Various esterquats are known as cationic fabric softening agents. See, for example, WO-A-93/25648, DE-A-4, 339, 643 and US-A-4, 339, 391 ; US-A-4, 767, 547, US- A-4, 874, 554 and US-A-5, 066, 414. Other examples of known quaternized ester-amines include US-A-5, 463, 094, which discloses quaternary ammonium compounds which the starting tertiary amine can include carboxylic esters of hydroxyalkyl groups. European Patent Application No. 97 105 620. 5 teaches a family of esterified alkanolamines prepared by first alkoxylating an alkanolamine having from 1 to 3 OH groups with alkylene oxides having from 2 to 6 carbons, then esterifying the compounds.

It has been recently reported in WO-A-97/42279 that quaternary ammonium ester-based softener compositions containing high diester content and low triester content have improved softening properties. The procedure reported by WO-A- 97/42279 to make such compositions requires the use of 1. 6 to 1. 8 moles of unsaturated fatty acids per mole of trialkanol amine. The unsaturated fatty acid is required to have a high level of the cis isomer, or an isomerizing step to convert esters to the desired cis/trans configuration. This reference also teaches a controlled heating protocol which is necessary in order to achieve the desired goal of high diester.

Similarly, DE-A-4, 243, 701 discloses that beneficial fabric softening properties can be seen from the diesterquat of triethanolamine (TEA), but this reference provides no method for obtaining such diesters in a reaction mixture.

It would be beneficial to be able to produce softener compositions having high diester content which could be made from a wider variety of carboxylic acids and which did not require an addition isomerization step, or restrictive heating procedures.

WO-A-97/03160 indicates the benefits of having cationic ester surfactants in laundry detergents. These benefits include superior greasy cleaning and improved

antiredeposition of soils during the wash process. Although the reference cites examples for the use of such cationic ester surfactants (CET) in both liquid and powder it is stated that the CET hydrolyses during the wash process. If the CET readily hydrolyses, it would make its use in liquid detergent formulations problematical, as it would likely be hydrolyzed to a great extent before use. The reference's stated preferred CET is a choline esterquat based on a C,2,4 fatty acid, which does readily hydrolyze. It would therefore be beneficial to develop a reaction mixture of partially esterified tertiary alkanolamines having a predominance of the monoester (whether the starting alkanolamine is a diol or a triol) which would be stable enough to be formulated in liquid laundry detergents.

Surprisingly, it has been discovered that when the alcohol groups on a di- or tri- alkanolamine are distributed between primary, secondary or even tertiary alcools, the resulting ester distribution between monoester, diester, and triester (and unreacted alkanolamine) is shifted towards less completely esterified molecules. Without intending to be bound by any particular theory, it is believed that this phenomenon is explained by the reactivity of the various alcools. Thus, it is believed that by limiting the amount of carboxylic acid to less than one mole of acid per mole of OH group, and by making some of the alcohol groups on the starting alkanolamine primary and some secondary or tertiary, the odds are increased that some types of alcohols will be esterified first, leaving a higher percentage of incompletely esterified alkanolamines.

Further it has surprisingly been discovered that if the alkanol groups on the alkanolamines are large enough, then formation of the incompletely esterified species is still favored, whether or not the starting alkanolamines are all of the same type of alcohol. It is thought, again without intending to be bound to any particular theory, that this observation is a result of steric hindrance, rather than chemical reactivity, but the effect is the same.

Reaction mixtures made according to the present invention exhibit improved softening or detergency properties and are more hydrolytically stable than reaction mixtures of the prior art. This makes them well-suited for use in fabric softeners, paper softeners, cleaners, detergents, and personal care applications.

In one embodiment of the present invention, a lower alkanolamine (i. e. a primary or secondary amine), or mixtures thereof, is alkoxylated with an alkylene oxide or a mixture of alkylene oxides, then esterified with a carboxylic acid, and then optionally neutralized or quaternized. The alkanolamines suitable as the starting material for this embodiment of the invention have the structure : where R1, R2, R3 and R4 are independently in each moiety H or an alkyl group ; n is independently in each moiety a number equal to 1 or greater; R', R2, R3, R4 and n are such that the number of carbon atoms between N and O is no more than 18 ; R 7 is H or R' ; and R5 is (CR'R2)n-CR3R4-oH, an alkyl having from 1-6 carbon atoms, a cycloalkyl having 6 carbon atoms, or an aryl group. The alkylene oxides suitable for use in the present invention correspond to the formula CYH2yO, where y is from 2 to 18, preferably 2 to 6. In order to facilitate the formation of the diester and monoester, the materials are chosen such that if y is only 2 then for at least some of the lower alkanolamines in the mixture, in at least one moiety on the N group, R3 or R4 will be an alkyl group.

In another embodiment of the present invention a reaction mixture is prepared which has a higher proportion of diester or monoester, at the expense of the completely esterified alkanolamine, than previously reported. When the alkanolamine has 3 OH groups prior to esterification the process of the invention can produce reaction mixtures having greater than 50 percent by weight of the diester component. When the alkanolamine has 2 OH groups, the monoester portion in the final reaction mixture can represent 60 percent or more by weight of the total reaction mixture. These reaction mixtures may then be neutralized or quaternized to facilitate their use in various applications.

It has been found that compositions of the present invention exhibit surprisingly high hydrolytic stability over a wide pH range, have unexpectedly low melting points, are more compatible with detergent and personal care ingredients and they can be more easily handled either in the diluted form or formulated as stable liquid concentrates as compared to corresponding reaction mixtures made from di- or tri-ethanolamines.

