CN121100170A - Composition and method for producing the same - Google Patents

Abstract

A detergent composition comprising 0.5 to 10% by weight of an alkoxylated cationic or zwitterionic diamine or polyamine polymer and an alkyl ether sulfate, wherein the alkyl ether sulfate comprises C12 and C14 alkyl chains and has a molar average of 2.0 to 4.0 ethoxylated units, and wherein the alcohol ether sulfate comprises less than 10% by weight of an alcohol ether sulfate having zero ethoxylated groups.

Description

Composition

This invention relates to detergent compositions comprising improved surfactants.

Despite existing technologies, there is still a need for improved anionic surfactants for detergent compositions.

Therefore, in a first aspect, a detergent composition comprising 0.01 to 8 wt% of an alkoxylated oligoamine cleaning enhancer and an alkyl ether sulfate is provided, wherein the alkyl ether sulfate comprises C12 and C14 alkyl chains and has a molar average of 2.0 to 4.0 ethoxylated units, wherein the alkyl ether sulfate comprises less than 10 wt% of an alkyl ether sulfate having zero ethoxylated groups.

Alcohol ether sulfates having a molar average of 2 to 4 ethoxylated groups are prepared by sulfation of the corresponding alcohol ethoxylates. The most widely used materials are based on straight-chain or branched C12-C15 alcohols. Typically, the ethoxylation reaction to form alcohol ethoxylates is catalyzed by a base using NaOH, KOH, or _NaOCH3 . This reaction produces a distribution of ethoxy chain lengths in the alcohol ethoxylate. Narrow-range ethoxylation provides a narrower distribution of ethoxy chain lengths than NaOH, KOH, or _NaOCH3 . Most notably, narrow-range ethoxylation produces significantly lower fractions of materials with exactly 0 or 1 ethoxylated groups.

Typically, formulators of laundry liquid compositions desire to include alkoxylated oligoamine cleaning enhancers to improve the cleaning performance of the composition.

However, when such polymers are included, they have a negative impact on the viscosity properties of the laundry liquid composition, and therefore further materials are required to rebuild the chassis.

We were surprised to find that surfactants with a narrow range of ethoxylate distributions were less affected by this viscosity decrease than their commonly used counterparts with a wide range.

Alkyl ether sulfates have a molar average of 2.0 to 4.0 ethoxylated units and contain less than 10% by weight of alcohol ether sulfates having zero ethoxylated groups.

Preferably, the alcohol ether sulfate contains less than 5% by weight of an alcohol ether sulfate having exactly zero ethoxylated groups.

Preferably, the alcohol ether sulfate contains less than 12% by weight of an alcohol ether sulfate having exactly one ethoxylated group.

Preferably, the alcohol ether sulfate has a molar average of 2.6 to 3.4, and most preferably 2.8 to 3.2 ethoxylate units.

Preferably, the composition comprises at least 60% by weight of water.

Preferably, the alkyl ether sulfate is present in 5-30% by weight of the composition.

Preferably, the polyester-based detergency polymer is present at 0.1-2% by weight of the composition.

Preferably, the composition is a liquid detergent composition.

Preferably, the composition is a unit dose composition of laundry liquid.

Preferably, the composition comprises C1214 alcohol ether sulfate, wherein the C12:14 ratio is from 5:1 to 1:20. More preferably, the C12:14 ratio is from 4:1 to 1:10, and most preferably, the C12:14 ratio is from 3:1 to 5:4.

Preferably, the alkyl ether sulfate is present in 1-30% by weight of the composition.

Preferably, the composition comprises a salt. Preferably, the salt is selected from sodium chloride, potassium chloride, and mixtures thereof.

Preferably, the salt is present in 0.1-5% by weight of the composition. More preferably, the salt is present in 0.8-4% by weight of the composition, and even more preferably, the salt is present in 0.1 to 1.8% by weight of the composition.

Most preferably, the composition contains 0.1-1.8% by weight of sodium chloride.

Preferably, the composition contains 0.1-3% by weight of betaine, more preferably cocamidopropyl betaine.

alcohol ether sulfate

Alcohol ether sulfates exist in the following forms:

R ₂ -O-(CH ₂ CH ₂ O) _p SO ₃ H

Wherein _R2 is an alkyl group, and p is a molar average value of 2.0 to 4.0. Preferably, more than 80% by weight, and more preferably more than 95% by weight, of _R2 is selected from C12 and C14 chains, and preferably the chains are straight chains.

The structure of an alcohol ether sulfate with exactly zero ethoxylated groups is as follows: R ₂ -O-SO ₃ H.

Alcohol ether sulfates are formed by the sulfation of the corresponding alcohol ethoxylates. Alcohol ethoxylates are formed by the ethoxylation of alcohols using a narrow-range ethoxylation catalyst.

Preferably, the alcohol ether sulfate contains less than 10% by weight, more preferably less than 4% by weight of chains other than C12 and C14, and most preferably less than 10% by weight of C16, C18 and C20 chains.

Preferably, alcohol ether sulfates can be obtained using narrow-range ethoxylation catalysts. Narrow-range ethoxylation catalysts are described in EP3289790 (Procter & Gamble), EP1747183 (Hacros); Santacesatia et al. Ind.Eng. Chem. Res. 1992, 31, 2419-2421; US4239917 (Conoco); Li et al. ACS Omega. 2021Nov 9; 6(44): 29774-29780; Hreczuch et al. J. Am. Oil Chem. Soc. 1996, 73, 73-78 and WO2022/129374 (Unilever). Ca or Ba-based catalysts are preferred, and most preferably in combination with sulfuric acid.

The standard 3EO described in the literature is not a disclosure of completely pure 3EO; in fact, 100% pure 3EO is not commercially available. Instead, 3EO is described as a mixture with varying ethoxylation rates averaging about 3. This 3EO is ethoxylated using KOH. To obtain a narrow range of ethoxylation distributions, a specialized catalyst must be used.

The following is a comparison between the standard 3EO and the narrow range.

Preferably, the total (n-1, n, n+1) is greater than 50%, more preferably greater than 55%, wherein n is 2 to 4 (n = the average number of moles of ethoxy groups).

Preferably, as measured by GC with flame ionization detection (FID), the total levels of 2EO, 3EO and 4EO in total alkyl ether sulfates are greater than 50% of total alcohol ether sulfates, more preferably greater than 55%.

Preferably, as measured by a GC with flame ionization detection (FID), the total proportion of 0EO and 1EO in total alkyl ether sulfate is less than 25% of total alcohol ether sulfate.

It should be understood that the alcohol ethoxylates are measured prior to sulfonation, but sulfonation does not substantially affect the ethoxylation ratio.

Alcohol ether sulfates are also known as alkyl ether sulfates.

Alkoxylated oligoamine cleaning enhancer

Alkoxylated oligoamine cleaning enhancers are polymers containing at least two, preferably at least four, nitrogen atoms and most preferably at least four polyalkoxy groups, wherein the polyalkoxy groups contain 10-30 individual alkoxy units. Preferably, at least one polyalkoxy group is directly linked to a nitrogen atom. Preferably, the alkoxy group is selected from ethoxy and propoxy, most preferably ethoxy. _- [ _CH₂CH₂O ] _n -H.

Preferably, the alkoxylated oligoamine contains 2 to 40, more preferably 2 to 10, and most preferably 3 to 8 nitrogen atoms.

Such polymers are described in WO2023/287834 (DOW), WO2023/287835 (DOW), WO2023/287836 (DOW), WO2021/165493 (BASF), WO2021/165468 (BASF), WO2022/136389 (BASF), WO2022/136409 (BASF), WO2004/24858 (Procter and Gamble) and WO2021239547 (Unilever).

Alkoxylated oligoamines preferably contain a permanent positive charge, wherein the positive charge is provided by the quaternization of the nitrogen atom of the amine.

Preferably, when the alkoxylated oligoamine contains 2 to 10, more preferably 3 to 6, nitrogen atoms, a charge is present. When the alkoxylated oligoamine contains a permanent positive charge, it also contains anionic groups through sulfation or sulfonation of the alkoxylation group.

Preferably, 50 mol% or more of the nitrogen-containing amine is quaternized, more preferably with methyl quaternization. Preferably, the polymer contains 3 to 10, more preferably 3 to 6, and most preferably 3 to 5 quaternized nitrogen-containing amines. Preferably, the alkoxy group is selected from ethoxy and propoxy, most preferably ethoxy.

Preferably, the alkoxylated oligoamine contains ester (COO) groups in its structure, and these groups are preferably placed such that when all the esters are hydrolyzed, at least one, preferably all, of the hydrolyzed fragments has a molecular weight of less than 4000, more preferably less than 2000, and most preferably less than 1000.

Preferably, the alkoxylated oligoamine is selected from alkoxylated polyethyleneimine, zwitterionic alkoxylated oligoamine, and tetraester alkoxylated oligoamine.

Alkoxylated polyethyleneimine is prepared from polyethyleneimine, which is a material composed of _{ethyleneimine} units _{-CH₂CH₂NH⁻} , and in the case of branching, the hydrogen on the nitrogen is replaced by another ethyleneimine unit chain. Preferred alkoxylated polyethyleneimines used in this invention have a polyethyleneimine backbone with a weight-average molecular weight ( _Mw ) of about 300 to about 10,000. The polyethyleneimine backbone can be linear or branched. It can be branched to the extent of being a dendritic polymer. When nitrogen atoms are alkoxylated, the preferred average degree of alkoxylation is 10-30 alkoxy atoms per modification, preferably 15-25 alkoxy atoms. A preferred material is ethoxylated polyethyleneimine, wherein the average degree of ethoxylation is 10-30 ethoxylated nitrogen atoms per ethoxylated nitrogen atom in the polyethyleneimine backbone, preferably 15-25 ethoxy atoms.

Zwitterionic alkoxylated oligoamines exist in the following forms:

Wherein _R1 is a C3 to C8 alkyl group, X is _a ( _C2H4O ) _nY group, where n is 15 to 30, preferably 18 to 25, where m is 1 to 10, preferably 2, 3, 4 or ⁵ , and where Y is selected from OH and _SO3- , and the number of _SO3- groups is greater than the number of OH groups. Preferably, it has 0 or 1 OH groups. ^X and _R1 may contain ester groups. X may contain _carbonyl groups, preferably ester groups. Preferably _, there is a _C2H4O unit separating the ester group from N, such that the structural unit _NC2H4O - _ester- ( _C2H4O ) _n-1Y is preferred.

Such polymers are described in WO2004/24858 (Procter and Gamble) and WO 2021239547 (Unilever). Preferred exemplary polymers are sulfated ethoxylated hexamethylenediamine, Example 4 of WO2004/24858 and Examples P1, P2, P3, P4, P5, and P6 of WO2021239547. The ester group can be incorporated by adding a lactone or sodium chloroacetate (modified Williamson synthesis) to an OH or NH group, followed by ethoxylation.

An exemplary reaction scheme for containing ester groups is:

The addition of lactones is discussed in WO2021/165468. Once the ester group is included, the polyamine containing the alkoxylated ester can be methylated and sulfated, for example, according to Example P6 of WO2021239547. Preferably, the product is neutralized to pH 7 at the end of the synthesis. If the ester undergoes some degree of hydrolysis, the hydrolyzed product can be removed or re-esterified.

Tetraester alkoxylated oligoamines exist in the following forms:

Where _R1 is a polyalkoxy group, R is a polyalkoxy group, x is 0, 1 or 2, and b is 2, 3 or 4. They are described in WO2023/287834 (DOW), WO2023/287835 (DOW), and WO2023/287836 (DOW).

Preferably, the alkoxylated oligoamine cleaning enhancer is present in the composition at 0.01 to 8% by weight, more preferably 0.5 to 3% by weight.

surfactants

The liquid detergent of the present invention preferably contains 2 to 60% by weight, most preferably 4 to 30% by weight, of total surfactant. Anionic and nonionic surfactants are preferred.

