WO1994009100A1

WO1994009100A1 - Liquid or gel dishwashing detergent composition containing polyhydroxy fatty acid amide and certain elements

Info

Publication number: WO1994009100A1
Application number: PCT/US1993/009579
Authority: WO
Inventors: Kofi Ofosu-Asante
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1992-10-13
Filing date: 1993-10-08
Publication date: 1994-04-28
Anticipated expiration: 1995-04-13
Also published as: AU5171393A; CN1088974A; EP0665874A1; MX9306340A

Abstract

Liquid or gel dishwashing detergent compositions containing anionic surfactant, polyhydroxy fatty acid amide, and certain elements for improved grease cleaning and stability are described.

Description

LIQUID OR GEL DISHWASHING DETERGENT COMPOSITION CONTAINING POLYHYDROXY FATTY ACID AMIDE AND CERTAIN ELEMENTS

TECHNICAL FIELD

The present invention relates to liquid or gel dishwashing detergent compositions containing anionic surfactant, polyhydroxy fatty acid amide and one or more elements selected from the group consisting of aluminum, gallium, boron, silicon and mixtures thereof. Preferred compositions comprise boron and calcium ions.

BACKGROUND OF THE INVENTION

The addition of certain amide surfactants such as polyhydroxy fatty acid amides to liquid or gel dishwashing detergents provides compositions with good grease removal and sudsing benefits. See for example, U.S. Patent 2,965,576, Wilson, issued December 20, 1960, and U.K. Patent Specification 809,060, published February 18, 1959. However, these compounds tend to hydrolyze in both acidic and alkaline conditions to form fatty acid and N-methylglucamine. The free fatty acid in the presence of divalent ions (i.e. calcium) may lead, particularly at low temperatures, to insoluble salt precipitate formation. Therefore, it is often necessary to limit the pH, add chelating agents and/or lime soap dispersants to avert the problem.

It has been found that certain group III B or group IV B element containing compounds, such as boric acid, when added to a light duty liquid detergent composition containing anionic surfactant and polyhydroxy fatty acid amide and having a pH of from about 6 to about 11, prevent pH drift and insoluble salt precipitation.

SUMMARY OF THE INVENTION

A liquid or gel dishwashing detergent composition comprising, by weight:

(a) from about 3% to about 40% of polyhydroxy fatty acid amide having the formula:

wherein R¹ is hydrogen, C_1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or mixtures thereof; R² is C₅-C₃₁ hydrocarbyl; and Z is a polyhydroxy-hydrocarbyl having a linear hydrocarbyl chain with at least three hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof;

(b) from about 0.001% to about 2% of one or more elements selected from the group consisting of aluminum, gallium, boron, silicon and mixtures thereof; and

(c) from about 3 to about 95% of anionic surfactant;

wherein said composition has a pH in a 10% solution in water at 20ºC between about 6 to about 11.

A particularly preferred embodiment also comprises from about 0.08% to about 4% of calcium ions; and from about 0.5% to about 12% of suds booster selected from the group including, but not limited to, alkyl amine oxide, alkyldimethylbetaine, alkylamidopropylbetaine, alkylmonoethanol amide and alkyldiethanol amide.

DETAILED DESCRIPTION OF THE INVENTION

The liquid or gel, preferably liquid, dishwashing detergent compositions of the present invention contain a polyhydroxy fatty acid amide, an anionic surfactant, and a group III B or group IV B element. Preferably boric acid, calcium ions and suds booster are ingredients of the compositions herein. These and other complementary optional ingredients typically found in liquid or gel dishwashing compositions which can be included herein are set forth below.

The term "light duty dishwashing detergent composition" as used herein refers to those compositions which are employed in manual (i.e. hand) dishwashing.

Polyhydroxy Fatty Acid Amide

The compositions of the present invention comprise from about 3% to about 40%, preferably from about 5% to about 30%, more preferably from about 8% to about 25%, by weight of the composition, of a polyhydroxy fatty acid amide having the structural formul a:

wherein: R¹ is H, C₁-C₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C₁-C₄ alkyl, more preferably C₁ or C₂ alkyl, most preferably C₁ alkyl (i.e., methyl); and R² is a C₅-C₃₁ hydrocarbyl, preferably straight-chain C₇-C₁₉ alkyl or alkenyl, more preferably straight-chain C₉-C₁₇ alkyl or alkenyl, most preferably straight-chain C₁₁-C₁₇ alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials. Z preferably will be selected from the group consisting of -CH₂-(CHOH)_n-CH₂OH, -CH(CH₂OH)-(CHOH)_n-1-CH₂OH, -CH₂-(CHOH)₂(CHOR')(CHOH)-CH₂OH, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH₂-(CHOH)₄-CH₂OH.

