materials that can be dispersed into a suspension with an average particle size of less than about 20 microns, or less than about 50 microns, under aqueous washing conditions.

[0810] The fibrous water-soluble unit dose article may include any of the disclosures in U.S. Patent Application No. 15 / 880,594, filed on January 26, 2018, U.S. Patent Application No. 15 / 880,599, filed on January 26, 2018, and U.S. Patent Application No. 15 / 880,604, filed on January 26, 2018, which are incorporated herein by reference in their entireties. The preferred water-soluble fibrous structure comprises particles having a ratio of linear alkylbenzene sulfonate to alkyl ethoxylated sulfate or alkyl sulfate greater than 1.

[0811] These fibrous water-soluble unit dose articles can dissolve under various washing conditions, such as low temperature, low water, and / or one or more short wash cycles, where the consumer has overloaded the machine, especially for items with high water-absorbing capacity, while providing sufficient surfactant delivery to achieve the desired effect on the target consumer substrate (having performance similar to today's liquid products). In addition, the water-soluble unit dose articles described herein can be produced in an economical manner by spinning fibers containing surfactants. The water-soluble unit dose articles described herein also have improved cleaning performance.

[0812] Method of Use.

[0813] The composition of the present invention prepared as described above can be used to form a washing / treating aqueous solution for use in laundry washing / treating fabrics. Generally, an effective amount of such a composition is added to water, such as in a conventional fabric automatic washing machine, to form such a laundry washing aqueous solution. Then, the laundry washing aqueous solution thus formed is usually brought into contact with the fabric to be washed / treated under agitation. The effective amount of the detergent composition herein added to water to form the laundry washing aqueous solution may contain an amount sufficient to form a washing aqueous solution of the composition of about 500 ppm to 7,000 ppm, or the laundry washing care composition herein will be provided in the form of a washing aqueous solution at about 1,000 ppm to 3,000 ppm.

[0814] Typically, a washing liquid is formed by contacting a laundry washing and care composition with a certain amount of wash water such that the concentration of the laundry detergent care composition in the washing liquid is 0 g / l or more up to 5 g / l, or 1 g / l and up to 4.5 g / l, or up to 4.0 g / l, or up to 3.5 g / l, or up to 3.0 g / l, or up to 2.5 g / l, or even up to 2.0 g / l, or even up to 1.5 g / l. The method of washing a laundry fabric or textile can be carried out in a top-loading or front-loading automatic washing machine or can be used in a hand laundry washing application. In these applications, the washing liquid formed and the concentration of the laundry detergent composition in the washing liquid are those in the main wash cycle. During any optional one or more rinsing steps, when determining the volume of the washing liquid, any added water is not included.

[0815] The washing liquid can contain 40 liters or less of water, or 30 liters or less, or 20 liters or less, or 10 liters or less, or 8 liters or less, or even 6 liters or less of water. The washing liquid can contain from more than 0 liters up to 15 liters, or 2 liters and up to 12 liters, or even up to 8 liters of water. It is typically added to the washing liquid at a dosage of 0.01 kg to 2 kg of fabric per liter of washing liquid. It is typically added to the washing liquid at a dosage of 0.01 kg, or 0.05 kg, or 0.07 kg, or 0.10 kg, or 0.15 kg, or 0.20 kg, or 0.25 kg of fabric per liter of washing liquid. Optionally, 50 g or less, 45 g or less, 40 g or less, 35 g or less, 30 g or less, 25 g or less, 20 g or less, even 15 g or less, or even 10 g or less of such a composition is contacted with water to form the washing liquid. Such compositions are typically used at a concentration of about 500 ppm to about 15,000 ppm in solution. When the washing solvent is water, the water temperature is typically in the range of about 5°C to about 90°C, and when the portion contains fabric, the ratio of water to fabric is typically about 1:1 to about 30:1. Typically, the washing liquid containing the laundry washing and care composition of the present invention has a pH of 3 to 11.5.

[0816] In one aspect, such a method comprises the steps of optionally washing and / or rinsing a surface or fabric, contacting the surface or fabric with any of the compositions disclosed in this specification, then optionally washing and / or rinsing the surface or fabric, and an optional drying step.

[0817] Drying of such surfaces or fabrics can be achieved by any of the common methods employed in household or industrial settings. The fabric can include any fabric capable of being laundered under normal consumer or institutional use conditions, and the present invention is applicable to cellulose substrates and, in some aspects, also to synthetic textiles such as polyester and nylon, and is applicable to treating mixed fabrics and / or fibers comprising synthetic and cellulose fabrics, and / or fibers. Examples of synthetic fabrics are polyester, nylon, which can be present in a mixture with cellulose fibers, such as a polyester-cotton fabric. The solution typically has a pH of 7 to 11, more typically 8 to 10.5. The composition is generally used at a concentration of 500 ppm to 5,000 ppm in the solution. The water temperature is typically in the range of about 5°C to about 90°C. The ratio of water to fabric is generally about 1:1 to about 30:1. Another method involves contacting a soiled material with a nonwoven substrate impregnated with a detergent composition. As used herein, "nonwoven substrate" can include any conventional style of nonwoven sheet or web having suitable basis weight, thickness (thick), absorbency, and strength characteristics. Non-limiting examples of suitable commercially available nonwoven substrates include those sold by DuPont under the trade name and those sold by JamesRiver Corp. under the trade name POLY .

[0818] Carbon Source of Raw Materials.

[0819] The raw materials used to prepare surfactants, polymers, and other ingredients can be based on fossil carbon or renewable carbon. Renewable carbon is a carbon source that avoids the use of fossil carbon, such as natural gas, coal, and petroleum. Generally, renewable carbon is derived from biomass, carbon capture, or chemical recycling.

[0820] Biomass is a renewable carbon source formed through photosynthesis in the presence of sunlight or through a chemical synthesis process in the absence of sunlight. In some cases, polymers isolated from biomass can be used directly or further derivatized to prepare performance polymers. For example, the use of polysaccharides (such as starch) and derivatized polysaccharides (such as cellulose derivatives, guar gum derivatives, dextran derivatives) in fabric home care compositions is known. In some cases, biomass can be converted into basic chemicals under certain thermal, chemical, or biological conditions. For example, bioethanol can be derived from biomass such as straw and further converted into bio-based polyethylene glycol. Other non-limiting examples of renewable carbon from biomass include plants (such as sugarcane, beets, corn, potatoes, citrus fruits, woody plants, lignocellulose, hemicellulose, cellulose waste), animals, animal fats, fish, bacteria, fungi, plant-based oils, and forestry products. These resources can be naturally occurring, hybrids, or genetically engineered organisms.

