EP4663732A1

EP4663732A1 - Use of graft polymer in a laundry detergent composition

Info

Publication number: EP4663732A1
Application number: EP24181130.6A
Authority: EP
Inventors: Renae Dianna Fossum; Frank Huelskoetter; Christian Jehn-Rendu; Florian Schoen; Gang SI
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 2024-06-10
Filing date: 2024-06-10
Publication date: 2025-12-17

Abstract

The present invention relates to use of a graft polymer in a laundry detergent composition that additionally comprise a detersive surfactant, to prevent dye transfer during a laundering process.

Description

FIELD OF THE INVENTION

BACKGROUND OF THE INVENTION

Dye transfer can be a problem when consumers laundering dark-coloured items together with light-coloured or white items. Technically, this problem can be minimized by sorting the items by colour and washing them separately. However, some consumers may not prefer the sorting approach because this may mean more time, washes, effort, energy consumption, carbon emission, and cost to complete their laundry. In addition, consumers become increasingly aware of the impact their choices have on the environment, they seek out products that are eco-friendly and have a lower carbon footprint. Therefore, there is a need for new sustainable technologies that can effectively prevent dye transfer during laundry process.
The inventors have surprisingly found that above need can be achieved by the use of a specific graft copolymer with improved biodegradation profile in a laundry detergent composition.

DETAILED DESCRIPTION OF THE INVENTION

Laundry detergent Composition:

Any laundry detergent compositions are suitable. Suitable laundry detergent compositions include laundry detergent powders, laundry beads, laundry detergent liquids, laundry detergent gel, laundry detergent sheets, fibrous articles and water-soluble unit dose laundry detergents.
The composition comprises from 0.01% to 20%, preferably from 0.05% to 15%, more preferably from 0.1% to 10%, and most preferably from 0.5% to 5% of the graft polymer, in relation to the total weight of the laundry detergent composition.
The composition comprises from 1.0% to 70% detersive surfactant. in relation to the total weight of the laundry detergent composition.

The graft polymer:

The graft polymer of the present invention comprises:

(A) a block copolymer backbone as a graft base, wherein said block copolymer backbone (A) comprises from 85% to 100%, by weight of the backbone (A), at least two monomers selected from the group of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, and 2,3-pentene oxide; and,
(B) polymeric sidechains grafted onto the block copolymer backbone, wherein said polymeric sidechains (B) comprises from 85% to 100%, by weight of the sidechains (B), N-vinyl lactam monomer (B 1) and vinyl ester monomer (B2),

For the purposes of this invention, aerobic biodegradation in wastewater according to OECD 301F is expressed as a percentage of the theoretical oxygen demand (ThOD, which is measured by the elemental analysis of the compound of interest), which is needed to completely biodegrade the compound sample. Thus, the amount of oxygen taken up by the microbial population during biodegradation of the test substance (corrected for uptake by blank inoculum, run in parallel) is expressed as a percentage of ThOD. The obtained values are preferably measured in triplicate using the OECD 301F manometric respirometry method. The consumption of oxygen is determined by measuring the change in pressure in the apparatus using an OxiTop^® C (Xylem 35 Analytics Germany Sales GmbH & Co KG). Details for the tests performed are given in the experimental section below. The biodegradable polymers of the present invention can be non-biodegradable or biodegradable, preferably biodegradable. The graft polymers that are biodegradable demonstrate at least 30%, preferably at least 40%, preferably at least 45%, more preferably at least 50%, more preferably at least 55%, or most preferably at least 60% biodegradability according to standard OECD 301F at 28 days.
The ratio of the block copolymer backbone (A) versus the polymeric side chains (B) within the graft polymers according to the present invention is not limited to specific values. Preferably, the graft polymer comprises in percentage by weight to the total weight of the graft polymer from 40 to 98%, preferably from 50 to 96%, preferably from 60 to 95%, more preferably from 65 to 90%, more preferably from 70 to 85%, more preferably from 75 to 80%, of block copolymer backbone (A), and from 2 to 60%, preferably from 4 to 50%, preferably from 5 to 40%, preferably from 10 to 35%, preferably from 15 to 30%, more preferably from 20 to 25%, of polymeric sidechains (B).
The graft polymer according to the present invention may have any molecular weight known to a person skilled in the art. However, it is preferred that the graft polymer has a mean molecular weight M_w of from 1,000 to 100,000 g/mol, preferably from 1,200 to 50,000 g/ mol preferably from 1,500 to 10,000 g/mol, preferably from 2,000 to 8,000 g/ mol and more preferably from 2,500 to 6,000 g/mol.
The graft polymers according to the present invention preferably have a low polydispersity. It is preferred that the graft polymer has a polydispersity M_w/M_n of < 3, preferably < 2.5, more preferably < 2.3, and most preferably in the range from 1.0 to 2.2 (with M_w = mean molecular weight and M_n = mean molecular mass $[\frac{g}{mol} / \frac{g}{mol}]$ ). The respective values of M_w and/or M_n can be determined as described within the experimental section below.
The block copolymer backbone (A) comprises from 85% to 100%, by weight of the backbone (A), at least two monomers selected from the group of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, and 2,3-pentene oxide.
It is possible that other monomers may be present in the block copolymer backbone (A). Other monomers can be any types of monomers that can copolymerize with ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, or 2,3-pentene oxide. Other monomers can also be any type of monomers that react with the block copolymer backbone (A). One example of other monomers is end-capping groups that can be attached to one or both end of the block copolymer backbone (A), such as C₁-C₂₅ alkyl groups. If present, the total amount of other monomers is less than 15%, preferably less than 10%, more preferrable less than 5%, more preferrable less than 2%, more preferably less than 1% (by weight of the backbone (A)). However, it is more preferred that other monomers are essentially not present or only present as impurities at trace amount (less than 0.5%).
The block copolymer backbone (A) has a number average molecular weight (Mn) in the range of from 600 to 90,000 g/mol. Preferably, the block copolymer backbone (A) has a number average molecular weight (Mn) of less than 10,000 g/mol, more preferably less than 5,000, more preferably less than 4,000, more preferably less than 3,000 g/mol. Most preferably, the block copolymer backbone (A) has a number average molecular weight in the range of 800 and 2,750, more preferably 1,000 and 2,500, more preferably 1,200 and 2,250, most preferably 1,400 to 2,000, such as 1,500, 1,800, 1,900 g/mol. Without wish to be bonded by any theory, when the block copolymer backbone (A) has a smaller number average molecular weight, the graft polymers are more biodegradable.
A particular preferred type of block copolymer backbone is a block copolymer comprising 2 to 5 blocks, such block being units derived from PEG and PPG. The most preferred block copolymer backbone of this type is selected a di- or triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG). Even more preferably, the block copolymer backbone is a tri-block copolymer polyethylene oxide (PEG) and polypropylene oxide (PPG). Various types of such block copolymer backbones are commercially available, for example under the trademark series "Pluronic" (BASF SE, Ludwigshafen, Germany). Specific examples are Pluronic PE 6100, Pluronic PE 6800 or Pluronic PE 3100, Pluronic RPE 1740. Suitable block copolymer backbones (A) to be employed within the present invention are described, for example, within EPA 0 362 688. Within the present invention, it is preferred that the respective monomer to be employed for preparing the individual blocks of the block copolymer backbone (A) are added in sequence. However, it is possible at the transition of the feed from one monomer to the other to produce so called "dirty structures" wherein at the edge/border of the respective block a small number of monomers of the respective neighboring block may be contained within the individual block to be considered. However, it is preferred that the block copolymer backbones (A) according to the present invention do not contain any so called "dirty structures" or "dirty passages" at the respective border of the blocks.
In one embodiment of the present invention, it is preferred that the block copolymer backbone (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG). Preferably, the triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG) having the structure according to formula (A1) or formula (A2) with formula (A1) is defined as follows: with

n: is an integer in the range of 2 to 100, preferably of 3 to 80, and
m: is an integer in the range of 2 to 100, preferably of 10 to 70, more preferably of 14 to 54, or, formula (A2) is defined as follows:

o: is an integer in the range of 2 to 100, preferably of 5 to 50, more preferably of 8 to 27, and
p: is an integer in the range of 2 to 100, preferably of 5 to 50, more preferably of 7 to 24.

More preferably, the triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG) having the structure according to formula (A2) as defined above.
The block copolymer backbone (A) may either be capped or not capped (uncapped) at the respective endgroups of the backbone. By consequence, within the present invention, it is possible that the block copolymer backbone (A) is optionally capped at one or both endgroups, preferably the block copolymer backbone (A) is not capped at both endgroups or, if the block copolymer backbone (A) is capped, the capping is done by C₁-C₂₅-alkyl groups.
Without wish to be bonded by any theory, the block copolymer backbone (A) enables the graft polymer of this invention to have better biodegradability than graft polymers based on polyalkylene oxide homopolymer backbone, or graft polymers based on random copolymer backbone comprising at least two monomers selected from the group of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, and 2,3-pentene oxide. Particularly, when the molecular weight of the backbones are identical.
The graft polymer comprising polymeric sidechains grafted onto the block copolymer backbone (A), wherein said polymeric sidechains (B) comprises from 85% to 100%, by weight of the sidechains (B), N-vinyl lactam monomer (B1) and vinyl ester monomer (B2)
The N-vinyl lactam monomer (B1) is selected from N-vinyl beta-lactam (four-membered ring), N-vinyl pyrrolidone (five-membered ring), N-vinyl-2-piperidone (six-membered ring), N-vinylcaprolactam (seven-membered ring), and combination thereof. Preferably, (B1) is selected from N-vinylpyrrolidone, N-vinylcaprolactam, and combination thereof. More preferably, (B1) is N-vinylpyrrolidone.
Typically, the polymer comprises, in relation to the total weight of the graft polymer, from 2 to 40%, more preferably from 4 to 35%, more preferably from 6 to 30%, more preferably from 8 to 25%, most preferably in the range of 10 to 20%, such as 12%, 14%, 16%, 18%, by weight of the polymeric sidechains (B 1). Without wish to be bound by any theory, when the graft polymer comprises lower amount of polymeric sidechains (B 1), the graft polymers are more biodegradable; however, when the amount of polymeric sidechains (B 1) is too low (below 6%), the graft polymer show lower performance on dye transfer prevention during a laundering process. Therefore, the optimum amount of polymeric sidechains (B 1), in relation to the total weight of the graft polymer, is in the range of 10 to 20%, such as 12%, 15%, 18%.
The vinyl ester monomer (B2) is known to a person skilled in the art. Typical vinyl esters have a structure of (B2-1) below:

CH₂=CH-O-(C=O)-R (B2-1)

wherein, R is selected from a linear or branched or cyclic, saturated or unsaturated C₁ to C₂₀ aliphatic group. Preferably, R is selected from C₁ to C₁₄ alkyl group. More preferably, (B2-1) is selected from vinyl acetate, vinyl propionate, vinyl laurate, or combination thereof. Most preferably, (B2-1) is vinyl acetate.
Typically, the graft polymer comprises, in relation to the total weight of the graft polymer, from 2 to 40%, preferably from 3 to 30%, more preferably from 4 to 20%, most preferably in the range of 5 to 15%, such as 6%, 8%, 10%, 12%, 14%, by weight of the polymeric sidechains (B2). Without wish to be bound by any theory, when the graft polymer comprises, in relation to the total weight of the graft polymer, low amount of the polymeric sidechains (B2), the graft polymer is more biodegradable; however, when the amount of polymeric sidechains (B2) is too low (below 5%), the grafting reaction which graft (B 1) and (B2) onto the backbone (A) becomes less effective. Therefore, the optimum amount by weight of polymeric sidechains (B2), in relation to the total weight of the graft polymer, is in the range of 5 to 15%, such as 8%, 10%, 12%. Without wish to be bonded by any theory, when the amount of sidechains (B2) is in preferred range, the graft polymer also show improved performance in the presence of hydrophobic dyes.
It is possible that other monomers may be present in the polymer sidechains (B). Other monomers can be any types of monomers comprising carbon-carbon double bonds (C=C) which can form polymeric side chains grafted onto the block copolymer backbone (A). Examples of other monomers include, but not limit to, α,β-unsaturated monocarboxylic acid and/or derivatives thereof. The "derivatives thereof" comprises, without limitation, salts, esters. Preferred ester here include C₁-C₁₈ alkyl esters, such as methyl ester, ethyl ester. Examples of other monomers also include, not limited to, vinylpyridine-N-oxide, vinylimidazole, quaternized vinylimidazole, vinylpyridine betaine. If present, the total amount of other monomers is less than 15%, preferably less than 10%, more preferrable less than 5%, more preferrable less than 2%, more preferably less than 1% (by weight of the backbone (A)). However, it is more preferred that other monomers are essentially not present or only present as impurities at trace amount (less than 0.5%).
The ratio of N-vinyl lactam monomer (B1) versus vinyl ester (B2) may have any value known to a person skilled in the art. However, it is preferred within the context of the present invention that the polymeric sidechains (B) are obtained by free radical polymerization of, in relation to the sum of (B 1) and (B2):

(B 1) 50 to 99%, preferably 60 to 90%, more preferably from 70 to 80% by weight of N-vinyl lactam monomer (B 1), and
(B2) 1 to 50%, preferably from 10 to 40%, more preferably from 20 to 30% by weight of vinyl ester monomer (B2). Preferably, (B2) comprises vinyl acetate and/or vinyl propionate, more preferably (B2) is vinyl acetate.

The polymeric sidechains (B) of the graft polymer according to the present invention maybe fully or partially hydrolyzed, after the graft polymer as such is obtained. This means that the full or at least partial hydrolyzation of the polymeric sidechains (B) of the graft polymer is carried out after the polymerization process of the polymeric sidechains (B) is finished. Due to this full or at least partial hydrolyzation of the polymeric sidechains (B) of the graft polymers according to the present invention, the respective sidechain units originating from the at least one vinyl ester monomer (B2) are changed from the respective ester function into the alcohol function within the polymeric sidechain (B). It has to be noted that the corresponding vinyl alcohol is not suitable to be employed as monomer within the polymerization process of the polymeric sidechains (B) due to stability aspects. In order to obtain an alcohol function (hydroxy substituent) within the polymeric sidechains (B) of the graft polymers according to the present invention, the alcohol function has to be introduced by hydrolyzing the ester function of the sidechains.
From a theoretical point of view, each ester function of the polymeric sidechain (B) may be replaced by an alcohol function (hydroxy group). In such a case, the polymeric sidechain is fully hydrolyzed (saponified). It has to be noted that for N-vinylpyrrolidone, no hydrolyzation takes place at those units of the polymeric sidechain (B) which originates from N-pyrrolidone.
The hydrolysis can be carried out by any method known to a person skilled in the art. For example, the hydrolysis can be induced by addition of a suitable base, such as sodium hydroxide or potassium hydroxide. However, within this embodiment of the present invention it is preferred that the hydrolyzation of the polymeric sidechains (B) is only carried out partially, for example, to an extend of up to 20%, 40% or 60%. Within this embodiment, it is preferred that the polymeric sidechains (B) are fully or partially hydrolyzed after polymerization, preferably to an extent of up to 50% in relation to the amount of the at least one vinyl ester monomer (B2) employed within the polymerization.
In one embodiment of this invention, the polymeric sidechains (B) are not hydrolyzed after polymerization.
Without wish to be bonded by any theory, optimized ratio of N-vinyl lactam monomer (B 1) versus vinyl ester (B2), together with optimized level of hydrolysis of the polymeric sidechains (B) ensure the graft polymer can provide dry transfer prevention benefit on a variety of dyes, including direct dye, reactive dye and disperse dye.
The graft polymers of the invention may contain a certain amount of ungrafted polymers ("ungrafted side chains") made of N-vinyl lactam(s), e.g. homo- and/or copolymers of N-vinyl lactam(s) with the other monomers. The amount of such ungrafted homo- and copolymers may be high or low, depending on the reaction conditions, but is preferably to be lowered and thus low. By this lowering, the amount of grafted side chains is preferably increased. Such lowering can be achieved by suitable reaction conditions, such as dosing of N-vinyl lactam and radical initiator and their relative amounts and also in relation to the amount of backbone being present. This is generally known to a person of skill in the present field.
The inventive graft polymers maybe characterized by their degree of grafting (number of graft sites of the polymeric sidechains (B) on the polymer backbone (A)). The degree of graft may be high or low, depending on the reaction conditions. Preferably, the degree of grafting is low to medium, more preferably low. "Low" in this aspect means that statistically less than 2 graft sites per 50 alkylene oxide units are present.
This adjustment of the degree of grafting and this amount of ungrafted polymers can be used to optimize the performance in areas of specific interest.
Preferably, inventive polymers have at least one of the following properties, preferably two or more, to be successfully employed in the various fields of applications targeted with this present invention:

a) bio-degradability of a certain level, such bio-degradability of the graft polymer being at least 20%, preferably at least 45 % such as at least 50, 55, 60, 65, 70, 75, 80 or 85%, within 28 days when tested under OECD301F (measurement method see experimental section).
b) Water-solubility of the polymers of a certain extent, to be able to employ the polymers within the aqueous environment typically present in the fields of applications as generally targeted with this present invention. Preferably inventive polymers should exhibit a medium to good, more preferably a very good solubility in the environment of an aqueous formulation as typically employed in such fields for the various kinds of formulations, e.g. dish washing, automatic dish-washing, hard surface cleaning, fabric cleaning, fabric care, cosmetic formulations etc.
c) Viscosities of the polymer solutions should be such that at reasonably high solid concentrations of the polymer as to be handled in and after production and to be provided to the user, which could be e.g. as a "pure" (then typically liquid) product, dissolved in a solvent, typically an aqueous solution containing water and organic solvents, only water or only organic solvents, the viscosity of such polymer or polymer solution being in a range that allows typical technical process steps such as pouring, pumping, dosing etc. Hence, the viscosities should be preferably in a range of about up to less than 4,000 mPas, more preferably up to 3,500 mPas, even more preferably up to 3,000 mPas, such as up to 4,500, 3,750, 3,250, 2,750 or even 2,600 or below such as 2,500, 2,000, 1,750, 1,500, 1,250, 1,000, 750, 500, 250, 200, 150, or 100 mPas, at concentrations of the polymer (based on the total solid content of the polymer in solution, as defined by weight percent of the dry polymer within the total weight of the polymer solution) of preferably at least 10 wt.%, more preferably at least 20, and even more preferably at least 40 wt.%, and most preferably at least 50 wt.%, such as at least 60, 70, 80 or even 90 wt.%. The viscosity may be measured at either 25 °C or at elevated temperature, e.g. temperatures of 50 or even 60 °C. By this a suitable handling of the polymer solutions in commercial scales is possible. It is of course evident that depending on the amount of solvent being added the viscosity is lower when the amount of solvent increases and vice versa, thus allowing for adjustment in case desired. It is also evident that the viscosity being measured depends on the temperature at which it is being measured, e.g. the viscosity of a given polymer with a given solid content of e.g. 80 wt.% will be higher when measured at lower temperature and lower when measured at a higher temperature. In a preferred embodiment the solid content is in between 70 and 99 wt.%, more preferably in between 75 and 85 wt.%, with no additional solvent being added but the polymer as prepared. In a more preferred embodiment, the solid content is in between 70 and 99 wt.%, more preferably in between 75 and 95 wt.%, with no additional solvent being added but the polymer as prepared, and the viscosity is lower than 3,000 mPas, more preferably 3,250, or even below 2,750, 2,600, 2,500, 2,000, 1,750, 1,500, 1,250, 1,000, 750, 500 or even 250 mPas, when measured at 60 °C. The viscosity may be determined as generally known for such polymers, preferably as described below in the experimental part.