In Formula (I), R¹ can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.

R²-CO-N< can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc. Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.

The most preferred polyhydroxy fatty acid amide has the general formula

wherein R² is a straight chain C₁₁-C₁₇ alkyl or alkenyl group.

Method of Preparation

In general, polyhydroxy fatty acid amides can be made by reacting an alkyl amine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product. Processes for making compositions containing polyhydroxy fatty acid amides are disclosed, for example, in G.B. Patent Specification 809,060, published February 18, 1959, U.S. Patent 2,965,576, issued December 20, 1960 to E. R. Wilson, and U.S. Patent 2,703,798, Anthony M. Schwartz, issued March 8, 1955, and U.S. Patent 1,985,424, issued December 25, 1934 to Piggott, each of which is incorporated herein by reference.

In one process for producing N-alkyl or N-hydroxyalkyl, N-deoxyglycityl fatty acid amides wherein the glycityl component is derived from glucose and the N-alkyl or N-hydroxy- alkyl functionality is N-methyl, N-ethyl, N-propyl, N-butyl, N-hydroxyethyl, or N-hydroxypropyl, the product is made by reacting N-alkyl- or N-hydroxyalkyl-glucamine with a fatty ester selected from fatty methyl esters, fatty ethyl esters, and fatty triglycerides in the presence of a catalyst selected from the group consisting of alkali metal alkoxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, disodium tartrate, dipotassium tartrate, sodium potassium tartrate, trisodium citrate, tripotassium citrate, sodium basic silicates, potassium basic silicates, sodium basic aluminosilicates, and potassium basic aluminosilicates, and mixtures thereof. The amount of catalyst is preferably from about 0.5 mole % to about 50 mole %, more preferably from about 2.0 mole % to about 10 mole %, on an N-alkyl or N-hydroxyalkyl-glucamine molar basis. The reaction is preferably carried out at from about 138ºC to about 170ºC for typically from about 20 to about 90 minutes. When triglycerides are utilized in the reaction mixture as the fatty ester source, the reaction is also preferably carried out using from about 1 to about 10 weight % of a phase transfer agent, calculated on a weight percent basis of total reaction mixture, selected from saturated fatty alcohol polyethoxylates, alkylpolyglucosides, linear glucamide surfactant, and mixtures thereof.

Preferably, this process is carried out as follows:

(a) preheating the fatty ester to about 138ºC to about 170ºC;

(b) adding the N-alkyl or N-hydroxyalkyl glucamine to the heated fatty acid ester and mixing to the extent needed to form a two-phase liquid/liquid mixture;

(c) mixing the catalyst into the reaction mixture; and

(d) stirring for the specified reaction time.

Also preferably, from about 2% to about 20% of preformed linear N-alkyl/N-hydroxyalkyl, N-linear glucosyl fatty acid amide product is added to the reaction mixture, by weight of the reactants, as the phase transfer agent if the fatty ester is a triglyceride. This seeds the reaction, thereby increasing reaction rate.

The polyhydroxy "fatty acid" amide materials used herein also offer the advantages to the detergent formulator that they can be prepared wholly or primarily from natural, renewable, non-petrochemical feedstocks and are degradable. They also exhibit low toxicity to aquatic life.

It should be recognized that along with the polyhydroxy fatty acid amides of Formula (I), the processes used to produce them will also typically produce quantities of nonvolatile by-product The level of these by-products will vary depending upon the particular reactants and process conditions, but are preferably kept to a minimum.

