MXPA01005518A - Cationic ester surfactants which are suitable for both liquid and powder formulations - Google Patents

Abstract

A class of cationic ester surfactants is described which has improved hydrolytic stability. In particular, the present invention relates to the use of quaternized alkanol amine ester compositions wherein the ester is based on a secondary or tertiary alcohol, and/or the use of a quaternized alkoxylated alkanol amine ester in detergent, cleaner, personal care, or fabric softening applications.

Description

ITS CATI ON I COSTER ESTERS, WHICH ARE SUITABLE FOR LITHIUM DAS FORMULATIONS LIKE POWDER The present invention relates to the use of a particular class of compositions in detergent applications, especially laundry and cleansing applications. In particular, the present invention relates to the use of quaternized alkanol amine ester compositions, wherein the ester is based on a secondary or tertiary alcohol, and / or the use of a quaternized alkoxylated alkanol amine ester in detergent applications, cleaner, personal care or fabric softening. Surfactant systems comprising cationic ester surfactants have been widely described for use in detergent applications. These compounds comprise at least one cationically charged group, usually an ammonium-based compound and at least one ester group. For example, WO-A-97/03160 indicates the benefits of having cationic ester surfactants in laundry detergents. These benefits include superior grease cleaning and improved anti-redeposition of stains during the washing 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 is easily hydrolyzed during the washing process. If TSC is easily hydrolyzed, it would make its use in liquid detergent formulations problematic, since It would probably be hydrolyzed to a good grade before use. Additionally, even in solid formulations, a product that is easily hydrolyzed can decompose in the wash before it has an opportunity to act on the target surface. WO 97/31 889 also describes the problem with this broad class of compounds that lack hydrolytic stability. In particular, this reference states, "Applicants have now found that a problem with the use of certain cationic ester surfactants is the tendency of the ester bond to be hydrolytically cut, thereby breaking the surfactant molecule under the washing conditions. of a normal laundry or washing method, which is why the performance of the surfactant in washing is compromised. " The solution proposed by WO 97/31 889 is to separate the ester group from the cationically charged group by a spacer group of at least three atoms. However, such spacer groups add cost to the composition and so is less than an ideal solution. Applicants of the present invention have discovered that esterifying the secondary or tertiary alcohols in place of the primary alcohols leads to cationic ester surfactants, which have greatly improved the hydrolytic stability over their primary alcohol counterparts. Applicants have also discovered that the introduction of oxide sequences also provides improved stability. This improved stability decreases the rate of surfactant breakage, which occurs in the wash environment and It also allows the surfactant to be used in liquid detergent formulations. It has been found that the compositions of the present invention exhibit a surprisingly high hydrolytic stability over a wide range of pH, have unexpectedly low melting points, are more compatible with detergents, softeners, cleansers and care ingredients. and can be handled more easily, either in diluted form or formulated as stable liquid concentrates, as compared to corresponding cationic ester surfactant having been esterified from primary alcohols. Accordingly, these compounds are advantageously used in applications such as detergents, softeners, cleansers and personal care articles. The compositions suitable for use in the present invention correspond to the general formula: wherein R is an alkyl or alkenyl group having 2 to 30 carbons; R1, R2, R3, R4, R8, R9, R10 and R1 are independently at each occurrence H or an alkyl group, preferably having from 1 to 6 carbons; n and m are independently in each occurrence a number equal to 1 or greater, preferably 1 to 5; z is 0 or greater, preferably 0 to 10, R5 and R6 are independently an alkyl having 1-6 carbon atoms, a cycloalkyl having 6 carbon atoms, or an aryl group; R7 is an alkyl group having 1 to 6 carbons, or an aryl group having 6 to 12 carbons, optionally substituted with an alkyl group, or HOCH R12CH2-, wherein R1 2 is H or an alkyl group having 1 to 4 carbons; and X "is an inorganic or organic acid anion, with the proviso that when z is 0, R3 and R4 are not both H. It is also preferred that when R5, R6 and R7 are all alkyl then, each has less than 3 carbons It is preferred that R has from 4 to 24 carbon atoms, and it is more preferred that R has from 7 to 22 carbon atoms The R group can be linear or branched and can have different levels of saturation. it is preferred that the R group has an iodine value of less than 140. The iodine values can be calculated by means known in the art For some applications, such as for use in concentrated, clear, clear fabric softeners, it is generally preferred that the R group has iodine values greater than 20, but in other applications, such as detergents, iodine values of less than 20 can be advantageously used, including fully saturated R groups For the purposes of this "clear" application it has the meaning of generally, it is transparent, so that vision is not obstructed significantly when viewed through a 1 cm cell, preferably 1 5 cm and most preferably 30 cm thick, containing the formulation. It is preferred that n and m be equal to 1, especially in those portions where R 3 or R 4 (or R 10 or R 1 1) is an alkyl group. It is also preferred that R1, R2, R8 and R9 are H. It is also generally preferred that not both 3 and R4 and not both R1 0 and R1 1 are alkyl groups in the same portion. Furthermore, it is preferred that when R3, R4, R10 or R1 1 is 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 the oxygen atom directly connected to CR3R4, including branches, is not greater than 6. Similarly, it is preferred that m and R8, R9, R10 and R1 1 are such that the number of carbon atoms between oxygen atoms, including branches, is not greater than 6. - It is preferred that z is from 0 to 1 0. The detergency properties may be to be optimized when z is 0, however, using alkanolamines where z is greater than 0, facilitates the use of slightly longer carboxylic acids in the esterification step. If z is 1, then it is preferred that R 3, R 4, R 10 and R 1 1 are not H. Preferably, the alkanolamine is formed by alkoxylating an alkyl amine with an alkylene oxide, wherein the alkyl amine corresponds to the formula: N ( R5) (R6) (H) where R5 and R6 are as defined above (ie, independently an alkyl having from 1 to 6 carbon atoms, a cycloalkyl having 6 carbon atoms, or an aryl group), and an alkylene oxide corresponds to the formula ula CyH2 and O, where y is 2 to 1 8, preferably 2 to 6. Preferred alkyl amines include dimethyl amine, diethyl amine and methyl ethyl amine. Preferred alkylene oxides include ethylene oxide, propylene oxide and butylene oxide, or mixtures thereof. Propylene oxide and butylene oxide are the most preferred oxides, especially in those compositions in which z is 0. Where oxide sequences are added (that is, in those species where z is not 0), the oxides can be added either by block or random addition). Although not necessary, this alkoxylation reaction process can be carried out in the presence of an alkaline catalyst, such as sodium, potassium, calcium, barium and strontium hydroxide, in an amount 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. When trying to form a composition in which z is 0, care must be taken not to alkoxylate the OH groups formed in the first step, and thus in such cases, the use of catalyst is not preferred. The temperature and the pressure are not critical, but conveniently, the alkoxylation reaction is carried out at an elevated temperature, preferably at a temperature of 50 ° C to 200 ° C, more preferably 80 ° C to 120 ° C and a pressure from 1 x 105 to 80 x 105 Pa. The alkaline catalysts suitable for use in this reaction are well known to a person skilled in the art.

