WO2017100051A2

WO2017100051A2 - Cold-water cleaning compositions and methods

Info

Publication number: WO2017100051A2
Application number: PCT/US2016/064146
Authority: WO
Inventors: Brian Holland; Branko Sajic; Randal J. Bernhardt; Xue Min Dong; Gregory P. Dado; Jeremy Aaron Weitgenant; Dennis S. Murphy; Michael R. Terry
Original assignee: Stepan Comapny
Priority date: 2015-12-07
Filing date: 2016-11-30
Publication date: 2017-06-15
Also published as: WO2017100051A3

Abstract

Compositions useful for cold-water cleaning are disclosed. The compositions comprise a detergent having at least one centrally located headgroup and two or more hydrophobic tails, wherein the headgroup and the tails may be joined by one or more linking groups. The headgroup may be a sulfonate, sulfate, ethoxylate, carboxylate, amine oxide, phosphate, quaternium, betaine, sulfobetaine, or combination thereof. The detergent may be an internal olefin sulfonate, a polyol ether sulfate, a dialkyi ester of a sulfonated dicarboxylic acid, or a variety of other compositions that share the common feature of a centrally located headgroup. Contrary to conventional wisdom, these compositions can provide exceptional performance in cold-water laundering of articles stained with greasy soils. In particular, combinations of the above compositions and linear alkylbenzene sulfonates effectively remove greasy stains such as beef tallow from soiled articles even at wash temperatures of 30°C or less.

Description

COLD-WATER CLEANING COMPOSITIONS AND METHODS

FIELD OF THE INVENTION

The invention relates to compositions useful for cold-water cleaning and related methods.

BACKGROUND OF THE INVENTION

Surfactants are essential components of everyday products such as household and industrial cleaners, agricultural products, personal care products, laundry detergents, oilfield chemicals, specialty foams, and many others.

Modern laundry detergents perform well in removing many kinds of soils from fabrics when warm or hot water is used for the wash cycle. Warmer temperatures soften or melt even greasy soils, which helps the surfactant assist in removing the soil from the fabric. Hot or warm water is not always desirable for washing, however. Warm or hot water tends to fade colors and may accelerate deterioration of the fabric. Moreover, the energy costs of heating water for laundry make cold-water washing more economically desirable and more environmentally sustainable. In many parts of the world, only cold water is available for laundering articles.

Of course, laundry detergents have now been developed that are designed to perform well in hot, warm, or cold water. One popular cold-water detergent utilizes a combination of a nonionic surfactant (a fatty alcohol ethoxylate) and two anionic surfactants (a linear alkylbenzene sulfonate ("NaLAS") and a fatty alcohol ethoxylate sulfate ("NaAES")) among other conventional components. Commercially available cold- water detergents tend to perform well on many common kinds of stains, but they have difficulty removing greasy dirt, particularly bacon grease, beef tallow, cooked beef fat, and the like. These soils are often deposited as liquids but quickly solidify and adhere tenaciously to textile fibers. Particularly in a cold-water wash cycle, the surfactant can be overmatched in the challenge to wet, liquefy, and remove these greasy, hardened soils.

According to conventional wisdom, locating a polar group at or near the central portion of a surfactant molecule results in poor detergency compared with locating the polar group at or near one end of the molecule. The belief is that surfactants with a higher degree of water solubility will be better able to clean. However, while this may be true when laundering articles in hot or warm water, in which oily soils more readily liquefy, the same is not true in cold water where oily soils such as beef tallow, bacon grease, or the like can crystallize and become fixed to fabrics. In cold water, solubility of the surfactant becomes less important than the ability of the surfactant to adhere to and liquefy the solidified stain.

Improved detergents are always in need, especially laundry detergents that perform well in cold water. Of particular interest are detergents that can tackle hydrophobic stains, e.g., bacon grease or beef tallow, because these stains solidify and adhere strongly to textile fibers. Ideally, the kind of cleaning performance on greasy dirt that consumers enjoy when using hot water could be realized even with cold water.

SUMMARY OF THE INVENTION

In one aspect, the invention relates to a composition useful for cold-water cleaning. The composition comprises a detergent having at least one centrally located headgroup and two or more hydrophobic tails, wherein the headgroup and the tails are optionally joined by one or more linking groups. In some aspects, the headgroup is a sulfonate, sulfate, ethoxylate, carboxylate, amine oxide, phosphate, quaternium, betaine, sulfobetaine, or combination thereof.

In some aspects, the detergent is an internal olefin sulfonate, a polyol ether sulfate, or a dialkyl ester of a sulfonated dicarboxylic acid.

In other aspects, the detergent is a sulfonated bis(C4-C2o alkyl-substituted aryl) ether, a sulfonated bisphenol C4-C20 dialkyl ether, a sulfonated C4-C20 alkyl-substituted arene, a sulfated polyol, a sulfated hydroxy-functional dendrimer, an alpha olefin sulfonate dimer, a cross-dimer of an alpha-olefin sulfonate and an olefin, a sulfonate of an unsaturated fatty ester, a vinylidene sulfonate, a sulfonated arene substituted with two or more C4-C20 alkyl ester or bis(C4-C2o alkyl) amide groups, a sulfonated arene substituted with one or more branched C4-C20 alkyl groups, a sulfonated C4-C20 diether or C4-C20 diester of catechol, resorcinol, or hydroquinone, a phosphate diester of a C4-C20 alcohol, a phosphate diester of a C4-C20 alcohol alkoxylate, a C1-C4 alkyl C4-C20 dialkylamine oxide, a C4-C20 dialkyl urea or carbamate of cystine, or a sulfonate- functionalized block copolymer comprising one or more recurring units selected from ethylene, propylene, butenes, isoprene, styrene, alkylated styrenes, butadiene, divinylbenzene, alkyl (meth)acrylates, and (meth)acrylic acid.

In other aspects, the invention relates to a laundering method. The method comprises laundering one or more textile articles in water having a temperature less than 30°C the presence of one of the inventive detergent compositions described above.

In still other aspects, the invention relates to a method of using the detergent compositions as a laundry pre-spotter or pre-soaker for cold-water manual or machine washing and to a method comprising using the compositions as an additive or booster component to improve the grease cutting or grease removal performance of a laundry product or formulation. Also included is a method which comprises liquefying a greasy soil in water at a temperature less than 30°C in the presence of the inventive detergent compositions.

We found that, contrary to conventional wisdom, compositions having at least one centrally located headgroup and two or more hydrophobic tails can provide exceptional performance in cold-water laundering of articles stained with greasy soils. Some of the detergent compositions work particularly well when they are used in combination with a linear alkylbenzene sulfonate. The general concept is validated herein with results using compositions comprising internal olefin sulfonates, polyol ether sulfates, and dialkyl esters of sulfonated dicarboxylic acids, each of which has a centrally located headgroup and two or more hydrophobic tails. Other classes of compounds have been identified that share this structural characteristic (e.g., sulfonated bisphenol C4-C20 dialkyl ethers or alpha-olefin sulfonate dimers), and these compounds should also provide benefits for detergents designed to be used for cold-water cleaning. The inventive compositions, which often utilize commercially available surfactants, deliver exceptional cleaning results on greasy soils, even in cold water. DETAILED DESCRIPTION OF THE INVENTION

In one aspect, the invention relates to compositions useful for cold-water cleaning. In particular, the compositions comprise a detergent having at least one centrally located headgroup and two or more hydrophobic tails. In preferred aspects, the headgroup and the tails are joined by one or more linking groups.

"Cold water" means water having a temperature less than 30°C, preferably from 5°C to 28°C, more preferably 8°C to 25°C. Depending on climate, sourced water will have a temperature in this range without requiring added heat.

"Centrally located headgroup" means a polar functional group, i.e., a functional group that includes one or more oxygen, nitrogen, sulfur, or phosphorus atoms, that is attached at or near the center of the molecule rather than at or near one end of the molecule. In most detergents, the polar group is located at a terminal carbon or at the penultimate carbon of a chain, and this has been thought to provide better solubility of the surfactant (and therefore better detergency). In contrast, the inventive detergents stand conventional thinking on its head by locating the headgroup centrally on the molecule. In some aspects, the centrally located headgroup is located at or near the center of the longest continuous alkyl chain.

The headgroup may be neutral or charged, but it is preferably positively or negatively charged. Suitable headgroups include, for example, sulfonate, sulfate, ethoxylate, carboxylate, amine oxide, phosphate, quaternium, betaine, sulfobetaine, and combinations thereof. Sulfate and sulfonate head groups are particularly preferred.

The detergents comprise two or more hydrophobic tails. By "hydrophobic tail," we mean a saturated or unsaturated, linear, branched or cyclic C4-C30 group, preferably a C5-C20 group. The tail can be substituted with other groups (halide, hydroxyl, trialkylsilyl, or the like) provided that the overall nature of the tail is hydrophobic. In preferred aspects, the tails consist of only carbon and hydrogen atoms.

The centrally located headgroup and the hydrophobic tails are optionally joined by one or more linking groups. A "linking group" is any multivalent moiety capable of connecting at least one centrally located headgroup to at least two hydrophobic tails. The linking group can be as simple a single carbon atom (e.g., a methine group) or it may comprise multiple atoms and have a variety of different functional groups. Suitable linking groups include, for example, saturated or unsaturated hydrocarbyl, monoester, diester, alcohol, ether, polyether, bisphenol, aryl, disulfide, amine, amide, or a combination thereof.

The general concept of a centrally located headgroup joined to two or more hydrophobic tails with an optional linking group is best illustrated with some specific, non- limiting examples. In sodium 8-hexadecyl sulfate, for instance, a single carbon is the linking group that joins the centrally located sulfate headgroup to hydrophobic Cz and Cs tails:

In sodium 2-hexyldecyl sulfate, the linking group is a two-carbon fragment (-CHCH2-) that joins the centrally located sulfate group to C6 and Cs hydrocarbyl groups. Guerbet alcohols are convenient starting materials for making the sulfate:

Similarly, in sodium 2-heptyldecyl sulfate, the linking group is a two- or three carbon fragment that joins the centrally located sulfate group to a pair of Cs hydrocarbyl groups. When n=1 , the alcohol precursors can be made by hydroformylation of internal olefins or by hydroboration/oxidation of the corresponding vinylidene compound. When n=2, the alcohol precursor can be made by hydroformylation of the vinylidene compound.

In the alpha-sulfonated ester shown below, the linking group is an acetic acid fragment (-CHCO2-) that joins the sulfonate group to a linear C10 chain and a 2-ethylhexyl group:

A residue of succinic acid is a convenient linking group to join a centrally located sulfonate group and a pair of hydrophobic tails, in this case, two 2-ethylhexyl groups. The sulfosuccinate is conveniently made by reacting maleic anhydride with 2 moles of the branched Cs alcohol, followed by sulfitation of the carbon-carbon double bond with sodium metabisulfite, then neutralization, all according to well-known methods:

In yet another example, the mixture of products formed in making an internal olefin sulfonate, i.e., the hydroxyalkane sulfonate and the alkene sulfonate shown as alternative products below are each characterized by a linking group that can be viewed as - CHCH(OH)- for the hydroxyalkane sulfonate or -CH-CH=CH- for the alkene sulfonate:

Polyol ether sulfates, such as glycerol 1 ,3-bis(dodecyl ether) sodium sulfate, have a three-carbon backbone derived from glycerol that serves as the linking group for the sulfate headgroup and the hydrophobic tails:

Itaconic acid is also a suitable linking group for a centrally located sulfonate headgroup and a pair of hydrophobic tails. The sulfonated itaconate ester (a sulfomethylsuccinate) is available from the reaction of itaconic anhydride with 2 moles of the branched Cs alcohol, followed by sulfitation of the vinylidene group using sodium metabisulfite and neutralization of the resulting sulfonic acid:

In some cases, there may be multiple centrally located headgroups, as in the sebacic acid derivative shown below:

Multiple hydrophobic tails can also be joined by a single linking group, as when pentaerythritol is the starting material and moiety that links a sulfate group and three hydrophobic tails:

In sum, it is apparent that there are many possible structures that can provide the required centrally located headgroup and at least two hydrophobic tails, optionally joined by one or more linking groups.

In some preferred aspects, the detergent is an internal olefin sulfonate (IOS), a polyol ether sulfate, or a dialkyl ester of a sulfonated dicarboxylic acid.

Suitable internal olefin sulfonates are compositions prepared by sulfonation of internal olefins. Usually, the internal olefins are mixtures of olefins within a particular carbon number range. Suitable internal olefin mixtures for making internal olefin sulfonates are commercially available, for example from Shell (Neodene® internal olefins). Commercially available carbon number ranges include C15-C18, C19-C23, C20-C24, and C24- C28. Shell also supplies internal olefin sulfonates made from these internal olefin mixtures under the Enordet™ mark. Preferred internal olefin sulfonates include lOSs prepared by sulfonating, for instance, C15-C18 or C20-C24 internal olefin mixtures.

In some aspects, the internal olefin sulfonate comprises a hydroxyalkane sulfonate, an alkene sulfonate, or a mixture thereof. As suggested earlier, sulfonation of internal olefins frequently produces a mixture of products that includes both alkene sulfonates and hydroxyalkane sulfonates. In some aspects, the detergent is a C15-C18 internal olefin sulfonate or a C20-C24 internal olefin sulfonate, and the composition further comprises a linear alkylbenzene sulfonate. As demonstrated in Table 6 below, we surprisingly found that these internal olefin sulfonates deliver outstanding performance in removing greasy stains when they are combined with a linear alkylbenzene sulfonate such as NaLAS. In contrast, performance was no better than the control formulation when these internal olefin sulfonates were paired with an alcohol ether sulfate surfactant such as NaAES.

In some aspects, the detergent is a cis- or trans- C18 internal olefin sulfonate, and the composition further comprises a linear alkylbenzene sulfonate or an alcohol ether sulfate. Metathesis of 1 -decene, for instance, provides primarily fra/is-9-octadecene. When the cis- isomer is desired, other chemistry such as the Wittig reaction can be used to generate it. Internal olefin sulfonates produced by sulfonating these C18 internal olefins have a centrally located headgroup and a pair of hydrophobic tails. As shown in Table 6, these IOS materials perform well in cold-water cleaning when used in combination with various anionic surfactants, particularly linear alkylbenzene sulfonates or alcohol ether sulfates.