Alternate Method

An alternate method for preparing the polyhydroxy fatty acid amides used herein is as follows. A reaction mixture consisting of 84.87g. fatty acid methyl ester (source: Procter & Gamble methyl ester CE1270), 75g. N-methyl-D-glucamine (source: Aldrich Chemical Company M4700-0), 1.04g. sodium methoxide (source: Aldrich Chemical Company 16,499-2), and 68.51g. methyl alcohol is used. The reaction vessel comprises a standard reflux set-up fitted with a drying tube, condenser and stir bar. In this procedure, the N-methyl glucamine is combined with methanol with stirring under argon and heating is begun with good mixing (stir bar; reflux). After 15-20 minutes, when the solution has reached the desired temperature, the ester and sodium methoxide catalyst are added. Samples are taken periodically to monitor the course of the reaction, but it is noted that the solution is completely clear by 63.5 minutes. It is judged that the reaction is, in fact, nearly complete at that point. The reaction mixture is maintained at reflux for 4 hours. After removal of the methanol, the recovered crude product weighs 156.16 grams. After vacuum drying and purification, an overall yield of 106.92 grams purified product is recovered. However, percentage yields are not calculated on this basis, inasmuch as regular sampling throughout the course of the reaction makes an overall percentage yield value meaningless. The reaction can be carried out at 80% and 90% reactant concentrations for periods up to 6 hours to yield products with extremely small by-product formation.

The following is not intended to limit the invention herein, but is simply to further illustrate additional aspects of the technology which may be considered by the formulator in the manufacture of a wide variety of detergent compositions using the polyhydroxy fatty acid amides.

It will be readily appreciated that the polyhydroxy fatty acid amides are, by virtue of their amide bond, subject to some instability under highly basic or highly acidic conditions. While some decomposition can be tolerated, it is preferred that the final light-duty dishwashing detergent product comprise a group III B or group IV B element compound, preferably boric acid, to minimize instability at all pH's.

During the manufacture of the polyhydroxy fatty acid amides it will typically be necessary to at least partially neutralize the base catalyst used to form the amide bond. While any acid can be used for this purpose, the detergent formulator will recognize that it is a simple and convenient matter to use an acid which provides an anion that is otherwise useful and desirable in the finished detergent composition. For example, citric acid can be used for purposes of neutralization and the resulting citrate ion (ca. 1%) be allowed to remain with a ca. 40% polyhydroxy fatty acid amide slurry and be pumped into the later manufacturing stages of the overall detergent-manufacturing process. The acid forms of materials such as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate, tartrate/succinate, and the like, can be used similarly.

The polyhydroxy fatty acid amides derived from coconut alkyl fatty acids (predominantly C₁₂-C₁₄) are more soluble than their tallow alkyl (predominantly C₁₆-C₁₈) counterparts. Accordingly, the C₁₂-C₁₄ materials are somewhat easier to formulate in liquid compositions, and are more soluble in cool-water laundering baths. However, the C₁₆-C₁₈ materials are also quite useful, especially under circumstances where warm-to-hot wash water is used. Indeed, the C₁₆-C₁₈ materials may be better detersive surfactants than their C₁₂-C₁₄ counterparts. Accordingly, the formulator may wish to balance ease-of-manufacture vs. performance when selecting a particular polyhydroxy fatty acid amide for use in a given formulation.

It will also be appreciated that the solubility of the polyhydroxy fatty acid amides can be increased by having points of unsaturation and/or chain branching in the fatty acid moiety. Thus, materials such as the polyhydroxy fatty acid amides derived from oleic acid and iso-stearic acid are more soluble than their n-alkyl counterparts. Likewise, the solubility of polyhydroxy fatty acid amides prepared from disaccharides, trisaccharides, etc., will ordinarily be greater than the solubility of their monosaccharide-derived counterpart materials. This higher solubility can be of particular assistance when formulating liquid compositions. Moreover, the polyhydroxy fatty acid amides wherein the polyhydroxy group is derived from maltose appear to function especially well as detergents when used in combination with conventional alkyl benzene sulfonate ("LAS" ) surfactants . Whi l e not intending to be l imi ted by theory, i t appears that for LAS containing compositions that the combination of LAS with the polyhydroxy fatty acid amides derived from the higher saccharides such as maltose causes a substantial and unexpected lowering of interfacial tension in aqueous media, thereby enhancing net detergency performance.

The polyhydroxy fatty acid amides can be manufactured not only from the purified sugars, but also from hydrolyzed starches, e.g., corn starch, potato starch, or any other convenient plant-derived starch which contains the mono-, di-, etc. saccharide desired by the formulator. This is of particular importance from the economic standpoint. Thus, "high glucose" corn syrup, "high maltose" corn syrup, etc. can conveniently and economically be used. De-lignified, hydrolyzed cellulose pulp can also provide a raw material source for the polyhydroxy fatty acid amides.

