Silicone depositing laundry detergent formulation

Abstract

A laundry detergent formulation is provided comprising: water; alcohol ethoxysulfate surfactant of formula I (I) wherein R1 and R2 is C1‑16 alkyl group; wherein sum of carbon atoms in R1 and R2 is 7-17; wherein M+ is cation; and wherein x is 1 in 95-100 mol% of alcohol ethoxysulfate surfactant; fabric softening silicone; and modified carbohydrate polymer, comprising cellulose ether base material functionalized with quaternary ammonium moieties of formula II (II); wherein each R3 is independently selected from the group consisting of a C1-7 alkyl group; wherein the modified carbohydrate polymer has Kjeldahl nitrogen, TKN, of 0.75-3 wt%; and hydrophobic substituents selected from the group consisting of C16 alkyl group and C16 alkyl glycidyl ether residue; wherein the modified carbohydrate polymer comprises 0.005-1.5 wt%, based on weight of the cellulose ether base material, of the hydrophobic substituents; wherein the cellulose ether base material has molecular weight, MW, of >1,000,000 Daltons.

Description

SILICONE DEPOSITING LAUNDRY DETERGENT FORMULATION

[0001] The present invention relates to laundry detergent formulations. In particular, the present invention relates to a laundry detergent formulation comprising: water; an alcohol ethoxysulfate surfactant of formula Iwherein each R1and R2is independently a Ci-16 alkyl group; wherein the sum of the carbon atoms in R1and R2is 7 to 17; wherein M+is a cation balancing the negative charge of the -SO3‘ anion of formula I; and wherein x is 1 in 95 to 100 mol% of the alcohol ethoxy sulfate surfactant of formula I; a fabric softening silicone; and a modified carbohydrate polymer, comprising a cellulose ether base material functionalized with (i) quaternary ammonium moieties of formula II(II); wherein each R3is independently selected from the group consisting of a C 1-7 alkyl group and wherein the modified carbohydrate polymer has a Kjeldahl nitrogen content, TKN, corrected for ash and volatiles, of 0.75 to 3 wt%; and (ii) hydrophobic substituents selected from the group consisting of a Ci6 alkyl group and a Ci6 alkyl glycidyl ether residue; wherein the modified carbohydrate polymer comprises 0.005 to 1.5 wt%, based on weight of the cellulose ether base material, of the hydrophobic substituents; wherein the quaternary ammonium moieties of formula II and the hydrophobic substituents are randomly distributed across the backbone of the cellulose ether base material; wherein the cellulose ether base material has a weight average molecular weight, Mw, of > 1,000,000 Daltons; and wherein the modified carbohydrate polymer comprises < 0.001 wt%, based on weight of modified carbohydrate polymer, of crosslinking units.

[0002] Laundry detergent formulations typically include an anionic surfactant, which is the principal suds producer, along with a secondary surfactant. Alkyl ethoxy sulfate anionic surfactants (e.g., alcohol ethoxysulfate surfactants (AES)) have established use in a variety of laundry detergent formulations. Conventional AES anionic surfactants; however, have beenassociated with undesirable 1,4 dioxane content. Regulators are increasingly restricting 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, a consumer product must contain less than 10 parts per million by weight (ppm) of 1,4 dioxane to be compliant with the regulations. One contributor of the unintended incorporation of 1,4 dioxane in consumer products can be the inclusion of alkyl ethoxy sulfate anionic surfactants.

[0003] Inclusion of 1 ,4 dioxane in conventional AES surfactants is believed to occur at multiple points in time. A first point of 1 ,4 dioxane generation in conventional AES surfactants is believed to occur during the sulfation process of alcohol ethoxylates to make alcohol ethoxy sulfates. The alcohol ethoxylate intermediates for the production of conventional alcohol ethoxy sulfate surfactants are made via ethoxylation (i.e., the reaction of an alcohol with ethylene oxide) that typically results in a distribution of alcohol ethoxylate oligomers. It is believed that under the sulfation process conditions during the manufacture of conventional AES surfactants, 1,4 dioxane can form. A second point of 1,4 dioxane generation in association with conventional AES surfactants is believed to occur during handling and processing of the conventional AES surfactants. Handling and processing of conventional AES surfactants often involves acidic conditions at ambient, or elevated, temperature. Prolonged exposure to acidic environments for conventional AES surfactants and their alcohol ethoxylate precursors may result in the formation of 1 ,4 dioxane. Further, exposure to elevated temperatures (e.g., up to 280 °C) during processing, storage and / or handling may result in the decomposition of conventional AES surfactants resulting in the formation of dioxane.

[0004] Traditionally, 1,4 dioxane content in conventional AES surfactants and products incorporating such surfactants has been addressed by the use of stripping techniques. For example, where 1,4 dioxane concentrations are above a target threshold, a stripping process is employed to remove excess 1 ,4 dioxane from the conventional AES surfactants or product incorporating same. The stripping process is not only expensive and time consuming, but also is not a guarantee to meet the increasingly stringent regulatory requirements. Further, as 1 ,4 dioxane may form over time as a response to how the conventional AES surfactant or product is handled and further processed, any previously applied stripping techniques may be nullified by the generation of new 1 ,4 dioxane. As such, ensuring that a product comprising an AES surfactant is compliant with the appropriate regulations by the time it is sold to an end consumer is a difficult challenge.

[0005] Accordingly, there remains a need for laundry detergent formulations having an anionic alcohol ethoxy sulfate surfactant that resists forming 1,4-dioxane both during the sulfation process to form the surfactant and subsequently when the alcohol ethoxysulfate surfactant is exposed to elevated temperatures of up to 280 °C.

[0006] The present invention provides a laundry detergent formulation comprising: water; an alcohol ethoxy sulfate surfactant of formula Iwherein each R1and R2is independently a Ci-16 alkyl group; wherein the sum of the carbon atoms in R1and R2is 7 to 17; wherein M+is a cation balancing the negative charge of the -SO3" anion of formula I; and wherein x is 1 in 95 to 100 mol% of the alcohol ethoxy sulfate surfactant of formula I; a fabric softening silicone; and a modified carbohydrate polymer, comprising a cellulose ether base material functionalized with (i) quaternary ammonium moieties of formula IIwherein each R3is independently selected from the group consisting of a C1-7 alkyl group and wherein the modified carbohydrate polymer has a Kjeldahl nitrogen content, TKN, corrected for ash and volatiles, of 0.75 to 3 wt%; and (ii) hydrophobic substituents selected from the group consisting of a Ci6 alkyl group and a Ci6 alkyl glycidyl ether residue; wherein the modified carbohydrate polymer comprises 0.005 to 1.5 wt%, based on weight of the cellulose ether base material, of the hydrophobic substituents; wherein the quaternary ammonium moieties of formula II and the hydrophobic substituents are randomly distributed across the backbone of the cellulose ether base material; wherein the cellulose ether base material has a weight average molecular weight, Mw, of > 1,000,000 Daltons; and wherein the modified carbohydrate polymer comprises < 0.001 wt%, based on weight of modified carbohydrate polymer, of crosslinking units.

[0007] The present invention provides a method of depositing silicone on cotton, comprising: providing a soiled cotton article of laundry; selecting a laundry7detergent formulation of thepresent invention having a synergistic combination of the alcohol ethoxysulfate surfactant of formula I and the modified carbohydrate polymer; providing a bath water; and applying the bath water and the laundry detergent formulation to the soiled cotton article of laundry to provide a cleaned cotton article of laundry; wherein the fabric softening silicone is associated with the cleaned cotton article of laundry.DETAILED DESCRIPTION

[0008] In addition to resisting the formation of 1 ,4 dioxane both during the sulfation process to form the alcohol ethoxysulfate surfactant of formula I and subsequently when the alcohol ethoxysulfate surfactant of formula I is exposed to elevated temperatures of up to 280 °C during processing, storage and / or handling; we have surprisingly found that a combination of such alcohol ethoxysulfate surfactant of formula I (as described herein) and a modified carbohydrate polymer (as described herein) significantly improves the deposition of silicone from laundry detergent onto cotton fabric during washing.