In some aspects, the detergent is a polyol ether sulfate selected from glycerol bis(C4-C2o alkyl ether) sulfates, pentaerythritol tris(C4-C2o alkyl ether) sulfates, pentaerythritol bis(C4-C2o alkyl ether) disulfates, trimethylolpropane bis(C4-C2o alkyl ether) sulfates, trimethylolethane bis(C4-C2o alkyl ether) sulfates, polyglycerol bis(C4-C2o alkyl ether) mono- and disulfates, dipentaerythritol tetrakis(C4-C2o alkyl) mono- and disulfates, and combinations thereof. In preferred aspects, the alkyl groups of the polyol ether sulfate are Cs-C moieties or C6-C10 moieties.

In some preferred aspects, the polyol ether sulfate is a glycerol bis(C6-Cio alkyl ether) sulfate or a pentaerythritol tris(Cs-C6 alkyl ether) sulfate.

Suitable polyol ether sulfates are produced from polyols (glycerol, trimethylolpropane, pentaerythritol, and the like) or their synthetic equivalents (for example, epichlorohydrin as a synthon for glycerol) and fatty alcohols or their synthetic equivalents (e.g., alkyl halides) to generate polyol ethers, followed by sulfation of any free hydroxyl groups. In other aspects, the detergent comprises a polyol ether sulfate and a linear alkylbenzene sulfonate or an alcohol ether sulfate. As shown in Table 3, excellent results in cold-water cleaning can be obtained with polyol ether sulfates and either NaLAS or NaAES. Some polyol esters may require reformulation or other cosurfactants to show an advantage for cold water cleaning; for instance, our limited work with pentaerythritol tris(2- ethylhexyl ether) sodium sulfate did not demonstrate an advantage when this surfactant was combined with either NaLAS or NaAES.

Suitable dialkyi esters of sulfonated dicarboxylic acids have C4-C20 alkyl groups as the hydrophobic tails, at least one sulfonic acid headgroup, and a dicarboxylic acid residue that serves as the linking group. The dicarboxylic acids are preferably C3-C12 saturated or unsaturated, linear or branched, dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, itaconic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. There may be one or two sulfonate groups, and they are preferably located in an alpha or beta position, preferably the alpha position, relative to a carbonyl group.

In some aspects, the detergent is a dialkyi sulfosuccinate or a dialkyi sulfomethylsuccinate, such as a C4-C14 dialkyi sulfosuccinate or sulfomethylsuccinate. The sulfosuccinates are succinic acid dialkyi esters having a sulfonate salt group on a carbon alpha to an ester group. The sulfomethylsuccinates are dialkyi esters of methylsuccinic acid in which a sulfonate salt group replaces one hydrogen atom of the original methyl group. The alcohol portion of the alkyl sulfosuccinate or sulfomethylsuccinate ester can have the same or different numbers of carbons. In some aspects, the dialkyi sulfosuccinate or sulfomethylsuccinate is a Ce to C12 dialkyi sulfosuccinate or sulfomethylsuccinate. Preferably, the dialkyi sulfosuccinate or dialkyi sulfomethylsuccinate is a Cs to C10 dialkyi sulfosuccinate or sulfomethylsuccinate. In other preferred aspects, the dialkyi sulfosuccinate or sulfomethylsuccinate is a Cs dialkyi sulfosuccinate or sulfomethylsuccinate. A minor proportion of disulfonated material can be present; preferably, the alkyl sulfosuccinate or sulfomethylsuccinate is monosulfonated.

In some aspects, the C4-C14 alkyl sulfosuccinate has the formula:

wherein each of R¹ and R² is independently a linear, branched, or cyclic saturated or unsaturated C4-C14 alkyl group, and M is solubilizing cation, preferably an alkali metal or an ammonium ion. In other aspects, M may be an alkaline earth metal cation that is coordinated to two dialkyi sulfosuccinate anions (or both sulfonate groups of a disulfonated material):

In some aspects, the C4-C14 alkyl sulfomethylsuccinate has the formula:

wherein each of R¹ and R² is independently a linear, branched, or cyclic saturated or unsaturated C4-C14 alkyl group, and M is solubilizing cation, preferably an alkali metal or an ammonium ion. In other aspects, M may be an alkaline earth metal cation that is coordinated to two dialkyi sulfomethylsuccinate anions. Suitable C4-C14 dialkyl sulfosuccinates are commercially available from Stepan Company under the Stepwet® mark (e.g., Stepwet® DOS 70), from Cytec under the Aerosol® mark, from Dow under the Triton™ mark, from AkzoNobel under the Lankropol® mark, and from Huntsman under the Surfonic® mark. Dioctyl sulfosuccinates such as sodium bis(2-ethylhexyl) sulfosuccinate are most commonly available and are preferred for use herein.

Dialkyl sulfosuccinates can also be synthesized using well-known methods. For instance, they can be made by directly esterifying sulfosuccinic acid (or its salts) with excess C4 to C alcohol (see, e.g., U.S. Pat. No. 2,028,091 ). In another approach, a maleate or fumarate diester is first made by reacting two equivalents of the C4-C14 alcohol with maleic anhydride or fumaric acid. This is converted to the dialkyl sulfosuccinate by reacting the maleate or fumarate diester with sodium bisulfite (NaHSO3) or sodium metabisulfite (Na2S2Os). See, e.g., U.S. Pat. Nos. 2,028,091 and 2,813,078; EP 8771 1 ; GB 565,675; GB 1 ,215,561 ; and GB 1 ,527,020. The teachings of U.S. Pat. Nos. 2,028,091 and 2,813,078 related to dialkyl sulfosuccinate preparation are incorporated herein by reference.

Suitable C4-C14 dialkyl sulfomethylsuccinates can be prepared using a modified version of the procedure described in U.S. Pat. No. 8,853,141 , the teachings of which are incorporated herein by reference, for making monoalkyl sulfomethylsuccinates. For instance, itaconic acid or itaconic anhydride can be reacted with an excess of an alcohol to give a dialkyl itaconate ester, followed by sulfitation of the vinylidene group to give the desired dialkyl sulfomethylsuccinate.

In a preferred aspect, the detergent is a C4-C20 dialkyl sulfomethylsuccinate, and the composition further comprises a linear alkylbenzene sulfonate or an alcohol ether sulfate.

In some aspects, the detergent is a C10-C14 dialkyl ester of a mono- or disulfonated C8-C12 dicarboxylic acid. In preferred aspects, the composition further comprises a linear alkylbenzene sulfonate. We found, for instance, that bis(2-butyloctyl) sebacate disodium α,α'-disulfonate provides an improvement in cold-water cleaning compared with the control when combined with NaLAS, but no improvement was seen when the disulfonate was coupled with NaAES (see Table 3). In some aspects, the detergent is a secondary alkyl sulfate. Suitable secondary alkyl sulfates are well known and are commercially available from WeylChem (e.g., Hostapur^® SAS-30LS or Hostapur^®SAS-60) or other suppliers. The secondary alkyl sulfates can be made by sulfoxidation of n-paraffins using sulfur dioxide, oxygen, water, and ultraviolet radiation, followed by separation of sulfonic acids from unreacted paraffins, neutralization, and further purification to remove paraffins. Secondary alkyl sulfates generally have randomly distributed sulfonate groups along the carbon backbone.

In preferred aspects, the composition further comprises a linear alkylbenzene sulfonate. As shown in Table 6, we surprisingly found that secondary alkyl sulfates provide excellent cold-water cleaning performance when they are used in combination with NaLAS, but the same performance advantages are not seen when secondary alkyl sulfates are coupled with NaAES. Although some of the headgroups in secondary alkyl sulfates may not be centrally located, there may be enough centrally located headgroups present to promote good cold-water cleaning performance when the surfactant is coupled with NaLAS.

In some aspects, the detergent is a sulfonated bis(C4-C2o alkyl-substituted aryl) ether. Such compositions have two or more aromatic rings joined by an oxygen. Each of the aromatic rings is substituted with at least one C4-C20 alkyl group. At least one of the aromatic rings, preferably both, is sulfonated. This provides a centrally located headgroup and hydrophobic tails with the diaryl ether as the linking group. For example:

R = C -C₂₀ alkyl

In some aspects, the detergent is a sulfonated bisphenol C4-C2o dialkyl ether. The bisphenol moiety, which serves as the linking group for the sulfonate group or groups and the hydrophobic tails, can be any bisphenol such as bisphenol A, bisphenol F, bisphenol S, bisphenol AP, bisphenol B, bisphenol G, bisphenol E, or the like. One or both of the aromatic rings can be sulfonated. An exemplary monosulfonated structure based on bisphenol A is shown below:

R = C₄-C₂₀ alkyl

In some aspects, the detergent is a sulfonated C4-C20 alkyl-substituted arene. Preferably, two or more alkyl groups are attached to the sulfonated aromatic ring. For example:

R, R', R" = C4-C20 alkyl

In some aspects, the detergent is a sulfated polyol. The polyol may be, for example, a tetrafunctional block copolymer having primary or secondary hydroxyl groups, such as Tetronic^® polyols (product of BASF). Sulfation of the polyols with one or more equivalents of a sulfating agent can provide a polymeric composition having a central concentration of headgroups and multiple hydrophobic tails.

In some aspects, the detergent is a sulfated hydroxy-functional dendrimer.

Dendrimers are repetitively branched molecules having a tree-like structure with a central core, interior branching, and an exterior surface having functional groups. When the surface has hydroxyl functionality, some of the hydroxyl groups can be sulfated to provide compositions that may have value as components of cold-water cleaning compositions.

By varying the degree of sulfation, different performance qualities can be achieved and regulated.

In some aspects, the detergent is an alpha-olefin sulfonate dimer. Alpha-olefin sulfonate dimers are well known for use in oilfield applications. Dimerization of alpha- olefin sulfonic acid (AOS acid) is described, for example, in U.S. Pat. Nos. 3,721 ,707 and 3,951 ,823. Briefly, AOS acid produced by sulfonation of one or more alpha-olefins, is heated at 1 10°C to 200°C to induce oligomerization. Under these conditions, intermediate sultones and alkene sulfonic acids are converted to alkane sulfonic acids and other products. The molecular weight of the product is roughly double that of the AOS acid, and hence the term "AOS dimer acid" to describe it. However, the structure of the product can be rather complex, as illustrated in the 707 patent. Neutralization with base provides the desired alpha-olefin sulfonate dimer. Alpha-olefin sulfonate dimers will normally have two centrally located sulfonate headgroups and a pair of hydrophobic tails.

In some aspects, the detergent is a cross-dimer of an alpha-olefin sulfonate and an olefin. The "cross-dimer" is an addition reaction product of (a) AOS acid; and (b) an unsulfonated olefin or unsulfonated olefin precursor. A cross-dimer can be made, for instance, by reacting AOS acid with 1 -octene or 1 -decene, followed by neutralization to give the sulfonate composition. The major component of this reaction product will have a single, centrally located headgroup and a pair of hydrophobic tails. There will normally be other components present as well, including some alpha-olefin sulfonate dimers and some non-functionalized olefin dimers, and these will normally be left in the product. For example, a dimer composition produced by reacting 1 -octene and a C -Ci 6 alpha-olefin sulfonic acid will contain the cross-dimer addition product of 1 -octene and the C14-C16 AOS acid, but it will also contain some dimers (or oligomers) of 1 -octene as well as some C14-C16 AOS dimer acid. In some instances, in addition to the dimers or oligomers mentioned above, the mixed dimer compositions may also contain some amount of undimerized starting material, i.e., some amount of unreacted AOS acid and/or some amount of unreacted unsulfonated olefin or olefin precursor.

In some aspects, the detergent is a sulfonate of an unsaturated fatty ester. Suitable unsaturated fatty esters include lower (C1 -C4) alkyl esters of mono- or polyunsaturated fatty acids. Preferred fatty esters have Δ⁹ unsaturation, such as oleate and ricinoleate esters. Sulfonation of the carbon-carbon double bond at the center of these predominantly C18 chains provides compositions having a centrally located headgroup and a pair of relatively hydrophobic tails. Methyl oleate and methyl ricinoleate are readily available starting materials. In some aspects, the detergent is a vinylidene sulfonate. Vinylidenes have the general structure CH2=CRR', where R and R' are alkyl groups, preferably the same or different C4-C20 alkyl groups. Vinylidenes are produced by dimerizing alpha-olefins. Suitable vinylidene sulfonates can be produced by sulfonation of these vinylidenes. Sulfonation results in a composition having a centrally located headgroup and a pair of hydrophobic tails. For example:

In some aspects, the detergent is a sulfonated arene substituted with two or more

C4-C20 alkyl ester or bis(C4-C2o alkyl) amide groups. Here, the arene links the sulfonate headgroup to the hydrophobic tails (R, R'). For example:

R, R' = C₄-C₂₀ alkyl R, R' = C₄-C₂₀ alkyl

In some aspects, the detergent is a sulfonated arene substituted with one or more branched C4-C20 alkyl groups. For example:

In some aspects, the detergent is a phosphate diester of a C4-C20 alcohol or a phosphate diester of a C4-C20 alcohol alkoxylate. For example:

R, R' = C₄-C₂₀ alkyl, n=0 to 5

In some aspects, the detergent is a C1-C4 alkyl C4-C2o dialkylamine oxide, as in N- methyl N,N-di(n-hexyl)amine oxide or N-ethyl N,N-di(n-octyl)amine oxide. (Note the absence of any group linking the headgroup to the hydrophobic tails in these compounds.)

In some aspects, the detergent is a C4-C20 dialkyl urea or carbamate of cystine. For example:

In some aspects, the detergent is a sulfonate-functionalized block copolymer comprising one or more recurring units selected from ethylene, propylene, butenes, isoprene, styrene, alkylated styrenes, butadiene, divinylbenzene, alkyl (meth)acrylates, and (meth)acrylic acid.

In some aspects, the detergent further comprises a nonionic surfactant, preferably a fatty alcohol ethoxylate. Additional suitable nonionic surfactants are described in more detail below.

In some aspects, the detergent further comprises an anionic surfactant.

Preferably, the anionic surfactant is selected from linear alkylbenzene sulfonates (e.g., NaLAS), fatty alcohol ethoxylate sulfates (e.g., NaAES), fatty alcohol sulfates, and mixtures thereof. Additional suitable anionic surfactants are described in detail below.

In another aspect, the invention relates to a method comprising laundering one or more textile articles in water at a temperature less than or equal to 30°C in the presence of a detergent comprising a surfactant blend. The surfactant blend comprises 10 to 90 wt.% of a linear alkylbenzene sulfonate, 10 to 90 wt.% of a Cs to Ci6 alcohol ethoxylate, and not more than 10 wt.%, based on the amount of surfactant blend, of an Cs to Ci6 alcohol ethoxylate sulfate. In some aspects, the surfactant blend used in the method further comprises 1 to 10 wt.%, based on the amount of surfactant blend, of a Cs to Ci6 amine oxide or a Cs to Ci6 amidoamine oxide. In other aspects, the detergent used in the method further comprises 2 to 15 wt.%, based on the amount of surfactant blend, of a lipase. In yet other aspects, the surfactant blend used in the method consists essentially of the linear alkylbenzene sulfonate and the Cs to Ci6 alcohol ethoxylate.

