Bleach alternative complex for stain removal in liquid detergents

Abstract

A liquid laundry detergent composition is disclosed containing 1 wt. % to 75 wt. % of an anionic surfactant, and 0.05 to 5.0% of a bleach alternative complex that includes a polyethyleneimine and a polycarboxylic acid.

Description

[0001] Henkel AG & Co. KGaA Dr. Mundt 2024PF00133

[0002] BLEACH ALTERNATIVE COMPLEX FOR STAIN REMOVAL IN LIQUID

[0003] DETERGENTS

[0004] FIELD OF INVENTION

[0005] [2] This disclosure relates to liquid detergent compositions.

[0006] BACKGROUND OF THE INVENTION

[0007] [3] Liquid laundry detergents often contain a blend of surfactants, builders, waterconditioners, dispersants, soil-release polymers, detersive enzymes, and oxidizing agents, to improve cleaning performance. Stains that are particularly difficult to remove are oxidizable stains such as coffee, tea, blackcurrant and lipstick. The color in the pigment of the stain is caused when molecules called chromophores absorb light in the visible wavelength range, and the wavelengths that are not absorbed will be reflected instead and are visible to the human eye.

[0008] [4] Chlorine and oxygen-based bleach remove oxidizable stains through oxidizing agents by breaking bonds within the chromophore to produce smaller fragments which do not absorb light in the visible region of light. While chlorine bleach, based on sodium hypochlorite, may whiten natural fibers, it also deteriorates the tensile strength of garments and fades colors over time. Oxygen based bleach, based on sodium percarbonate, is often found in solid powder form, and becomes active when combined with water. Oxygen based bleach releases hydrogen peroxide, which then becomes an active oxidizing agent, and removes a stain by breaking down the colored section of the chromophores. Oxygen based bleach is less damaging to fibers than sodium hypochlorite and more environmentally friendly. However, oxygen-based bleach does not function as a good stain remover below 40°C, and it is challenging in formulating in liquid detergents.

[0009] [5] Consumers are increasingly conscious of the environmental impact of traditional detergent ingredients, and brands are responding by developing detergents with plantbased, biodegradable, and reduced ecological footprint. This trend aligns with the growing demand for sustainable products that reduce the ecological footprint associated with laundry routines. 2024PF00133

[0010] 2

[0011] [6] Soil-release polymers (SRPs) are additives in laundry detergents. They enable soil release from fabric and prevent soil redeposition during the washing cycle by forming a coat or barrier on the surface of the fibers and protect them from deeper penetration of soil / dirt into the fibers. SRPs are polymeric surfactants / reagents applied to the fabric to make it more soil resistant.

[0012] [7] One such eco-friendly soil release polymer in laundry detergents includes cationic polyethylene imines. They are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered through a washing cycle, and serve as an anchor for hydrophobic segments. This enables stains occurring subsequent to treatment with the release agent to be more easily cleaned in later washing procedures.

[0013] [8] Another such eco-friendly soil release polymer in laundry detergents includes polyacrylate / polymethacrylate-based soil-release polymer finishes.

[0014] [9] However, cationic polyethylene imines and polyacrylate soil release polymers on their own have not been found to be effective against bleachable stains with difficult to remove chromophores. Instead, typically, consumers have to resort to sodium carbonate peroxide or chlorine bleach to deactivate such chromophores, while risking damaging to fabrics, adding separate powder, using high temperature and using other ingredients that may not an eco-friendly choice.

[0015]

[0010] There is a need in the laundry detergent industry to make a liquid formula more effective against bleachable stains without having to resort to sodium carbonate peroxide or chlorine bleach.

[0016]

[0011] Further, when liquid detergents contain chlorine, it is typically unable to also contain synthetic or natural dyes due to reactivity. Dyes are useful in laundry detergents for making a product more attractive looking to a consumer, such as with different colors in a pod swirl. Some dyes can also be an optical brightener, which converts UV (ultraviolet) light waves into blue light and thus reduces yellow light intensity to give a whiter appearance of whiter skin. Formulations containing dyes and / or optical brighteners with a stable bleach alternative would also be desirable. 2024PF00133

[0017] 3

[0018] BRIEF SUMMARY OF THE INVENTION

[0019]

[0012] The present invention is based on the discovery of a bleach alternative complex in which a combination of a positively charged PEI polymer and a polymeric acid has been discovered to significantly improve the performance of liquid detergent against bleachable stains. While not being bound by theory, it is believed that when both ingredients are combined in a liquid detergent in a mildly alkaline pH, such as 8 to 8.3, the polymeric acid is large enough to capture and chelate negative ions in the medium. This in turn allows the nitrogen groups in the positively charged PEI polymer to effectively maintain a high level of protonation of its nitrogens, which in turn allows it to become an oxidizing agent and break double bonds of the chromophores of difficult stains. Further, unlike bleach, the bleach alternative complex does not impact laundry dyes and optical brighteners and permits such ingredients in laundry detergent formulations.

[0020] DETAILED DESCRIPTION OF THE INVENTION

[0021]

[0013] The following description provides specific details, such as materials and dimensions, to provide a thorough understanding of the present invention. The skilled artisan, however, will appreciate that the present invention can be practiced without employing these specific details. Indeed, the present invention can be practiced in conjunction with processing, manufacturing or fabricating techniques conventionally used in the detergent industry. Moreover, the processes below describe only steps, rather than a complete process flow, for manufacturing the aqueous surfactant system and unit dose composition containing the aqueous surfactant system according to the present invention.

[0022]

[0014] As used herein, "a," "an," or "the" means one or more unless otherwise specified.

[0023]

[0015] The term "or" can be conjunctive or disjunctive.

[0024]

[0016] Open terms such as "include," "including," "contain," "containing" and the like mean "comprising."

[0025]

[0017] The term "about" as used herein, includes the recited number ±10%. For example, "about 10" means 9 to 11.

[0026]

[0018] The term "solvent" used herein does not include water. It also does not include neutralization agents, such as triethanolamine, monoethanolamine, sodium hydroxide, and acids, or agents that are conventionally used as surfactants. 2024PF00133

[0027] 4

[0028]

[0019] The phrase "substantially free of' means that a composition contains little or no specified ingredient / component, such as less than about 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, 0.5 wt%, or 0.1 wt%, or below the detectable level of the specified ingredient. For example, the phrase "substantially free of chlorine bleaching agents" refers to an aqueous composition of the present disclosure that contains little or no hypochlorites. An aqueous composition of the present disclosure that is substantially free of chlorine bleaching agents may contain, for example, less than about 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, 0.5 wt%, or 0.1 wt% of hypochlorites, based on the total weight of the composition.

[0029]

[0020] The "%" described in the present disclosure refers to the weight percentage unless otherwise indicated.

[0030]

[0021] Compositions of the Invention

[0031]

[0022] In one aspect, the present disclosure provides a liquid laundry detergent composition comprising a bleach alternative complex comprising a polyethyleneimine and a polycarboxylic acid. A typical liquid laundry detergent chassis further includes an anionic surfactant, a nonionic surfactant, water, fatty acid, and optionally optical brighteners and or colorants.

[0032]

[0023] Bleach Alternative Complex

[0033]

[0024] According to the invention, the bleach alternative complex is a combination of a polyethyleneimine (PEI) and a polycarboxylic acid. Further, the bleach alternative complex is selective in that it protects fabrics and dyes, and targets stains without bleaching the color fabrics.