[0009] Unless otherwise indicated, ratios, percentages, parts, and the like are by weight (e.g., “ppm” means parts per million by weight).

[0010] The term “solids weight” as used herein and in the appended claims in reference to the laundry detergent formulation and the alcohol ethoxysulfate surfactant of formula I means dry weight, i.e., excluding any water that may be present.

[0011] As used herein, unless otherwise indicated, the phrase "molecular weight" or Mw refers to the weight average molecular weight as measured in a conventional manner with gel permeation chromatography (GPC) and conventional standards, such as polyethylene glycol standards. GPC techniques are discussed in detail in Modern Size-Exclusion Liquid Chromatography - Practice of Gel Permeation and Gel Filtration Chromatography, Second Edition, A.M. Striegel, W. W. Yau, J. J. Kirkland, D. D. Bly; John Wiley & Sons, Inc. 2009. Molecular weights are reported herein in units of Daltons, or equivalently, g / mol.

[0012] Preferably, the laundry detergent formulation of the present invention, comprises: water (preferably, 43 to 94.9 wt% (more preferably, 45 to 94 wt%; still more preferably, 57.5 to 85 wt%; most preferably, 70 to 75 wt%), based on weight of the laundry detergent formulation, of water); an alcohol ethoxysulfate surfactant of formula I (preferably, 0.01 to 35 wt% (more preferably, 0.1 to 20 wt%; still more preferably, 1 to 15 wt%; most preferably, 2.5 to 10 wt%), based on weight of the laundry detergent formulation, of the alcohol ethoxysulfate surfactant of formula I)wherein each R1and R2is independently a Ci-16 alkyl group (preferably, a C1-15 alkyl group; more preferably, a C 1-14 alkyl group; most preferably, a linear C1-13); wherein the sum of the carbon atoms in R1and R2is 7 to 17 (preferably, 10 to 16; more preferably, 11 to 15; still more preferably, 11 to 13; most preferably, 11 or 13)(preferably, wherein R1and R2are linear alkyl groups; more preferably, wherein R1is a methyl group and R2is a linear C10-12 alkyl group; most preferably, wherein R1is a methyl group and R2is a linear C10 alkyl group); wherein M+is a cation balancing the negative charge of the -SCh’ anion in formula I (preferably, wherein M+is a cation selected from the group consisting of a nitrogen containing cation (e.g., an ammonium cation), a metal cation (e.g., an alkali metal cation, an alkaline earth metal cation), a boron containing cation and a phosphorous containing cation; more preferably, an ammonium cation, an alkali metal cation and an alkaline earth metal cation; still more preferably, an ammonium cation, a sodium cation and a calcium cation; most preferably, a sodium cation); and wherein is 1 in 95 to 100 mol% (preferably, 96 to 100 mol%; more preferably, 97 to 100 mol%; most preferably, 97.5 to 100 mol%) of the alcohol ethoxy sulfate surfactant of formula I (preferably, as determined using13C nuclear magnetic resonance characterization); a fabric softening silicone (preferably, 0.05 to 12 wt% (preferably, 0.1 to 10 wt%; more preferably, 1 to 7.5 wt%; most preferably, 3 to 7 wt%), based on weight of the laundry detergent formulation, of the fabric softening silicone); and a modified carbohydrate polymer (preferably, 0.5 to 10 wt% (preferably, 0.1 to 8 wt% (more preferably, 0.5 to 5 wt%; most preferably, 2 to 3 wt%), based on the weight of the laundry detergent formulation, of the modified carbohydrate polymer), comprising a cellulose ether base material functionalized with (i) quaternary ammonium moieties of formula IIwherein each R3is independently selected from the group consisting of a C1-7 alkyl group (preferably, a C1-4 alkyl group; more preferably, a methyl group and an ethyl group; most preferably, a methyl group) and wherein the modified carbohydrate polymer has a Kjeldahlnitrogen content, TKN, corrected for ash and volatiles, of 0.75 to 3 wt% (preferably, 1 to 2.75 wt%; more preferably, 1.25 to 2.5 wt%; most preferably, 1.4 to 2.4 wt%)(measured according to ASTM method D-2364); and (ii) hydrophobic substituents selected from the group consisting of a Ci6 alkyl group and a Ci6 alkyl glycidyl ether residue (preferably, a Ci6 alkyl group); wherein the modified carbohydrate polymer comprises 0.005 to 1.5 wt% (preferably, 0.1 to 1.1 wt%: more preferably, 0.3 to 0.8 wt%; most preferably, 0.4 to 0.6 wt%), based on weight of the cellulose ether base material, of the hydrophobic substituents (measured by GC- MS similar to ASTM method D-4794); wherein the quaternary ammonium moieties of formula II and the hydrophobic substituents are randomly distributed across the backbone of the cellulose ether base material; wherein the cellulose ether base material has a weight average molecular weight, Mw, of > 1,000,000 Daltons (preferably, 1,100,000 to 4,000,000 Daltons; more preferably, 1,200,000 to 2,000,000 Daltons; most preferably, 1,300,000 to 1,600,000 Daltons); and wherein the modified carbohydrate polymer comprises < 0.001 wt% (preferably, < 0.0001 wt%; more preferably, < 0.00001 wt%; most preferably, less than the detectable limit), based on weight of modified carbohydrate polymer, of crosslinking units.

[0013] Preferably, the laundry detergent formulation of the present invention, comprises: 43 to 94.9 wt% (preferably, 45 to 94 wt%; more preferably, 57.5 to 85 wt%; most preferably, 70 to 75 wt%), based on the weight of the laundry detergent formulation, of water. More preferable, the laundry detergent formulation of the present invention, comprises: 43 to 94.9 wt% (preferably, 45 to 94 wt%; more preferably, 57.5 to 85 wt%; most preferably, 70 to 75 wt%), based on the weight of the laundry detergent formulation, of water; wherein the water is at least one of distilled water, deionized water and industrial soft water. Still more preferably, the laundry detergent formulation of the present invention, comprises: 43 to 94.9 wt% (preferably, 45 to 94 wt%; more preferably, 57.5 to 85 wt%; most preferably, 70 to 75 wt%), based on the weight of the laundry detergent formulation, of water, wherein the water is distilled and deionized. Most preferably, the laundry detergent formulation of the present invention, comprises: 43 to 94.9 wt% (preferably, 45 to 94 wt%; more preferably, 57.5 to 85 wt%; most preferably, 70 to 75 wt%), based on the weight of the laundry detergent formulation, of a water, wherein the water is distilled, deionized and industrial soft to avoid introduction of undesirable metal ions to the laundry detergent formulation.

[0014] Preferably, the laundry detergent formulation of the present invention, comprises 0.01 to 35 wt% (preferably, 0.1 to 20 wt%; more preferably, 1 to 15 wt%; most preferably, 2.5 to 10 wt%), based on weight of the laundry detergent formulation, of an alcohol ethoxysulfate surfactant of formula I; wherein each R1and R2is independently a Ci-i6 alkyl group(preferably, a C1-15 alkyl group; more preferably, a C1-14 alkyl group; most preferably, a linear C1-13); wherein the sum of the carbon atoms in R1and R2is 7 to 17 (preferably, 10 to 16; more preferably, 11 to 15; still more preferably, 11 to 13; most preferably, 11 or 13)(preferably, wherein R1and R2are linear alkyl groups; more preferably, wherein R1is a methyl group and R2is a linear C10-12 alkyl group; most preferably, wherein R1is a methyl group and R2is a linear C10 alkyl group); wherein M+is a cation balancing the negative charge of the -SOy anion in formula I (preferably, wherein M+is a cation selected from the group consisting of a nitrogen containing cation (e.g., an ammonium cation), a metal cation (e.g., an alkali metal cation, an alkaline earth metal cation), a boron containing cation and a phosphorous containing cation; more preferably, an ammonium cation, an alkali metal cation and an alkaline earth metal cation; still more preferably, an ammonium cation, a sodium cation and a calcium cation; most preferably, a sodium cation); and wherein x is 1 in 95 to 100 mol% (preferably, 96 to 100 mol%; more preferably, 97 to 100 mol%; most preferably, 97.5 to 100 mol%) of the alcohol ethoxysulfate surfactant of formula I (preferably, as determined usingnC nuclear magnetic resonance characterization).