In another aspect, the invention relates to a detergent that is especially useful for cold-water textile laundering. The detergent comprises a surfactant blend. The surfactant blend comprises 10 to 90 wt.% of a linear alkylbenzene sulfonate, 10 to 90 wt.% of a Cs to Ci6 alcohol ethoxylate, and not more than 10 wt.%, based on the amount of surfactant blend, of an Cs to Ci6 alcohol ethoxylate sulfate. In some aspects, the surfactant blend further comprises 1 to 10 wt.%, based on the amount of surfactant blend, of a Cs to Ci6 amine oxide or a Cs to Ci6 amidoamine oxide. In other aspects, the detergent further comprising 2 to 15 wt.%, based on the amount of surfactant blend, of a lipase. In yet other aspects, the surfactant blend consists essentially of the linear alkylbenzene sulfonate and the Cs to Ci6 alcohol ethoxylate.

In some aspects, the detergent composition is in the form of a liquid, powder, paste, granule, tablet, molded solid, water-soluble sheet, water-soluble sachet, capsule, or water-soluble pod.

Laundering methods

Methods for laundering fabrics with the inventive compositions described herein are contemplated. In some aspects, the methods involve placing fabric articles to be laundered in a high efficiency washing machine or a regular (non-high efficiency) washing machine and placing an amount of the detergent composition sufficient to provide a concentration of the composition in water of from about 0.001 % to about 5% by weight when the machine is operated in a wash cycle. A high efficiency machine is defined by the Soap and Detergent Association as any machine that uses 20% to 66% of the water, and as little as 20% - 50% of the energy, of a traditional, regular agitator washer (SDA "Washers and Detergents" publication 2005; see www.cleaning101 .com). The wash cycle is actuated or started to launder the fabric articles. Hand washing using the detergent compositions is also contemplated.

As used herein, "cold water" refers to water having a temperature less than or equal to 30°C, preferably from 5°C to 30°C. Depending on climate, sourced water will have a temperature in this range without requiring added heat. Thus, in one aspect, the invention is a method which comprises laundering one or more textile articles in water having a temperature less than 30°C, preferably from 5°C to 30°C, the presence of an inventive detergent composition as described herein. "Laundering" may refer to using the detergent in the traditional sense of adding it and water to a washing machine (or a tub or other container for manual washing) along with textile articles and using the detergent as the principal cleaning agent. "Laundering" also includes using the detergent as a pre-spotter or pre-soaker composition for manual or machine washing.

Thus, in one aspect, the detergent is used in a laundry pre-spotter composition. In this application, greasy or oily soils on the garments or textile fabrics are contacted directly with the pre-spotter in advance of laundering either manually or by machine. Preferably, the fabric or garment is treated for 5-30 minutes. The pre-spotter composition will normally contain 0.5 to 50 wt.%, more preferably 1 to 30 wt.%, and most preferably 5 to 20 wt.% of combined detergent actives. Treated fabric is machine laundered as usual, preferably at a temperature within the range of 5°C and 30°C, more preferably 10°C to 20°C, most preferably 12°C to 18°C.

In another aspect, the detergent is used in a pre-soaker composition for manual or machine washing. When used for manual washing, the pre-soaker composition is combined with cold water in a washing tub or other container. The pre-soaker composition comprises 0.5 to 100 wt.%, more preferably 1 to 80 wt.%, and most preferably 5 to 50 wt.% of combined detergent actives. Garments or textile fabrics are preferably saturated with pre-soaker in the tub, allowed to soak for 15-30 minutes, and laundered as usual.

When used for machine washing, the pre-soaker composition is preferably added to a machine containing water at a temperature within the range of 5°C and 30°C, more preferably 10°C to 20°C, most preferably 12°C to 18°C. The pre-soaker composition preferably comprises 0.5 to 100 wt.%, more preferably 1 to 80 wt.%, and most preferably 5 to 50 wt.% of combined detergent actives. Garments/textile fabrics are added to the machine, allowed to soak (usually with a pre-soak cycle selected on the machine) for 5- 10 minutes, and then laundered as usual.

In some aspects, the detergent is used an additive for a laundry product or formulation. In such applications, the combined detergent actives help to improve or boost the grease removal or grease cutting performance of the laundry product or formulation. Preferably, the amount of detergent actives used will be within the range of

1 to 10 wt.%, more preferably 2 to 8 wt.%, and most preferably 3 to 5 wt.%.

In yet another aspect, the detergent is used as an additive to produce a modified surfactant having improved grease removal or grease cutting properties. Preferably, the amount of detergent actives used will be within the range of 1 to 10 wt.%, more preferably

2 to 8 wt.%, and most preferably 3 to 5 wt.% in the additive formulation. The resulting modified surfactant will help to achieve improved grease cutting/removal in commercial products. Such products may be used at a temperature within the range of 5°C and 30°C, preferably 10°C to 20°C, and more preferably 12°C to 18°C.

In some preferred aspects, the detergent is used in combination with a linear alkylbenzene sulfonate. Linear alkylbenzene sulfonates (and the sulfonic acid counterparts) are well-known surfactants for laundry detergents. They are commercially available from many sources such as Stepan Company (under the Bio-Soft^®, Nacconol^®, and Ninate^® marks), BASF (as "LAS"), Kao (under the Neopelex™ mark), Solvay (under the Rhodacal^® mark), AkzoNobel (under the Witconate^® mark), Pilot Chemical (under the Calsoft^® mark), and other suppliers. Linear alkylbenzene sulfonates have a sulfonated aromatic ring that is also substituted with a linear alkyl chain. The alkyl chain usually has 8 to 20 carbons, more typically 10 to 14 carbons or 1 1 to 14 carbons. Because many suitable alkylbenzene sulfonate products are readily available, these will normally not require synthesis. Industrially, the linear alkylbenzene sulfonates are made by dehydrogenating normal paraffins to give olefins, followed by alkylation of benzene in a fixed-bed process, sulfonation of the benzene ring, and neutralization. In some processes, the alkylbenzenes are produced by HF-catalyzed alkylation of benzene with olefins or AlC -catalyzed alkylation with alkyl halides.

In some aspects, the alkylbenzene sulfonate may be represented by the formula:

R⁶ArSO₃M

where R⁶ is an alkyl group of 8 to 18 carbon atoms, Ar is a benzene ring (-C6H₄-) and M is a solubilizing cation. R⁶ may be a mixture of chain lengths. A mixture of isomers is typically used, and different grades are commercially available for use depending on formulation needs. It may be more desirable to formulate the detergent using the corresponding alkylbenzene sulfonic acid ("HLAS") and including enough sodium hydroxide or other hydroxide base to convert the sulfonic acid groups to sulfonate salts.

Preferably, the detergent comprises water in addition to the inventive detergent composition and any other surfactants, such as the linear alkylbenzene sulfonate. The amount of water present may vary over a wide range and will normally depend on the intended application, the form in which the detergent is delivered, the desired actives level, and other factors. In actual use, the detergents will normally be diluted with a small, large, or very large proportion of water, depending on the equipment available for washing. Generally, the amount of water used will be effective to give 0.001 to 5 wt.% of active surfactant in the wash.

In some aspects the detergent comprises one or more nonionic surfactants in addition to the inventive detergent composition and any linear alkylbenzene sulfonate surfactant. Preferred nonionic surfactants are fatty alcohol ethoxylates, especially C9-C15 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly C12-C15 primary alcohols containing 5-8 moles of ethylene oxide per mole of alcohol (e.g., Bio-Soft^® N25-7, product of Stepan Company).

The detergents may include other components, including, for example, other surfactants, hydrotropes, fatty acids or soaps, alkalinity adjusters, buffers, pH adjusters, or other components. These are described more completely in the paragraphs that follow.

General Considerations for Laundry Detergents

Desirable surfactant attributes for laundry detergents include having the ability to be formulated as heavy duty liquid (HDL) detergents, powders, bar soaps, sachets, pods, or other detergents forms.

For HDLs, this includes being in liquid form at room temperature, an ability to be formulated in cold-mix applications, and an ability to perform as well as or better than existing surfactants.

Desirable attributes for HDLs include, for example, the ability to emulsify, suspend or penetrate greasy or oily soils and suspend or disperse particulates, in order to clean surfaces; and then prevent the soils, grease, or particulates from re-depositing on the newly cleaned surfaces.

It is also desirable to have the ability to control the foaming. For use of an HDL in a high-efficiency washing machine, low foam is desired to achieve the best cleaning and to avoid excess foaming. Other desirable properties include the ability to clarify the formulation and to improve long-term storage stability under both extreme outdoor and normal indoor temperatures.

The skilled person will appreciate that the inventive detergent compositions as described above may not be mere "drop-in" substitutions in an existing detergent formulation. Some amount of re-formulation is typically necessary to adjust the nature and amounts of other surfactants, hydrotropes, alkalinity control agents, and/or other components of the formulation in order to achieve a desirable outcome in terms of appearance, handling, solubility characteristics, and other physical properties and performance attributes. For example, a formulation might need to be adjusted by using, in combination with the inventive detergent compositions, a more highly ethoxylated nonionic surfactant instead of one that has fewer EO units. This kind of reformulating is considered to be within ordinary skill and is left to the skilled person's discretion.

A wide variety of detergent compositions can be made that include the inventive detergent compositions, with or without other ingredients as specified below. Formulations are contemplated including 1 % to 99% of the inventive detergent compositions, more preferably between 1 % and 60%, even more preferably between 1 % and 30%, with 99% to 1 % water and, optionally, other ingredients as described here.

Additional Surfactants

The detergent compositions can contain co-surfactants, which can be anionic, cationic, nonionic, ampholytic, zwitterionic, or combinations of these.

Anionic Surfactants

Formulations useful for the inventive compositions and methods can include anionic surfactants. "Anionic surfactants" are defined here as amphiphilic molecules with an average molecular weight of less than about 10,000, comprising one or more functional groups that exhibit a net anionic charge when present in aqueous solution at the normal wash pH, which can be a pH between 6 and 1 1 . The anionic surfactant can be any anionic surfactant that is substantially water soluble. "Water soluble" surfactants are, unless otherwise noted, here defined to include surfactants which are soluble or dispersible to at least the extent of 0.01 % by weight in distilled water at 25°C. At least one of the anionic surfactants used may be an alkali or alkaline earth metal salt of a natural or synthetic fatty acid containing between about 4 and about 30 carbon atoms. A mixture of carboxylic acid salts with one or more other anionic surfactants can also be used. Another important class of anionic compounds is the water soluble salts, particularly the alkali metal salts, of organic sulfur reaction products having in their molecular structure an alkyl radical containing from about 6 to about 24 carbon atoms and a radical selected from the group consisting of sulfonic and sulfuric acid ester radicals.

Specific types of anionic surfactants are identified in the following paragraphs. Carboxylic acid salts are represented by the formula:

R COOM

where R¹ is a primary or secondary alkyl group of 4 to 30 carbon atoms and M is a solubilizing cation. The alkyl group represented by R¹ may represent a mixture of chain lengths and may be saturated or unsaturated, although it is preferred that at least two thirds of the R¹ groups have a chain length of between 8 and 18 carbon atoms. Non- limiting examples of suitable alkyl group sources include the fatty acids derived from coconut oil, tallow, tall oil and palm kernel oil. For the purposes of minimizing odor, however, it is often desirable to use primarily saturated carboxylic acids. Such materials are well known to those skilled in the art, and are available from many commercial sources, such as Uniqema (Wilmington, DE) and Twin Rivers Technologies (Quincy, MA). The solubilizing cation, M, may be any cation that confers water solubility to the product, although monovalent such moieties are generally preferred. Examples of acceptable solubilizing cations for use with the present technology include alkali metals such as sodium and potassium, which are particularly preferred, and amines such as triethanolammonium, ammonium and morpholinium. Although, when used, the majority of the fatty acid should be incorporated into the formulation in neutralized salt form, it is often preferable to leave a small amount of free fatty acid in the formulation, as this can aid in the maintenance of product viscosity.

Primary alkyl sulfates are represented by the formula:

R²OSO₃M

where R² is a primary alkyl group of 8 to 18 carbon atoms and can be branched or linear, saturated or unsaturated. M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like). The alkyl group R² may have a mixture of chain lengths. It is preferred that at least two-thirds of the R² alkyl groups have a chain length of 8 to 18 carbon atoms. This will be the case if R² is coconut alkyl, for example. The solubilizing cation may be a range of cations which are in general monovalent and confer water solubility. An alkali metal, notably sodium, is especially envisaged. Other possibilities are ammonium and substituted ammonium ions, such as trialkanolammonium or trialkylammonium.

Alkyl ether sulfates are represented by the formula:

where R³ is a primary alkyl group of 8 to 18 carbon atoms, branched or linear, saturated or unsaturated, and n has an average value in the range from 1 to 6 and M is a solubilizing cation. The alkyl group R³ may have a mixture of chain lengths. It is preferred that at least two-thirds of the R³ alkyl groups have a chain length of 8 to 18 carbon atoms. This will be the case if R³ is coconut alkyl, for example. Preferably n has an average value of 2 to 5. Ether sulfates have been found to provide viscosity build in certain of the formulations of the present technology, and thus are considered a preferred ingredient.

Other suitable anionic surfactants that can be used are alkyl ester sulfonate surfactants including linear esters of Cs - C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 (see, e.g., J. Am. Oil Chem. Soc. 52 (1975) 323). Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, and the like.

Preferred alkyl ester sulfonate surfactants, especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula:

R³-CH(SO₃M)-C(O)-OR⁴

where R³ is a Ce -C20 hydrocarbyl, preferably an alkyl or combination thereof R⁴ is a Ci -C6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation that forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine. The group R³ may have a mixture of chain lengths. Preferably at least two-thirds of these groups have 6 to 1 2 carbon atoms. This will be the case when the moiety R³CH(-)CO2(- ) is derived from a coconut source, for instance. Preferably, R³ is C10 -C16 alkyl, and R⁴ is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates where R³ is C10 -C16 alkyl.

