Aqueous laundry detergent composition

Abstract

There is provided an aqueous laundry detergent composition, the aqueous laundry detergent composition comprising: water; a cleaning surfactant; wherein the cleaning surfactant comprises a blend of a nonionic surfactant and an anionic surfactant; wherein the anionic surfactant comprises an alcohol ethoxysulfate surfactant of formula I wherein R1 and R2 are each independently a C1-16 alkyl group; wherein the sum of carbon atoms in R1 and R2 is from 7 to 17; wherein M + is a negatively charged cation that balances the-SO3-anion of formula I; and wherein n is 1 in 95 mol% to 100 mol% of the alcohol ethoxysulfate surfactant of formula (I). # imgabs0 #

Description

[0001] The present invention relates to an aqueous laundry detergent composition. Specifically, the present invention relates to an aqueous laundry detergent composition, the aqueous laundry detergent composition comprising: water; a cleaning surfactant; wherein the cleaning surfactant comprises a blend of a nonionic surfactant and an anionic surfactant; wherein the anionic surfactant comprises an alcohol ethoxysulfate surfactant of formula I

[0002]

[0003] Where R 1 and R 2 Each is independently C 1-16 Alkyl group; wherein R 1 and R 2 The total number of carbon atoms in the + It is -SO3 of balanced formula I - anionic negatively charged cation; and wherein n is 1 in 95 mol % to 100 mol % of the alcohol ethoxysulfate surfactant of formula I.

[0004] Aqueous laundry detergent formulations typically include alkyl ethoxy sulfate anionic surfactants (e.g., alcohol ethoxy sulfate surfactants). However, such surfactants are associated with undesirable 1,4 dioxane levels. Regulatory agencies have increasingly stringent restrictions on the amount of 1,4 dioxane that may be present in consumer products. For example, New York State has banned all but trace amounts of 1,4 dioxane in cleaning products. Typically, the content of 1,4 dioxane in consumer products must be less than 10 parts per million ("ppm") by weight to comply with regulations. One reason for the unintentional inclusion of 1,4 dioxane in consumer products may be the inclusion of alkyl ethoxy sulfate anionic surfactants.

[0005] It is believed that the inclusion of 1,4 dioxane in conventional AES surfactants occurs at multiple time points. It is believed that the first time point for the generation of 1,4 dioxane in conventional AES surfactants occurs during the sulfation process of alcohol ethoxylates, which is used to prepare alcohol ethoxy sulfates. The alcohol ethoxylate intermediates used to produce conventional alcohol ethoxy sulfate surfactants are prepared by ethoxylation reactions (i.e., the reaction of alcohols with ethylene oxide), which typically result in an alcohol ethoxylate oligomer distribution. It is believed that 1,4 dioxane can be formed under the conditions of the sulfation process during the preparation of conventional AES surfactants. It is believed that the second time point for the generation of 1,4 dioxane associated with conventional AES surfactants occurs during the handling and processing of conventional AES surfactants. The handling and processing of conventional AES surfactants typically involves acidic conditions at ambient or elevated temperatures. Prolonged exposure of conventional AES surfactants and their alcohol ethoxylate precursors to acidic environments may result in the formation of 1,4 dioxane. Furthermore, exposure to high temperatures (eg, up to 280° C.) during processing, storage, and / or handling may cause conventional AES surfactants to decompose, resulting in the formation of dioxanes.

[0006] Traditionally, 1,4-dioxane content in conventional AES surfactants and products incorporating such surfactants has been addressed through the use of stripping techniques. For example, when 1,4-dioxane concentrations are above a target threshold, a stripping process is used to remove excess 1,4-dioxane from conventional AES surfactants or products incorporating such surfactants. Stripping processes are not only expensive and time-consuming, but also do not guarantee compliance with increasingly stringent regulatory requirements. Furthermore, since 1,4-dioxane may be formed over time due to the way conventional AES surfactants or products are handled and further processed, any stripping techniques previously employed may be ineffective due to the formation of new 1,4-dioxane. Therefore, it is a daunting challenge to ensure that products containing AES surfactants comply with relevant regulations when sold to the end consumer.

[0007] Thus, there remains a need for aqueous laundry detergent compositions having anionic alcohol ethoxysulfate surfactants that resist the formation of 1,4-dioxane both during the sulfation process to form the surfactant and subsequently when the alcohol ethoxysulfate surfactant is exposed to elevated temperatures up to 280°C.

[0008] The present invention provides an aqueous laundry detergent composition, which comprises: water; a cleaning surfactant; wherein the cleaning surfactant comprises a blend of a nonionic surfactant and an anionic surfactant; wherein the anionic surfactant comprises an alcohol ethoxysulfate surfactant of formula I

[0009]

[0010] Where R 1 and R 2 Each independently is C 1-16 Alkyl group; wherein R 1 and R 2 The total number of carbon atoms in the + It is -SO3 of balanced formula I - anionic negatively charged cation; and wherein n is 1 in 95 mol % to 100 mol % of the alcohol ethoxysulfate surfactant of formula I.

[0011] The present invention provides an aqueous laundry detergent composition, which comprises: water; a cleaning surfactant; wherein the cleaning surfactant comprises a blend of a nonionic surfactant and an anionic surfactant; wherein the anionic surfactant comprises an alcohol ethoxysulfate surfactant of formula I; wherein R 1 and R 2 Each independently is C 1-16 Alkyl group; wherein R 1 and R 2 The total number of carbon atoms in the + It is -SO3 of balanced formula I - anionic negatively charged cation; wherein n is 1 in 95 mol % to 100 mol % of the alcohol ethoxy sulfate surfactant of formula I; and wherein the alcohol ethoxy sulfate surfactant of formula I contains <9 ppm of 1,4-dioxane.

[0012] The present invention provides an aqueous laundry detergent composition, which comprises: water; a cleaning surfactant; wherein the cleaning surfactant comprises a blend of a nonionic surfactant and an anionic surfactant; wherein the anionic surfactant comprises an alcohol ethoxysulfate surfactant of formula I; wherein R 1 and R 2 Each independently is C 1-16 Alkyl group; wherein R 1 and R 2 The total number of carbon atoms in the + It is -SO3 of balanced formula I - anionic negatively charged cation; wherein n is 1 in 95 mol % to 100 mol % of the alcohol ethoxy sulfate surfactant of formula I; wherein the alcohol ethoxy sulfate surfactant of formula I contains <9 ppm of 1,4-dioxane; and wherein the aqueous laundry detergent composition contains <1 wt % of the alcohol sulfate surfactant of formula II, based on the solid weight of the aqueous laundry detergent composition

[0013]

[0014] Where R 3 and R 4 Each is independently C 1-16 Alkyl group; wherein R 3 and R 4 The total number of carbon atoms in the + It is -SO3 in Equation II - Anions have a negative charge on cations.

[0015] The present invention provides a method for laundering a soiled fabric article, the method comprising: providing a soiled fabric article; providing a laundry detergent composition according to the present invention; providing wash water; and applying the wash water and the laundry detergent composition to the soiled fabric article to provide a cleaned fabric article. DETAILED DESCRIPTION

[0016] We surprisingly found that the alcohol ethoxysulfate surfactant of formula I

[0017]

[0018] Where R 1 and R 2 Each is independently C 1-16 Alkyl group; wherein R 1 and R 2 The total number of carbon atoms in the + It is -SO3 in the equilibrium formula I - anionic negatively charged cation; and wherein n is 1 in 95 mol % to 100 mol % of the alcohol ethoxy sulfate surfactant of formula I, the alcohol ethoxy sulfate surfactant resists the formation of 1,4 dioxane both during the sulfation process to form the alcohol ethoxy sulfate surfactant of formula I and subsequently when the alcohol ethoxy sulfate surfactant of formula I is exposed to elevated temperatures up to 280° C. during processing, storage and / or handling.