In one most preferred embodiment, the graft polymer comprises:

(A) a block copolymer backbone (A) as a graft base, wherein said block copolymer backbone (A) comprises from 85% to 100%, by weight of the backbone (A), at least two monomers selected from the group of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, and 2,3-pentene oxide,
(B) polymeric sidechains grafted onto the block copolymer backbone (A), wherein said polymeric sidechains (B) comprises from 85% to 100%, by weight of the sidechains (B), N-vinyl lactam monomer (B 1) and vinyl ester monomer (B2),

the block copolymer backbone (A) has a number average molecular weight (Mn) less than 2500, and
the graft polymer comprises in percentage by weight to the total weight of the graft polymer:
- from 65 to 85% of block copolymer backbone (A), and
- from 10 to 20% of polymeric sidechains (B) derived from N-vinylpyrrolidone monomer (B 1), and
- from 5 to 15% of polymeric sidechains (B) derived from vinyl acetate monomer (B2).

The graft polymer of this embodiment demonstrates optimum balances between biodegradability, performance, solubility and processability.
Therefore, the invention also related to a laundry detergent composition comprising a detersive surfactnat, and a graft polymer, wherein,

the detersive surfactant comprises anionic surfactant, and
the the graft polymer comprises:
1. (A) a block copolymer backbone (A) as a graft base, wherein said block copolymer backbone (A) comprises from 85% to 100%, by weight of the backbone (A), at least two monomers selected from the group of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, and 2,3-pentene oxide,
2. (B) polymeric sidechains grafted onto the block copolymer backbone (A), wherein said polymeric sidechains (B) comprises from 85% to 100%, by weight of the sidechains (B), N-vinyl lactam monomer (B 1) and vinyl ester monomer (B2),
wherein,
- the block copolymer backbone (A) has a number average molecular weight (Mn) less than 2500, and
- the graft polymer comprises in percentage by weight to the total weight of the graft polymer:
  - from 65 to 85% of block copolymer backbone (A), and from 10 to 20% of polymeric sidechains (B) derived from N-vinylpyrrolidone monomer (B 1), and
  - from 5 to 15% of polymeric sidechains (B) derived from vinyl acetate monomer (B2).

In order to achieve best dye transfer prevention performance in the presence of hydrophilic stains (such as clay) and hydrophobic stains (such as sebum and grease), it is preferred that laundry detergent composition further comprises hydrophobic cleaning polymers and hydrophilic cleaning polymers, such as other graft polymers and modified polyamine dispersing agent.

Process of Making the Graft Polymer

Another subject-matter of the present invention is a process for preparing the inventive graft polymers as described above in the various embodiments and variations thereof. Within this process for obtaining at least one graft polymer according to the present invention, at least one monomer (B 1) and at least one monomer (B2) are polymerized in the presence of at least one polymer backbone (A).
It has to be noted that the grafting process as such, wherein a polymeric backbone, such as a polymer backbone (A), is grafted with polymeric sidechains, is known to a person skilled in the art. Any process known to the skilled person in this respect can be employed within the present invention.
Within the process of the present invention, it is preferred that the polymeric sidechains (B) are obtained by radical polymerization.
The radical polymerization as such is also known to a skilled person. The person skilled in the art also knows that the inventive process can be carried out in the presence of a radical-forming initiator (C) and/or at least one solvent (D). The skilled person knows the respective components as such.
The term "radical polymerization" as used within the context of the present invention comprises besides the free radical polymerization also variants thereof, such as controlled radical polymerization. Suitable control mechanisms are RAFT, NMP or ATRP, which are each known to the skilled person, including suitable control agents.
In a preferred embodiment, the process to produce a graft polymer of the invention and/or as detailed before comprises the polymerization of at least one N-vinyl lactam monomer (B1) and at least one (B2) in the presence of at least one polymer backbone (A), a free radical-forming initiator (C) and, if desired, up to 50% by weight, based on the sum of components (A), (B1), (B2), and (C) of at least one organic solvent (D), at a mean polymerization temperature at which the initiator (C) has a decomposition half-life of from 40 to 500 min, in such a way that the fraction of unconverted graft monomers (B1) and monomer (B2) and initiator (C) in the reaction mixture is constantly kept in a quantitative deficiency relative to the copolymer backbone (A).
The amount of ((free) radical-forming) initiator (C) is preferably from 0.1 to 5% by weight, in particular from 0.3 to 3.5% by weight, based in each case on the polymeric sidechains (B).
For the process according to the invention, it is preferred that the steady-state concentration of radicals present at the mean polymerization temperature is substantially constant and the graft monomers (B1) and/or (B2) are present in the reaction mixture constantly only in low concentration (for example of not more than 5% by weight in total). This allows the reaction to be controlled, and graft polymers can be prepared in a controlled manner with the desired low polydispersity.
The term "mean polymerization temperature" is intended to mean here that, although the process is substantially isothermal, there may, owing to the exothermicity of the reaction, be temperature variations which are preferably kept within the range of +/- 10°C, more preferably in the range of +/- 5°C.
According to the invention, the (radical-forming) initiator (C) at the mean polymerization temperature should have a decomposition half-life of from 40 to 500 min, preferably from 50 to 400 min and more preferably from 60 to 300 min.
According to the invention, the initiator (C) and the graft monomers (B1) and/or (B2) are advantageously added in such a way that a low and substantially constant concentration of undecomposed initiator and graft monomers (B1) and/or (B2) is present in the reaction mixture. The proportion of undecomposed initiator in the overall reaction mixture is preferably ≤ 15% by weight, in particular ≤ 10% by weight, based on the total amount of initiator metered in during the monomer addition.
Examples of suitable initiators (C), and organic solvent (D), as well as preferred process conditions are disclosed in detail in WO2021160795 and WO2021160851 .

Detersive Surfactant:

The laundry detergent composition additionally comprises a detersive surfactant. Typically, the composition comprises, by weight of the composition, from about 1% to about 70% of a detersive surfactant system. The detersive surfactant system may comprise a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and mixtures thereof. Those of ordinary skill in the art will understand that a detersive surfactant encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.
Suitable surfactants include anionic surfactants, non-ionic surfactant, cationic surfactants, zwitterionic surfactants and amphoteric surfactants and mixtures thereof. Suitable surfactants may be linear or branched, substituted or un-substituted, and may be derived from petrochemical material or biomaterial. Preferred surfactant systems comprise both anionic and nonionic surfactant, preferably in weight ratios from 90:1 to 1:90. In some instances a weight ratio of anionic to nonionic surfactant of at least 1:1 is preferred. However, a ratio below 10:1 may be preferred. When present, the total surfactant level is preferably from 0.1% to 60%, from 1% to 50% or even from 5% to 40% by weight of the subject composition.
Anionic Surfactant: Anionic surfactants include, but are not limited to, those surface-active compounds that contain an organic hydrophobic group containing generally 8 to 22 carbon atoms or generally 8 to 18 carbon atoms in their molecular structure and at least one water-solubilizing group preferably selected from sulfonate, sulfate, and carboxylate so as to form a water-soluble compound. Usually, the hydrophobic group will comprise a C₈-C₂₂ alkyl, or acyl group. Such surfactants are employed in the form of water-soluble salts and the salt-forming cation usually is selected from sodium, potassium, ammonium, magnesium and mono-, with the sodium cation being the usual one chosen.
Anionic surfactants of the present invention and adjunct anionic cosurfactants, may exist in an acid form, and said acid form may be neutralized to form a surfactant salt which is desirable for use in the present detergent compositions. Typical agents for neutralization include the metal counterion base such as hydroxides, e.g., NaOH or KOH. Further preferred agents for neutralizing anionic surfactants of the present invention and adjunct anionic surfactants or cosurfactants in their acid forms include ammonia, amines, oligamines, or alkanolamines. Alkanolamines are preferred. Suitable non-limiting examples including 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 may be done to a full or partial extent, e.g. part of the anionic surfactant mix may be neutralized with sodium or potassium and part of the anionic surfactant mix may be neutralized with amines or alkanolamines.
Suitable sulphonate surfactants include methyl ester sulphonates, alpha olefin sulphonates, alkyl benzene sulphonates, especially alkyl benzene sulphonates, preferably C_10-C₁₃ alkyl benzene sulphonate. Suitable alkyl benzene sulphonate (LAS) is obtainable, preferably obtained, by sulphonating commercially available linear alkyl benzene (LAB). Suitable LAB includes low 2-phenyl LAB, such as those supplied by Sasol under the tradename Isochem^® or those supplied by Petresa under the tradename Petrelab^®, other suitable LAB include high 2-phenyl LAB, such as those supplied by Sasol under the tradename Hyblene^®. A suitable anionic surfactant is alkyl benzene sulphonate that is obtained by DETAL catalyzed process, although other synthesis routes, such as HF, may also be suitable. In one aspect a magnesium salt of LAS is used.
Suitable LAS may comprise a component obtained from waste plastic feedstock. Preferably LAS obtained from waste plastic feedstock comprises from 0.001 to 100% wt. of the total LAS, more preferably from 0.01 to 50 wt.%, more preferably from 0.1 to 20 wt.%, most preferably from 0.5 to 10%. Suitable LAS obtained from waste plastic feedstock are described for example in WO2023057604 , WO2023057531 and WO2023057530 .
Preferably, the composition may contain from about 0.5% to about 30%, by weight of the laundry composition, of a HLAS surfactant selected from alkyl benzene sulfonic acids, alkali metal or amine salts of C₁₀-C₁₆ alkyl benzene sulfonic acids, wherein the HLAS surfactant comprises greater than 50% C₁₂, preferably greater than 60%, preferably greater than 70% C₁₂, more preferably greater than 75%.
Suitable sulphate surfactants include alkyl sulphate, preferably C_8-18 alkyl sulphate, or predominantly C₁₂ alkyl sulphate.
A preferred sulphate surfactant is alkyl alkoxylated sulphate, preferably alkyl ethoxylated sulphate, preferably a C₈-C₁₈ alkyl alkoxylated sulphate, preferably a C₈-C₁₈ alkyl ethoxylated sulphate, preferably the alkyl alkoxylated sulphate has an average degree of alkoxylation of from 0.5 to 20, preferably from 0.5 to 10, preferably the alkyl alkoxylated sulphate is a C₈-C₁₈ alkyl ethoxylated sulphate having an average degree of ethoxylation of from 0.5 to 10, preferably from 0.5 to 5, more preferably from 0.5 to 3 or from about 1.5 to 3 or from about 1.8 to 2.5. The alkyl alkoxylated sulfate may have a broad alkoxy distribution or a peaked alkoxy distribution. The alkyl portion of the AES may include, on average, from 13.7 to about 16 or from 13.9 to 14.6 carbons atoms. At least about 50% or at least about 60% of the AES molecule may include having an alkyl portion having 14 or more carbon atoms, preferable from 14 to 18, or from 14 to 17, or from 14 to 16, or from 14 to 15 carbon atoms.
The alkyl sulphate, alkyl alkoxylated sulphate and alkyl benzene sulphonates may be linear or branched, including 2 alkyl substituted or mid chain branched type, substituted or un-substituted, and may be derived from petrochemical material or biomaterial. Preferably, the branching group is an alkyl. Typically, the alkyl is selected from methyl, ethyl, propyl, butyl, pentyl, cyclic alkyl groups and mixtures thereof. Single or multiple alkyl branches could be present on the main hydrocarbyl chain of the starting alcohol(s) used to produce the sulfated anionic surfactant used in the detergent of the invention. Most preferably the branched sulfated anionic surfactant is selected from alkyl sulfates, alkyl ethoxy sulfates, and mixtures thereof.
Alkyl sulfates and alkyl alkoxy sulfates are commercially available with a variety of chain lengths, ethoxylation and branching degrees. Commercially available sulfates include those based on Neodol alcohols ex the Shell company, Lial - Isalchem and Safol ex the Sasol company, natural alcohols ex The Procter & Gamble Chemicals company.
Other suitable anionic surfactants include alkyl ether carboxylates, comprising a C₁₀-C₂₆ linear or branched, preferably C₁₀-C₂₀ linear, most preferably C₁₆-C₁₈ linear alkyl alcohol and from 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 or ammonium salt, may be used, and the alkyl chain may contain one cis or trans double bond. Alkyl ether carboxylic acids are available from Kao (Akypo^®), Huntsman (Empicol^®) and Clariant (Emulsogen^®).
Other suitable anionic surfactants are rhamnolipids. The rhamnolipids may have a single rhamnose sugar ring or two rhamnose sugar rings.
Non-ionic Surfactant: Suitable non-ionic surfactants are selected from the group consisting of: C₈-C₁₈ alkyl ethoxylates, such as, NEODOL^® non-ionic surfactants from Shell; C₆-C₁₂ alkyl phenol alkoxylates wherein preferably the alkoxylate units are ethyleneoxy units, propyleneoxy units or a mixture thereof; C₁₂-C₁₈ alcohol and C₆-C₁₂ alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic^® from BASF; alkylpolysaccharides, preferably alkylpolyglycosides; methyl ester ethoxylates; polyhydroxy fatty acid amides; ether capped poly(oxyalkylated) alcohol surfactants; and mixtures thereof.
Suitable non-ionic surfactants are alkylpolyglucoside and/or an alkyl alkoxylated alcohol.
Suitable non-ionic surfactants include alkyl alkoxylated alcohols, preferably C₈-C₁₈ alkyl alkoxylated alcohol, preferably a C₈-C₁₈ alkyl ethoxylated alcohol, preferably the alkyl alkoxylated alcohol has an average degree of alkoxylation of from 1 to 50, preferably from 1 to 30, or from 1 to 20, or from 1 to 10, preferably the alkyl alkoxylated alcohol is a C₈-C₁₈ alkyl ethoxylated alcohol having an average degree of ethoxylation of from 1 to 10, preferably from 1 to 7, more preferably from 1 to 5 and most preferably from 3 to 7. In one aspect, the alkyl alkoxylated alcohol is a C_12-C₁₅ alkyl ethoxylated alcohol having an average degree of ethoxylation of from 7 to 10. The alkyl alkoxylated alcohol can be linear or branched, and substituted or un-substituted. Suitable nonionic surfactants include those with the trade name Lutensol^® from BASF. The alkyl alkoxylated sulfate may have a broad alkoxy distribution for example Alfonic 1214-9 Ethoxylate or a peaked alkoxy distribution for example Novel 1214-9 both commercially available from Sasol.
Cationic Surfactant: Suitable cationic surfactants include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl ternary sulphonium compounds, and mixtures thereof.
Preferred cationic surfactants are quaternary ammonium compounds having the general formula:

(R)(R₁)(R₂)(R₃)N⁺ X^-

wherein, R is a linear 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 hydroxyl, hydroxymethyl or a hydroxyethyl moiety, X is an anion which provides charge neutrality, preferred anions include: halides, preferably chloride; sulphate; and sulphonate.
The fabric care compositions of the present invention may contain up to about 30%, alternatively from about 0.01% to about 20%, more alternatively from 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 quat 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-oxyethyl) N-(2 hydroxyethyl) N-methyl ammonium methyl sulfate; N,N-bis(stearoyl-isopropoxy)N,N-dimethyl ammonium methyl sulfate, N,N-bis(tallowoyl-isopropoxy)N,N-dimethyl ammonium methyl sulfate, 1, 2 di (stearoyl-oxy) 3 trimethyl ammoniumpropane chloride; dialkylenedimethylammonium salts such as dicanoladimethylammonium chloride, di(hard)tallowdimethylammonium chloride dicanoladimethylammonium methyl sulfate; 1-methyl-1-stearoylamidoethyl-2-stearoylimidazolinium methylsulfate; 1-tallowylamidoethyl-2-tallowylimidazoline; N,N"-dialkyldiethylenetriamine ;the reaction product of N-(2-hydroxyethyl)-1,2-ethylenediamine or N-(2-hydroxyisopropyl)-1,2-ethylenediamine with glycolic acid, esterified with fatty acid, where 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 (PGEs), oily sugar derivatives, and wax emulsions and a mixture of the above.
It will be understood that combinations of softener actives disclosed above are suitable for use herein.
Amphoteric and Zwitterionic surfactant: Suitable amphoteric or zwitterionic surfactants include amine oxides, and/or betaines. Preferred amine oxides are alkyl dimethyl amine oxide or alkyl amido propyl dimethyl amine oxide, more preferably alkyl dimethyl amine oxide and especially coco dimethyl amino oxide. Amine oxide may have a linear or mid-branched alkyl moiety. Typical linear amine oxides include water-soluble amine oxides containing one R¹ Cs-C₁₈ alkyl moiety and 2 R² and R³ moieties selected from the group consisting of C₁-C₃ alkyl groups and C₁-C₃ hydroxyalkyl groups. Preferably amine oxide is characterized by the formula R¹ - N(R²)(R³) O wherein R¹ is a C₈-C₁₈ alkyl and R² and R³ are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxethyl, 2-hydroxypropyl and 3-hydroxypropyl. The linear amine oxide surfactants in particular may include linear C₁₀-C₁₈ alkyl dimethyl amine oxides and linear C₈-C₁₂ alkoxy ethyl dihydroxy ethyl amine oxides.
Other suitable surfactants include betaines, such as alkyl betaines, alkylamidobetaine, amidazoliniumbetaine, sulfobetaine (INCI Sultaines) as well as Phosphobetaines.

Other Laundry Detergent Ingredient:

The laundry detergent composition of the invention may comprise at least one laundry detergent ingredient different from the graft polymer and detersive surfactant.
Suitable ingredient include, enzymes, enzyme stabilizers, builders, dispersants, structurants or thickeners, other polymers, additional amines, catalytic materials, bleaching agents, bleaching catalysts, bleach activators, polymeric dispersing agents, soil removal/ anti-redeposition agents, polymeric grease cleaning agents, amphiphilic copolymers, fluorescent brightener, fabric hueing agents, chelating agent, encapsulates, perfume, pro-perfumes, malodor reduction materials, conditioning agents, probiotics, organic acids, anti-oxidants, anti-microbial agents and/or preservatives, neutralizers and/ or pH adjusting agents, processing aids, rheology modifiers, corrosion and/or anti-tarnishing agents, hygiene Agent, pearlescent agent, pigments, opacifier, solvents, carriers, hydrotrope, suds suppressor and mixtures thereof. More details are described below:

Enzymes:

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, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, galactanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ß-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. A typical combination is an enzyme cocktail that may comprise, for example, a protease and lipase in conjunction with amylase. When present in the composition, the aforementioned additional enzymes may be present at levels from about 0.00001% to about 2%, from about 0.0001% to about 1% or even from about 0.001% to about 0.5% enzyme protein by weight of the composition.
Proteases. Preferably the composition comprises one or more proteases. Suitable proteases include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62). Suitable proteases include those of animal, vegetable or microbial origin. In one aspect, such suitable protease may be of microbial origin. The suitable proteases include chemically 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:

(a) subtilisins (EC 3.4.21.62), especially those derived from Bacillus, such as Bacillus sp., Bacillus sp., B. lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, B. gibsonii, B. akibaii, B. clausii and B. clarkii 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 , WO2017089093 , WO2020156419 .
(b) trypsin-type or chymotrypsin-type proteases, such as trypsin (e.g., of porcine or bovine origin), including the Fusarium protease described in WO 89/06270 and the chymotrypsin proteases derived from Cellumonas described in WO 05/052161 and WO 05/052146 .
(c) metalloproteases, especially those derived from Bacillus amyloliquefaciens decribed in WO07/044993A2 ; from Bacillus, Brevibacillus, Thermoactinomyces, Geobacillus, Paenibacillus, Lysinibacillus or Streptomyces spp. Described in WO2014194032 , WO2014194054 and WO2014194117 ; from Kribella alluminosa described in WO2015193488 ; and from Streptomyces and Lysobacter described in WO2016075078 .
(d) Protease having at least 90% identity to the subtilase from Bacillus sp. TY145, NCIMB 40339, described in WO92/17577 (Novozymes A/S), including the variants of this Bacillus sp TY145 subtilase described in WO2015024739 , and WO2016066757 .