Anionic surfactants are discussed in *Anionic Surfactants: Organic Chemistry*, edited by Helmut W. Stache (Marcel Dekker 1995), published in the Surfactant Science Series by CRC Press. Preferred anionic surfactants are sulfonate and sulfate surfactants, preferably alkylbenzene sulfonates, alkyl sulfates, and alkyl ether sulfates.

Anionic surfactants are preferably added to detergent compositions in the form of salts. Preferred cations are alkali metal ions, such as sodium and potassium. However, the salt form of anionic surfactants can be formed in situ by neutralizing the acidic form of the surfactant with a base (such as sodium hydroxide) or an amine (such as monoethanolamine, diethanolamine, or triethanolamine). Weight ratios are calculated for protonated surfactants. In both anionic and nonionic surfactants, the ethoxy unit can be partially replaced by the propoxy unit.

Other examples of suitable anionic surfactants are rhamnolipids, α-olefin sulfonates, olefin sulfonates, chain olefin sulfonates, alkane-2,3-dimethylbis(sulfates), hydroxyalkane sulfonates and disulfonates, fatty alcohol sulfates (FAS), paraffin sulfonates, ester sulfonates, sulfonated fatty acid glycerides, methyl ester sulfonates, alkyl succinic acid or alkenyl succinic acid, dodecenyl/tetradecenyl succinic acid (DTSA), fatty acid derivatives of amino acids, DATEMs, CITREMs, and diesters and monoesters of sulfosuccinic acid.

Examples of preferred nonionic surfactants are alcohol ethoxylates and methyl ester ethoxylates. Preferably, the level of nonionic surfactant in the formulation is less than 2% by weight. Preferred alcohol ethoxylates are C12/14 alcohols having a molar average of 7 to 9 ethoxylates and C16/C18:1 alcohol ethoxylates having a molar average of 8 to 12 ethoxylates.

Linear alkylbenzene sulfonates are preferred anionic surfactants other than alcohol ether sulfates.

linear alkylbenzene sulfonates

LAS (linear alkylbenzene sulfonate) is a preferred anionic surfactant.

The key intermediate compounds in LAS production are related chain olefins. These chain olefins (olefins) can be produced by any of the methods mentioned above and can be formed from primary sugars, biomass, waste plastics, MSW, carbon capture, methane capture, marine carbon, etc.

In the above method, the olefin is alternatively processed by hydroformylation and oxidation to form a straight-chain alcohol, and the olefin reacts with benzene and then with sulfonic acid to form LAS.

A straight-chain alkylbenzene sulfonate having an alkyl chain length of 10 to 18 carbon atoms. Commercial LAS are mixtures of closely related isomers and homologues of alkyl chains, each containing an aromatic ring sulfonated in the "para" position and attached to the straight-chain alkyl chain at any position except the terminal carbon. The straight-chain alkyl chain preferably has a chain length of 11 to 15 carbon atoms, with the main material having a chain length of about C12. Each alkyl chain homologue consists of a mixture of all possible sulfophenyl isomers except for the 1-phenyl isomer. LAS are typically formulated into the composition as an acid (i.e., HLAS) and then at least partially neutralized in situ. Preferably, the straight-chain alkylbenzene sulfonate surfactant is present at 1 to 20% by weight of the composition, more preferably 2 to 15% by weight, and most preferably 8 to 12% by weight.

Branched surfactants

The compositions of the present invention preferably comprise branched C8-11 alcohol ether sulfate surfactants in the following forms:

RO-(EO) _{n SO3X}

Wherein R is preferably a branched C8 to C11 alkyl chain (R), more preferably C9 or C10; n is 1 to 6, more preferably 2.5 to 5, and most preferably 3.5 to 4.5; and X is a cation, preferably sodium or amine. The integer n is the molar average. EO represents ethoxy.

Preferably, the branched alcohol ether sulfate surfactant has the following structure:

Where p and m are greater than 1, more preferably m is 4, and p is 2 or m = p+2.

Preferably, the branched alcohol ether sulfate is prepared from Guerbet alcohol. Preferably, the alcohol used to prepare the branched alcohol ether sulfate surfactant has a single alkyl chain length and configuration greater than 80 mol%. Most preferably, it is a C10 branched alcohol ether sulfate with 4 moles of average ethoxylated 2-propylheptanol.

Farbe et al. discussed branched alcohols in the chapter on Alcohols, Aliphatic in Ullmann's Encyclopedia of Industrial Chemistry.

Branched alcohols are available from Sasol, Exxon and BASF.

Preferably, the branched surfactant accounts for 1 to 20% by weight of the total surfactant in the composition.

Considering the typical surfactant loading of the composition as a whole, it is preferred that the content of branched surfactant is 0.05 to 3% by weight of the composition.

Preferably, the weight ratio of total anionic and/or nonionic surfactant to C8 to C11 branched alcohol ether sulfate is 100:1 to 30:1, more preferably 80:1 to 40:1.

Methyl ester ethoxylate (MEE)

Preferred nonionic surfactants include methyl ester ethoxylates. Methyl ester ethoxylate surfactants are available in the following forms:

R3(-C=O)-O-(CH ₂ CH ₂ -O) _n -CH ₃

R3COO represents the fatty acid portion, such as oleic acid, stearic acid, and palmitic acid. Fatty acid nomenclature uses two numbers, A:B, to describe fatty acids, where A is the number of carbon atoms and B is the number of double bonds. For example, oleic acid is 18:1, stearic acid is 18:0, and palmitic acid is 16:0. The position of the double bonds on the chain can be given in parentheses: oleic acid is 18:1(9), linoleic acid is 18:2(9,12), where 9 is the carbon number starting from the end of the COOH group.

The integer n is the molar average of the ethoxylate.

Methyl ester ethoxylate (MEE) is described in G. A. Smith's Biobased Surfactants (2nd edition), Chapter 8, Synthesis, Properties, and Applications, pp. 287-301 (AOCS press 2019); Cox M. E. and Weerasooriva U's J. Am. Oil. Chem. Soc. vol 74 (1997), pp. 847-859; Hreczuch et al.'s Tenside Surf. Det. vol. 28 (2001), pp. 72-80; C. Kolano's Household and Personal Care Today (2012), pp. 52-55; and A. Hama et al.'s J. Am. Oil. Chem. Soc. vol. 72 (1995), pp. 781-784. MEE can be produced by the reaction of methyl ester with ethylene oxide using calcium or magnesium-based catalysts. The catalyst can be removed or retained in the MEE.

Alternative preparation routes include transesterification of methyl esters or esterification of carboxylic acids with polyethylene glycol that is capped at one end of the chain with methyl groups.

Methyl esters can be prepared by transesterification of methanol with triglycerides or by esterification of methanol with fatty acids. The transesterification of triglycerides to fatty acid methyl esters and glycerol is discussed in Fattah et al. (Front. Energy Res., June 2020, Vol. 8, Article 101) and its references. Common catalysts used for these reactions include sodium hydroxide, potassium hydroxide, and sodium methoxide. Esterases and lipases can also be used. Triglycerides are naturally occurring in vegetable fats or oils, with preferred sources being rapeseed oil, castor oil, corn oil, cottonseed oil, olive oil, palm oil, safflower oil, sesame oil, soybean oil, high-stearic acid/high-oleic acid sunflower oil, high-oleic acid sunflower oil, inedible vegetable oils, tall oil, any mixture thereof, and any derivative thereof. Oils derived from trees are called tall oils. Used cooking oils can be used. Triglycerides can also be obtained from algae, fungi, yeast, or bacteria. Plant sources are preferred.

Distillation and fractionation methods can be used to produce methyl esters or carboxylic acids to produce the desired carbon chain distribution. Preferred sources of triglycerides are those that contain less than 35% by weight of polyunsaturated fatty acids in the oil prior to distillation, fractionation, or hydrogenation.

Fatty acids and methyl esters can be obtained from oleochemical suppliers such as Wilmar, KLK Oleo, and Unileveroleochemical Indonesia. Biodiesel is a methyl ester and can be obtained from these sources.

When the ESB is a MEE, it preferably has a molar average of 8 to 30, more preferably 10 to 20 ethoxylate groups (EO). The most preferred ethoxylate contains 12 to 18 EO.

Preferably, at least 10% by weight, more preferably at least 30% by weight, of the total C18:1 MEE in the composition has 9 to 11 EO, and even more preferably at least 10% by weight exactly 10 EO. For example, when the MEE has a molar average of 10 EO, then at least 10% by weight of the MEE should consist of ethoxylates having 9, 10, and 11 ethoxylate groups.

The methyl ester ethoxylate preferably has a molar average of 8 to 13 ethoxylate groups (EO). The most preferred ethoxylate has a molar average of 9 to 11 EO, and even more preferably 10 EO. When the MEE has a molar average of 10 EO, then at least 10% by weight of the MEE should consist of ethoxylates having 9, 10, and 11 ethoxylate groups.

In cases of broader MEE contribution, it is preferred that at least 40% by weight of the total MEE in the composition is C18:1.

In addition, it is preferred that the MEE component also contains some C16 MEE.

Therefore, it is preferred that the total MEE composition comprises 5 to 50% by weight of C16 MEE. Preferably, the C16 MEE is greater than 90% by weight, more preferably greater than 95% by weight of C16:0.

Furthermore, it is preferred that the total MEE composition contains less than 15% by weight of the total MEE, more preferably less than 10% by weight, and most preferably less than 5% by weight of polyunsaturated C18, namely C18:2 and C18:3. Preferably, C18:3 is present in amounts of less than 1% by weight, more preferably less than 0.5% by weight, and most preferably substantially absent. The level of polyunsaturation can be controlled by distillation, fractionation, or partial hydrogenation of the feedstock (triglycerides or methyl esters) or MEE.

Furthermore, it is preferred that the C18:0 component is less than 10% by weight of the total MEE present.

Furthermore, it is preferred that the component having a carbon chain of 15 or shorter accounts for less than 4% of the total weight of the present MEE.

The particularly preferred MEE has 2 to 26% by weight of C16:0 chain, 1 to 10% by weight of C18:0 chain, 50 to 85% by weight of C18:1 chain and 1 to 12% by weight of C18:2 chain.

Preferred sources of alkyl groups for MEE include methyl esters derived from distilled palm oil and distilled high-oleic methyl esters derived from palm kernel oil, partially hydrogenated methyl esters from low-erucic rapeseed oil, methyl esters from high-oleic sunflower oil, methyl esters from high-oleic safflower oil, and methyl esters from high-oleic soybean oil.

High-oleic oils are available from DuPont (Plenish high-oleic soybean oil), Monsanto (Visitive Gold soybean oil), Dow (ω-9 canola oil, ω-9 sunflower oil), the National Sunflower Association, and Oilseeds International.

Preferably, the double bonds in the MEE are in the cis configuration, with a weight percentage greater than 80%.

Preferably, the 18:1 component is oleic acid. Preferably, the 18:2 component is linoleic acid.

The methyl group of a methyl ester can be replaced by an ethyl or propyl group. Methyl is the preferred choice.

Preferably, the methyl ester ethoxylate constitutes 0.1 to 95% by weight of the methyl ester ethoxylate in the composition. More preferably, the composition contains 2 to 40% by weight of MEE, and most preferably 4 to 30% by weight of MEE.

Preferably, the composition contains at least 50% by weight of water, but this depends on the total surfactant content and is adjusted accordingly.

The weight of anionic surfactants is calculated in protonated form.

zwitterionic surfactants

The composition may contain 0 to 3% by weight of a zwitterionic surfactant.