Paraffin sulfonates having about 8 to about 22 carbon atoms, preferably about 1 2 to about 16 carbon atoms, in the alkyl moiety, are contemplated for use here. They are usually produced by the sulfoxidation of petrochemically derived normal paraffins. These surfactants are commercially available as, for example, Hostapur SAS from Clariant (Charlotte, NC).

Olefin sulfonates having 8 to 22 carbon atoms, preferably 1 2 to 1 6 carbon atoms, are also contemplated for use in the present compositions. The olefin sulfonates are further characterized as having from 0 to 1 ethylenic double bonds; from 1 to 2 sulfonate moieties, of which one is a terminal group and the other is not; and 0 to 1 secondary hydroxyl moieties. U.S. Pat. No. 3,332,880 contains a description of suitable olefin sulfonates, and its teachings are incorporated herein by reference. Such materials are sold as, for example, Bio-Terge® AS-40, a product of Stepan.

Organic phosphate-based anionic surfactants include organic phosphate esters such as complex mono- or diester phosphates of hydroxyl-terminated alkoxide condensates, or salts thereof. Suitable organic phosphate esters include phosphate esters of polyoxyalkylated alkylaryl phenols, phosphate esters of ethoxylated linear alcohols, and phosphate esters of ethoxylated phenols. Also included are nonionic alkoxylates having a sodium alkylenecarboxylate moiety linked to a terminal hydroxyl group of the nonionic through an ether bond. Counterions to the salts of all the foregoing may be those of alkali metal, alkaline earth metal, ammonium, alkanolammonium and alkylammonium types.

Other anionic surfactants useful for detersive purposes can also be included in the detergent compositions. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C8-C22 primary of secondary alkanesulfonates, C8-C24 olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British Pat. No. 1 ,082,1 79, C8-C24 alkyl poly glycol ether sulfates (containing up to 1 0 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyi glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C12-C18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated Ce- C12 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic non-sulfated compounds being described below), and alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2O)kCH2COO-M+ where R is a Cs- C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Pat. Nos. 3,929,678 and 6,949,498, the teachings of which are incorporated herein by reference.

Other anionic surfactants contemplated include isethionates, sulfated triglycerides, alcohol sulfates, ligninsulfonates, naphthelene sulfonates and alkyl naphthelene sulfonates, and the like. For a more general description of suitable anionic surfactants, see U.S. Pat. No. 5,929,022, the teachings of which are incorporated herein by reference.

Nonionic or Ampholytic Surfactants

Examples of suitable nonionic surfactants include alkyl polyglucosides ("APGs"), alcohol ethoxylates, nonylphenol ethoxylates, methyl ester ethoxylates ("MEEs"), and others. The nonionic surfactant may be used as from 1 % to 90%, more preferably from 1 to 40% and most preferably between 1 % and 32% of a detergent composition. Other suitable nonionic surfactants are described in U.S. Pat. No. 5,929,022, from which much of the following discussion comes.

One class of nonionic surfactants useful herein are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 14, more preferably from 12 to 14. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

For "low HLB" nonionics, low HLB can be defined as having an HLB of 8 or less and preferably 6 or less. A "low level" of co-surfactant can be defined as 6% or less of the HDL and preferably 4% or less of the HDL.

Especially preferred nonionic surfactants of this type are the C9-C15 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the C12-C15 primary alcohols containing 5-8 moles of ethylene oxide per mole of alcohol. One suitable example of such a surfactant is polyalkoxylated aliphatic base, sold for example as Bio-Soft^® N25-7 by Stepan Company.

Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula:

where Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x has an average value from 1 .3 to 4. The compounds include less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides. Compounds of this type and their use in detergent compositions are disclosed in EP-B 0 070 077, EP 0 075 996 and EP 0 094 1 18.

Also suitable as nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula:

R²-C(O)-N(R¹)-Z

where R¹ is H, or R¹ is C1 -4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R² is C5-C31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R¹ is methyl, R² is a straight C11-15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.

Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and where one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato, or phosphono (see U.S. Pat. Nos. 3,664,961 and 3,929,678, the teachings of which are incorporated herein by reference). Suitable ampholytic surfactants include fatty amine oxides, fatty amidopropylamine oxides, fatty betaines, and fatty amidopropylamine betaines. Examples of suitable betaines are coco betaine (CB) and cocoamidopropyl betaine (CAPB). Commercially available betaines include Amphosol^® HCG or Amphosol^® HCA (cocamidopropyl betaine) surfactants (Stepan). Suitable amine oxides include laurylamine oxide, myristylamine oxide, lauryl amidopropylamine oxide, myristyl amidopropylamine oxide, and the like, and mixtures thereof. Commercially available amine oxides include Ammonyx^® LO, Ammonyx^® MO, and Ammonyx^® LMDO surfactants (Stepan).

Ampholytic surfactants can be used at a level from 1 % to 50%, more preferably from 1 % to 10%, even more preferably between 1 % and 5% of the formulation, by weight.

Amine oxide surfactants are suitable ampholytic surfactants. Compositions herein may comprise an amine oxide in accordance with the general formula : R¹ (EO)x(PO)_y(BO)zN(O)(CH2R')2^■ H₂O

In general, it can be seen that the preceding formula provides one long-chain moiety R¹(EO)x(PO)_y(BO)_z and two short chain moieties, -CH2R'. R' is preferably selected from hydrogen, methyl and -CH2OH. In general R¹ is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R¹ is a primary alkyl moiety. When x+y+z=0, R¹ is a hydrocarbyl moiety having a chain length of from about 8 to about 18. When x+y+z is different from 0, R¹ may be somewhat longer, having a chain length in the range C12-C24. The general formula also encompasses amine oxides where x+y+z=0, R¹ is C8-C18, R' is H and q= from 0 to 2, preferably 2. These amine oxides are illustrated by C12-14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide and their hydrates, especially the dihydrates as disclosed in U.S. Pat. Nos. 5,075,501 and 5,071 ,594, the teachings of which are incorporated herein by reference.

Also suitable are amine oxides where x+y+z is different from zero. Specifically, x+y+z is from about 1 to about 10, and R¹ is a primary alkyl group containing about 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms. In these embodiments y+z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy. Such amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.

Preferred amine oxides are solids at ambient temperature. More preferably, they have melting points in the range of 30°C to 90°C. Amine oxides suitable for use are made commercially by Stepan, AkzoNobel, Procter & Gamble, and others. See McCutcheon's compilation and a Kirk-Othmer review article for alternate amine oxide manufacturers.

Suitable detergents may include, e.g., hexadecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, hexadecyltris(ethyleneoxy)dimethylamine oxide, and tetradecyldimethylamine oxide dihydrate.

In certain aspects in which R' is H, there is some latitude with respect to having R' slightly larger than H. Specifically, R' may be CH2OH, as in hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2- hydroxyethyl)amine oxide and oleylbis(2-hydroxyethyl)amine oxide.

Zwitterionic Surfactants

Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium and phosphonium or tertiary sulfonium compounds, in which the cationic atom may be part of a heterocyclic ring, and in which the aliphatic radical may be straight chain or branched, and where one of the aliphatic substituents contains from about 3 to 18 carbon atoms, and at least one aliphatic substituent contains an anionic water-solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato, or phosphono (see U.S. Pat. No. 3,664,961 , the teachings of which are incorporated herein by reference). Zwitterionic surfactants can be used as from 1 % to 50%, more preferably from 1 % to 10%, even more preferably from 1 % to 5% by weight of the present formulations.

Mixtures of any two or more individually contemplated surfactants, whether of the same type or different types, are contemplated herein.

Formulation and Use

Four desirable characteristics of a laundry detergent composition, in particular a liquid composition (although the present disclosure is not limited to a liquid composition, or to a composition having any or all of these attributes) are that (1 ) a concentrated formulation is useful to save on shelf space of a retailer, (2) a "green" or environmentally friendly composition is useful, (3) a composition that works in modern high efficiency washing machines which use less energy and less water to wash clothes than previous machines is useful, and (4) a composition that cleans well in cold water, i.e., less than 30°C, preferably 5°C to 30°C.

To save a substantial amount of retailer shelf space, a concentrated formulation is contemplated having two or even three, four, five, six, or even greater (e.g., 8x) times potency per unit volume or dose as conventional laundry detergents. The use of less water complicates the formulation of a detergent composition, as it needs to be more soluble and otherwise to work well when diluted in relatively little water. To make a "green" formula, the surfactants should be ultimately biodegradable and non-toxic. To meet consumer perceptions and reduce the use of petrochemicals, a "green" formula may also advantageously be limited to the use of renewable hydrocarbons, such as vegetable or animal fats and oils, in the manufacture of surfactants.

High efficiency (HE) washing machines present several challenges to the detergent formulation. As of January 201 1 , all washing machines sold in the U.S. must be HE, at least to some extent, and this requirement will only become more restrictive in the coming years. Front loading machines, all of which are HE machines, represent the highest efficiency, and are increasingly being used.

Heavy duty liquid detergent formulas are impacted by HE machines because the significantly lower water usage requires that less foam be generated during the wash cycle. As the water usage levels continue to decrease in future generations of HE machines, detergents may be required to transition to no foam. In addition, HE HDLs should also disperse quickly and cleanly at lower wash temperatures.

To work in a modern high efficiency washing machine, the detergent composition needs to work in relatively concentrated form in cold water, as these washing machines use relatively little water and cooler washing temperatures than prior machines. The sudsing of such high-efficiency formulations must also be reduced, or even eliminated, in a low-water environment to provide effective cleaning performance. The anti-redeposition properties of a high efficiency detergent formulation also must be robust in a low-water environment. In addition, formulations that allow the used wash water to be more easily rinsed out of the clothes or spun out of the clothes in a washing machine are also contemplated, to promote efficiency.

Liquid fabric softener formulations and "softergent" (fabric softener/detergent dual functional) single-add formulations also may need to change as water usage continues to decline in HE machines. A washer-added softener is dispensed during the rinse cycle in these machines. The inventive detergent compositions can be used in formulations that provide softening in addition to cleaning.

Laundry detergents and additives containing the presently described inventive detergent compositions are contemplated to provide high concentration formulations, or "green" formulations, or formulations that work well in high efficiency washing machines. Such detergents and additives are contemplated that have at least one of the advantages or desirable characteristics specified above, or combinations of two or more of these advantages, at least to some degree. The ingredients contemplated for use in such laundry detergents and additives are found in the following paragraphs.

In addition to the surfactants as previously described, a laundry detergent composition commonly contains other ingredients for various purposes. Some of those ingredients are also described below. Builders and Alkaline Agents

Builders and other alkaline agents are contemplated for use in the present formulations.

Any conventional builder system is suitable for use here, including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid. Though less preferred for environmental reasons, phosphate builders could also be used here.

Suitable polycarboxylate builders for use here include citric acid, preferably in the form of a water-soluble salt, and derivatives of succinic acid of the formula:

R-CH(COOH)CH₂(COOH)

where R is C10-20 alkyl or alkenyl, preferably C12-C16, or where R can be substituted with hydroxyl, sulfo, sulfoxyl, or sulfone substituents. Specific examples include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenylsuccinate, or 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium, and alkanolammonium salts.

Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid, as described in U.S. Pat. No. 4,663,071 .

Especially for a liquid detergent composition, suitable fatty acid builders for use here are saturated or unsaturated C10-C-18 fatty acids, as well as the corresponding soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acid is oleic acid. Another preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.

Some examples of alkaline agents include alkali metal (Na, K, or NH₄) hydroxides, carbonates, citrates, and bicarbonates. Another commonly used builder is borax.

For powdered detergent compositions, the builder or alkaline agent typically comprises from 1 % to 95% of the composition. For liquid compositions, the builder or alkaline agent typically comprises from 1 % to 60%, alternatively between 1 % and 30%, alternatively between 2% and 15%. See U.S. Pat. No. 5,929,022, the teachings of which are incorporated by reference, from which much of the preceding discussion comes. Other builders are described in PCT Int. Publ. WO 99/05242, which is incorporated here by reference.

Enzymes

The detergent compositions may further comprise one or more enzymes, which provide cleaning performance and/or fabric care benefits. The enzymes include cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta-glucanases, arabinosidases or mixtures thereof.

A preferred combination is a detergent composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with the lipolytic enzyme variant D96L at a level of from 50 LU to

8500 LU per liter of wash solution.

Suitable cellulases include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Pat.

No. 4,435,307, which discloses fungal cellulase produced from Humicola insolens.

Suitable cellulases are also disclosed in GB-A-2 075 028; GB-A-2 095 275 and DE-OS-

2 247 832.

Examples of such cellulases are cellulases produced by a strain of Humicola insolens {Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800. Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50,000, an isoelectric point of 5.5 and containing 415 amino acid units. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in EP Appl. No. 91202879.2.

Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, and the like. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloro- and bromoperoxidase. Peroxidase-containing detergent compositions are disclosed, for example, in PCT Int. Appl. WO 89/099813 and in EP Appl. No. 91202882.6.

The cellulases and/or peroxidases are normally incorporated in the detergent composition at levels from 0.0001 % to 2% of active enzyme by weight of the detergent composition.

Preferred commercially available protease enzymes include those sold under the tradenames Alcalase^®, Savinase^®, Primase^®, Durazym^®, and Esperase^® by Novo Nordisk A/S (Denmark), those sold under the tradename Maxatase^®, Maxacal^® and Maxapem^® by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean^® and Optimase^® by Solvay Enzymes. Other proteases are described in U.S. Pat. No. 5,679,630 can be included in the detergent compositions. Protease enzyme may be incorporated into the detergent compositions at a level of from about 0.0001 % to about 2% active enzyme by weight of the composition.

A preferred protease here referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for the amino acid residue at a position in the carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101 , +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in U.S. Pat. No. 5,679,630, the teachings of which are incorporated herein by reference.

Highly preferred enzymes that can be included in the detergent compositions include lipases. It has been found that the cleaning performance on greasy soils is synergistically improved by using lipases. Suitable lipase enzymes include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Pat. No. 1 ,372,034. Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereafter referred to as "Amano-P." Further suitable lipases are lipases such as M1 Lipase^® and Lipomax^® (Gist-Brocades). Highly preferred lipases are the D96L lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa as described in U.S. Pat. No. 6,017,871 . Preferably, the Humicola lanuginosa strain DSM 4106 is used. This enzyme is incorporated into the detergent compositions at a level of from 50 LU to 8500 LU per liter wash solution. Preferably, the variant D96L is present at a level of from 100 LU to 7500 LU per liter of wash solution. A more preferred level is from 150 LU to 5000 LU per liter of wash solution.