Suitable commercially available protease enzymes include those sold under the trade names Alcalase^®, Savinase^®, Primase^®, Durazym^®, Polarzyme^®, Kannase^®, Liquanase^®, Liquanase Ultra^®, Savinase Ultra^®, Liquanase^® Evity^®, Savinase^® Evity^®, Ovozyme^®, Neutrase^®, Everlase^®, Coronase^®, Blaze^®, Blaze Ultra^®, Blaze^® Evity^®, Blaze^® Exceed, Blaze^® Pro, Esperase^®, Progress^® Uno, Progress^® Excel, Progress^® Key, Ronozyme^®, Vinzon^® and Het Ultra^® by Novozymes A/S (Denmark); those sold under the tradename Maxatase^®, Maxacal^®, Maxapem^®, Properase^®, Purafect^®, Purafect Prime^®, Purafect Ox^®, FN3^®, FN4^®, Excellase^®, Ultimase^® and Purafect OXP^® by Dupont; those sold under the tradename Opticlean^® and Optimase^® by Solvay Enzymes; and those available from Henkel/Kemira, namely BLAP (sequence shown in Figure29 of US 5,352,604 with the following mutations S99D + S101 R + S103A + V104I + G159S, hereinafter referred to as BLAP), BLAP R (BLAP with S3T + V4I + V199M + V205I + L217D), BLAP X (BLAP with S3T + V4I + V205I) and BLAP F49 (BLAP with S3T + V4I + A194P + V199M + V205I + L217D); and KAP (Bacillus alkalophilus subtilisin with mutations A230V + S256G + S259N) from Kao and Lavergy^®, Lavergy^® Pro, Lavergy^® C Bright from BASF.
Amylases. Preferably the composition may comprise an amylase. Suitable alpha-amylases include those of bacterial or fungal origin. Chemically or genetically modified mutants (variants) are included. A preferred alkaline alpha-amylase is derived from a strain of Bacillus, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus sp., such as Bacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375 ( USP 7,153,818 ) DSM 12368, DSMZ no. 12649, KSM AP1378 ( WO 97/00324 ), KSM K36 or KSM K38 ( EP 1,022,334 ). Preferred amylases include:

(a) variants described in WO 94/02597 , WO 94/18314 , WO96/23874 and WO 97/43424 , especially the variants with substitutions in one or more of the following positions versus the enzyme listed as 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.
(b) variants described in USP 5,856,164 and WO99/23211 , WO 96/23873 , WO00/60060 and WO 06/002643 , especially the variants with one or more substitutions in the following positions versus the AA560 enzyme listed as SEQ ID No. 12 in WO 06/002643 :
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 that also contain the deletions of D183* and G184*.
(c) variants exhibiting at least 90% identity with SEQ ID No. 4 in WO06/002643 , the wild-type enzyme from Bacillus SP722, especially variants with deletions in the 183 and 184 positions and variants described in WO 00/60060 , which is incorporated herein by reference.
(d) variants exhibiting at least 95% identity with the wild-type enzyme from Bacillus sp.707 (SEQ ID NO:7 in US 6,093 , 562 ), especially those comprising one or more of the following mutations M202, M208, S255, R172, and/or M261. Preferably said 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.
(e) variants described in WO 09/149130 , preferably those exhibiting at least 90% identity with SEQ ID NO: 1 or SEQ ID NO:2 in WO 09/149130 , the wild-type enzyme from Geobacillus Stearophermophilus or a truncated version thereof.
(f) variants exhibiting at least 89% identity with SEQ ID NO:1 in WO2016091688 , especially those comprising deletions at positions H183+G184 and additionally one or more mutations at positions 405, 421, 422 and/or 428.
(g) variants exhibiting at least 60% amino acid sequence identity with the "PcuAmyl α-amylase" from Paenibacillus curdlanolyticus YK9 (SEQ ID NO:3 in WO2014099523 ).
(h) variants exhibiting at least 60% amino acid sequence identity with the "CspAmy2 amylase" from Cytophaga sp. (SEQ ID NO:1 in WO2014164777 ).
(i) variants exhibiting at least 85% identity with AmyE from Bacillus subtilis (SEQ ID NO:1 in WO2009149271 ).
(j) Variants exhibiting at least 90% identity variant with the wild-type amylase from Bacillus sp. KSM-K38 with accession number AB051102.

Suitable commercially available alpha-amylases include DURAMYL^®, LIQUEZYME^®, TERMAMYL^®, TERMAMYL ULTRA^®, NATALASE^®, SUPRAMYL^®, STAINZYME^®, STAINZYME PLUS^®, FUNGAMYL^® and BAN^® (Novozymes A/S, Bagsvaerd, Denmark), KEMZYM^® AT 9000 Biozym Biotech Trading GmbH Wehlistrasse 27b A-1200 Wien Austria, RAPIDASE^® , PURASTAR^®, ENZYSIZE^®, OPTISIZE HT PLUS^®, POWERASE^® and PURASTAR OXAM^® (Genencor International Inc., Palo Alto, California) and KAM^® (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku Tokyo 103-8210, Japan). In one aspect, suitable amylases include NATALASE^®, STAINZYME^® and STAINZYME PLUS^® and mixtures thereof.
Lipases. Preferably the composition comprises one or more lipases, including "first cycle lipases" such as those described in U.S. Patent 6,939,702 B1 and US PA 2009/0217464 . Preferred lipases are first-wash lipases. The composition may comprise a first wash lipase.
First wash lipases includes a lipase which is a polypeptide having an amino acid sequence which: (a) has at least 90% identity with the wild-type lipase derived from Humicola lanuginosa strain DSM 4109; (b) compared to said wild-type lipase, comprises a substitution of an electrically neutral or negatively charged amino acid at the surface of the three-dimensional structure within 15A of E1 or Q249 with a positively charged amino acid; and (c) comprises a peptide addition at the C-terminal; and/or (d) comprises a peptide addition at the N-terminal and/or (e) meets the following limitations: i) comprises a negative amino acid in position E210 of said wild-type lipase; ii) comprises a negatively charged amino acid in the region corresponding to positions 90-101 of said wild-type lipase; and iii) comprises a neutral or negative amino acid at a position corresponding to N94 or said wild-type lipase and/or has a negative or neutral net electric charge in the region corresponding to positions 90-101 of said wild-type lipase.
Preferred are variants of the wild-type lipase from Thermomyces lanuginosus comprising one or more of the T231R and N233R mutations. The wild-type sequence is the 269 amino acids (amino acids 23 - 291) of the Swissprot accession number Swiss-Prot O59952 (derived from Thermomyces lanuginosus (Humicola lanuginosa)). Other suitable lipases include: Liprl 139, e.g. as described in WO2013171241 ; TfuLip2, e.g. as described in WO2011084412 and WO2013033318 ; Pseudomonas stutzeri lipase, e.g. as described in WO2018228880 ; Microbulbifer thermotolerans lipase, e.g. as described in WO2018228881 ; Sulfobacillus acidocaldarius lipase, e.g. as described in EP3299457 ; LIP062 lipase e.g. as described in WO2018209026 ; PinLip lipase e.g. as described in WO2017036901 and Absidia sp. lipase e.g. as described in WO2017005798 .
Preferred lipases would include those sold under the tradenames Lipex^® and Lipolex^® and Lipoclean^®.
Cellulases. Suitable enzymes include cellulases of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g., the fungal cellulases produced from Humicola insolens, Myceliophthora thermophila and Fusarium oxysporum 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 the alkaline or neutral cellulases having colour care benefits. Commercially available cellulases include CELLUZYME^®, CAREZYME^® and CAREZYME PREMIUM (Novozymes A/S), CLAZINASE^®, and PURADAX HA^® (Genencor International Inc.), and KAC-500(B)^® (Kao Corporation).
The bacterial cleaning cellulase may be a glycosyl hydrolase having enzymatic activity towards amorphous cellulose substrates, wherein the glycosyl hydrolase is selected from GH families 5, 7, 12, 16, 44 or 74. Suitable glycosyl hydrolases may also be selected from the group consisting of: GH family 44 glycosyl hydrolases from Paenibacillus polyxyma (wild-type) such as XYG1006 described in US 7,361,736 or are variants thereof. GH family 12 glycosyl hydrolases from Bacillus licheniformis (wild-type) such as SEQ ID NO:1 described in US 6,268,197 or are variants thereof; GH family 5 glycosyl hydrolases from Bacillus agaradhaerens (wild type) or variants thereof; GH family 5 glycosyl hydrolases from Paenibacillus (wild type) such as XYG1034 and XYG 1022 described in US 6,630,340 or variants thereof; GH family 74 glycosyl hydrolases from Jonesia sp. (wild type) such as XYG1020 described in WO 2002/077242 or variants thereof; and GH family 74 glycosyl hydrolases from Trichoderma Reesei (wild type), such as the enzyme described in more detail in Sequence ID NO. 2 of US 7,172,891 , or variants thereof. Suitable bacterial cleaning cellulases are sold under the tradenames Celluclean^® and Whitezyme^® (Novozymes A/S, Bagsvaerd, Denmark).
The composition may comprise a fungal cleaning cellulase belonging to glycosyl hydrolase family 45 having a molecular weight of from 17kDa to 30 kDa, for example the endoglucanases sold under the tradename Biotouch^® NCD, DCC and DCL (AB Enzymes, Darmstadt, Germany).
Pectate Lyases. Other preferred enzymes include pectate lyases sold under the tradenames Pectawash^®, Pectaway^®, Xpect^® and mannanases sold under the tradenames Mannaway^® (all from Novozymes A/S, Bagsvaerd, Denmark), and Purabrite^® (Genencor International Inc., Palo Alto, California).
Nucleases. The composition may comprise a nuclease enzyme. The nuclease enzyme is an enzyme capable of cleaving the phosphodiester bonds between the nucleotide sub-units of nucleic acids. The nuclease enzyme herein is preferably a deoxyribonuclease or ribonuclease enzyme or a functional fragment thereof. By functional fragment or part is meant the portion of the nuclease enzyme that catalyzes the cleavage of phosphodiester linkages in the DNA backbone and so is a region of said nuclease protein that retains catalytic activity. Thus, it includes truncated, but functional versions, of the enzyme and/or variants and/or derivatives and/or homologues whose functionality is maintained. Suitable DNases include wild-types and variants described in detail by WO2017162836 and WO2018108865 , and variants of the Bacillus cibi DNase including those described in WO2018011277 .
RNase: suitable RNases include wild-types and variants of DNases described in WO2018178061 and WO2020074499 .
Preferably the nuclease enzyme is a deoxyribonuclease, preferably selected from any of the 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.
Hexosaminidases. The composition may comprise one or more hexosaminidases. The term hexosaminidase includes "dispersin" and the abbreviation "Dsp", which means a polypeptide having hexosaminidase activity, EC 3.2.1 .- that catalyzes the hydrolysis of β-1,6-glycosidic linkages of N-acetyl-glucosamine polymers found in soils of microbial origin. The term hexosaminidase includes polypeptides having N-acetylglucosaminidase activity and β-N-acetylglucosaminidase activity. Hexosaminidase activity may 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 Terribacillus saccharophilus hexosaminidase defined by SEQ ID NO: 1 of WO2020207944 may be preferred, especially the variants with improved thermostability disclosed in that publication.
Mannanases. The composition may comprise an extracellular-polymer-degrading enzyme that includes a mannanase enzyme. The term "mannanase" means a polypeptide having mannan endo-1,4-beta-mannosidase activity (EC 3.2.1.78) from the glycoside hydrolase family 26 that catalyzes the hydrolysis of 1,4-3-D-mannosidic linkages in mannans, galactomannans and glucomannans. Alternative names of mannan endo-1,4-beta-mannosidase are 1,4-3-D-mannan mannanohydrolase; endo-1,4-3-mannanase; endo- β-1,4-mannase; β-mannanase B; 3-1,4-mannan 4-mannanohydrolase; endo-3-mannanase; and β-D-mannanase. For purposes of the present disclosure, mannanase activity may be determined using the Reducing End Assay as described in the experimental section of WO2015040159 . Suitable examples from class EC 3.2.1.78 are described in WO2015040159 , such as the mature polypeptide SEQ ID NO: 1 described therein.
Galactanases. The composition may comprise an extracellular polymer-degrading enzyme that includes an endo-beta-1,6-galactanase enzyme. The term "endo-beta-1,6-galactanase" or "a polypeptide having endo-beta-1,6-galactanase activity" means a endo-beta-1,6-galactanase activity (EC 3.2.1.164) from the glycoside hydrolase family 30 that catalyzes the hydrolytic cleavage of 1,6-3-D-galactooligosaccharides with a degree of polymerization (DP) higher than 3, and their acidic derivatives with 4-O-methylglucosyluronate or glucosyluronate groups at the nonreducing terminals. For purposes of the present disclosure, endo-beta-1,6-galactanase activity is determined according to the procedure described in WO 2015185689 in Assay I. Suitable examples from class EC 3.2.1.164 are described in WO 2015185689 , such as the mature polypeptide SEQ ID NO: 2.

Enzyme Stabilizing System:

The composition may optionally comprise from about 0.001% to about 10%, in some examples from about 0.005% to about 8%, and in other examples, from about 0.01% to about 6%, by weight of the composition, of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. In the case of aqueous detergent compositions comprising protease, a reversible protease inhibitor, such as a boron compound, including borate, 4-formyl phenylboronic acid, phenylboronic acid and derivatives thereof, or compounds such as calcium formate, sodium formate and 1,2-propane diol may be added to further improve stability.

Builders:

The composition may optionally comprise a builder. Built compositions typically comprise at least about 1% builder, based on the total weight of the composition. Liquid compositions may comprise up to about 10% builder, and in some examples up to about 8% builder, of the total weight of the composition. Granular compositions may comprise up to about 30% builder, and in some examples up to about 5% builder, by weight of the composition.
Builders selected from aluminosilicates (e.g., zeolite builders, such as zeolite A, zeolite P, and zeolite MAP) and silicates assist in controlling mineral hardness in wash water, especially calcium and/or magnesium, or to assist in the removal of particulate soils from surfaces. Suitable builders may be selected from the group consisting of phosphates, such as polyphosphates (e.g., sodium tri-polyphosphate), especially sodium salts thereof; carbonates, bicarbonates, sesquicarbonates, and carbonate minerals other than sodium carbonate or sesquicarbonate; organic mono-, di-, tri-, and tetracarboxylates, especially water-soluble nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as well as oligomeric or water-soluble low molecular weight polymer carboxylates including aliphatic and aromatic types; and phytic acid. These may be complemented by borates, e.g., for pH-buffering purposes, or by sulfates, especially sodium sulfate and any other fillers or carriers which may be important to the engineering of stable surfactant and/or builder-containing compositions. Additional suitable builders may be selected from citric acid, lactic acid, fatty acid and salt thereof.
Suitable builders may include polycarboxylate and salt thereof, for example, homopolymers of acrylic acid, copolymers of acrylic acid and maleic acid, and copolymers of acrylic acid and/or maleic acid, and other suitable ethylenic monomers with various types of additional functionalities. More suitable polycarboxylate are described in polycarboxylate polymers section of this patent.
Also suitable for use as builders herein are synthesized crystalline ion exchange materials or hydrates thereof having chain structure and a composition represented by the following general anhydride form: x(M₂O)·ySiO₂·zM'O wherein M is Na and/or K, M' is Ca and/or Mg; y/x is 0.5 to 2.0; and z/x is 0.005 to 1.0.
Alternatively, the composition may be substantially free of builder.

Structurant / Thickeners:

Suitable structurant / thickeners include:

Di-benzylidene Polyol Acetal Derivative
Bacterial Cellulose
Coated Bacterial Cellulose
Cellulose fibers non-bacterial cellulose derived
Non-Polymeric Crystalline Hydroxyl-Functional Materials
Polymeric Structuring Agents
Di-amido-gellants
Any combination of above.

Other polymers:

The compositions may include one or more other polymers. Typically, the level of other polymers is from about 0.01% to about 10.0 % by weight of the composition, preferably from about 0.1% to about 5%, and more preferably from about 0.2% to about 3.0% by weight of the composition. In some situations where the composition is in concentrated form, such as concentrated fabric and home care products in any forms which designed for consumer to dilute at home and then use following their regular dosing habits, the level of the polymers maybe higher than 10.0%, or higher than 5.0%, by weight of the composition.
Depending on the structure of the polymer, polymers can provide various benefits for the composition, including but not limit to, hydrophobic and hydrophilic stain removal, surfactant boosting, soil suspension, whiteness maintenance, soil release, malodor control, dye transfer inhibition, enhanced softness, enhanced freshness, etc. Polymers are normally multi-functional, which means one specific given type of polymer may provide more than one types of benefit as mentioned above. For example, a specific soil release polymer may provide soil release benefit as primary benefit, while also providing other benefits such as whiteness maintenance, malodor control, soil suspension, dye transfer inhibition.
Suitable other polymers including, but not limited to the following:
Other graft polymers based on polyalkylene oxide. The composition may comprise graft polymers which comprising block copolymer backbone (A) as a graft base and polymeric sidechains (B) grafted thereon. The polymeric sidechains (B) are obtainable by polymerization of at least one vinyl ester monomer. The block copolymer backbone (A) is obtainable by polymerization of at least two monomers selected from the group of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1 ,2-pentene oxide or 2,3-pentene oxide. Such graft polymers are known as effective soil suspension polymers for hydrophobic and hydrophilic stains, surfactant boosters, and sometimes as dye transfer inhibitors.
Suitable graft polymers include amphilic graft co-polymer comprises polyethylene glycol backbone (A) as a graft base, and at least one pendant sidechains (B) selected from polyvinyl acetate, polyvinyl alcohol and mixtures thereof. A preferred graft polymer of this type is Sokalan HP22 available from BASF.
Suitable graft polymers are also described in WO2007/138053 as amphiphilic graft polymers based on water-soluble polyalkylene oxides (A) as a graft base and side chains formed by polymerization of a vinyl ester component (B), said polymers having an average of < one graft site per 50 alkylene oxide units and mean molar masses M of from 3,000 to 100,000 g/mol. One specific preferred graft polymer of this type is polyvinyl acetate grafted polyethylene oxide copolymer having a polyethylene oxide as graft base and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6,000 g/mol and the weight ratio of the polyethylene oxide to polyvinyl acetate is about 40 to 60 and no more than 1 grafting point per 50 ethylene oxide units. The most preferred polymer of this type is available from BASF as Sokalan PG101. Other examples of suitable amphiphilic graft polymers are described in WO2023017064 and WO2023019153 , where molecular weight (Mn) of the backbone is within 500 to 7,000, and preferably not more than 3,000 or even not more than 2,500 g/mol.
Suitable graft polymer also include graft polymer comprising a block copolymer backbone (A) as a graft base, wherein said block copolymer backbone (A) is obtainable by polymerization of at least two monomers selected from the group of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide, wherein the number (x) of individual blocks within the block copolymer backbone (A) is an integer, wherein x is from 2 to 10 and preferably 3 to 5, and (B) polymeric sidechains grafted onto the block copolymer backbone, wherein said polymeric sidechains (B) are obtainable by polymerization of at least one vinyl ester monomer. Suitable graft polymers of this type are described in WO2021160795 and WO2021160851 , these polymers have improved biodegradation profiles.
Suitable graft polymers also include graft polymers based on random copolymer backbone, wherein the backbone is obtainable by polymerization of at least two monomers selected from the group of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2- pentene oxide or 2,3-pentene oxide. Graft polymer of this type is described in WO2023017062 and WO2023019152 .