Examples of zwitterionic surfactants include derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphorus, or tertiary sulfonium compounds. Betaines include C10-C14 alkyldimethyl betaine and cocodimethylamidopropyl betaine, C10 to C14 amine oxides, and sulfonyl and hydroxy betaines, such as N-alkyl-N,N-dimethylamino-1-propane sulfonate, wherein the alkyl group can be C10 to C14.

surfactant ratio

Preferably, the weight ratio of total ether sulfate surfactant to total anionic surfactant is 1 to 0.5, more preferably 1 to 0.8.

Source of alkyl chains

The alkyl chain of the surfactant is preferably obtained from a renewable source, more preferably from triglycerides. A renewable source is one in which the material is generated through the natural ecological cycle of a living species, preferably from plants, algae, fungi, yeast, or bacteria, more preferably from plants, algae, or yeast.

Preferred plant sources of oil are rapeseed, sunflower, corn, soybean, cottonseed, olive oil, and trees. Oils from trees are known as tall oils. Most preferably, the sources are palm kernel oil and coconut oil. The desired C12:C14 ratio can be obtained through fractionation/distillation and blending of the components.

Algal oils are discussed in Saad M.G. et al.'s *Energies*, 2019, 12, 1920: *Algal Biofuels: Current Status and Key Challenges*. A method for producing triglycerides from biomass using yeast is described in Masri M. A. et al.'s *Energy Environ. Sci.*, 2019, 12, 2717: *Asustainable, high-performance process for the economic production of waste-free microbial oils that can replace plant-based equivalents*.

Inedible vegetable oils may be used, preferably from the following fruits and seeds: Jatropha curcas, Calophyllum inophyllum, Sterculia feotida, Madhuca indica (broadleaf mahua), Pongamia glabra (koroch seeds), flax seeds, Pongamia pinnata (karanja), Hevea brasiliensis (rubber seeds), Azadirachta indica (neem), Camelina sativa, Lesquerella fendleri, Nicotiana tabacum (tobacco leaves), Deccan hemp, Ricinus communis L. (castor), Simmondsia chinensis (Jojoba), and Eruca (arugula). sativa. L.), sea mango (Cerbera odollam), coriander (Coriandrum sativum L.), croton megalocarpus, Pilu, sea cabbage (Crambe), clove, kusum (Scheleichera triguga), stillingia, sal tree (Shorea robusta), terminalia (Terminalia belerica roxb), cuphea, camellia, champaca, simarouba glauca, garcinia indica, rice bran, balanites (oak), desert date, cardoon, Syrian milkweed (Asclepias) Syriaca (milkweed), Guizotia abyssinica, Radish Ethiopian mustard, Syagrus, Tung tree, Idesia polycarpa var. vestita, algae, Argemonemexicana L. (Mexican prickly poppy), Putranjivaroxburghii (lucky bean tree), Sapindus mukorossi (Soapnut), M. azedarach (syringe), Thevettia peruviana (yellow oleander), Copaiba, Milk bush, Laurel, Cumaru, Andiroba, Piqui, Brassica napus, Zanthoxylum bungeanum).

C12-C14 straight-chain alcohols suitable as an intermediate step in the manufacture of C12-C14 ether sulfates can be obtained from many different sustainable sources. These include:

Primary sugar

Primary sugars are obtained from sugarcane or sugar beets, etc., and can be fermented to form bioethanol. Bioethanol is then dehydrated to form bioethylene, which then undergoes olefin metathesis to form alkenes. These alkenes are then processed into straight-chain alcohols by hydroformylation or oxidation.

An alternative method can be used, which also utilizes primary sugars to form straight-chain alcohols, wherein the primary sugars are microbially converted by algae to form triglycerides. These triglycerides are then hydrolyzed into straight-chain fatty acids, which are then reduced to form straight-chain alcohols.

biomass

Biomass, such as forestry products, rice husks, and straw, can be gasified into syngas. These substances are then processed into alkanes via the Fischer-Tropsch reaction, which are subsequently dehydrogenated to form alkenes. These alkenes can be processed in the same manner as the chain alkenes described above [primary sugars].

An alternative method involves converting the same biomass into polysaccharides via steam explosion, which can be enzymatically degraded into secondary sugars. These secondary sugars are then fermented to form bioethanol, which is subsequently dehydrated to form bioethylene. This bioethylene is then processed into a straight-chain alcohol as described above for [primary sugars].

waste plastics

Waste plastics are pyrolyzed to form pyrolysis oil. The pyrolysis oil is then graded to form straight-chain alkanes, which are subsequently dehydrogenated to form alkenes. These alkenes are processed as described above in [Primary Sugars].

Alternatively, the pyrolysis oil is cracked to form ethylene, which is then processed via olefin metathesis to form the desired chain olefins. These are then processed into straight-chain alcohols as described above for [primary sugars].

Urban solid waste

MSW is converted into syngas through gasification. From the syngas, it can be processed as described above [primary sugars], or it can be converted into ethanol via an enzymatic process before dehydrogenation to ethylene. Ethylene can then be converted into straight-chain alcohols via the Ziegler process.

MSW can also be converted into pyrolysis oil by gasification, which is then fractionated to form alkanes. These alkanes are then dehydrogenated to form alkenes, and then straight-chain alcohols.

Ocean carbon

Various carbon sources exist from marine communities such as seagrass and algae. From such marine communities, triglycerides can be separated from these sources and subsequently hydrolyzed to form fatty acids, which are then reduced to straight-chain alcohols in the usual manner.

Alternatively, the raw materials can be isolated into polysaccharides, which are then enzymatically degraded to form secondary sugars. These can be fermented to produce bioethanol, which is then processed as described above for [primary sugars].

waste oil

Waste oil (such as used cooking oil) can be physically separated into triglycerides, which are broken down into straight-chain fatty acids, and then form straight-chain alcohols as described above.

Alternatively, used cooking oil can undergo the Neste process, whereby the oil is catalytically cracked to produce bio-ethylene. It is then processed as described above.

Methane capture

Methane capture methods capture methane from landfills or fossil fuel production. Methane can be gasified to form syngas. Syngas can be processed as described above, thereby converting syngas into methanol (Fischer-Tropsch reaction), then into olefins, and subsequently into straight-chain alcohols via hydroformylation oxidation.

Alternatively, the syngas can be converted into alkanes, and then into alkenes via Fischer-Tropsch and subsequent dehydrogenation.

carbon capture

Carbon dioxide can be captured by any of a variety of known methods. Carbon dioxide can be converted to carbon monoxide via a reverse water-gas shift reaction, and it can then be converted to syngas using hydrogen in an electrolytic reaction. The syngas is then processed as described above and converted to methanol and/or alkanes before reacting to form olefins.

Alternatively, the captured carbon dioxide is mixed with hydrogen before enzymatic treatment to form ethanol. This is a process developed by Lanzatech. From this, ethanol is converted to ethylene, then processed into olefins and then, as described above, into straight-chain alcohols.

The above process can also be used to obtain the C12/14 chain of C12/14 ether sulfate.

Preferably, the composition is visually clear.

Preferably, the composition contains 10-80% by weight of water.

Preferably, the liquid detergent contains 1 to 5% by weight of ethanol.

Liquid laundry detergent

In the context of this invention, the term "laundry detergent" refers to a formulation intended for and capable of wetting and cleaning household clothing, such as garments, linens, and other home textiles. The object of this invention is to provide a composition that, upon dilution, can form a liquid laundry detergent composition in the manner now described.

In a preferred embodiment, the liquid composition is isotropic.

The term "linen products" is commonly used to describe certain types of laundry items, including sheets, pillowcases, towels, tablecloths, napkins, and uniforms. Textiles may include woven fabrics, nonwoven fabrics, and knitted fabrics; and may include natural or synthetic fibers such as silk, linen, cotton, polyester, polyamide fibers (such as nylon), acrylic fibers, acetate fibers, and their blends (including cotton and polyester blends).

Examples of liquid laundry detergents include heavy-duty liquid laundry detergents for use in the wash cycle of automatic washing machines, as well as liquid fine-wash and liquid color-protecting detergents, such as detergents suitable for washing delicate garments (e.g., those made of silk or wool) by hand or in the wash cycle of an automatic washing machine.

In the context of this invention, the term "liquid" means that the continuous phase or main component of the composition is liquid, and that the composition is flowable at temperatures of 15°C and above. Therefore, the term "liquid" can include emulsions, suspensions, and compositions having a flowable but firmer consistency, referred to as gels or pastes. The viscosity of the composition is preferably from 200 to about 10,000 mPa·s at a shear rate of 21 ^sec⁻¹ at 25°C. This shear rate is the shear rate typically applied to the liquid when poured from the bottle. Pourable liquid detergent compositions preferably have a viscosity of 200 to 1,500 mPa·s, more preferably 200 to 700 mPa·s.

The compositions according to the invention may suitably have an aqueous continuous phase. "Aqueous continuous phase" refers to a water-based continuous phase. Preferably, the composition contains at least 50% by weight of water, more preferably at least 70% by weight of water.

Alcohol ethoxylates can be provided in a single feedstock component or as a mixture of components.

Preferably, the choice and amount of surfactant make the composition and the diluted mixture is isotropic in nature.

Aminocarboxylate

Preferably, the composition comprises an aminocarboxylate chelating agent. Preferably, the aminocarboxylate is selected from GLDA and MGDA.

Preferably, the aminocarboxylate is present in the composition in an amount of 0.1 to 15% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.3 to 5% by weight, even more preferably 0.8 to 3% by weight, and most preferably 1 to 2.5% by weight (based on the weight of the composition).

Glutamic acid diacetic acid (GLDA)

GLDA can exist as a salt of GDLA or a mixture of GDLA and GDLA salts. Preferred salt forms include mono-, di-, tri-, or tetra-alkali metal salts and mono-, di-, tri-, or tetra-ammonium salts of GLDA. The alkali metal salt of glutamate diacetate (GDLA) is preferably selected from lithium salts, potassium salts, and more preferably sodium salts of GLDA.

Glutamic acid diacetic acid (GLDA) can be partially or preferably completely neutralized with a corresponding base. Preferably, the average 3.5 to 4 COOH groups of GLDA are neutralized with an alkali metal, preferably sodium. Most preferably, the composition comprises a tetrasodium salt of GLDA.

GLDA is at least partially neutralized with alkali metals, more preferably with sodium or potassium, with sodium being the most preferred neutralization.

GLDA salts can be alkali metal salts of L-GLDA, alkali metal salts of D-GLDA, or mixtures of enantiomer-enriched isomers.

Preferably, the composition comprises a mixture of L- and D-enantiomers of glutamic acid diacetic acid (GLDA) or their corresponding mono-, di-, tri-, or tetra-alkali metal salts or mono-, di-, tri-, or tetra-ammonium salts or mixtures thereof, said mixture mainly containing the corresponding L-isomer, with an enantiomer excess in the range of 10% to 95%.

Preferably, the GLDA salt is essentially L-glutamic acid diacetic acid that is at least partially neutralized with an alkali metal.

Sodium salts of GLDA are preferred.

A suitable commercial source of GLDA in tetrasodium form is DISSOLVINE® GL, which is available from Nouryon.

Preferably, GLDA is present in the composition in 0.1 to 15% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.3 to 5% by weight, even more preferably 0.8 to 3% by weight, and most preferably 1 to 2.5% by weight (based on the weight of the composition).

Methylglycine diacetic acid (MGDA)

Preferred salt forms include mono-, di-, tri-, or tetra-alkali metal salts and mono-, di-, tri-, or tetra-ammonium salts of MGDA. The alkali metal salts are preferably selected from lithium and potassium salts of MGDA, and more preferably sodium salts.

Sodium salts of methylglycine diacetic acid are preferred. Trisodium salts of MGDA are particularly preferred.

MGDA can be partially or preferably completely neutralized with a corresponding alkali metal. Preferably, an alkali metal, and more preferably sodium, is used to neutralize the average 2.7-3 COOH groups per molecule of MGDA.