[0015] Preferably, the alcohol ethoxysulfate surfactant of formula 1 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; yet still 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 detectable limit), based on solids weight of the alcohol ethoxysulfate surfactant of formula I, of 1 ,4-dioxane (preferably, wherein the 1,4-dioxane content is measured by liquid injection low temperature gas chromatography-mass spectrometry method for organic layer and liquid chromatographymass spectrometry method for aqueous layer).

[0016] Preferably, the alcohol ethoxysulfate surfactant of formula I contains < 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%), based on solids weight of the alcohol ethoxysulfate surfactant of formula I, of an alcohol sulfate surfactant of formula IVwherein each R9and R10is independently a C1-16 alkyl group (preferably, a C1-15 alkyl group; more preferably, a C1-14 alkyl group; most preferably, a linear C1-13); wherein the sum of thecarbon atoms in R9and R10is 7 to 17 (preferably, 10 to 16; more preferably, 11 to 15; still more preferably, 11 to 13; most preferably, 11 or 13)(preferably, wherein R7and R8are linear alkyl groups; more preferably, wherein R9is a methyl group and R10is a linear C 10-12 alkyl group; most preferably, wherein R9is a methyl group and R10is a linear C10 alkyl group); and wherein A+is a cation balancing the negative charge of the -SO3" anion in formula IV (preferably, wherein A+is a cation selected from the group consisting of a nitrogen containing cation (e.g., an ammonium cation), a metal cation (e.g., an alkali metal cation, an alkaline earth metal cation), a boron containing cation and a phosphorous containing cation; more preferably, an ammonium cation, an alkali metal cation and an alkaline earth metal cation; still more preferably, an ammonium cation, a sodium cation and a calcium cation; most preferably, a sodium cation).

[0017] Preferably, the laundry detergent formulation of the present invention comprises an alcohol ethoxysulfate surfactant of formula I as described above, wherein the alcohol ethoxy sulfate surfactant of formula I has elevated thermal stability. More preferably, the laundry detergent formulation of the present invention comprises an alcohol ethoxysulfate surfactant of formula I as described above, wherein the alcohol ethoxysulfate surfactant of formula I has enhanced thermal stability. The term “elevated thermal stability” as used herein and in the appended claims means that the alcohol ethoxysulfate surfactant of formula I when heated to 110 °C 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), based on solids weight of the alcohol ethoxysulfate surfactant of formula I, of 1,4-dioxane (preferably, wherein the 1,4-dioxane content is measured by liquid injection low temperature gas chromatography-mass spectrometry method for organic layer and liquid chromatography-mass spectrometry method for aqueous layer). The term “enhanced thermal stability” as used herein and in the appended claims means that the alcohol ethoxy sulf ate surfactant of formula I when heated to 280 °C contains < 10 ppm, based on solids weight of the alcohol ethoxy sulfate surfactant of formula I, of 1,4-dioxane (preferably, wherein the 1,4-dioxane content is measured by liquid injection gas chromatography-mass spectrometry method for organic layer and liquid chromatographymass spectrometry method for aqueous layer).

[0018] Preferably, the laundry detergent formulation of the present invention, comprises: 0.05 to 12 wt% (preferably, 0.1 to 10 wt%; more preferably, 0.1 to 7.5 wt%; most preferably, 3 to 7 wt%), based on weight of the laundry detergent formulation, of a fabric softeningsilicone; wherein the fabric softening silicone is selected from the group consisting of a nitrogen free silicone polymer, an anionic silicone polymer, a nonionic silicone polymer and mixtures thereof. More preferably, the laundry detergent formulation of the present invention, comprises: 0.05 to 12 wt% (preferably, 0.1 to 10 wt%; more preferably, 0.1 to 7.5 wt%; most preferably, 3 to 7 wt%), based on the weight of the laundry detergent formulation, of a fabric softening silicone; wherein the fabric softening silicone is selected from the group consisting of a nitrogen free silicone polymer, an anionic silicone polymer, a nonionic silicone polymer and mixtures thereof; and wherein the fabric softening silicone is in the form of an emulsion (preferably, wherein the silicone emulsion is a nonionic emulsion of a high molecular weight polydimethylsiloxane, for example a Dimethicone (and) Laureth-4(and) Laureth-23).

[0019] Preferred nitrogen free silicone polymers include nonionic nitrogen free silicone polymers, zwitterionic nitrogen free silicone polymers, amphoteric nitrogen free silicone polymers and mixtures thereof. Preferred nitrogen free silicone polymers have formula V, VI or VII (preferably, formula V or VII):(VII) wherein each R4is independently selected from the group consisting of a C1-20 alkyl group, a C2-20 alkenyl group, a C6-20 aryl group, a C7-20 arylalkyl group, a C7-20 alkylaryl group, a C7-20 arylalkenyl group and a C7-20 alkenylaryl group (preferably, wherein R4is selected from the group consisting of a methyl group, a phenyl group and a phenylalkyl group); wherein eachR5is independently selected from the group consisting of a -OH group, a C1-20 alkyl group, a C2-20 alkenyl group, a C6-20 aryl group, a C7-20 arylalkyl group, a C7-20 alkylaryl group, a C7-20 arylalkenyl group, a C7-20 alkenylaryl group and a poly(ethyleneoxide / propyleneoxide) copolymer group having formula VIII-(CH2)„O(C2H4O)m(C3H6O)pR6(VIII) wherein each R6is independently selected from the group consisting of a hydrogen, a CM alkyl group and an acetyl group; wherein a has a value such that the viscosity of the nitrogen free silicone polymer according to formula V or formula VII is 2 to 50,000,000 centistokes at 20 °C (preferably, 10,000 to 10,000,000 centistokes at 20 °C); wherein b is 1 to 50 (preferably, 1 to 30); wherein c is 1 to 50 (preferably, 1 to 30); wherein n is 1 to 50 (preferably, 3 to 5); wherein m is 1 to 100 (preferably, 6 to 100); wherein p is 0 to 14 (preferably, 0 to 3); wherein m + p is 5 to 150 (preferably, 7 to 100) (preferably, wherein R5is selected from the group consisting of a -OH group, methyl group, a phenyl group, a phenylalkyl group and a group having formula VIII). Most preferred nitrogen free silicone polymers have formula VII, wherein R4is a methyl and wherein a has a value such that the viscosity of the nitrogen free silicone polymer is 60,000 to 5,000,000 centistokes at 20 °C.

[0020] Preferred nitrogen free silicone polymers include anionic silicone polymers. Anionic silicone polymers are described, for example, in The Encyclopedia of Polymer Science, volume 11, p. 765. Examples of anionic silicone polymers include silicones that incorporate carboxylic, sulphate, sulphonic, phosphate and / or phosphonate functionality. Preferred anionic silicone polymers incorporated carboxyl functionality (e.g., carboxylic acid or carboxylate anion). Preferred anionic silicone polymers have a weight average molecular weight of 1,000 to 100,000 Daltons (preferably, 2,000 to 50,000 Daltons; more preferably, 5,000 to 50,000 Daltons; most preferably, 10,000 to 50,000 Daltons). Preferably, the anionic silicone polymer has an anionic group content of at least 1 mol% (more preferably, at least 2 mol%). Preferably, the anionic groups on the anionic silicone polymer are not located on the terminal position of the longest linear silicone chain. Preferred anionic silicone polymers have anionic groups at a midchain position on the silicone. More preferred anionic silicone polymers have anionic groups located at least 5 silicone atoms from a terminal position on the longest linear silicone chain in the anionic silicone polymer.