Accordingly, in another embodiment of the present invention these compounds are used in such applications as fabric softeners, paper softeners, detergents, cleaners and personal care items.

In one embodiment, the composition of the present invention comprises a reaction mixture comprising monoester (II), diester (III), triester (IV) and optionally free alkanolamine (I) components corresponding to the following formulae : wherein : R is an alkyl group having 1 to 30 carbons ; R', R2, R3 and R4 are independently in each moiety H or an alkyl group provided that R3 and R4 are not all H in all of the moieties ; n is independently in each moiety a number equal to 1 or greater ; n and R', R2, R3 and R4 are such that the number of carbon atoms between N and O is no more than 18 ; Rs is (CR'R2)n-CR3R4-oH, an alkyl having from 1-6 carbon atoms, a cycloalkyl having 6 carbon atoms, or an aryl group ; Q is H, an alkyl group having 1 to 6 carbons, or an aryl group having 6-12 carbons, optionally substituted with an alkyl group, or HOCHR6CH2-, wherein Rs is H or an alkyl group having 1 to 4 carbons ;

X is an inorganic or organic acid anion ; and p is from 0 to 1, the reaction mixture having been prepared at least in part from the esterification of an alkanolamine corresponding to the formula : wherein R¹, R², R³ R4, R5 and n are as defined above, and when R'is (CR'R) n-CR3R ~OH, the diester content resulting from that particular alkanolamine is greater than 50 percent by weight calculated when p is 0 ; and when R5 is other than (CR'R2)n-CR3R4-oH, there is no component corresponding to formula IV above resulting from that particular alkanolamine.

In another embodiment, the composition of the present invention comprises a reaction mixture comprising monoester (vil), diester (ici), triester (IV) and, optionally, free alkanolamine (I) components corresponding to the following formulae :

wherein : R is an alkyl group having 1 to 30 carbons ; R', R2, R3 and R4 are independently in each moiety H or an alkyl group provided that R3 and R° are not all H in all of the moieties in the reaction mixture ; n is independently in each moiety a number equal to 1 or greater ; n and R', R2, R3 and R'are such that the number of carbon atoms between N and O is no more than 18 ; R'is (CR'R2) n-CR'R 4-OH, an alkyl having from 1-6 carbon atoms, a cycloalkyl having 6 carbon atoms, or an aryl group ; Q is H, an alkyl group having 1 to 6 carbons, or an aryl group having 6-12 carbons, optionally substituted with an alkyl group, or HoCHR5CH2-, wherein R6 is H or an alkyl group having 1 to 4 carbons ; X is an inorganic or organic acid anion ; and p is from 0 to 1, the reaction mixture having been prepared at least in part from the esterification of an alkanolamine corresponding to the formula : wherein R', R', R', R', R'and n are as defined above, and the monoester content resulting from the alkanolamine is greater than 50 percent, more preferably greater than 55 percent, still more preferably greater than 60 percent and most preferably greater than 65 percent.

It should be understood that the term"composition"includes both a single chemical entity and mixtures of chemical entities which correspond to the same general formula. It should also be understood that as used herein, the term"moiety"means a group of inter-connected atoms which is attached to the central nitrogen atom.

It is preferred that R have from 4-24 carbon atoms, and more preferred that R have from 7-22 carbon atoms. The R group may be straight or branched, and may have different levels of saturation. Generally, it is preferred that the R group have an lodine value less than 140. Iodine values can be calculated by ways known in the art.

For some applications, such as concentrated fabric softeners or clear transparent formulations, it is generally preferred that the R group have lodine values greater than 20, but in other applications, such as detergents, lodine values less than 20, including fully saturated R groups can be advantageously used. For general, less concentrated fabric softener use, the lodine values have not been shown to have a significant effect and so all ranges may be used.

It is preferred that n be equal to 1, especially in those moieties where R3 or R4 is an alkyl group. It is also preferred that R'and R2 are H. It is also generally preferred that not both R3 and R4are alkyl groups in the same moiety. Furthermore it is preferred that when R or R"is an alkyl group, it is an alkyl group having 1 or 2 carbons. It is also preferred that n and R', R2, R3 and R4 are such that the number of carbon atoms between N and O is no more than 6.

It should be understood that p represents an average, showing the degree of neutralization or quaternization, but that for any particular molecule, it will be 0 or 1. It is also within the scope of this invention to not quaternize the reaction mixture at all, although this is not preferred.

In another embodiment, the invention comprises a procedure to make esterified alkanolamines, wherein the reaction mixture will have a disproportionate amount of not fully esterified product than would normally be expected. The procedure comprises esterifying an alkanolamine (or mixtures thereof) corresponding to the following formula :

wherein R1, R2, R3 and R4 are independently in each moiety H or an alkyl group provided that R3 and R4 are not all H in all of the moieties in the mixture ; n is independently in each moiety a number equal to 1 or greater ; n and R1, R2, R3 and R4 are such that the number of carbon atoms between N and O is no more than 18 ; R5 is (CR¹R²)n-CR³R4-OH, an alkyl having from 1-6 carbon atoms, a cycloalkyl having 6 carbon atoms, or an aryl group.