By "D96L lipolytic enzyme variant," we mean the lipase variant as described in PCT Int. Appl. WO 92/05249, where the native lipase ex Humicola lanuginosa aspartic acid (D) residue at position 96 is changed to leucine (L). According to this nomenclature, the substitution of aspartic acid to leucine in position 96 is shown as: D96L.

Also suitable are cutinases [EC 3.1 .1 .50] which can be considered as a special kind of lipase, namely lipases that do not require interfacial activation. Addition of cutinases to detergent compositions is described, e.g. in PCT Int. Appl. No. WO 88/09367.

The lipases and/or cutinases are normally incorporated in the detergent composition at levels from 0.0001 % to 2% of active enzyme by weight of the detergent composition. Amylases (a and/or β) can be included for removal of carbohydrate-based stains. Suitable amylases are Termamyl^® (Novo Nordisk), Fungamyl^® and BAN^® amylases (Novo Nordisk).

The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and/or yeast origin. See U.S. Pat. No. 5,929,022, the teachings of which are incorporated herein by reference, from which much of the preceding discussion comes. Preferred compositions optionally contain a combination of enzymes or a single enzyme, with the amount of each enzyme commonly ranging from 0.0001 % to 2%.

Other enzymes and materials used with enzymes are described in PCT Int. Appl.

No. WO99/05242, which is incorporated here by reference.

Adjuvants

The detergent compositions optionally contain one or more soil suspending agents or resoiling inhibitors in an amount from about 0.01 % to about 5% by weight, alternatively less than about 2% by weight. Resoiling inhibitors include anti-redeposition agents, soil release agents, or combinations thereof. Suitable agents are described in U.S. Pat. No. 5,929,022, and include water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties. Examples of such soil release and anti-redeposition agents include an ethoxylated tetraethylenepentamine. Further suitable ethoxylated amines are described in U.S. Pat. 4,597,898, the teachings of which are incorporated herein by reference. Another group of preferred clay soil removal/anti-redeposition agents are the cationic compounds disclosed in EP Appl. No. 1 1 1 ,965. Other clay soil removal/anti- redeposition agents which can be used include the ethoxylated amine polymers disclosed in EP Appl. No. 1 1 1 ,984; the zwitterionic polymers disclosed in EP Appl. No. 1 12,592; and the amine oxides disclosed in U.S. Pat. No. 4,548,744, the teachings of which are incorporated herein by reference.

Other clay soil removal and/or anti-redeposition agents known in the art can also be utilized in the compositions hereof. Another type of preferred anti-redeposition agent includes the carboxymethylcellulose (CMC) materials.

Anti-redeposition polymers can be incorporated into HDL formulations described herein. It may be preferred to keep the level of anti-redeposition polymer below about 2%. At levels above about 2%, the anti-redeposition polymer may cause formulation instability (e.g., phase separation) and or undue thickening.

Soil release agents are also contemplated as optional ingredients in the amount of about 0.1 % to about 5% (see, e.g., U.S. Pat. No. 5,929,022).

Chelating agents in the amounts of about 0.1 % to about 10%, more preferably about 0.5% to about 5%, and even more preferably from about 0.8% to about 3%, are also contemplated as an optional ingredient (see, e.g., U.S. Pat. No. 5,929,022).

Polymeric dispersing agents in the amount of 0% to about 6% are also contemplated as an optional component of the presently described detergent compositions (see, e.g., U.S. Pat. No. 5,929,022).

A suds suppressor is also contemplated as an optional component of the present detergent composition, in the amount of from about 0.1 % to about 15%, more preferably between about 0.5% to about 10% and even more preferably between about 1 % to about 7% (see, e.g., U.S. Pat. No. 5,929,022).

Other ingredients that can be included in a liquid laundry detergent include perfumes, which optionally contain ingredients such as aldehydes, ketones, esters, and alcohols. More compositions that can be included are: carriers, hydrotropes, processing aids, dyes, pigments, solvents, bleaches, bleach activators, fluorescent optical brighteners, and enzyme stabilizing packaging systems.

The co-surfactants and fatty acids described in U.S. Pat. No. 4,561 ,998, the teachings of which are incorporated herein by reference, can be included in the detergent compositions. In conjunction with anionic surfactants, these improve laundering performance. Examples include chloride, bromide and methylsulfate Cs-Ci6 alkyl trimethylammonium salts, Cs-Ci6 alkyl di(hydroxyethyl) methylammonium salts, Cs-Ci6 alkyl hydroxyethyldimethylammonium salts, and Cs-Ci6 alkyloxypropyl trimethylammonium salts.

Similar to what is taught in U.S. Pat. 4,561 ,998, the compositions herein can also contain from about 0.25% to about 12%, preferably from about 0.5% to about 8%, more preferably from about 1 % to about 4%, by weight of a cosurfactant selected from the group of certain quaternary ammonium, diquaternary ammonium, amine, diamine, amine oxide and di(amine oxide) surfactants. The quaternary ammonium surfactants are particularly preferred.

Quaternary ammonium surfactants can have the following formula:

[R²(OR³)y][R⁴(OR³)_y]₂R⁵N⁺X- wherein R² is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain; each R³ is selected from the group consisting of

-CH2CH2--, ~CH₂CH(CH3)~, ~CH2CH(CH₂OH)~, -CH2CH2CH2-, and mixtures thereof; each R⁴ is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl, ring structures formed by joining the two R⁴ groups,

--CH2CHOHCHOHCOR⁶CHOHCH₂OH wherein R⁶ is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R⁵ is the same as R⁴ or is an alkyl chain wherein the total number of carbon atoms of R² plus R⁵ is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.

Preferred of the above are the alkyl quaternary ammonium surfactants, especially the mono-long chain alkyl surfactants described in the above formula when R⁵ is selected from the same groups as R⁴. The most preferred quaternary ammonium surfactants are the chloride, bromide and methylsulfate Cs-Ci6 alkyl trimethylammonium salts, Cs-Ci6 alkyl di(hydroxyethyl) methylammonium salts, Cs-Ci6 alkyl hydroxyethyldimethylammonium salts, and Cs-Ci6 alkyloxypropyl trimethylammonium salts. Of the above, decyl trimethylammonium methylsulfate, lauryl trimethylammonium chloride, myristyl trimethylammonium bromide and coconut trimethylammonium chloride and methylsulfate are particularly preferred.

U.S. Pat. No. 4,561 ,998 also provides that under cold water washing conditions, in this case less than about 65°F (18.3°C), the Cs-C-io alkyltrimethyl ammonium surfactants are particularly preferred since they have a lower Kraft boundary and, therefore, a lower crystallization temperature than the longer alkyl chain quaternary ammonium surfactants herein.

Diquaternary ammonium surfactants can be of the formula:

[R²(OR³)y][R⁴OR³]y]2N⁺R³N⁺R⁵[R⁴(OR³)y]2(X^" )₂ wherein the R², R³, R⁴, R⁵, y and X substituents are as defined above for the quaternary ammonium surfactants. These substituents are also preferably selected to provide diquaternary ammonium surfactants corresponding to the preferred quaternary ammonium surfactants. Particularly preferred are the Cs-16 alkyl pentamethyl- ethylenediammonium chloride, bromide and methylsulfate salts.

Amine surfactants useful herein are of the formula:

[R²(OR³)y][R⁴(OR³)y]R⁵N

wherein the R², R³, R⁴, R⁵ and y substituents are as defined above for the quaternary ammonium surfactants. Particularly preferred are the C12-16 alkyl dimethyl amines.

Diamine surfactants herein are of the formula

[R²(OR³)y][R⁴(OR³)y]NR³NR⁵[R⁴(OR³)_y]

wherein the R², R³, R⁴, R⁵ and y substituents are as defined above. Preferred are the C12-C16 alkyl trimethylethylene diamines.

Amine oxide surfactants useful herein are of the formula:

[R²(OR³)y][R⁴(OR³)_y]R⁵N^O

wherein the R², R³, R⁴, R⁵ and y substituents are also as defined above for the quaternary ammonium surfactants. Particularly preferred are the C12-16 alkyl dimethyl amine oxides.

Di(amine oxide) surfactants herein are of the formula:

wherein the R², R³, R⁴, R⁵ and y substituents are as defined above, preferably is C12-16 alkyl trimethylethylene di(amine oxide).

Other common cleaning adjuncts are identified in U.S. Pat. No. 7,326,675 and PCT Int. Publ. WO 99/05242. Such cleaning adjuncts are identified as including bleaches, bleach activators, suds boosters, dispersant polymers (e.g., from BASF Corp. or Dow Chemical) other than those described above, color speckles, silvercare, anti-tarnish and/or anti-corrosion agents, pigments, dyes, fillers, germicides, hydrotropes, anti- oxidants, enzyme stabilizing agents, pro-perfumes, carriers, processing aids, solvents, dye transfer inhibiting agents, brighteners, structure elasticizing agents, fabric softeners, anti-abrasion agents, and other fabric care agents, surface and skin care agents. Suitable examples of such other cleaning adjuncts and levels of use are found in U.S. Pat. Nos. 5,576,282, 6,306,81 2, 6,326,348 and PCT Int. Publ. WO99/05242, the teachings of which are incorporated herein by reference.

Fatty Acids

Similar to that disclosed in U.S. Pat. No. 4,561 ,998, the detergent compositions may contain a fatty acid containing from about 1 0 to about 22 carbon atoms. The fatty acid can also contain from about 1 to about 1 0 ethylene oxide units in the hydrocarbon chain. Suitable fatty acids are saturated and/or unsaturated and can be obtained from natural sources such as plant or animal esters (e.g., palm kernel oil, palm oil, coconut oil, babassu oil, safflower oil, tall oil, castor oil, tallow and fish oils, grease, and mixtures thereof) or synthetically prepared (e.g., via the oxidation of petroleum or by hydrogenation of carbon monoxide via the Fisher-Tropsch process). Examples of suitable saturated fatty acids for use in the detergent compositions include capric, lauric, myristic, palmitic, stearic, arachidic and behenic acid. Suitable unsaturated fatty acid species include: palmitoleic, oleic, linoleic, linolenic and ricinoleic acid. Examples of preferred fatty acids are saturated Cio -CM (coconut) fatty acids, from about 5:1 to about 1 :1 (preferably about 3:1 ) weight ratio mixtures of lauric and myristic acid, and mixtures of the above lauric/myristic blends with oleic acid at a weight ratio of about 4:1 to about 1 :4 mixed lauric/myristic:oleic.

U.S. Pat. No. 4,507,21 9 identifies various sulfonate surfactants as suitable for use with the above-identified co-surfactants. The disclosures of U.S. Pat. Nos. 4,561 ,998 and 4,507,21 9 with respect to co-surfactants are incorporated herein by reference.

Softerqents

Softergent technologies as described in, for example, U.S. Pat. Nos. 6,949,498, 5,466,394 and 5,622,925 can be used in the detergent compositions. "Softergent" refers to a softening detergent that can be dosed at the beginning of a wash cycle for the purpose of simultaneously cleaning and softening fabrics. The inventive detergent compositions can be used to make stable, aqueous heavy duty liquid laundry detergent compositions containing a fabric-softening agent that provide exceptional cleaning as well as fabric softening and anti-static benefits.

Some suitable softergent compositions contain about 0.5% to about 10%, preferably from about 2% to about 7%, more preferably from about 3% to about 5% by weight of a quaternary ammonium fabric-softening agent having the formula:

wherein Ri and R2 are individually selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and ~(C2H₄O)x H where x has a value from 2 to 5; X is an anion; and (1 ) R3 and R 4 are each a Cs-Ci4 alkyl or (2) R3 is a C8-C22 alkyl and R4 is selected from the group consisting of C1-C10 alkyl, C-C10 hydroxy alkyl, benzyl, and --(C2 H4O)x H where x has a value from 2 to 5.

Preferred fabric-softening agents are the mono-long chain alkyl quaternary ammonium surfactants wherein in the above formula Ri , R2, and R3 are each methyl and R4 is a Cs-Cie alkyl. The most preferred quaternary ammonium surfactants are the chloride, bromide and methylsulfate Cs-Ci6 alkyl trimethyl ammonium salts, and Cs-Ci6 alkyl di(hydroxyethyl)-methyl ammonium salts. Of the above, lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride and coconut trimethylammonium chloride and methylsulfate are particularly preferred.

Another class of preferred quaternary ammonium surfactants are the di-Cs-Ci4 alkyl dimethyl ammonium chloride or methylsulfates; particularly preferred is di- C12-C14 alkyl dimethyl ammonium chloride. This class of materials is particularly suited to providing antistatic benefits to fabrics.

A preferred softergent comprises the detergent composition wherein the weight ratio of anionic surfactant component to quaternary ammonium softening agent is from about 3:1 to about 40: 1 ; a more preferred range is from about 5:1 to 20:1 . Odor Control

Odor control technologies as described in, for example, U.S. Pat. No. 6,878,695 can be used in the detergent compositions.

For example, a composition containing the inventive detergent compositions can further comprise a low-degree of substitution cyclodextrin derivative and a perfume material. The cyclodextrin is preferably functionally-available cyclodextrin. The compositions can further comprise optional cyclodextrin-compatible and -incompatible materials, and other optional components. Such a composition can be used for capturing unwanted molecules in a variety of contexts, preferably to control malodors including controlling malodorous molecules on inanimate surfaces, such as fabrics, including carpets, and hard surfaces including countertops, dishes, floors, garbage cans, ceilings, walls, carpet padding, air filters, and the like, and animate surfaces, such as skin and hair.

The low-degree of substitution cyclodextrin derivatives useful herein are preferably selected from low-degree of substitution hydroxyalkyi cyclodextrin, low-degree of substitution alkylated cyclodextrin, and mixtures thereof. Preferred low-degree of substitution hydroxyalkyi beta-cyclodextrins have an average degree of substitution of less than about 5.0, more preferably less than about 4.5, and still more preferably less than about 4.0. Preferred low-degree of substitution alkylated cyclodextrins have an average degree of substitution of less than about 6.0, more preferably less than about 5.5, and still more preferably less than about 5.0.