MGDA can be selected from racemic mixtures of alkali metal salts of MGDA and racemic mixtures of pure enantiomers, such as alkali metal salts of L-MGDA, alkali metal salts of D-MGDA and mixtures of enantiomer-enriched isomers.

Suitable commercial sources of MGDA in the trisodium form are TRILON® M from BASF and Dissolvine® M-40 from Nouryon.

Preferably, MGDA is present in the composition at 0.1 to 15% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.3 to 5% by weight, even more preferably 0.8 to 3% by weight, and most preferably 1 to 2.5% by weight (based on the weight of the composition).

Small amounts of aminocarboxylate may contain cations other than alkali metals. Therefore, it is possible to carry small amounts (e.g., 0.01 to 5 mol%) of alkaline earth metal cations, such as ^Mg²⁺ or ^Ca²⁺ , or Fe(II) or Fe(III) cations. GLDA may contain small amounts of impurities derived from its synthesis, such as lactic acid, alanine, propionic acid, etc. In this case, "small amount" means a total of 0.1 to 1% by weight involving the chelating agent aminocarboxylate.

organic acids

The composition preferably contains an organic acid. Preferably, the organic acid has the general formula R-CH(OH)-COOH, wherein R is a straight-chain C1-C5, more preferably C2-C4, and most preferably C4 alkyl.

Preferably, at least two of the C1-4 straight-chain carbon atoms, more preferably all carbon atoms, are replaced by OH groups. Preferably, R contains a terminal COOH group.

Preferred examples are lactic acid, tartaric acid, gluconic acid, mucoic acid, and glucoheponic acid. Most preferably, the organic acid is gluconic acid.

Organic acids can be in their D or L form.

Gluconic acid can be selected from racemic mixtures of gluconic acid salts (glucuronides) and pure enantiomers (such as alkali metal salts of L-gluconic acid, alkali metal salts of D-gluconic acid) and mixtures of enantiomer-enriched isomers. The D-isomer form is preferred.

Preferably, the organic acid is present in the range of 0.1 to 15% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.2 to 4% by weight, still more preferably 0.5 to 3% by weight, and most preferably 0.8 to 2% by weight (based on the weight of the composition). Measurements are taken regarding its protonated form.

In the most preferred embodiment, the composition comprises GLDA and/or MGDA and gluconic acid, more preferably GLDA and gluconic acid.

External structuring agent

The compositions of the present invention can be further modified in terms of their rheological properties by using one or more external structuring agents that form a structured network within the composition. Examples of such materials include crystallizable glycerides, such as hydrogenated castor oil; microfibrillated cellulose; and citrus pulp fibers. The presence of external structuring agents can provide shear-thinning rheology and also enable materials such as encapsulants and visual cues to be stably suspended in liquids.

The composition preferably contains crystallizable glycerides.

Crystallizable glycerides can be used to form externally structured systems as described in WO2011/031940, the contents of which (particularly concerning the manufacture of ESS) are incorporated herein by reference. When an ESS is present, the ESS of the present invention preferably comprises: (a) a crystallizable glyceride; (b) an alkanolamine; (c) an anionic surfactant; (d) additional components; and (e) optional components. Each of these components is discussed in detail below.

Crystallizable glycerides used herein preferably include “hydrogenated castor oil” or “HCO”. HCO, as used herein, can most generally be any hydrogenated castor oil, as long as it is capable of crystallizing in an ESS premix. Castor oil may include glycerides, particularly triglycerides, which contain a C10 to C22 alkyl or alkenyl moiety incorporating a hydroxyl group. The hydrogenation conversion of castor oil to prepare HCO can be performed as a double bond present in the feedstock oil as a ricinoleyl moiety to convert the ricinoleyl moiety into a saturated hydroxyalkyl moiety, for example, a hydroxystearyl group. In some embodiments, the HCO herein may be selected from: trihydroxystearin; dihydroxystearin; and mixtures thereof. HCO can be processed in any suitable starting form, including but not limited to those selected from solids, melts, and mixtures thereof. HCO is generally present in the ESS of the present invention at a level of about 2% to about 10%, about 3% to about 8%, or about 4% to about 6% by weight of the structured system. In some embodiments, the corresponding percentage of hydrogenated castor oil delivered to the final laundry detergent product is less than about 1.0%, typically 0.1% to 0.8%.

Useful HCOs may have the following properties: a melting point of about 40°C to about 100°C, or about 65°C to about 95°C; and/or an iodine value ranging from 0 to about 5, 0 to about 4, or 0 to about 2.6. The melting point of an HCO can be measured using ASTM D3418 or ISO 11357; both tests utilize DSC: Differential Scanning Calorimetry. HCOs used in this invention include those commercially available. Non-limiting examples of commercially available HCOs used in this invention include THIXCIN(R) from Rheox, Inc. Other examples of useful HCOs can be found in U.S. Patent 5,340,390. The castor oil used for hydrogenation to form HCOs can be from any suitable origin, such as Brazil or India. In a suitable embodiment, the castor oil is hydrogenated using a noble metal (e.g., a palladium catalyst), and the hydrogenation temperature and pressure are controlled to optimize the hydrogenation of the double bonds in natural castor oil while avoiding unacceptable levels of dehydroxylation.

This invention is not intended to relate solely to the use of hydrogenated castor oil. Any other suitable crystallizable glycerides can be used. In one example, the structuring agent is a triglyceride of substantially pure 12-hydroxystearic acid. This molecule represents the pure form of a fully hydrogenated triglyceride of 12-hydroxy-9-cis-octadecenoic acid. In nature, the composition of castor oil is fairly constant but may vary slightly. Similarly, the hydrogenation process can vary. Any other suitable equivalent material can be used, such as a mixture of triglycerides, wherein at least 80% by weight is derived from castor oil. Exemplary equivalent materials comprise primarily of or consist substantially of triglycerides; or comprise primarily of or consist substantially of a mixture of diglycerides and triglycerides; or comprise primarily of or consist substantially of a mixture of triglycerides and diglycerides and a limited amount (e.g., less than about 20% by weight of the mixture of glycerides) of monoglycerides; or comprise primarily of or consist substantially of any of the aforementioned glycerides and a limited amount (e.g., less than about 20% by weight of the corresponding acid hydrolysis product of any of the glycerides). The above premise is that the major portion (typically at least 80% by weight) of any of the stated glycerides is chemically identical to a fully hydrogenated glyceride of castor oil, i.e., a glyceride of 12-hydroxystearic acid. For example, it is well known in the art to modify hydrogenated castor oil such that, in a given triglyceride, there are two 12-hydroxystearic acid moieties and one stearic acid moieties. Similarly, it can be anticipated that hydrogenated castor oil may not be fully hydrogenated. Conversely, the present invention does not include poly(alkoxylated) castor oil when it does not meet the melting criteria.

The melting point of the crystallizable glycerides used in this invention can be from about 40 degrees Celsius to about 100 degrees Celsius.

Hydroxamic acid

Preferably, the composition comprises isohydroxamic acid.

Whenever the terms “hydroxamic acid” or “hydroxamic acid salt” are used, unless otherwise stated, they cover both hydroxamic acid and the corresponding hydroxamic acid salts (salts of hydroxamic acid).

Hydroxamic acids are a class of chemical compounds in which hydroxylamine is inserted into a carboxylic acid. The general structure of hydroxamic acids is as follows:

(Equation 1)

^R1 is an organic residue, such as an alkyl or alkenyl group. Hydroxamic acids can exist as their corresponding alkali metal salts or hydroxamic acid salts. Preferred salts are potassium salts.

Hydroxamic acid salts can be readily formed from the corresponding hydroxamic acids by substituting the hydrogen atom with a cation:

(Equation 2)

L ⁺ is a monovalent cation, such as an alkali metal (e.g., potassium, sodium), or ammonium or substituted ammonium.

In this invention, isohydroxamic acid or its corresponding isohydroxamic acid salt has the following structure:

(Equation 3)

Where ^R1 is

Straight-chain or branched _C4 - _C20 alkyl groups, or

Straight-chain or branched substituted _C4 - _C20 alkyl groups, or

Straight-chain or branched _C4 - _C20 alkenyl groups, or

Straight-chain or branched substituted _C4 - _C20 alkenyl groups, or

Alkyl ether group _CH3 ( _CH2 ) _n (EO) _m , where n is 2 to 20 and m is 1 to 12, or

The substituted alkyl ether group is _CH3 ( _CH2 ) _n (EO) _m , where n is 2 to 20 and m is 1 to 12, and the substitution type includes one or more of _NH2 , OH, S, -O- and COOH.

Furthermore, ^R2 is selected from hydrogen and part of a ring structure formed with the branched ^R1 group.

Preferred hydroxamic acid salts are those in which ^R2 is hydrogen and ^R1 is a _C8 to _C14 alkyl group, preferably a n-alkyl group, and most preferably a saturated one.

The general structure of hydroxamic acids in the context of this invention is indicated in Formula 3, and ^R1 is as defined above. When ^R1 is an alkyl ether group _CH3 ( _CH2 ) _n (EO) _m , where n is 2 to 20 and m is 1 to 12, the alkyl portion terminates the side group. Preferably, ^R1 is selected from _C4 , _C5 , _C6 , _C7 , _C8 , _C9 , _C10 , _C11 , _C12 , and _C14 n-alkyl groups, and most preferably ^R1 is at least _C8-14 n-alkyl. When using _C8 materials, this is referred to as octyl hydroxamic acid. Potassium salts are particularly useful.

Potassium octyl isohydroxamic acid

However, other hydroxamic acids, while less preferred, are also suitable for this invention. Suitable compounds of this kind include, but are not limited to, the following:

These hydroxamic acids include lysine hydroxamic acid HCl, methionine hydroxamic acid, and valine hydroxamic acid, and are commercially available.

Hydroxamic acid salts are thought to work by binding to metal ions present in dirt on fabrics. This binding (which is essentially the known chelating property of hydroxamic acid salts) itself does nothing to remove dirt from fabrics. The key is the "tail" of the hydroxamic acid salt, namely the group ^R1 minus any branching that folds back to the nitrogen of the acid salt via the group ^R2 . The tail is chosen to have an affinity for surfactant systems. This means that the dirt-removing ability of already optimized surfactant systems is further enhanced by using hydroxamic acid salts, as they effectively label hard-to-remove particulate matter (clay) as "dirt" and remove it by acting on the surfactant system of hydroxamic acid salt molecules now fixed to the particles via their binding to metal ions embedded in the clay-type particles. Non-soap-based detergency surfactants adhere to the hydroxamic acid salts, resulting in more surfactant interaction with the fabric overall, leading to better dirt release. Thus, hydroxamic acid acts as a linker molecule, thereby promoting the removal and suspension of particulate dirt from the fabric into the washing liquid, and thus improving the primary detergency.

Hydroxamic acid salts have a higher affinity for transition metals (such as iron) than for alkaline earth metals (such as calcium and magnesium). Therefore, hydroxamic acid mainly functions to improve the removal of dirt on fabrics, especially particulate dirt, rather than as an auxiliary agent for calcium and magnesium.

Preferred hydroxamic acid salts are 80% solids cocoisoxamic acid, available from Axis House under the trade name RK853. The corresponding potassium salt is available from Axis House under the trade name RK852. Axis House also supplies cocoisoxamic acid as a 50% solids material under the trade name RK858. A 50% potassium salt of cocoisoxamic acid is available under the trade name RK857. Another preferred material is RK842, an alkyl hydroxamic acid prepared from palm kernel oil from Axis House.

Preferably, the hydroxamic acid salt is present in the composition at 0.1 to 3% by weight, more preferably 0.2 to 2% by weight.

Preferably, the weight ratio of isohydroxamic acid salt to surfactant is 0.05 to 0.3, more preferably 0.75 to 0.2, and most preferably 0.8 to 1.2. The weight is calculated based on the protonated form.