[0019] We have also surprisingly found alcohol ethoxysulfate surfactants of formula I; wherein R 1 and R 2 Each is independently C 1-16 Alkyl group; wherein R 1 and R 2 The total number of carbon atoms in the + It is -SO3 in the equilibrium formula I -anionic negatively charged cation; and wherein n is 1 in 95 mol % to 100 mol % of the alcohol ethoxy sulfate surfactant of formula I, which provides comparable primary cleaning performance and comparable or even improved anti-redeposition performance when replacing conventional AES surfactants in aqueous laundry detergent formulations.

[0020] Unless otherwise indicated, ratios, percentages, parts, etc., are by weight (eg, "ppm" means parts per million by weight).

[0021] As used herein and in the appended claims with respect to aqueous laundry detergent compositions and the alcohol ethoxysulfate surfactant of Formula I, the term "solids weight" refers to dry weight, ie, excluding any water that may be present.

[0022] Preferably, the aqueous laundry detergent composition of the present invention is a liquid formulation. More preferably, the aqueous laundry detergent composition of the present invention is an aqueous liquid formulation. Most preferably, the aqueous laundry detergent composition of the present invention is an aqueous liquid laundry detergent formulation.

[0023] Preferably, the aqueous laundry detergent composition of the present invention comprises: water (preferably 10 wt % to 99 wt % (more preferably 20 wt % to 94 wt %; still more preferably 30 wt % to 85 wt %; most preferably 40 wt % to 80 wt %) of water, based on the weight of the aqueous laundry detergent composition); a cleaning surfactant (preferably 1 wt % to 90 wt % (more preferably 5 wt % to 75 wt %; still more preferably 10 wt % to 60 wt %; most preferably 15 wt % to 40 wt %) of a cleaning surfactant, based on the weight of the aqueous laundry detergent composition); wherein the cleaning surfactant comprises a blend of a nonionic surfactant and an anionic surfactant; wherein the anionic surfactant comprises an alcohol ethoxysulfate surfactant of formula I

[0024]

[0025] Where R 1 and R 2 Each is independently C 1-16 Alkyl group; (preferably, C 1-15 More preferably, C 1-14 Alkyl groups; most preferably, straight chain C 1-13 );where R 1 and R 2 The sum of carbon atoms in the alkylene oxide is 7 to 17 (preferably, 10 to 16; more preferably, 11 to 15; most preferably, 12 to 14) (preferably, wherein R 1 and R 2is a straight chain alkyl group); wherein M + It is -SO3 in the equilibrium formula I - The negatively charged cation of the anion (preferably, wherein M + is a cation selected from the group consisting of nitrogen-containing cations (e.g., ammonium cations), metal cations (e.g., alkali metal cations, alkaline earth metal cations), boron-containing cations, and phosphorus-containing cations; more preferably, ammonium cations, alkali metal cations, and alkaline earth metal cations; still more preferably, ammonium cations, sodium cations, and calcium cations; most preferably, sodium cations); and wherein n is 1 (preferably, as used in 95 mol % to 100 mol % (preferably, 96 mol % to 100 mol %; more preferably, 97 mol % to 100 mol %; most preferably, 97.5 mol % to 100 mol %) of the alcohol ethoxysulfate surfactant of formula I 13 C NMR characterization).

[0026] Preferably, the aqueous laundry detergent composition of the present invention comprises, based on the weight of the aqueous laundry detergent composition, 10% to 99% by weight (preferably, 20% to 94% by weight; more preferably, 30% to 85% by weight; most preferably, 40% to 80% by weight) of water. More preferably, the aqueous laundry detergent composition of the present invention comprises, based on the weight of the aqueous laundry detergent composition, 10% to 99% by weight (preferably, 20% to 94% by weight; more preferably, 30% to 85% by weight; most preferably, 40% to 80% by weight) of water; wherein the water is at least one of distilled water and deionized water. Most preferably, the aqueous laundry detergent composition of the present invention comprises, based on the weight of the aqueous laundry detergent composition, 10% to 99% by weight (preferably, 20% to 94% by weight; more preferably, 30% to 85% by weight; most preferably, 40% to 80% by weight) of water; wherein the water is distilled and deionized.

[0027] Preferably, the aqueous laundry detergent composition of the present invention comprises, based on the weight of the aqueous laundry detergent composition, 1 wt % to 90 wt % (preferably, 5 wt % to 75 wt %; more preferably, 10 wt % to 60 wt %; preferably, 15 wt % to 40 wt %) of a cleansing surfactant; wherein the cleansing surfactant comprises a blend of a nonionic surfactant and an anionic surfactant; wherein the anionic surfactant comprises an alcohol ethoxysulfate surfactant of formula I

[0028]

[0029] Where R 1 and R 2 Each is independently C1-16 Alkyl group; wherein R 1 and R 2 The total number of carbon atoms in the + It is -SO3 of balanced formula I - anionic negatively charged cation; and wherein n is 1 in 95 mol % to 100 mol % of the alcohol ethoxy sulfate surfactant of formula I. More preferably, the aqueous laundry detergent composition of the present invention comprises, based on the weight of the aqueous laundry detergent composition, 1 wt % to 90 wt % (preferably, 5 wt % to 75 wt %; more preferably, 10 wt % to 60 wt %; preferably, 15 wt % to 40 wt %) of a cleansing surfactant; wherein the cleansing surfactant comprises a blend of a nonionic surfactant and an anionic surfactant; wherein the anionic surfactant comprises a mixture of other anionic surfactants and an alcohol ethoxy sulfate surfactant of formula I; wherein R 1 and R 2 Each is independently C 1-16 Alkyl group; wherein R 1 and R 2 The total number of carbon atoms in the + It is -SO3 of balanced formula I - anionic negatively charged cation; and wherein n is 1 in 95 mol % to 100 mol % of the alcohol ethoxysulfate surfactant of formula I.

[0030] Nonionic surfactants include alkoxylates, polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers, hydroxy mixed ethers, fatty acid polyglycol esters and mixtures thereof. Preferred nonionic surfactants include alkoxylates. More preferred nonionic surfactants are according to formula A

[0031]