[0021] Preferably, the laundry detergent formulation of the present invention comprises 0.5 to 10 wt% (preferably, 0.1 to 8 wt% (more preferably, 0.5 to 5 wt%; most preferably, 2 to 3 wt%), based on the weight of the laundry detergent formulation, of a modified carbohydrate polymer; wherein the modified carbohydrate polymer comprises a cellulose ether basematerial functionalized with (i) quaternary ammonium moieties of formula II; wherein each R3is independently selected from the group consisting of a C1-7 alkyl group (preferably, a Ci- 4 alkyl group; more preferably, a methyl group and an ethyl group; most preferably, a methyl group) and wherein the modified carbohydrate polymer has a Kjeldahl nitrogen content, TKN, of 0.75 to 3 wt% (preferably, 1 to 2.75 wt%; more preferably, 1.25 to 2.5 wt%; most preferably, 1.4 to 2.4 wt%)(measured according to ASTM method D-2364); and (ii) hydrophobic substituents selected from the group consisting of a Ci6 alkyl group and a Ci6 alkyl glycidyl ether residue (preferably, a Ci6 alkyl group); wherein the modified carbohydrate polymer comprises 0.005 to 1.5 wt% (preferably, 0.1 to 1.1 wt%; more preferably, 0.3 to 0.8 wt%; most preferably, 0.4 to 0.6 wt%), based on weight of the cellulose ether base material, of the hydrophobic substituents (measured by GC-MS similar to ASTM method D-4794); wherein the quaternary ammonium moieties of formula II and the hydrophobic substituents are randomly distributed across the backbone of the cellulose ether base material and are bonded to the cellulose ether base material through at least one of an ether linkage (e.g., an ether linkage alone or an ether linkage and a 2-hydroxypropyl group) and an ester linkage; wherein the cellulose ether base material is selected from the group consisting of hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose and mixtures thereof (preferably, hydroxy ethyl cellulose, hydroxypropyl cellulose and mixtures thereof; more preferably, hydroxyethyl cellulose); wherein the cellulose ether base material has a weight average molecular weight, Mw, of > 1,000,000 Daltons (preferably, 1,100,000 to 4,000,000 Daltons; more preferably, 1,200,000 to 2,000,000 Daltons; most preferably, 1,300,000 to 1,800,000 Daltons); wherein the modified carbohydrate polymer comprises < 0.001 wt% (preferably. < 0.0001 wt%; more preferably, < 0.00001 wt%; most preferably, less than the detectable limit), based on weight of modified carbohydrate polymer, of crosslinking units; and wherein the modified carbohydrate polymer contains < 0.1 moles (preferably, < 0.01 moles; more preferably, < 0.001 moles; most preferably, less than a detectable limit) of quaternary ammonium moieties having formal III per mole of the cellulose ether base materialwherein each R7is independently selected from a methyl group and an ethyl group and wherein R8is selected from a Cs-3o alkyl group.

[0022] Preferably, the modified carbohydrate polymer is of formula (IX)wherein y is determined based on the weight average molecular weight, Mw, of the cellulose ether base material; wherein R11is selected from the group consisting of an alkyl group having 16 carbon atoms and the residue of a Ci6 alkyl glycidyl ether; and wherein each R12is independently selected from the group consisting of a C1-7 alkyl group (preferably, a C1-4 alkyl group; more preferably, a methyl group and an ethyl group; most preferably, a methyl group); and wherein the cellulose ether base material has a weight average molecular weight, Mw, of > 1,000,000 Daltons (preferably, 1,100,000 to 4,000,000 Daltons; more preferably, 1,200,000 to 2,000,000 Daltons; most preferably, 1,300,000 to 1,800,000 Daltons); and wherein the modified carbohydrate polymer comprises < 0.001 wt% (preferably, < 0.0001 wt%; more preferably, < 0.00001 wt%; most preferably, less than the detectable limit), based on weight of modified carbohydrate polymer, of crosslinking units.

[0023] Preferably, the laundry detergent formulation of the present invention, further comprises an additional cleaning surfactant. More preferably, the laundry detergent formulation of the present invention further comprises 0.01 to 35 wt% (preferably, 0.1 to 20 wt%; more preferably, 1 to 15 wt%: most preferably, 2.5 to 10 wt%), based on weight of the laundry detergent formulation, of an additional cleaning surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants and mixtures thereof. Still more preferably, the laundry detergent formulation of the present invention further comprises 0.01 to 35 wt% (preferably, 0. 1 to 20 wt%; more preferably, 1 to 15 wt%; most preferably, 2.5 to 10 wt%), based on weight of the laundry detergent formulation, of an additional cleaning surfactant; wherein the additional cleaning surfactant includes an alkyl benzene sulfonic acid or salt thereof. Most preferably, the laundry detergent formulation of the present invention further comprises 0.01 to 35 wt%(preferably, 0.1 to 20 wt%; more preferably, 1 to 15 wt%; most preferably, 2.5 to 10 wt%), based on weight of the laundry detergent formulation, of an additional cleaning surfactant; wherein the additional cleaning surfactant includes a sodium salt of a linear alkyl benzene sulfonic acid.

[0024] Preferably, the laundry detergent formulation of the present invention, further comprises an additive. Preferably, the laundry detergent formulation of the present invention, further comprises an additive selected from the group consisting of a salt, a builder, an enzyme, a corrosion inhibitor, an acid, a bleaching agent, a bleaching catalyst, an abrasive, an antimicrobial agent, a chelating agent, a pH adjuster, a buffering agent, a rheology modifier, a structurant, a fragrance and mixtures thereof.

[0025] Preferably, the method of depositing silicone on cotton, comprising: providing a soiled cotton article of laundry; selecting a laundry detergent formulation of the present invention having a synergistic combination of an alcohol ethoxysulfate surfactant of formula I and a modified carbohydrate polymer; providing a bath water; and applying the bath water and the laundry detergent formulation to the soiled cotton article of laundry to provide a cleaned cotton article of laundry; wherein the fabric softening silicone is associated with the cleaned cotton article of laundry.

[0026] Some embodiments of the present invention will now be described in detail in the following Examples.Experimental MaterialsSynthesis SI: C12EO

[0027] A 3 liter (L) 3-neck glass round bottom flask, equipped with an overhead stirred through the center neck, reflux condenser and-a heating jacket was used for the etherification of 1 -dodecene and monoethylene glycol with the catalyst. To ensure good mixing, a pitch blade impeller was used for agitation. A reaction mixture of 551.7 grams (g) ethylene glycol and 505.8 g 1 -dodecene was prepared and loaded in the reactor together with 61-g catalyst in powdered form at 23 °C. The impeller stirring rate was set to be at 400 revolutions per minute (“rpm”). The reactor was heated to 135 °C in over the course of 30 minutes, held at 135 °C for 18 hours and then the reactor was cooled down to 23 °C by shutting off the heater. The reaction mixture was separated into a monoethylene glycol and catalyst phase and an olefin phase using a separation funnel.