Modified Polyamine Dispersing Agent:

The composition may comprise one or more modified polyamine dispersing agent. The modified polyamine dispersant comprises a polyamine core structure and a plurality of alkoxylate groups attached to the core structure. The polyamine core structure includes polyalkyleneimine, and linear or branched oligoamine.
The polyamine core structure and the alkoxylate groups attached to the core structure can be further derivatized. For example, the polyamine core structure can be further partly or completely quaternized with C₁-C₃₀ linear or branched alkyl, more preferably C₁-C₁₀ or even C₁-C₅ linear or branched alkyl, most preferably methyl. The alkoxylate group can be further sulphated, sulphonated and/or substituted with an amino functional group.
Suitable modified polyamine dispersing agent includes ethoxylated polyethyleneimine (EPEI). EPEI are effective dispersing agent for hydrophilic stains, especially hydrophilic particulate stain such as clay.
In one embodiment, the EPEI has a polyethyleneimine backbone of weight average molecular weight of between 100 g/mol and 2,000 g/mol, preferably between 200 g/mol and 1,500 g/mol, more preferably between 300 g/mol and 1,000 g/mol, even more preferably between 400 g/mol and 800 g/mol, most preferably between 500 g/mol and 700 g/mol, preferably about 600. The ethoxylation chains within the EPEI may be from 200 g/mol to 2,000 g/mol weight average molecular weight, preferably from 400 g/mol to 1500 g/mol weight average molecular weight, more preferably from 600 g/mol to 1,000 g/mol weight average molecular weight, most preferably about 880 g/mol weight average molecular weight per ethoxylated chain. The ethoxylation chains within the EPEI have on average 5 to 40, preferably 10 to 30, more preferably 15 to 25, even more preferably 18 to 22, most preferably about 20 ethoxy units per ethoxylation chain. The EPEI may have a total weight average molecular weight of from 5,000 g/mol to 20,000 g/mol, preferably from 7,500 g/mol to 17,500 g/mol, more preferably from 10,000 g/mol to 15,000 g/mol, even more preferably from 12,000 g/mol to 13,000 g/mol, most preferably about 12,700 g/mol. A preferred example is polyethyleneimine core (with average molecular weight about 600 g/mol) ethoxylated to 20 EO groups per NH. Suitable EPEI this type includes Sokalan HP20 available from BASF, 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.
In another embodiment, the EPEI comprises polyethyleneimine has an average molecular weight (Mw) ranging from 1,800 to 5,000 g/mol (prior to ethoxylation), and the polyoxyethylene side chains have an average of from 25 to 40 ethoxy units per side chain bonded to the polyethyleneimine backbone. Such EPEI is described in WO2020030760 and WO2020030469 .
Suitable modified polyamine dispersing agent includes amphiphilic alkoxylated polyalkyleneimine polymer. These polymers have balanced hydrophilic and hydrophobic properties such that they remove grease and body soil particles from fabrics and surfaces, and keep the particles suspended in washing liquor. Suitable amphiphilic water-soluble alkoxylated polyalkyleneimine polymer is described in WO2009061990 and WO2006108857 , which comprising in polyalkyleneimine, preferable polyethyleneimine core, and alkoxylate group of below connected to the core:

*-[A²-O]_m-[CH₂-CH₂-O]_n-[A³-O]_p-R (V)

wherein

"*" in each case denotes one-half of bond to the nitrogen atom of the core.
A² is in each case independently selected from 1,2-propylene, 1,2-butylene, and 1,2-isobutylene;
A³ is 1,2-propylene;
R is in each case independently selected from hydrogen and C₁-C₄-alkyl, preferably hydrogen;
m has an average value in the range of from 0 to 2, preferably 0;
n has an average value in the range of 5 to 50; and
p has an average value in the range of 3 to 50;

The polymer comprising a degree of quaterization ranging from 0 to 50, preferably from 0 to 20, and more preferably from 0 to 10.
A preferred alkoxylated polyalkyleneimine polymer is polyethyleneimine (MW = 600) modified with 24 ethoxylate groups per -NH and 16 propoxylate groups per -NH. Another preferred alkoxylated polyalkyleneimine polymer is polyethyleneimine (MW = 600) modified with 10 ethoxylate groups per -NH and 7 propoxylate groups per -NH.
Suitable alkoxylated polyalkyleneimine polymer of this type includes Sokalan HP30 Booster available from BASF.
Suitable alkoxylated polyalkyleneimine polymer also include amphiphilic alkoxylated poly(ethylene/propylene)imine, such as polymer examples disclosed in WO2021254828 .
Another Suitable modified polyamine dispersing agent is described in WO2021061774 .
Suitable modified polyamine dispersing agent also includes zwitterionic polyamines. Said zwitterionic polyamine is selected from zwitterionic polyamines according to the following formula:

R is each independently C₃-C₂₀ linear or branched alkylene;
R¹ is an anionic unit-capped polyalkyleneoxy unit having the formula: -(R²O)_xR³, wherein
- R² is C₂-C₄ linear or branched alkylene, preferably C₂ (ethylene);
- R³ is hydrogen, an anionic unit, and mixtures thereof, in which not all R³ groups are hydrogen, preferably wherein R³ anionic units are selected from -(CH₂)_pCO₂M; - (CH₂)_qSO₃M; - (CH₂)_qOSO₃M; -(CH₂)_qCH(SO₃M)-CH₂SO₃M; - (CH₂)_qCH(OSO₃M)CH₂OSO3M; - (CH₂)_qCH(SO₃M)CH₂SO₃M; -(CH₂)_pPO₃M; - PO₃M ;-SO₃M and mixtures thereof; wherein M is hydrogen or a water soluble cation, preferably selected from sodium, potassium, ammonium, and mixtures thereof and in sufficient amount to satisfy charge balance;
- x is from 5 to 50, preferably from 10 to 40, even more preferably from 15 to 30, most preferably from 20 to 25;
Q is a quaternizing unit selected from the group consisting of C₁-C₃₀ linear or branched alkyl, C₆-C₃₀ cycloalkyl, C₇-C₃₀ substituted or unsubstituted alkylenearyl, and mixtures thereof, preferably C₁-C₃₀ linear or branched alkyl, even more preferably C₁-C₁₀ or even C₁-C₅ linear or branched alkyl, most preferably methyl; the degree of quaternization preferably is more than 50%, more preferably more than 70%, even more preferably more than 90%, most preferably about 100;.
X^- is an anion present in sufficient amount to provide electronic neutrality, preferably a water-soluble anion selected from the group consisting of chlorine, bromine, iodine, methyl sulfate, and mixtures thereof, more preferably chloride;
n is from 0 to 8, preferably 0 to 4, preferably 0 to 2, most preferably 0.

A suitable zwitterionic polyamine having the following general structure: bis((C₂H₅O)(C₂H₄O)n)(CH₃)-N⁺-C_xH_2x-N⁺-(CH₃)-bis((C₂H₅O)(C₂H₄O)n), wherein n = from 20 to 30, and x = from 3 to 8, or sulphated or sulphonated variants thereof.
A particular preferred zwitterionic polyamine is available from BASF as Lutensit Z96 polymer (zwitterionic hexamethylene diamine according to below formula: 100% quaternized and about 40% of the polyethoxy (EO₂₄) groups are sulfonated).
Another suitable zwitterionic polyamine is amphoterically-modified oligopropyleneimine ethoxylates as described in WO2021239547 .

Polyester Soil Release Polymers:

The composition may comprise one or more soil release polymer (SRP). Preferred polyester SRP soil release polymers include terephthalate-derived polyester polymers, which comprise structure unit (1) and/or (II):

(I) -[(OCHR¹-CHR²)_a-O-OC-Ar-CO-]_d

(II) -[(OCHR³-CHR⁴)_b-O-OC-sAr-CO-]_e

wherein:

a, b are from 1 to 200;
d, e are from 1 to 50;
Ar is independently selected from 1,4-substituted phenylene, and 1,3-substituted phenylene sAr is 1,3-substituted phenylene substituted in position 5 with -SO₃M; wherein M is a counterion selected from Na, Li, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri-, or tetraalkylammonium wherein the alkyl groups are C₁-C₁₈ alkyl or C₂-C₁₀ hydroxyalkyl, or mixtures thereof;
R¹, R², R³, R⁴ are independently selected from H or C₁-C₁₈ n-alkyl or iso-alkyl; preferably selected from H or C₁ alkyl.

Optionally, the polymer further comprises one or more terminal group (III) derived from polyalkylene glycolmonoalkylethers, preferably selected from structure (III-a)

-O-[C₂H₄-O]_c-[C₃H₆-O]_d-[C₄H₈-O]_e-R₇ (III-a)

wherein:

R7: is a linear or branched C_1-30 alkyl, C₂-C₃₀ alkenyl, or a cycloalkyl group with 5 to 9 carbon atoms, or a C₈-C₃₀ aryl group, or a C₆-C₃₀ arylalkyl group; preferably C_1-4 alkyl, more preferably methyl; and
c, d and e: are, based on molar average, a number independently selected from 0 to 200, where the sum of c+d+e is from 2 to 500,

₂

₄

₃

₆

₄

₈

₂

₄

₃

₆

₄

₈

₇

₃

₆

Optionally, the polymer further comprises one or more anionic terminal unit (IV) and/or (V) as described in EP3222647 . Where M is a counterion selected from Na⁺, Li⁺, K⁺, ½ Mg²⁺, ½ Ca²⁺, 1/3 Al³⁺, ammonium, mono-, di-, tri-, or tetraalkylammonium wherein the alkyl groups are C₁-C₁₈ alkyl or C₂-C₁₀ hydroxyalkyl, or mixtures thereof.

-O-CH₂CH₂-SO₃M (IV)
Optionally, the polymer may comprise crosslinking multifunctional structural unit which having at least three functional groups capable of the esterification reaction. The functional which may be for example acid -, alcohol -, ester -, anhydride - or epoxy groups, etc.
Optionally, other di- or polycarboxylic acids or their salts or their (di)alkylesters can be used in the polyesters, 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, decan-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.
One type of preferred polyester SRPs are nonionic polyester SRP, which does not comprise above structure unit (II). A particular preferred nonionic terephthalate-derived soil release polymer has a structure according to formula below: wherein:

R5 and R6: is independently selected from H or CH₃. More preferably, one of the R₅ and R₆ is H, and another is CH₃.
c, d: are, based on molar average, a number independently selected from 0 to 200, where the sum of c+d is from 2 to 400,

More preferably, d is from 0 to 50, c is from 1 to 200,
More preferably, d is 1 to 10, c is 5 to 150,

R7

is C_1-C₄ alkyl and more preferably methyl,

n

is, based on molar average, from 1 to 50.

One example of most preferred above suitable terephthalate-derived nonionic SRP has one of the R₅ and R₆ is H, and another is CH₃; d is 0; c is from 5-100 and R₇ is methyl, and n is from 3-10.
Other suitable terephthalate-derived polyester SRP are described in patent WO2014019903 , WO2014019658 and WO2014019659 . The end capping group of these SRPs are selected from

X-(OC₂H₄)_n-(OC₃H₆)_m-

-wherein X is C₁-C₄ alkyl and preferably methyl, the -(OC₂H₄) groups and the -(OC₃H₆) groups are arranged blockwise and the block consisting of the -(OC₃H₆) groups is bound to a COO group, n is based on a molar average a number of from 40 to 50, m is based on a molar average a number of from 1 to 10 and preferably of from 1 to 7.
Polyester soil release polymers may be available or convert into different forms, include powder, particle, liquid, waxy or premix. Other materials (for example, water, alcohol, other solvents, salt, surfactant, etc.) may be needed to convert the polyester soil release polymer into different forms mentioned above, the wt% of active soil release polymer in the powder, particle, liquid, waxy or premix is in the range from 10% to 100%, for example 15%, 20%, 40%, 60%, 70%, 80%, 90%, 95%, 100%. Useful soil release polymer premix examples are described in EP351759 and WO2022100876 . When the soil release polymers exist in liquid or premix from, the premix maybe transparent or opaque, white or slightly yellowish. Premix in opaque maybe use to provide an opaque appearance for the finish product or part of the finish product.
The polyester may or may not be biodegradable, preferred soil release polymers are readily biodegradable.
Example of suitable soil release polymers include TexCare^® series supplied by Clariant, including noniconic soil release polymers Texcare^® SRN 100, SRN 170, SRN 170 C, SRN 170 Terra, SRN 172, SRN 240, SRN 260, SRN 260 life, SRN 260 SG Terra, SRN UL50, , SRN UL50 Terra, SRN 300, SRN 325; and anionic soil release polymers TexCare^® SRA 100, SRA 300, SRA300 F. Example of suitable soil release polymers also include REPEL-O-TEX^® line of polymers supplied by Rhodia/Solvay, including nonionic soil release polymer REPEL-O-TEX^® Crystal, Crystal PLUS, Crystal NAT, SRP6; and anionic soil release polymer REPEL-O-TEX^® SF-2. Other example of commercial soil release polymers also includes WeylClean^® series of soil release polymers supplied by WeylChem, including noniconic soil release polymers WeylClean^® PLN1, PLN2; and anionic soil release polymers WeylClean^® PSA1. Other examples of commercial soil release polymers are Marloquest^® polymers, such as Marloquest^® SL, HSCB, L235M, U, B, and G82, supplied by Sasol. Other suitable commercial soil release polymers include Sorez 100 (from ISP or Ashland, CAS: 9016-88-0).

Polymers Based on Polysaccharide:

Various polysaccharides have proven to be useful starting material to make polymers for fabric and home care products, including cellulose, starch, guar, dextran, polyglucan, chitin, curdlan, xylose, Inulin, pullulan, locust bean gum, cassia gum, tamarind gum (xyloglucan), xanthan gum, amylose, amylopectin, scleroglucan and mixtures thereof.
The most common type of modified polysaccharide is modified cellulose.
Modified cellulose polymers include anionic modified cellulose polymers which been modified with functional groups that contain negative charge. Suitable anionic modified cellulose polymers include carboxyalkyl cellulose, such as carboxymethyl cellulose. The carboxymethyl cellulose may have a degree of carboxymethyl substitution of from about 0.5 to about 0.9 and a molecular weight from about 80,000 to about 300,000 g/mol. Suitable carboxymethylcellulose is described in WO2011031599 and WO2009154933 . Suitable carboxymethylcellulose include Finnfix^® series sold by CP Kelco or Nouryon, which include Finnfix^® GDA, a hydrophobically modified carboxymethylcellulose, e.g., the alkyl ketene dimer derivative of carboxymethylcellulose sold under the tradename Finnfix^® SH1, or the blocky carboxymethylcellulose sold under the tradename Finnfix^®V. Other suitable anionic modified cellulose polymers include sulphoalkyl group which described in WO2006117056 , sulfoethyl cellulose which described in WO2014124872 .
Modified cellulose polymers also include nonionic modified cellulose polymers which been modified by functional group that does not contain any charge. Suitable nonionic modified cellulose polymers include alkyl cellulose, hydroxyalkyl cellulose, hydroxyalkyl alkylcellulose, alkylalkoxyalkyl cellulose. Suitable nonionic modified cellulose polymers also include nonionic cellulose carbamates which described in WO2015044061 ; nonionic 6-desoxy-6-amino-celluloses derivative which described in US20180346846 . Example of alkyl cellulose include methyl cellulose (MC), ethyl cellulose (EC), etc. Suitable ethyl cellulose are sold under tradename Ethocel^™ by Dow Chemicals, DuPont, or IFF. Example of hydroxyalkyl cellulose include hydroxyethyl cellulose (HEC) and hydroxypropyl cellulose (HPC). Suitable HEC are sold under tradename Natrosol^™ hydroxyethylcellulose by Ashland, such as Natrosol^™ 250 with different grade available which has a total molar substitution (MS) of 2.5. Suitable HEC are also sold under tradename CELLOSIZE^™ Hydroxyethyl Cellulose by Dow Chemicals. Suitable HPC are sold under tradename Klucel^™ by Ashland. Example of hydroxyalkyl alkylcellulose include hydroxypropyl methylcellulose (HPMC), suitable HPMC are sold under tradename Methocel^™ with different grade available by Dow Chemicals, DuPont or IFF, and under tradename Benecel^™ by Ashland.
Modified cellulose polymers also include cationic modified cellulose polymers which been modified by functional group that contain cationic charge. Suitable cationic modified celluloses include quaternized hydroxyethyl cellulose (Polyquaternium-10), which available under the tradename of Ucare by Dow Chemical, such as Ucare LR400, Ucare LR30M, Ucare JR125, Ucare JR400, etc. Suitable cationic modified cellulose polymers also include quaternised hydroxyethyl cellulose (HEC) polymers with cationic substitution of trimethyl ammonium and dimethyldodecyl ammonium (Polyquaternium-67), which available under trade the tradename of SoftCAT by Dow Chemical, such as SoftCAT SK, SoftCAT SK-MH, SoftCAT SX, SoftCAT SL. Other suitable cationic modified celluloses include those sold under tradename SupraCare^™ by Dow Chemical, such as SupraCare^™ 150, SupraCare^™ 133, SupraCare^™ 212.
Suitable cationic modified cellulose polymers also include those modified with cationic group and/or a hydrophobic group and described as soil release polymers in WO2019111948 , WO2019111949 , WO2019111946 and WO2019111947 ; suitable polymers is also disclosed in WO2022060754 , WO2021242942 and WO2020091988 .
Another common type of modified polysaccharide is modified guar. Similar to modified cellulose, modified guar can be nonionic modified, and anionic modified. Suitable nonionic modified guar includes hydroxypropyl guar, such as N-Hance^™ HP40 and HP40S guar available from Ashland. Suitable example of modified guar also include carboxymethyl hydroxypropyl guar (CMHPG) which is anionic and nonionic modified, such as Galactasol^™ available from Ashland. Other nonionic and/or anionic modified guar include for example Jaguar^® HP 105 (Hydroxypropyl Guar gum), Jaguar^® SOFT and HP-120 COS (Carboxymethyl Hydroxypropyl Guar Gum).
Suitable modified polysaccharide polymers also include modified starch. Examples of modified starch include carboxylate ester of starch as described in WO2015144438 , esterification product of starch with e.g. C₆-C₂₄ alk(en)yl succinic anhydride as described in EP0703243 ; starch maleates (starch react with maleic acid anhydride) as described US 6063914 . Examples of modified starch also include, but not limit to, acetylated starch, acetylated distarch adipate, distarch phosphate, hydroxypropyl starch, hydroxy propyl distarch phosphate, phosphated distarch ohosphate, acetylated distarch phosphate, starch sodium octenyl succinate.
Suitable modified polysaccharide polymers also include polymers based on other polysaccharide, such as cationic dextran polymers described in WO2021194808 , the cationic dextran polymers are commercially available under brand name CDC, CDC-L, CD C-H by Meito Sangyo.
Suitable modified polysaccharide polymers also include polymers based on polyglucans. Suitable modified polyglucans are based on alpha 1,3-polyglucans and/or 1,6-polyglucans. The modified polyglucans can be cationic modified, such as cationic modified alpha 1,3-polyglucan which described in WO2021225837 ; such as cationic modified alpha 1,6-polyglucans which described in WO2021257793 , WO2021257932 , and WO2021/257786 . The modified polyglucans can be hydrophobic and/or hydrophilic modified, such as those described in WO2018112187 , WO2019246228 , WO2019246171 , WO2021252558 , WO2021252560 , WO2021252561 , EP3922704 , WO2021252569 , WO2021252562 , WO2021252559 , WO2021252575 , WO2021252563 . Along the hydrophobic and/or hydrophilic modified polyglucans, the polyglucan esters which described in WO2021252562 , WO2021252559 , WO2021252575 , WO2021252563 are especially preferred due to their performance and biodegradability profiles.
Other suitable polysaccharide polymers also include those based on inulin. Example of modified inulin include carboxymethyl group modified inulin (CMI), suitable CMI are Carboxyline series sold by Cosun Beet Company, including Carboxyline 25-40D, Carboxyline 25 D Powder, Carboxyline 20 LS D Powder, Carboxyline 25, Carboxyline 25-30 UP. Example of modified inulin also include cationic modified inulin, suitable cationic modified inulin are as described in US20190274943 , US20180119055 ; suitable cationic modified inulin are Quatin series sold by Cosun Beet Company, including Quatin 350, Quatin 380 and Quatin 1280 which are characterized by different degree of substitution (DS), cationic density (meq/g) and molecular weight (g/mol).
Suitable modified polysaccharide polymers also include polymers based on other polysaccharide, such as xylose carbamates as described in US20210115358 ; carboxy or sulfo-alkylated pullulan as described in WO2019243072 ; carboxy- or sulfo-alkylated chitosan as described in WO2019/243108 and WO2021156093 .