The detergent compositions can comprise a mixture of cyclodextrins and derivatives thereof such that the mixture effectively has an average degree of substitution equivalent to the low-degree of substitution cyclodextrin derivatives described hereinbefore. Such cyclodextrin mixtures preferably comprise high-degree of substitution cyclodextrin derivatives (having a higher average degree of substitution than the low- degree substitution cyclodextrin derivatives described herein) and non-derivatized cyclodextrin, such that the cyclodextrin mixture effectively has an average degree of substitution equivalent to the low-degree of substitution cyclodextrin derivative. For example, a composition comprising a cyclodextrin mixture containing about 0.1 % non- derivatized beta-cyclodextrin and about 0.4% hydroxypropyl beta-cyclodextrin having an average degree of substitution of about 5.5, exhibits an ability to capture unwanted molecules similar to that of a similar composition comprising low-degree of substitution hydroxypropyl beta-cyclodextrin having an average degree of substitution of about 3.3. Such cyclodextrin mixtures can typically absorb odors more broadly by complexing with a wider range of unwanted molecules, especially malodorous molecules, having a wider range of molecular sizes preferably at least a portion of a cyclodextrin mixture is alpha- cyclodextrin and its derivatives thereof, gamma-cyclodextrin and its derivatives thereof, and/or beta-cyclodextrin and its derivatives thereof; more preferably a mixture of alpha- cyclodextrin, or an alpha-cyclodextrin derivative, and derivatized beta-cyclodextrin, even more preferably a mixture of derivatised alpha-cyclodextrin and derivatized beta- cyclodextrin; and most preferably a mixture of hydroxypropyl alpha-cyclodextrin and hydroxypropyl beta-cyclodextrin, and/or a mixture of methylated alpha-cyclodextrin and methylated beta-cyclodextrin.

The cavities within the functionally-available cyclodextrin in the detergent compositions should remain essentially unfilled (i.e., the cyclodextrin remains uncomplexed and free) or filled with only weakly complexing materials when in solution, in order to allow the cyclodextrin to absorb (i.e., complex with) various unwanted molecules, such as malodor molecules, when the composition is applied to a surface containing the unwanted molecules. Non-derivatized (normal) beta-cyclodextrin can be present at a level up to its solubility limit of about 1 .85% (about 1 .85 g in 100 grams of water) at room temperature. Beta-cyclodextrin is not preferred in compositions which call for a level of cyclodextrin higher than its water solubility limit. Non-derivatized beta- cyclodextrin is generally not preferred when the composition contains surfactant since it affects the surface activity of most of the preferred surfactants that are compatible with the derivatized cyclodextrins.

The level of low-degree of substitution cyclodextrin derivatives that are functionally-available in the odor control compositions is typically at least about 0.001 %, preferably at least about 0.01 %, and more preferably at least about 0.1 %, by weight of the detergent composition. The total level of cyclodextrin in the present composition will be at least equal to or greater than the level of functionally-available cyclodextrin. The level of functionally-available will typically be at least about 10%, preferably at least about 20%, and more preferably at least about 30%, by weight of the total level of cyclodextrin in the composition.

Concentrated compositions can also be used. When a concentrated product is used, i.e., when the total level of cyclodextrin used is from about 3% to about 60%, more preferably from about 5% to about 40%, by weight of the concentrated composition, it is preferable to dilute the concentrated composition before treating fabrics in order to avoid staining. Preferably, the concentrated cyclodextrin composition is diluted with about 50% to about 6000%, more preferably with about 75% to about 2000%, most preferably with about 100% to about 1000% by weight of the concentrated composition of water. The resulting diluted compositions have usage concentrations of total cyclodextrin and functionally-available cyclodextrin as discussed hereinbefore, e.g., of from about 0.1 % to about 5%, by weight of the diluted composition of total cyclodextrin and usage concentrations of functionally-available cyclodextrin of at least about 0.001 %, by weight of the diluted composition.

Forms

The detergent compositions can take any of a number of forms and any type of delivery system, such as ready-to-use, dilutable, wipes, or the like.

For example, the detergent compositions can be a dilutable fabric detergent, which may be an isotropic liquid, a surfactant-structured liquid, a granular, spray-dried or dry- blended powder, a tablet, a paste, a molded solid, a water soluble sheet, or any other laundry detergent form known to those skilled in the art. A "dilutable" fabric detergent composition is defined, for the purposes of this disclosure, as a product intended to be used by being diluted with water or a non-aqueous solvent by a ratio of more than 100:1 , to produce a liquor suitable for treating textiles. "Green concentrate" compositions like those on the market today for Fantastic^®, Windex^® and the like, can be formulated such that they could be a concentrate to be added to a bottle for final reconstitution.

The detergent compositions can also be formulated as a gel or a gel packet or pod like the dishwasher products on the market today. Water-soluble sheets, sachets, or pods such as those described in U.S. Pat. Appl. No. 2002/0187909, the teachings of which are incorporated herein by reference, are also envisaged as a suitable form. The detergent composition can also be deposited on a wiper or other substrate.

Polymeric suds enhancers

In some aspects, polymeric suds enhancers such as those described in U.S. Pat. No. 6,903,064 can be used in the detergent compositions. For example, the compositions may further comprise an effective amount of polymeric suds volume and suds duration enhancers. These polymeric materials provide enhanced suds volume and suds duration during cleaning.

Examples of polymeric suds stabilizers suitable for use in the compositions:

(i) a polymer comprising at least one monomeric unit having the formula:

wherein each of R¹ , R² and R³ are independently selected from the group consisting of hydrogen, Ci to Ce alkyl, and mixtures thereof; L is O; Z is CH2 ; z is an integer selected from about 2 to about 12; A is NR⁴R⁵, wherein each of R⁴ and R⁵ is independently selected from the group consisting of hydrogen, Ci to Cs alkyl, and mixtures thereof, or NR⁴R⁵ form an heterocyclic ring containing from 4 to 7 carbon atoms, optionally containing additional hetero atoms, optionally fused to a benzene ring, and optionally substituted by Ci to Cs hydrocarbyl;

(ii) a proteinaceous suds stabilizer having an isoelectric point from about 7 to about

1 1 .5;

(iii) a zwitterionic polymeric suds stabilizer; or

(iv) mixtures thereof.

Preferably, the exemplary polymeric suds stabilizer described above has a molecular weight of from about 1 ,000 to about 2,000,000; more preferably the molecular weight is about 5,000 to about 1 ,000,000. Other applications

Although we found that the inventive detergent compositions have considerable value for laundry detergents, other end uses should benefit from their use. Thus, the surfactants should also be valuable in applications where greasy substances require removal or cleaning at low temperature. Such applications include, for example, household cleaners, degreasers, sanitizers and disinfectants, light-duty liquid detergents, hard and soft surface cleaners for household, autodish detergents, rinse aids, laundry additives, carpet cleaners, spot treatments, softergents, liquid and sheet fabric softeners, industrial and institutional cleaners and degreasers, oven cleaners, car washes, transportation cleaners, drain cleaners, industrial cleaners, oil dispersants, foamers, defoamers, institutional cleaners, janitorial cleaners, glass cleaners, graffiti removers, adhesive removers, concrete cleaners, metal/machine parts cleaners, and food service cleaners, and other similar applications for which removal of greasy soils is advantageously accomplished, particularly at room temperature or below. The detergents may also be beneficial for certain personal care applications such as hand soaps and liquid cleansers, shampoos, and other hair/scalp cleansing products, especially for oily/greasy hair, scalp, and skin, which are also beneficial when effective with lukewarm or cold water. Additionally, the detergents may also benefit applications requiring solubilization of active materials, such as agricultural compositions, in which the detergent might function as a solvent, surfactant, or adjuvant.

The following examples merely illustrate the invention; those skilled in the art will recognize many variations that are within the spirit of the invention and scope of the claims.

Sodium pentaervthritol tris(n-hexyl ether) sulfate Pentaervthritol tris(n-hexyl ether)

The procedure of J. Org. Chem. 50 (1985) 3296; 52 (1987) 2995 and Chem. Eur. iL 13 (2007) 5585 is generally followed with modifications as indicated below. A reaction vessel is charged with 50% aq. sodium hydroxide solution (400 g, 5.0 mol), and the solution is heated to 80°C under nitrogen. Pentaerythritol (product of Celanese, 100 g, 0.734 mol) is added, and the mixture is stirred for 1 h. The mixture becomes clear and homogeneous. Heptane (150 mL) is added along with 1 - bromohexane (Acros, 363.7 g, 2.20 mol) and tetrabutylammonium bromide (15 g). The reaction mixture stirs at 80°C overnight.

Stirring is discontinued, and the reaction mixture is combined with water and hexanes. The organic phase is separated and retained. The aqueous phase is extracted with hexanes. The combined organic extracts are filtered through silica gel and concentrated to give a clear liquid (about 200 mL). The liquid is stripped at 75°C under vacuum to remove volatiles. Increasing the temperature to 100°C removes no further distillate. The concentrated product is vacuum distilled. A forerun (about 20 mL) collected at pot temperature 100-190°C is discarded. The desired product is collected at pot temperature 190-200°C, overhead temperature 160-170°C. Yield: 180 g (63%). ¹ H NMR results are consistent with the desired pentaerythritol tris(n-hexyl ether).

Sulfation of pentaerythritol tris(n-hexyl ether)

A reaction vessel is charged with sulfur trioxide-pyridine complex (21 .5 g, 0.135 mol) and chloroform (200 mL). The mixture is magnetically stirred under nitrogen and warmed to 50°C. Pentaerythritol tris(n-hexyl ether) prepared as described above (50.0 g, 0.129 mol) is added dropwise from an addition funnel over about 1 h. A mild exotherm is noted. When the addition is complete, the mixture is stirred for 0.5 h at 50°C. The reaction mixture is light brown and hazy with some insoluble material present. The mixture is filtered through diatomaceous earth, which removes a tan solid. The filtrate is stripped to give a brown syrup. The syrup is combined with methanol (200 mL) and stirred magnetically at room temperature. Sodium hydroxide solution (10.8 g of 50% aq. NaOH) is added dropwise to neutralize the product. After cooling, the mixture is filtered through diatomaceous earth, then concentrated and dried overnight under vacuum at room temperature.

The resulting sticky semi-solid is dissolved in acetone (200 mL) with gentle warming. The solution is concentrated to about 50 mL by rotary evaporation. Meanwhile, acetonitrile (about 200 ml_ total) is added using a wash bottle. When the acetonitrile is added, an oil precipitates. Upon storage in a freezer (-40°C) for 1 h, the precipitated oil solidifies. Liquids are decanted and discarded. The acetone wash and acetonitrile precipitation steps are repeated. The second washing is mostly clear. The washed oil is stripped and dried under high vacuum to give a viscous yellow syrup. Yield of sodium pentaerythritol tris(n-hexyl ether) sulfate: 50 g. ¹ H NMR analysis of the product is consistent with the desired sodium sulfate product.

Sodium pentaerythritol tris(n-pentyl ether) sulfate

The procedures used to make sodium pentaerythritol tris(n-hexyl ether) sulfate are generally followed, except that 1 -bromopentane is used instead of 1 -bromohexane in the first step.

Sodium glycerol 1 ,3-bisdauryl ether) sulfate

Glycerol 1 ,3-bisdauryl ether)

The procedure of PCT Publ. No. WO 01 /76626 is generally followed with the modifications indicated below.

A reaction vessel equipped with mechanical stirring, thermocouple, nitrogen inlet, and condenser is charged with lauryl alcohol (C12-C14 mixture; 200 g, 1 .0 mol). Potassium tert-butoxide (56 g, 0.50 mol) is added, and the mixture is heated to 60-70°C. A mild exotherm is noted. The mixture is stirred overnight at 50°C, resulting in a clear, yellow solution.

Epichlorohydrin (23.5 g, 0.25 mol) is added dropwise to the alkoxide solution at 60-70°C, and the temperature is kept at or below 70°C with cooling. After the addition is complete, the mixture stirs for 2 h at 70°C. Analysis of a small, quenched sample by ¹H NMR shows that no unreacted epichlorohydrin remains.

The mixture is cooled briefly and water (25 imL) is added, causing no exotherm. The reactor contents are transferred to a separatory funnel and combined with more water. The aqueous phase is isolated and set aside. The organic phase is washed with water (250 imL) and 20% aq. sodium chloride (50 imL). All of the aqueous phases are retained and combined. The organic phase is diluted with dichloromethane, washed with 20% aq. NaCI (100 mL), and concentrated to give an orange oil. The combined aqueous portion is acidified with 50% aq. sulfuric acid. This aqueous mixture is extracted with dichloromethane (200 mL). All of the organic portions are combined and stripped to give an orange oil. The oil is diluted with ethyl acetate (150 mL) and filtered through silica gel to give a clear yellow solution, which is then concentrated. ¹H NMR analysis of the concentrate reveals a mixture of lauryl alcohol and the desired glycerol diether.

Acetonitrile (250 mL) is added to the oil and the mixture is swirled. On standing, an orange oil separates out. The yellow acetonitrile phase is decanted away, and the process is repeated twice. Concentration of the acetonitrile extracts provides 100 mL of a light yellow liquid, which is confirmed by ¹H NMR to be lauryl alcohol.

The washed orange oil is combined with acetonitrile (250 mL) and acetone (20 mL), and the mixture is stirred mechanically while cooling in an ice/water bath. As the mixture cools, a pasty solid precipitates. Stirring continues until the liquid phase is clear. The liquid is removed via cannula tipped with filter paper using suction and a filter flask. The washing process is repeated 5x, after which the fatty alcohol remains at only trace levels.

The resulting product is a light tan, waxy solid (mp: 30°C). ¹H NMR is consistent with the desired glycerol diether. The product is dried overnight under high vacuum. Yield: 50.1 g (45% based on charged epichlorohydrin).

Sulfation of glycerol 1 ,3-bisdauryl ether)

A reaction vessel is charged with sulfur trioxide-pyridine complex (8.92 g, 56 mmol) and chloroform (100 mL). The mixture is magnetically stirred under nitrogen and warmed to 50°C. A solution of glycerol 1 ,3-bis(lauryl ether) prepared as described above (25.0 g, 56 mmol) in chloroform (50 mL) is added from an addition funnel over 0.5 h at 50°C to the stirred mixture. No exotherm is noted. When the addition is complete, the mixture is stirred for 1 .5 h at 50°C.

The hazy mixture is concentrated to give a pasty semi-solid. Ethanol (3A, 150 mL) is added and the mixture is stirred magnetically. Aqueous sodium hydroxide (50% solution) is added dropwise to adjust the pH to >9. A hazy yellow solution results. The mixture is filtered through diatomaceous earth to remove a fine precipitate. The filter cake is rinsed with methanol. Concentration of the filtrates provides a yellow flocculent solid. Acetone (100 mL) is added, which provides an off-white solid and a yellow solution. The liquid is decanted and concentrated, providing nothing of interest. The washed solids are redissolved in acetone (100 mL) with heating and swirling. Addition of acetonitrile (100 mL) yields a white precipitate. The mixture is cooled to complete the precipitation. The liquid is removed via cannula. The precipitation process is repeated to give a light tan solid, which is dried under high vacuum to a white powder. The ¹H NMR spectrum is consistent with the desired sodium glycerol 1 ,3-bis(lauryl ether) sulfate product. Yield: 21 .3 g.