The technique . After the completion of the reaction, ie, for example, when the pressure does not change further, the catalyst is removed by a suitable method, such as by filtration on an absorbent clay, for example, magnesium silicate or is 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 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 in the alkanolamine, with the 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 to 24 carbon atoms, and it is more preferred that R have from 7 to 22 carbon atoms. The R group can be linear or branched and can have different levels of saturation. In general, it is preferred that the R group have an iodine value of less than 140. The iodine values can be calculated by means known in the art. For some applications, it is preferred that group R have iodine values greater than 20, but in other applications, iodine values less than 20, including fully saturated R groups, can be advantageously used. Suitable examples of carboxylic acids useful in the esterification reaction include valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmic acid, stearic acid, arachidonic acid, behenic acid and lignoceric acid, and the branched isomers of the isms (for example, isovaleric acid) or the unsaturated isomers thereof (for example, ji-i, -oleic acid). These fatty acids are well known to the person of ordinary skill in the art. The esterification reaction is conveniently carried out at an elevated temperature, preferably at a temperature from 50 ° C to 250 ° C, more preferably from 1 80 ° C to 220 ° C, and reduced pressure, preferably from 2000 to 20,000 Pa. The carboxylic acid can be added in the range of 0.5 to 5 moles of carboxylic acid per mole of alkanolamine. It is preferred that the carboxylic acid be added at approximately an equimolar ratio to the alkanolamine, although slight excesses of carboxylic acid can help accelerate the reaction. The esterified alkanolamines can then be quaternized by contacting the esterified alkanolamines with a composition corresponding to the formula R7X, under conditions sufficient to cause at least a portion of the esterified alkanolamines form a quaternized product. R7 is the above formula is an alkyl group having 1 to 6 carbons, or an aryl group having 6 to 12 carbons, optionally substituted with an alkyl group, or HOC HR 2CH2-, wherein R12 is H or an alkyl group having 1 to 4 carbons; and X is an inorganic or organic acid anion.