Preferably the alkanolamine is formed by alkoxylating a primary or secondary alkanolamine (or mixtures thereof) with one or more alkylene oxides where the primary or secondary alkanolamine corresponds to the formula : where R¹, R², R³ and R4 are independently in each moiety H or an alkyl group ; n is independently in each moiety a number equal to 1 or greater ; n, R', R2, R3 and R4 are such that the number of carbon atoms between N and O is no more than 18; R7is H or R5 ; and R5is (CR'R2)n-CR3R4-oH, an alkyl having from 1-6 carbon atoms, a cycloalkyl having 6 carbon atoms, or an aryl group ; and the alkylene oxide corresponds to the formula CyH2yO7 where y is from 2 to 18, preferably 2 to 6. In order to facilitate the formation of the diester and monoester, the materials are chosen such that if y is only 2 then for at least some of the lower alkanolamines in the mixture, in at least one moiety on the N group) R3 or R4 will be an alkyl group. It is preferred that n be equal to 1, especially in those moieties where R3 or R4 are an alkyl group. It is also preferred that R' and R2 are H. It is also generally preferred that not both R3 and R"are alkyl groups in the same moiety. Furthermore it is preferred that when R3 or R4is an alkyl group, it is an alkyl group having 1 or 2 carbons. It is also preferred that n and R1, R2, R3 and R4 are such that the number of carbon atoms between N and O is no more than 6.

Preferred alkylene oxides include ethylene oxide, propylene oxide and butylene oxide.

Although not necessary, this alkoxylation reaction process may be carried out in the presence of an alkaline catalyst, such as sodium, potassium, calcium, barium and strontium hydroxide, in an amount of from 0. 01 to 5, preferably 0. 1 to 0. 5, percent by

weight based on the total weight of the mixture at the completion of the reaction. Care must be taken when using catalyst not to alkoxylate the OH groups, and so in general, the use of catalyst is not preferred for this invention. Temperature and pressures are not critical, but conveniently the alkoxylation reaction is carried out at an elevated temperature, preferably at a temperature from 50°C to 200°C, more preferably from 80°C to 120°C and a pressure of from 1 to 80 bars. The alkaline catalysts suitable for use in this reaction are well known to a person skilled in the art. After completion of the reaction, that is, for example, when the pressure does not change any more, the catalyst is removed by a suitable method, such as by filtration over an absorbing clay, for example, magnesium silicate, or neutralized with an inorganic acid such as, for example, hydrochloric acid, or an organic acid such as, for example, acetic acid. If desired, an excess of an acid can be used, so that the excess of the acid can serve as a catalyst in the subsequent reaction step. It is advantageous to carry out the alkoxylation reaction in the presence of a defoaming agent.

The esterification reaction comprises contacting the alkanolamine with a carboxylic acid (or a mixture of carboxylic acids) under conditions sufficient to cause at least a portion of the carboxylic acid to react with at least a portion of the OH groups on the alkanolamine so as to form esters. The carboxylic acid corresponds to the formula RCOOH, where R is an alkyl group having 1 to 30 carbons. It is preferred that R have from 4-24 carbon atoms, and more preferred that R have from 7-22 carbon atoms. The R group may be straight or branched, and may have different levels of saturation.

Generally, it is preferred that the R group have an lodine value less than 140. lodine values can be calculated by ways known in the art. For some applications it is preferred that the R group have lodine values greater than 20, but in other applications, lodine values less than 20, including fully saturated R groups can be advantageously used.

Where unsaturated R groups are used, it is preferred that the ratio of the cis to trans isomer be 80 : 20 or greater. Suitable examples of carboxylic acids useful in the esterification reaction include valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid, and the branched isomers thereof (isovaleric acid, for example), or the unsaturated isomers thereof (for example, oleic acid). These fatty acids are wetl-known to the person of ordinary skill in the art.

The esterification reaction conveniently is carried out at an elevated temperature, preferably at a temperature from 50°C to 250°C, more preferably from 180°C to 220°C, and reduced pressure, preferably from 1 to 500 mbar, more preferably from 20 to 200 mbar. It should be readily understood that the amount of carboxylic acid

used will correlate to the degree of esterification in the final composition. The more acid which is used, the higher the percentage of the completely esterified component which will be in the final product. Similarly, the less acid used, the higher the percentage of unreacted alkanolamine which will be seen in the final composition. Accordingly, for reactions using trialkanolamines as a starting material, it is preferred that the acid be added in an amount of from 0. 5 to 0. 7 moles of carboxylic acid per mole of OH on the alkanolamine (1.5 to 2. 1 moles acid per mole trialkanolamine). Surprisingly, it has been discovered that using the process of the invention, reaction mixtures of trialkanolamines with a diester content greater than 50 percent by weight can be observed even when adding the acid at ratios of greater than 1.8 moles of acid per mole of trialkanolamine (0. 6 moles of acid per mole equivalent of trialkanolamine) or less than 1. 6 moles of acid per mole of trialkanolamine (0.53 moles of acid per mole equivalent of trialkanolamine).

If a monoester of a trialkanolamine is desired, then it is preferred that the acid be added in an amount of from 0. 4 to 1. 1 moles of acid per mole of trialkanolamine (0. 13 to 0. 37 moles of acid per mole of OH on the trialkanolamine). Surprisingly, at these ratios reaction mixtures having greater than 55 percent by weight can be obtained. If a monoester of a dialkanol amine is desired, then it is preferred that the acid be added in an amount of from 0. 4 to 1. 1 moles of acid per mole of dialkanol amine (0. 2 to 0. 55 moles of acid per mole of OH on the dialkanol amine). At these ratios, reaction mixtures having greater than 60 percent monoester can be obtained.