[0821] Carbon capture is another renewable carbon source that uses various methods to capture CO2 or methane (direct capture) from industrial or natural processes, or directly from the air. The captured methane and CO2 can be converted to syngas and / or further converted to basic chemicals, including but not limited to methanol, ethanol, fatty alcohols such as C 12 / C 14 or even C 16 / C 18 alcohols, other alcohols, olefins, alkanes, saturated and unsaturated organic acids, etc. These basic chemicals can be used as monomers or further converted to monomers for conversion to useful chemicals by, for example, catalytic methods such as the Fischer-Tropsch process or by fermentation of C1-fixing microorganisms.

[0822] Chemical recycling is another renewable carbon source that allows plastics from the waste management industry to be recycled and converted into basic chemicals and chemical feedstocks. In some cases, waste plastics that cannot be reused or mechanically recycled are converted into hydrocarbons or basic petrochemical products through gasification, pyrolysis, or hydrothermal treatment processes, and the hydrocarbons and basic petrochemical products can be further converted into monomers for polymers. In some cases, waste plastics are depolymerized into monomers to prepare new polymers. Waste plastics can also be depolymerized into oligomers, which can be used as building blocks for manufacturing new polymers. Waste plastics from waste plastic raw materials converted into the above materials can be used alone or in combination with traditional surfactant raw materials (such as kerosene, polyolefins derived from natural gas, coal, crude oil, or even biomass, or paraffins and olefins derived from waste fats / oils) to produce biodegradable surfactants for detergents and other industries (thus providing beneficial effects to society).

[0823] Preferably, the surfactants, polymers, and other components contain renewable carbon, and the renewable carbon index (RCI, a measure of sustainability obtained by dividing the number of carbons from renewable sources by the total number of carbons in the active ingredient) of the polymer is higher than 10%, more preferably higher than 30%, more preferably higher than 50%, more preferably higher than 60%, more preferably between 70% and 100%, and most preferably 100%.

[0824] Examples

[0825] The following examples are intended to illustrate the invention in detail but not to limit the invention. Unless otherwise clearly stated, all percentages given are weight percentages (% by weight or wt%).

[0826] Prepare the following main chains of the graft polymers of the present invention.

[0827] A: 35EO + 3CL + 9EO + 3CL + 35EO

[0828] B: 3CL + 34EO + 3CL

[0829] C: 51EO + 3CL + 9EO + 3CL + 51EO

[0830] D: 3CL + 78EO + 3CL

[0831] E: 1.5CL + 34EO + 1.5CL

[0832] F: 5CL + 61EO + 5CL

[0833] G: 1.5CL + 61EO + 1.5CL

[0834] H: 23EO + 4CL + Neopentyl glycol + 4CL + 23EO

[0835] I: 20EO / 2PO + 4CL + Neopentyl glycol + 4CL + 20EO / 2PO

[0836] J: 20EO + 1CL + Neopentyl glycol + 1CL + 20EO

[0837] K: [Random-(3-caprolactone + 35EO)] + 9EO + [Random-(3-caprolactone + 35EO)]

[0838] General Synthesis Method of Main Chains A, C, H, I, and J (Table 5):

[0839] Caprolactone is oligomerized prior to the polymerization of the alkylene oxide to form a mixed random / block structure, and the main chain is obtained by the alkoxylation reaction of the polycaprolactone.

[0840] Such polycaprolactones can be obtained by polymerizing caprolactone onto a starter having 2 hydroxy groups, such as a diol, such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, ethylene oxide and propylene oxide block copolymers, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.

[0841] The polymerization reaction of caprolactone is carried out in the presence of various catalysts, such as the transesterification catalyst tin(II) alkanoate.

[0842] The alkoxylation reaction of such polycaprolactones is carried out under typical alkoxylation conditions. Since alkoxylation needs to be carried out under basic reaction conditions, transesterification may occur at the ester bond in the polycaprolactone, thereby obtaining a mixed random / block structure.

[0843] Table 5.

[0844]

[0845] *The molecular weights given are weights calculated based on the total molar amounts of the components used in the preparation reactions. Since these reactions proceed substantially to completion, this is an acceptable way to calculate the molecular weights

[0846] General Synthesis Method of Main Chains B, D, E, F, and G (Table 6):

[0847] Caprolactone is added after the alkylene oxide polymerization to form a block structure, namely polycaprolactone - polyalkylene oxide - polycaprolactone.

[0848] A triblock copolymer having an intermediate polyalkylene oxide block, with caprolactone and alkylene oxide as raw materials, and its synthesis method includes: 1. reacting a diol or water with an alkylene oxide to form a polyalkoxylate; and 2. polymerizing and grafting caprolactone onto the polyalkoxylate.

[0849] These two reactions can be carried out respectively under the typical reaction conditions of alkoxylation reaction (to form polyalkoxylate) and the typical reaction conditions of caprolactone polymerization (to form polycaprolactone block).

[0850] Table 6.

[0851]

[0852] *The molecular weights given are weights calculated based on the total molar amounts of the components used in the preparation reactions. Since these reactions proceed substantially to completion, this is an acceptable way to calculate the molecular weights

[0853] General Synthesis Concept of Main Chain K:

[0854] React a suitable starting material with a premixed combination of alkylene oxide and caprolactone.

[0855]

[0856] *The molecular weights given are weights calculated based on the total molar amounts of the components used in the preparation reactions. Since these reactions proceed substantially to completion, this is an acceptable way to calculate the molecular weights

[0857] Synthesis of Graft Polymers 1 - 21 of the Present Invention:

[0858] Based on the main chain A - K, the following graft polymers 1 - 21 of the present invention are synthesized (Table 7).

[0859] Table 7.

[0860]

[0861] Note:

[0862] VAc = vinyl acetate; VL = vinyl laurate; VP = vinyl pyrrolidone;

[0863] *The molecular weights given are weights calculated based on the total molar amount of the components used in the preparation reactions. Since those reactions proceed essentially to completion, this is an acceptable way to calculate the molecular weights.

[0864] **Partial hydrolysis: Degree of hydrolysis is 40 mol% based on total VAc.

[0865] Additional exemplary graft polymer embodiments, namely Embodiments 22 and 23 of the present invention, are listed below:

[0866]

[0867] *The molecular weights given are weights calculated based on the total molar amount of the components used in the preparation reactions. Since those reactions proceed essentially to completion, this is an acceptable way to calculate the molecular weights.

[0868] Example 1 (Invention 1)

[0869] Example 1a: Polyethylene glycol (molecular weight 400 g / mol), modified with 6 moles of caprolactone

[0870] 240.0 g of polyethylene glycol (molecular weight 400 g / mol) and 0.75 g of tin(II) ethylhexanoate were added to a four-necked reaction flask equipped with a thermometer, reflux condenser, nitrogen inlet, dropping funnel, and stirrer, and heated to 100 °C.

[0871] 415.0 g of ε-caprolactone was added within 15 minutes. The reaction mixture was heated to 160 °C and stirred at this temperature under a nitrogen atmosphere for 14 hours. After cooling to room temperature, 645.0 g of an orange oil was obtained. 1H-NMR in MeOD 1 indicated 99.5% conversion of caprolactone.