The quaternization reaction is preferably carried out at a proportion of 0.1 to 20 moles of R7X per mole of esterified alkanolamine, at a temperature of 30 ° C to 1 50 ° C, and a pressure of from 1 x1 05 to 50x1 05 Pa. Any known quaternizing agent can be used as the compound of R7X. Suitable quaternizing agents of formula R7X 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 may 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, including after the reaction has been completed. In addition, it is possible to add the additives at different stages of the reaction, for example, an additive during the quaternization reaction and then either more of the same additive or a new additive after the quaternization reaction has ended. These additives can be especially useful when the quaternized product is not a liquid at room temperature. Suitable additives include materials such as water, isopropanol, propanediol, dipropylene glycol, PEG, PPG, alkoxylated fatty acids and alcohols having more than 3 carbons in the fatty chain, glycol ether solvents, such as DOWANOLMR series P and E, diether solvents, such as PROGLYDEM R DMM, tetrahydrofuran, methanol, ethanol, hexanediol and acetone, and mixtures of the same. If such additives are used, it is preferred that the final reaction mixture contain at least 70 percent by weight, more preferably at least 75 percent by weight and most preferably 80 percent by weight of the cationic ester surfactant. In the context of the present invention, "hydrolytically stable" means that less than 30 percent, preferably less than 20 percent of the composition, is hydrolyzed after 4 weeks of a 5 percent aqueous solution having a pH value of 4. , at a temperature of 50 ° C. It should be understood that the degree of hydrolysis defined above is valid for a pH value of 4, and that the degree of hydrolysis would decrease with decreasing pH and an increase with increasing pH. The improved hydrolytic stability of the compositions of the present invention allows them to be used in formulations of liquid detergent or gel, softener and detergent together, cleanser, personal care or softener. Additionally, the improved hydrolytic stability facilitates the perseverance of the material in the washing environment by itself, and thus makes the compositions useful also in solid formulations, such as granules, powders and tablets. Moreover, the compositions of the present invention are compatible even with detergent ingredients, which are not normally compatible with known cationic ester surfactants without the presence of special additives.

The formulations of the present invention may also incorporate one or more known ingredients used in detergent, fabric softener, cleanser or personal care formulations. Such materials are known in the art (for example, many are described in WO 97/31 889 and WO 98/35002) and include, but are not limited to the following: (a) Enzymes and enzyme stabilizers - Enzymes They can be included for various fabric cleaning purposes. Non-limiting 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 can be stabilized by the presence of water soluble sources of calcium and / or magnesium ions in the finished compositions, which provide such ions. Any salt soluble in water, calcium or magnesium, can be used as a source of calcium or magnesium ions. A wide range of enzyme materials and useful enzyme stabilizers are described in WO-A-95/19951 and WO-A-21715 and EP-A-0579295 and EP-A-05835836. (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 bleach, percarboxylic acid bleach, peroxygen bleach and mixtures thereof. The bleach activator can also be used.