Optionally, the esterified alkanolamines can then be neutralized or quaternized by contacting the esterified alkanolamines with a composition corresponding to the formula QX, under conditions sufficient to cause at least a portion of the esterified alkanolamines to form a quaternized, or neutralized product. Q in the above formula is H, an alkyl group having 1 to 6 carbons, or an aryl group having 6-12 carbons, optionally substituted with an alkyl group, or HoCHR5CH2-, wherein R6 is H or an alkyl group having 1 to 4 carbons ; and X is an inorganic or organic acid anion.

When Q is H, the neutralization reaction is preferably carried out at the molar ratio of from 0. 05 to 2 moles QX per mole of esterified alkanolamine. Such a reaction can be carried out at room temperature or above the melting point of the alkoxylated ester-amine compound, and at a pressure of from 1 to 50 bars. When Q is something other than H, the quaternization reaction is preferably carried out at the ratio of from 0. 1 to 20 moles QX per mole of esterified alkanolamine, at a temperature of from 30°C to 150°C, and a pressure of from 1 to 50 bars. Any known inorganic acid such as, for example, hydrochloric acid, or organic acid such as, for example, citric acid can be used as the HX compound to protonate the alkoxylated ester-amine (see for example, WO-A-

94/04641 and WO-A-94/04642). Any known quaternizing agent can be used as the QX compound. Suitable quaternizing agents of formula QX include alkyl halides, dialkyl sulfates, and trialkyl phosphates. Preferred alkyl halides include methyl chloride, ethyl chloride, methyl bromide, and ethyl bromide ; preferred dialkyl sulfates include dimethyl sulfate, and diethyl sulfate, and preferred trialkyl phosphates include trimethyl phosphate and triethyl phosphate. It is advantageous to carry out the quaternization reaction in the presence of a defoaming agent. It can also be advantageous to carry out the quaternization reaction in the presence of an additive which can lower the melting point of the reaction mixture, as is known in the art. These additives can be added at any stage of the reaction. Suitable additives include materials such as water, isopropanol, propanediol, dipropylene glycol, PEG, PPG, alkoxylated fatty acids and alcools having more than 3 carbons in the fatty chain, glycol ether solvents such as DOWANOLTM P and E series, diether solvents such as PROGLYDETM DMM, tetrahydrofuran, methanol, ethanol, hexanediol, and acetone.

The compositions of the present invention exhibit good softening, detergency, antifoaming and antistatic properties, they have low melting points, and are hydrolytically stable at various pH values. In general, the compositions of the invention which have higher diester content tend to be especially well suited for the fabric and paper softening applications, while those compositions with high monoester content tend to show improved detergency properties.

In the context of the present invention,"hydrolytically stable"means that less than 30 percent, preferably less than 20 percent, of composition of Formulas (I-IV) above when Q is not H and p is greater than 0. 75 and less than 40 percent of a composition of Formulas (I-IV) above when p is 0, or Q is H, hydrolyzes after 4 weeks from a 5 percent aqueous solution having a pH value of 4, at a temperature of 50°C.

With regards to esterified dialkanolamines having greater than 50 percent monoester, "hydrolytically stable"means that less than 45 percent, preferably less than 30 percent hydrolyzes after 4 weeks from a 5 percent aqueous solution having a pH value of 4, at a temperature of 50°C, when p is greater than 0. 8. tut should be understood that the extent of hydrolysis defined above is valid for a value of pH 4 and that hydrolysis extent would decrease with decreasing pH and increase with increasing pH. The improved hydrolytic stability of the compositions of the present invention allow them to be used in liquid or gel detergent, softergent or softener formulations.

Moreover, the compositions of the present invention are compatible even with fabric and paper softeners'ingredients and detergents ingredients which are normally

not compatibie with known softening compounds without the presence of special additives. Due to these properties the composition mixtures of the present invention can be formulated into formulations suitable for various end use applications such as, for example, fabric and paper softening formulations, formulation for cleaning and conditioning fabric materials ("softergents"), antifoaming formulations, personal care formulations, lubricating formulations, drilling fluid formulations and hard surface cleaning formulations.

Thus, in another aspect the present invention concerns a fabric softening, paper softening, detergent, personal care, or cleaner formulation comprising the composition of the invention. The formulations of the present invention can also incorporate one or more known ingredients commonly used in fabric softening, paper softening, detergent, personal care or cleaner formulations.

The fabric and paper softening formulations of the present invention can be in various forms, such as, for example, aqueous or anhydrous liquid formulations, super concentrate liquid formulations, solid formulations obtained by a suitable process such as grinding the softener composition or depositing it onto solid substrates such as powders or granules, or onto cellulosic substrate sheets for use in tumble dryers. The fabric softening formulations can be used in a tumbler dryer or in the rinse cycle in a washing machine for example by dispensing the fabric softening formulation via a dispensing compartment optionally with dilution prior to dosing into the dispensing compartment. The fabric and paper softening formulations of the present invention which have a pH below 8 when diluted for normal use conditions are preferred. Normal use conditions are known in the art but are generally in the range of from 0. 01 to 0. 5 percent by weight active ingredient, and most commonly about 0. 05 percent.

Thus in another embodiment the present invention concerns an anhydrous or aqueous fabric and paper softening formulation comprising at least 0. 01, preferably from 0. 01 to 95 percent by weight the composition of the invention.