[0872] Example 1b (Main Chain A): Polyethylene glycol (molecular weight 400 g / mol), modified with 6 moles of caprolactone and ethoxylated with 70 moles of ethylene oxide Example 1c (Graft Polymer)

[0873] 271.2 g of polyethylene glycol (molecular weight 400 g / mol) modified with 6 moles of caprolactone (Example 1a) and 2.1 g of potassium tert-butoxide were added to a 2 L autoclave, and then the mixture was heated to 80 °C. The vessel was purged with nitrogen three times and the mixture was heated to 140 °C. 770.9 g of ethylene oxide was added within 14 hours. To complete the reaction, the mixture was reacted at 140 °C for an additional 5 hours. The reaction mixture was stripped with nitrogen, and volatile compounds were removed under vacuum at 80 °C. After filtration, 1041.0 g of a light brown solid was obtained. 1H-NMR in CDCl3 confirmed the expected structure.

[0874] Example 2 (Invention 2)

[0875] In a polymerization reactor equipped with a stirrer and a reflux condenser, the main chain A (455.00 g) was first charged under a nitrogen atmosphere, and then heated to 90 °C. Feed 1 (a solution of 2.81 g of tert-butyl peroxy-2-ethylhexanoate in 24.76 g of tripropylene glycol) and Feed 2 (245.00 g of vinyl acetate) were metered into the stirred reactor according to the following procedure: First, Feed 1 was started with a variable feed rate (0 h 0 min to 0 h 10 min: 9.20 g / h; 0 h 10 min to 6 h 10 min: 4.34 g / h). Ten minutes after the start of Feed 1, Feed 2 was started, and Feed 2 maintained a constant feed rate (0 h 10 min to 6 h 10 min: 40.8 g / h). After Feed 1 and Feed 2 were completed, Feed 3 (a solution of 1.79 g of tert-butyl peroxy-2-ethylhexanoate in 15.72 g of tripropylene glycol) was metered in at a constant feed rate at 90 °C within 0 h 56 min. After the feeding was completed, the mixture was continuously stirred at 90 °C for 1 h. The polymerization mixture was heated to 95 °C, and a vacuum of 500 mbar was applied to remove volatile substances. The yield of the polymer solution was 745 g.

[0876] Example 3 (Invention 3)

[0877] In a polymerization reactor equipped with a stirrer and a reflux condenser, the main chain A (450.00 g) was first charged under a nitrogen atmosphere, and then heated to 90 °C. Feed 1 (a solution of 10.08 g of tert-butyl peroxy-2-ethylhexanoate in 36.89 g of tripropylene glycol) and Feed 2 (450.50 g of vinyl acetate) were metered into the stirred reactor according to the following procedure: First, Feed 1 was started with a variable feed rate (0 h 0 min to 0 h 10 min: 15.7 g / h; 0 h 10 min to 6 h 10 min: 7.39 g / h). Ten minutes after the start of Feed 1, Feed 2 was started, and Feed 2 maintained a constant feed rate (0 h 10 min to 6 h 10 min: 75.0 g / h). After Feed 1 and Feed 2 were completed, Feed 3 (a solution of 3.19 g of tert-butyl peroxy-2-ethylhexanoate in 11.66 g of tripropylene glycol) was metered in at a constant feed rate at 90 °C within 0 h 56 min. After the feeding was completed, the mixture was continuously stirred at 90 °C for 1 h. The polymerization mixture was heated to 95 °C, and a vacuum of 500 mbar was applied to remove volatile substances. The yield of the polymer solution was 961 g.

[0878] Example 3a (Main Chain C): Polyethylene glycol (molecular weight 400 g / mol), modified with 6 moles of caprolactone and ethoxylated with 102.2 moles of ethylene oxide

[0879] Example 3b (Graft Polymer): Example 4 (Invention 4)

[0880] 192.9 g of polyethylene glycol modified with 6 moles of caprolactone (molecular weight 400 g / mol) (Example 1a) and 2.0 g of potassium tert-butoxide were added to a 2 L autoclave, and the mixture was then heated to 80 °C. The vessel was purged with nitrogen three times and the mixture was heated to 140 °C. 801.8 g of ethylene oxide was added over 14 hours. To complete the reaction, the mixture was reacted for an additional 5 hours at 140 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. After filtration, 990.0 g of a light brown solid was obtained. 1H-NMR in CDCl3 confirmed the expected structure.

[0881] Example 5 (Invention 5)

[0882] In a polymerization reactor equipped with a stirrer and a reflux condenser, main chain C (455.00 g) was first charged under a nitrogen atmosphere and then heated to 90 °C. Feed 1 (a solution of 2.81 g of tert-butyl peroxy-2-ethylhexanoate in 24.76 g of tripropylene glycol) and Feed 2 (245.00 g of vinyl acetate) were metered into the stirred reactor according to the following procedure: First, Feed 1 was started with a variable feed rate (0 h 0 min to 0 h 10 min: 9.20 g / h; 0 h 10 min to 6 h 10 min: 4.34 g / h). Feed 2 was started 10 minutes after Feed 1 was started and Feed 2 maintained a constant feed rate (0 h 10 min to 6 h 10 min: 40.8 g / h). After Feed 1 and Feed 2 were completed, Feed 3 (a solution of 1.79 g of tert-butyl peroxy-2-ethylhexanoate in 15.72 g of tripropylene glycol) was metered in at a constant feed rate at 90 °C within 0 h 56 min. After the addition was complete, the mixture was stirred continuously at 90 °C for 1 hour. The polymerization mixture was heated to 95 °C and 500 mbar of vacuum was applied to remove volatile substances. The yield of the polymer solution was 745 g.

[0883] Example 5a: Polyethylene glycol (molecular weight 1500 g / mol), ethoxylated with 44 moles of ethylene oxide

[0884] In a polymerization reactor equipped with a stirrer and a reflux condenser, under a nitrogen atmosphere, first load the main chain C (400.00 g), and then heat it to 90 °C. Feed 1 (a solution of 7.24 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 31.90 g of tripropylene glycol) and Feed 2 (600.00 g of vinyl acetate) are metered into the stirred reactor according to the following procedure: First, start Feed 1, which uses a variable feed rate (0:00 to 0:10: 13.1 g / h; 0:10 to 6:10: 5.13 g / h). After Feed 1 starts for 10 minutes, start Feed 2, and Feed 2 maintains a constant feed rate (0:10 to 6:10: 83.4 g / h). After Feed 1 and Feed 2 are completed, Feed 3 (a solution of 4.80 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 21.12 g of tripropylene glycol) is metered in at a constant feed rate at 90 °C within 0:56. After the feeding is completed, the mixture is continuously stirred at 90 °C for 1 hour. The polymerization mixture is heated to 95 °C, and a vacuum of 500 mbar is applied to remove volatile substances. The yield of the polymer solution is 1065 g.