[0034]

[0025] Polyethyleneimine

[0035]

[0026] The bleach alternative complex contains a positively charged class of polymers such as polyethyleneimine (PEI) and its derivatives such as ethoxylated (PEI) polymers, polyamines, polyquats, polyglycerol quats, and other PEI derivatives, their salts or mixtures may be use in the compositions of the invention. PEI is a polymeric amine or a polyamine, and include, polyethyleneimine compounds (PEI) and / or its derivatives. Polyethyleneimines may include primary, secondary or tertiary amine compounds. The polyethyleneimine compounds and / or its derivatives may include linear and / or branched polyethyleneimines. Still further, polyethyleneimines and / or its derivatives can vary significantly in molecular weight, topology and shape, including for example linear, branched or comb-like structures as a result of ring-opening polymerization of the 2024PF00133

[0036] 5 ethylenimine. According to an aspect of the invention, the bleach activator may be a linear and / or branched polyethyleneimine.

[0037]

[0027] Exemplary PEI products include multifunctional cationic polyethyleneimines with branched polymer structures according to the following formulas ( — (CH2 — CH2 — NH)n— ), with a molecular mass of 43.07 (as repeating units). In certain aspects the formula ( — (CH2 — CH2 — NH)n— ) has a value of n that is at least 10 to 105, and wherein the nitrogen to carbon ratio is 1:2. Exemplary PEI polymers useful in the complex generally have following polymer structure:

[0038]

[0029] PEI products can also be represented by the following general formula, which may vary according to substitutions, size, molecular weight, branching, and the like: — NHCH2CH2— )x[— N(CH2CH2NH2)CH2CH2— ]y wherein x is an integer that is 1 or greater and y is an integer that is 1 or greater than 1. Preferably, wherein x is an integer from about 1 to about 120,000, preferably from about 2 to about 60,000, more preferably from about 3 to about 24,000 and y is an integer from about 1 to about 60,000, preferably from about 2 to about 30,000, more preferably from about 3 to about 12,000.

[0039]

[0030] Various commercial polyethyleneimines are available, including for example those sold under the tradename Lupasol® (BASF), including for example Lupasol® FG, Lupasol® G, Lupasol® PR 8515, Lupasol® WF, Lupasol® G 20 / 35 / 100, Lupasol® HF, Lupasol® P, Lupasol® PS, Lupasol® PO 100, Lupasol® PN 50 / 60, and Lupasol® SK. Such exemplary polyethyleneimines are available as anhydrous polyethyleneimines and / or modified polyethyleneimines provided in aqueous solutions or methoyxypropanol (Lupasol® PO 100). Commercially-available examples of such preferred PEIs include the BASF products LUPASOL® WF (25 kDa; 16-20 meq / g) and Lupasol® FG (800 Daltons; 2024PF00133

[0040] 6

[0041] 16-20 meq / g), and the BASF products in the SOKALAN® family of polymers, e g., SOKALAN® HP20, SOKALAN® HP22 G, and the like. The molar mass of the polyethyleneimines, including modified polyethyleneimines can vary from about 800 g / mol to at least 2,000,000 g / mol.

[0042]

[0031] In certain aspects the PEI is from about 100 Daltons to about 2 million Daltons (PEI-2,000,000), more preferably from about 100 Daltons to about 1 million Daltons (PEI- 1,000,000), more preferably from about 500 Daltons to about 500 kDa (PEI-500,000), more preferably from about 500 Daltons to about 50 kDa (PEI-50,000), more preferably from about 800 Daltons to about 50 kDa (PEI-50,000), more preferably from about 800 Daltons to about 10 kDa (PEI-10,000).

[0043]

[0032] In an aspect, a polymeric amine may contain other substituents and / or and copolymers. For example, a polymeric amine may also include substituents, including for example ethoxylates and propoxylates.

[0044]

[0033] The cationic polymer, PEI is present in an amount of from about 0.01 wt. % 1 to about 5 wt. %. At greater than 5 wt. % the affect is decreased and this appears to be an upper limit.

[0045]

[0034] Polycarboxylic Acid

[0046]

[0035] The polycarboxylic acid may be a homopolymer of a C3-C6 carboxylic acid or dicarboxylic acid or a copolymer of acrylic acid and maleic acid. The polymeric acid may be partly neutralized, e.g. with sodium hydroxide, and, therefore, the polymeric acid may also contain sodium salts of carboxylic acid groups.

[0047]

[0036] The polymeric acid may be an alkoxylated homopolymer of a C3-C6 carboxylic acid or an alkoxylated copolymer of acrylic acid and maleic acid.

[0048]

[0037] Alkoxylated polycarboxylates may be prepared from, for example, poly(meth)acrylates. Chemically, these materials comprise poly(meth)acrylates having one ethoxy side-chain per every 7-8 (meth)acrylate units. The side-chains are of the formula — (CH2CH2O)m(CH2)nCH3 wherein m is 2-3 and n is 6-12. The side-chains are ester-linked to the polyacrylate “backbone” to provide a “comb” polymer type structure. The molecular weight can vary, but is typically in the range of about 2000 to about 50,000.

[0049]

[0038] The polycarboxylic acid may be a polyacrylic acid with a molecular weight Mn of from about 1,000 g / mol to about 1,000,000 g / mol, as determined by gel permeation chromatography and referring to the free acid. The polymeric acid may be a copolymer of 2024PF00133

[0050] 7 acrylic acid and maleic acid, having a molecular weight of from about 1000 g / mol to about 1,000,000 g / mol.

[0051]

[0039] Surfactants

[0052]

[0040] The liquid laundry detergent also contains surfactants comprising an anionic surfactant and nonionic surfactants

[0053]

[0041] Linear alkylbenzene sulfonate (LAS)

[0054]

[0042] Linear alkylbenzenesulfonate (LAS) is a water-soluble salt of a linear alkyl benzene sulfonic acid having between 8 and 22 carbon atoms in the linear alkyl group. The salt can be an alkali metal salt, or an ammonium, alkylammonium, or alkanolammonium salt. In one embodiment, the LAS comprises an alkali metal salt of Cio- Ci6 alkyl benzene sulfonic acids, such as C11-C14 alkyl benzene sulfonic acids. Suitable LAS includes sodium and potassium linear alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is between 11 and 14. Sodium C11-C14 (e.g., C12) LAS is one suitable anionic surfactant for use herein.

[0055]

[0043] In some embodiments, the amount of LAS in the surfactant system is selected so as to form a structured surfactant system. In some embodiments, the surfactant system contains about 1 to about 20 wt.%, about 2 to about 15 wt.%, or about 3 to 10 wt.% of linear alkylbenzenesulfonate, based on the total weight of the surfactant system.

[0056]

[0044] Alcohol ethoxylsulfate (AES)

[0057]

[0045] Alcohol ethoxysulfate (AES), also known as alkyl ether sulfates or alkyl polyethoxylate sulfates, are compounds having Formula (I):

[0058] Ri-O-(C2H4O)n-SO3M (I), wherein Ri is a C8-C22 alkyl group, n is from 1 to 20, and M is a salt-forming cation. Preferably, Ri is a Cio-Cis alkyl, or a C10-C15 alkyl, n is from 1 to 15, 1 to 10, or 1 to 8, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium. More preferably, Ri is a C12-C16 alkyl, n is from 1 to 6, and M is sodium. In one embodiment, the alkyl ether sulfate is sodium lauryl ether sulphate (SLES). The AES will generally be used in the form of mixtures comprising varying Ri chain lengths and varying degrees of ethoxylation. Frequently such mixtures will inevitably also contain some unethoxylated alkyl sulfate materials, i.e., n=0 in the above Formula (I). Unethoxylated alkyl sulfates may also be added separately to the aqueous surfactant system of present disclosure and 2024PF00133

[0059] 8 used as or in any anionic surfactant component which may be present. Suitable unalkoyxylated, e.g., unethoxylated, alkyl ether sulfate surfactants are those made by the sulfation of higher C8-C20 fatty alcohols. Conventional alkyl sulfate surfactants may also be suitable herein, which have the general formula of: R1OSO3M . wherein Ri and M each has the same definition as described above. Exemplary AES includes those sold under the tradename CALFOAM® 303 (Pilot Chemical Company, California).