Several non-limiting examples of useful bleaching agents and bleach activators are given in WO-A-95/1 9951. (c) Formers - Inorganic and organic formers commonly used in fabric washing formulations can be used to aid in the removal of particulate solids. Suitable formers include, but are not limited to, phosphates, polyphosphates, silicates, alumosilicates, phosphonates, carboxylates, zeolites and succinates. Non-limiting examples of suitable formers are described in WO-A-95/1 9951 and EP-A-0579295 and EP-A-0580245. (d) Stain release agents - Any known polymeric stain release agent used in laundry cleaning formulations can be used. Stain-release polymeric 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 from 2 to 10, or (c) a mixture of oxyalkylene units comprising oxyethylene and from 1 to 30 oxypropylene units, (d) cellulose derivatives, such as, hydroxyether cellulose polymers, (e) copolymer blocks of terephthalate with oxide of polyethylene or polypropylene oxide. Non-limiting examples of useful stain release agents are given in WO-A-95/04802, WO-A-93/2351 0 and WO-A-93/25648. (e) Chelating agents - 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 the wash solutions through the formation of soluble chelates. Non-limiting examples of suitable chelating agents are described in WO-A-95/1 9951 and WO-A-96/21715. (f) Removal agents / anti-redeposition of soil stains Any water-soluble alkoxylated amine, which has the properties of removal and anti-redeposition of soil stains normally used in granular or liquid detergents, may be used. Non-limiting examples of useful soil spot removal / anti-redeposition agents are described in WO-A-95/19951. (g) Dispersing agents - Suitable dispersing agents are polymeric dispersing agents, such as, for example, polymeric polycarboxylates and polyethylene glycols, commonly used in detergents. Non-limiting examples of the dispersing agents are given in WO-A-95/19951. The protonated amines, such as those described in WO-A-93/25648 and terephthalate / alkylene oxide copolymers, such as those described in WO-A-96/21 71 5, can be used to enhance the stability of the dispersion. (h) Optical brighteners - Any known brightener used in detergents may be used. Suitable brighteners include, but are not limited to, stilbene, pyrazoline, coumarin derivatives and carboxylic acid. Non-limiting examples of suitable brighteners are given in WO-A-95/1 9951 and WO-A-96/2171 5. (i) Foam suppressants - Any known compound that suppresses or reduces foam formation 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-95/1 9951 and EP-A-0579295. (j) Fabric softeners - Any known fabric softening compound can be used. Non-limiting examples of suitable fabric softening compounds include clay softeners, conventional quaternary ammonium softening agents, anionic softeners, non-ionic softeners and cationic softeners. These and other suitable fabric softeners are described in WO-A-95/04802, WO-A-95/1 9951 and WO-A-96/21715 and EP-A-0580245. (k) Detersive Surfactants - Various surfactant materials may be used, such as anionic, nonionic, cationic, ampholytic and zwitterionic surfactants. Non-limiting examples of suitable surfactants include linear alkyl sulfonates ("LAS"), alkyl benzene sulfonates of C? rC18 ("AS") and polyhydroxy fatty acid amide surfactants. These and other suitable surfactants are described in WO 93/23510, WO 25648, WO 95/1 9951, WO 98/35002, EP-A-0579296, EP-A-05838536 and EP-A-0580245. Specifically, the compositions of the present invention can be formulated with other surfactants cationics, which do not correspond to the formula in claim 1, especially those described in WO 98/35002. Other materials, which may be optionally included, are liquid carriers, such as, for example, water and monohydric alcohols of Ci to C4, thickening agents, viscosity control agents, cyclic amines of di- (higher alkyl) ), aqueous emulsions of predominantly linear polyalkyl or alkylaryl siloxane absorber, pH modifiers, such as bases and acids, nonionic and other deflocculating agents, hydrotropes, dyes, perfumes, perfume carriers, preservatives, opacifiers, fluorescence, anti-shrinkage agents, anti-wrinkle agents, anti-stain agents, bactericides, germicides, fungicides, anti-corrosion agents, crease-imparting agents, antistatic agents, ironing agents, wetting agents, strength additives, such as carboxymethylcellulose and water-soluble cationic polymers. These optional materials are well known and widely used in the art. See, for example, WO-A-97/03155, WO-A-95/1 9951, WO-A-93/25648, WO-A-93/2351 0, WO-A-96/21 71 5, WO -A-96/09436 and WO-A-94/29521 and EP-A-0580245. Various processes for formulating active ingredients with additional materials in formulations useful in fabric softening applications, laundry 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 hereinabove.

The formulations of the present invention may be in various forms, such as, for example, aqueous or anhydrous liquid formulations, super concentrated liquid formulations, gel formulations, or solid formulations, such as granules, powders or tablets. . These solid formulations can be obtained by a suitable process known in the art, such as grinding the composition, or depositing it on solid substrates. Preferred are the formulations of the present invention, which have a pH below 1 1, when diluted for conditions of normal use. It is also preferred that the formulations have a pH above 1.5 when diluted for normal use. Conditions of normal use are known in the art. Thus, in another embodiment, the present invention relates to formulations comprising at least 0.01, preferably from 0.1 to 40, most preferably from 1 to 15 percent by weight of the cationic ester surfactant of the invention. The liquid formulations of the present invention can be prepared by mixing the composition of the invention with a liquid carrier and, optionally, at least one of the aforementioned ingredients in a standard formulation mixing equipment and in accordance with known techniques for a person skilled in the art. The low-cut mixing is generally sufficient to adequately and uniformly mix the composition within the formulation. The final formulation, either in concentrated or diluted form, must be easily emptied by the end user.