Decontamination polymer

Stain-removing polymers (SRPs) help improve the removal of dirt from fabrics by modifying the fabric surface during washing. The affinity between the chemical structure of SRPs and the target fibers promotes the adsorption of SRPs on the fabric surface.

The SRP used in this invention may comprise various charged (e.g., anionic) and uncharged monomer units, and the structure may be linear, branched, or star-shaped. The SRP structure may also include end-capping groups for controlling molecular weight or altering polymer properties (such as surface activity). The weight-average molecular weight ( _Mw ) of the SRP may suitably range from about 1,000 to about 20,000, and preferably from about 1,500 to about 10,000.

The SRP used in this invention may suitably be selected from copolyesters of dicarboxylic acids (e.g., adipic acid, phthalic acid, or terephthalic acid), glycols (e.g., ethylene glycol or propylene glycol), and polyglycols (e.g., polyethylene glycol or polypropylene glycol). The copolyester may also include monomer units substituted with anionic groups, such as, for example, sulfonated isophthaloyl units. Examples of such materials include oligomers produced by transesterification/oligopolymerization of poly(ethylene glycol) methyl ether, dimethyl terephthalate (“DMT”), propylene glycol (“PG”), and polyethylene glycol (“PEG”); partially and fully anionic-terminated oligomers, such as oligomers derived from ethylene glycol (“EG”), PG, DMT, and sodium 3,6-dioxa-8-hydroxyoctanesulfonate; nonionic-terminated block polyester oligomers, such as those produced by combinations of DMT, Me-terminated PEG and EG and/or PG, or DMT, EG and/or PG, Me-terminated PEG and sodium 5-dimethylsulfonate, and those produced by block copolymers of polyethylene terephthalate or propylene terephthalate with polyethylene terephthalate oxide or propylene terephthalate oxide.

Other types of SRPs used in this invention include cellulose derivatives such as hydroxy ether cellulose polymers, _C1 - _C4 alkyl celluloses, and _C4 hydroxyalkyl celluloses; polymers having hydrophobic poly(vinyl ester) segments, such as graft copolymers of poly(vinyl ester), for example, _C1 - _C6 vinyl esters grafted onto a polyepoxide backbone (e.g., poly(vinyl caprolactam)); poly(vinyl caprolactam) and related copolymers with monomers such as vinylpyrrolidone and/or dimethylaminoethyl methacrylate; and polyester polyamide polymers prepared by condensation of adipic acid, caprolactam, and polyethylene glycol.

Preferred SRPs used in this invention comprise copolyesters formed by the condensation of terephthalate and glycol, preferably 1,2-propanediol, and further comprise alkyl-terminated repeating units formed from epoxy alkyl groups. Examples of such materials have structures corresponding to general formula (I):

Where ^R1 and ^R2 are independently X-( _{OC2H4 ) n-} ( _{OC3H6 ) m} ;

Wherein X is a _C1-4 alkyl group, preferably methyl;

n is a number between 12 and 120, preferably between 40 and 50;

m is a number from 1 to 10, preferably 1 to 7; and

a is a number between 4 and 9.

Because they are averages, m, n, and a are not necessarily integers for the whole polymer.

A mixture of any of the above materials may also be used.

The overall level of polyester-based SRP can range from 0.1% to 10%, depending on the level of polymer intended for use in the final dilution composition, and is ideally from 0.3% to 7%, more preferably from 0.5% to 5% (based on the total weight of the dilution composition by weight).

Suitable detergency polymers are described in more detail in U.S. Patent Nos. 5,574,179; 4,956,447; 4,861,512; 4,702,857; WO 2007/079850 and WO2016/005271. If used, the detergency polymer is typically incorporated into the liquid laundry detergent compositions herein at a concentration ranging from 0.01% to 10%, more preferably from 0.1% to 5% by weight of the composition.

enzymes

The composition preferably contains an enzyme selected from cellulase, protease, and a mixture of amylase/mannanase.

In addition, other enzymes may exist, such as those described below.

Preferably, the composition may contain an effective amount of one or more enzymes, preferably selected from the group consisting of: lipase, hemicellulase, peroxidase, xylanase, xanthan gumase, lipase, phospholipase, esterase, keratinase, pectinase, carrageenanase, pectic acid lyase, keratinase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, amylopectinase, tanninase, pentosanase, malicase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, tanninase, nuclease (such as deoxyribonuclease and/or ribonuclease), phosphodiesterase, or mixtures thereof.

Preferably, the enzyme content is 0.1 to 100 mg of the finished laundry liquid composition per 100 g, more preferably 0.5 to 50 mg, and most preferably 5 to 30 mg of active enzyme protein.

Examples of preferred enzymes are sold under the following trade names: Purafect Prime®, Purafect®, Preferenz® (DuPont), Savinase®, Pectawash®, Mannaway®, Lipex®, Lipoclean®, Whitzyme® Stainzyme®, Stainzyme Plus®, Natalase®, Mannaway®, Amplify® Xpect®, Celluclean® (Novozymes), Biotouch (AB Enzymes), and Lavergy® (BASF).

Detergent enzymes are discussed in WO2020/186028 (Procter and Gamble), WO2020/200600 (Henkel), WO2020/070249 (Novozymes), WO2021/001244 (BASF) and WO2020/259949 (Unilever).

Nucleases are enzymes capable of cleaving phosphodiester bonds between nucleotide subunits of nucleic acids, and are preferably deoxyribonucleases or ribonucleases. Preferably, the nuclease is a deoxyribonuclease, preferably selected from category 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.

Proteases hydrolyze bonds within peptides and proteins, which, in the case of laundry, results in enhanced removal of protein- or peptide-containing stains. Examples of suitable protease families include aspartic proteases; cysteine proteases; glutamate proteases; asparagine peptide lyases; serine proteases; and threonine proteases. Such families of proteases are described in the MEROPS peptidase database (http://merops.sanger.ac.uk). Serine proteases are preferred. Substantia nigra-type serine proteases are more preferred. The term “substantia nigra enzyme” refers to a subgroup of serine proteases according to Siezen et al., Protein Engng. 4 (1991) 719-737 and Siezen et al., Protein Science 6 (1997) 501-523. Serine proteases are a subgroup of proteases characterized by having a serine residue at the active site that forms a covalent adduct with the substrate. Substances can be divided into six subgroups: the substance protease family, the thermophilic protease family, the proteinase K family, the lanantibiotic peptidase family, the Kexin family, and the Pyrolysin family.

Examples of subtilisases are those derived from the genus Bacillus, such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus, and Bacillus gibsonii, described in US7262042 and WO09/021867, as well as subtilis protease lentus, subtilis protease Novo, subtilis protease Carlsberg, Bacillus licheniformis, subtilis protease BPN’, subtilis protease 309, subtilis protease 147, and subtilis protease 168, described in WO89/06279, and protease PD138, described in (WO93/18140). Other useful proteases may be those described in WO92/175177, WO01/016285, WO02/026024, and WO02/016547. Examples of trypsin-like proteases are trypsin (e.g., those of porcine or bovine origin) and Fusarium proteases described in WO89/06270, WO94/25583, and WO05/040372, as well as chymotrypsin derived from the genus Cellumonas described in WO05/052161 and WO05/052146.

Most preferably, the protease is subtilisin (EC 3.4.21.62).

Examples of subtilisinases are those derived from the genus Bacillus such as Bacillus tarda, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus, and Bacillus giganteus, described in US7262042 and WO09/021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN’, subtilisin 309, subtilisin 147, and subtilisin 168, described in WO89/06279, and protease PD138, described in (WO93/18140). Preferably, the subtilisin is derived from the genus Bacillus, particularly Bacillus tarda, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus, and Bacillus giganteus, as described in US 6,312,936 B1, US 5,679,630, US 4,760,025, US 7,262,042, and WO 09/021867. Most preferably, the subtilisin is derived from Bacillus giganteus or Bacillus tarda.

Suitable commercially available proteases include those sold under the trade names Alcalase®, Blaze®; DuralaseTm, DurazymTm, Relase®, Relase® Ultra, Savinase®, Savinase® Ultra, Primase®, Polarzyme®, Kannase®, Liquanase®, Liquanase® Ultra, Ovozyme®, Coronase®, Coronase® Ultra, Neutrase®, Everlase®, and Esperase®, all of which can be sold as Ultra® or Evity® (Novozymes A/S).

Suitable amylases (α and/or β) include those of bacterial or fungal origin. This includes chemically modified or protein-engineered mutants. Amylases include, for example, α-amylases derived from the genus *Bacillus*, such as specific strains of *Bacillus licheniformis* described in more detail in GB 1,296,839, or *Bacillus* strains disclosed in WO 95/026397 or WO00/060060. Commercially available amylases are Duramyl™, Termamyl™, Termamyl Ultra™, Natalase™, Stainzyme™, Fungamyl™, and BAN™ (Novozymes A/S), Rapidase™, and Purastar™ (from Genencor International Inc.).

Suitable cellulases include those of bacterial or fungal origin. This includes chemically modified or protein-engineered mutants. Suitable cellulases include those from the genera *Bacillus*, *Pseudomonas*, *Pyrophyllus*, * Fusarium *, * Thielavia terrestris*, and * Acremonium *, such as fungal cellulases produced by *Humicola insolens*, *Thielavia terrestris*, *Myceliophthora thermophila*, and *Fusarium oxysporu*, as disclosed in US 4,435,307, US 5,648,263, US 5,691,178, US 5,776,757, WO89/09259, WO96/029397, and WO98/012307. Commercially available cellulases include Celluzyme™, Carezyme™, Celluclean™, Endolase™, Renozyme™ (Novozymes A/S), Clazinase™, Puradax HA™ (Genencor International Inc.), and KAC-500(B)™ (Kao Corporation). Celluclean™ is preferred.

Lipase

Lipase is a lipid esterase, and the terms lipid esterase and lipase are used synonymously in this article.

The composition preferably contains 0.0005 to 0.5% by weight, more preferably 0.005 to 0.2% by weight of lipase.

Clean lipases are discussed in Enzymesin Detergency (1997 Marcel Dekker, New York), edited by Jan H. van Ee, Onno Misset, and Erik J. Baas.

Lipoesterases may be selected from lipases in E.C. categories 3.1 or 3.2 or combinations thereof.

Preferably, the clean lipase is selected from:

(1) Triacylglycerol lipase (E.C. 3.1.1.3)

(2) Carboxyl ester hydrolases (E.C. 3.1.1.1)

(3) Keratinase (E.C. 3.1.1.74)

(4) Sterol esterase (E.C. 3.1.1.13)

(5) Wax ester hydrolase (E.C. 3.1.1.50)

The most preferred is triacylglycerol lipase (E.C. 3.1.1.3).

Suitable triacylglycerol lipases can be selected from variants of lipases from Humicola lanuginosa (Thermomyces lanuginosus). Other suitable triacylglycerol lipases can be selected from variants of Pseudomonas lipases, such as those from *P. alcaligenes* or *P. pseudoalcaligenes* (EP 218272), *P. cepacia* (EP 331 376), *P. stutzeri* (GB 1,372,034), *P. fluorescens*, *P. spp.* strains SD 705 (WO95/06720 and WO96/27002), *P. wisconsinensis* (WO96/12012), and *Bacillus* lipases, for example, those from *Bacillus subtilis* (Dartois et al. (1993), *Biochemica et Biophysica*). Acta, 1131, 253-360, B. stearothermophilus (JP 64/744992) or B. pumilus (WO91/16422).

Suitable carboxyl ester hydrolases can be selected from wild-type or variants of endogenous carboxyl ester hydrolases from Bacillus gladioli, Pseudomonas fluorescens, Pseudomonas putida, Bacillus acidocaldarius, Bacillus subtilis, Bacillus stearothermophilus, Streptomyces chrysomallus, Streptomyces diastatochromogenes, and Saccharomyces cerevisiae.