[0885] Example 5b (Main Chain D): Polyethylene glycol (molecular weight 1500 g / mol), ethoxylated with 44 moles of ethylene oxide and modified with 6 moles of caprolactone

[0886] Example 5c (Graft Polymer)

[0887] Add 599.9 g of polyethylene glycol (molecular weight 1500 g / mol) and 2.7 g of potassium tert-butoxide to a 2-liter autoclave, and then heat the mixture to 80 °C. Purge the vessel three times with nitrogen and heat the mixture to 140 °C. Add 754.2 g of ethylene oxide within 14 hours. To complete the reaction, allow the mixture to react for an additional 5 hours at 140 °C. Strip the reaction mixture with nitrogen and remove volatile compounds under vacuum at 80 °C. After filtration, 1350.0 g of a light brown solid is obtained. 1H-NMR in CDCl3 confirmed the expected structure.

[0888] Example 6 (Invention 6) Example 7 (Invention 7)

[0889] Add 1044.1 g of polyethylene glycol (molecular weight 1500 g / mol) ethoxylated with 44 moles of ethylene oxide (Example 5a) and 1.25 g of tin(II) ethylhexanoate to a four-necked reactor equipped with a thermometer, a reflux condenser, a nitrogen inlet, a dropping funnel, and a stirrer, and heat to 90 °C.

[0890] Add 205.5 g of ε-caprolactone within 15 minutes. Heat the reaction mixture to 160 °C and continuously stir at this temperature under a nitrogen atmosphere for 10 hours. After cooling to room temperature, 1236.0 g of an orange oil is obtained. In CDCl3 11H-NMR indicated that the conversion rate of caprolactone reached 98.8%.

[0891] Example 7a (Main Chain E): Polyethylene glycol (molecular weight 1500 g / mol), modified with 3 moles of caprolactone

[0892] In a polymerization reactor equipped with a stirrer and a reflux condenser, under a nitrogen atmosphere, the main chain D (455.00 g) was first charged, and then heated to 90 °C. Feed 1 (a solution of 2.81 g of tert-butyl peroxy-2-ethylhexanoate in 24.76 g of tripropylene glycol) and Feed 2 (245.00 g of vinyl acetate) were metered into the stirred reactor according to the following procedure: First, Feed 1 was started with a variable feed rate (0 h 0 min to 0 h 10 min: 9.20 g / h; 0 h 10 min to 6 h 10 min: 4.34 g / h). Ten minutes after the start of Feed 1, Feed 2 was started, and Feed 2 maintained a constant feed rate (0 h 10 min to 6 h 10 min: 40.8 g / h). After Feed 1 and Feed 2 were completed, Feed 3 (a solution of 1.79 g of tert-butyl peroxy-2-ethylhexanoate in 15.72 g of tripropylene glycol) was metered in at a constant feed rate at 90 °C within 0 h 56 min. After the addition was completed, the mixture was continuously stirred at 90 °C for 1 h. The polymerization mixture was heated to 95 °C, and a vacuum of 500 mbar was applied to remove volatile substances. The yield of the polymer solution was 745 g.

[0893] Example 7b (Graft Polymer)

[0894] In a polymerization reactor equipped with a stirrer and a reflux condenser, under a nitrogen atmosphere, the main chain D (679.00 g) was first charged, and then heated to 90 °C. Feed 1 (a solution of 10.87 g of tert-butyl peroxy-2-ethylhexanoate in 39.76 g of tripropylene glycol) and Feed 2 (a mixture of 242.50 g of vinyl acetate and 48.50 g of vinyl laurate) were metered into the stirred reactor according to the following procedure: First, Feed 1 was started with a variable feed rate (0 h 0 min to 0 h 10 min: 16.9 g / h; 0 h 10 min to 6 h 10 min: 7.97 g / h). Ten minutes after the start of Feed 1, Feed 2 was started, and Feed 2 maintained a constant feed rate (0 h 10 min to 6 h 10 min: 48.5 g / h). After Feed 1 and Feed 2 were completed, Feed 3 (a solution of 3.43 g of tert-butyl peroxy-2-ethylhexanoate in 12.56 g of tripropylene glycol) was metered in at a constant feed rate at 90 °C within 0 h 56 min. After the addition was completed, the mixture was continuously stirred at 90 °C for 1 h. The polymerization mixture was heated to 95 °C, and a vacuum of 500 mbar was applied to remove volatile substances. The yield of the polymer solution was 1036 g.

[0895] Example 8 (Invention 8)

[0896] Example 8a: Polyethylene glycol (molecular weight 600 g / mol), ethoxylated with 47.2 moles of ethylene oxide

[0897] 480.0 g of polyethylene glycol (molecular weight 1500 g / mol) and 0.6 g of tin(II) 2-ethylhexanoate were added to a four-necked reaction flask equipped with a thermometer, a reflux condenser, a nitrogen inlet, a dropping funnel and a stirrer, and heated to 80 °C.

[0898] 109.6 g of ε-caprolactone was added within 5 minutes. The reaction mixture was heated to 160 °C and continuously stirred at this temperature for 10 hours under a nitrogen atmosphere. After cooling to room temperature, 580.0 g of an orange oil was obtained. 1 1H-NMR in CDCl3 indicated that the conversion of caprolactone reached 96.7%.

[0899] Example 8b (Main Chain F): Polyethylene glycol (molecular weight 600 g / mol), ethoxylated with 47.2 moles of ethylene oxide and modified with 10 moles of caprolactone

[0900] In a polymerization reactor equipped with a stirrer and a reflux condenser, under a nitrogen atmosphere, the main chain E (540.00 g) was first charged and then heated to 90 °C. Feed 1 (a solution of 7.56 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 27.67 g of tripropylene glycol) and Feed 2 (135.00 g of vinyl acetate) were metered into the stirred reactor according to the following procedure: First, Feed 1 was started with a variable feed rate (0 h 0 min to 0 h 10 min: 11.8 g / h; 0 h 10 min to 6 h 10 min: 5.55 g / h). Feed 2 was started 10 minutes after Feed 1 was started, and Feed 2 maintained a constant feed rate (0 h 10 min to 6 h 10 min: 22.5 g / h). After Feed 1 and Feed 2 were completed, Feed 3 (a solution of 2.39 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 8.74 g of tripropylene glycol) was metered in at a constant feed rate at 90 °C within 0 h 56 min. After the feeding was completed, the mixture was continuously stirred at 90 °C for 1 hour. The polymerization mixture was heated to 95 °C and a vacuum of 500 mbar was applied to remove volatile substances. The yield of the polymer solution was 721 g.