[0028] A distillation apparatus was constructed using a 1 -liter round bottom flask connected to a short path distillation head with a thermometer adapter and a condenser with a vacuum adapter at the outlet. The distillation flask was heated in an aluminum block by an IKAheated stir-plate. The distillation pot was charged with the combined olefin phase and then stirring and vacuum were applied. Significant boiling was observed but no condensate was observed or collected. The temperature of the heating block was raised to 75 °C and unreacted dodecane was collected at a distillation head temperature of 25 °C to 50 °C and a pressure of 13.3-40 pascals (Pa). The heating block temperature was raised gradually to 140 °C and an intermediate fraction containing both monoether alcohol ethoxylates and dodecenes was recovered while the head temperature increased from 50 °C to 75 °C at a pressure of 13 Pa. The C 12EO was collected at a head temperature of 70 °C to 115 °C and a pressure of 6 Pa to 33 Pa. The heating block temperature was raised gradually to 200 °C and an intermediate fraction containing both monoether alcohol ethoxylates and diether was collected while the head temperature increased from 115 °C to 130 °C at a pressure of 6 Pa. The distillation was discontinued and the diether, which remained in the pot, was collected. The C12EO was carried to the next sulfation process to make sulfate anionic surfactant.Synthesis S2: C12EO Sulfate

[0029] All chemical manipulations were conducted under a dry nitrogen atmosphere. Prior to the experiment all glassware was heated in a laboratory oven to remove residual water. A 2-L three-neck round bottom flask was loaded with dichloromethane (500 mL) and C12EO prepared according to Synthesis SI (48.4 g, 0.21 mol, 1.0 equivalents). The reaction flask was equipped with an overhead mechanical stirrer, additional funnel, and thermocouple. Next, chlorosulfonic acid (14.5 mL, 0.221 mol, 1.1 equivalents) was carefully loaded into the additional funnel. The reaction flask was then submerged into an ice-bath and allowed to cool for 20 minutes, down to 0 °C. Once the reaction was cooled, chlorosulfonic acid was added to the reaction flask dropwise, at a rate of approx. 1.0 mL per minute, over approximately 20 minutes. During the addition of chlorosulfonic acid the reaction temperature did not exceed 5 °C. After the addition, the reaction was allowed to react, and the temperature was kept between 0 and 5 °C, for 3 hours. At this time, the reaction was neutralized by slow dropwise addition of an aqueous NaOH solution (18.0 g NaOH in 500 mL of water, 0.9 molar). The rate of addition was slow enough to not exceed 5 °C over the course of addition. The addition of the aqueous NaOH solution continued until the reaction became basic. The crude biphasic product was analyzed for dioxane content.Dichloromethane was then carefully removed from the crude biphasic product in vacuo. During the removal of the dichloromethane, a large amount of foam was observed. Upon removal of the dichloromethane, the remaining aqueous solution was placed in a freeze drier / lyophilizer to yield a purified secondary alcohol ethoxylate sulfate product, C12EOSulfate, as a whiteish solid (47.7 grams). The purified product was used for the performance and property testing.Synthesis S3: ALEO1 Sulfate

[0030] ALEO1 sulfate was prepared from ALEO1 in the same manner as described in Synthesis S2.Synthesis S4: SA3EO Sulfate

[0031] SA3EO sulfate was prepared from SA3EO in the same manner as described in Synthesis S2.Synthesis S5: Hydrophobically Modified Cellulose Ether Base Material

[0032] A 500 mL, four necked, round bottomed flask was charged with cellulose ether base material (27.3 g, CELLOSIZE™ QP-52,000H hydroxyethyl cellulose with weight average molecular weight of -1,600,000 Daltons available from The Dow Chemical Company), isopropyl alcohol (126.6 g) and deionized water (17.5 g). The flask was fitted with a nitrogen inlet connected to a 60 mL pressure equalizing addition funnel, rubber septum cap, a stirring paddle connected to an electric motor and a Claisen adaptor connected to a Friedrich condenser with a mineral oil bubbler outlet. The addition funnel was then charged with hexadecyl glycidyl ether (1.9 g) in isopropyl alcohol (7.5 g). The stirring paddle was engaged and the head space in the flask was purged with a slow, steady flow of nitrogen (one bubble per second) for one hour to remove any entrained oxygen. Then a 50% aqueous sodium hydroxide solution (1.6 g) was added dropwise to the flask contents over two (2) minutes. The flask contents were left to stir for an hour following addition of the 50% sodium hydroxide solution. The hexadecyl glycidyl ether in isopropyl alcohol solution in the addition funnel was then charged dropwise to the flask contents over three (3) minutes. The flask contents were left to stir for twenty (20) minutes following the addition of the hexadecyl glycidyl ether in isopropyl alcohol. Then heat was applied to the contents of the flask using a heating mantle. The flask contents were allowed to reflux with continued stirring under nitrogen for four and a half (4.5) hours. The flask was then placed in an ice water bath while maintaining a positive nitrogen pressure in the flask to cool the flask contents. The flask contents were then neutralized via the addition thereto of glacial acetic acid (3.0 g) using a syringe. The flask contents were left to stir for ten (10) minutes under nitrogen. The flask contents were then vacuum filtered through a large fritted metal Buchner funnel to recover the hydrophobically modified cellulose ether base material. The recovered hydrophobically modified cellulose ether base material was then washed in the Buchner funnel by stirring in the funnel for five (5) minutes with the specified wash solvents followed by vacuum removalof the wash liquor: deionized water (36 g) in isopropyl alcohol (164 g); deionized water (20 g) in isopropyl alcohol (180 g); and then isopropyl alcohol (200 g) for desiccation. To confer cold-water dispersibility on the final polymer, a 40% aqueous glyoxal (0.44 g) and acetic acid (0.14 g) were added to the final desiccation wash. The washed product hydrophobically modified cellulose ether base material was then briefly air dried and then dried overnight in vacuo at 50 °C. The dried product hydrophobically modified cellulose ether base material was then sieved through a #30 mesh US standard sieve and obtained as an off-white solid with a volatiles content of 3.0 %, an ash content (as sodium acetate) of 4.8%. The 1 % solution viscosity (corrected for ash and volatiles) was measured at 6.31 sec1using a TA Instruments DHR-3 rheometer equipped with a 40 mm, 2.0° stainless steel cone & plate sensor at 25.0 °C and was found to be 7,962 mPa-s. The degree of substitution of the hydrophobe, DShydrophobe, was measured to be 0.006.Synthesis S6: Hydrophobically / Cationically Modified Carbohydrate Polymer

[0033] A 500 mL, four necked, round bottomed flask was charged with hydrophobically modified cellulose ether base material prepared according to Synthesis S5 (14.6 g), isopropyl alcohol (155.9 g) and deionized water (28.1 g). The flask was fitted with a nitrogen inlet connected to a 20 mL pressure equalizing addition funnel, rubber septum cap, a stirring paddle connected to an electric motor and a Claisen adaptor connected to a Friedrich condenser with a mineral oil bubbler outlet. The addition funnel was then charged with 70% aqueous glycidyl trimethylammonium chloride (10.5 g, available from QU AB Chemicals under the trade name QU AB® 151). While stirring the flask contents, the apparatus was slowly purged with nitrogen for one hour to remove any entrained oxygen. After the nitrogen purge was completed, a 25% aqueous sodium hydroxide solution (1.8 g) was added to the flask contents with stirring under nitrogen through the serum cap using a plastic syringe over two minutes. After stirring for one hour, the contents of the addition funnel were added drop wise into the flask contents over three minutes. The flask contents were stirred under nitrogen for 20 minutes. Then heat was applied to the flask contents using the J-KEM controller with a set point temperature of 55 °C. The flask contents were left to reflux for 1.5 hours with stirring under nitrogen. The flask contents were then cooled to room temperature while maintaining a positive nitrogen pressure in the flask. The flask contents were then neutralized by adding glacial acetic acid (1.9 g) by syringe. After stirring for 10 minutes, cationic hydrophobically modified hydroxyethyl cellulose polymer (cationic hmHEC polymer) was recovered from the flask contents by vacuum filtration through a metal fritted Buchner funnel. The recovered cationic hmHEC polymer was then washed in the Buchnerfunnel once each with the following: a mixture of isopropyl alcohol (164 g) and deionized water (36 g), a mixture of isopropyl alcohol (180 g) and deionized water (20 g) and a mixture of isopropyl alcohol (200 g), 40% glyoxal (0.44 g) and glacial acetic acid (0.14 g). The cationic hmHEC polymer was then briefly air dried and dried overnight in vacuo at 50 °C. The dried cationic hmHEC polymer was then manually group using a mortar & pestle and screened through a #30 mesh US standard sieve to give 16.7 g of product cationic hmHEC polymer. The product cationic hmHEC polymer had a volatiles content of 2.67 %, an ash content of 2.26 % (as sodium chloride) and a Kjeldahl nitrogen content of 1 .51 %. The 1 % solution viscosity (corrected for ash and volatiles) was measured at 6.31 sec1using a TA Instruments DHR-3 rheometer equipped with a 40 mm, 2.0° stainless steel cone & plate sensor at 25.0 °C and was found to be 4,360 mPa-s.Syntheses S7: Hydroxy Ethyl Cellulose