[0032] wherein w is an average value of 5 to 40 (preferably, 7 to 27; more preferably, 8 to 20; most preferably, 7 to 12); wherein R 11 Selected from the group consisting of: hydrogen and straight or branched C 1-20 Alkyl groups (preferably hydrogen and straight or branched C 1-15 Alkyl group; more preferably, a straight chain C 1-15 alkyl group); wherein R 12 Selected from the group consisting of: straight or branched chain C 1-20 Alkyl groups and straight or branched C 1-4 Hydroxyalkyl groups (preferably linear or branched C 1-15 Alkyl groups and straight or branched C 1-4More preferably, a linear C 1-15 Alkyl groups and straight or branched C 1-3 Hydroxyalkyl groups; most preferably, straight chain C 1-15 alkyl); wherein each R 13 is independently selected from the group consisting of hydrogen, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-butyl group and a 2-methyl-2-butyl group (preferably, hydrogen, a methyl group and an ethyl group; more preferably, hydrogen and a methyl group; most preferably, hydrogen); and with the condition that R 11 and R 12 The total number of carbon atoms in is 5 to 21 (preferably, 6 to 20 carbon atoms; more preferably, 7 to 18 carbon atoms; most preferably, 11 to 15 carbon atoms). Still more preferred nonionic surfactants are according to Formula I; wherein w is an average value of 8 to 16; wherein R 11 Selected from hydrogen and straight chain C 1-15 The group consisting of alkyl groups; wherein R 12 A group consisting of: straight or branched chain C 1-15 Alkyl groups and straight or branched C 1-4 Hydroxyalkyl; wherein R 13 is selected from the group consisting of: hydrogen, a methyl group, and an ethyl group; and provided that R 11 and R 12 The total number of carbon atoms in is 6 to 20. The most preferred nonionic surfactant is according to Formula I; wherein w is an average value of 7 to 12; wherein R 11 Selected from hydrogen and straight chain C 1-15 The group consisting of alkyl groups; wherein R 12 Selected from the group consisting of: straight chain C 1-15 Alkyl groups and straight or branched C 1-3 A hydroxyalkyl group; wherein R 13 is hydrogen; and provided that R 11 and R 12 The total number of carbon atoms in the carbon atoms is 7 to 18.

[0033] Preferably, the aqueous laundry detergent composition of the present invention comprises from 0.01 wt % to 35 wt % (preferably, from 0.1 wt % to 20 wt %; more preferably, from 1 wt % to 15 wt %; most preferably, from 2.5 wt % to 10 wt %) of an alcohol ethoxysulfate surfactant of formula I, based on the weight of the aqueous laundry detergent composition; wherein R 1 and R 2 Each independently is C 1-16 Alkyl groups (preferably C 1-15 More preferably, C 1-14 Alkyl groups; most preferably, straight chain C1-13 );where R 1 and R 2 The sum of carbon atoms in the alkylene oxide is 7 to 17 (preferably, 10 to 16; more preferably, 11 to 15; most preferably, 12 to 14) (preferably, wherein R 1 and R 2 is a straight chain alkyl group); wherein M + It is -SO3 in the equilibrium formula I - The negatively charged cation of the anion (preferably, wherein M + is a cation selected from the group consisting of nitrogen-containing cations (e.g., ammonium cations), metal cations (e.g., alkali metal cations, alkaline earth metal cations), boron-containing cations, and phosphorus-containing cations; more preferably, ammonium cations, alkali metal cations, and alkaline earth metal cations; still more preferably, ammonium cations, sodium cations, and calcium cations; most preferably, sodium cations); and wherein n is 1 (preferably, as used in 95 mol % to 100 mol % (preferably, 96 mol % to 100 mol %; more preferably, 97 mol % to 100 mol %; most preferably, 97.5 mol % to 100 mol %) of the alcohol ethoxysulfate surfactant of formula I 13 C NMR characterization).

[0034] Preferably, the alcohol ethoxy sulfate surfactant of formula I contains <9 ppm (preferably, <8 ppm; more preferably, <7 ppm; still more preferably, <6 ppm; yet more preferably, <5 ppm; still yet more preferably, <4 ppm; even more preferably, <3 ppm; still even more preferably, <2 ppm; yet even more preferably, <1 ppm; still yet even more preferably, <0.25 ppm; most preferably, less than the detection limit) 1,4-dioxane (preferably, wherein the 1,4-dioxane content is measured by liquid injection cryogenic gas chromatography-mass spectrometry for the organic layer and by liquid chromatography-mass spectrometry for the aqueous layer), based on the solid weight of the alcohol ethoxy sulfate surfactant of formula I.

[0035] Preferably, the alcohol ethoxy sulfate surfactant of formula I contains, based on the solid weight of the alcohol ethoxy sulfate surfactant of formula I, <2 wt% (preferably, <1.75 wt%; more preferably, <1.5 wt%; still more preferably, <1.25 wt%; yet more preferably, <1.1 wt%; most preferably, ≤1 wt%) of the alcohol sulfate surfactant of formula II

[0036]

[0037] Where R 3 and R 4 Each independently is C 1-16Alkyl groups (preferably C 1-15 More preferably, C 1-14 Alkyl groups; most preferably, straight chain C 1-13 );where R 1 and R 2 The sum of carbon atoms in the alkylene oxide is 7 to 17 (preferably, 10 to 16; more preferably, 11 to 15; most preferably, 12 to 14) (preferably, wherein R 1 and R 2 is a straight chain alkyl group); wherein A + It is -SO3 in Equation II - Anions are negatively charged cations (preferably, wherein A + The cation is selected from the group consisting of nitrogen-containing cations (e.g., ammonium cations), metal cations (e.g., alkali metal cations, alkaline earth metal cations), boron-containing cations, and phosphorus-containing cations; more preferably, ammonium cations, alkali metal cations, and alkaline earth metal cations; still more preferably, ammonium cations, sodium cations, and calcium cations; most preferably, sodium cations).

[0038] Preferably, the aqueous laundry detergent composition of the present invention comprises an alcohol ethoxy sulfate surfactant of formula I as described above, wherein the alcohol ethoxy sulfate surfactant of formula I has improved thermal stability. More preferably, the aqueous laundry detergent composition of the present invention comprises an alcohol ethoxy sulfate surfactant of formula I as described above, wherein the alcohol ethoxy sulfate surfactant of formula I has enhanced thermal stability. The term "enhanced thermal stability" as used herein and in the appended claims means that the alcohol ethoxy sulfate surfactant of Formula I contains <9 ppm (preferably, <8 ppm; more preferably, <7 ppm; still more preferably, <6 ppm; yet more preferably, <5 ppm; still yet more preferably, <4 ppm; even more preferably, <3 ppm; still even more preferably, <2 ppm; yet even more preferably, <1 ppm; most preferably, <0.5 ppm) 1,4-dioxane (preferably, wherein the 1,4-dioxane content is measured by liquid injection cryogenic gas chromatography-mass spectrometry for the organic layer and by liquid chromatography-mass spectrometry for the aqueous layer) based on the solid weight of the alcohol ethoxy sulfate surfactant of Formula I when heated to 110°C. The term "enhanced thermal stability" as used herein and in the appended claims means that the alcohol ethoxy sulfate surfactant of Formula I contains <10 ppm of 1,4-dioxane based on the solid weight of the alcohol ethoxy sulfate surfactant of Formula I when heated to 280°C (preferably, wherein the 1,4-dioxane content is measured by liquid injection gas chromatography-mass spectrometry for the organic layer and liquid chromatography-mass spectrometry for the aqueous layer).