[0901] Example 8c (Graft Polymer)

[0902] Example 9 (Invention 9)

[0903] 222.5 g of polyethylene glycol (molecular weight 600 g / mol) and 2.0 g of potassium tert-butoxide were added to a 2 L autoclave, and then the mixture was heated to 80 °C. The vessel was purged with nitrogen three times and the mixture was heated to 130 °C. 770.0 g of ethylene oxide was added over 10 hours. To complete the reaction, the mixture was reacted at 140 °C for an additional 5 hours. The reaction mixture was stripped with nitrogen, and volatile compounds were removed under vacuum at 80 °C. After filtration, 990.0 g of a light brown solid (hydroxyl value: 45.8 mg KOH / g) was obtained.

[0904] Example 10 (Invention 10) ​

[0905] 617.9 g of polyethylene glycol (molecular weight 600 g / mol) ethoxylated with 47.2 moles of ethylene oxide (Example 8a) and 0.9 g of tin(II) ethylhexanoate were added to a four-necked reactor equipped with a thermometer, reflux condenser, nitrogen inlet, dropping funnel, and stirrer, and heated to 80 °C.

[0906] 288.8 g of ε-caprolactone was added over 15 minutes. The reaction mixture was heated to 160 °C and stirred continuously at this temperature under a nitrogen atmosphere for 12 hours. After cooling to room temperature, 900.0 g of an orange oil was obtained. 1 1H-NMR in CDCl3 indicated that the conversion of caprolactone reached 99.0%.

[0907] ​

[0908] In a polymerization reactor equipped with a stirrer and a reflux condenser, the main chain F (397.29 g) was first charged under a nitrogen atmosphere and then heated to 90 °C. Feed 1 (a solution of 3.16 g of tert-butyl peroxy-2-ethylhexanoate in 35.56 g of 1,2-propanediol), Feed 2 (238.37 g of vinyl acetate), and Feed 3 (158.92 g of N-vinylpyrrolidone) were metered into the stirred reactor according to the following procedure: First, Feed 1 was started with a variable feed rate (0 h 0 min to 0 h 10 min: 12.9 g / h; 0 h 10 min to 6 h 10 min: 6.09 g / h). Ten minutes after the start of Feed 1, Feed 2 and Feed 3 were started simultaneously, and Feed 2 and Feed 3 maintained a constant feed rate (Feed 2, 0 h 10 min to 6 h 10 min: 39.7 g / h; Feed 3, 0 h 10 min to 6 h 10 min: 26.5 g / h). After Feed 1, Feed 2, and Feed 3 were completed, Feed 4 (a solution of 2.03 g of tert-butyl peroxy-2-ethylhexanoate in 22.80 g of 1,2-propanediol) was metered in at a constant feed rate at 90 °C within 0 h 56 min. After the feeding was completed, the mixture was continuously stirred at 90 °C for 1 h. The polymerization mixture was heated to 95 °C, and a vacuum of 500 mbar was applied to remove volatile substances. The yield of the polymer solution was 721 g.

[0909] ​

[0910] In a polymerization reactor equipped with a stirrer and a reflux condenser, the main chain F (50.00 g) was first charged under a nitrogen atmosphere and then heated to 90 °C. Feed 1 (a solution of 1.12 g of tert-butyl peroxy-2-ethylhexanoate in 4.10 g of tripropylene glycol) and Feed 2 (50.00 g of vinyl acetate) were metered into the stirred reactor according to the following procedure: First, Feed 1 was started with a variable feed rate (0 h 0 min to 0 h 10 min: 1.74 g / h; 0 h 10 min to 6 h 10 min: 0.82 g / h). Ten minutes after the start of Feed 1, Feed 2 was started, and Feed 2 maintained a constant feed rate (0 h 10 min to 6 h 10 min: 8.33 g / h). After Feed 1 and Feed 2 were completed, Feed 3 (a solution of 0.35 g of tert-butyl peroxy-2-ethylhexanoate in 1.30 g of tripropylene glycol) was metered in at a constant feed rate at 90 °C within 0 h 56 min. After the feeding was completed, the mixture was continuously stirred at 90 °C for 1 h. The polymerization mixture was heated to 95 °C, and a vacuum of 500 mbar was applied to remove volatile substances. The yield of the polymer solution was 107 g

[0911] ​

[0912] Example 10a:

[0913] Polyethylene glycol (molecular weight 600 g / mol), ethoxylated with 47.2 moles of ethylene oxide and modified with 3 moles of caprolactone (main chain G). In a four-necked reaction flask equipped with a thermometer, reflux condenser, nitrogen inlet, dropping funnel, and stirrer, 669.8 g of polyethylene glycol (molecular weight 600 g / mol) ethoxylated with 47.2 moles of ethylene oxide (Example 8a) and 0.8 g of tin(II) ethylhexanoate were added and heated to 80 °C.

[0914] 85.6 g of ε-caprolactone was added within 15 minutes. The reaction mixture was heated to 160 °C and continuously stirred at this temperature for 12 hours under a nitrogen atmosphere. After cooling to room temperature, 746.0 g of an orange solid was obtained. The 1 1H-NMR in CDCl3 indicated that the conversion of caprolactone reached 98.0%.

[0915] Example 10b (graft polymer)

[0916] In a polymerization reactor equipped with a stirrer and a reflux condenser, under a nitrogen atmosphere, the main chain G (75.00 g) was first charged and then heated to 90 °C. Feed 1 (a solution of 1.68 g of tert-butyl peroxy-2-ethylhexanoate in 6.15 g of tripropylene glycol) and Feed 2 (75.00 g of vinyl acetate) were metered into the stirred reactor according to the following procedure: First, Feed 1 was started with a variable feed rate (0 h 0 min to 0 h 10 min: 2.61 g / h; 0 h 10 min to 6 h 10 min: 1.23 g / h). Feed 2 was started 10 minutes after Feed 1 was started and maintained a constant feed rate (0 h 10 min to 6 h 10 min: 12.50 g / h). After Feed 1 and Feed 2 were completed, Feed 3 (a solution of 0.53 g of tert-butyl peroxy-2-ethylhexanoate in 1.94 g of tripropylene glycol) was metered in at a constant feed rate at 90 °C within 0 h 56 min. After the feeding was completed, the mixture was continuously stirred at 90 °C for 1 hour. The polymerization mixture was heated to 95 °C and a vacuum of 500 mbar was applied to remove volatile substances. The yield of the polymer solution was 160 g.

[0917] Example 11 (invention 11)

[0918] In a polymerization reactor equipped with a stirrer and a reflux condenser, the main chain G (97.50 g) was first charged under a nitrogen atmosphere and then heated to 90 °C. Feed 1 (a solution of 0.60 g of tert-butyl pe...