Polycarboxylate Polymers:

The composition may also include one or more polycarboxylate polymers which comprise at least one carboxy group-containing monomer. The carboxy group-containing monomers are selected from acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and salts thereof, and anhydride thereof.
Suitable polycarboxylate polymers include polyacrylate homopolymer having a molecular weight of from 4,000 to 9,000 g/mol, or from 6,000 to 9,000 g/mol. Other suitable carboxylate polymers include copolymer of acrylic acid (and/or methacrylic acid) and maleic acid having a molecular weight of from 50,000 to 120,000 g/mol, or from 60,000 to 80,000 g/mol. The polyacrylate homopolymer and copolymer 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 Itaconix^® DSP 2K^™ sold by Itaconix, and Amaze SP available from Nouryon.
Suitable polycarboxylate polymers also include co-polymers comprising carboxy group-containing monomers and one or more sulfonate or sulfonic group-containing monomers. The sulfonate or sulfonic group containing monomers are selected rom 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy-propanesulfonic acid, ally sulfonic acid, methallysulfonic acid, 3-allyloxy-2-hydroxy-1-propanesulfonic acid, 2-methyl-2-propenen-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropylmethacrylate, sulfomethylacrylamide, sulfomethylmethacrylamide and water soluble salts thereof. Suitable polymers comprise maleic acid, acrylic acid, and 3-allyloxy-2-hydroxy-1-propanesulfonic acid, such polymers are as described in US8450261 and US8389458 . Suitable polymers comprise acrylic acid and 2-acrylamido-2-methyl-propane sulfonate, such as those sold under tradename Acusol 588 by Dow Chemicals, Sokalan CP50 by BASF, Aquatreat AR-545, Versaflex 310 and Versaflex 310-37 by Nouryon. Suitable polymers also include Poly(itaconic acid-co-AMPS) sodium salt, such as Itaconix^® TSI^™ 322 and Itaconix^® CHT^™ 122 available from Itaconix.
Suitable polymer also includes those contain other structure units in addition to the sulfonate or sulfonic group group-containing monomers and carboxy group-containing monomers. Suitable polymer examples are described in WO2010024468 and WO2014032267 , the additional monomers herein are ether bond-containing monomers represented by formula (1) and (2) below:
Wherein in Formula (1)

R₀ represents a hydrogen atom or CH₃ group,
R represents a CH₂ group, CH₂CH₂ group or single bond,
x represents a number 0-50, preferable 0-20, more preferable 0-5 (provided x represents a number 1-5 when R is a single bond), and
R₁ is a hydrogen atom or C₁ to C₂₀ organic group
Wherein in Formula (2),
R₀ represents a hydrogen atom or CH₃ group,
R represents a CH₂ group, CH₂CH₂ group or single bond,
x represents a number 0-5, and
R₁ is a hydrogen atom or C₁ to C₂₀ organic group.

A specific preferred polymer of this type comprises structure units derived from 1 to 49 wt% of 1-(allyloxy)-3-butoxypropan-2-ol, from 50 to 98 wt% acrylic acid or methacrylic acid, and from 1 to 49 wt% of 3-allyloxy-2-hydroxy-1-propanesulfonic acid, and the has a weight average molecular weight of from about 20,000 to about 60,000 g/mol. a specific preferred polymer of this type comprises structure units derived from 1 to 10 wt% of 1-(allyloxy)-3-butoxypropan-2-ol, from 70 to 89 wt% acrylic acid or methacrylic acid, and from 10 to 20 wt% of 3-allyloxy-2-hydroxy-1-propanesulfonic acid, and the has a weight average molecular weight of from about 30,000 to about 60,000 g/mol. Herein, 1-(allyloxy)-3-butoxypropan-2-ol is a preferred monomer as represented by formula (2) when R₀ is H, R is CH₂, x is 0, and R₁ is n-butyl (C₄-alkyl).
Suitable polycarboxylate polymers also include co-polymers comprising carboxy group-containing monomers and other suitable monomers. Other suitable monomers here are selected from esters and/or amide of the carboxy group-containing monomers, such as C₁-C₂₀ alkyl ester of acrylic acid; alkylene; vinyl ethers, such as methyl vinyl ether, styrene and any mixtures thereof. One specific preferred polymer family of this type is sold under tradename Gantrez by Ashland, which includes Gantrez An (alternating co-polymer of methyl vinyl ether and maleic anhydride), Gantrez S (alternating co-polymer of methyl vinyl ether and maleic acid), Gantrez ES (alternating co-polymer of methyl vinyl ether and maleic acid ester), Gantrez MS (alternating co-polymer of methyl vinyl ether and maleic acid salt).
Suitable polycarboxylate polymers also include polyepoxy succinic acid polymers (PESA). A most preferred polyepoxy succinic acid polymer can be identified using CAS number: 51274-37-4 or 109578-44-1. Suitable polyepoxy succinic acid polymers are commercially available from various suppliers, such as Aquapharm Chemicals Pvt. Ltd (commercial name: Maxinol 600); Shandong Taihe Water Treatment Technologies Co., Ltd (commercial name: PESA), and Sirius International (commercial name: Briteframe PESA).
Suitable polycarboxylate polymers also include polymer comprising a monomer having at least one aspartic acid group or a salt thereof, this polymer comprises at least 25 mol%, 40 mol%, or 50 mol%, of said monomer. A preferable example is sodium salt of poly(aspartic acid) having a molecular weight of from 2,000 to 3,000 g/mol which is avilable as Baypure^® DS 100 from Lanxess.

Block polymers of alkylene oxide :

The composition may comprise 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 copolymer, wherein the copolymer comprises a first EO block, a second EO block and PO block wherein the first EO block and the second EO block are linked to the PO block. Blocks of ethylene oxide, propylene oxide, butylene oxide can also be arranged in other ways, such as (EO/PO) diblock copolymer, (PO/EO/PO) triblock copolymer. The block polymers may also contain additional butylene oxide (BO) block. Suitable block polymers are for example Pluronic PE series from BASF, including Pluronic PE3100, PE4300, PE6100, PE6200, PE6400, PE6800, PE8100, PE9200, PE9400, PE10100, PE10500, PE10400. Suitable block polymers also available as Tergitol L series from Dow Chemicals, such as Tergitol L-61, L-62, L-64, L-81, L-101. Due to the hydrophobic and hydrophilic nature, such block polymer sometime is also considered as nonionic surfactant in literature.

Dye transfer inhibiting polymers

The composition may comprise dye transfer inhibiting polymers (also called dye transfer inhibitor, or dye fixatives), which include, but are not limited to, polyvinylpyrrolidone polymers (PVP), poly(vinylpyridine-N-oxide) polymer (PVNO), poly(vinylimidazole), polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. dye transfer inhibiting agents 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.
Suitable other polymers also include a copolymer comprising N-isopropylacrylamide units, such as described in WO2019197188 , WO2019197187 , WO2019197185 and WO2019197186 . Suitable other polymers also include polyester soil release polymers derived from bio-based 2,5-furandicarboxylic acid and derivatives thereof, useful examples are described in WO2019105938 , WO2019105939 , WO2019096942 and JP2015105373 .

Additional Amines:

Additional amines may be used in the compositions described herein for added removal of grease and particulates from soiled materials. The compositions described herein may comprise from about 0.1% to about 10%, in some examples, from about 0.1% to about 4%, and in other examples, from about 0.1% to about 2%, by weight of the composition, of additional amines. Non-limiting examples of additional amines may include, but are not limited to, polyamines, oligoamines, triamines, diamines, pentamines, tetraamines, or combinations thereof. Specific examples of suitable additional amines include tetraethylenepentamine, triethylenetetraamine, diethylenetriamine, or a mixture thereof.

Bleaching Agents:

It may be preferred for the composition to comprise one or more bleaching agents. Suitable bleaching agents other than bleaching catalysts include photobleaches, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, pre-formed peracids and mixtures thereof. In general, when a bleaching agent is used, the compositions of the present invention may comprise from about 0.1% to about 50% or even from about 0.1% to about 25% bleaching agent or mixtures of bleaching agents by weight of the subject composition. Examples of suitable bleaching agents include:

(1) photobleaches for example sulfonated zinc phthalocyanine sulfonated aluminium phthalocyanines, xanthene dyes, thioxanthones, and mixtures thereof;
(2) pre-formed peracids: Suitable preformed peracids include, but are not limited to compounds selected from the group consisting of pre-formed peroxyacids or salts thereof typically a percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, for example, Oxone ^®, and mixtures thereof. Particularly preferred peroxyacids are phthalimido-peroxy-alkanoic acids, in particular ε-phthalimido peroxy hexanoic acid (PAP). Preferably, the peroxyacid or salt thereof has a melting point in the range of from 30°C to 60°C.
(3) sources of hydrogen peroxide, for example, inorganic perhydrate salts, including alkali metal salts such as sodium salts of perborate (usually mono- or tetra-hydrate), percarbonate, persulphate, perphosphate, persilicate salts and mixtures thereof. When employed, inorganic perhydrate salts are typically present in amounts of from 0.05 to 40 wt%, or 1 to 30 wt% of the overall fabric and home care product and are typically incorporated into such fabric and home care products as a crystalline solid that may be coated. Suitable coatings include, inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as water-soluble or dispersible polymers, waxes, oils or fatty soaps; and
(4) bleach activators having R-(C=O)-L wherein R is an alkyl group, optionally branched, having, when the bleach activator is hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when the bleach activator is hydrophilic, less than 6 carbon atoms or even less than 4 carbon atoms; and L is leaving group. Examples of suitable leaving groups are benzoic acid and derivatives thereof - especially benzene sulphonate. Suitable bleach activators include dodecanoyl oxybenzene sulphonate, decanoyl oxybenzene sulphonate, decanoyl oxybenzoic acid or salts thereof, 3,5,5-trimethyl hexanoyloxybenzene sulphonate, tetraacetyl ethylene diamine (TAED) and nonanoyloxybenzene sulphonate (NOBS).
(5) Bleach Catalysts. The compositions of the present invention may also include one or more bleach catalysts capable of accepting an oxygen atom from a peroxyacid and/or salt thereof, and transferring the oxygen atom to an oxidizeable substrate. Suitable bleach catalysts include, but are not limited to: iminium cations and polyions; iminium zwitterions; modified amines; modified amine oxides; N-sulphonyl imines; N-phosphonyl imines; N-acyl imines; thiadiazole dioxides; perfluoroimines; cyclic sugar ketones and alpha amino-ketones and mixtures thereof. One particularly preferred catalyst is acyl hydrazone type such as 4-(2-(2-((2-hydroxyphenylmethyl)methylene)-hydrazinyl)-2-oxoethyl)-4-methylchloride.
(6) The composition may preferably comprise catalytic metal complexes. One preferred type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cations.

If desired, the compositions herein can be catalyzed by means of a manganese compound. Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. 5,576,282 . An additional source of oxidant in the composition may not be not present, molecular oxygen from air providing the oxidative source. Cobalt bleach catalysts useful herein are known, and are described, for example, in U.S. 5,597,936 ; U.S. 5,595,967 .

Fluorescent Brightener:

Commercial fluorescent brighteners suitable for the present disclosure can be classified into subgroups, including but not limited to: derivatives of stilbene, pyrazoline, coumarin, benzoxazoles, carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents.
The fluorescent brightener may be selected from the group consisting of disodium 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate (brightener 15, commercially available under the tradename Tinopal AMS-GX by BASF), disodium4,4'-bis{[4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl]-amino}-2,2'-stilbenedisulonate (commercially available under the tradename Tinopal UNPA-GX by BASF), disodium 4,4'-bis { [4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl]-amino}-2,2'-stilbenedisulfonate (commercially available under the tradename Tinopal 5BM-GX by BASF). More preferably, the fluorescent brightener is disodium 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate or 2,2'-([1,1'-Biphenyl]-4,4'-diyldi-2,1-ethenediyl)bis-benzenesulfonic acid disodium salt. The brighteners may be added in particulate form or as a premix with a suitable solvent, for example nonionic surfactant, propanediol.

Fabric Hueing Agents:

The compositions may comprise a fabric hueing agent (sometimes referred to as shading, bluing or whitening agents). Typically, the hueing agent provides a blue or violet shade to fabric. Hueing agents can be used either alone or in combination to create a specific shade of hueing and/or to shade different fabric types. This may be provided for example by mixing a red and green-blue dye to yield a blue or violet shade. Hueing agents may be selected from any known chemical class of dye, including but not limited to acridine, anthraquinone (including polycyclic quinones), azine, azo (e.g., monoazo, disazo, trisazo, tetrakisazo, polyazo), including premetallized azo, benzodifurane and benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane, formazan, hemicyanine, indigoids, methane, naphthalimides, naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthenes and mixtures thereof.

Chelating Agent:

Preferably the composition comprises chelating agents and/or crystal growth inhibitor. Suitable molecules include copper, iron and/or manganese chelating agents and mixtures thereof. Suitable molecules include hydroxamic acids, aminocarboxylates, aminophosphonates, succinates, salts thereof, and mixtures thereof. Non-limiting examples of suitable chelants for use herein include ethylenediaminetetracetates, N- (hydroxyethyl)ethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriamine-pentaacetates, ethanoldiglycines, ethylenediaminetetrakis (methylenephosphonates), diethylenetriamine penta(methylene phosphonic acid) (DTPMP), ethylenediamine disuccinate (EDDS), hydroxyethanedimethylenephosphonic acid (HEDP), methylglycinediacetic acid (MGDA), diethylenetriaminepentaacetic acid (DTPA), N,N-Dicarboxymethyl glutamic acid (GLDA) and salts thereof, and mixtures thereof. Other nonlimiting examples of chelants of use in the present invention are found in U.S. Patent Nos. 7445644 , 7585376 and 2009/0176684A1 . Other suitable chelating agents for use herein are the commercial DEQUEST series, and chelants from Monsanto, DuPont, and Nalco, Inc. Yet other suitable chelants include the pyridinyl N Oxide type.

Encapsulates:

The compositions may comprise an encapsulate. In some aspects, the encapsulate comprises a core, a shell having an inner and outer surface, where the shell encapsulates the core.
In certain aspects, the encapsulate comprises a core and a shell, where the core comprises a material selected from perfumes; brighteners; dyes; insect repellants; silicones; waxes; flavors; vitamins; fabric softening agents; skin care agents, e.g., paraffins; enzymes; anti-bacterial agents; bleaches; sensates; or mixtures thereof; and where the shell comprises a material selected from polyethylenes; polyamides; polyvinylalcohols, optionally containing other co-monomers; polystyrenes; polyisoprenes; polycarbonates; polyesters; polyacrylates; polyolefins; polysaccharides, e.g., alginate and/or chitosan; gelatin; shellac; epoxy resins; vinyl polymers; water insoluble inorganics; silicone; aminoplasts, or mixtures thereof. In some aspects, where the shell comprises an aminoplast, the aminoplast comprises polyurea, polyurethane, and/or polyureaurethane. The polyurea may comprise polyoxymethyleneurea and/or melamine formaldehyde.

Perfume:

Preferred compositions of the invention comprise perfume. Typically the composition comprises a perfume that comprises one or more perfume raw materials, selected from the group as described in WO08/87497 . However, any perfume useful in a laundry care composition may be used. A preferred method of incorporating perfume into the compositions of the invention is via an encapsulated perfume particle comprising either a water-soluble hydroxylic compound or melamine-formaldehyde or modified polyvinyl alcohol.

Malodor Reduction Materials:

The cleaning compositions of the present disclosure may comprise malodour reduction materials. Such materials are capable of decreasing or even eliminating the perception of one or more malodors. These materials can be characterized by a calculated malodor reduction value ("MORV"), which is calculated according to the test method shown in WO2016049389 .
As used herein "MORV" is the calculated malodor reduction value for a subject material. A material's MORV indicates such material's ability to decrease or even eliminate the perception of one or more malodors.
The cleaning compositions of the present disclosure may comprise a sum total of 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%, most preferably from about 0.01% to about 0.05%, by weight of the composition, of 1 or more malodor reduction materials. The cleaning composition may comprise from about 1 to about 20 malodor reduction materials, more preferably 1 to about 15 malodor reduction materials, most preferably 1 to about 10 malodor reduction materials.
One, some, or each of the malodor reduction materials may have a MORV of at least 0.5, preferably from 0.5 to 10, more preferably from 1 to 10, most preferably from 1 to 5. One, some, or each of the malodor reduction materials may have a Universal MORV, defined as all of the MORV values of >0.5 for the malodors tested as described herein. The sum total of malodor reduction materials may have a Blocker Index of less than 3, more preferable 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 total of malodor reduction materials may have a Blocker Index average of from about 3 to about 0.001.
In the cleaning compositions of the present disclosure, the malodor reduction materials 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 a Fragrance Fidelity Index average of 3 to about 0.001 Fragrance Fidelity Index. As the Fragrance Fidelity Index decreases, the malodor reduction material(s) provide less and less of a scent impact, while continuing to counteract malodors.
The cleaning compositions of the present disclosure may comprise a perfume. The weight ratio of parts of malodor reduction composition to parts of perfume may be from about 1 :20,000 to about 3,000:1, 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 malodor reduction composition to parts of perfume is tightened, the malodor reduction material(s) provide less and less of a scent impact, while continuing to counteract malodors.