Suitable keratinases can be selected from wild-type or variant keratinases endogenously derived from Aspergillus strains (especially Aspergillus oryzae), Alternaria strains (especially Alternaria brassicae), Fusarium strains (especially Fusarium solani pisi, Fusarium oxysporum cepa, Fusarium roseum sambucium), Helicobacter strains (especially Helminthosporum sativum), Pyrophyte strains (especially Pyrophyte spp.), Pseudomonas strains (especially Pseudomonas mendoza or Pseudomonas putida), Rhizoctonia strains (especially Rhizoctonia solani), Streptomyces strains (especially Streptomyces scabica), Coprinus strains (especially Coprinus spp.), Bifidobacterium strains (especially Schizospora thermophila), Megaloceros strains (especially Blastomyces oryzae), or Ulocladium consortiale strains (especially wild-type or variant keratinases).

In a preferred embodiment, the keratinase is selected from variants of the Mendoza Pseudomonas keratinase described in WO 2003/076580 (Genencor), such as variants with three substitutions at I178M, F180V and S205G.

In another preferred embodiment, the keratinase is a wild-type or variant of one of the six endogenous keratinases of Coprinus gracilis described in H. Kontkanen et al., App. Environ. Microbiology, 2009, pp. 2148-2157.

In another preferred embodiment, the keratinase is a wild-type or variant of two endogenous keratinases from Trichoderma reesei described in WO2009007510 (VTT).

In the most preferred embodiment, the keratinase is derived from a strain of *Pyrophyllus*, particularly *Pyrophyllus* strain DSM 1800. *Pyrophyllus* keratinase is described in WO 96/13580, which is incorporated herein by reference. The keratinase can be a variant, such as one of the variants disclosed in WO 00/34450 and WO 01/92502. Preferred keratinase variants include those listed in Example 2 of WO 01/92502. Preferred commercial keratinases include Novozym 51032 (available from Novozymes, Bagsvaerd, Denmark).

Suitable sterol esterases can be derived from Ophiostoma strains, such as Ophiostoma piceae, Pseudomonas strains, such as Pseudomonas aeruginosa, or Melanocarpus strains, such as Melanocarpus salbomyces.

In the most preferred embodiment, the sterol esterase is Melanocarpus albomyces sterol esterase as described in H. Kontkanen et al., Enzyme Microb Technol., 39, (2006), 265-273.

Suitable wax-ester hydrolases can be derived from wax trees.

The lipase is preferably selected from E.C. category 3.1.1.1 or 3.1.1.3 or a combination thereof, with the most preferred being the lipase of E.C. 3.1.1.3.

Examples of lipases in EC 3.1.1.3 include those described in WIPO publications WO 00/60063, WO 99/42566, WO 02/062973, WO 97/04078, WO 97/04079 and US 5,869,438. Preferred lipases are produced by *Absidia reflexa*, *Absidia corymbefera*, *Rhizmucormiehei*, *Rhizopus deleman*, *Aspergillus niger*, *Aspergillus tubigensis*, *Fusarium oxysporum*, *Fusarium heterosporum*, *Aspergillus oryzea*, *Penicilium camembertii*, *Aspergillus foetidus*, *Aspergillus niger*, *Landerina penisapora*, and especially *Landerina penisapora*. Certain preferred lipases are provided by Novozymes under the trade names Lipolase®, Lipolase Ultra®, Lipoprime®, Lipoclean®, and Lipex® (registered trademarks of Novozymes), and LIPASE P "AMANO®" (purchased from Areao Pharmaceutical Co. Ltd., Nagoya, Japan) and AMANO-CES® (purchased from Toyo Jozo Co., Tagata, Japan); and other Chromobacter viscosum lipases from Amersham Pharmacia Biotech., Piscataway, New Jersey, U.S.A., and Diosynth Co., Netherlands, as well as other lipases such as Pseudomonas gladioli. Other useful lipases are described in WIPO publications WO02062973, WO 2004/101759, WO 2004/101760, and WO 2004/101763. In one embodiment, a suitable lipase includes the “first-cycle lipase” described in WO00/60063 and U.S. Patent 6,939,702B1, preferably a variant of SEQ ID No. 2, more preferably a variant of SEQ ID No. 2 having at least 90% homology to SEQ ID No. 2, in which an electrically neutral or negatively charged amino acid at any position of 3, 224, 229, 231, and 233 is replaced by R or K, and the most preferred variant contains the T231R and N233R mutations, which is marketed under the trade name Lipex® (Novozymes).

The above-mentioned lipases can be used in combination (any mixture of lipases can be used). Suitable lipases are available from Novozymes, Bagsvaerd, Denmark; Areao Pharmaceutical Co. Ltd., Nagoya, Japan; ToyoJozo Co., Tagata, Japan; Amersham Pharmacia Biotech., Piscataway, New Jersey, U.S.A.; Diosynth Co., Oss, Netherlands and/or prepared according to the examples contained herein.

As described in WO2007/087243, lipases with reduced odor generation potential and good relative performance are particularly preferred. These include lipoclean® (Novozyme).

Preferred commercially available lipases include Lipolase ^™ and Lipolase Ultra ^™ , Lipex ^™ and Lipoclean ^™ (Novozymes A/S).

Fragrance

The composition contains a fragrance, and preferably, the fragrance is present in the composition at 0.01-5% by weight, more preferably 0.1-1% by weight.

Preferably, the fragrance comprises a component selected from the following: ethyl-2-methylvalerate (matricyl ester), limonene, (4Z)-cyclopentadecano-4-en-1-one, dihydromyrcenol, dimethyl benzyl carbonate acetate, benzyl acetate, spiro[1,3-dioxolane-2,5'-(4',4',8',8'-tetramethyl-hexahydro-3',9'-methylenenaphthalene)], benzyl acetate, rose ether, geraniol, methyl nonyl acetaldehyde, decanal, octanal, undecaneal, tricyclodecenyl acetate, tert-butylcyclohexyl acetate, cyclamal, β-ionone, hexyl salicylate, tuna musk, [2-(cyclohexyloxy) Raw materials including phenafleur, tetramethyl acetophenone (OTNE), benzene, toluene, and xylene (BTX), such as 2-phenylethanol, phenoxyethanol and mixtures thereof; cyclododecanone raw materials, such as habolonolide; phenolic raw materials, such as hexyl salicylate; C5 block or oxygen-containing heterocyclic raw materials, such as γ-decyl lactone, methyl dihydrojasmonate and mixtures thereof; terpene raw materials, such as dihydromyrcenol, linalool, terpinene, camphor, citronellol and mixtures thereof; alkyl alcohol raw materials, such as ethyl-2-methylbutyrate; diacid raw materials, such as ethylene glycol brassinate; and mixtures thereof.

Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component ethyl-2-methylvalerate (chamomile ester).

Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component limonene.

Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component (4Z)-cyclopentadecan-4-en-1-one.

Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component dimethyl benzyl carbonate acetate.

Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component dihydromyrcene alcohol.

Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component rose ether.

Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component tert-butylcyclohexyl acetate.

Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component tricyclodecenyl acetate.

Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component benzyl acetate.

Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component spiro[1,3-dioxolane-2,5'-(4',4',8',8'-tetramethyl-hexahydro-3',9'-methylenenaphthalene)].

Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component geraniol.

Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component methylnonylacetaldehyde.

Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component cyclamate.

Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component β-ionone.

Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component hexyl salicylate.

Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component tuna musk.

Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component [2-(cyclohexyloxy)ethyl]benzene.

Preferably, the fragrance contains a component selected from benzene, toluene, and xylene (BTX) raw materials. More preferably, the fragrance component is selected from 2-phenylethanol, phenylamyl alcohol, and mixtures thereof.

Preferably, the fragrance contains a component selected from cyclododecyl ketone raw materials. More preferably, the fragrance component is habolonolide.

Preferably, the fragrance contains a component selected from phenolic raw materials. More preferably, the fragrance component is hexyl salicylate.

Preferably, the fragrance comprises a component selected from C5 block or oxygen-containing heterocyclic raw materials. More preferably, the fragrance component is selected from γ-decanolide, methyl dihydrojasmonate, and mixtures thereof.

Preferably, the fragrance contains a component selected from terpene raw materials. More preferably, the fragrance component is selected from linalool, terpinene, camphor, citronellol, and mixtures thereof.

Preferably, the fragrance contains a component selected from alkyl alcohol raw materials. More preferably, the fragrance component is ethyl-2-methylbutyrate.

Preferably, the fragrance contains a component selected from diacid raw materials. More preferably, the fragrance component is ethylene glycol brassinate.

Preferably, the fragrance components listed above are present in the final detergent composition at a weight percentage of 0.0001 to 1%.

fluorescent agents

Preferably, the composition contains a fluorescent agent. More preferably, the fluorescent agent contains sulfonated stilbene biphenyl fluorescent agents, such as those discussed in Chapter 7 of Industrial Dyes (edited by K. Hunger, Wiley VCH 2003).

Sulfonated stilbene biphenyl fluorescent agents are discussed in US5145991 (Ciba Geigy). 4,4' ^- stilbene biphenyl is preferred. Preferably, the fluorescent agent contains two _SO₃⁻ groups. Most preferably, the fluorescent agent has the following structure:

Wherein X is a suitable counterion, preferably selected from metal ions, ammonium ions or amine salt ions, more preferably alkali metal ions, ammonium ions or amine salt ions, and most preferably Na or K.

Preferably, the fluorescent agent is present at a level of 0.01% to 1% by weight of the composition, more preferably 0.05% to 0.4% by weight, and most preferably 0.11% to 0.3% by weight.

C16 and/or C18 alkyl-based surfactants, whether alcohol ethoxylates or alkyl ether sulfates, are typically obtained as a mixture of feedstocks with C16 and C18 alkyl chain lengths.

Defoamer

The composition may also contain an antifoaming agent, but preferably not. Antifoaming agents are well known in the art and include siloxanes and fatty acids.

Preferably, the fatty acid soap is present in 0 to 0.5% by weight of the composition (as measured with reference to the acid added to the composition), more preferably 0 to 10% by weight, and most preferably absent.

Suitable fatty acids in the context of this invention include aliphatic carboxylic acids of the formula RCOOH, wherein R is a straight-chain or branched alkyl or alkenyl chain containing 6 to 24, more preferably 10 to 22, and most preferably 12 to 18 carbon atoms and 0 or 1 double bond. Preferred examples of such materials include saturated C12-18 fatty acids, such as lauric acid, myristic acid, palmitic acid, or stearic acid; and fatty acid mixtures wherein 50 to 100% (by weight, based on the total weight of the mixture) consists of saturated C12-18 fatty acids. Such mixtures are typically derived from natural fats and/or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil, or tallow).

Fatty acids can exist in the form of their sodium, potassium or ammonium salts and/or soluble salts of organic bases (such as monoethanolamine, diethanolamine or triethanolamine).

A mixture of any of the above materials may also be used.

For formulation calculation purposes, fatty acids and/or their salts (as defined above) are not included in the content of surfactants or builder agents in the formulation.

Preferably, the composition comprises 0.2 to 10% by weight of a clean polymer.

Preferably, the cleaning polymer is selected from alkoxylated polyethyleneimine, polyester detergency polymers, and copolymers of PEG/vinyl acetate.

preservative

Food preservatives are discussed in Food Chemistry (Belitz H.-D., Grosch W., Schieberle), 4th edition of Springer.

The formulation preferably contains a preservative or a mixture of preservatives selected from benzoic acid and its salts, alkyl esters of p-hydroxybenzoic acid and their salts, sorbic acid, diethyl pyrocarbonate, dimethyl pyrocarbonate, preferably benzoic acid and its salts, and most preferably sodium benzoate.

Preferred alternative preservatives are selected from sodium benzoate, phenoxyethanol, dehydroacetic acid, and mixtures thereof.

The preservative is present in amounts of 0.1% to 3% by weight, preferably 0.3% to 1.5% by weight. Where appropriate, weight is calculated for the protonated form.