The liquid fabric and paper softening formulations of the present invention may be prepared by mixing the composition of the invention with a liquid carrier and, optionally, at least one other above mentioned ingredient in a standard formulation mixing equipment and in accordance with techniques known to a person skilled in the art. Low-shear mixing is generally sufficient to adequately and uniformly mix the softening composition within the softening formulation. The final softening formulation, whether in concentrated or diluted form must be easily pourable by the end user. For concentrated softening formulation, which can be used without any dilution if desired,

the formulation may be formulated to be diluted (for example, for refill packs) by a factor of generally 4 : 1 or more, preferably up to 8 : 1 or even up to 20 : 1.

Commercial fabric softener formulations contain normally from 5 to 20 percent of softening agent. They are normally opaque milky emulsions of various viscosities. In general the viscosity of fabric softening formulations increase with the increase in concentration of its fabric softening agent. Additives are normally used to stabilize more concentrated fabric softening formulations (for example, those containing between 10 and 20 percent softening agent). It should be noted that WO-A-96/21715 teaches the use of special deflocculating nonionic polymeric surfactants to allow incorporation of up to 35 percent of a softening agent. The absence of additives would lead to gelling of softening formulations containing more than 15 percent of a softener agent.

It has now surprisingly been discovered that not only do the compositions of the present invention which have a high diester content have unexpectedly higher hydrolytic stability than known softening agents, but they also have lower melting points than known softening agents based on esterquats of ethanolamine. Without the desire to be bound to a theory, it is believed that this unique combination of high hydrolytic stability and low melting points of the compositions allow for the formulation of stable super-concentrated and, if desired, anhydrous fabric softening formulations with or without the incorporation of stabilizing additives. Even more surprisingly, it has been discovered that super concentrated and anhydrous fabric softening formulations incorporating the composition of the invention are transparent in most instances.

The present invention also encompasses the super concentrated fabric softening formulations comprising from 10 to 100 percent of the composition of the invention. These super concentrated formulations, whether transparent or not, can be used for example, for a refill pack (to be diluted in a large bottle) or as concentrates for direct use by a consumer, or can help save transportation costs of the softener or the fabric or paper softening formulations.

Mixtures of fabric softeners and detergents (softergents) are commercially available. Such formulations can be in liquid, paste or granular form. Such softergents normally contain soft clays and/or cationic surfactants having only one long alkyl group in the molecule (for example, lauryltrimethyl ammonium chloride). Known softergents have a number of limitations. For example, the softening performance of these softergents is inferior to the performance of a fabric softener used separately in the last rinse of the wash process. Another limitation is the difficulty in formulating softergents

containing cationic softener having more than one long alkyl chain in the molecule (common softening agent used in softening formulations). Still another limitation is the fact that a cationic softener having one or more ester links must be formulated at a low pH which does not correspond to typical neutral-to-alkaline pH of the detergent.

It has now surprisingly been discovered that due to the compatibility of compositions of the present invention with conventional detergent ingredients and because they are hydrolytically stable at typical detergent pH's they can conveniently be formulated with any known detergent ingredients into a softergent having none of the aforementioned limitations.

Thus, in another aspect the present invention concerns a powder or liquid softergent formulation comprising 1 to 90 weight percent of at least one composition of the invention, which softergent formulation has a pH in the range of from 1. 5 to 12. In case of powder softergent, the absence of solvent in the composition of the invention makes the softergent safer to use. Moreover, the composition permits the selection of a softener which has a low enough melting point to be suitable for making powder softergent and allows optimum dispersion during the wash cycle.

The compositions of the present invention can suitably be formulated with a wide variety of known materials commonly found in fabric or paper softening formulations, laundry detergents, hard surface cleaning formulations and personal care formulations. Such materials used in fabric or paper softening formulations, laundry detergents, hard surface cleaning formulations and personal care formulations include, but are not limited to the following : (a) Enzymes and Enzyme Stabilizers - Enzymes can be included for various fabric cleaning and fabric softening purposes. Nonlimiting examples of suitable enzymes include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof. The enzymes may be of any suitable origin, such as vegetable, animal, bactericidal, fungal and yeast origin. The enzymes used may be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions. Any water-soluble calcium or magnesium salt can be used as a source of calcium or magnesium ions. A wide range of useful enzyme and enzyme stabilizer materials are described in WO-A-95/19951 and WO-A-96/21715, and EP-A-0579295 and EP-A-0583536.

(b) Bleaching Agents and Bleach Activators - Any known bleaching agent used in fabric or paper treatment applications can be used. Nonlimiting examples

of suitable bleaching agents include oxygenated bleaches, percarboxylic acid bleaches, peroxygen bleaches and mixtures thereof. Bleach activator can also be used. Various nonlimiting examples of useful bleaching agents and bleach activators are given in WO- A-95/19951.

(c) Builders - Inorganic and organic builders commonly used in fabric laundering formulations to assist in removal of particulate solids can be used. Suitable builders include, but are not limited to, phosphates, polyphosphates, silicates, aluminosilicates, phosphonates, carboxylates, zeolites and succinates. Nonlimiting examples of suitable builders are described in WO-A-95/19951 and EP-A-0579295, and EP-A-0580245.

(d) Soil Release Agents - Any known polymeric soil release agent used in laundry cleaning formulations can be used. Polymeric soil release agents include, but are not limited to, the compounds having : (i) at least one nonionic hydrophilic component consisting essentially of (a) polyoxyethylene segments with a degree of polymerization of at least 2, or (b) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, or (c) a mixture of oxyalkylene units comprising oxyethylene and from 1 to 30 oxypropylene units, (d) cellulosic derivatives such as hydroxyether cellulosic polymers, (e) copolymeric blocks of terephthalate with polyethylene oxide or polypropylene oxide. Nonlimiting examples of useful soil release agents are given in WO-A-95/04802, WO-A-93/23510 and WO-A- 93/25648.