[0039] Preferably, the other anionic surfactant is selected from the group consisting of alkyl sulfates, alkylbenzene sulfates, alkylbenzene sulfonic acids, alkylbenzene sulfonates, paraffin sulfonic acids, paraffin sulfonates, olefin sulfonic acids, olefin sulfonates, α-sulfocarboxylates, esters of α-sulfocarboxylates, alkyl glyceryl ether sulfonic acids, alkyl glyceryl ether sulfonates, sulfates of fatty acids, sulfonates of fatty acids, sulfonates of fatty acid esters, alkylphenols, 2-acryloyloxy-alkane-1-sulfonic acids, 2-acryloyloxy-alkane-1-sulfonates, amine oxides and mixtures thereof. More preferably, the other anionic surfactant is selected from the group consisting of C 8-20 Alkylbenzene sulfate, C 8-20 Alkylbenzenesulfonic acid, C 8-20 Alkylbenzene sulfonate, paraffin sulfonic acid, paraffin sulfonate, α-olefin sulfonic acid, α-olefin sulfonate, C 8-20 Alkylphenols, amine oxides, sulfonates of fatty acids, sulfonates of fatty acid esters and mixtures thereof. Still more preferably, the other anionic surfactant is selected from the group consisting of: C 12-16 Alkylbenzenesulfonic acid, C 12-16 Alkylbenzene sulfonate, C 12-18 Paraffin-sulfonic acid, C 12-18 Paraffin-sulfonates and mixtures thereof. Most preferably, the other anionic surfactant is selected from the group consisting of: C 12-16 Alkylbenzenesulfonic acid, C 12-16 Alkylbenzene sulfonates and mixtures thereof.

[0040] Preferably, the aqueous laundry detergent composition of the present invention comprises from 1 wt % to 90 wt % (preferably, from 5 wt % to 75 wt %; more preferably, from 10 wt % to 60 wt %; preferably, from 15 wt % to 40 wt %) of a cleansing surfactant, based on the weight of the aqueous laundry detergent composition; wherein the cleansing surfactant comprises a blend of a nonionic surfactant and an anionic surfactant; wherein the anionic surfactant comprises an alcohol ethoxysulfate surfactant of formula I; and wherein the weight ratio of the nonionic surfactant to the anionic surfactant in the blend is from 10:1 to 1:10 (preferably, from 7.5:1 to 1:7.5; more preferably, from 5:1 to 1:7.5, most preferably, from 2.5:1 to 1:6). More preferably, the aqueous laundry detergent composition of the present invention comprises, based on the weight of the aqueous laundry detergent composition, 1 wt % to 90 wt % (preferably, 5 wt % to 75 wt %; more preferably, 10 wt % to 60 wt %; preferably, 15 wt % to 40 wt %) of a cleansing surfactant; wherein the cleansing surfactant comprises a blend of a nonionic surfactant and an anionic surfactant; wherein the anionic surfactant comprises an alcohol ethoxysulfate surfactant of formula I; and wherein the weight ratio of the nonionic surfactant to the alcohol ethoxysulfate surfactant of formula I is 5:1 to 1:5 (preferably, 4:1 to 1:2.5; more preferably, 3:1 to 1:2, most preferably, 2:1 to 1:1).

[0041] Preferably, the aqueous laundry detergent composition of the present invention further comprises an additive. Preferably, the aqueous laundry detergent composition of the present invention further comprises an additive selected from the group consisting of: amphoteric / zwitterionic surfactants; bleach activators (tetraacetylethylenediamine (TAED)); bleaches (e.g., sodium percarbonate, sodium perborate, sodium hypochlorite); builders (e.g., sodium bicarbonate, sodium carbonate, zeolite, sodium citrate, sodium tripolyphosphate and aminocarboxylates (such as methylglycine diacetic acid sodium salt or glutamic acid diacetic acid sodium salt)); cationic surfactants; colorants; conditioning agents; dyes; enzymes ( For example, proteases, cellulases, lipases, amylases, mannanases); fillers; fluorescent whitening agents; foam control agents (e.g., fatty acids, polydimethylsiloxanes); fragrances (e.g., essential oils such as D-limonene); hydrotropes (e.g., sodium xylene sulfonate); optical brighteners; organic solvents (e.g., ethanol, polyethylene glycol); pigments; pH adjusters; pH buffers; preservatives; rheology modifiers; stabilizers; structurants; softeners (e.g., softening silicones, cationic polymers) and mixtures thereof.

[0042] Preferably, the aqueous laundry detergent composition of the present invention further comprises: based on the weight of the aqueous laundry detergent composition, 0 wt % to 30 wt % (preferably, 0.1 wt % to 15 wt %; more preferably, 1 wt % to 10 wt %; most preferably, 2.5 wt % to 7.5 wt %) of a builder. More preferably, the aqueous laundry detergent composition of the present invention further comprises: 0 wt% to 30 wt% (preferably, 0.1 wt% to 15 wt%; more preferably, 1 wt% to 10 wt%; most preferably, 2.5 wt% to 7.5 wt%) of a builder, based on the weight of the aqueous laundry detergent composition; wherein the builder is selected from the group consisting of: inorganic builders (e.g., tripolyphosphates, pyrophosphates); alkali metal carbonates; borates; bicarbonates; hydroxides; zeolites; citrates (e.g., sodium citrate); polycarboxylates; monocarboxylates; aminotrimethylenephosphonic acid; salts of aminotrimethylenephosphonic acid; hydroxyethylidene diphosphonic acid; salts of hydroxyethylidene diphosphonic acid; diethylenetriamine penta(methylenephosphonic acid); salts of diethylenetriamine penta(methylenephosphonic acid); ethylenediaminetetraethylenephosphonic acid; salts of ethylenediaminetetraethylenephosphonic acid; oligomeric phosphonates; polymeric phosphonates; mixtures thereof. Most preferably, the aqueous laundry detergent composition of the present invention further comprises: 0 wt % to 30 wt % (preferably, 0.1 wt % to 15 wt %; more preferably, 1 wt % to 10 wt %; most preferably, 2.5 wt % to 7.5 wt %) of a builder, based on the weight of the aqueous laundry detergent composition; wherein the builder comprises a citrate (preferably, sodium citrate).

[0043] Preferably, the aqueous laundry detergent composition of the present invention further comprises: based on the weight of the aqueous laundry detergent composition, 0 wt % to 12 wt % (preferably, 0.1 wt % to 12 wt %; more preferably, 0.5 wt % to 10 wt %; most preferably, 1 wt % to 8 wt %) of an organic solvent. Preferably, the aqueous laundry detergent composition of the present invention further comprises: based on the weight of the aqueous laundry detergent composition, 0 wt % to 12 wt % (preferably, 0.1 wt % to 12 wt %; more preferably, 0.5 wt % to 10 wt %; most preferably, 1 wt % to 8 wt %) of an organic solvent; wherein the organic solvent is miscible with water. More preferably, the aqueous laundry detergent composition of the present invention further comprises: based on the weight of the aqueous laundry detergent composition, 0 wt % to 12 wt % (preferably, 0.1 wt % to 12 wt %; more preferably, 0.5 wt % to 10 wt %; most preferably, 1 wt % to 8 wt %) of an organic solvent; wherein the organic solvent is selected from the group consisting of: aliphatic alcohols (e.g., C 1-6 Alkyl alcohol, C 1-6alkyl glycol); glycol (e.g., propylene glycol); monoalkylene glycol ethers (e.g., ethylene glycol propyl ether, ethylene glycol n-butyl ether, ethylene glycol tert-butyl ether, propylene glycol propyl ether, propylene glycol n-butyl ether, propylene glycol tert-butyl ether, propylene glycol methyl ether acetate, propylene glycol diacetate); polyalkylene glycol ethers (e.g., diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol n-butyl ether, diethylene glycol tert-butyl ether, diethylene glycol hexyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol n-butyl ether, dipropylene glycol tert-butyl ether, dipropylene glycol phenyl ether, dipropylene glycol methyl ether acetate, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, tripropylene glycol propyl ether, tripropylene glycol n-butyl ether, tripropylene glycol tert-butyl ether) and mixtures thereof. Still more preferably, the aqueous laundry detergent composition of the present invention further comprises: 0 wt% to 12 wt% (preferably, 0.1 wt% to 12 wt%; more preferably, 0.5 wt% to 10 wt%; most preferably, 1 wt% to 8 wt%) of an organic solvent, based on the weight of the aqueous laundry detergent composition; wherein the organic solvent is selected from the group consisting of isopropanol, ethanol, propylene glycol, 2-(2-butoxyethoxy)ethanol, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol propyl ether, propylene glycol tert-butyl ether, dipropylene glycol methyl ether, dipropylene glycol propyl ether, dipropylene glycol n-butyl ether and mixtures thereof. Still more preferably, the aqueous laundry detergent composition of the present invention further comprises: based on the weight of the aqueous laundry detergent composition, 0 wt % to 12 wt % (preferably, 0.1 wt % to 12 wt %; more preferably, 0.5 wt % to 10 wt %; most preferably, 1 wt % to 8 wt %) of an organic solvent; wherein the organic solvent comprises a mixture of ethanol and propylene glycol. Most preferably, the aqueous laundry detergent composition of the present invention further comprises: based on the weight of the aqueous laundry detergent composition, 0 wt % to 12 wt % (preferably, 0.1 wt % to 12 wt %; more preferably, 0.5 wt % to 10 wt %; most preferably, 1 wt % to 8 wt %) of an organic solvent; wherein the organic solvent is a mixture of ethanol and propylene glycol.