As noted above, polyhydroxy fatty acid amides derived from the higher saccharides, such as maltose, lactose, etc., are more soluble than their glucose counterparts. Moreover, it appears that the more soluble polyhydroxy fatty acid amides can help solubilize their less soluble counterparts, to varying degrees. Accordingly, the formulator may elect to use a raw material comprising a high glucose corn syrup, for example, but to select a syrup which contains a modicum of maltose (e.g., 1% or more). The resulting mixture of polyhydroxy fatty acids will, in general, exhibit more preferred solubility properties over a broader range of temperatures and concentrations than would a "pure" glucose-derived polyhydroxy fatty acid amide. Thus, in addition to any economic advantages for using sugar mixtures rather than pure sugar reactants, the polyhydroxy fatty acid amides prepared from mixed sugars can offer very substantial advantages with respect to performance and/or ease-of-formulation. In some instances, however, some loss of grease removal performance may be noted at fatty acid maltamide levels above about 25% and some loss in sudsing above about 33% (said percentages being the percentage of maltamide-derived polyhydroxy fatty acid amide vs. glucose-derived polyhydroxy fatty acid amide in the mixture). This can vary somewhat, depending on the chain length of the fatty acid moiety. Typically, then, the formulator electing to use such mixtures may find it advantageous to select polyhydroxy fatty acid amide mixtures which contain ratios of monosaccharides (e.g., glucose) to di- and higher saccharides (e.g., maltose) from about 4:1 to about 99:1.

The manufacture of preferred, uncyclized polyhydroxy fatty acid amides from fatty esters and N-alkyl polyols can be carried out in alcohol solvents at temperatures from about 30ºC-90ºC, preferably about 50ºC-80ºC. It has now been determined that it may be convenient for the formulator of, for example, liquid compositions to conduct such processes in 1,2-propylene glycol solvent, since the glycol solvent need not be completely removed from the reaction product prior to use in the finished detergent formulation.

Fatty Acids

For compositions where especially high sudsing is desired, i.e. dishwashing compositions, it is preferred that less than about 5%, preferably less than about 2%, most preferably no C₁₄ or higher fatty acids be present, since these can suppress sudsing. Liquid detergent compositions herein are preferably substantially free of a suds-suppressing amount of C₁₄ and higher fatty acid. Accordingly, the formulator of high sudsing compositions will desirably avoid the introduction of suds-suppressing amounts of such fatty acids into high sudsing compositions with the polyhydroxy fatty acid amide, and/or avoid the formation of C₁₄ and higher fatty acids on storage of the finished compositions. One simple means is to use C₁₂ ester reactants to prepare the polyhydroxy fatty acid amides herein. The use of amine oxide or sulfobetaine surfactants can overcome some of the negative sudsing effects caused by the fatty acids. In fact, although group III B or group IV B element containing compounds can avoid potential precipitation problems, any fatty acids should be avoided (less than about 2.5% by weight is preferred).

The formulator wishing to add anionic optical brighteners to liquid detergents containing relatively high concentrations (e.g., 10% and greater) of anionic or polyanionic substituents such as the polycarboxylate builders may find it useful to pre-mix the brightener with water and the polyhydroxy fatty acid amide, and then to add the pre-mix to the final composition.

It will be appreciated by those skilled in the chemical arts that the preparation of the polyhydroxy fatty acid amides herein using the di- and higher saccharides such as maltose will result in the formation of polyhydroxy fatty acid amides wherein linear substituent Z is "capped" by a polyhydroxy ring structure. Such materials are fully contemplated for use herein and do not depart from the spirit and scope of the invention as disclosed and claimed.

Elements

The compositions of the present invention comprise sufficient amounts of group III B or IV B elements to complex with the polyhydroxy fatty acid amide. Preferably from about 0.001% to about 2%, preferably from about 0.1% to about 1.5%, more preferably from about 0.1% to about 0.8%, by weight of the composition, of one or more elements selected from the group consisting of aluminum, gallium, boron, silicon, and mixtures thereof are added to the compositions of the present invention. Preferably compositions of the present invention comprise boron, the elements are added to the composition as a compound selected from the group consisting of boric acid, boron trihalides such as boron trichloride, alkali metal borates such as NaBO₂ (e.g. borax, Na₂B₄O₇ with 5 or 10 H₂O), and mixtures thereof. Other suitable element containing compounds are selected from the group consisting of aluminum hydroxide, aluminum trichloride, silicic acid, silicon tetrachloride and mixtures thereof. The levels of element containing compounds added to the composition comprise from about 0.006% to about 12%, preferably from about 0.6% to about 9%, most preferably from about 0.6% to about 5%, by weight of the composition.