(e) Chelatina aqents - Any known chelating agent is suitable for use.

Suitable chelating agents include, but are not limited to, amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof. It is believed that the benefit of the chelating materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates. Nonlimiting examples of suitable chelating agents are described in WO-A-95/19951 and WO-A-96/21715.

(f) Clay Soil Removal/Anti-Redeposition Aqents - Any water-soluble alkoxylated amines having clay soil removal and anti-redeposition properties normally used in granular or liquid detergents can be used. Nonlimiting examples of useful clay soil removal/anti-redeposition agents are described in WO-A-95/19951.

(g) Dispersina Aaents - Suitable dispersing agents are polymeric dispersing agents such as, for example, polymeric polycarboxylates and polyethylene

glycols, normally used in detergents. Nonlimiting examples of the dispersing agents are given in WO-A-95/19951. Protonated amines, such as those described in WO-A- 93/25648, and terephthalate/alkylene oxide copolymers, such as those described in WO-A-96/21715 can be used to enhance dispersion stability.

(h) Optical Briahteners - Any known brightener used in detergents can be used. Suitable brighteners include, but are not limited to, derivatives of stilbene, pyrazoline, coumarin, and carboxylic acid. Nonlimiting examples of suitable brighteners are given in WO-A-95/19951 and WO-A-96/21715.

(i) Suds Suppressors - Any known compound that suppresses or reduces the formation of suds is suitable for use. Such compounds include, but are not limited to, silicones, silica-silicone mixtures, monocarboxylic fatty acids and soluble salts thereof, high molecular weight hydrocarbons such as paraffin, and fatty acid esters of monoalcohols. These and other suitable suds suppressors are described in WO-A- 95/19951 and EP-A-0579295.

(j) Fabric Softeners - Any known fabric softener compound can be used. Nonlimiting examples of suitable fabric softener compounds include clay softeners, conventional quaternary ammonium softening agents, anionic softeners, nonionic softeners, and cationic softeners. These and other suitable fabric softeners are described in WO-A-95/04802, WO-A-95/19951, and WO-A-96/21715, and EP-A-0580245.

(k) Detersive Surfactants - Various surfactant materials such as anionic, nonionic, cationic, ampholytic, and zwitterionic surfactants can be used.

Nonlimiting examples of suitable surfactant include linear alkyl sulfonates ("LAS")" C,1- C,8 alkyl benzene sulfonates, primary and secondary branched-chain and random Ci. - C20 alkyl sulfates ("AS"), and polyhydroxy fatty acid amide surfactants. These and other suitable surfactants are described in WO-A-93/23510, WO-A-25648 and WO-A-95/19951, EP-A-0579296, EP-A-0583536 and EP-A-0580245.

Other materials which can optionally be included are liquid carriers such as, for example, water and Cl-c4 monohydric alcools, thickening agents, viscosity control agents, di- (higher alkyl) cyclic amines, aqueous emulsions of predominantly linear polydialkyl or alkylaryl siloxanes absorbency enhancers, pH modifiers such as bases and acids, nonionic or other deflocculating agents, hydrotropes, colorants, perfumes, perfume carriers, preservatives, opacifiers, fluorescers, anti-shrinking agents, anti- wrinkle agents, anti-spotting agents, bactericides, germicides, fungicides, anti-corrosion

agents, drape imparting agents, antistatic agents, ironing agents, wetting agents, strength additives such as carboxymethyl cellulose and water-soluble cationic polymers.

These optional materials are well known and widely used in the art. See, for example, WO-A-95/19951, WO-A-93/25648, WO-A-93/23510, WO-A-96/21715, WO-A-96/09436 and WO-A-94/29521, and EP-A-0580245.

Various processes for formulating active ingredients with addition materials into formulations useful in fabric or paper softening applications, taundry detergent applications, hard surface cleaning applications and personal care applications are known and widely used in the industry. Some of the processes are described in the references cited herein before.

The following examples are included for illustration purposes and should not be interpreted as limiting the scope of the invention or the claims. Unless otherwise indicated all percentages are by weight. The following designations, symbols, terms and abbreviations which are used in the examples have the following meanings : BO is butylene oxide PO is propylene oxide MEA is monoethanolamine DEA is diethanolamine TEA is triethanolamine MDEA is methyidiethanolamine MAE is methyl amino ethanol (methyl monoethanolamine) DMAE is dimethyl amino ethanol MDIPA is methyl diisopropanolamine TIPA is triisopropanolamine DMS is dimethyl sulfate MeCI is methyl chloride

Examples 1-2 Preparation of Polyalkanolamines with 2 Primary and 1 Secondary Hydroxyl Group An example to prepare polyalkanolamines with 2 primary and 1 secondary hydroxyl group is by reaction in a 1 : 1 mole ratio of DEA with propylene- or butylene oxide to form [bis(2-hydroxyethyl)]-[2-hydroxypropyl]amine (DEA-1 PO) or [bis (2- hydroxyethyl)]-[2-hydroxybutyl]amine (DEA-1 BO). This reaction can be conveniently carried out by addition of the alkylene oxide to the DEA in a pressure vessel at temperatures from 50°C to 200°C, preferably from 80°C to 120°C and at a pressure of 1 to 80 bars.