Sodium glycerol 1 ,3-bis(n-octyl ether) sulfate

The procedures used to make sodium glycerol 1 ,3-bis(lauryl ether) sulfate are generally followed using 1 -octanol instead of lauryl alcohol.

Sodium glycerol 1 ,3-bis(2-ethylhexyl ether) sulfate

The procedures used to make sodium glycerol 1 ,3-bis(lauryl ether) sulfate are generally followed using 2-ethylhexyl alcohol instead of lauryl alcohol. Disodium bis(2-ethylhexyl) sebacate α,α'-disulfonate

Dimethyl sebacate is sulfonated using known methods to provide the corresponding α,α'-disulfonic acid (mol. wt. 390.4 g/mol). The disulfonic acid (200 g, 0.512 mol) is warmed and transferred to a reaction flask and is stirred at 40°C under nitrogen. 2-Ethylhexyl alcohol (200.1 g, 1 .54 mol) is added slowly to the disulfonic acid, resulting in a moderate exotherm. The reaction temperature is increased to 80°C, and a mild vacuum (25 mm) is applied to remove volatiles. After 3 h at 80°C, the reaction temperature is increased to 85°C and held at that temperature for 1 h. The reaction continues for another 3 h at 85°C under vacuum (25 mm Hg). Upon cooling overnight, the mixture separates into two layers. The mixture is reheated to 85°C/25 mm Hg for 2 h. More 2-ethylhexyl alcohol (66.7 g, 0.512 mol) is added, and the reaction continues at 80°C/25 mm Hg for 4 h. After cooling to room temperature overnight, heating resumes to 85°C for 2 h. Vacuum is increased to full vacuum for another hour. More 2-ethylhexyl alcohol (25 g) is added, and the reaction continues at 85°C/full vacuum for 2.5 h.

The crude product is cooled, diluted to about 1 L with methanol, and neutralized with 50% aq. NaOH solution. Hydrogen peroxide (9 g of a 4.5 wt.% aq. solution made from 50% H2O2) is added to the cool solution, but no bleaching occurs. Increasing the temperature to 60°C for 0.5 h also results in no color improvement. The mixture is re- cooled, and 50% aqueous sodium hydroxide solution (75 g) is added to achieve a stable pH of about 8.5, while maintaining a temperature below 30°C during the neutralization.

The neutralized mixture is concentrated to give a pasty semi-solid. Acetonitrile (500 mL) is added and mixed on the rotary evaporator. The mixture is allowed to sit for 0.5 h. The clear acetonitrile phase is decanted from the resulting solids. Acetone (500 mL) is added to give an orange/brown powder precipitate in an orange solution. More acetone (250 mL) is added to convert all of the pasty solids to a powder precipitate. The mixture stands at room temperature, and the liquid phase is removed using Teflon tubing tipped with filter paper. Fresh portions of acetone are used to wash the precipitate.

The product is dried under high vacuum to give a free-flowing powder. ¹ H HMR analysis is consistent with the desired disodium bis(2-ethylhexyl)sebacate α,α'- disulfonate as the major product, along with a small proportion of methyl esters. Yield: 250 g.

Disodium bis(2-butyloctyl) sebacate α,α'-disulfonate

The procedures used to prepare disodium bis(2-ethylhexyl) sebacate α,α'- disulfonate are generally followed using 2-butyloctyl alcohol instead of 2-ethylhexyl alcohol.

Sodium 7rans-Ci8 Internal Olefin Sulfonate

7rans-9-octadecene

Alumina is activated by heating at 120°C for 4 h; the alumina is then stored in a dessicator for several days. 1 -Decene (300 g, 2.14 mol) and activated alumina (30.0 g) are combined in an Erlenmeyer flask fitted with a drying tube, and the mixture is stirred overnight. The alumina is removed by filtration, and the olefin mixture is transferred to a reaction flask equipped with condenser, rubber septum, nitrogen inlet, thermocouple, heating mantle, magnetic stirring, and an outlet from the condenser to an oil bubbler for monitoring ethylene evolution. The mixture is sparged with nitrogen during heating to 60°C and then sparged for another 30 min. Metathesis catalyst (catMETium^® RF3, product of Evonik, 0.094 g, 0.107 mmol) is introduced via a funnel weigh boat. The mixture foams as ethylene is produced over the next 48 h. The mixture is filtered through diatomaceous earth. ¹ H NMR analysis shows the absence of vinyl protons, indicating complete conversion of 1 -decene to metathesis products. The product mixture comprises about 80% frans-9-octadecene and about 20% c/s-9-octadecene.

Sulfonation

A sample of the 9-octadecene mixture described above (19.36 g, 0.0767 mol) is charged to a reactor maintained at 10°C with a pre-established nitrogen flow (4 L/min). Over 0.5 h, sulfur trioxide (7.22 g, 0.0902 mol) is evaporated via a 140°C flash-pot and is bubbled through the olefin mixture using the nitrogen stream. The reaction temperature is maintained from 20°C to 26°C. After the addition is complete, the reaction mixture is held for another 5 min, then transferred to a jar and frozen until it can be neutralized.

The frozen sulfonic acid product is thawed, and a sample (57.2 g) is poured into a solution of water (50 mL), methanol (5 mL), and 50% aqueous sodium hydroxide (6.2 g). The mixture is heated to 78°C and stirred 17 h at this temperature, during which the pH drops to about 3. Additional 50% aq. sodium hydroxide is added to increase the pH to about 9. Analysis by ¹ H NMR shows that unhydrolyzed sultone is present. Hydrolysis continues for another 48 h, with more additions of aq. NaOH solution as needed. When the reaction is deemed complete, the mixture is partitioned with a mixture of petroleum ether (200 mL) and SDA 3A ethanol (200 mL). The aqueous phase is retained and is washed with petroleum ether (6 x 200 mL). The product is an aqueous solution containing mostly sodium Cis internal olefin sulfonate from fra/is-9-octadecene. Sodium C/S-C18 Internal Olefin Sulfonate

C/s-9-octadecene

Wittig chemistry is used to produce c/s-9-octadecene from the reaction of nonanal and the triphenylphosphonium ylid generated from 1 -bromononane and triphenylphosphine according to well-known methods.

Sulfonation

The procedure described above for sulfonating fra/is-9-octadecene is generally followed. The thawed sulfonic acid product is poured into a solution of water (20 imL) and 50% aqueous sodium hydroxide (6.4 g). After stirring, methanol (5 imL) is added, and the mixture is heated to 85°C and maintained at 85°C for 65 h. Analysis by ¹ H NMR shows that hydrolysis is complete. The mixture is partitioned using petroleum ether and 3A ethanol as described above. After isolation of the aqueous phase, the pH is adjusted with concentrated sulfuric acid. The product is an aqueous solution containing mostly sodium C18 internal olefin sulfonate from c/s-9-octadecene.

Test formulations

Tables 1 and 4 summarize the laundry detergent formulations tested for the inventive examples, while Tables 2 and 5 summarize the formulations tested for the comparative examples.

Procedure for testing laundry detergent samples

Laundry detergent (to give 0.1 % actives in washing solution) is charged to a washing machine, followed by soiled/stained fabric swatches that are attached to pillowcases. Wash temperature: 60°F. Rinse temperature: 60°F. The swatches are detached from pillowcases, dried, and ironed. Swatches are scanned to measure the L^* a^* b^* values, which are used to calculate a soil removal index (SRI) for each type of swatch. Finally, the ASRI is calculated, which equals the experimental sample SRI minus the SRI of a pre-determined standard laundry detergent formula (or control). When | ASRl | > 0.5 differences are perceivable to the naked eye. If the value of ASRI is greater than or equal to 0.5, the sample is superior. If ASRI is less than or equal to -0.5, the sample is inferior. If ASRI is greater than -0.5 and less than 0.5, the sample is considered equal to the standard.

The following standard soiled/stained fabric swatches are used: bacon grease, cooked beef fat, and beef tallow. At least three of each kind of swatch are used per wash. Swatches are stapled to pillowcases for laundering, and extra pillowcases are included to complete a six-pound load.

The same procedure is used to launder all of the pillowcases/swatches, with care taken to ensure that water temperature, wash time, manner of addition, etc. are held constant for the cold-water wash process. When the cycle is complete, swatches are removed from the pillowcases, dried at low heat on a rack, and pressed gently and briefly with a dry iron.

A Hunter LabScan^® XE spectrophotometer is used to determine the L^* a^* b^* values to calculate the SRI for every type of swatch, and the stain removal index (SRI) is calculated as follows:

SRI— 100 - i^L ^ clean L ^ washed ~h ^ i ^ clean CI ^ washed ~h (j ^ clean I? ^ washed

SRI— SRIsample— SRIs tan dard

Performance results for cold-water cleaning of cotton fabric treated with bacon grease, cooked beef fat, and beef tallow greasy soils are compared. All formulations are tested at 0.1 % actives levels. Wash cycles are 30 min in front-loading high-efficiency washing machines. The target performance (which corresponds to a ASRI value of 0.0) is that of a commercial cold-water detergent or a control cold-water detergent used with a cold-water wash (60°F) and cold-water rinse (60°F). Results

Table 3 summarizes cold-water cleaning results using detergents comprising polyol ether sulfates (e.g., sodium pentaerythritol tris(n-pentyl ether) sulfate and sodium glycerol 1 ,3-bis(n-octyl ether) sulfate) or disodium dialkyi esters of sulfonated dicarboxylic acids (e.g., disodium bis(2-ethylhexyl)sebacate α,α'-disulfonate). The detergents include either a sodium linear alkylbenzene sulfonate ("NaLAS") or a sodium C12-C14 alcohol ethoxylate (3 EO) sulfate ("NaAES"). As the table shows, the cleaning performance on these greasy soils can be remarkable, with overall changes in stain removal index (ASRI) as high as 24, where a ASRI value of greater than 3 can be significant. In some cases, the results are relatively unimpressive (negative ASRI values). Optimization is needed to identify, for instance, which anionic surfactant will work best with which polyol ether sulfate. In general, however, the glycerol-based polyol ether sulfates having a pair of linear or branched Cs tails performed well with either NaLAS or NaAES. With regard to the pentaerythritol-based polyol ether sulfates, the compositions with three Cs or C6 tails generally outperform those with three branched Cs tails. Results from the dialkyl esters of sulfonated dicarboxylic acids are less clear.

Table 6 summarizes cold-water cleaning results using detergents comprising internal olefin sulfonates (e.g., sodium C15-C18 IOS, sodium C20-C24 IOS, sodium cis- or frans-ds lOSs) and secondary alkyl sulfates (e.g., Hostapur^® SAS-60, Hostapur^® SAS- 30LS). Here, there is a clear trend favoring coupling of these surfactants with NaLAS rather than NaAES. Only the sodium c/^'s-C18 IOS performs well with NaAES. On the other hand, all of the IOS and SAS surfactants deliver double-digit improvements in ASRI versus the control for cleaning greasy stains in cold water when they are coupled with NaLAS.

Table 3. Performance in Cold-Water Cleaning Greasy Soil Stain Set

ASRI of Cleaning Data at 60°F wash/60°F rinse

Test formulation (0.1 % actives) Bacon Beef Cooked Overall

Grease Tallow Beef Fat ASRI

Control 0.0 0.0 0.0 0.0

Inventive examples

Na pentaerythritol tris(n-pentyl ether)

6.79 16.43 0.85 24.07 sulfate/Nal_AS/N25-7 (Formulation A)

Na pentaerythritol tris(n-hexyl ether)

6.44 14.83 2.44 23.71 sulfate/Nal_AS/N25-7 (Formulation C)

Na pentaerythritol tris(n-hexyl ether)

5.05 1 1 .86 0.19 17.10 sulfate/NaAES/N25-7 (Formulation D)

Na glycerol 1 ,3-bis(n-octyl ether)

4.59 8.61 -1 .06 12.14 sulfate/Nal_AS/N25-7 (Formulation G)

Na glycerol 1 ,3-bis(n-octyl ether)

4.25 5.48 -2.22 7.51 sulfate/NaAES/N25-7 (Formulation H)

Na glycerol 1 ,3-bis(2-ethylhexyl ether)

6.13 17.78 -0.66 23.25 sulfate/Nal_AS/N25-7 (Formulation I)

Na glycerol 1 ,3-bis(2-ethylhexyl ether)

4.35 1 1 .13 -2.36 13.12 sulfate/NaAES/N25-7 (Formulation J)

Di-Na bis(2-butyloctyl) sebacate α,α'-

3.37 2.93 -0.41 5.89 disulfonate/NaLAS/N25-7 (Formulation K)

Comparative examples

Na pentaerythritol tris(n-pentyl ether)

2.81 1 .15 -2.29 1 .67 sulfate/NaAES/N25-7 (Formulation B)

Na pentaerythritol tris(2-ethylhexyl ether)

3.26 -3.21 -3.53 -3.48 sulfate/Nal_AS/N25-7 (Formulation E)

Na pentaerythritol tris(2-ethylhexyl ether)

3.73 -0.44 -3.12 0.17 sulfate/NaAES/N25-7 (Formulation F)

Di-Na bis(2-butyloctyl) sebacate α,α'-

2.02 -5.84 -2.86 -6.68 disulfonate /NaAES/N25-7 (Formulation L)

Di-Na bis(2-ethylhexyl) sebacate α,α'-

2.24 -5.29 -2.40 -5.45 disulfonate /NaLAS/N25-7 (Formulation M)

Di-Na bis(2-ethylhexyl) sebacate α,α'-

2.46 -2.15 -3.78 -3.47 disulfonate /NaAES/N25-7 (Formulation N)

ormua on

Evaluation of Hvdrophile-Lipophile Deviation (HLD) Parameters of Central Headqroup Surfactants

Preparation of sodium 2-hexyl-1 -decyl sulfate

2-Hexyl-1 -decanol (100.3 g) is added to a 1 -L flask equipped with mechanical stirrer, nitrogen inlet, and reflux condenser. 1 ,4-Dioxane (500 imL) is added, and the mixture is stirred. Sulfamic acid (42.7 g) and urea (10.2 g) are added. The mixture is slowly heated to reflux (105°C) and refluxing continues for 7 h. The mixture is cooled. Urea and residual sulfamic acid are removed by filtration. The mixture is concentrated to remove 1 ,4-dioxane. Methanol is added to the 2-hexyl-1 -decyl sulfate ammonium salt, and then 50% aq. NaOH solution is added to achieve a pH of about 10.4. Methanol is removed. ¹H NMR analysis shows significant impurities. The product is purified using a separatory funnel and 50:50 EtOH:deionized water with petroleum ether as extractant. The resulting mixture, which contains sodium 2-hexyl-1 -decyl sulfate, is stripped and analyzed (96.9% actives by ¹H NMR).