Claims

1. A fabric and home care composition comprising: (i) A graft polymer; and (ii) One or more fabric and home care ingredients, wherein the graft polymer consists of: (A) 20% to 95%, preferably 30% to 90%, more preferably 40% to 85%, most preferably 50% to 80% of a polymer backbone that serves as a graft substrate, which contains at least one subunit (a1) and at least one subunit (a2), where (a1) is a unit containing the following moiety, preferably consisting essentially of the following moiety: A moiety derived from at least one alkylene oxide monomer and / or at least one polyalkylene oxide polymer having two hydroxy end groups, said alkylene oxide monomer being selected from the group consisting of C2 to C 10 alkylene oxides, preferably C2 to C5 alkylene oxides, (a2) is a unit containing the following moiety, preferably consisting of the following moiety: at least one lactone and / or at least one hydroxy acid, such a subunit (a2) is a moiety derived from a single lactone and / or hydroxy acid, or an oligomeric or polymeric unit composed of at least one type of lactone and / or at least one type of hydroxy acid, wherein preferably, the at least one lactone and / or hydroxy acid is selected from group (i) and / or group (ii), where (i) Lactones, i.e., cyclic esters, starting from α-lactones (three ring atoms), followed by β-lactones (four ring atoms), γ-lactones (five ring atoms), and so on; such lactones are preferably β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, ε-caprolactone, δ-decalactone, γ-decalactone, ε-decalactone; preferably caprolactone; and (ii) Hydroxy acids that can be derived by hydrolysis from any lactone, particularly from any lactone within group (i) above, specifically α-hydroxy acids, β-hydroxy acids, or γ-hydroxy acids derived by hydrolysis from the corresponding lactones, as well as lactic acid, glycolic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 12-hydroxystearic acid, citric acid; preferably lactic acid or caprolactone, more preferably caprolactone, wherein the polymer backbone is obtained by: (A1) Copolymrizing at least one subunit (a1) with at least one subunit (a2), where in the copolymerization of at least one subunit (a1) and at least one subunit (a2), optionally at least one oligomer or polymer prepared from at least one subunit (a1) or at least one subunit (a2) can also be used; (A2) First oligomerizing / polymerizing the subunit (a2), and then polymerizing the product with the subunit (a1); or (A3) First oligomerizing / polymerizing the subunit (a1), and then copolymerizing the product with the subunit (a2); (A4) First, provide an oligomeric or polymeric subunit (a1) with a capping group on one side. The subunit is preferably etherified with an alcohol, more preferably etherified with a C1 - C4 short - chain alcohol. The subunit then reacts as a starting block with at least one subunit (a2) and / or at least one subunit (a1), where the subunit (a1) can be different from the subunit (a1) in the starting block or can be arranged in a different order compared to the subunit (a1) in the starting block, to attach a new block containing a portion of the subunits used in the (co)polymerization reaction to the uncapped side of the starting block, thereby obtaining a diblock structure, i.e., [capping group]-[subunit (a1)]-[subunit (a2)] or [capping group]-[subunit (a1)]-[random - {subunit (a2)-subunit (a1)}]; where in the case where more than one subunit (a1) and / or more than one subunit (a2) already exist in the oligomer or polymer used, these subunits can be arranged in any order within this used oligomer or polymer, and where in the case where more than one subunit (a1) and / or more than one subunit (a2) are used for the polymerization reaction, these subunits (and any optional oligomers / polymers if used) can be arranged in any order within the obtained main chain; and (B) 5% to 80%, preferably 10% to 70%, more preferably 15% to 60%, most preferably 20% to 50% of polymer side chains (B) grafted onto the polymer backbone (A), where the polymer side chains (B) can be obtained by the (co)polymerization reaction of: at least one vinyl ester monomer (B1), optionally vinyl pyrrolidone as monomer (B2), optionally other monomers (B3), and optionally other monomers, where all percentages are expressed as weight percentages based on the total weight of the graft polymer.

2. A fabric and household care composition, comprising: (i) A graft polymer; and (ii) One or more fabric and household care ingredients, where the graft polymer consists of: (A) 20% to 95%, preferably 30% to 90%, more preferably 40% to 85%, most preferably 50% to 80% of a polymer backbone, which serves as a grafting substrate, which contains at least one subunit (a1) and at least one subunit (a2), where (a1) is a unit containing the following part, preferably consisting essentially of the following part: A moiety derived from at least one alkylene oxide monomer and / or at least one polyalkylene oxide polymer having two hydroxy end groups, the alkylene oxide monomer being selected from the group consisting of C2 to C 10 alkylene oxides, preferably C2 to C5 alkylene oxides, (a2) is a unit containing the following part, preferably consisting of: at least one lactone and / or at least one hydroxy acid. Such a subunit (a2) is a part derived from a single lactone and / or hydroxy acid, or is an oligomeric or polymeric unit composed of at least one type of lactone and / or at least one type of hydroxy acid, where preferably, the at least one lactone and / or hydroxy acid is selected from group i) and / or group ii), where i) Lactones, i.e., cyclic esters, starting from α-lactones (three ring atoms), followed by β-lactones (four ring atoms), γ-lactones (five ring atoms), and so on; such lactones are preferably β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, ε-caprolactone, δ-decalactone, γ-decalactone, ε-decalactone; preferably caprolactone; and ii) Hydroxy acids, which can be derived by hydrolysis from any lactone, particularly from any lactone within group i) above, specifically α-hydroxy acids, β-hydroxy acids or γ-hydroxy acids derived by hydrolysis from the corresponding lactone, as well as lactic acid, glycolic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 12-hydroxystearic acid, citric acid; preferably lactic acid or caprolactone, more preferably caprolactone, wherein the polymer backbone is selected from (A1) A backbone composed of monomeric, oligomeric and / or polymeric (a1) subunits and monomeric, oligomeric and / or polymeric (a2) subunits in a random arrangement order, where there is more than one subunit (a1) and / or more than one subunit (a2); (A2) A backbone composed of oligomeric or polymeric subunit (a2) as an inner block and two oligomeric and / or polymeric (a1) subunit outer blocks, defined as "-[(a1) block]-[(a2) block]-[(a1) block]-", and may also include higher-order block polymers such as pentablock, heptablock, nonablock, etc., where (a1) and (a2) blocks are further connected outside the triblock structure, such as the pentablock structure "[(a1) block]-[(a2) block]-[(a1) block]-[(a2) block]-[(a1) block]-[(a2) block]-[(a1) block]"; and (A3) A backbone composed of oligomeric and / or polymeric (a1) subunit inner block and two oligomeric or polymeric subunit (a2) outer blocks, in the form of at least a triblock polymer, defined as "-[(a2) block]-[(a1) block]-[(a2) block]-", (A4) A backbone composed of a first block, One end thereof has a capping group - such a capping group is a C1 to C 18 alkyl group attached to the first block via an ether functional group, preferably a C1 to C4 alkyl group; and bearing oligomeric or polymeric subunit (a1); and a second block, which is attached to the first block at the opposite end of the first block via an ether or ester functional group ("opposite" is relative to the capping group of the first block), the second block being composed of at least one subunit (a2) and optionally at least one subunit (a1), wherein the optional subunit (a1) in the second block can be different from the subunit (a1) in the first block, or can be arranged in a different order compared to the subunit (a1) in the first block, and the subunits (A1) and (a2) can also be arranged in any order, including a random structure, This diblock structure has the following idealized structure when only using subunit (a2): [capping group]-[subunit (a1)]-[subunit (a2)] Or when using subunits (a1) and (a2): [End group]-[Subunit (a1)]-[Random-{Subunit (a2)-Subunit (a1)}]; and (B) 5% to 80%, preferably 10% to 70%, more preferably 15% to 60%, most preferably 20% to 50% of polymer side chains (B) grafted onto the polymer backbone (A), where the polymer side chains (B) can be obtained by the (co)polymerization reaction of: at least one vinyl ester monomer (B1), optionally vinyl pyrrolidone as monomer (B2), optionally other monomers (B3), and optionally other monomers, where all percentages are expressed as weight percentages based on the total weight of the graft polymer.