[0060]

[0046] In some embodiments, the amount of AES in the aqueous surfactant system of the present disclosure is selected so as to form a structured surfactant system. In some embodiments, the surfactant system contains from about 1 to about 40 wt%, about 3 to about 20 wt%, or about 5 to 10 wt% of AES, based on the total weight of the surfactant system.

[0061]

[0047] In some embodiments, the weight ratio of LAS to AES in the surfactant system is from about 1:1 to about 1:5, from about 1:1 to about 1:3, or from about 1:1.5 to about 1:2. In some embodiments, the weight ratio of LAS to AES is about 1:1.7.

[0062]

[0048] Non-ionic surfactant The surfactant system of the present disclosure contains a non-ionic surfactant. A wide range of non-ionic surfactants can be used herein. For example, the non-ionic surfactants include, but are not limited to alkoxylated alcohols, polyoxyalkylene alkyl ethers (e.g., those marketed under the trade name Pluronic® (e.g., Pluronic® PE or Pluronic® RPE, available from BASF), polyoxyalkylene alkylphenyl ethers, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbitol fatty acid esters, polyalkylene glycol fatty acid esters, alkyl polyalkylene glycol fatty acid esters, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyalkylene castor oils, polyoxyalkylene alkylamines, glycerol fatty acid esters, alkylglucosamides, alkylglucosides, alkylamine oxides, or a combination thereof. Preferably, the non-ionic surfactant is an alcohol ethoxylate (AE).

[0063]

[0049] The AE may be primary and secondary alcohol ethoxylates, especially the C8-C20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles, or from 3 to 8 moles of ethylene oxide per mole of alcohol.

[0064]

[0050] Exemplary AEs are the condensation products of aliphatic C8-C20, preferably Cs-Cie, primary or secondary, linear or branched chain alcohols with ethylene oxide. In 2024PF00133

[0065] 9 some embodiments, the alcohol ethoxylates contain 1 to 20, or 3 to 8 ethylene oxide groups, and may optionally be end-capped by a hydroxylated alkyl group.

[0066]

[0051] In one embodiment, the AE has Formula (II):

[0067] R2-(-O-C2H4-)m-OH (II) wherein R2is a hydrocarbyl group having 8 to 16 carbon atoms, 8 to 14 carbon atoms, 8 to 12 carbon atoms, or 8 to 10 carbon atoms; and m is from 1 to 20, or 3 to 8.

[0068]

[0052] The hydrocarbyl group may be linear or branched, and saturated or unsaturated. In some embodiments, R2is a linear or branched Cs-Ci6 alkyl or a linear group or branched Cs-Cie alkenyl group. Preferably, R2is a linear or branched Cs-Ci6 alkyl, Cs-Ci4 alkyl, or C8-C10 alkyl group. In case (e.g., commercially available materials) where materials contain a range of carbon chain lengths, these carbon numbers represent an average. The alcohol may be derived from natural or synthetic feedstock. In one embodiment, the alcohol feedstock is coconut, containing predominantly C12-C14 alcohol, and oxo Ci2-Cis alcohols.

[0069]

[0053] One suitable AE is Tomadol® 25-7 (available from Air Product). Other suitable AEs include Genapol® C200 (available from Clariant), which is a coco alcohol having an average degree of ethoxylation of 20.

[0070]

[0054] In some embodiments, the amount of non-ionic surfactant in the surfactant system is selected so as to form a structured surfactant system. In some embodiments, the aqueous surfactant system comprises about 30 to about 70 wt% of a non-ionic surfactant, based on the total weight the surfactant system.

[0071]

[0055] In some embodiments, the surfactant system of the present disclosure comprises from about 1 to about 20 wt%, from about 2 to about 15 wt%, about 3 to about 10 wt%, from about 4 to about 7 wt% of AE, based on the total weight the surfactant system.

[0072]

[0056] Water

[0073]

[0057] The unit dose compositions of the present disclosure contain a high content of water. The aqueous composition may comprise greater than 10 wt%, greater than 20 wt%, greater than 30 wt%, greater than 40 wt%, greater than 50 wt%, or greater than 60 wt%, greater than 70 wt%, or greater than 75 wt% of water, based on the total weight of the aqueous composition. The aqueous composition may comprise less than 95 wt%, less than 90 wt%, less than 80 wt%, by weight of water, based on the total weight of the aqueous 2024PF00133

[0074] 10 composition. In some embodiments, the aqueous composition contains about 50 to about 95 wt%, about 60 to about 85 wt%, about 70 to about 80 wt%. In one embodiment, the aqueous composition contains about 75 to about 80 wt% or about of water, based on the total weight of the aqueous composition.

[0075]

[0058] In some embodiments, the weight ratio of LAS to non-ionic surfactant (e.g. AE) in the surfactant system is from about 1 : 1 to about 1:10. In some embodiments, the weight ratio of LAS to AE in the surfactant system is from about 1:1 to about 1:10, from about 1:1 to 1:8, or from about 1:1 to 1:6. In one embodiment, the weight ratio of LAS to AE is about 1:1.4.

[0076]

[0059] Fatty Acid

[0077]

[0060] The surfactant system may also contain a fatty acid. Suitable fatty acid may be any fatty acid having formula: R.3-C(O)OH, wherein R3 is a C5-C21 linear or branched aliphatic group. Preferably, the R3 is a C13-C21 linear or branched aliphatic group.

[0078]

[0061] In some embodiments, the fatty acid is hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid, docosanoic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, or a mixture thereof.

[0079]

[0062] In some embodiments, the fatty acid is dodecanoic acid (also known as coconut fatty acid).

[0080]

[0063] In some embodiments, the amount of the fatty acid in the surfactant system is selected so as to form a structured surfactant system. In some embodiments, the surfactant system of the present disclosure contains from about 1 to about 15 wt%, from about 1 to about 10 wt%, from about 1 to about 7 wt%, from about 1 to about 6 wt%, from about 1 to 5 wt%, or from 1 about to 4 wt% of fatty acid, based on the total weight the surfactant system. In some embodiments, the surfactant system of the present disclosure contains from about 8 wt% of fatty acid based on the total weight the surfactant system.

[0081]

[0064] In some embodiments, the weight ratio of LAS to fatty acid in the aqueous surfactant system is from about 6:1 to about 1:1, from about 5:1 to about 1:1, from about 4:1 to about 1: 1, or from about 3:1 to about 1:1. In one embodiment, the weight ratio of LAS to fatty acid is about 3:1. 2024PF00133

[0082] 11

[0083]

[0065] In some embodiments, the weight ratio of LAS : AES : AE in the surfactant system is about 1-1.2 : 1.6-2 : 1.4-1.8. In one embodiment, the weight ratio of LAS : AES : AE is about 1 : 1.6 : 1.4.