[0044] Amphoteric surfactants include betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amine oxides, acylated amino acids, derivatives of fatty quaternary ammonium compounds, and mixtures thereof. Preferred amphoteric surfactants include derivatives of fatty quaternary ammonium compounds. More preferred amphoteric surfactants include derivatives of fatty quaternary ammonium compounds having long chain groups (having 8 to 18 carbon atoms). Still more preferred amphoteric surfactants include at least one of the following: C 12-14 Alkyl dimethyl amine oxide, 3-(N,N-dimethyl-N-hexadecyl-ammonio) propane-1-sulfonate, 3-(N,N-dimethyl-N-hexadecyl ammonio)-2-hydroxypropane-1-sulfonate. The most preferred amphoteric surfactants include C12-14 At least one of alkyl dimethyl amine oxides.

[0045] Cationic surfactants include quaternary surface-active compounds. Preferred cationic surfactants include quaternary surface-active compounds having at least one of an ammonium group, a sulfonium group, a phosphonium group, an iodonium group, and an arsonium group. More preferred cationic surfactants include at least one of dialkyldimethylammonium chloride and alkyldimethylbenzylammonium chloride. Still more preferred cationic surfactants include at least one of the following: C 16-18 Dialkyldimethylammonium chloride, C 8-18 Alkyl dimethyl benzyl ammonium chloride ditallow dimethyl ammonium chloride and ditallow dimethyl ammonium chloride. The most preferred cationic surfactants include ditallow dimethyl ammonium chloride.

[0046] Preferably, the aqueous laundry detergent composition of the present invention optionally further comprises, based on the weight of the aqueous laundry detergent composition, 0 wt % to 3 wt % (preferably, 0.05 wt % to 2.5 wt %; more preferably, 0.1 wt % to 2 wt %; most preferably, 0.5 wt % to 1.5 wt %) of a fragrance. More preferably, the aqueous laundry detergent composition of the present invention optionally further comprises, based on the weight of the aqueous laundry detergent composition, 0.01 wt % to 3 wt % (preferably, 0.05 wt % to 2.5 wt %; more preferably, 0.1 wt % to 2 wt %; most preferably, 0.5 wt % to 1.5 wt %) of a fragrance; wherein the fragrance comprises a component selected from the group consisting of benzyl alcohol, citronellol, linalool, limonene and mixtures thereof (preferably, benzyl alcohol, limonene, citronellol and mixtures thereof). Still more preferably, the aqueous laundry detergent composition of the present invention comprises, based on the weight of the aqueous laundry detergent composition, 0 wt% to 3 wt% (preferably, 0.05 wt% to 2.5 wt%; more preferably, 0.1 wt% to 2 wt%; most preferably, 0.5 wt% to 1.5 wt%) of a fragrance; wherein the fragrance comprises a component selected from the group consisting of benzyl alcohol, limonene, citronellol, and mixtures thereof. Most preferably, the aqueous laundry detergent composition of the present invention comprises, based on the weight of the aqueous laundry detergent composition, 0 wt% to 3 wt% (preferably, 0.05 wt% to 2.5 wt%; more preferably, 0.1 wt% to 2 wt%; most preferably, 0.5 wt% to 1.5 wt%) of a fragrance; wherein the fragrance comprises a component selected from the group consisting of limonene, benzyl alcohol, and mixtures thereof.

[0047] Preferably, the aqueous laundry detergent composition of the present invention further comprises: based on the weight of the aqueous laundry detergent composition, 0 wt % to 10 wt % (preferably, 1 wt % to 10 wt %; more preferably, 2 wt % to 8 wt %; most preferably, 5 wt % to 7.5 wt %) of a hydrotrope. More preferably, the aqueous laundry detergent composition of the present invention further comprises: based on the weight of the aqueous laundry detergent composition, 0 wt % to 10 wt % (preferably, 1 wt % to 10 wt %; more preferably, 2 wt % to 8 wt %; most preferably, 5 wt % to 7.5 wt %) of a hydrotrope; wherein the hydrotrope is selected from the group consisting of: alkyl hydroxides; glycols, urea; monoethanolamine; diethanolamine; triethanolamine; calcium, sodium, potassium, ammonium and alkanolammonium salts of xylenesulfonic acid, toluenesulfonic acid, ethylbenzenesulfonic acid and isopropylbenzenesulfonic acid; their salts and mixtures thereof. Still more preferably, the aqueous laundry detergent composition of the present invention further comprises: based on the weight of the aqueous laundry detergent composition, 0 wt% to 10 wt% (preferably, 1 wt% to 10 wt%; more preferably, 2 wt% to 8 wt%; most preferably, 5 wt% to 7.5 wt%) of a hydrotrope; wherein the hydrotrope is selected from the group consisting of ethanol, propylene glycol, sodium toluene sulfonate, potassium toluene sulfonate, sodium xylene sulfonate, ammonium xylene sulfonate, potassium xylene sulfonate, calcium xylene sulfonate, sodium cumene sulfonate, ammonium cumene sulfonate, and mixtures thereof. Still more preferably, the aqueous laundry detergent composition of the present invention further comprises: based on the weight of the aqueous laundry detergent composition, 0 wt% to 10 wt% (preferably, 1 wt% to 10 wt%; more preferably, 2 wt% to 8 wt%; most preferably, 5 wt% to 7.5 wt%) of a hydrotrope; wherein the hydrotrope comprises at least one of ethanol, propylene glycol and sodium xylene sulfonate. Most preferably, the aqueous laundry detergent composition of the present invention further comprises: 0 wt % to 10 wt % (preferably, 1 wt % to 10 wt %; more preferably, 2 wt % to 8 wt %; most preferably, 5 wt % to 7.5 wt %) of a hydrotrope, based on the weight of the aqueous laundry detergent composition; wherein the hydrotrope is a mixture of ethanol, propylene glycol and sodium xylene sulfonate.