Preparation of sodium 2-octyl-1 -decyl sulfate/ sodium 2-hexyl-1 -dodecyl sulfate

2-Octyl-1 -decanol/2-hexyl-1 -dodecanol (199.6 g) is added to a 1 -L flask equipped with mechanical stirrer, nitrogen inlet, and reflux condenser. 1 ,4-Dioxane (400 imL) is added, and the mixture is stirred. Sulfamic acid (62.2 g) and urea (15.4 g) are added. The mixture is slowly heated to reflux (105°C) and refluxing continues for 6.5 h. The mixture is cooled. Urea and residual sulfamic acid are removed by filtration. The mixture is concentrated to remove 1 ,4-dioxane. Methanol is added to the 2-octyl-1 -decyl/2-hexyl- 1 -dodecyl sulfate ammonium salt, and then 50% aq. NaOH solution is added to achieve a pH of about 10.4. Methanol is removed. ¹H NMR analysis shows significant impurities. The product is purified using a separatory funnel and 50:50 EtOH:deionized water with petroleum ether as extractant. The resulting mixture, which contains sodium 2-octyl-1 - decyl sulfate/ sodium 2-hexyl-1 -dodecyl sulfate, is stripped and analyzed (98.5% actives by ¹H NMR).

a us e p . . .

A control liquid laundry detergent formulation and two experimental formulations are prepared as shown in Table 7. In Formulation AA, the NaAES component of the control is replaced with sodium 2-hexyl-1 -decyl sulfate. In Formulation BB, the NaAES component of the control is replaced with a mixture of sodium 2-octyl-1 -decyl sulfate and 2-hexyl-1 -dodecyl sulfate.

The HLD parameters of the formulation components are determined experimentally as has been previously described (see: J. L. Salager et al., SPE-7054-PA 19 (April, 1979) 107; J. L. Salager et al., SPE-7584-PA 19 (October, 1979) 271 ; and E. J. Acosta, J. Surf. Deterq. V\_ (2008) 145). See also: A. Witthayapanyanon et al., J. Colloid Interface Sci. 325 (2008) 259.

At optimum salinity, the HLD value of the mixture is zero, and the measured optimum salinity of the mixture (S*mix) is related to the empirical constant (Kmix) and the characteristic curvature (Ccmix) by the following simplified expression, which applies for ionic surfactant systems with no added alcohol or cosurfactant:

ln(S*mix) = Kmix x EACN - Ccmix - ατΔΤ where EACN is the equivalent alkane carbon number, Kmix =∑ Xi Ki and Ccmix =∑ Xi Cci where xi is the mole fraction of each surfactant, Ki is the K value for each individual surfactant, Cci is the characteristic curvature for each individual surfactant, ατ is a constant, and ΔΤ is the temperature deviation from 25°C.

When a plot of ln(S*mix) versus EACN is made for mixtures of surfactants with a series of hydrocarbons (e.g., hexane, octane, decane), the slope will have a value of Kmix and the y-intercept will have a value of -Ccmix. Because the mole fraction of each surfactant component will be known in advance, the value of Ki for each component of the surfactant mixture can be calculated.

Table 8 provides the overall HLD and individual HLD parameters for each surfactant component of the control formulation, with values calculated at 15°C with beef tallow as the soil. As shown in Table 8, the overall HLD for the control formula is about - 3.55. For Steol^® CS-330 the K value is 0.028, and the characteristic curvature is about - 3.6. As shown below in Table 1 1 , this formulation is used as the control and does not provide particular benefits for cold-water cleaning.

Table 9 shows the corresponding HLD parameters for the formulation using 2- hexyl-1 -decyl sulfate in replacement of the Steol^® CS-330 from the control formula. The overall HLD for the formula with 2-hexyl-1 -decyl sulfate is about -3.14. The 2-hexyl-1 - decyl sulfate has a K value of 0.133, and the characteristic curvature is about -0.19. The larger K value for the cold water surfactant of this example versus the control may indicate a stronger interaction of the surfactant with the beef tallow. Both the Cc and overall HLD in this example are less negative compared with the control. As shown in Table 1 1 , relative to the control, this formulation provides substantial benefits for cold-water cleaning.

Table 10 shows the corresponding HLD parameters for the formulation using 2- octyl-1 -decyl sulfate. The overall HLD for the formulation containing 2-octyl-1 -decyl sulfate in replacement of the Steol^® CS-330 from the control formula is about -3.16. The 2-octyl-1 -decyl sulfate has a K value of 0.173, and the characteristic curvature is about 0.35. The larger K value for 2-octyl-1 -decyl sulfate versus the control may indicate a stronger interaction with the beef tallow. The Cc value for sodium 2-octyl-1 -decylsulfate is slightly positive. The overall HLD is less negative compared with the control. The optimal HLD for improved cold-water cleaning may be less than that for a conventional detergent optimized for warm- or hot-water cleaning. Use of a surfactant with a greater Cc may help to create a system with a more optimized balance for cold-water cleaning.

Tables 12 and 13 demonstrate the sharp decline in cold-water cleaning performance when the amount of NaAES in a formulation with NaLAS and a nonionic surfactant exceeds about 10 wt.%.

Table 1 1 . Performance in Cold-Water Cleaning Greasy Soil Stain Set

ASRI of Cleaning Data at 60°F wash/60°F rinse

Test formulation (0.1 % Bacon Cooked Beef

actives) Grease Butter Fat Beef Tallow

Na LAS/Na AES (3 EO)/ 0.0 0.0 0.0 0.0 Neodol^® 25-7 (control)

Sodium 2-hexyl-1 -decyl 4.50 0.27 3.92 9.63 sulfate/Na LAS/Neodol^® 25-7

(Formulation AA)

Sodium 2-octyl-1 -decyl/2- 3.49 0.33 1 .15 10.19 hexyl-1 -dodecyl sulfate/

Na LAS/Neodol^® 25-7

(Formulation BB)

Table 1 3. Performance in Cold-Water Cleaning Greasy Soil Stain Set

ASRI of Cleaning Data: Cold water wash/rinse

Detergency for Individual Soils (ASRI)

Test formulation Cooked Beef Bacon Overall ASRI (0.1% actives) Beef Tallow Fat Grease vs Formulation 1

2 -1 .01 -0.21 -0.15 -1 .37

3 -3.30 0.24 0.28 -2.78

4 -4.77 0.32 -0.24 -4.69

C5 -10.74 -0.28 -0.90 -1 1 .92

C6 -1 1 .02 -0.99 -1 .04 -13.05

7 9.10 1 .60 - 10.70

8 6.41 2.94 - 9.35

Test conditions: front-loadinq washinq machine; surfactant concentration: 1000 ppm; wash/rinse temperature: 60°F/60°F; wash/rinse time: 30 min./20 min.; total load: 6 lb.

The preceding examples are meant only as illustrations; the following claims define the invention.

Claims

We claim:

1. A composition, useful for cold-water cleaning, comprising a detergent having at least one centrally located headgroup and two or more hydrophobic tails, wherein the headgroup and the tails are optionally joined by one or more linking groups.

2. The composition of claim 1 wherein the headgroup is selected from the group consisting of sulfonate, sulfate, ethoxylate, carboxylate, amine oxide, phosphate, quaternium, betaine, sulfobetaine, and combinations thereof.

3. The composition of claim 1 or claim 2 wherein each tail is independently a saturated or unsaturated, linear, branched, or cyclic C4-C30 group.

4. The composition of any of claims 1 to 3 wherein the linking group is selected from the group consisting of saturated or unsaturated hydrocarbyl, monoester, diester, alcohol, ether, polyether, bisphenol, aryl, disulfide, amine, amide, or a combination thereof.

5. The composition of any of claims 1 to 4 wherein the detergent is selected from the group consisting of internal olefin sulfonates, polyol ether sulfates, and dialkyi esters of sulfonated dicarboxylic acids.

6. The composition of claim 5 wherein the internal olefin sulfonate comprises a hydroxyalkane sulfonate, an alkene sulfonate, or a mixture thereof.

7. The composition of claim 5 wherein the detergent is a C15-C18 internal olefin sulfonate, and the composition further comprises a linear alkylbenzene sulfonate.

8. The composition of claim 5 wherein the detergent is a C20-C24 internal olefin sulfonate, and the composition further comprises a linear alkylbenzene sulfonate.

9. The composition of claim 5 wherein the detergent is cis- or trans- C18 internal olefin sulfonate, and the composition further comprises a linear alkylbenzene sulfonate or an alcohol ether sulfate.

10. The composition of claim 5 wherein the detergent is a polyol ether sulfate selected from the group consisting of glycerol bis(C4-C2o alkyl ether) sulfates, pentaerythritol tris(C4-C2o alkyl ether) sulfates, pentaerythritol bis(C4-C2o alkyl ether) disulfates, trimethylolpropane bis(C4-C2o alkyl ether) sulfates, trimethylolethane bis(C4- C20 alkyl ether) sulfates, polyglycerol bis(C4-C2o alkyl ether) mono- and disulfates, dipentaerythritol tetrakis(C4-C2o alkyl) mono- and disulfates, and combinations thereof.

11. The composition of claim 10 wherein the polyol ether sulfate is a glycerol bis(C6-Cio alkyl ether) sulfate.

12. The composition of claim 10 wherein the polyol ether sulfate is a pentaerythritol tris(C5-C6 alkyl ether) sulfate.

13. The composition of any of claims 10 to 12 further comprising a linear alkylbenzene sulfonate or an alcohol ether sulfate.

14. The composition of claim 5 wherein the detergent is a C4-C20 dialkyl sulfomethylsuccinate, and the composition further comprises a linear alkylbenzene sulfonate or an alcohol ether sulfate.

15. The composition of claim 5 wherein the detergent is a C10-C14 dialkyl ester of a mono- or disulfonated C8-C12 dicarboxylic acid, and the composition further comprises a linear alkylbenzene sulfonate.

16. The composition of any of claims 1 to 4 wherein the detergent is a secondary alkyl sulfate, and the composition further comprises a linear alkylbenzene sulfonate.

17. The composition of any of claims 1 to 4 wherein the detergent is a sulfonated bis(C4-C2o alkyl-substituted aryl) ether, a sulfonated bisphenol C4-C20 dialkyl ether, or a sulfonated C4-C20 alkyl-substituted arene.

18. The composition of any of claims 1 to 4 wherein the detergent is a sulfated polyol or a sulfated hydroxy-functional dendrimer.

19. The composition of any of claims 1 to 4 wherein the detergent is an alpha- olefin sulfonate dimer, a cross-dimer of an alpha-olefin sulfonate and an olefin, or a sulfonates of an unsaturated fatty ester.

20. The composition of any of claims 1 to 4 wherein the detergent is a vinylidene sulfonate, a sulfonated arene substituted with two or more C4-C20 alkyl ester or bis(C4-C2o alkyl) amide groups, or a sulfonated arene substituted with one or more branched C4-C20 alkyl groups.

21. The composition of any of claims 1 to 4 wherein the detergent is a sulfonated C4-C20 diether or a C4-C20 diester of catechol, resorcinol, or hydroquinone.

22. The composition of any of claims 1 to 4 wherein the detergent is a phosphate diester of a C4-C20 alcohol or a phosphate diester of a C4-C20 alcohol alkoxylate.

23. The composition of any of claims 1 to 4 wherein the detergent is a C1-C4 alkyl C4-C2o dialkylamine oxide.

24. The composition of any of claims 1 to 4 wherein the detergent is a C4-C20 dialkyl urea or carbamate of cystine.

25. The composition of any of claims 1 to 4 wherein the detergent is a sulfonate- functionalized block copolymer comprising one or more recurring units selected from the group consisting of ethylene, propylene, butenes, isoprene, styrene, alkylated styrenes, butadiene, divinylbenzene, alkyl (meth)acrylates, and (meth)acrylic acid.

26. The composition of any of claims 1 to 25 further comprising a nonionic surfactant.

27. The composition of claim 26 wherein the nonionic surfactant is a fatty alcohol ethoxylate.

28. The composition of any of claims 1 to 27 further comprising an anionic surfactant.

29. The composition of claim 28 wherein the anionic surfactant is selected from the group consisting of linear alkylbenzene sulfonates, fatty alcohol ethoxylate sulfates, fatty alcohol sulfates, and mixtures thereof.

30. A liquid, powder, paste, granule, tablet, molded solid, water-soluble sheet, water-soluble sachet, capsule, or water-soluble pod comprising the composition of any of claims 1 to 29.

31. A method which comprises laundering one or more textile articles in water having a temperature less than 30°C the presence of the composition of any of claims 1 to 29.

32. The method of claim 31 wherein the water has a temperature within the range of 5°C to 30°C.

33. A method which comprises using the composition of any of claims 1 to 29 as a laundry pre-spotter or pre-soaker for cold-water manual or machine washing.

34. A method which comprises using the composition of any of claims 1 to 29 as an additive or booster component to improve the grease cutting or grease removal performance of a laundry product or formulation.

35. A mixture comprising a surfactant and the composition of any of claims 1 to 29, wherein the composition is used in an amount effective to improve the grease cutting or grease removal performance of the mixture.

36. A method which comprises liquefying a greasy soil in water at a temperature less than 30°C in the presence of the composition of any of claims 1 to 29.

37. The method of claim 36 wherein the soil is selected from the group consisting of beef tallow, bacon grease, butter, cooked beef fat, and mixtures thereof.

38. The method of claim 36 or claim 37 wherein the soil is liquefied in water at a temperature within the range of 5°C to 25°C.

39. A laundry detergent comprising 1 to 15 wt.% of a surfactant having a K value greater than 0.1 .

40. A laundry detergent comprising 1 to 15 wt.% of a surfactant having a Cc value greater than -1 .

41. The laundry detergent of claim 39 or claim 40 wherein the surfactant has a K value within the range of 0.12 to 0.20 and a Cc value within the range of -0.2 to 0.5.

42. A laundry detergent comprising 1 to 15 wt.% of a surfactant having an HLD greater than -3.5 when beef tallow is the soil.

43. The laundry detergent of claim 42 wherein the HLD is within the range of -3.4 to -1 .5.

44. The laundry detergent of claim 42 wherein the HLD is within the range of -3.4 to -3.0.