[0084]

[0066] In one embodiment, the surfactant system of the present disclosure contains about 2 to 6 wt% LAS, about 2 to 9 wt% AES, about 2 to 8 wt% of AE, and about 0.5 to 3 wt% fatty acid based on the total weight of the surfactant system.

[0085]

[0067] In one embodiment, the surfactant system of the present disclosure contains about 3.7 wt% LAS, about 6 wt% AES, about 5.3 wt% of AE, and about 1.4 wt% fatty acid based on the total weight of the surfactant system.

[0086]

[0068] Optical Brighteners and Colorants

[0087]

[0069] Advantageously, the bleach complex does not deactivate aesthetic colorants or optical brighteners. Accordingly, the liquid bleach composition may comprise one or more aesthetic colorants and / or optical colorants. Suitable aesthetic colorants include dyes, dyeclay conjugates, pigments, and Liquitint® polymeric colorants (Milliken & Company, Spartanburg, S.C., USA). In one aspect, suitable dyes and pigments include small molecule dyes and polymeric dyes. The aesthetic colorant may include at least one chromophore constituent selected from the group consisting of acridines, anthraquinones, azines, azos, benzodifuranes, benzodifuranones, carotenoids, coumarins, cyanines, diazahemicyanines, diphenylmethanes, formazans, hemicyanines, indigoids, methanes, methines, naphthalimides, naphthoquinones, nitros, nitrosos, oxazines, phenothiazine, phthalocyanines (such as copper phthalocyanines), pyrazoles, pyrazolones, quinolones, stilbenes, styryls, triarylmethanes (such as triphenylmethanes), xanthenes, and mixtures thereof.

[0088]

[0070] Aesthetic colorants include Liquitint® Blue AH, Liquitint® Blue BB, Liquitint® Blue 275, Liquitint® Blue 297, Liquitint® Blue BB, Cyan 15, Liquitint® Green 101, Liquitint® Orange 272, Liquitint® Orange 255, Liquitint® Pink AM, Liquitint® Pink AMC, Liquitint® Pink ST, Liquitint® Violet 129, Liquitint® Violet LS, Liquitint® Violet 291, Liquitint® Yellow FT, Liquitint® Blue Buf, Liquitint® Pink AM, Liquitint® Pink PV, Acid Blue 80, Acid Blue 182, Acid Red 33, Acid Red 52, Acid Violet 48, Acid Violet 126, Acid Blue 9, Acid Blue 1, and mixtures thereof.

[0089]

[0071] Optical brighteners can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring 2024PF00133

[0090] 12 heterocycles, and other miscellaneous agents. Suitable stilbenes include for example TINOPAL® AMS; distyrylbiphenyl derivatives such as TINOPAL® CBS-X, stilbene / naphthotriazole blends (e.g., TINOPAL® RA-16, available from Ciba Geigy); oxazole derivatives, or coumarin brighteners. Brighteners include Disodium 4,4' -bis {[4- anilino-6-[bis(2-hydroxyethyl)amino-s-triazin-2-yl]-amino}-2,2' -stilbenedisulfonate, 4,4' -bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2' -stilbenedisulfonate, Disodium 4,4" -bis[(4,6-di-anilino-s-triazin-2-yl)-amino]-2,2' -stilbenedisulfonate and disodium 4,4' -bis-(2-sulfostyryl)biphenyl.

[0091]

[0072] Other Components

[0092]

[0073] The liquid detergent composition of the present disclosure may further contain a buffer. A wide range of buffers can be used herein. For example, the buffer may comprise a citrate or a formate, and optionally an amine (e.g., triethanolamine). In some embodiments, the aqueous composition contains from about 1 to about 15 wt%, preferably from about 5 to about 10 wt% of the buffer, based on the total weight of the aqueous composition.

[0093]

[0074] A water binding agent can used in an aqueous composition to reduce its water activity. Examples of the water binding agent include, but are not limited to, a salt, a saccharide, an organic solvent, and a mixture thereof. In some embodiments, the water binding agent is a salt and the composition contains no saccharide or organic solvent. In other embodiments, the water binding agent is saccharide or an organic solvent only.

[0094]

[0075] A salt comprises a cation and an anion, and can be an inorganic salt or an organic salt. The cation can be inorganic or organic, such as sodium, calcium, potassium, magnesium, quaternary ammonium, pyridinium, tris(2-hydroxyethyl)methyl ammonium, or a mixture thereof. The anion can be inorganic or organic, such as a halide, phosphate, sulphate, formate, acetate, citrate, maleate, succinate, methylsulfate, and a mixture thereof.

[0095]

[0076] In some embodiments, the salt can be an ionic liquid, which includes but is not limited to, tris(2-hydroxyethyl)methyl ammonium methylsulfate, trioctyl methyl amine dioctyl sulfosuccinate, triisooctyl methyl amine C12-C13 methyl branched dodecyl sulfate, tetraoctyl amine dodecyl sulfate, N-dodecyl-N,N-dimethyl-N-hydroxyammonium dodecyleethoxysulfate, N-(dodecylamindopropyl)-N, N-dimethyl-N- carboxymethylammonium, and N-decyl-N,N-dimethyl-N-hydroxyammonium 2,4,8 -trimethylnonyl-6-(tri-ethoxysulfate). 2024PF00133

[0096] 13

[0097]

[0077] In some embodiments, the salt is sodium chloride, sodium citrate, or sodium formate. In one embodiment, the salt is sodium citrate. Sodium citrate can be trisodium citrate.

[0098]

[0078] In some embodiments, the aqueous composition of the present disclosure is substantially free of a salt.

[0099]

[0079] In some embodiments, the water binding agent is an organic solvent. Examples of the organic solvent include, but are not limited to, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, 2-methyl-l,3- propanediol, diethylene glycol, triethylene glycol, glycerol, 1,3-propanediol, triacetin, ethyl acetate, benzyl alcohol, and a mixture thereof.

[0100]

[0080] In some embodiments, the aqueous composition of the present disclosure is substantially free of an organic solvent.

[0101]

[0081] In some embodiments, the water binding agent is a saccharide. Examples of the saccharide include, but are not limited to, fructose, glucose, sucrose, xylitol, sorbitol, mannitol, erythritol, dulcitol, inositol, adonitol, tagatose, trehalose, galactose, rhamnose, cyclodextrin, maltodextrin, dextran, sucrose, glucose, ribulose, fructose, threose, arabinose, xylose, lyxose, allose, altrose, mannose, idose, lactose, maltose, invert sugar, isotrehalose, neotrehalose, palatinose or isomaltulose, erythrose, deoxyribose, gulose, idose, talose, erythrulose, xylulose, psicose, turanose, cellobiose, amylopectin, glucosamine, mannosamine, fucose, glucuronic acid, gluconic acid, glucono-lactone, abequose, galactosamine, beet oligosaccharides, isomalto-oligosaccharides, xylo-oligosaccharides, gentio-oligoscaccharides, sorbose, nigero-oligosaccharides, palatinose oligosaccharides, fucose, fractooligosaccharides, maltotetraol, maltotriol, malto-oligosaccharides, lactulose, melibiose, raffinose, rhamnose, ribose, high fructose com / starch syrup, coupling sugars, soybean oligosaccharides, or glucose syrup, and a mixture thereof.

[0102]

[0082] In some embodiments, the aqueous composition of the present disclosure is substantially free of a saccharide.