On a small scale, alkylene oxide is added at 110°C to DEA (1 : 1 mole ratio) in a 2 liter vessel, the temperature being controlled by cooling the vessel and controlling the feed rate of the alkylene oxide. This reaction takes usually 2 to 3 hours to a point where the pressure becomes constant. The product thus obtained, contains ! 98 weight percent DEA-1 PO or DEA-1 BO and does not need further purification.

Examples 3-4 Preparation of Polyalkanolamines with 1 Primary and 2 Secondary Hydroxyl Groups An example to prepare polyalkanolamines with 1 primary and 2 secondary hydroxyl groups is by reaction in a 1 : 2 mole ratio of MEA with propylene- or butylene oxide to form [(2-hydroxyethyl)]-[bis(2-hydroxypropyl)]amine (MEA-2PO) or [ (2- hydroxyethyl)]-[bis(2-hydroxybutyl)]amine (MEA-2BO). This reaction can be conveniently carried out by addition of the alkylene oxide to the MEA in a pressure vessel at temperatures from 50°C to 200°C, preferably from 80°C to 120°C and at a pressure of 1 to 80 bars.

On a small scale, alkylene oxide is added at 110°C to MEA (2:1 mole ratio) in a 2 liter vessel, the temperature being controlled by cooling the vessel and controlling the feed rate of the alkylene oxide. This reaction takes usually 2 to 3 hours to a point where the pressure becomes constant. The product obtained, contains ! 98 weight percent MEA-2PO or MEA-2BO and does not need further purification.

Examples 5-6 Preparation of Polyalkanolamines with 1 Primary and 1 Secondary Hydroxyl Group An example to prepare polyalkanolamines with 1 primary and 1 secondary hydroxyl group is by reaction in a 1 : 1 mole ratio of MAE (N-methyl-2-aminoethanol) with propylene- or butylene oxide to form N-methyl- (2-hydroxyethyl) - (2-hydroxypropyl) amine

(MAE-1 PO) or N-methyl-(2-hydroxyethyl)-(2-hydroxybutyl)amine (MAE-1 BO). This reaction can be conveniently carried out by addition of the alkylene oxide to the MAE in a pressure vessel at temperatures from 50°C to 200°C, preferably from 80°C to 120°C and at a pressure of 1 to 80 bars.

On a small scale, alkylene oxide is added at 110°C to MEA (2 : 1 mole ratio) in a 2-liter vessel, the temperature being controlled by cooling the vessel and controlling the feed rate of the alkylene oxide. This reaction takes usually 2 to 3 hours to a point where the pressure becomes constant. The product, thus obtained, contains 2 98 weight percent MAE-1 PO or MAE-1 BO and does not need further purification.

Examples 7-8 Preparation of Polyalkanolamines Having no Primary Hydroxyl Groups Polyalkanolamines having no primary hydroxyl groups can be prepared by standard methods known in the art. For example, these products can be made by reaction of ammonia or monoalkylamine with a C3 or higher alkyleneoxide. In particular, ammonia can be reacted with propylene oxide to form TIPA and methylamine can be reacted with propyleneoxide to form MDIPA.

Examples 9-27 Esters and Ester Distribution The polyalkanolamines prepared in Examples 1 to 8 can be esterified with a carboxylic acid or a carboxylic acid mixture of choice under conventional conditions, known to those skilled in the art. Typically the polyalkanolamine is mixed with a carboxylic acid in the desired mole ratio in a vessel equipped with stirrer and a Dean- Stark set-up and reacted at a temperature of 50°C to 250°C, preferably 100°C to 200°C and at reduced pressure of 1 to 500 mbar, preferably 20 to 200 mbar, in order to make the removal of the water formed during the reaction easier. For these Examples the esterification reaction took place at approximately 200°C and 20 mbar. ! n general the esterification reaction is continued until the residual acid content is less than 5 percent, preferably less than 2 percent, which level is usually reached after 4 to 12 hours.

The esters obtained were analyzed by GC, GPC or NMR for unreacted alkanolamine, mono-, di- and triester. The results, in percent by weight, are presented in Table 1. The results show the effect of using PO vs. BO, of changing the particular carboxylic acid, of changing the mole ratio of carboxylic acid reacted, and the effect of using different combinations of primary and secondary alcools, and using di vs. trialkanolamines. Examples 14,15, 19 and 22 are comparative Examples which do not form a part of this invention but which were prepared according to the same procedure

as the other Examples. These comparative examples demonstrate the manner in which the method of the present invention alters the resulting ester distribution.

Examples 28-29 Effect of Temperature In order to show the effect of temperature, Examples 11 and 12 were repeated except that the esterification reaction was carried out at a temperature of about 160°C rather than 200°C. The results, which are included in Table 1, demonstrate the temperature of esterification had little effect on the resulting distribution.