Conditioning Agents:

Suitable conditioning agents include high melting point fatty compounds. The high melting point fatty compound useful herein has a melting point of 25°C or higher and is selected from the group consisting of 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.
Suitable conditioning agents include those conditioning agents characterized generally as silicones (e.g., silicone oils, polyoils, 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 which otherwise form liquid, dispersed particles in the aqueous surfactant matrix herein. The compositions of the present invention may also comprise from about 0.05% to about 3% of at least one organic conditioning oil as the conditioning agent, either alone or in combination with other conditioning agents, such as the silicones (described herein). Suitable conditioning oils include hydrocarbon oils, polyolefins, and fatty esters.

Probiotics:

The composition may comprise probiotics, such as those described in WO2009/043709 .

Organic acids:

The detergent comprises one or more organic acids selected from the group consisting of acetic acid, adipic acid, aspartic acid, carboxymethyloxymalonic acid, carboxymethyloxysuccinic 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-disuccinic acid, tartaric-monosuccinic acid, or mixtures thereof. Preferably, the detergent composition may comprise an organic acid selected from the group consisting of acetic acid, lactic acid, and citric acid.

Anti-oxidant:

The composition may optionally contain an anti-oxidant present in the composition from about 0.001 to about 2% by weight. Preferably the antioxidant is present at a concentration in the range 0.01 to 0.08% by weight. Mixtures of anti-oxidants may be used.

Hygiene Agent:

The compositions of the present invention may also comprise components to deliver hygiene and/or malodour benefits such as one or more of zinc ricinoleate, thymol, quaternary ammonium salts such as Bardac^®, polyethylenimines (such as Lupasol^® from BASF) and zinc complexes thereof, silver and silver compounds, especially those designed to slowly release Ag+ or nano-silver dispersions.
The cleaning compositions of the present invention may also contain antimicrobial agents. Preferably, the anti-microbial agent is selected from the group consisting of 4-4'-dichloro-2-hydroxy diphenyl ether ("Diclosan"), 2,4,4'-trichloro-2'-hydroxy diphenyl ether ("Triclosan"), and a combination thereof. Most preferably, the anti-microbial agent is 4-4'-dichloro-2-hydroxy diphenyl ether, commercially available from BASF, under the trademark name Tinosan^®HP100.

Pearlescent Agent:

Non-limiting examples of pearlescent agents include: mica; titanium dioxide coated mica; bismuth oxychloride; fish scales; mono and diesters of alkylene glycol. The pearlescent agent may be ethyleneglycoldistearate (EGDS).

Opacifier:

The composition might also comprise an opacifier. As the term is used herein, an "opacifier" is a substance added to a material in order to make the ensuing system opaque. Preferably, the opacifier is Acusol, which is available from Dow Chemicals. Acusol opacifiers are provided in liquid form at a certain % solids level. As supplied, the pH of Acusol opacifiers ranges from 2.0 to 5.0 and particle sizes range from 0.17 to 0.45 um. Preferably, Acusol OP303B and 301 can be used.
The opacifier may be an inorganic opacifier. Preferably, the inorganic opacifier can be TiO₂, ZnO, talc, CaCO₃, and combination thereof. The composite opacifier-microsphere material is readily formed with a preselected specific gravity, so that there is little tendency for the material to separate.

Solvents:

The solvent system in the present compositions can be a solvent system containing water alone or mixtures of organic solvents either without or preferably with water. The compositions may optionally comprise an organic solvent. Suitable organic solvents include C₄-C₁₄ ethers and diethers, glycols, alkoxylated glycols, C₆-C₁₆ glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C₁-C₅ alcohols, linear C₁-C₅ alcohols, amines, C₈-C₁₄ alkyl and cycloalkyl hydrocarbons and halohydrocarbons, and mixtures thereof. Preferred organic solvents include 1,2-propanediol, 2,3 butane diol, ethanol, glycerol, ethoxylated glycerol, dipropylene glycol, methyl propane diol and mixtures thereof 2 ethyl hexanol, 3,5,5,trimethyl-1 hexanol, and 2 propyl heptanol. Solvents may be a polyethylene or polypropylene glycol ether of glycerin. Other lower alcohols, C₁-C₄ alkanolamines such as monoethanolamine and triethanolamine, can also be used. Solvent systems can be absent, for example from anhydrous solid embodiments of the invention, but more typically are present at levels in the range of from about 0.1% to about 98%, preferably at least about 1% to about 50%, more usually from about 5% to about 25%, alternatively from about 1% to about 10% by weight of the liquid detergent composition of said organic solvent. These organic solvents may be used in conjunction with water, or they may be used without water.

Hydrotrope:

The composition may optionally comprise a hydrotrope in an effective amount, i.e. from about 0% to 15%, or about 1% to 10% , or about 3% to about 6%, so that compositions are compatible in water. Suitable hydrotropes for use herein include anionic-type hydrotropes, particularly sodium, potassium, and ammonium xylene sulfonate, sodium, potassium and ammonium toluene sulfonate, sodium potassium and ammonium cumene sulfonate, and mixtures thereof, as disclosed in U.S. Patent 3,915,903 .

Suds Suppressor:

Compounds for reducing or suppressing the formation of suds can be incorporated into the water-soluble unit dose articles. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" and in front-loading style washing machines. Examples of suds supressors include monocarboxylic fatty acid and soluble salts therein, high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C₁₈-C₄₀ ketones (e.g., stearone), N-alkylated amino triazines, waxy hydrocarbons preferably having a melting point below about 100 °C, silicone suds suppressors, and secondary alcohols. Preferred fatty acid blends may be mixtures enriched or Fatty acid mixtures enriched with 2-alkyl fatty acid, preferably 2-methyl octanoic acid.
Additional suitable antifoams are those derived from phenylpropylmethyl substituted polysiloxanes.
The detergent composition may comprise a suds suppressor selected from organomodified silicone polymers with aryl or alkylaryl substituents combined with silicone resin and a primary filler, which is modified silica. The detergent compositions may comprise from about 0.001% to about 4.0%, by weight of the composition, of such a suds suppressor.
The detergent composition comprises a suds suppressor selected from: a) mixtures of from about 80 to about 92% ethylmethyl, methyl(2-phenylpropyl) siloxane; from about 5 to about 14% MQ resin in octyl stearate; and from about 3 to about 7% modified silica; b) mixtures of from about 78 to about 92% ethylmethyl, methyl(2-phenylpropyl) siloxane; from about 3 to about 10% MQ resin in octyl stearate; from about 4 to about 12% modified silica; or c) mixtures thereof, where the percentages are by weight of the anti-foam.

Liquid laundry detergent composition.

The fabric and home care product can be a laundry detergent composition, such as a liquid laundry detergent composition. Suitable liquid laundry detergent compositions can comprise a non-soap surfactant, wherein the non-soap surfactant comprises an anionic non-soap surfactant and a non-ionic surfactant. The laundry detergent composition can comprise from 10% to 60%, or from 20% to 55% by weight of the laundry detergent composition of the non-soap surfactant. The non-soap anionic surfactant to nonionic surfactant are from 1:1 to 20:1, from 1.5:1 to 17.5:1, from 2:1 to 15:1, or from 2.5:1 to 13:1. Suitable non-soap anionic surfactants include linear alkylbenzene sulphonate, alkyl sulphate or a mixture thereof. The weight ratio of linear alkylbenzene sulphonate to alkyl sulphate can be from 1:2 to 9:1, from 1:1 to 7:1, from 1:1 to 5:1, or from 1:1 to 4:1. Suitable linear alkylbenzene sulphonates are C₁₀-C₁₆ alkyl benzene sulfonic acids, or C₁₁-C₁₄ alkyl benzene sulfonic acids. Suitable alkyl sulphate anionic surfactants include alkoxylated alkyl sulphates, non-alkoxylated alkyl sulphates, and mixture thereof. Preferably, the HLAS surfactant comprises greater than 50% C₁₂, preferably greater than 60%, preferably greater than 70% C₁₂, more preferably greater than 75% C₁₂. Suitable alkoxylated alkyl sulphate anionic surfactants include ethoxylated alkyl sulphate anionic surfactants. Suitable alkyl sulphate anionic surfactants include ethoxylated alkyl sulphate anionic surfactant with a mol average degree of ethoxylation of from 1 to 5, from 1 to 3, or from 2 to 3. The alkyl alkoxylated sulfate may have a broad alkoxy distribution or a peaked alkoxy distribution. The alkyl portion of the AES may include, on average, from 13.7 to about 16 or from 13.9 to 14.6 carbons atoms. At least about 50% or at least about 60% of the AES molecule may include having an alkyl portion having 14 or more carbon atoms, preferable from 14 to 18, or from 14 to 17, or from 14 to 16, or from 14 to 15 carbon atoms. The alkyl sulphate anionic surfactant may comprise a non-ethoxylated alkyl sulphate and an ethoxylated alkyl sulphate wherein the mol average degree of ethoxylation of the alkyl sulphate anionic surfactant is from 1 to 5, from 1 to 3, or from 2 to 3. The alkyl fraction of the alkyl sulphate anionic surfactant can be derived from fatty alcohols, oxo-synthesized alcohols, Guerbet alcohols, or mixtures thereof. Preferred alkyl sulfates include optionally ethoxylated alcohol sulfates including 2-alkyl branched primary alcohol sulfates especially 2-branched C_12-15 primary alcohol sulfates, linear primary alcohol sulfates especially linear C_12-14 primary alcohol sulfates, and mixtures thereof. The laundry detergent composition can 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 the non-soap anionic surfactant.
Suitable non-ionic surfactants can be selected from alcohol broad or narrow range alkoxylates, an oxo-synthesised alcohol alkoxylate, Guerbet alcohol alkoxylates, alkyl phenol alcohol alkoxylates, or a mixture thereof. The laundry detergent composition can 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 non-ionic surfactant.
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 soap, such as a fatty acid salt. Such soaps can be amine neutralized, for instance using an alkanolamine such as monoethanolamine.
The laundry detergent composition can comprises an adjunct ingredient selected from the group comprising builders including citrate, enzymes, bleach, bleach catalyst, dye, hueing dye, Leuco dyes, brightener, cleaning polymers including alkoxylated polyamines and polyethyleneimines, amphiphilic copolymers, soil release polymer, surfactant, solvent, dye transfer inhibitors, chelant, diamines, perfume, encapsulated perfume, polycarboxylates, structurant, pH trimming agents, antioxidants, antibacterial, antimicrobial agents, preservatives and mixtures thereof.
The laundry detergent composition can have a pH of from 2 to 11, or from 6.5 to 8.9, or from 7 to 8, wherein the pH of the laundry detergent composition is measured at a 10% product concentration in demineralized water at 20°C.
The liquid laundry detergent composition can be Newtonian or non-Newtonian, preferably non-Newtonian.
For liquid laundry detergent compositions, the composition can comprise from 5% to 99%, or from 15% to 90%, or from 25% to 80% by weight of the liquid detergent composition of water.

The detergent composition according to the invention can be liquid laundry detergent composition. The following are exemplary liquid laundry detergent formulations (Table 1). Preferably the liquid laundry detergent composition comprises from between 0.1 to 20.0%, preferably 0.2% to 10%, preferably between 0.3% and 5.0%, preferably between 0.5% and 3%, more preferably between 1% to 2.5% by weight of the detergent composition of the polymer according to the invention.

Table 1.

Raw Material	Comp. 1 %wt	Comp. 2 %wt	Comp. 3 %wt	Comp. 4 %wt
Branched Alkyl Sulfate	0.0	5.3	0.0	5.3
Sodium Lauryl Sulfate	0.0	3.0	0.0	3.0
Linear alkylbenzene sulfonate	18.0	5.0	6.0	5.0
AE₃S Ethoxylated alkyl sulphate with an average degree of ethoxylation of 3	5.0	0.0	1.3	0.0
C₂₅AES Ethoxylated alkyl sulphate with an average degree of ethoxylation of 2.5¹	0.0	3.0	1.4	0.0
Amine oxide surfactant	0.7	1.0	0.4	0.8
C_12-14 alkyl ethoxylate (EO7)	8.4	0.0	12.9	5.0
C_12-14 alkyl ethoxylate (EO9)	0.0	8.7	0.0	3.7
C_12-15 alkyl ethoxylate (EO7)	0.0	2.7	0.0	2.7
Citric acid	2.9	2.3	0.7	2.3
Palm kernel fatty acid	0.0	1.0	0.0	1.0
Topped kernel fatty acid	2.9	0.0	2.3	0.0
Mannanase	0.0017	0.0017	0.0017	0.0017
Pectawash	0.00342	0.00342	0.00342	0.00342
Amylase	0.00766	0.00766	0.00766	0.00766
Protease	0.07706	0.07706	0.07706	0.07706
Nuclease³	0.010	0.01	0.01	0.01
Sodium tetraborate	0.0	1.7	0.0	1.7
MEA-Boric Acid Salt	0.0	0.0	0.8	0.0
Calcium/sodium formate	0.0	0.04	0.01	0.04
Sodium/Calcium Chloride	0.04	0.02	0.03	0.02
Ethoxylated polyethyleneimine²	0.0	2.0	1.1	2.0
Amphiphilic graft copolymer	1.5	0.0	0.0	0.0
Ethoxylated-Propoxylated polyethyleneimine	0.0	2.0	0.8	2.0
Zwitterionic polyamine	0.5	0.0	0.0	0.0
Nonionic polyester terephthalate	1.0	1.0	1.0	1.0
Graft polymer of the present invention	3.0	2.5	1.2	2.5
DTPA	0.0	0.1	0.2	0.1
EDDS	0.1	0.0	0.0	0.0
GLDA	0.4	0.3	0.1	0.0
MGDA	0.2	0.0	0.0	0.5
Diethylene triamine penta(methyl phosphonic) acid (DTPMP)	1.1	0.0	0.0	0.0
Fluorescent Brightener⁸	0.06	0.22	0.03	0.15
Ethanol	0.7	1.9	0.0	1.9
propylene glycol	5.5	5.5	0.33	5.5
Sorbitol	0.01	0.01	0.0	0.01
Monoethanolamine	0.2	0.2	0.6	0.2
DETA	0.1	0.08	0.0	0.08
Antioxidant 1	0.0	0.1	0.1	0.1
Antioxidant 2	0.1	0.0	0.0	0.0
Hygiene Agent	0.0	0.0	0.05	0.0
NaOH	4.7	4.7	1.1	4.7
NaCS	3.2	1.7	3.2	1.7
Hydrogenated Castor Oil	0.2	0.1	0.12	0.1
Aesthetic dye	0.10	0.01	0.006	0.01
Leuco dye	0.05	0.01	0.0	0.01
Perfume	2.0	1.3	0.5	1.3
Perfume microcapsules	0.5	0.05	0.1	0.05
Silicone antifoam⁷	0.02	0.01	0.0	0.01
Phenyloxyethanol	0.002	0.01	0.0	0.01
Hueing dye	0.01	0.1	0.05	0.1
Water & miscellaneous	balance	balance	balance	balance

Description of super-script numbers: 1 C_12-15EO_2.5S AlkylethoxySulfate where the alkyl portion of AES includes from about 13.9 to 14.6 carbon atoms
2 PE-20 commercially available from BASF
3 Nuclease enzyme is as claimed in co-pending European application 19219568.3
4 Antioxidant 1 is 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, methyl ester [6386-38-5]
5 Antioxidant 2 is Tinogard TS commercially available from BASF
6 Hygiene Agent is agent is Tinosan HP 100 commercially available from BASF
7 Dow Corning supplied antifoam blend 80-92% ethylmethyl, methyl(2-phenyl propyl)siloxane; 5-14% MQ Resin in octyl stearate a 3-7% modified silica.
8 Fluorescent Brightener is disodium 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate or 2,2'-([1,1'-Biphenyl]-4,4'-diyldi-2,1-ethenediyl)bis-benzenesulfonic acid disodium salt.

Water Soluble Unit Dose Article.

The fabric and home care product can be a water-soluble unit dose article. The water-soluble unit dose article comprises at least one water-soluble film orientated to create at least one unit dose internal compartment, wherein the at least one unit dose internal compartment comprises a detergent composition. The water-soluble film preferably comprises polyvinyl alcohol homopolymer or polyvinyl alcohol copolymer, for example a blend of polyvinylalcohol homopolymers and/or polyvinylalcohol copolymers, for example copolymers selected from sulphonated and carboxylated anionic polyvinylalcohol copolymers especially carboxylated anionic polyvinylalcohol copolymers, for example a blend of a polyvinylalcohol homopolymer and a carboxylated anionic polyvinylalcohol copolymer. In some examples water soluble films are those supplied by Monosol under the trade references M8630, M8900, M8779, M8310. The detergent product comprises a detergent composition, more preferably a laundry detergent composition. Preferably the laundry detergent composition enclosed in the water-soluble unit dose article comprises from between 0.1% and 8%, preferably between 0.5% and 7%, more preferably 1.0% to 6.0% by weight of the detergent composition of the polymer of the present invention. Preferably the soluble unit dose laundry detergent composition comprises a non-soap surfactant, wherein the non-soap surfactant comprises an anionic non-soap surfactant and a non-ionic surfactant. More preferably, the laundry detergent composition comprises between 10% and 60%, or between 20% and 55% by weight of the laundry detergent composition of the non-soap surfactant. The weight ratio of non-soap anionic surfactant to nonionic surfactant preferably is from 1:1 to 20:1, from 1.5:1 to 17.5:1, from 2:1 to 15:1, or from 2.5:1 to 13:1. The non-soap anionic surfactants preferably comprise linear alkylbenzene sulphonate, alkyl sulphate or a mixture thereof. The weight ratio of linear alkylbenzene sulphonate to alkyl sulphate preferably is from 1:2 to 9:1, from 1:1 to 7:1, from 1:1 to 5:1, or from 1:1 to 4:1. Example linear alkylbenzene sulphonates are C₁₀-C₁₆ alkyl benzene sulfonic acids, or C₁₁-C₁₄ alkyl benzene sulfonic acids. By 'linear', we herein mean the alkyl group is linear. Example alkyl sulphate anionic surfactant may comprise alkoxylated alkyl sulphate or non-alkoxylated alkyl sulphate or a mixture thereof. Example alkoxylated alkyl sulphate anionic surfactants comprise an ethoxylated alkyl sulphate anionic surfactant. Example alkyl sulphate anionic surfactant may comprise an ethoxylated alkyl sulphate anionic surfactant with a mol average degree of ethoxylation from 1 to 5, from 1 to 3, or from 2 to 3. Example alkyl sulphate anionic surfactant may comprise a non-ethoxylated alkyl sulphate and an ethoxylated alkyl sulphate wherein the mol average degree of ethoxylation of the alkyl sulphate anionic surfactant is from 1 to 5, from 1 to 3, or from 2 to 3. Example alkyl fraction of the alkyl sulphate anionic surfactant are derived from fatty alcohols, oxo-synthesized alcohols, Guerbet alcohols, or mixtures thereof. Preferably the laundry detergent composition comprises between 10% and 50%, between 15% and 45%, between 20% and 40%, or between 30% and 40% by weight of the laundry detergent composition of the non-soap anionic surfactant. In some examples, the non-ionic surfactant is selected from alcohol alkoxylate, an oxo-synthesised alcohol alkoxylate, Guerbet alcohol alkoxylates, alkyl phenol alcohol alkoxylates, or a mixture thereof. Preferably, the laundry detergent composition comprises between 0.01% and 10%, or between 0.01% and 8%, or between 0.1% and 6%, or between 0.15% and 5% by weight of the liquid laundry detergent composition of a non-ionic surfactant. Preferably, the laundry detergent composition comprises between 1.5% and 20%, between 2% and 15%, between 3% and 10%, or between 4% and 8% by weight of the laundry detergent composition of soap, in some examples a fatty acid salt, in some examples an amine neutralized fatty acid salt, wherein in some examples the amine is an alkanolamine preferably monoethanolamine. Preferably the liquid laundry detergent composition comprises less than 15%, or less than 12% by weight of the liquid laundry detergent composition of water. Preferably, the laundry detergent composition comprises between 10% and 40%, or between 15% and 30% by weight of the liquid laundry detergent composition of a non-aqueous solvent selected from 1,2-propanediol, dipropylene glycol, tripropyleneglycol, glycerol, sorbitol, polyethylene glycol or a mixture thereof. Preferably the liquid laundry detergent composition comprises from 0.1% to 10%, preferably from 0.5% to 8% by weight of the detergent composition of further soil release polymers, preferably selected from the group of nonionic and/or anionically modified polyester terephthalate soil release polymers such as commercially available under the Texcare brand name from 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 from 0.1% to 10% preferably from 1% to 5% of a chelant. In some examples, the laundry detergent composition comprises an adjunct ingredient selected from the group comprising builders including citrate, enzymes, bleach, bleach catalyst, dye, hueing dye, brightener, cleaning polymers including (zwitterionic) alkoxylated polyamines, surfactant, solvent, dye transfer inhibitors, perfume, encapsulated perfume, polycarboxylates, structurant, pH trimming agents, 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 as a 10% product concentration in demineralized water at 20°C. When liquid, the laundry detergent composition may be Newtonian or non-Newtonian, preferably non-Newtonian.