[0048] Preferably, the aqueous laundry detergent composition is in liquid form with a pH of 6 to 12.5, preferably at least 6.5, preferably at least 7, preferably at least 7.5, preferably not more than 12.25, preferably not more than 12, preferably not more than 11.5. Suitable bases for adjusting the pH of the formulation include inorganic bases such as sodium hydroxide (including soda ash) and potassium hydroxide; sodium bicarbonate, sodium silicate, ammonium hydroxide; and organic bases such as monoethanolamine, diethanolamine or triethanolamine; or 2-dimethylamino-2-methyl-1-propanol (DMAMP). A mixture of bases can be used. Suitable acids for adjusting the pH of the aqueous medium include inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid; and organic acids such as acetic acid. Acid mixtures can be used. The formulation can be adjusted to a higher pH with a base and then back-titrated to the above range with an acid.

[0049] Preferably, the method of laundering a stained fabric article of the present invention comprises: providing a stained fabric article; providing wash water; providing rinse water; providing a laundry detergent composition of the present invention; applying the wash water and the laundry detergent composition to the stained fabric article to provide a washed fabric article; and then rinsing the washed fabric article with rinse water.

[0050] Preferably, in the method for washing stained fabric articles of the present invention, the stained fabric articles are treated with a laundry detergent composition and wash water using well-known techniques. Preferably, the laundry detergent composition is mixed with the wash water in a weight ratio of 1:100 to 1:1,000 laundry detergent composition to wash water.

[0051] Some embodiments of the present invention will now be described in detail in the following examples.

[0052] Experimental Materials

[0053]

[0054]

[0055] Synthesis S1:C 12 EO

[0056] When using the catalyst to etherify 1-dodecene and monoethylene glycol, a 3 liter (L) three-necked glass round bottom flask equipped with an overhead stirrer for stirring through the center neck, a reflux condenser and a heating jacket was used. To ensure good mixing, a paddle impeller was used for stirring. A reaction mixture of 551.7 grams (g) of ethylene glycol and 505.8 g of 1-dodecene was prepared and charged into the reactor at 23° C. together with 61 g of powdered catalyst. The impeller stirring rate was set to 400 revolutions per minute (“rpm”). The reactor was heated to 135° C. over the course of 30 minutes, maintained at 135° C. for 18 hours, and then the reactor was cooled to 23° C. by turning off the heater. The reaction mixture was separated into monoethylene glycol and catalyst phases and olefin phases using a separatory funnel.

[0057] The distillation apparatus consisted of a 1-liter round-bottom flask connected to a short-path still head with a thermometer connection and a condenser with a vacuum connection at the outlet. The distillation flask was heated in an aluminum block by an IKA heated stirring plate. The combined olefin phases were charged to the distillation pot, which was then stirred and evacuated. Obvious boiling was observed, but no condensate was observed or collected. The temperature of the heating block was increased to 75°C, and the unreacted dodecane was collected at a distillation head temperature of 25°C to 50°C and a pressure of 13.3 Pascals to 40 Pascals (Pa). The temperature of the heating block was gradually increased to 140°C, and an intermediate fraction containing both monoether alcohol ethoxylate and dodecene was recovered at a pressure of 13 Pa when the head temperature was increased from 50°C to 75°C. C was collected at a head temperature of 70°C to 115°C and a pressure of 6 Pa to 33 Pa. 12 EO. The heating block temperature was gradually raised to 200°C. At a pressure of 6 Pa, when the head temperature increased from 115°C to 130°C, an intermediate fraction containing both monoether alcohol ethoxylate and diether was collected. The distillation was stopped and the diether retained in the tank was collected. 12 The EO is sent to the next sulfation process to prepare sulfate anionic surfactant.

[0058] Synthesis of S2:C 14 EO

[0059] A 300 mL Parr reactor with a heating jacket and controller was used for the etherification of 1-tetradecene and monoethylene glycol using the catalyst. To ensure good mixing, a paddle impeller was used for stirring.

[0060] A reaction mixture of 100.0 g of monoethylene glycol and 100.0 g of 1-tetradecene was prepared and loaded into a reactor at 23 ° C with 10.0 g of a powdered catalyst. The impeller stirring rate was set to at least 600 rpm. The reactor was heated to 135 ° C in 30 minutes, kept at 135 ° C for 6 hours, and then cooled to room temperature by turning off the heater. The reaction mixture was separated with a separatory funnel. The reaction mixture was separated into monoethylene glycol and catalyst phases and olefin phases using a separatory funnel. 15 batches were produced, and the olefin phases were collected and combined for distillation.

[0061] C was distilled using the same distillation apparatus as used in Synthesis S1. 14 EO. The distillation tank was charged with the product of the olefin phase produced by the operation of multiple batch reactors, then stirred and evacuated. Obvious boiling was observed, but no condensate was observed or collected. The temperature of the heating block was increased to 95°C, and the unreacted 1-tetradecene was collected under the conditions of a distillation head temperature of 30°C to 60°C and a pressure of 27Pa to 5Pa. The temperature of the heating block was gradually increased to 170°C, and at a pressure of 7Pa to 5Pa, when the head temperature was increased from 60°C to 85°C, an intermediate fraction containing both monoether and tetradecene was recovered. C was collected under the conditions of a head temperature of 80°C to 115°C and a pressure of 8Pa to 5Pa. 14 EO. When the temperature of the distillation pot was set to 170°C, the distillation was stopped when no more material was distilled out.

[0062] Synthesis of S3:C 12 EO Sulfate

[0063] All chemical manipulations were performed under a dry nitrogen atmosphere. Prior to the experiments, all glassware was heated in a laboratory oven to remove residual moisture. A 2 L three-necked round bottom flask was charged with dichloromethane (500 mL) and C prepared according to Synthesis S1. 12EO (40g, 0.173mol, 1.0 equivalent). The reaction flask was equipped with an overhead mechanical stirrer, a charging funnel and a thermocouple. Next, chlorosulfonic acid (12.7mL, 0.191mol, 1.1 equivalents) was carefully loaded into the charging funnel. The reaction flask was then immersed in an ice bath and cooled for 20 minutes to 0°C. After the reaction was cooled, chlorosulfonic acid was added dropwise to the reaction flask at a rate of about 1.0mL / min in about 20 minutes. During the addition of chlorosulfonic acid, the reaction temperature did not exceed 5°C. After addition, the reactants were reacted and the temperature was maintained between 0°C and 5°C for 3 hours. At this point, the reaction was neutralized by slowly adding a NaOH aqueous solution (500mL aqueous solution of 18.0gNaOH, 0.9 moles) dropwise. The addition rate was slow enough not to exceed 5°C during the addition process. After adding about 300mL 0.9 molar NaOH solution, the solution became alkaline. The dichloromethane was then carefully removed from the two phase reaction in vacuo. During the dichloromethane removal, a large amount of foaming was observed. After the dichloromethane was removed, the remaining aqueous solution was placed in a freeze dryer / lyophilizer to obtain the secondary alcohol ethoxylate sulfate product, C 12 EO sulfate as a white solid (61.9 g).