TABLE I Example No. alkanolamine fatty acid FA mole unreacted mono di triester ratio DEA-1 PO Radiacid 1.6 3 27 52 18 409 10 DEA-1BO Radiacid 1. 6 2 27 54 17 409 11 DEA-1PO Radiadd 2 - 14 52 32 409 12 DEA-1BO RadiacidTM 2 - 15 55 30 409 13 MEA-2PO RadiacidTM 2 - 14 55 31 409 14 (comp. ) TEA stearic 1. 5 4 26 42 28 acid 15 (comp. ) TEA stearic 2 1 14 43 42 acid 16 MEA-2PO RadiacidTM 1 10 61 23 6 626 17 MEA-2PO dodecanol 1 11 55 32 2 c acid 18 MEA-2BO dodecanol 1 13 57 28 1 c acid 19 (comp.) TEA RadiacidTM 1 12 37 38 13 406 20 MAE-1PO RadiacidTM 1 5 62 33 0 600 21 MAE-1 BO RadiacidTM 1 6 64 30 0 600 22 (comp. ) MDEA RadiacidTM 1 8 41 51 0 406 23 TIPA RadiacidTM 2 - 14 58 28 406 24 TIPA RadiacidTM 1 11 52 33 4 406 25 TtPA Radiacid 1 10 67 23 0 600 26 TI PA stearic 2 - 13 58 29 27 MDIPA RadiacidTM 1 6 70 24 0 600 28 DEA- 1PO Radiacid 14 55 30 TEMP >160 409 29 DEA 1BO RadiacidTM 2 - 14 56 30 TEMP >160 409 1 Radiacid 406= partly hydrogenated C16-C18 fatty acid mixture from Fina Chemicats RadiacidTm 409= Cl 6-Cl 8 fatty acid mixture from Fina Chemicats Radiacid 626 = C12-C14 fatty acid mixture from Fina Chemicals<BR> <BR> Radiacid 600 = C12-C14 fatt acid mixture from Fina Chemicals The Table demonstrates the favorable effect of the"mixed"alkanolamines versus TEA or MDEA, that is, a shift from diesters to monoesters or triesters to diesters.

Quaternization Examples 30-52 Some of the reaction mixtures prepared in the earlier examples were quaternized with dimethylsulfate (DMS), or methyl chloride (MeCI). The percentage quaternized is reported in Table II. The quaternization is carried out according to conditions known to those skilled in the art. In general, it consists of heating the polyalkanolamine diester with DMS or MeCI with or without addition additives to lower the melting point, at 30°C -150°C, preferably at 75°C -95°C for 1 to 5 hours.

The ester quats, obtained in this way, were tested for melting point and hydrolytic stability. The hydrolytic stability test used was as follows : 5 weight percent dispersions of the esterquats in water were adjusted to pH 4 and kept at 50°C. After four weeks the percent hydrolysis was measured. The results are shown in Table II.

Note that Comparative Examples 36,37, and 45 were MeCI quats of completely esterified materials (diesters in the case of Examples 36,37, monoester in the case of Example 45), and as there was no ester distribution to report, these esters were not reported in Table 1.

Table 11 Example no product meeting % hydrolysis quarternization range,°C 30 DMS quat of ex 9 91 48-100 15 31 DMS quat of ex 10 90 33-60 - 32 DMS quat of ex 11 92 50-95 12 33 DMS quat of ex 12 90 37-60 14 34 (comp.) MeCI quat of ex 14 86 80-110 50 35 (comp.) MeCI quat of ex 15 69 81-134 68 36 (comp.) MeCI quat of MDEA 89 45-85 71 Radiacid 406 diester 37 (comp.) MeCI quat of MDEA 95 85-143 52 stearic acid diester 38 DMS quat of ex 16 90 -6-10 12 39 MeCI quat of ex 16 78 0-25 23 40 DMS quat of ex 17 91 0-15 11 41 DMS quat of ex 18 91 0-15 8 42 (comp.) MeCl quat of ex 19 93 18-32 42 43 DMS quat of ex 20 90 0-20 45 44 DMS quat of ex 21 90 0-20 24 45 (comp.) MeCI quat of DMAE 100 >130 12 Radiacid626 monoester 46 DMS quat of ex 23 88 25-30 2 47 DMS quat of ex 24 90 18-32 8 48 DMS quat of ex 25 90 -5-20 7 49 MeCI quat of ex 26 2 - 12 50 DMS quat of ex 27 90 20-25 20 51 DMS quat of ex 28 92 41-65 15 52 DMS quat of ex 29 92 39-60 8

From Table II it is clear that the compositions of the present invention tend to have lower melting points than the comparatives, which would aid in formulating the materials.

Furthermore, the compositions of the present invention tend to be more hydrolytically stable, which is also advantageous, especially in liquid formulations.

Formulation Examples 53-58 A reaction mixture of DEA-reacted with 1 mole of BO, then esterified with 2 mole Radiacid 406, then quaternized with DMS (Example 53) and Examples 35,40, 45,48, and 50 were added to a commercial laundry detergent to evaluate and compare the stability of the compositions of the present invention in a formulation. Five percent by weight of product was added to a retail sample of Procter & Gamble Company's ARIEL ULTRA LIQUIDTM (AUL). The formation of a precipitate upon mixing was noted as failing the physical stability test. Several of the mixtures (with a pH of about 8. 5) were kept for 2 weeks at a temperature of about 35°C. The percentage of product which was found to have hydrolyzed is reported in Table 111. This data shows the general trend that the compositions of the present invention show improved hydrolytic stability over the comparative examples.

Table lit Examp ! e product %quarternizatio physical % no n stability in AUL hydrolysis in AUL 53 See 90 yes not specification measured 54 (comp. ) product of ex 69 no not 35 measured 55 product of ex 91 yes 25 40 56 product of ex 90 yes 8 48 57 product of ex 90 yes 35 50 58 (comp. ) product of ex 100 yes 33 45 It should be realized by those skilled in the art that the invention is not limited to the exact configuration or methods illustrated above, but that various changes and modifications may be made without departing from the spirit and scope of the invention as claimed in the following claims.