[0103]

[0083] In some embodiments, the water binding agent is present in an amount of from about 0.01% to about 50% by weight, from about 0.5% to about 25% by weight, from about 0.5% to about 20%, from about 2% to about 10%, from about 0.5% to about 5%, or from 5% to about 10%, based on the weight of the aqueous composition. In some embodiments, the water binding agent is present in an amount of from about 1% to about 50%, from about 1% to about 40%, from about 1% to about 30%, from about 1% to about 2024PF00133

[0104] 14

[0105] 20%, from about 1% to about 15%, from about 1% to about 10%, from about 1% to about 5%, from about 5% to about 50%, from about 5% to about 40%, from about 5% to about 30%, from about 5% to about 20%, from about 5% to about 15%, from about 5% to about 10%, from about 10% to about 50%, from about 10% to about 40%, from about 10% to about 30%, from about 10% to about 20%, or from about 10% to about 15% by weight.

[0106]

[0084] The liquid detergent of the present disclosure may contain a surfactant stabilizer. Examples of the surfactant stabilizer include, but are not limited to, polysorbate, quillaja extract, octenyl succinic anhydride (OSA) modified starch, gum acacia, modified gum acacia, and a mixture thereof.

[0107]

[0085] The liquid detergent of the present disclosure may also contain other components commonly included in a detergent composition, for example, a builder and a beneficial agent including, but not limited to, an anti-redeposition agent, an enzyme, a fragrance, a dispersing agent, a defoamer, a color component, a bleaching catalyst, a bleaching agent, a bleach activator, a whitening agent, a brightening agent, an anticorrosion agent, a deodorizing agent, a color / texture rejuvenating agent, a soil releasing polymer, a preservative, and a bittering agent, or a combination thereof.

[0108]

[0086] Suitable builders include organic or inorganic detergency builders. Examples of water-soluble inorganic builders that can be used, either alone or in combination with themselves or with organic alkaline sequestrant builder salts, are glycine, alkyl and alkenyl succinates, alkali metal carbonates, alkali metal bicarbonates, phosphates, polyphosphates and silicates. Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium pyrophosphate and potassium pyrophosphate. Examples of organic builder salts that can be used alone, or in combination with each other, or with the preceding inorganic alkaline builder salts, are alkali metal polycarboxylates, water-soluble citrates such as sodium and potassium citrate, sodium and potassium tartrate, sodium and potassium ethylenediaminetetracetate, sodium and potassium N(2-hydroxyethyl)-nitrilo triacetates, sodium and potassium N-(2-hydroxyethyl)-nitrilo diacetates, sodium and potassium oxy disuccinates, and sodium and potassium tartrate mono- and di-succinates, such as those described in U.S. Pat. No. 4,663,071.

[0109]

[0087] Fragrance (perfume) refer to and include any fragrant substance or mixture of substances including natural (obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants), artificial (mixture of natural oils or oil constituents) and 2024PF00133

[0110] 15 synthetically produced odoriferous substances. The fragrance can comprise an ester, an ether, an aldehyde, a ketone, an alcohol, a hydrocarbon, or a mixture thereof.

[0111]

[0088] Typically, perfumes are complex mixtures of blends of various organic compounds such as alcohols, aldehydes, ethers, aromatic compounds and varying amounts of essential oils (e.g., terpenes). The essential oils themselves are volatile odoriferous compounds and also serve to dissolve the other components of the perfume.

[0112]

[0089] In some embodiments, the fragrance component is in the form of free fragrance. In some embodiments, at least some of the fragrance can be encapsulated in, for example, water-insoluble shell, microcapsule, nanocapsule or any combination thereof. The microcapsules can be water-soluble or water-insoluble.

[0113]

[0090] The fragrance (perfume) can have, for example, a musky scent, a putrid scent, a pungent scent, a camphoraceous scent, an ethereal scent, a floral scent, a peppermint scent, or any combination thereof. The fragrance comprises methyl formate, methyl acetate, methyl butyrate, ethyl butyrate, isoamyl acetate, pentyl butyrate, pentyl pentanoate, octyl acetate, myrcene, geraniol, nerol, citral, citronellol, linalool, nerolidol, limonene, camphor, terpineol, alpha-ionone, thujone, benzaldehyde, eugenol, cinnamaldehyde, ethyl maltol, vanillin, anisole, anethole, estragole, thymol, indole, pyridine, furaneol, 1 -hexanol, cis-3- hexenal, furfural, hexyl cinnamaldehyde, fructone, hexyl acetate, ethyl methyl phenyl glycidate, dihydrojasmone, oct-l-en-3-one, 2-acetyl-l-pyrroline, 6-acetyl-2, 3,4,5- tetrahydropyridine, gamma-decalactone, gamma-nonalactone, delta-octal one, jasmine lactone, massoia lactone, wine lactone, sotolon, grapefruit mercaptan, methanthiol, methyl phosphine, dimethyl phosphine, nerolin, 2,4,6-trichloroanisole, or any combination thereof.

[0114]

[0091] Suitable enzymes include those known in the art, such as amylolytic, proteolytic, cellulolytic or lipolytic type, and those listed in U.S. Pat. No. 5,958,864. One preferred protease, sold under the trade name SAVINASE® by Novo Nordisk Industries A / S, is a subtillase from Bacillus lentus. Other suitable enzymes include proteases, amylases, lipases and cellulases, such as ALCALASE® (bacterial protease), EVERLASE® (protein- engineered variant of SAVINASE®), ESPERASE® (bacterial protease), LIPOLASE® (fungal lipase), LIPOLASE ULTRA (Protein-engineered variant of LIPOLASE), LIPOPRIME® (protein-engineered variant of LIPOLASE), TERMAMYL® (bacterial amylase), BAN (Bacterial Amylase Novo), CELLUZYME® (fungal enzyme), and CAREZYME® (monocomponent cellulase), sold by Novo Nordisk Industries A / S. Also suitable for use in the present disclosure are blends of two or more of these enzymes, for 2024PF00133

[0115] 16 example a protease / lipase blend, a protease / amylase blend, a protease / amylase / lipase blend, and the like.

[0116]

[0092] All dyes (colorants) suitable for use in detergent composition can be used in herein. A variety of dye colors can be used, such as blue, yellow, green, orange, purple, clear, etc. Suitable dyes include, but are not limited to chromophore types, e.g., azo, anthraquinone, triarylmethane, methine quinophthalone, azine, oxazine thiazine, which may be of any desired color, hue or shade. Suitable dyes can be obtained from any major supplier such as Clariant, Ciba Speciality Chemicals, Dystar, Avecia or Bayer. In some embodiments, the colorant is Liquitint® Blue HP (available from Milliken Chemical), which can be added in the form of a 1% aqueous dye solution, i.e., 1% active dye+99% water.

[0117]

[0093] Suitable biocidal agents include an anti-microbial, a germicide, or a fungicide. For example, a biocidal agent includes triclosan (5-chloro-2-(2,4-dichloro-phenoxy) phenol)), and the like.

[0118]

[0094] Suitable foam stabilizing agents include a polyalkoxylated alkanolamide, amide, amine oxide, betaine, sultaine, Cs-Cis fatty alcohols, and those disclosed in U.S. Pat. No. 5,616,781. An auxiliary foam stabilizing surfactant, such as a fatty acid amide surfactant, may also be included in the aqueous composition disclosed herein. Suitable fatty acid amides include C8-C20 alkanol amides, monoethanolamides, diethanolamides, or isopropanolamides.