[0064] Synthesis of S4:C 14 EO Sulfate

[0065] All chemical manipulations were performed under a dry nitrogen atmosphere. Prior to the experiment, all glassware was heated in a laboratory oven to remove residual moisture. A 2 L three-necked round bottom flask was charged with dichloromethane (500 mL) and C prepared according to Synthesis S2. 14 EO (50g, 0.193mol, 1.0 equivalent). The reaction flask was equipped with an overhead mechanical stirrer, a charging funnel and a thermocouple. Next, chlorosulfonic acid (14.2mL, 0.213mol, 1.1 equivalents) was carefully loaded into the charging funnel. The reaction flask was then immersed in an ice bath and cooled for 20 minutes to 0°C. After the reaction was cooled, chlorosulfonic acid was added dropwise to the reaction flask at a rate of about 1.0mL / min in about 20 minutes. During the addition of chlorosulfonic acid, the reaction temperature did not exceed 5°C. After addition, the reactants were reacted and the temperature was maintained between 0°C and 5°C for 3 hours. At this point, the reaction was neutralized by slowly adding a NaOH aqueous solution (500mL aqueous solution of 18.0gNaOH, 0.9 moles) dropwise. The addition rate was slow enough not to exceed 5°C during the addition process. After adding about 400mL 0.9 molar NaOH solution, the solution became alkaline. The dichloromethane was then carefully removed from the two phase reaction in vacuo. During the removal of DCM, a large amount of foaming was observed. After the DCM was removed, the remaining aqueous solution was placed in a freeze dryer / lyophilizer to give the secondary alcohol ethoxylate sulfate product (68.6 g).

[0066] Synthetic S5: ALEO1 Sulfate

[0067] ALEO1 sulfate was prepared from ALEO1 in the same manner as described in the synthesis of S3.

[0068] Synthetic S6: SA3EO sulfate

[0069] SA3EO sulfate was prepared from SA3EO in the same manner as described in the synthesis of S3.

[0070] EO distribution of surfactants

[0071] The distribution of EO adducts in the surfactants listed in Table 1 was measured by NMR or UHPLC-MS as indicated using the methodology listed below, and the results are provided in Table 1.

[0072] Nuclear Magnetic Resonance EO Distribution Characterization (NMR)

[0073] The surfactant samples to be analyzed were prepared by dissolving the surfactant in deuterated dimethyl sulfoxide containing 0.025 M chromium (III) acetylacetonate. The NMR ( 13 C NMR) spectrum, parameters are as follows: 90 ° pulse, anti-gated decoupling, 1.38 seconds acquisition time and 6.4 seconds cycle delay. Collect 2048 scans. Data are processed in MNOVA, and chemical shift is based on the solvent peak at 39.52ppm. DEPT-135 experiment is also collected with the same parameters, but the cycle delay is 2.0 seconds and the number of scans is 2048 times. The ratio of different EO adducts is calculated by accumulating and comparing the oxirane alcohol end group intensity of about 60ppm to 61ppm, the oxirane main chain group intensity of about 69ppm to 70ppm, the oxirane end group ether peak intensity of about 71ppm to 72ppm, the unreacted primary alcohol peak intensity of about 60ppm to 61ppm and the unreacted secondary alcohol peak intensity of about 65ppm to 66ppm.

[0074] Analysis of Sodium Lauryl Ether Sulfate by UHPLC-MS

[0075] Ultra-high performance liquid chromatography-mass spectrometry (UHPLC-MS) conditions:

[0076]

[0077] program: Compositions containing commercial surfactants were analyzed by ultra-high performance liquid chromatography mass spectrometry (UHPLC-MS) with electrospray ionization (ESI). For analysis, a stock solution at a concentration of 25 ppm was prepared in a 50 / 50 mixture of methanol / water. Alcohol ethoxylate samples were diluted 1:100 in 50 / 50 methanol / water in duplicate and vortexed for a few seconds. They were then diluted 1:10 in 50 / 50 methanol / water to give a final dilution of 1:1,000. LA-4 is the standard for commercial 1 mole sodium laureth sulfate, and LA-7 is a standard for commercial 3 mole sodium laureth sulfate. Calibration standards of 10 ppm, 5 ppm, 2 ppm and 1 ppm were prepared in 50 / 50 methanol / water.

[0078] Dilute the prepared alkyl sulfate salt 1:1,000 in 50 / 50 methanol / water to give a 1:20,000 final solution. BN-5 was used as the standard for alkyl sulfate analysis. Standards were prepared in 50 / 50 methanol / water at concentrations of 5 ppm, 2 ppm, 1 ppm and 0.5 ppm.

[0079] A Waters BEH C18 1.7 μm 1×50 mm column was used. The samples were analyzed by UPLC system. Mass spectrometry was performed using a Waters LCT Premier TOF mass spectrometer with ESI. Measurements were performed in positive and negative ion modes. Each sample preparation was injected three times for analysis. The ratios of different EO adducts were calculated by peak area and reported in Table 1.

[0080] Table 1

[0081]

[0082] At least 95 mol% of the oligomers of the products of synthesizing S4 and S5 have n ≥ 1, and no more than 5 mol% of the oligomers have n ≥ 2. Specifically, ≥ 98 mol% of the oligomers of the products of synthesizing S4 and S5 have n ≥ 1, and ≤ 2 mol% of the oligomers have n ≥ 2.

[0083] 1,4-Dioxane content of surfactant

[0084] The 1,4-dioxane content of the surfactants listed in Table 2 was measured by liquid injection cryogenic gas chromatography-mass spectrometry (GC-MS) method for the organic layer and liquid chromatography-mass spectrometry (LC-MS) method for the aqueous layer, as indicated using the methodology listed below, and the results are provided in Table 2.

[0085] For the measurement of 1,4-dioxane in the organic layer Gas chromatography-mass spectrometry (GC-MS) conditions :

[0086]

[0087] Standards were prepared by adding a solution of dioxane in tetrahydrofuran ("THF") and diluting to 0.1 ppm to 100 ppm.

[0088] The sample was prepared by mixing 3.3 g of the crude mixture organic (DCM) layer with 6.7 g THF, and then the solution was shaken for about 20 minutes. The solid was then centrifuged to the bottom and the supernatant was placed in an autosampler vial. The spiked samples were prepared by spiking a THF solution of dioxane standards into individual samples at 5 ppm to 10 ppm.

[0089] For measuring the 1,4-dioxane content in the water layer Liquid chromatography-mass spectrometry (LC-MS) conditions :

[0090]

[0091]

[0092] Samples were injected neat or diluted 1:4 with water. Standards were prepared by preparing a stock solution of dioxane in THF and diluting with water to 0.1 ppm to 100 ppm.

[0093] Calculation of dioxane content relative to solids

[0094] The ppm value of dioxane content relative to the solid content in the sample was calculated according to Equation 1.

[0095]

[0096] Table 2

[0097]

[0098]

[0099] GC results for the SA3EO sulfate surfactant indicated that the secondary alcohol with an average of 3 moles of ethylene oxide per molecule contained 2 ppm of 1,4-dioxane in the organic phase at 110°C and indicated that structures with n ≥ 2 have the potential to generate 1,4-dioxane. Interestingly, the dioxane content of the SA3EO sulfate in the organic phase increased from 2 ppm to 1,471 ppm 1,4-dioxane when the inlet temperature was increased to 280°C. This result suggests that sulfated surfactants with n ≥ 2 may generate observable 1,4-dioxane at 110°C, but also suggests that such surfactants may be unstable at elevated temperatures of 280°C, resulting in significant 1,4-dioxane formation. Similar to the SA3EO sulfate, the GC results for the ALEO1 sulfate surfactant indicated the formation of >9 ppm 1,4-dioxane relative to the solid at 110°C. In addition, the ALEO1 sulfate surfactant also showed a large amount of 1,4-dioxane generation (259 ppm) at 280°C, indicating that the ALEO1 sulfate surfactant lacks stability at high temperatures. 12 EO sulfate surfactants exhibit low 1,4-dioxane content. Surprisingly, the C 12 The EO sulfate surfactant also exhibited very low 1,4-dioxane content and was below the limit of detection (LOD) of the GC and LC methods. Based on the LOD, this indicates that at 110°C, C 12 The dioxane content of EO sulfate was <1.6 ppm relative to solids. Interestingly, when the inlet temperature was increased to 280°C, the C 12 The 1,4-dioxane content of the EO sulfate material is still less than 1 ppm (i.e., 0.58 ppm), which indicates that the C 12 EO sulfate has improved thermal stability relative to the comparative material.