Due to the compatibility of the compositions of the present invention with conventional detergent ingredients and because they are hydrolytically stable at normal detergent pHs, they can be conveniently formulated in detergents, including softener and detergent together. Additionally, the compositions of the present invention, being compatible with softening active ingredients and being hydrolytically stable at normal pHs, can be conveniently formulated with any known softening active ingredient in a fabric softener, especially for the design of light fabric softening formulations. . The following examples are included for purposes of illustration and should not be construed as limiting the scope of the invention or the claims. Unless stated otherwise, all percentages are by weight.

Example 1 (comparative): Preparation of fatty acid ester of 2-dimethylaminoethanol (DMAE) and subsequent quaternization with methyl chloride (choline esterquat) Two hundred thirty grams (230 g) of 2- (dimethylamino) ethanol (DMAE, 3 moles) with 421 g of Radiazid ™ 626 (2 moles) in a 1 liter reaction flask, equipped with a vigreux column of 20 cm by 2.5 cm and warmed slowly. DMAE is commercially available, but could be formed by reacting dimethylamine with ethylene oxide, as is known in the art. Radiacid ™ 626 reportedly corresponds to a mixture of fatty acids having normal chain lengths, mainly in the range of C12.14, but having approximately 1 3 percent of the acid chain lengths in the range of C6-C1 0. The reported iodine values of RadiacidM R 626 were 7 to 1 1. The temperature was gradually increased to 200 ° C, continuously distilling the excess DMAE and the water of reaction at a temperature of 90 ° C to 100 ° C, over a period of 1 2 hours. The mixture was then heated for one hour at 1 30 ° C / 1,0000 Pa to remove any residual DMAE. The product contained 98 weight percent of esters as determined by gas chromatography and was liquid at room temperature. The stearam was then dissolved in acetone (60 percent solution), mixed with 50 percent molar excess of methyl chloride and subsequently quaternized at 95 ° C for a period of 17 hours. After this, the conversion of the esteramine was 100 percent, as determined by titration of free amine with perchloric acid. The acetone evaporated, leaving a sticky product with a melting point greater than 1 30 ° C, at which temperature the product began to decompose.

Example 2 Preparation of fatty acid ester of 1-dimethylamino-2-propanol (DMAP) and subsequent quaternization with dimethyl sulfate / methyl chloride The equipment and procedure were as described in Example 1. In this case, the reaction mixture consisted of 255 g of 1- (dimethylamino) -2-propanol (DMAP, 2.45 moles) and 362 g (1.63 moles) of Radiacid R 600. The Radiacid ™ 600 reportedly corresponds to a mixture of fatty acids having normal chain lengths, mainly in the range of C12-? , but with less than 1.53 percent of the acids having chain lengths in the range of C6 to C10. The reported iodine values of Radiacid ™ 600 are 8 to 12. The reaction procedure took 1 3 hours. The final product contained 98 percent ester and was liquid at room temperature. The esteramine thus formed was then quaternized as an 80 percent solution in isopropanol (I PA) with dimethyl sulfate (DMS) (1: 09 molar ratio). This exothermic reaction took less than 1 hour at 1 00 ° C. The final product was 90 percent quaternized. The melting range was 20 ° C to 40 ° C (20 percent of I PA); the I PA free product was melted at a temperature greater than 100 ° C. The esteramine formed in this Example was also quaternized using methyl chloride. An 80 percent solution of the esteramine in acetone was reacted with 50 percent molar excess of methyl chloride at 95 ° C for a period of 16 hours, and resulted in a degree of quaternization of 100 percent. The acetone-free product was a sticky solid that decomposed above 1 30 ° C.

Example 3 Preparation of 1-dimethylamino-2-butanol fatty acid ester (DMAB) and subsequent quaternization A similar procedure as described under Example 1 or 2, can also be used to esterify DMAB and then quaternize the esterified product.