[0119]

[0095] Suitable anti-redeposition agents are typically polycarboxylate materials. Polycarboxylate materials, which can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, are admixed in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40 wt% of the polymer.

[0120]

[0096] Particularly suitable polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerised acrylic acid. The average molecular weight of such polymers in the acid form ranges from about 2,000 to 10,000, from about 4,000 to 7,000, or from about 4,000 to 2024PF00133

[0121] 17

[0122] 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials (e.g., those described in U.S. Pat. No. 3,308,067). In one embodiment, the poly carboxylate is sodium polyacrylate.

[0123]

[0097] Acrylic / maleic-based copolymers may also be used as a component of the antiredeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form ranges from about 2,000 to 100,000, from about 5,000 to 75,000, or from about 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, or from about 10:1 to 2:1. Water-soluble salts of such acrylic acid / maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers are known materials (e.g., those described in EP 193360). Other useful polymers include maleic / acrylic / vinyl alcohol terpolymers (e.g., a terpolymer containing 45 / 43 / 10 of acrylic / maleic / vinyl alcohol as described in EP 193360).

[0124]

[0098] Polyethylene glycol can act as a clay soil removal-anti-redeposition agent. Molecular weight of suitable polyethylene glycol can range from about 1,000 to about 50,000, or about 3,000 to about 10,000. Polyaspartate and poly glutamate dispersing agents may also be used herein.

[0125]

[0099] Any polymeric soil release agent known to those skilled in the art can optionally be employed herein as well. Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.

[0126]

[0100] Exemplary anti-redeposition agents include an acrylic polymer selected from SOKALAN PA 30, SOKALAN PA 20, SOKALAN PA 15, and SOKALAN CP 10 (BASF GmbH, Germany) and ACUSOL 445G and ACUSOL 445N (The Dow Chemical Company, Midland, Michigan); an acrylic acid / maleic acid copolymer selected from ACUSOL 460N and ACUSOL 505N (The Dow Chemical Company) and SOKALAN CP 5, SOKALAN CP 45, and SOKALAN CP 7 (BASF GmbH, Germany); and an anionic polymer selected from ALCOSPERSE 725 and ALCOSPERSE 747 (Alco Chemical, 2024PF00133

[0127] 18

[0128] Chattanooga, TN) and ACUSOL 480N (The Dow Chemical Company, Midland, Michigan); and DEQUEST SPE 1202 (Italmatch Chemicals, Genova, Italy); and an ethoxylated polyethylene imine SOKALAN HP 20 (BASF, Germany).

[0129]

[0101] Suitable soil-releasing polymers include, but are not limited to, TEXCARE SRN - a nonionic polyester of polypropylene terephthalate (Clariant); REPEL-O-TEX SRP - a polyethylene glycol polyester (Solvay); end-capped and non-end-capped sulfonated and unsulfonated PET / POET polymers of the type as disclosed in WO 2010 / 069957 and WO 1995 / 032997; polyethylene glycol / polyvinyl alcohol graft copolymers such as SOKALAN HP 22 (BASF, Germany); and anionic hydrophobic polysaccharides of the type as disclosed in U.S. Patent No. 6,764,992. Each of the patent references is incorporated herein by reference in its entirety.

[0130]

[0102] Any suitable process can be used to make the aqueous compositions of the present disclosure.

[0131]

[0103] Unit Dose Composition

[0132]

[0104] In one aspect, the present disclosure provides a unit dose composition comprising, a water-soluble container and an aqueous composition of the present disclosure. The unit dose may be a pouch that comprises a water-soluble or water- dispersible film which fully encloses the aqueous composition in at least one compartment. The water-soluble container (e.g., pouch) of the present disclosure may be in any desirable shape and size, e.g., square, rectangular, oval, elliptoid, superelliptical, or circular shape. In an embodiment, the pouch is transparent and allows a colorant and / or optical brightener formulated together with the bleach alternative complex to show through the film.

[0133]

[0105] The water-soluble container of the present disclosure is made from a water- soluble or water-dispersible material which dissolves, ruptures, disperses, or disintegrates upon contact with water, releasing thereby the composition or cleaning system contained within the container. In preferred embodiments, the water soluble single-compartment container, which may be in the form of a pouch, is formed from a water soluble polymer. Non-limiting examples of suitable water soluble polymers include polyvinyl alcohol, cellulose ethers, polyethylene oxide, starch, polyvinylpyrrolidone, polyacrylamide, polyacrylonitrile, polyvinyl methyl ether-maleic anhydride, polymaleic anhydride, styrene maleic anhydride, hydroxyethylcellulose, methylcellulose, polyethylene glycols, carboxymethylcellulose, polyacrylic acid salts, alginates, acrylamide copolymers, guar gum, casein, ethylene-maleic anhydride resins, polyethyleneimine, ethyl 2024PF00133

[0134] 19 hydroxyethylcellulose, ethyl methylcellulose, hydroxyethyl methylcellulose, and mixtures thereof.

[0135]

[0106] In some embodiments, the water-soluble or water-dispersible film material can be polyvinyl alcohol (PVOH), polyvinyl acetate (PVA), film forming cellulosic polymer, polyacrylic acid, polyacrylamide, polyanhydride, polysaccharide, or a mixture thereof. In some embodiments, the water-soluble or water-dispersible film material is polyvinyl alcohol (PVOH) or polyvinyl acetate (PVA).

[0136]

[0107] In one embodiment, the water soluble container is made from a lower molecular weight water-soluble polyvinyl alcohol (PVOH) film-forming resin.

[0137]

[0108] Suitable PVOH resins are sold under trade name MONOSOL® (e.g., Monosol film M8630, available from MonoSol LLC, Merrillville, Indiana). The preferred grade is MONOSOL® film having a weight average molecular weight range of about 55,000 to 65,000 and a number average molecular weight range of about 27,000 to 33,000. In some embodiments, the film material will have a thickness of approximately 3 mil or 75 micrometers. Other suitable PVOH film forming resins include those sold under trade name Solublon®, available from Aicello Corporation (e.g., Solublon® PT75, Aiichi, Japan; North American subsidiary in North Vancouver, BC, Canada).

[0138]

[0109] In some embodiments, the water-soluble container may further contain a crosslinking agent, e.g., a cross-linking agent selected from the group consisting of formaldehyde, polyesters, epoxides, isocyanates, vinyl esters, urethanes, polyimides, acrylics with hydroxyl, carboxylic, isocyanate or activated ester groups, bis(methacryloxypropyl)tetramethylsiloxane (styrenes, methylmetacrylates), n-diazopyruvates, phenylboronic acids, cis-platin, divinylbenzene (styrenes, double bonds), polyamides, dialdehydes, triallyl cyanurates, N-(2-ethanesulfonylethyl)pyridinium halides, tetraalkyltitanates, titanates, borates, zireonates, or mixtures thereof. In one embodiment, the cross-linking agent is boric acid or sodium borate.

[0139] [HO] In some embodiments, the water soluble container can have a protective layer between the film polymer and the composition in the container. In some embodiments, the protective layer may comprise polytetrafluoroethylene (PTFE).

[0140] [Hl] In some embodiments, the water-soluble or water-dispersible film material is between about 50 to about 120 microns thick, preferably about 60 to about 100 microns. In some embodiments, the water-soluble or water-dispersible film material has a thickness of from about 50 to about 120 microns, from about 50 to about 100 microns, from about 50 to 2024PF00133

[0141] 20 about 80 microns, from about 50 to about 60 microns, from about 60 to about 120 microns, from about 60 to about 100 microns, from about 60 to about 80 microns, or from about 60 to about 70 microns.