[0034] A pressure vessel was fitted with a mechanical stirring paddle, a nitrogen inlet, a rubber serum cap, and a reflux condenser connected to a mineral oil bubbler. The vessel was charged with Biofloc 94 wood pulp (24.5 g; from Tembec Cellutions), isopropyl alcohol (223.2 g) and distilled water (31.8 g). While stirring the mixture, the vessel was purged with nitrogen for one hour to remove any entrained oxygen in the system. While stirring under nitrogen, 50% aqueous sodium hydroxide solution (14.2 g) was added dropwise over five minutes using a syringe. The mixture was then allowed to stir for 30 minutes under nitrogen. A charge of ethylene oxide (30. 1 g) was added to the reaction vessel with continuous stirring and sealed. The reaction was warmed to 75° C and stirred for one hour. The mixture was then cooled to room temperature, optionally viscosity adjusted by the addition of hydrogen peroxide, and neutralized with glacial acetic acid (11.1 g) and stirring for 10 minutes. The polymer product was recovered by vacuum filtration and washed in a Waring blender: five times with 250 mL of 4:1 (by volume) of acetone / water and twice with 250 mL of pure acetone. The polymer product was glyoxal-treated by adding 40% aqueous glyoxal (0.40 g) and of glacial acetic acid (0.25 g) to the last acetone desiccation. The polymer product was then dried in vacuo at 50° C overnight. The 2% aqueous viscosity of the product polymer (corrected for ash and volatiles) at 25.0° C was measured by Brookfield LVT, 30 rpm, spindle #4 at 500 mPa-s and had a weight average molecular weight of 400,000 Daltons.Syntheses S8-S9: Cationically Modified Carbohydrate Polymer

[0035] A 500 mL, four-necked, round-bottomed flask fitted with a 60 ml pressure-equalizing addition funnel connected to a nitrogen inlet, a rubber serum cap, a stirring paddle and electric motor, and a Claisen adaptor connected to a subsurface thermocouple connected to aJ-KEM controller, and a Friedrich condenser connected to a mineral oil bubbler was charged with A g of hydroxyethyl cellulose prepared according to Synthesis S7, B g of isopropyl alcohol and C g of deionized water. The 60 ml pressure-equalizing addition funnel was then charged with D g of 70% aqueous QUAB 151 (glycidyl trimethylammonium chloride). While stirring the flask contents, the head space of the flask was purged with a steady flow of nitrogen at about one bubble per second for one hour to remove any entrained oxygen. The values for A-D are provided in TABLE 1.

[0036] With continued stirring under nitrogen, 7.3 g of 25% aqueous sodium hydroxide solution was then added dropwise to the contents of the flask using a plastic syringe over about 1 minute. The flask contents were then allowed to stir for 30 minutes before the QUAB 151 in the addition funnel was added dropwise to the flask contents over 5 minutes. The flask contents were then allowed to stir for 10 minutes under nitrogen, then the temperature set point on the J-Kem controller was set to 55 °C and the heating mantle was applied to the flask. With continued stirring under nitrogen, the flask contents were maintained at 55 °C for 3 hours.

[0037] Then the flask contents were cooled by placing the flask in a cold water bath while maintaining a positive nitrogen pressure in the flask. The flask contents were then neutralized by adding 3.2 g of glacial acetic acid to the flask contents using a syringe and allowing the flask contents to stir for 10 minutes. The flask contents were then vacuum filtered through a large fritted Buchner funnel. The filter cake was washed three times in the Buchner funnel by stirring in the funnel for three minutes with the specified wash solvent for each washing followed by vacuum removal of the wash liquor: first wash was with a wash solvent mixture of 246 g of isopropyl alcohol and 54 g of distilled water, the second wash was with a wash solvent mixture of 270 g of isopropyl alcohol and 30 g of distilled water, and the third wash was with a wash solvent mixture of 300 g of isopropyl alcohol containing 0.4 g of 40% glyoxal and 0.1 g of glacial acetic acid. The product modified hydroxyethyl cellulose wash then recovered by vacuum filtration, briefly air dried, and then dried overnight in vacuo at 50 °C.

[0038] The product modified hydroxyethyl cellulose obtained was evaluated for Kjeldahl nitrogen content (corrected for ash and volatiles), TKN, with the result provided in TABLE 1.TABLE 1Active Sulfate (EO-O) Content of Surfactants

[0039] The active sulfate concentration in the surfactants noted in TABLE 2 was determined using a procedure modification of Tumey, M.E., Cannell, D.W. Alkaline methylene blue method for determination of anionic surfactants and for amine oxides in detergents. J. Am. Oil Chem. Soc., 42, 544-46 (1965) and Epton, S.R. A new method for the rapid titrimetric analysis of sodium alkyl sulphates and related compounds. Trans. Faraday Soc., 44, 226-30 (1948).Determination of Moles of Hyamine

[0040] Sodium Dioctyl Sulfosuccinate (SDOSS), Control Solution: A 20 mL scintillation vial was loaded with 0.8 g (± O.lmg) of sodium dioctyl sulfosuccinate of known purity (>99%). The vial was filled with 10 mL of deionized water and was transferred to a 250 mL volumetric flask. This process was repeated 3-5 times to ensure the sample was transferred. Once the transfer was complete, the sample was diluted to 250 mL with deionized water. The flask was then stoppered, and the solution was thoroughly mixed by repeatedly inverting the flask.

[0041] Methylene Blue Chloride Solution: A 20 mL scintillation vial was loaded with 0.050 g (± 0.005) of methylene blue chloride. The vial was filled with 10 mL of deionized water and was transferred to a 1 L graduated cylinder. This process was repeated 3-5 times to ensure the sample was transferred. The methylene blue solution was then diluted to 1 L with deionized water. This solution was then transferred to a 2 L glass jug. Once transfer was complete, 10 mL of concentrated sulfuric acid and 50 g of anhydrous sodium sulfate was carefully added to the methylene blue solution and mixed thoroughly.

[0042] Hyamine 1622 Solution: A 20 mL scintillation vial was loaded with 1.1 grams of Hyamine 1622. The vial was filled with 10 mL of deionized water and was transferred to a 1 L volumetric flask. This process was repeated 3-5 times to ensure the sample was transferred. The sample was then diluted to 1 L with deionized water. The solution was thoroughly mixed by repeatedly inverting the flask and was then filtered into a 1 L glass bottle.