[0100] Comparative Examples CF1 to CF2 and Examples F1 to F3: Aqueous Laundry Detergent Compositions

[0101] Aqueous laundry detergent compositions were prepared in each of Comparative Examples CF1 to CF2 and Examples F1 to F3, which had formulations as described in Table 3 and were prepared by standard laundry detergent formulation preparation procedures. The formulation stability of the aqueous laundry detergent compositions was observed, and those that showed phase separation were identified as unstable. These observations are reported in Table 3.

[0102] Table 3

[0103]

[0104] Primary cleaning performance

[0105] The primary cleaning performance of the liquid laundry detergent formulations of Comparative Examples CF1 to CF2 and Examples F1 to F3 was evaluated in a Launder-Ometer (SDL Atlas, Model M228AA) at a set test temperature of 22°C using a 30 minute wash cycle. Twenty 1.2 liter cans filled with 500 mL of 100 ppm by mass of Ca 2+ Mg 2+ The washed fabrics were stirred at ambient temperature in an Eberbach E6000 reciprocating shaker in 300 mL of 100 ppm (2 / 1 Ca 2+ / Mg 2+ ) hardness adjusted water at 260osc / min pm for 5 minutes. The soiled fabric and soiled ballast used in the test were PCS-S-132 High Resolution Sebum BEY Pigment and PCS-S-94 Sebum / Dust ASTM stains from Testfabrics sewn to pre-shrunk double cotton fabric. The size of the double cotton was 5x5cm. The soiled sample was 2.5x3cm. A 5x5cm cut SBL-CFT soil ballast was added to each tank to provide a baseline soil for the wash solution. The total surfactant concentration in the wash solution was 200ppm.

[0106] Reflectance Measurement and Soil Removal Index (SRI)

[0107] The Soil Removal Index (SRI) of each liquid laundry detergent formulation evaluated in the Primary Cleaning Performance Test was determined using ASTM Method D4265-14. The average SRI taken from 8 samples (two samples per can, 4 cans) for each condition is provided in Table 4.

[0108] L of stained fabric * 、a * and b * The values ​​were measured before and after washing using a Mach 5 spectrophotometer from Colour Consult. * 、a * and b * Values ​​are measured in the SRI calculation as follows:

[0109]

[0110] Where US is the unwashed stain area, UF is the unwashed (unstained) fabric area, WS is the washed stain area, ΔE * (US-UF) is the ΔE between the unwashed stain and the unwashed fabric * Chromatic aberration, and ΔE* (WS-UF) is the ΔE between the washed stain and the unwashed fabric * Color difference. ΔE * The value of is calculated as

[0111] ΔE * =(ΔL *2 +Δa *2 +Δb *2 ) 1 / 2 .

[0112] Table 4

[0113]

[0114] Anti-redeposition

[0115] The anti-redeposition performance of the standard liquid laundry detergent + cleaning enhancer combinations of Comparative Examples CF1-CF2 and Examples F1-F3 were evaluated in a Terg-o-tometer Model 7243ES under the conditions shown in Table 5 at 90 cycles per minute agitation.

[0116] Table 5

[0117]

[0118] The anti-redeposition performance was determined by calculating the ΔE measured with a MACH 5+ instrument (L, a & b). The results are reported in Table 6, where ΔE * According to the following equation:

[0119] ΔE * =ΔE aw -ΔE bw

[0120] where ΔE aw Measured from washed fabric, and ΔE bw Measured from fabric before washing. Higher ΔE * Corresponding to better anti-redeposition performance. For each fabric tested, the blend (1:1 wt%) of the products synthesized from S3 and S4 provided the highest anti-redeposition performance.

[0121] Table 6

[0122]

Claims

1. An aqueous laundry detergent composition, comprising: water; A cleansing surfactant; wherein the cleansing surfactant comprises a blend of: Nonionic surfactants and Anionic surfactant; wherein the anionic surfactant comprises an alcohol ethoxy sulfate surfactant of formula I Where R 1 and R 2 Each independently is C 1-16 Alkyl group; wherein R 1 and R 2 The total number of carbon atoms in the + It is -SO3 of balanced formula I - anionic negatively charged cation; and wherein n is 1 in 95 mol % to 100 mol % of the alcohol ethoxy sulfate surfactant of formula I.

2. An aqueous laundry detergent composition according to claim 1, wherein the alcohol ethoxysulfate surfactant of formula I contains <9 ppm of 1,4-dioxane.

3. The aqueous laundry detergent composition of claim 2, wherein the alcohol ethoxysulfate surfactant of Formula I has enhanced thermal stability.

4. The aqueous laundry detergent composition of claim 2, wherein the aqueous laundry detergent composition contains <1 wt % of an alcohol sulfate surfactant of Formula II based on the solid weight of the aqueous laundry detergent composition. Where R 3 and R 4 Each independently is C 1-16 Alkyl group; wherein R 3 and R 4 The total number of carbon atoms in the + It is -SO3 in Equation II - Anions have a negative charge on cations.

5. The aqueous laundry detergent composition of claim 4, wherein the aqueous laundry detergent composition comprises: 30% to 97% by weight, based on the weight of the aqueous laundry detergent composition, of water; 10 wt. % to 60 wt. % of the cleansing surfactant, based on the weight of the aqueous laundry detergent composition; wherein the weight ratio of the nonionic surfactant to the anionic surfactant in the blend is from 5:1 to 1:7.

5.

6. The aqueous laundry detergent composition of claim 5, further comprising an organic solvent.

7. The aqueous laundry detergent composition of claim 6, further comprising an additional anionic surfactant; wherein the additional anionic surfactant is a linear alkylbenzene sulfonate surfactant.

8. The aqueous laundry detergent composition of claim 7, further comprising an additive selected from the group consisting of: amphoteric / zwitterionic surfactants; bleach activators; bleaching agents; builders; cationic surfactants; colorants; conditioning agents; dyes; enzymes; fillers; fluorescent brighteners; foam control agents; fragrances; hydrotropes; optical brighteners; organic solvents; pigments; pH adjusters; pH buffers; preservatives; rheology modifiers; stabilizers; structurants; softeners and mixtures thereof.

9. A method for laundering a soiled fabric article, the method comprising: Providing soiled fabric products; Providing a laundry detergent composition according to claim 1; Provide washing water; Provide rinse water; applying the wash water and the laundry detergent composition to the soiled fabric article to provide a washed fabric article; and rinsing the washed fabric article with the rinse water.

10. The method of claim 9, wherein the aqueous laundry detergent composition is an aqueous laundry detergent composition according to claim 8.

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