[0142]

[0112] The unit dose may optionally comprise additional compartments, which may comprise an additional composition. The additional composition may be liquid, solid, or mixtures thereof. Alternatively, any additional solid components may be suspended in a liquid-filled compartment. Each compartment may have the same or different compositions. In a further embodiment, the pouch is multicolored with multiple chambers containing the liquid detergent composition that include the bleach alternative complex.

[0143]

[0113] The water-soluble container (e.g., pouch) of the present disclosure may be prepared in any suitable way, such as via molding, casting, extruding or blowing, and is then filled using an automated filling process. Examples of processes for producing and filling water-soluble containers, suitable for use in accordance with the present disclosure, are described in U.S. Pat. Nos. 3,218,776; 3,453,779; 4,776,455; 5,699,653; 5,722,217; 6,037,319; 6,727,215; 6,878,679; 7,259,134; 7,282,472; 7,304,025; 7,329,441; 7,439,215; 7,464,519; and 7,595,290, each of which is incorporated herein by reference in its entirety.

[0144]

[0114] Use

[0145]

[0115] The liquid detergent composition or unit dose composition of the present disclosure can be added to a wash liquor to which laundry is present, or to which laundry is added. It may be used in combination with other laundry detergent compositions such as fabric softeners or stain removers. It may also be used in an automatic washing machine operation and added directly to the drum or to the dispenser drawer.

[0146]

[0116] In summary, the following subjects, inter aha, are provided by this application:

[0147] 1. A liquid laundry detergent composition comprising:

[0148] 1 wt. % to 75 wt. % of an anionic surfactant, and

[0149] 0.05 to 5.0% of a bleach alternative complex comprising a polyethyleneimine and a poly carboxylic acid.

[0150] 2. A use of a bleach alternative complex in a liquid laundry detergent comprising a polyethyleneimine and a poly carboxylate, wherein the liquid laundry detergent comprises 1 wt. % to 75 wt. % of an anionic surfactant. 2024PF00133

[0151] 21

[0152] 3. A method of pretreating or treating a soiled fabric comprising contacting a soiled fabric with a detergent composition comprising:

[0153] 1 wt. % to 75 wt. % of an anionic surfactant, and

[0154] 0.05 to 5.0% of a bleach alternative complex comprising a polyethyleneimine and a poly carboxylic acid.

[0155] 4. The detergent composition of point 1, or the use according to point 2, or the method according to point 3, wherein the poly carboxy late acid is derived from acrylic acid, maleic acid, fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methyl enemaionic acid, and combinations thereof.

[0156] 5. The detergent composition, the use or the method according to any of the proceeding points, wherein the poly carboxylate acid is derived from acrylic acid and has a molecular weight between 2000 and 20,000 g / mol.

[0157] 6. The detergent composition, the use or the method according to any of the proceeding points, wherein the detergent composition further comprises an optical brightener and / or an aesthetic colorant.

[0158] 7. The detergent composition, the use or the method according to any of the proceeding points, wherein the anionic surfactant comprises at least 5% by weight of a linear alkylbenzene sulfonate (LAS) and an alkyl-ether sulfate (AES) surfactant

[0159] 8. The detergent composition, the use or the method according to any of the proceeding points, wherein the polyethyleneimine and the poly carboxylic acid are in weight ratio of 5 : 1 to 2: 1.

[0160] 8. The detergent composition, the use or the method according to any of the proceeding points, wherein the liquid detergent is substantially free of chlorine bleaching agents.

[0161] 9. The detergent composition, the use or the method according to any of the proceeding points, wherein the anionic surfactant comprises:

[0162] 1 to 15 wt.% of linear alkylbenzene sulfate (LAS) of the liquid detergent composition; and

[0163] 2 to 15 wt.% of alcohol ether sulfate (AES) of the liquid detergent composition; and wherein the liquid detergent composition further comprises

[0164] 2 to 15wt. % of alcohol ethoxylate (AE) and 2024PF00133

[0165] 22

[0166] 0.5 to 5 wt% of faty alcohol.

[0167] 10. The detergent composition, the use or the method according to point 9, wherein LAS : AES : AE is about 1-1.2 : 1.6-2 : 1.4-1.8.

[0168] 11. The detergent composition, the use or the method according to any of the proceeding points, wherein the liquid detergent is 60% to 90% by weight of water.

[0169] 12. A unit dose pouch comprising a water soluble film and the detergent composition of any of the proceeding points.

[0170]

[0117] In some embodiments, the unit dose composition of the present disclosure is substantially free of hypochlorites.

[0171]

[0118] In some embodiments, the aqueous composition of the present disclosure comprises a beneficial composition comprising a color care agent or a softening agent.

[0172]

[0119] The following examples are illustrative and non-limiting, of the device, products and methods of the present invention. Suitable modifications and adaptations of the variety of conditions, formulations and other parameters normally encountered in the field and which are obvious to those skilled in the art in view of this disclosure are within the spirit and scope of the invention.

[0173] Examples

[0174] Example 1: Synergy of Builder Ingredients

[0175]

[0120] By utilizing various combinations of builder ingredients that included cationic PEI against a control formulation that did not contain such ingredients, it was discovered that cationic PEI combined with polyacrylic acid effectively and unexpectedly acted as a bleach alternative complex. Seven samples, shown below, were prepared with a substantially similar chassis as a Control formulation, with differences being different types of builders shown below.

[0176]

[0121] Table 1

[0177] 1Persil Power Gel Liquid Laundry Detergent 2024PF00133

[0178] 23

[0179]

[0122] Formulation 1A and IB contains cationic PEI alone, at 0.5 and 1.0 wt.%, respectively of active material. Formulation 2A and 2B have the combination of cationic PEI and maleic acid / olefin copolymer, with 2A at 0.25 and 0.05 wt.%, and 2B at 0.5 and 0.1 wt.%, respectively. Formulation 2C contains a combination of cationic PEI and polyacrylic acid at 0.5 and 0.5 wt.%, respectively. Total water level of formulations for all samples were about 77%. The pH for all samples were measured to be about 8.4. Viscosity was 1500 mPas at 20°C (Sp.3, Speed.20) for all samples. The density at 20°C was 1.045 g / ml for all samples.

[0180]

[0123] Due to the amount of fabric stains and samples, testing had to be divided into two groups and performed at different time intervals in substantially similar conditions, as described below.

[0181]

[0124] Test 1

[0182]

[0125] In Test 1, the performance of the formulations 1A, IB, 2A and 2B, along with the comparative formulation, were tested on 35 stained fabrics, along with 9 oxidizable stains in a washing machine, of which 17 were directed to bleachable stains. For all tests, the washing machine was set at 30°C, and the dosage was 100g. Categories of stains included stains that are typically removable via bleach, enzymes, and enzymatic and surfactants. Examples of bleach stains include highly colored juice, coffee, tea or ink. Optical

[0183] 2In order to achieve substantially similar viscosities between control and samples, the surfactants had to be slightly adjusted.

[0184] 3Sokalan® HP 20 in liquid form at 25 °C, about 80% dry content as represented in the chart

[0185] 4Sokalan® CP 9, in liquid form at 25°C, about 25% dry content

[0186] 5Sokalan® PA Cl 30 in liquid form at 25°C, about 25% dry content and mean molar mass 8500 g / mol. 2024PF00133

[0187] 24 evaluations were performed and evaluated through a t-test statistical analysis that compared the control to a sample. A rating system was used that evaluated the performance as Superior, Parity or Inferior to the Control formulation as shown in Table 2.