Example 4 Preparation of fatty acid ester of ethoxylated 1-dimethylamino-2-propanol and subsequent KOH quaternization as a 55 percent by weight solution can be dissolved in DMAP at a level of 0.4 percent by weight. This mixture can then be placed in a pressure-jacketed vessel, equipped with an agitator, and heated to 120 ° C. Then ethylene oxide (EO) can be added slowly in a molar ratio EO: DMAP of 3: 1. The reaction will be exothermic and the temperature should be controlled by gradual addition of EO. The reaction should be finished within 1 hour after the addition is complete. Subsequently, the KOH catalyst can be neutralized, such as, by the addition of acetic acid, or it can be removed, such as, by absorption using magnesium silicate and then filtration. The DMAP-3EO alkanolamine thus formed can then be esterified, by heating it with an equimolar amount of fatty acid at 200 ° C / 2000 Pa for a period of about 10 hours, while distilling the water formed during the reaction. Any fatty acid can be used, such as Radiacid® 409, and it is reported to correspond to a mixture of fatty acids having normal chain lengths mainly in the range of C1 6-1 8. and iodine values less than 2.

Other fatty acids that can be used in a suitable manner, especially to facilitate the formation of clear formulations, include oleic acid (such as Radiacid ™ 21 2 or 150), soft bait (Radiacid ™ 441 or 403), or partially hydrogenated soft bait ( Radiacid R 406). A 98 percent conversion can be achieved. The DMAP-3EO ester thus formed can be quaternized according to the methods mentioned in Examples 1 or 2, so that 90 percent of quaternized dimethyl sulfate product or 100 percent of quaternized methyl chloride can be formed.

Example 5 Preparation of alkoxylated 1-dimethylamino-2-propanol fatty acid ester and subsequent quaternization As in Example 4, KOH can be added as a catalyst to DMAE, DMAP or DMAB, as described in Example 4. This mixture can then be placed in a reaction vessel and heated as described in Example 4. The alkylene oxide can then be added as before, replacing the 3 moles of EO with, for example, 3 moles of propylene oxide (PO), 1 mole of PO followed by 2.5 moles of EO, 2 moles of EO followed by 2 moles of PO, or 1 mole of oxide of butylene (BO) followed by 2.5 moles of EO. Reactions with more than one alkylene oxide can also be carried out with the simultaneous addition of the different oxides (for example, 2 moles of an EO and 2 moles of PO can be fed simultaneously into the reactor), so that alkanolamines are formed with random alkylene oxide sequences.

Furthermore, it is possible, as is known in the art, to alternate blocking and random feeds in the same preparation. As before, the reaction will be exothermic and the temperature should be controlled by gradual addition of alkylene oxide. The reaction should be finished within 1 hour after the addition is complete. Subsequently, the KOH catalyst can be neutralized with acetic acid. The alkanolamine thus formed can then be esterified on heating with an equimolar amount of fatty acid at 200 ° C / 2000 Pa for a period of about 10 hours, while distilling the water formed during the reaction, followed by the exposed procedure in Example 4. The ester formed can then be quaternized, following the procedure set forth in Example 4.

Example 6 Hydrolysis tests The monestercuats of Example 1 and Example 2 were tested for their hydrolytic stability by a) monitoring (by titration) the acid formation of a 5 percent by weight dispersion in water at 50 ° C, adjusted to pH 4, over a period of 4 weeks, and b) monitoring (again by titration) the acid formation of a 5 percent by weight dispersion in Ariel Futur ™ (commercially available liquid formulation produced by Procter &Gamble and purchased in the Netherlands in February 1,998), at 35 ° C, and a pH of about 8, over a period of 2 weeks. The results, shown in Table I, demonstrate the improved hydrolytic stability of the compounds identified by the applicants.

TABLE Those skilled in the art should realize 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.

Claims (26)

1. A process for preparing a formulation for use in detergent, personal care, cleanser or fabric softener applications, wherein the process comprises incorporating a composition into the formulation, which corresponds to the formula: R6-? wherein R is an alkyl or alkenyl group having 2 to 30 carbons; R | 1 ?, R n2, R D 3J,, R-, 44, RB, Rb, R1U and R11 are independently in each occurrence H or an alkyl group; n and m are independently in each occurrence a number equal to 1 or greater; z is 0 or greater; R5 and R6 are independently an alkyl having 1-6 carbon atoms, a cycloalkyl having 6 carbon atoms, or an aryl group; R7 is an alkyl group having 1 to 6 carbons, or an aryl group having 6 to 12 carbons, optionally substituted with a group alkyl, or HOCHR1 2CH2-, wherein R1 2 is H or an alkyl group having 1 to 4 carbons; X "is an inorganic or organic acid anion, with the proviso that when z is 0, R3 and R4 are not both H.