Preferably, the composition comprises 0.1% to 3% by weight, more preferably 0.3% to 1.5% by weight, of sodium benzoate.

Preferably, the composition comprises 0.1% to 3% by weight, more preferably 0.3% to 1.5% by weight, of phenoxyethanol.

Preferably, the composition comprises 0.1% to 3% by weight, preferably 0.3% to 1.5% by weight, of dehydroacetic acid.

Preferably, the composition contains less than 0.1% by weight, more preferably less than 0.05% by weight of an isothiazolinone-based preservative.

Polymer cleaning enhancer

Anti-redeposition polymers stabilize dirt in detergent solutions, thereby preventing redeposition of dirt. Detergent polymers suitable for use in this invention include alkoxylated polyamines, preferably alkoxylated polyethyleneimine. Polyethyleneimine is a material composed of ethyleneimine units _{-CH₂CH₂NH₻} , and in the case of branching, _the hydrogen on the nitrogen atom is replaced by the chain of another ethyleneimine unit. Preferred alkoxylated polyethyleneimines used in this invention have a polyethyleneimine backbone with a weight-average molecular weight ( _Mw ) of about 300 to about 10,000. The polyethyleneimine backbone can be linear or branched. It can be branched to the extent of being a dendritic polymer. Alkoxylation can typically be ethoxylation or propoxylation, or a mixture of both. When nitrogen atoms are alkoxylated, the preferred average degree of alkoxylation is 10-30 alkoxy atoms per modification, preferably 15-25 alkoxy atoms. Preferred materials are ethoxylated polyethyleneimines, wherein the average degree of ethoxylation is 10-30 ethoxylated nitrogen atoms per ethoxylated nitrogen atom in the polyethyleneimine backbone, preferably 15-25 ethoxy atoms.

A mixture of any of the above materials may also be used.

More preferably, the polyamine is an alkoxylated cationic or zwitterionic diamine or polyamine polymer, wherein the positive charge is provided by quaternization of the nitrogen atom of the amine, and the anionic group (if present) is provided by sulfation or sulfonation of the alkoxylated group.

Preferably, the alkoxy compound is selected from propoxy and ethoxy, with ethoxy being the most preferred.

Preferably, 50 mol% or more of the nitrogen-containing amine is quaternized, more preferably with methyl quaternization. Preferably, the polymer contains 2 to 10, more preferably 2 to 6, and most preferably 3 to 5 quaternized nitrogen-containing amines. Preferably, the alkoxy group is selected from ethoxy and propoxy groups, most preferably ethoxy.

Preferably, the polymer contains ester (COO) or amide (CONH) groups in its structure, and these groups are preferably placed such that when all the ester or amide groups are hydrolyzed, at least one, preferably all, of the hydrolyzed fragments has a molecular weight of less than 4000, more preferably less than 2000, and most preferably less than 1000.

Preferably, the polymer has the following form:

Wherein _R1 is a C3 to C8 alkyl group, X is a ( _C2H4O ) _nY group, where n is 15 to 30, where m is 2 to 10, preferably 2 _, 3, 4 or 5, and where Y is selected from ^{OH and} _SO3- , and preferably the number of _SO3- groups is greater than the number of OH groups. Preferably, there are 0, 1 or 2 OH groups. X and _R1 may contain ester groups. X may contain _{carbonyl groups, preferably ester groups. Preferably, there is one C2H4O unit separating} the ester group from N, such that the structural unit _{NC2H4O -} ester-( _C2H4O ) _n-1Y is preferred.

Such polymers are described in WO 2021239547 (Unilever). Exemplary polymers are sulfated ethoxylated hexamethylenediamine and examples P1, P2, P3, P4, P5, and P6 of WO2021239547. The amide and ester groups can be added to the OH or NH groups, respectively, using a lactone or sodium chloroacetate (modified Williamson synthesis), followed by ethoxylation to include them.

An exemplary reaction scheme for containing ester groups is:

The addition of lactones is discussed in WO2021/165468.

The compositions of the present invention preferably contain 0.025-8% by weight of one or more anti-redeposition polymers, such as alkoxylated polyethyleneimine or zwitterionic polyamine described above.

Water-soluble

The compositions of the present invention can be incorporated with non-aqueous carriers, such as co-solvents, co-solvents, and phase stabilizers. Such materials are typically low molecular weight, water-soluble or water-miscible organic liquids, such as C1 to C5 monohydric alcohols (e.g., ethanol and n-propanol or isopropanol); C2 to C6 dihydric alcohols (e.g., monopropylene glycol and dipropylene glycol); C3 to C9 trihydric alcohols (e.g., glycerol); polyethylene glycols with a weight-average molecular weight ( _Mw ) ranging from about 200 to 600; C1 to C3 alkanolamines, such as monoethanolamine, diethanolamine, and triethanolamine; and alkyl aryl sulfonates (e.g., xylene, toluene, ethylbenzene, and sodium and potassium cumene sulfonates) having up to three carbon atoms in the lower alkyl group.

A mixture of any of the above materials may also be used.

When included, the non-aqueous carrier may be present in an amount ranging from 0.1% to 3%, preferably from 0.5% to 1% (based on the total weight of the composition). The amount of the co-water-soluble solvent used is related to the amount of surfactant, and it is desirable to use the amount of co-water-soluble solvent to control the viscosity in such compositions. Preferred co-water-soluble solvents are monopropylene glycol and glycerin.

Co-surfactants

In addition to the aforementioned non-soap anionic and/or nonionic detergency surfactants, the compositions of the present invention may also contain one or more co-surfactants (such as amphoteric (amphoionic) and/or cationic surfactants).

Specific cationic surfactants include C8 to C18 alkyl dimethyl ammonium halides and their derivatives, wherein one or two hydroxyethyl groups replace one or two methyl groups, and mixtures thereof. When included, the cationic surfactant may be present in an amount ranging from 0.1% to 5% (by weight based on the total weight of the composition).

Specific amphoteric (ampholy) surfactants include alkylamine oxides, alkyl betaines, alkylamidopropyl betaines, alkyl sulfobetaine (sulfobetaine), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoteric acetates, alkyl amphoteric propions, alkyl amphoteric glycinates, alkylamidopropyl hydroxysulfobetaine, acyl taurate, and acyl glutamate, having an alkyl group containing about 8 to about 22 carbon atoms, preferably selected from C12, C14, C16, C18, and C18:1. The term "alkyl" is used for alkyl moiety comprising a higher acyl group. When included, the amphoteric (ampholy) surfactant may be present in an amount ranging from 0.1% to 5% (by weight based on the total weight of the composition).

A mixture of any of the above materials may also be used.

Detergent builders and chelating agents

Detergent compositions may also optionally contain relatively low levels of organic detergent builders or chelating agents. Examples include alkali metals, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates, and polyacetylacetates. Specific examples include sodium, potassium, and lithium salts of oxadisuccinic acid, benzohexanic acid, benzene polycarboxylic acids, and citric acid. Other examples are DEQUEST™, an organophosphonic acid chelating agent sold by Monsanto, and alkyl hydroxyphosphonates.

Other suitable organic builders include high molecular weight polymers and copolymers known to have builder properties. For example, such materials include suitable polyacrylic acid, polymaleic acid, and polyacrylic acid/polymaleic acid copolymers and their salts, such as those sold by BASF under the name SOKALAN™. If used, the organic builder material may comprise from about 0.5% to 20% by weight of the composition, preferably from 1% to 10% by weight. Preferably, the builder content is less than 10% by weight of the composition, and more preferably less than 5% by weight of the composition.

More preferably, the liquid laundry detergent formulation is a non-phosphate-based laundry detergent formulation, i.e., containing less than 1% by weight of phosphate. Most preferably, the laundry detergent formulation is non-agent-based, i.e., containing less than 1% by weight of a detergent builder. Typically, in liquids, the preferred chelating agent is HEDP (1-hydroxyethylidene-1,1-diphosphonic acid), for example, sold as Dequest 2010. Dequest® 2066 (diethylenetriaminepenta(methylenephosphonic acid) or DTPMP heptasodium) is also suitable, but less preferred because of its poorer cleaning effect. However, it is preferred that the composition contains less than 0.5% by weight of a phosphonate-based chelating agent, more preferably less than 0.1% by weight of a phosphonate-based chelating agent. Most preferably, the composition does not contain any phosphonate-based chelating agent.

polymer thickener

The compositions of the present invention may contain one or more polymer thickeners. Suitable polymer thickeners used in the present invention include hydrophobically modified alkali-swellable emulsion (HASE) copolymers. Exemplary HASE copolymers used in the present invention include linear or crosslinked copolymers prepared by addition polymerization of a monomer mixture comprising at least one acidic vinyl monomer such as (meth)acrylic acid (i.e., methacrylic acid and/or acrylic acid) and at least one associating monomer. In the context of the present invention, the term "associating monomer" refers to a monomer having an olefinically unsaturated segment (for addition polymerization with other monomers in the mixture) and a hydrophobic segment. Preferred types of associating monomers comprise a polyoxyethylene segment between the olefinically unsaturated segment and the hydrophobic segment. The preferred HASE copolymers used in this invention comprise linear or crosslinked copolymers prepared by addition polymerization of (meth)acrylic acid with (i) at least one associating monomer selected from linear or branched _C8 - _C40 alkyl (preferably linear _C12 - _C22 alkyl) polyethoxylated (meth)acrylates; and (ii) at least one other monomer selected from _C1 - _C4 alkyl (meth)acrylates, polyoxovinyl monomers (such as maleic acid, maleic anhydride, and/or their salts), and mixtures thereof. The polyethoxylated portion of the associating monomer (i) typically comprises about 5 to about 100, preferably about 10 to about 80, more preferably about 15 to about 60 oxyethylene repeating units.

A mixture of any of the above materials may also be used.

When included, the compositions of the present invention preferably comprise 0.01 to 5% by weight of the composition, but depending on the amount intended for use in the final diluted product, and ideally 0.1 to 3% by weight, based on the total weight of the diluted composition.

Toning dyes

Tinting dyes can be used to improve the properties of a composition. Preferred tinting dyes are purple or blue. It is believed that low levels of these hues mask yellowing of the fabric upon deposition. A further advantage of tinting dyes is that they can be used to mask any yellow tint within the composition itself.

Toning dyes are well-known in the field of liquid laundry detergent formulations.

Suitable and preferred categories of dyes include direct dyes, acid dyes, hydrophobic dyes, basic dyes, reactive dyes, and dye conjugates. Preferred examples are Disperse Violet 28, Acid Violet 50, anthraquinone dyes covalently bonded to ethoxylated or propoxylated polyethyleneimine, as described in WO2011/047987 and WO2012/119859, alkoxylated mono-azothiophene, dyes having CAS-No 72749-80-5, Acid Blue 59, and phenazine dyes selected from:

in:

_X3 is selected from: -H; -F; _-CH3 ; _{-C2H5 ; -OCH3} ; _{and -OC2H5} ;

_X4 is selected from: -H; _-CH3 ; _{-C2H5 ; -OCH3} ; _{and -OC2H5} ;

Y ₂ is selected from: -OH; -OCH ₂ CH ₂ OH; -CH(OH)CH ₂ OH; -OC(O)CH ₃ ; and C(O)OCH ₃ .

Alkoxylated thiophene dyes are discussed in WO2013/142495 and WO2008/087497.

The tinting dye is preferably present in the composition in the range of 0.0001 to 0.1% by weight. Depending on the properties of the tinting dye, there is a preferred range that depends on the effectiveness of the tinting dye (which depends on the category and the specific effectiveness within any particular category).

Microcapsules

One type of particulate matter suitable for this invention is microcapsule.

Microencapsulation can be defined as the process of encapsulating or covering one substance within another at a very small scale, resulting in capsules ranging in size from less than one micrometer to several hundred micrometers. The encapsulated material can be called the core, active ingredient or drug, filler, payload, core, or internal phase. The material encapsulating the core can be called a coating, membrane, shell, or wall material.