3. The composition according to claim 1, wherein at least two different alkylene oxides are used to prepare the backbone / present in the backbone.

4. The composition according to any one or more of claims 1 to 3, wherein the monomers are: (B1) at least one vinyl ester selected from vinyl acetate, vinyl propionate, and / or vinyl laurate, and any other vinyl esters known to those skilled in the art, such as vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl decanoate, and / or vinyl benzoate; Optionally (B2) N-vinyl pyrrolidone; Optionally (B3) at least one other monomer, such as 1-vinyl oxazolidinone and other vinyl oxazolidinones, 4-vinyl pyridine-N-oxide, N-vinyl formamide and the amine formed by its hydrolysis after polymerization, N-vinyl acetamide, N-vinyl-N-methyl acetamide, any one or more of (meth)acrylic acid alkyl esters; and Optionally at least one other monomer different from the foregoing monomers, and this other monomer is present in an amount of less than 2% in the total amount of monomers used to obtain the polymer side chains (B), and is preferably present only as an impurity and not deliberately added for the polymerization reaction.

5. The composition according to any one or more of claims 1 to 4, wherein the amounts of the following items are - if (B2) is present - (B) is 10% to 60%, preferably at most 50%, more preferably at most 40%, and preferably at least 20%; (B1) vinyl ester is 9% to 55% by weight based on the total weight of the graft polymer, preferably at most 50%, more preferably at most 40%, even more preferably at most 35%, and even more preferably at most 30%; (B2) vinyl pyrrolidone is 1% to 20% by weight based on the total weight of the graft polymer, more preferably at most 15%, such as 1% to 15%, more preferably 5% to 15%, and further such as at most 10%, at most 19%, 18%, 17%, 16%, 14%, 13%, 12%, 11%, and each value between 1% and 20%, where preferably, the amount of (B2) is not higher than the amount of (B1) and - if (B2) is not present - (B) is from 5% to 60%, preferably at most 50%, and preferably at least 20%; (B1) The vinyl ester, based on the total weight of the graft polymer, is the weight percentage of the total amount of (B) minus the total amount of (B3). (B2) Vinyl pyrrolidone is 0%. And it is further stipulated that in all the foregoing cases (B3) (other monomers) is from 0% to 10%, preferably at most 2%, more preferably at most 1%, even more preferably about 0%, but in all cases at most 10% of the amount of (B1), and does not exceed the amount of (B2).

6. The composition according to one or more of claims 1 to 5, wherein At least 10% by weight of the total amount of the vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably selected from vinyl acetate and vinyl laurate, and most preferably is vinyl acetate, and the remaining amount of the vinyl ester can be any other known vinyl ester, wherein preferably at least 80% by weight, more preferably at least 90% by weight and most preferably substantially only vinyl acetate is used as the vinyl ester (weight percentage based on the total weight of the vinyl ester monomer B1 used).

7. The composition according to one or more of claims 1 to 6, wherein (A) The polyalkoxylate-ester main chain contains moieties derived from the following (i) alkylene oxide (AO), which contains at least one of ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO), preferably contains at least one of EO and PO, The amount of the AO is from 40% to 99% by weight, preferably at most 90% by weight, preferably at least 50% by weight, more preferably at least 60% by weight, and even more preferably at least 70% by weight, and any value and range between the above values, each based on the total weight of the main chain, Based on the total AO, the amount of EO is from 0% to 100% by weight, preferably at least 10% by weight, more preferably at least 20% by weight, even more preferably at least 30% by weight, even more preferably at least 40% by weight, such as at least 50% by weight, 60% by weight, 70% by weight, 80% by weight or even at least 90% by weight, The total amount of PO and / or BO is respectively from 0% to 100% by weight, preferably at most 90% by weight, more preferably at most 80% by weight, even more preferably at most 70% by weight, even more preferably at most 60% by weight, and most preferably at most 50% by weight, and any value between the above values, such as at most 5% by weight, 10% by weight, 15% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 55% by weight, 65% by weight, 75% by weight, 85% by weight or at most 95% by weight, and more preferably at least 10% by weight, even more preferably at least 20% by weight, even further more preferably at least 30% by weight, such as at least 40% by weight, 50 wt%, 60 wt%, 70 wt%, 80 wt% or even at least 90 wt%, each based on the total weight of AO, wherein for the sum of PO and BO, the total amount of PO and BO totals 100 wt%, wherein the total amount of AO totals 100 wt%; (ii) lactone / hydroxy acid monomer, in an amount of at least 1 wt% and at most 60 wt%, preferably at most 50 wt%, more preferably at most 40 wt%, most preferably at most 30 wt%, and preferably at least 2 wt%, more preferably at least 3 wt%, even more preferably at least 4 wt% and most preferably at least 5 wt%, each based on the total weight of the main chain, preferably only caprolactone; wherein the total weight of the subunits (a1) and (a2) in the main chain (A) totals 100 wt%.

8. The composition according to claim 7, wherein (i) alkylene oxide (AO) is selected from ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO), preferably only EO and PO, the amount of AO is 40 wt% to 99 wt%, preferably at most 90 wt%, preferably at least 50 wt%, more preferably at least 60 wt%, and even more preferably at least 70 wt%, and any value and range between the above values, each based on the total weight of the main chain, based on total AO, the amount of EO is 10 wt% to 90 wt%, preferably 20 wt% to 80 wt%, more preferably 30 wt% to 70 wt%, and most preferably 40 wt% to 60 wt%, the total amount of PO and BO is 10 wt% to 90 wt%, preferably 20 wt% to 80 wt%, more preferably 30 wt% to 70 wt%, and most preferably 40 wt% to 60 wt%, each based on the total weight of AO, wherein for the sum of PO and BO, the total amount of PO and BO totals 100 wt%, and wherein the total amount of AO totals 100 wt%; (ii) lactone / hydroxy acid monomer, in an amount of at least 1 wt% and at most 60 wt%, preferably at most 40 wt%, more preferably at most 30 wt%, even more preferably at most 25 wt%, even further more preferably at most 20 wt%, most preferably at most 15 wt%, and preferably at least 2 wt%, more preferably at least 3 wt%, even more preferably at least 4 wt and most preferably at least 5 wt%, each based on the total weight of the main chain, preferably only caprolactone; wherein the total weight of the subunits (a1) and (a2) in the main chain (A) totals 100 wt%.