The following is an 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 split over multiple compartments resulting in below "averaged across compartments" full article composition. The composition is enclosed within a polyvinyl alcohol-based water soluble, the polyvinyl alcohol comprising a blend of a polyvinyl alcohol homopolymer and an anionic e.g. carboxylated polyvinyl alcohol copolymer.

Table 2.

Ingredients	Comp. 5 (wt%)
Fatty alcohol ethoxylate non-ionic surfactant, C_12-14 average degree of ethoxylation of 7	3.8
Lutensol XL100	0.5
Linear C_11-14 alkylbenzene sulphonate	24.6
AE₃S Ethoxylated alkyl sulphate with an average degree of ethoxylation of 3	12.5
Citric acid	0.7
Palm Kernel Fatty acid	5.3
Nuclease enzyme* (wt% active protein)	0.01
Protease enzyme (wt% active protein)	0.07
Amylase enzyme (wt% active protein)	0.005
Xyloglucanese enzyme (wt% active protein)	0.005
Mannanase enzyme (wt% active protein)	0.003
Ethoxylated polyethyleneimine (Lutensol FP620 - PEI600EO20)	1.4
Amphiphilic graft copolymer**	1.6
Zwitterionic polyamine (Lutensit Z96)	1.5
Anionic polyester terephthalate (Texcare SRA300)	0.6
Graft polymer of the present invention	2.5
HEDP	2.2
Brightener 49	0.4
Silicone anti-foam	0.3
Hueing dye	0.05
1,2 PropaneDiol	11.0
Glycerine	4.7
DPG (DiPropyleneGlycol)	1.7
TPG (TriPropyleneGlycol)	0.1
Sorbitol	0.1
Monoethanolamine	10.2
K₂SO₃	0.4
MgCl₂	0.3
water	10.5
Hydrogenated castor oil	0.1
Perfume	2.1
Aesthetic dye & Minors	Balance to 100
pH (10% product concentration in demineralized water at 20°C)	7.4

Description of super-scripts: *Nuclease enzyme is as claimed in co-pending European application 19219568.3
**polyethylene glycol graft polymer comprising a polyethylene glycol backbone (Pluriol E6000) and hydrophobic vinyl acetate side chains, comprising 40% by weight of the polymer system of a polyethylene glycol backbone polymer and 60% by weight of the polymer system of the grafted vinyl acetate side chains

Solid Free-flowing Particulate Laundry Detergent Composition.

The fabric and home care product can be solid free-flowing particulate laundry detergent composition. The following is an exemplary solid free-flowing particulate laundry detergent composition (Table 3).

Table 3.

Ingredient	Comp. 7 (wt%)
Anionic detersive surfactant (such as alkyl benzene sulphonate, alkyl ethoxylated sulphate and mixtures thereof)	from 8wt% to 15wt%
Non-ionic detersive surfactant (such as alkyl ethoxylated alcohol)	from 0.1wt% to 4wt%
Cationic detersive surfactant (such as quaternary ammonium compounds)	from 0wt% to 4wt%
Other detersive surfactant (such as zwiterionic detersive surfactants, amphoteric surfactants and mixtures thereof)	from 0wt% to 4wt%
Carboxylate polymer (such as co-polymers of maleic acid and acrylic acid and/or carboxylate polymers comprising ether moieties and sulfonate moieties)	from 0.1wt% to 4wt%
Polyethylene glycol polymer (such as a polyethylene glycol polymer comprising polyvinyl acetate side chains)	from 0wt% to 4wt%
Polyester soil release polymer (such as Repel-o-tex and/or Texcare polymers)	from 0wt% to 2wt%
Cellulosic polymer (such as carboxymethyl cellulose, methyl cellulose and combinations thereof)	from 0.5wt% to 2wt%
Graft polymer of the present invention	From 0.1wt% to 5wt%
Other polymer (such as polymers based on polysaccharide)	from 0wt% to 4wt%
Zeolite builder and phosphate builder (such as zeolite 4A and/or sodium tripolyphosphate)	from 0wt% to 4wt%
Other co-builder (such as sodium citrate and/or citric acid)	from 0wt% to 3wt%
Carbonate salt (such as sodium carbonate and/or sodium bicarbonate)	from 0wt% to 20wt%
Silicate salt (such as sodium silicate)	from 0wt% to 10wt%
Filler (such as sodium sulphate and/or bio-fillers)	from 10wt% to 70wt%
Source of hydrogen peroxide (such as sodium percarbonate)	from 0wt% to 20wt%
Bleach activator (such as tetraacetylethylene diamine (TAED) and/or nonanoyloxybenzenesulphonate (NOBS))	from 0wt% to 8wt%
Bleach catalyst (such as oxaziridinium-based bleach catalyst and/or transition metal bleach catalyst)	from 0wt% to 0.1wt%
Other bleach (such as reducing bleach and/or pre-formed peracid)	from 0wt% to 10wt%
Photobleach (such as zinc and/or aluminium sulphonated phthalocyanine)	from 0wt% to 0.1wt%
Chelant (such as ethylenediamine-N'N'-disuccinic acid (EDDS) and/or hydroxyethane diphosphonic acid (HEDP))	from 0.2wt% to 1wt%
Hueing agent (such as direct violet 9, 66, 99, acid red 50, solvent violet 13 and any combination thereof)	from 0wt% to 1wt%
Brightener (C.I. fluorescent brightener 260 or C.I. fluorescent brightener 351)	from 0.1wt% to 0.4wt%
Protease (such as Savinase, Savinase Ultra, Purafect, FN3, FN4 and any combination thereof)	from 0.1wt% to 0.4wt%
Amylase (such as Termamyl, Termamyl ultra, Natalase, Optisize, Stainzyme, Stainzyme Plus and any combination thereof)	from 0wt% to 0.2wt%
Cellulase (such as Carezyme and/or Celluclean)	from 0wt% to 0.2wt%
Lipase (such as Lipex, Lipolex, Lipoclean and any combination thereof)	from 0wt% to 1wt%
Other enzyme (such as xyloglucanase, cutinase, pectate lyase, mannanase, bleaching enzyme)	from 0wt% to 2wt%
Fabric softener (such as montmorillonite clay and/or polydimethylsiloxane (PDMS))	from 0wt% to 15wt%
Flocculant (such as polyethylene oxide)	from 0wt% to 1wt%
Suds suppressor (such as silicone and/or fatty acid)	from 0wt% to 4wt%
Perfume (such as perfume microcapsule, spray-on perfume, starch encapsulated perfume accords, perfume loaded zeolite, and any combination thereof)	from 0.1wt% to 1wt%
Aesthetics (such as coloured soap rings and/or coloured speckles/noodles)	from 0wt% to 1wt%
Miscellaneous	balance to 100wt%

Fibrous Water-soluble Unit Dose Article.

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 in water. In other words, the unit dose article, fibrous structure, or fibrous element is capable of forming a homogeneous solution with water at ambient conditions. "Ambient conditions" as used herein means 23°C ± 1.0°C and a relative humidity of 50% ± 2%. The water-soluble unit dose article may contain insoluble materials, which are dispersible in aqueous wash conditions to a suspension mean particle size that is less than about 20 microns, or less than about 50 microns.
The fibrous water-soluble unit dose article may include any of the disclosures found in U.S. Patent Application No. 15/880,594 filed on January 26, 2018 ; U.S. Patent Application No. 15/880,599 filed January 26, 2018 ; and U.S. Patent Application No. 15/880,604 filed January 26, 2018 ; incorporated by reference in their entirety. Preferred water-soluble fibrous structure comprises particles having a ratio of Linear Alkylbenzene Sulfonate to Alkylethoxylated Sulfate or Alkyl Sulfate of greater than 1.
These fibrous water-soluble unit dose articles can be dissolved under various wash conditions, e.g., low temperature, low water and/or short wash cycles or cycles where consumers have been overloading the machine, especially with items having high water absorption capacities, while providing sufficient delivery of active agents for the intended effect on the target consumer substrates (with similar performance as today's liquid products). Furthermore, the water-soluble unit dose articles described herein can be produced in an economical manner by spinning fibers comprising active agents. The water-soluble unit dose articles described herein also have improved cleaning performance.

Method of Use.

The compositions of this invention, prepared as hereinbefore described, can be used to form aqueous washing/treatment solutions for use in the laundering/treatment of fabrics. Generally, an effective amount of such compositions is added to water, for example in a conventional fabric automatic washing machine, to form such aqueous laundering solutions. The aqueous washing solution so formed is then contacted, typically under agitation, with the fabrics to be laundered/treated therewith. An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering solutions can comprise amounts sufficient to form from about 500 to 7,000 ppm of composition in aqueous washing solution, or from about 1,000 to 3,000 ppm of the laundry care compositions herein will be provided in aqueous washing solution.
Typically, the wash liquor is formed by contacting the laundry care composition with wash water in such an amount so that the concentration of the laundry care composition in the wash liquor is from above 0g/l to 5g/l, or from 1g/l, and to 4.5g/l, or to 4.0g/l, or to 3.5g/l, or to 3.0g/l, or to 2.5g/l, or even to 2.0g/l, or even to 1.5g/l. The method of laundering fabric or textile may be carried out in a top-loading or front-loading automatic washing machine or can be used in a hand-wash laundry application. In these applications, the wash liquor formed and concentration of laundry detergent composition in the wash liquor is that of the main wash cycle. Any input of water during any optional rinsing step(s) is not included when determining the volume of the wash liquor.
The wash liquor may comprise 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 wash liquor may comprise from above 0 to 15 liters, or from 2 liters, and to 12 liters, or even to 8 liters of water. Typically, from 0.01kg to 2kg of fabric per liter of wash liquor is dosed into said wash liquor. Typically, from 0.01kg, or from 0.05kg, or from 0.07kg, or from 0.10kg, or from 0.15kg, or from 0.20kg, or from 0.25kg fabric per liter of wash liquor is dosed into said wash liquor. Optionally, 50g or less, or 45g or less, or 40g or less, or 35g or less, or 30g or less, or 25g or less, or 20g or less, or even 15g or less, or even 10g or less of the composition is contacted to water to form the wash liquor. Such compositions are typically employed at concentrations of from about 500 ppm to about 15,000 ppm in solution. When the wash solvent is water, the water temperature typically ranges from about 5 °C to about 90 °C and, when the situs comprises a fabric, the water to fabric ratio is typically from about 1:1 to about 30:1. Typically the wash liquor comprising the laundry care composition of the invention has a pH of from 3 to 11.5.
In one aspect, such method comprises the steps of optionally washing and/or rinsing said surface or fabric, contacting said surface or fabric with any composition disclosed in this specification then optionally washing and/or rinsing said surface or fabric is disclosed, with an optional drying step.
Drying of such surfaces or fabrics may be accomplished by any one of the common means employed either in domestic or industrial settings. The fabric may comprise any fabric capable of being laundered in normal consumer or institutional use conditions, and the invention is suitable for cellulosic substrates and in some aspects also suitable for synthetic textiles such as polyester and nylon and for treatment of mixed fabrics and/or fibers comprising synthetic and cellulosic fabrics and/or fibers. As examples of synthetic fabrics are polyester, nylon, these may be present in mixtures with cellulosic fibers, for example, polycotton fabrics. The solution typically has a pH of from 7 to 11, more usually 8 to 10.5. The compositions are typically employed at concentrations from 500 ppm to 5,000 ppm in solution. The water temperatures typically range from about 5°C to about 90°C. The water to fabric ratio is typically from about 1:1 to about 30:1.
Another method includes contacting a nonwoven substrate, which is impregnated with the detergent composition, with a soiled material. As used herein, "nonwoven substrate" can comprise any conventionally fashioned nonwoven sheet or web having suitable basis weight, caliper (thickness), absorbency, and strength characteristics. Non-limiting examples of suitable commercially available nonwoven substrates include those marketed under the trade names SONTARA^® by DuPont and POLY WEB^® by James River Corp.

Carbon Source of Raw Materials.

The raw materials for preparation of the surfactant, polymers and other ingredients can be based on fossil carbon or renewable carbon. Renewable carbon is a carbon source that avoid the use of fossil carbon such as natural gas, coal, petroleum. Typically, renewable carbon is derived from the biomass, carbon capture, or chemical recycling.
Biomass is a renewable carbon source formed through photosynthesis in the presence of sunlight, or chemosynthesis process in the absence of sunlight. In some cases, polymers isolated from biomass can be used directly, or further derivatized to make performance polymers. For example, the use of polysaccharide (such as starch) and derivatized polysaccharide (such as cellulose derivatives, guar derivatives, dextran derivatives) in fabric home care composition are 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 convert to biobased polyethylene glycol. Other nonlimiting examples of renewable carbon from biomass include plants (e.g., sugar cane, beets, corn, potatoes, citrus fruit, woody plants, lignocellulosics, hemicellulosics, cellulosic waste), animals, animal fats, fish, bacteria, fungi, plant-based oils, and forestry products. These resources can be naturally occurring, hybrids, or genetically engineered organisms.
Carbon capture is another renewable carbon source which use various process to capture CO₂ or methane from industrial or natural processes, or directly from air (direct capture). Captured methane and CO₂ maybe converted into syngas, and/or further convert to basic chemicals, including but not limit to methanol, ethanol, fatty alcohols such as C₁₂/C₁₄ or even C₁₆/C₁₈ alcohols, other alcohols, olefins, alkanes, saturated and unsaturated organic acids, etc. These basic chemicals can used as or further convert to monomers for making transformed to usable chemicals by e.g. catalytic processes, such as the Fischer-Tropsch process or by fermentation by C₁-fixing microorganisms.
Chemical recycling is another renewable carbon source which allow plastics from waste management industry to be recycled and converted into base chemicals and chemical feedstocks. In some cases, waste plastics which cannot be re-used or mechanical recycled are convert to hydrocarbons or basic petrochemicals through gasification, pyrolysis or hydrothermal treatment processes, the hydrocarbons and basic petrochemicals can be further convert into monomers for polymers. In some cases, waste plastics are depolymerized into monomers to make new polymers. It is also possible that waste plastics are depolymerized into oligomers, the oligomers can be used as building blocks to make new polymers. The waste plastic converted by various processes to a waste plastic feedstock for the above materials may either be used alone or in combination with traditional surfactant feedstocks, such as kerosene, polyolefins derived from natural gas, coal, crude oil or even biomass, or waste fat/oil-derived paraffin and olefin, to produce biodegradable surfactants for use in detergents and other industries (thereby providing a benefit to society).
Preferably, the surfactant, polymers and other ingredients contains renewable carbon, the Renewable Carbon Index (RCI, a measure of sustainability by dividing the number of carbons derived from renewable sources by the total number of carbons in an active ingredient) of the polymer is above 10%, more preferably above 30%, more preferably above 50%, more preferably above 60%, more preferably between 70% to 100%, and most preferably 100%.

EXAMPLES

Methods.

Fabric Treatment

Before testing for dye transfer, the white acceptor fabrics are "de-sized" and/or "stripped" to remove any manufacturer's finish that may be present. Fabrics are dried, cut in 2 cm x 2.75 cm swatches and treated with a detergent composition containing dye extracted from test fabrics using the Wrist Shaker Dye Transfer method designed to mimic full-scale washing machine conditions. Dye transfer onto the white acceptor fabrics is measured on a spectrophotometer according to the Dye Transfer Measurement Method on treated Fabrics.
Stripping of fabrics. New 100% cotton knit fabrics (WFK CK-19502) are stripped by washing five times in a high capacity front-loading washing machine such as a Milnor model number 30022X8J at 60 °C (140°F) using 0 gpg water. The machine is programmed to fill and drain 15 times for a total of 1420 L (375 gallons) of water. The first and second wash cycles use 175 g of detergent (AATCC 2003 Standard Reference Liquid Detergent without optical brightener, available from Test Fabrics Inc., West Pittston, PA), which is added to a 20-23 kg load of fabric. Each wash cycle is followed by two rinses, and the second wash cycle is followed by three additional wash cycles without detergent or until no suds are observed. The fabrics are then dried in a tumble dryer until completely dry, cut to size and used in the Wrist Shaker Dye Transfer Method.
Wrist Shaker Dye Transfer Method. A concentrated solution of extractable dye is prepared by heating and shaking four pieces (7.6 cm x 7.6 cm) of test fabric knits (Style 460 bleached tubular cotton knit dyed with 3% dye solution, Test Fabrics, Inc. in West Pittston, PA) for a minimum 24h at 50 °C in a 38 mL of deionized water in a 40 mL scintillation vial (Qorpak VWR supplier part #18087-086). Vials are heated using a Multi Temperature Zone Reaction Blocks, KEM Scientific, SN: 26197 on top of an orbital Shaker at Speed: 2 (VWR Standard Analog Shaker, Model: 3500, SN: 191011001, NA CAT No: 89032-092). Vials are removed from heat, fabric swatches and solution are transferred to a disposable syringe fitted with a 1.1micron glass filter (Thermo Scientific, #722-2000) and filtered into a clean vial. The UV-VIS is measured in a1 cm disposable cuvette (VWR 97000-588) on a spectrophotometer such as Beckman Coulter DU800. Solutions are diluted to 0.25 absorbance at λ_max into 15 gpg water. To 3.4 g of the hardness adjusted dye solution is added 0.09g of a 10% solution of detergent followed by stripped White Acceptor Fabrics (2 x 2.75 cm, 100% cotton knit, WFK CK-19502). The fabrics in solution are shaken for 30 min at ambient temperature to simulate a wash on a Wrist Action Shaker (Burrell Model 75 single speed). After shaking, fabrics are transferred to a countertop spin dryer to remove excess liquid (Mini Countertop Spin Dryer from The Laundry Alternative) for 1.5 min. Spun fabrics are transferred to a new flask and rinsed using 3.5g of 15 gpg water and shaken on the wrist shaker for 15 min. Rinsed fabrics are placed on the spin dryer for 1.5 mins, then dried on racks in food dehydrator (NESCO American Harvest) set at 52 °C for 1 hour. Dye transfer on the dried fabrics is measured using a spectrophotometer such as a Konica Minolta Spectrophotomer CM-3610d. Dye Transfer Measurement Method on treated Fabrics. As used herein and as will be familiar one of ordinary skill, the "L*C*h color space" and "L*a*b* color space" are three dimensional colorimetric models developed by Hunter Associates Laboratory and recommended by the Commission Internationale d'Eclairage ("CIE") to measure the color or change in color of a dyed article. The CIE L*a*b* color space ("CIELAB") has a scale with three-fold axes with the L axis representing the lightness of the color space (L* = 0 for black, L* = 100 for white), the a* axis representing color space from red to green (a* > 0 for red, a* < 0 for green) and the b* axis representing color space from yellow to blue (b* > 0 for yellow, b* < 0 for blue). The L*C*h color space is an approximately uniform scale with a polar color space. The CIE L*C*h color space ("CIELCh") scale values are determined instrumentally and may also be calculated from the CIELAB scale values. Term definitions and equation derivations are available from Hunter Associates Laboratory, Inc. and from www.hunterlab.com, and are incorporated in their entirety by reference herein.
The amount of dye transfer onto the acceptor fabrics can be described, for example, in terms of the change in L*C*h before and after treatment of the fabric as measured via spectrophotometry (for example, via a Spectrophotomer CM-3610d, manufactured by Konica Minolta, Tokyo, Japan) and is reported as dE2000 value. As used herein, the dE2000 value includes the vector associated with the distance in the L*C*h space between the initial L*C*h value and the final L*C*h value and corrected for perception according to the procedure detailed in G. Sharma, et al, in "The CIE dE2000 Colour Difference Formula: Implementation Notes, Supplementary test Data and Mathematical Observations," Color Research and Application, Vol 30 (1), 2005, p 21-30. Test fabrics are folded in half to double the thickness before measuring, except for test fabrics that are sewn onto the t-shirt, which are measured against the backing of the t-shirt. An average of two L*a*b* measures are taken per test fabric, and two fabrics are measured per example.
Relatively higher dE2000 values correspond to a greater color change, indicating that relatively more dye transferred to the fabric in question.