Microcapsules typically have at least one continuous, usually spherical shell surrounding a core. Depending on the materials and encapsulation techniques used, the shell may contain pores, vacancies, or interstitial openings. Multiple shells may be made of the same or different encapsulating materials and may be arranged in layers of varying thicknesses around the core. Alternatively, microcapsules may be asymmetrically and variablely shaped, having a certain amount of smaller core material droplets embedded throughout the microcapsule.

The shell can function as a barrier protecting the core material from the external environment of the microcapsule, but it can also be used as a means of regulating the release of the core material, such as a fragrance. Therefore, the shell can be water-soluble or water-swellable and can initiate fragrance release in response to microcapsule exposure to a humid environment. Similarly, if the shell is temperature-sensitive, the microcapsule can release the fragrance in response to increased temperature. The microcapsule can also release the fragrance in response to shear forces applied to its surface.

A preferred type of polymer microparticle suitable for use in this invention is a polymer core-shell microcapsule, wherein at least one continuous shell of polymeric material, typically spherical, surrounds a core containing a fragrance formulation (f2). The shell typically comprises at most 20% by weight based on the total weight of the microcapsules. The fragrance formulation (f2) typically comprises about 10% to about 60% by weight based on the total weight of the microcapsules, and preferably about 20% to about 40% by weight. The amount of fragrance (f2) can be determined by taking a slurry from the microcapsules, extracting it into ethanol, and measuring it by liquid chromatography.

Further optional ingredients

The compositions of the present invention may contain further optional ingredients to improve performance and/or consumer acceptability. Examples of such ingredients include foam enhancers, preservatives (e.g., bactericides), polyelectrolytes, anti-shrinkage agents, anti-wrinkle agents, antioxidants, sunscreens, anti-corrosion agents, draping agents, antistatic agents, ironing aids, colorants, pearlescent agents and/or opacifiers, and tinting dyes. Each of these ingredients is present in an amount that effectively achieves its purpose. Typically, these optional ingredients are contained individually in amounts up to 5% (by weight based on the total weight of the diluted composition), and thus adjusted according to the dilution ratio of water used.

Automatic quantitative feeding

In a further aspect, the compositions of the present invention can be used in automatic metering washing machines.

Therefore, in a further aspect, a washing machine is provided, which includes a detergent reservoir containing 80 ml to 3000 ml of liquid detergent according to the first aspect.

In a further aspect, a method for cleaning fabrics is provided, comprising filling a reservoir of a washing machine with 80 ml to 3000 ml of a liquid detergent composition according to the first aspect, and performing at least two washing cycles before adding further liquid detergent to the reservoir.

In a further aspect, a method for cleaning fabrics is provided, comprising filling a reservoir of a washing machine with 80 ml to 3000 ml of a liquid laundry detergent composition according to the first aspect, and performing a washing cycle that draws a portion of the liquid detergent from the reservoir and leaves at least 20 ml in the reservoir.

In a further aspect, a method for cleaning a first fabric is provided, the method comprising filling a reservoir of a washing machine with 80 ml to 3000 ml of a liquid detergent composition according to the first aspect, and performing a first washing cycle by drawing a portion of the liquid detergent from the reservoir and combining it with water to form a first washing liquid in the washing machine and washing the first fabric.

Optional rinsing; and removing the first fabric from the washing machine; and

A further washing cycle is performed to clean the further fabric by drawing a portion of liquid detergent from the reservoir and combining it with water to form a further washing solution and washing the further fabric.

Optional rinsing; and removing the further fabric from the washing machine;

Optional, repeat further washing cycles; and

Add further liquid detergent to the reservoir.

The amount of liquid detergent, from 80 ml to 3000 ml, indicates a washing dose of more than one dose. Preferably, the reservoir contains 250 ml to 2500 ml, more preferably 400 ml to 2000 ml of liquid detergent.

The washing machine preferably includes a detergent reservoir capable of storing up to 3000 ml of detergent. Such washing machines are marketed as automatic dispensing washing machines and are capable of storing sufficient liquid detergent for more than one washing cycle, and preferably for multiple washing cycles. A typical example of such a washing machine can be found in EP-A-3 071 742 (Electrolux). Preferably, the washing machine is a front-loading automatic washing machine.

Preferably, the washing machine includes a housing, a washing tub (arranged inside the housing with its opening or spout directly facing a clothes loading/unloading opening realized on the front wall of the housing), a detergent dispensing assembly (configured to supply detergent to the washing tub), a main clean water supply circuit (configured to connect to the main water supply pipe and to selectively direct the flow of clean water from the main water supply pipe to the detergent dispensing assembly and/or the washing tub), and an electrical control panel (configured to allow the user to manually select the desired washing cycle).

The washing machine detergent dispensing assembly also includes an automatic metering detergent dispenser configured to automatically dispense an appropriate amount of detergent to be used during the selected wash cycle based on the selected wash cycle, and the automatic metering detergent dispenser includes: one or more detergent reservoirs, each configured to receive a certain amount of detergent for performing multiple wash cycles; and for each detergent reservoir, a corresponding detergent feed pump configured to selectively draw an amount of detergent from the corresponding detergent reservoir for performing the selected wash cycle and pump/direct the specific amount of detergent into a detergent collection chamber in fluid communication with the wash tub.

In addition to a reservoir capable of holding a required amount of liquid detergent, the washing machine of the present invention also includes a motor for driving the agitation of the drum. Water is rinsed through the washing machine, and a predetermined dose of detergent is added to the water to form a washing liquid.

With an automatic dispensing washing machine, consumers can run multiple wash cycles before needing to add further liquid detergent to the reservoir. Typically, the reservoir is sufficient for five or more washes, and possibly up to 20 or more, depending on the size of the reservoir in the washing machine and the dosage used in each wash cycle.

Each washing cycle includes drawing a volume of liquid laundry detergent from the reservoir sufficient to form a suitable washing solution to clean the fabric.

Preferably, the volume is 10 to 75 ml, but this may depend on the amount of fabric, the stain to be cleaned, and the amount of surfactants and other detergents in the liquid laundry detergent composition.

After the first wash cycle is completed, the remaining liquid detergent remains in the washing machine until the next cycle begins, at which point a further dose is pumped from the reservoir and mixed with water to form a washing solution.

Alternatively, the composition described herein may be loaded into the washing machine via a drum that is compatible with components of the washing machine. The drum may contain the necessary volume of the desired liquid detergent composition, and may be from 200 ml to 3000 ml.

Example

Example 1

A calcium catalyst was prepared according to EP1747183, having the following composition: 73.5 wt% n-butanol, 15 wt% calcium hydroxide, 3.5 wt% 2-ethylhexanoic acid, and 7.8 wt% concentrated sulfuric acid from Example 1, which was used in this example to prepare a narrow range of ethoxylates.

915 g of C14 alcohol (C12 = 10 wt%, C14 = 89 wt%, C16 = 1 wt%) was added to a 2-gallon stainless steel autoclave equipped with a top stirrer, internal steam heating, water cooling, and thermocouples. The C14 alcohol was vacuum dried at 90 °C, then 2.1 g of catalyst was added and vacuum stripped at 90 °C until all solvent was removed (approximately 5 minutes). The reactor was heated to 140 °C and ethylene oxide was slowly added. After the induction period, a small exothermic reaction was observed, at which point ethylene oxide was continued to be added at a pressure of 2 bar until a total of 3 moles of ethylene oxide had been consumed. The temperature was controlled using water cooling and brought to 180 °C. When the ethylene oxide at a molar ratio of 3:1 reacted with the C14 alcohol to form an alcohol ethoxylate, the temperature was lowered to 90 °C and the product was vacuum stripped for 3 hours.

The narrow-range ethoxylation procedure was repeated using ( _C11H23COO ) _2Ba as described in Ind. Eng. Chem. Res. 1992, 31, 2419-2421, the methanesulfonic acid catalyst described in US10099964, and the barium oxide _/ sulfuric acid catalyst described in WO2012028435 (Kolb).

The distribution of ethoxylates in the methanesulfonic acid catalyst was measured and compared with a fairly wide range of materials prepared using KOH as a catalyst. The results are given in the table below.

The narrow-range materials have lower fractions of AE-0 and AE-1 materials, where AE-0 is an unethoxylated alcohol (zero ethoxylated groups) and AE-1 is an alcohol ethoxylated with one ethoxylated group.

The resulting material was sulfated using _SO3 in a falling film reactor to produce sodium ether sulfate.

Example 2

Liquid laundry detergent is made from the following composition:

Alkoxylated oligoamines are polyethyleneimines (molecular weight = 600) with 20 ethoxylated groups per -NH group (from BASF).

Once prepared, various amounts of salt are added, and the viscosity is recorded at 21 Hz using a viscometer.

Alkyl ether sulfates (AES) are based on C12/14 alcohols having a molar average of 3 ethoxy units. The C12:C14 weight ratio is 7.0:2.3. The experiment was repeated using alkyl ether sulfates prepared by broad-range (BR) ethoxylation (NaOH catalyst) and narrow-range (NR) ethoxylation. The entire experiment was repeated with matching formulations of de-alkoxylated zwitterionic diamines or polyamine polymers.

The effect of NR AES on viscosity is calculated as a ratio ø, where

ø = viscosity for NR AES / viscosity for BR AES.

Surprisingly, in the presence of alkoxylated oligoamines, NR AES exhibits a greater increase in viscosity than BR AES.

Example 3

Typical formulations include:

^1,2 were also prepared using the C12-18 form.

C12-14 alkylethoxy(3) sulfate is a narrow-range AES as described herein.

The fragrance contains aromatic components selected from the following: limonene, tuna musk, octahydrotetramethylacetophenone (OTNE), cyclamen aldehyde, C8 to C12 straight-chain and branched aldehydes, β-ionone, dihydromyrcenol, hexyl salicylate, and mixtures thereof.

Claims (14)

1. A detergent composition comprising 0.5 to 10 wt% of an alkoxylated oligoamine cleaning enhancer and an alcohol ether sulfate, wherein the alcohol ether sulfate comprises C12 and C14 alkyl chains and has a molar average of 2.0 to 4.0 ethoxylated units, wherein the alcohol ether sulfate comprises less than 10 wt% of an alcohol ether sulfate having zero ethoxylated groups. 2. The composition according to claim 1, wherein it is a liquid detergent composition. 3. The composition according to claim 1 or 2, wherein it comprises at least 60% by weight of water. 4. The composition according to claim 1, wherein the alkoxylated oligoamine is selected from alkoxylated polyethyleneimine, zwitterionic alkoxylated oligoamine, and tetraester alkoxylated oligoamine. 5. The composition according to any one of the preceding claims, wherein the ratio of C12:14 is from 5:1 to 1:20. 6. The composition according to any one of the preceding claims, wherein the ratio of C12:14 is from 3:1 to 5:4. 7. The composition according to any one of the preceding claims, wherein the alkyl ether sulfate is present in 1-30% by weight of the composition. 8. The composition according to any one of the preceding claims, comprising a salt. 9. The composition according to claim 8, wherein the salt is selected from sodium chloride, potassium chloride, and mixtures thereof. 10. The composition according to claim 8 or 9, wherein the salt is present in 0.1-5% by weight of the composition. 11. The composition according to claim 10, wherein the salt is present in 0.1-1.8% by weight of the composition. 12. The composition according to any one of the preceding claims, wherein the alkoxylated polyamine alkoxyl group is selected from ethoxy and propoxy, with ethoxy being the most preferred. 13. The composition according to any one of the preceding claims, having a pH of 5 to 10, more preferably 6 to 8, and most preferably 6.1 to 7.0. 14. The composition according to any one of the preceding claims, comprising 0.1 to 3% by weight of betaine.