9. The composition according to claim 8, wherein alkylene oxide (AO) is selected from ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO), preferably only EO and PO, more preferably only EO, based on total AO, the amount of EO is 20 wt% to 100 wt%, The total amount of PO and BO is from 0 wt% to 80 wt%, preferably at most 50 wt%, more preferably at most 30 wt%, even more preferably at most 20 wt%, even further preferably at most 10 wt%, and most preferably 0 wt%, such as 45 wt%, 45 wt%, 45 wt%, 25 wt%, 15 wt%, 7 wt% and 5 wt%, and any value between the above values, each based on the total weight of AO, wherein for the sum of PO and BO, the total amount of PO and BO totals 100 wt%, wherein the total amount of AO totals 100 wt%; (ii) lactone / hydroxy acid monomers, the amount of which is at least 5 wt% and at most 50 wt%, preferably at most 40 wt%, more preferably at most 35 wt%, even more preferably at most 30 wt%, and the lower limit is preferably at least 7 wt%, more preferably at least 10 wt%, even more preferably at least 12 wt%, most preferably at least 15 wt%, such as 6 wt%, 8 wt%, 9 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt% and 15 wt%, and any value between the above values as the lower limit, and such as 30 wt%, 33 wt%, 37 wt%, 45 wt% and any value between the above values as the upper limit, each based on the total weight of the main chain, preferably only caprolactone; wherein the total weight of the subunits (a1) and (a2) in the main chain (A) totals 100 wt%.

10. The composition according to any one of claims 1 to 9, wherein (B) the monomers are: (B1) at least one vinyl ester selected from vinyl acetate, vinyl propionate and / or vinyl laurate, the amount of which is 70 wt% to 100 wt% of the total weight of the monomers grafted onto the main chain (A), preferably only vinyl acetate, and (B2) optionally N-vinylpyrrolidone, wherein the vinyl ester monomer (B1) is optionally partially or completely hydrolyzed after the polymerization reaction.

11. The composition according to any one of claims 1 to 10, wherein substantially no other monomer (B2) or (B3) is used.

12. The composition according to any one of claims 1 to 11, wherein there are monomers (B1) and (B2), and no other monomers are used.

13. The composition according to any one of claims 1 to 12, wherein the moiety derived from the at least one vinyl ester monomer (B1) is partially or completely hydrolyzed after the polymerization reaction, preferably partially hydrolyzed, based on the total moles of (B1) used, more preferably at most 50 mol%, and preferably at least 20 mol%, more preferably 20 mol% to 50 mol%, even more preferably 30 mol% to 45 mol%, such as about 40 mol%.

14. The composition according to any one of claims 1 to 13, wherein wherein at least one of i), ii) and iii) is satisfied: i) The polymer main chains (A1), (A2), and (A3) can carry two hydroxyl groups as end groups, or can be capped with C1 to C 22 alkyl groups, preferably C1 to C4 alkyl groups; such end groups are attached using standard means after the final preparation of the main chain, and for (A4), this capping treatment is completed on the oligomeric / polymeric subunit (a1) before the polycondensation reaction using the subunit (a2); ii) The polydispersity (PDI) Mw / Mn of the graft polymer is at most 10, preferably at most 5, more preferably at most 3, and most preferably in the range of 1.0 to 2.6; And is any value a as an upper or lower limit, and is any range in between, such as 1.3 to 2.6, 1 to 3, etc. (where Mw = weight-average molecular weight; Mn = number-average molecular weight [g / mol / g / mol]); iii) The biodegradability of the graft polymer is at least 35%, more preferably at least 40%, even more preferably at least 45%, even further more preferably at least 50%, such as 46%, 47%, 48%, 49%, 50%, 55%, 60%, 65%, 70%, 75%, etc., and any value between the above values and up to 100% within 28 days when tested according to OECD 301F.

15. The composition according to any one of claims 1 to 14, wherein the composition is a fabric and home care product, preferably a laundry detergent or a dishwashing composition, Optionally further comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, DNases, xylanases, oxidoreductases, dispersins, mannanases, peroxidases, and combinations of at least two of the foregoing types. Preferably, at least one enzyme is selected from lipases, hydrolases, amylases, proteases, cellulases, Wherein the at least one graft polymer is present in an amount in the range of about 0.01% to about 20%, preferably about 0.05% to 15%, more preferably about 0.1% to about 10%, and most preferably about 0.5% to about 5% based on the total weight of such composition or product, and Such product or composition further comprises a surfactant system in an amount of about 1% to about 70% by weight.

16. The composition according to any one of claims 1 to 15, further comprising an antimicrobial agent selected from the group consisting of 2-phenoxyethanol; preferably comprising the antimicrobial agent in an amount in the range of 2 ppm to 5% by weight of the composition; more preferably comprising 0.1% to 2% by weight of phenoxyethanol.

17. The composition according to any one of claims 1 to 16, comprising 4,4'-dichloro-2-hydroxy diphenyl ether at a concentration of 0.001% to 3% by weight of the composition, preferably 0.002% to 1%, more preferably 0.01% to 0.6%.

18. The composition according to any one of claims 1 to 17, comprising one or more fabric and home care ingredients selected from the group consisting of: surfactant systems, fatty acids and / or their salts, enzyme stabilizers, builders, dispersants, structurants or thickeners, polymers, additional amines, catalytic materials, bleaches, bleach catalysts, bleach activators, polymeric dispersants, soil release / anti-redeposition agents, polymeric grease cleaners, amphiphilic copolymers, optical brighteners, fabric toners, chelating agents, encapsulating agents, fragrances, pre-fragrances, malodor reducing materials, conditioners, probiotics, organic acids, antioxidants, antimicrobial agents and / or preservatives, neutralizing agents and / or pH regulators, processing aids, rheology modifiers, corrosion and / or rust inhibitors, sanitizing agents, pearlescents, pigments, opacifiers, solvents, carriers, hydrotropes, foam suppressants, and mixtures thereof.

19. The composition according to any one of claims 1 to 18, wherein the composition is in the form of a liquid composition, a granular composition, a single-compartment sachet, a multi-compartment sachet, a sheet, a tablet-like granule or bead, a fibrous article, a solid article, a tablet, a block, a flake or a mixture thereof.

20. A method of washing fabrics or cleaning hard surfaces, the method comprising treating the fabrics or hard surfaces with the composition according to any one of the preceding claims.

Images