Example 1. Synthesis Examples:

Graft polymer Example 1A

Graft polymerization of vinyl pyrrolidone and vinyl acetate in a ratio of polyalkylene oxide / VP / VAc (80 /15 / 5), wherein the polyalkylene oxide is triblock copolymer (PO₈-EO₂₂-PO8).

A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone (800 g, Mn = 1,950 g/mol, wt% EO = 50%) under nitrogen atmosphere and heated to 90°C. Feed 1 (5.10 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 39.0 g of tripropylene glycol) and 10 min upon the start of Feed 1, Feed 2 (50.0 g of vinyl acetate) and Feed 3 (150 g of N-Vinylpyrrolidone) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 4.04 g/h and 00:10 h to 06:10 h: 7.22 g/h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 8.33 g/h) and Feed 3 (00:10 h to 06:10 h: 27.3 g/h). Upon completion of Feed 1, Feed 2 and Feed 3, Feed 4 (4.08 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 31.1 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was heated under stirring for 1:00 h at 95°C upon complete addition of the feed. Destination for 1 h at 95°C with a vacuum of 50 mbar was carried out to remove the volatiles. The yield was 1070 g of a polymer mixture.

Graft polymer Example 1C

Graft polymerization of vinyl pyrrolidone and vinyl acetate in a ratio of polyalkylene oxide / VP / VAc (60/ 15 / 20), wherein the polyalkylene oxide is triblock copolymer (PO₈-EO₂₂-PO8).

A polymerization vessel equipped with stirrer and reflux condenser was initially charged with Backbone (650 g, Mn = 1,950g/mol, wt% EO = 50%) under nitrogen atmosphere and heated to 90°C. Feed 1 (8.16 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 46.7 g of tripropylene glycol) and 10 min upon the start of Feed 1, Feed 2 (200.0 g of vinyl acetate) and Feed 3 (150 g of N-Vinylpyrrolidone) were started simultaneously and dosed to the stirred vessel with a variable feed rate of Feed 1 (0:00 h to 00:10 h: 5.03 g/h and 00:10 h to 06:10 h: 9.00 g/h) and a constant feed rate of Feed 2 (00:10 h to 06: 10 h: 33.3 g/h) and Feed 3 (00:10 h to 06: 10 h: 27.3 g/h). Upon completion of Feed 1, Feed 2 and Feed 3, Feed 4 (4.08 g of tert-Butyl peroxy-2-ethylhexanoate dissolved in 23.3 g of tripropylene glycol) was dosed within 0:56 h with constant feed rate at 90°C. The mixture was heated under stirring for 1:00 h at 95°C upon complete addition of the feed. Destination for 1 h at 95°C with a vacuum of 50 mbar was carried out to remove the volatiles. The yield was 1060 g of a polymer mixture.

Example 1H: hydrolysis of Example 1C

The polymer of example 1C (250 g) was dissolved in a mixture of THF (100 g) and water (25 g). Subsequently, a sodium hydroxide solution (21.5 g, 50 wt% in water) was added at 65°C within 1 h. The residues of THF and water were removed by reduced pressure and a temperature of 80°C. Other inventive and comparative graft polymers can be synthesized following similar procedure. The structure of inventive and comparative graft polymers is summarized in Table 4.

Table 4.

	Backbone				Graft			Biodeg 28d
Ex.	Type	Wt% EO in backbone	MW (g/mol)	wt %	B1 wt %	B2 wt %	Hydrolyzed (%)	Biodeg 28d
1A	PO-EO-PO	50	1,950	80	15	5	No	63%
1B	PO-EO-PO	50	1,950	75	15	10	No	60%
1C	PO-EO-PO	50	1,950	65	15	20	No	49%
1D	PO-EO-PO	46	2,650	60	20	20	No	43%
1E	PO-EO-PO	46	2,650	50	20	30	No	48%
1F	PO-EO-PO	46	2,650	70	10	20	Yes	51%
1G	PO-EO-PO	46	2,650	50	20	30	Yes	55%
1H	PO-EO-PO	50	1,950	65	15	20	Yes (50%)	50%
Comp 1	PEG	100	6,000	50	20	30	Yes	<20%

B 1 = N-vinyl pyrrolidone; B2 =Vinyl acetate

Example 2. Polymer biodegradation:

Method of testing polymer biodegradation

Biodegradation in wastewater was tested in triplicate using the OECD 301F manometric respirometry method. OECD 301F is an aerobic test that measures biodegradation of a sample by measuring the consumption of oxygen. To a measured volume of medium, 100 mg/L test substance, which is the nominal sole source of carbon is added along with the inoculum (30 mg/L, aerated sludge taken from Mannheim wastewater treatment plant). This is stirred in a closed flask at a constant temperature (20°C or 25°C) for 28 or 56 days, respectively. The consumption of oxygen is determined by measuring the change in pressure in the apparatus using an OxiTop^® C (Xylem 35 Analytics Germany Sales GmbH & Co KG). Evolved carbon dioxide is absorbed in a solution of sodium hydroxide. Nitrification inhibitors are added to the flask to prevent usage of oxygen due to nitrification. The amount of oxygen taken up by the microbial population during biodegradation of the test substance (corrected for uptake by blank inoculum, run in parallel) is expressed as a percentage of ThOD (Theoretical oxygen demand, which is measured by the elemental analysis of the compound). A positive control Glucose/Glucosamine is run along with the test samples for each cabinet.

Polymer biodegradation results

Biodegradability of following inventive polymers (as synthesized, without further purification step) is tested using method described above, the result is summarized in Table 4. Inventive polymers have high or low biodegradability, preferred polymers show higher biodegradability.
The number average molecular weight (Mn), the weight average molecular weight (Mw) and the polydispersity Mw/Mn of the inventive graft polymers can be determined by gel permeation chromatography in dimethylacetamide. The mobile phase (eluent) to be used is dimethylacetamide comprising 0.5 wt% LiBr. The concentration of graft polymer in the solvent is 4.0 mg per mL. After filtration (pore size 0.2 µm), 100 µL of this solution are to be injected into the GPC system. Four columns (heated to 60°C) may be used for separation (PLgel precolumn, 3 Plgel MIXED-E column). The GPC system is operated at a flow rate of 1 mL per min. A DRI Agilent 1100 may be used as the detection system. Poly(ethylene glycol) (PEG) standards (PL) having a molecular weight Mn from 106 to 1,378,000 g/mol may be used for the calibration.
The molecular weights given in the tables are calculated weights unless "Mw" or "Mn" is stated, based on the total molar amounts of ingredients employed for the preparation reaction. As those reactions proceed basically to completeness, this is an acceptable way of calculation the molecular weights.

Example 3. Liquid or Gel Detergents

The following inventive or comparative detergent composition 2A to 2I can be made by mixing ingredients together (Table 5).

Table 5.

Ingredient (wt%)	2A	2B	2C	2D	2E	2F	2G	2H	21
C₁₂-C₁₅ alkyl polyethoxylate sulfate¹	2.3	2.6	7.0	0.5	3.9	1.8	1.9	3.0	-
C_11.8 linear alkylbenzene sulfonic acid²	11.6	13.4	9.4	5.9	3.9	2.8	8.6	4.2	8.5
sodium laureth sulfate	-	4.7	5.3	-	-	-	-	-	2.1
C₁₅ branched 2-alkylated alcohol³	-	-	-	7.1	-	-	-	-	8.2
C₁₂-C₁₅ alkyl 7-ethoxylate¹	4.1	3.8	-	-	5.9	9.5	6.5	3.1	-
C₁₂-C₁₄ alkyl 9-ethoxylate¹	8.1	6.0	6.4	9.2	-	-	-	-	-
C₁₂-C₁₄ amine oxide	2.8	0.2	0.4	0.4	-	0.5	-	0.4	0.7
C_12-C₁₈ Fatty Acid⁴	-	-	-	-	1.1	1.0	1.8	2.6	2.2
Fluorescent Whitening Agent⁵	-	0.04	0.2	-	0.02	0.08	-	-	-
Hueing dye	0.02	0.02	0.02	0.02	-	-	-	-	-
Graft Co-polymer acc. to present disclosure, if any	0.0 - 10.0%
Cleaning Polymer^{6, 7}	3.1	3.7	3.8	1.6	-	-	-	-	2.8
Cleaning Polymer⁸	-	-	-	-	-	1.8	1.8	0.6	-
Zwitterionic ethoxylated quaternized sulfated hexamethylene diamine⁹	-	-	-	-	-	-	0.4	0.2	-
Hydrogenated castor oil¹⁰	0.2	0.2	0.2	0.3	-	-	0.3	0.3	-
Water, enzymes^{11, 12}, hue dye^13, perfumes, encapsulated perfume¹⁴, dyes, buffers, neutralizers, chelants, solvents, stabilizers, and other optional components	Balance to 100%, pH 7.0-8.5

¹ Available from Shell Chemicals, Houston, TX.
² Available from Huntsman Chemicals, Salt Lake City, UT. Sasol Chemicals, Johannesburg, South Africa
³ Described in WO 2021247801 A1 and available from Scion (Pasadena, TX, USA)
⁴ Available from The Procter & Gamble Company, Cincinnati, OH.
⁵ Available from Ciba Specialty Chemicals, High Point, NC
⁶ 600 g/mol molecular weight polyethylenimine core with 20 ethoxylate groups per -NH and available from BASF (Ludwigshafen, Germany)
⁷ 600 g/mol molecular weight polyethylenimine core with 24 ethoxylate groups per -NH and 16 propoxylate groups per -NH. Available from BASF (Ludwigshafen, Germany)
⁸ Described in US 8,143,209 and available from BASF (Ludwigshafen, Germany)
described in WO 01/05874 and available from BASF (Ludwigshafen, Germany)
¹⁰ Available under the tradename ThixinR from Elementis Specialties, Highstown, NJ
¹¹Available from DuPont-Genencor, Palo Alto, CA.
¹² Available from Novozymes, Copenhagen, Denmark
¹³ Available from Milliken Chemical, Spartanburg, SC
¹⁴Available from Encapsys of Appleton, WI

Example 4. Effect of Graft Copolymer on Dye Transfer in Detergent 2X

In this example, a graft copolymer according to Example 1A-1C above is added to detergent composition Example 2A above and are compared in performance to corresponding compositions that do not include the graft copolymer.
The wrist shaker dye transfer method is used to assess the amount of dye that has transferred in one wash cycle from a detergent wash liquor containing dye previously extracted from test fabric onto a white 100% cotton knitted fabric.

A dE2000 value is calculated comparing results from before and after the test; a higher dE2000 value corresponds to a greater color change, indicating that relatively more dye transferred to the fabric in question.

Table 6.

Example	Dye¹	Graft Copolymer²	B2 =Vinyl acetate (wt %)	dE2000 (vs initial)	ddE2000 (vs REF)
3A	Blue Dye 171	none	N/A	7.8	REF
3B	Blue Dye 171	1A	5	6.7	1.1 units less
3C	Blue Dye 171	1B	10	6.4	1.4 units less
3D	Blue Dye 171	1C	20	5.7	2.1 units less
3E	Yellow Dye145	none	N/A	3.7	REF
3F	Yellow Dye145	1A	5	2.9	0.8 units less
3G	Yellow Dye145	1B	10	2.6	1.1 units less
3H	Yellow Dye145	1C	20	2.3	1.4 units less

1) Blue dye 171 is Reactive Blue 171 (Permabril Navy), Yellow dye 145 is Reactive Yellow 145 (Permabril Yellow 3RX 150%). 2) Unless noted, the graft copolymer is added at 1.7%. Cotton test fabric knit available from WfK, Testgewebe GmbH, Brüggen, Germany

The results show that treatment with a composition that includes a graft copolymer according to the present disclosure leads to lower dE2000 values (i.e., less color change), and therefore likely less dye transfer, compared to treatments with compositions that do not include the graft copolymer. These results also show that the response to different dye types is affected by the vinyl acetate composition of the polymer where increasing vinyl acetate increases the benefit on the Blue Dye 171 and Yellow Dye 145.

Example 5. Effect of Hydrolyzed Graft Copolymer on Dye Transfer in Detergent 2X

In this example, a graft copolymer according to Example 1G above is added to detergent composition Example 2X (1.7%) above and are compared in performance to corresponding compositions that do not include the graft copolymer or include Comparative Example 1. Table 7

Example Dye¹ Graft Copolymer dE2000 (vs initial) ddE2000 (vs REF)

4A Red Dye 120 none 11.5 REF

4B Red Dye 120 Comparative 1 7.1 4.4 units less

4C Red Dye 120 1B 6.1 5.4 units less

1) Red dye 120 is Reactive Red 120 (Permabril Red HE3B). Cotton test fabric knit available from WfK, Testgewebe GmbH, Brüggen, Germany

The data shows that the PO-EO-PO grafting base is more effective than PEG6000 since there is an incremental 1 unit less dye transfer with 4C than 4B.

Example 6. Effect of Graft Copolymer on Dye Transfer in Detergent 2E

In this example, a graft copolymer according to Example 1D-1F above is added to detergent composition Example 2E and are compared in performance to corresponding compositions that do not include the graft copolymer.
The wrist shaker dye transfer method is used to assess the amount of dye that has transferred in one wash cycle from a detergent wash liquor containing dye previously extracted from test fabric onto a white 100% cotton knitted fabric.

Table 8.

Example	Dye¹	Graft Copolymer²	B1 = VP (wt %)	dE2000 (vs initial)	ddE2000 (vs REF)
3A	Blue Dye 21	none	N/A	4.5	REF
3B	Blue Dye 21	1D	20	2.5	2.0 units less
3C	Blue Dye 21	1E	20	2.4	2.1 units less
3D	Blue Dye 21	1F	10	3.2	1.3 units less
3E	Red Dye 195	none	N/A	7.3	REF
3F	Red Dye 195	1D	20	5.2	2.1 units less
3G	Red Dye 195	1E	20	5.4	1.9 units less
3H	Red Dye 195	1F	10	6.1	1.2 units less

1) Blue dye 21 is Reactive Blue 21 (Permabril Turquoise RP), Red dye 195 is Reactive Red 195 (Remazol Brill Red 3BS). 2) Unless noted, 0.8% of the graft copolymer that is the subject of the invention is added to the detergent.

The results in Table 8 show the dye transfer benefit when the graft copolymer is added to detergent and demonstrate that the benefit with increasing B 1 monomer, vinyl pyrrolidone.
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

Claims

Use of a graft polymer comprising:
(A) a block copolymer backbone as a graft base, wherein said block copolymer backbone (A) comprises from 85% to 100%, by weight of the backbone (A), at least two monomers selected from the group of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, and 2,3-pentene oxide; and,

(B) polymeric sidechains grafted onto the block copolymer backbone, wherein said polymeric sidechains (B) comprises from 85% to 100%, by weight of the sidechains (B), N-vinyl lactam monomer (B1) and vinyl ester monomer (B2),
in a laundry detergent composition that additionally comprises a detersive surfactant, to prevent dye transfer during a laundering process.
The use according to claim 1, wherein the N-vinyl lactam monomer (B1) is N-vinylpyrrolidone.
The use according to any preceding claim, wherein the polymer comprises from 60 to 90 wt% block copolymer backbone (A) and from 10 to 40 wt% polymeric sidechains (B) (in relation to the total weight of the graft polymer).
The use according to any preceeding claim, the graft polymer comprises from 70 to 85 wt% block copolymer backbone (A), and from 15 to 30 wt% polymeric sidechains (B) (in relation to the total weight of the graft polymer).
The use according to any preceding claim, wherein the polymer side chain (B) comprises from 5 to 25 wt% N-vinyl lactam monomer (B1) (in relation to the total weight of the graft polymer).
The use according to any preceding claim, wherein the polymer side chain (B) comprises from 1 to 20 wt% vinyl ester monomer (B2) (in relation to the total weight of the graft polymer).
The use according to any preceding claim, wherein the block copolymer backbone (A) comprises from 2 to 5 blocks.
The use according to any preceding claim, wherein the block copolymer backbone (A) has a number average molecular weight of less than 5,000, preferably less than 4,000, more preferably less than 3,000 g/mol.
The use according to any preceding claim, wherein:
(i) the graft polymer has a mean weight average molecular weight M_w of from 1,500 to 50,000 g/mol; and/or

(ii) the graft polymer has a polydispersity M_w/M_n of < 3 (with M_w = mean weight average molecular weight and M_n = mean number average molecular weight [^g/_mol/^g/_mol]); and/or

(iii) the block copolymer backbone (A) is not capped; and/or

(iv) the block copolymer backbone (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG).
The use according to any preceding claim, wherein the block copolymer backbone (A) has the structure according to formula (A1) or formula (A2) wherein
formula (A1) is defined as follows: with
n is an integer from 2 to 100, and

m is an integer from 2 to 100, and

formula (A2) is defined as follows: with
o is an integer from 2 to 100, and

p is an integer from 2 to 100.
The use according to any preceding claim, wherein from 0.5wt% to 50wt% of the vinyl ester monomers (B2) are hydrolyzed.
The use according to any preceding claim, wherein the weight ratio the N-vinyl lactam monomer (B1) to vinyl ester monomer (B2) is in the range from greater than 1:1 to 6:1.
The use according to any preceding claim, wherein the graft polymer is present in the laundry detergent composition in an amount ranging from about 0.01% to about 10%, in relation to the total weight of the laundry detergent composition.
The use according to any preceding claim, wherein the composition comprises from 1.0wt% to 70.0% of the detersive surfactant.
The use according to any preceding claim, wherein the detergent composition is a laundry detergent liquid composition that additionally comprises amylase and/or protease.