[0043] Standardization of Hyamine Solution: A 100 mL glass bottle was loaded with 5 mL of the sodium dioctyl sulfosuccinate solution via pipette. Next, 20 mL of methylene blue chloride solution and 25 mL of chloroform was added via pipette. The 100 mL bottle was capped and shaken thoroughly for several seconds. Hyamine 1622 solution was then titrated into the methylene blue / chloroform biphasic mixture at 0.5 mL increments. After each addition the bottle was capped and shaken vigorously. The additions of Hyamine 1622, in0.5 mL increments, were continued until the blue color in the chloroform layer (or lower layer) began to migrate to the upper layer. At this point, the incremental additions of Hyamine 1622 were decreased to 0.1 mL and continued until the endpoint is reached. The endpoint was reached when the blue color intensity of both layers was matched. This standardization was completed in triplicate. The moles of the Hyamine 1622 was then calculated using the following formulawherein MOIH is the moles of hyamine; CSyoiis the volume of control solution tested (i.e., 5 mL); CSmass is the total grams of control (SDOSS) added to the control solution (g); Hcsvoi is the amount of hyamine solution required to reach the endpoint (mL); GS'mv is the molecular weight of the control solution, SDOSS (i.e., 444.56 g / mol).Determination of active sulfate in surfactants

[0044] A 20 mL scintillation vial was loaded with 0.9 to 1. 1 grams of surfactant sample, weighed to the nearest 0.1 mg. The vial was then filled with 10 mL of deionized water and transferred to a 250 mL volumetric flask. This process was repeated 3-5 times to ensure the sample was transferred. Once the transfer was complete, the sample was diluted with deionized water to 250 mL. The flask was then stoppered, and the solution was thoroughly mixed by repeatedly inverting the flask. Next, a 100 mL glass bottle was loaded with 5 mL of the test sample solution via pipette. The 100 mL glass bottle was then loaded with 20 mL of the methylene blue solution and 25 mL of chloroform via pipette. The glass bottle was capped and shaken vigorously for several seconds. Hyamine 1622 solution was then titrated into the methylene blue / chloroform biphasic mixture at 0.5 mL increments. After each addition the bottle was capped and shaken vigorously. The additions of Hyamine 1622, in 0.5 mL increments, was continued until the blue color in the chloroform layer (or lower layer) began to migrate to the upper layer. At this point, incremental additions of Hyamine 1622 were reduced to 0.1 mL and continued until the endpoint was reached. The endpoint being the point at which the color intensity of both layers was matched. Each sample was repeated in triplicate. The percent active sulfate content (wt%) was calculated using by the following formula: 100wherein Hsvoi is the amount of Hyamine solution required to reach the endpoint (mL); MOIH is the moles of Hyamine (determined from standard solution described above); SMW is theweight average molecular weight of surfactant (g / mol); Svoi is the volume of surfactant tested (i.e., 5 mL); Smass is the total grams of surfactant added to 250 mL solution (g). The results are provided in TABLE 2.EQ Distribution of Surfactants

[0045] The distribution of EO adducts in the surfactants listed in TABLE 2 was determined by NMR or UHPLC-MS as noted using the methodology set forth below with the results provided in TABLE 2.Nuclear Magnetic Resonance EO Distribution Characterization (NMR)

[0046] Samples of surfactant to be analyzed were prepared by dissolving the surfactant in deuterated dimethyl sulfoxide containing 0.025 M chromium (III) acetylacetonate. Nuclear magnetic resonance (13C NMR) spectra of the samples were then collected on a Bruker AVANCE 400 MHz spectrometer equipped with a 10 mm cryo-probe set to 25 °C, with the following parameters: a 90°-pulse, inverse-gated decoupling, a 1.38 second acquisition time, and a 6.4 second recycle delay. 2048 scans were collected. The data was processed in MNOVA, and the chemical shifts were referenced to the solvent peak at 39.52 ppm. A DEPT-135 experiment was also acquired with the same parameters, but with a 2.0 second recycle delay, and 2048 scans. The ratios of different EO adducts are calculated by integrating and comparing the intensity of the ethylene oxide alcohol end groups from about 60-61 ppm, the ethylene oxide backbone groups from about 69-70 ppm, the ethylene oxide end group ether peak from about 71-72 ppm, the unreacted primary alcohol peaks from about 60-61 ppm, and the unreacted secondary alcohol peaks from about 65-66 ppm.Sodium lauryl ether sulfate analysis by UHPLC-MS

[0047] Ultra high performance liquid chromatography-mass spectrometry (UHPLC-MS) conditions:

[0048] Procedure: The compositions containing commercial surfactants were analyzed by ultra-high performance liquid chromatography mass spectrometry (UHPLC-MS) with electrospray ionization (ESI). For the analysis, stock solutions were prepared at concentrations of 25 ppm in a 50 / 50 mixture of methanol / water. The alcohol ethoxylate samples were diluted 1 :100 in 50 / 50 methanol / water in duplicate and vortexed for a few seconds. Then they were diluted 1:10 in 50 / 50 methanol / water to give a final dilution of 1 : 1 ,000. Ethal® LA-4 was the standard used for the commercial 1 -mole sodium laureth sulfate and Ethal® LA-7 was the standard used for the commercial 3 -mole sodium laureth sulfate. Calibration standards were prepared at 10 ppm, 5 ppm, 2 ppm and 1 ppm in 50 / 50 methanol / water.

[0049] Alkyl sulfates were diluted from the 1 : 1,000 preparation in 50 / 50 methanol / water to give a final solution of 1:20,000. POLYSTEP® B-N-5 was used as the standard for the alkyl sulfate analysis. Standards were prepared in 50 / 50 methanol / water at concentrations of 5 ppm, 2 ppm, 1 ppm and 0.5 ppm.

[0050] The samples were analyzed using a Waters ACQUITY® UPLC system equipped with a Waters BEH Cl 8 1.7 pm 1 x 50 mm column. Mass spectrometry was conducted using a Waters LCT Premier TOF Mass Spectrometer with ESI. Measurements were conducted in both positive and negative ion mode. Each sample preparation was injected three times foranalysis. The ratios of the different EO adducts were calculated by the peak area and are reported in TABLE 2.TABLE 2

[0051] At least 95 mol% of the oligomers of the product of Synthesis S2 had an n of 1 and no more than 5 mol% the oligomers have an n of > 2. Specifically, > 98 mol% of the oligomers of the product of Synthesis S2 had an n of 1 and < 2 mol% of the oligomers had an n of > 2.1,4-Dioxane Content of Surfactants

[0052] The 1,4-dioxane content in the surfactants listed in TABLE 3 was determined by liquid injection low temperature gas chromatography-mass spectrometry (GC-MS) method for organic layer and liquid chromatography-mass spectrometry (LC-MS) method for aqueous layer as noted using the methodology set forth below with the results provided in TABLE 3.

[0053] Gas chromatography-Mass spectrometry (GC-MS) conditions for organic layer 1 ,4-dioxane measurement:

[0054] Standards were prepared by adding dioxane in tetrahydrofuran (“THF”) and diluting down to 0.1-100 ppm.

[0055] Samples were prepared by mixing 3.3 g from the organic (DCM) layer of the crude process mixture and 6.7 g of THF, the solution was then allowed to shake for about 20 minutes. The solids were then centrifuged to the bottom and the supernatant was vialed in an autosampler vial. Spiked samples were prepared by spiking dioxane standard in THF into separate samples at 5-10 ppm.