2. The process as in claim 1, wherein z is different from 0.

3. The process as in claim 2, wherein z is 1, then R3, R4-, R1 0 and R1 are not all H.

4. The process as in claim 1, wherein z is 0.

5. The process as in claim 4, wherein n and R1, R2, R3 and R4 are such, that the number of carbon atoms between N and oxygen directly connected to CR3R4, including ramifications, is not greater than

6. and R 8, R 9, R 10 and R 1 1 are such that the number of carbon atoms between oxygen atoms, including branches, is not greater than 6. The process as in claim 1, wherein R has from 4 to 24 carbon atoms.

7. The process as in claim 6, wherein R has 7-22 carbons.

8. The process as in claim 1, wherein R has an iodine value from 20-140.

9. The process as in claim 1, wherein the iodine value of R is less than 20.

The process as in claim 7, wherein R is completely saturated. eleven .

The process as in claim 1, wherein when R5, R6 and R7 are all alkyl, then each has less than 3 carbons.

12. The process as in claim 1, wherein n and m are 1.

13. The process as in claim 12, wherein R1, R2, R8 and R9 are H.

14. The process as in claim 12, wherein either R3 or R4, and either R10 or R11 are H.

15. The process as in claim 14, wherein the group R3 or R4 and the group R10 or R11, which is not H, has 1 or 2 carbons.

16. The process as in claim 1, wherein n and m are 1, R1, R2, R8 and R9 are H, either R3 or R4, and either R10 or R11 are H, and the group R3 or R4 and the group R10 or R11, which is not H, has 1 or 2 carbons.

17. The process as in claim 1, wherein the composition comprises 0.01 percent by weight to 40 percent by weight of the formulation.

18. The process as in claim 1, wherein the formulation has a pH of 1.5 to 11.

The process as in claim 1, wherein the formulation is in the form of a gel or liquid.

20. The process as in re-excitation 1, wherein the formulation is in the form of a solid powder, tablets or granules.

21. The process as in claim 1, wherein the formulation: further comprises cationic surfactants, which do not correspond to the formula in claim 1.

22. The process as in claim 1, wherein the formulation is used in a detergent application.

23. The process as in claim 1, wherein the formulation is used in a fabric softener application.

24. The process as in claim 23, wherein the formulation is clear.

25. A process for preparing a formulation for use in detergent, personal care, cleanser or fabric softener applications, wherein the process comprises incorporating a composition into the formulation, which corresponds to the formula: wherein R is an alkyl or alkenyl group, having 10 to 18 carbons; R1, R2, R3 and R4 are independently H or an alkyl group having 1 to 2 carbons; n is independently a number equal to 1 or greater; R5 and R6 are independently an alkyl having 1-6 carbon atoms, a cycloalkyl having 6 carbon atoms or an aryl group; R7 is an alkyl group having 1 to 6 carbons, or an aryl group having 6-12 carbons, optionally substituted with an alkyl group, or HOCHR12CH2-, wherein R12 is H or an alkyl group having 1 to 4 carbons; X "is an inorganic or organic acid anion, with the proviso that R3 and R4 are not both H, and R5, R6 and R7 are not all alkyl

26. A process for preparing a formulation for use in detergent applications, personal care, cleanser or softener, wherein the process comprises incorporating a composition in the formulation, which corresponds to the formula: wherein R is an alkyl or alkenyl group, having 10 to 18 carbons; R1, R2, R3 and R4 are independently H or an alkyl group having 1 to 2 carbons; n is independently a number equal to 1 or greater; R5, R6 and R7 are independently an alkyl having 1 -2 carbon atoms; X "is an inorganic or organic acid anion, with the proviso that R3 and R4 are not both H. SUMMARY A class of cationic ester surfactants is described, which has improved hydrolytic stability. In particular, the present invention relates to the use of quaternized alkanolamine ester compositions, wherein the ester is based on a secondary or tertiary alcohol, and / or the use of a quaternized alkoxylated alkanolamine ester in detergent, cleaner, personal care or fabric softener.