[0188]

[0126] Table 2

[0189]

[0127] Comparing bleachable stains for 1A and IB (Cationic PEI alone) and 2A and 2B (cationic PEI and maleic acid / olefin copolymer), Formulations 2A and 2B performed very well indicating that the combination of cationic PEI and maleic acid / olefin copolymer were providing a bleachable effect. Of the 17 bleachable stains, 5 were rated superior to the comparison formula, 12 were rated parity, and none were rated inferior. However, with cationic PEI alone in 1A and IB, of the 17 bleachable stains, few were rated superior (2 in 1A), most were parity (10 in 1A and 15 in IB), and several showed a surprising inferior performance (5 in 1A) in bleachable stain performance. Further, while Formulations 2A and 2B performed very well for bleachable stains. However, as noted above, the biodegradability profile of maleic acid / olefin copolymer is not ideal for environmental considerations.

[0190]

[0128] Test 2

[0191]

[0129] Test two was performed in a substantially similar manner as Test 1 with the formulations set forth above. Formulation 2B was retested. Test two also involved comparing the performance of the formulations 2C (containing cationic PEI and polyacrylic acid) against the control formation. Formulations 3A and 3B contained only maleic acid / olefin copolymer, at dosages of 0.1 and 0.2 respectively.

[0192]

[0130] Table 3 2024PF00133

[0193] 25

[0194]

[0131] Of all the formulations, 2B and 2C performed the best. For 2C in particular, of the 17 bleachable stains, 7 were rated superior, 10 parity, and none were inferior against the current formulation. Compared to formulations 1A and IB of cationic PEI alone, the combination of both cationic PEI and polyacrylic acid in 2C shows superior results. Likewise, in 2B a combination of PEI and maleic acid also showed strong stain removal results such that of the 17 bleachable stains, 6 were superior and 11 were parity as compared to the control sample.

[0195]

[0132] Accordingly, the experiments above appear to support a conclusion that a polymeric acid is large enough to capture and chelate negative ions in the medium. This in turn allows the nitrogen groups in the positively charged PEI polymer to effectively maintain a high level of protonation of its nitrogens, which in turn allows it to become an oxidizing agent and break double bonds of the chromophores of difficult stains and effectively act as a bleachable complex. 2C is biodegradable.

[0196]

[0133] Formulations 3A and 3B, maleic acid / olefin copolymer alone was added at different dosages of 0.1 and 0.2, without PEI. Compared to 2A and 2B containing both cationic PEI and maleic acid / olefin copolymer, Formulations 3A and 3B showed neither an advantage or disadvantage. Thus, it appears that maleic acid / olefin copolymer alone does not provide a bleach alterative effect.

[0197]

[0134] Test 3 - Greying Effect

[0198]

[0135] Test 3 involved examining greying effects with the formulations. Often times, polymers that are based on a cellulosic backbone accumulate on a fabric, causing greying layer over time. This test evaluates whether the builders are accumulating on the fabrics. Formulations 2 A, 2B and 2C were tested after 20 washes in similar conditions above, and no whitening or greying effects were observed. For example, for 2C containing cationic PEI and polyacrylic acid, 22 white fabrics were washed twenty times and examined with a spectrophotometer. Out of those twenty -two, for 2C, 13 were better at maintaining whiteness verses the control formula, while 9 were less white. For 2B containing cationic PEI and maleic acid / olefin copolymer, 20 were better at maintaining whiteness while 2 were less white. Thus, it appears that this test confirms that the protonated center of the polyacrylic acid or maleic acid / olefin copolymer is pH dependent and the complex does 2024PF00133

[0199] 26 not stick to the fabric, thereby not acting as a redeposition agent and not causing greying over multiple wash cycles.

[0200]

[0136] Test 4 - Tensile strength

[0201]

[0137] Test 4 involved evaluating whether a benefit to whitening occurs at the expense of loss of tensile strength on cotton fabric. Fabrics were washed with samples 2A, 2B and 2C at a temperature of 30°C with 20 washes and 100 g / dose and pulled between two clamps until the fabric tore. Compared to the control, the samples all were found to be within 5% tensile strength measurement on a non-washed fabric sample, thus leading to a conclusion of no significant statistic difference. In other words, it reasonable to conclude from this that there is no buildup of charge or pH, resulting in a corrosiveness of the textile and whitening effect and a loss of tensile strength. From this experiment it further confirms the theory that the protonation of cationic PEI is attacking the chromophores, breaking a double or triple bond of the chromophore, and then neutralizing the charge.

[0202]

[0138] The breadth and scope of the present invention should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents.

[0203]

[0139] All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. In addition, section headings, the materials, methods, and examples are illustrative only and not intended to be limiting.

Claims

2024PF0013327WHAT IS CLAIMED IS:

1. A liquid laundry detergent composition comprising:1 wt. % to 75 wt. % of an anionic surfactant, and 0.05 to 5.0% of a bleach alternative complex comprising a polyethyleneimine and a poly carboxylic acid.

2. A use of a bleach alternative complex in a liquid laundry detergent comprising a polyethyleneimine and a poly carboxylate, wherein the liquid laundry detergent comprises 1 wt. % to 75 wt. % of an anionic surfactant.

3. A method of pretreating or treating a soiled fabric comprising contacting a soiled fabric with a detergent composition comprising:1 wt. % to 75 wt. % of an anionic surfactant, and 0.05 to 5.0% of a bleach alternative complex comprising a polyethyleneimine and a poly carboxylic acid.

4. The detergent composition of claim 1, or the use according to claim 2, or the method according to claim 3, wherein the poly carboxylate acid is derived from acrylic acid, maleic acid, fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and combinations thereof.

5. The detergent composition, the use or the method according to any of the preceding claims, wherein the poly carboxylate acid is derived from acrylic acid and has a molecular weight between 2000 and 20,000 g / mol.

6. The detergent composition, the use or the method according to any of the preceding claims, wherein the detergent composition further comprises an optical brightener and / or an aesthetic colorant.2024PF00133287. The detergent composition, the use or the method according to any of the preceding claims, wherein the anionic surfactant comprises at least 5% by weight of a linear alkylbenzene sulfonate (LAS) and an alkyl-ether sulfate (AES) surfactant8. The detergent composition, the use or the method according to any of the proceeding claims, wherein the polyethyleneimine and the poly carboxylic acid are in weight ratio of 5 : 1 to 2: 1.

9. The detergent composition, the use or the method according to any of the preceding claims, wherein the liquid detergent is substantially free of chlorine bleaching agents.

10. The detergent composition, the use or the method according to any of the preceding claims, wherein the anionic surfactant comprises:1 to 15 wt.% of linear alkylbenzene sulfate (LAS) of the liquid detergent composition; and2 to 15 wt.% of alcohol ether sulfate (AES) of the liquid detergent composition; and wherein the liquid detergent composition further comprises2 to 15wt. % of alcohol ethoxylate (AE) and 0.5 to 5 wt% of fatty alcohol.

11. The detergent composition, the use or the method according to Claim 10, wherein LAS : AES : AE is about 1-1.2 : 1.6-2 : 1.4-1.8.

12. The detergent composition, the use or the method according to any of the preceding claims, wherein the liquid detergent is 60% to 90% by weight of water.

13. A unit dose pouch comprising a water soluble film and the detergent composition of any of the preceding claims.

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