[0056] Liquid chromatography-mass spectrometry (LC-MS) conditions for aqueous layer 1 ,4-dioxane content measurement:

[0057] Samples were injected neat or diluted with water 1 :4. Standards were prepared by preparing a dioxane in THF stock solution and the diluting down with water to 0.1-100 ppm.Calculation of Dioxane Content Relative to Solids

[0058] The ppm of dioxane content relative to solids content in the sample is calculated according to the following equation.Concentration of Dioxane in Solution Hr^or ppM ) * Total Reaction Volume (L)- — - - - x 10Theoretical Yield of product (mg)6T BLE 3

[0059] The gas chromatography results for the SA3EO sulfate surfactant indicate 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 indicates the potential for structures having n > 2 to produce 1,4-dioxane. Interestingly, when the inlet temperature was increased to 280 °C, the dioxane content of SA3EO sulfate increased from 2 ppm to 1,471 ppm 1 ,4-dioxane in the organic phase. This result indicates that sulfated surfactants having n > 2 may develop observable 1,4-dioxane at 110 °C, but also that such surfactants may be unstable at elevated temperatures of 280 °C which could result in significant 1,4-dioxane formation. Similarly to SA3EO sulfate, gas chromatography results for the ALEO1 sulfate surfactant indicate the formation of > 9 ppm of 1,4-dioxane relative to the solids at 110 °C. Further, the ALEO1 sulfate surfactant also exhibited a large generation of 1,4-dioxane (259 ppm) at 280 °C, suggesting that the ALEO1 sulfate surfactant lacks stability at high temperatures. The inventive C12EO sulfate surfactant with > 95 mol% having n of 1 and < 5 mol% having n > 2 demonstrates a low 1 ,4-dioxane content. Surprisingly, the inventive C12EO sulfate surfactant also demonstrates an extremely low 1 ,4-dioxane content and falls below the limitof detection (LOD) of the GC and LC methods. Using the LOD as a basis, this indicates that the dioxane content for the C12EO sulfate is < 1.6 ppm relative to solids, at 110 °C. Interestingly, the inventive C12EO sulfate, when the inlet temperature is increased to 280 °C, the 1,4-dioxane content of the material is still less than 1 ppm (i.e., 0.58 ppm), which indicates that the inventive C12EO sulfate has increased thermal stability relative to the comparative materials.Comparative Examples CF1-CF7 and Example Fl: Laundry Detergent Formulations

[0060] Laundry detergent formulations of Comparative Examples CF1-CF7 and Example Fl were prepared by mixing together the components in the weight proportions noted in TABLE 4 adjusted to pH 8 (as necessary) with sodium hydroxide.TABLE 4Silicone Deposition Onto Cotton Fabric

[0061] The silicone deposition onto cotton fabric from laundry detergent formulations prepared according to Comparative Examples CF1-CF7 and Example Fl was quantified using X-ray photoelectron spectroscopy (XPS), which gives a quantitative elemental and chemical state information from the top 10 nm of the cotton fabric.

[0062] Cotton fabric was cut into 0.5 inch diameter disks using a circular die and arbor press. Then 20 mL of 200 ppm (3:1 Ca2+:Mg2+) water was added to a separate 25 mL vial for each one of the laundry detergent formulations. A magnetic stir bar was added to each vial along with 0.2 g of a laundry detergent formulation prepared according to Comparative Examples CF1-CF7 and Example Fl to form a wash solution. The vials were placed on a 15 positionstir plate set to stir at 300 rpm. Three cotton disks were added to each vial and were allowed to agitate in the wash solution for 16 minutes. The cotton disks were then moved to fresh 25 mL vials with 20 mL of 200 ppm (3: 1 Ca2+:Mg2+) water and a stir bar. The fresh vials were left to agitate for 3 minutes to rinse the cotton disks. The cotton disks were then removed from the vials and allowed to dry on a metal rack. The dry cotton disks were then sealed in clean 25 mL vials. The cotton disks were then evaluated for silicone deposition using XPS. The instrument parameters used are provided in TABLE 5. The mol% of the silicon from the laundry detergent formulation deposited on the cotton disks is reported in T BLE 6.TABLE 5TABLE 6

Claims

We claim:

1. A laundry detergent formulation comprising: water; an alcohol ethoxysulfate surfactant of formula Iwherein each R1and R2is independently a Ci-16 alkyl group; wherein the sum of the carbon atoms in R1and R2is 7 to 17; wherein M+is a cation balancing the negative charge of the -SO3‘ anion of formula I; and wherein x is 1 in 95 to 100 mol% of the alcohol ethoxy sulfate surfactant of formula I; a fabric softening silicone; and a modified carbohydrate polymer, comprising a cellulose ether base material functionalized with (i) quaternary ammonium moieties of formula IIwherein each R3is independently selected from the group consisting of a C1-7 alkyl group and wherein the modified carbohydrate polymer has a Kjeldahl nitrogen content, TKN, corrected for ash and volatiles, of 0.75 to 3 wt%; and (ii) hydrophobic substituents selected from the group consisting of a Ci6 alkyl group and a Ci6 alkyl glycidyl ether residue; wherein the modified carbohydrate polymer comprises 0.005 to 1.5 wt%, based on weight of the cellulose ether base material, of the hydrophobic substituents; wherein the quaternary ammonium moieties of formula II and the hydrophobic substituents are randomly distributed across the backbone of the cellulose ether base material; wherein the cellulose ether base material has a weight average molecular weight, Mw, of > 1,000,000 Daltons; and wherein the modified carbohydrate polymer comprises < 0.001 wt%, based on weight of modified carbohydrate polymer, of crosslinking units.

2. The laundry detergent formulation of claim 1 , further comprising an additional cleaning surfactant; wherein the additional cleaning surfactant includes a sodium salt of a linear alkyl benzene sulfonic acid.

3. The laundry detergent formulation of claim 2, wherein R1is a methyl group and R2is a linear C 10-12 alkyl group.

4. The laundry detergent formulation of claim 3, wherein R2is a linear C10 alkyl group.

5. The laundry detergent formulation of claim 4, wherein the base carbohydrate polymer is a hydroxyethyl cellulose; and wherein the base carbohydrate polymer has a weight average molecular weight of 1,300,000 to 1,800,000 Daltons.

6. The laundry detergent formulation of claim 5, wherein each R3is a methyl; wherein the modified carbohydrate polymer has a Kjeldahl nitrogen content corrected for ash and volatiles, TKN, of 1.4 to 2.4 wt%; wherein the hydrophobic substituents are Ci6 alkyl groups; wherein the modified carbohydrate polymer comprises 0.4 to 0.6 wt%, based on weight of the cellulose ether base material, of the hydrophobic substituents.

7. The laundry detergent formulation of claim 6, wherein the laundry detergent formulation comprises:43 to 94.9 wt%, based on weight of the laundry detergent formulation, of water;0.01 to 35 wt%, based on weight of the laundry detergent formulation, of the alcohol ethoxy sulfate surfactant of formula I;0.05 to 12 wt%, based on weight of the laundry detergent formulation, of the fabric softening silicone;0.5 to 10 wt%, based on weight of the laundry detergent formulation, of the modified carbohydrate polymer; and0.01 to 35 wt%, based on weight of the laundry detergent formulation, of the additional cleaning surfactant.

8. The laundry detergent formulation of claim 7, wherein the laundry detergent formulation comprises:70 to 75 wt%, based on weight of the laundry detergent formulation, of water;2.5 to 10 wt%, based on weight of the laundry detergent formulation, of the alcohol ethoxy sulfate surfactant of formula I;3 to 7 wt%, based on weight of the laundry detergent formulation, of the fabric softening silicone;2 to 3 wt%, based on weight of the laundry detergent formulation, of the modified carbohydrate polymer; and2.5 to 10 wt%, based on weight of the laundry detergent formulation, of the additional cleaning surfactant.

9. A method of depositing silicone on cotton, comprising: providing a soiled cotton article of laundry; selecting a laundry detergent formulation of claim 1 having a synergistic combination of the alcohol ethoxysulfate surfactant of formula I and the modified carbohydrate polymer; providing a bath water; and applying the bath water and the laundry detergent formulation to the soiled cotton article of laundry to provide a cleaned cotton article of laundry; wherein the fabric softening silicone is associated with the cleaned cotton article of laundry.

10. The method of claim 9, wherein the selected laundry detergent formulation is of claim 8.

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