Without being bound by theory, it is believed that the presence of a Group III B or IV B elements, such as boron, in a composition containing polyhydroxy fatty acid amide promotes the formation of an element: polyhydroxy fatty acid amide complex. For example, boron can be sandwiched between two molecules of polyhydroxy fatty acid amide.

This tetradente "sandwich" structure can be rigid, be less prone to hydrolysis and have a pKa of about 6 to about 7. The addition of boric acid to a product with an initial pH between 5 and 8 can adequately buffer the product pH in the 5 to 8 pH range. This buffering prevents the product pH from drifting and minimizes the formation of fatty acid via hydrolysis.

The amount of Group III B or IV B containing compound, preferably boric acid, added to the compositions of the invention will be dependent upon the amount of total polyhydroxy fatty acid amide present therein. In a composition of the present invention containing boron, the molar ratio of boron to polyhydroxy fatty acid amide is preferably from about 0.25:1 to about 1:2.

Moderate levels of calcium ions described hereinbelow can be added to give good grease cleaning benefits. The level of Group III B or Group IV B element should be carefully controlled. Too much of these elements in the presence of calcium may result in the precipitation of insoluble salts such as calcium borate.

Composition pH

Traditionally, liquid dishwashing compositions have a pH of about 7. Dishwashing compositions of the invention will be subjected to acidic stresses created by food soils when put to use, i.e., diluted and applied to soiled dishes. Products of the present invention are effective at buffering in the pH range between 5 and 8. If a composition with a pH greater than 8 is desired a buffering agent should be added. The buffering agent should be capable of maintaining the alkaline pH in the composition and in dilute solutions, i.e., about 0.1% to 0.4% by weight aqueous solution, of the composition. The pKa value of this buffering agent should be about 0.5 to 1.0 pH units below the desired pH value of the composition. Preferably, the pKa value of the buffering agent should be between about 7 and about 9.5. Under these conditions the buffering agent most effectively controls the pH while using the least amount thereof. Preferably the composition of the present invention will have a pH in a 10% solution of water at 20ºC between about 6.0 and about 11, more preferably for boron containing compositions between about 7.0 and about 10, most preferably between about 7.0 and about 9.

The buffering agent may be an active detergent in its own right, or it may be a low molecular weight, organic or inorganic material that is used in this composition solely for maintaining an alkaline pH. Preferred buffering agents for compositions of this invention are nitrogen-containing materials. Some examples are amino acids or lower alcohol amines like mono-, di-, and tri-ethanolamine. Other preferred nitrogen-containing buffering agents are 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methylpropanol, and 2-amino-2-methyl-1,3-propanediol, tris-(hydroxymethyl)aminomethane (a.k.a. tris). N-methyl diethanolamine, 1,3-diamino-2-propanol N,N'-tetramethyl-1,3-diamino-2-propanol, N,N-bis(2-hydroxyethyl)glycine (a.k.a. bicine), and N-tris (hydroxymethyl)methyl glycine (a.k.a. tricine) are also preferred. Mixtures of any of the above are acceptable.

The buffering agent is present in the compositions of the invention hereof at a level of from about 0.1% to 15%, preferably from about 1% to 10%, most preferably from about 2% to 8%, by weight.

Anionic Surfactant

The detergent compositions of the present invention comprise from about 3% to about 95%, more preferably from about 5% to about 60%, most preferably from about 10% to about 40%, by weight of the composition of one or more anionic surfactants. Preferably the anionic surfactant is selected from the group consisting of alkyl sulfate, alkyl ether sulfate, polyethercarboxylate, secondary olefin sulfonates, sarcosinates, methyl ester sulphonates alkylglycerol ether sulphonates and mixtures thereof. The most preferred anionic surfactants are anionic sulfate surfactants which may be any organic sulfate surfactant. It is preferably selected from the group consisting of C₁₀-C₁₆ alkyl sulfate which has been ethoxylated with from about 0.5 to about 20 moles of ethylene oxide per molecule, C₉-C₁₇ acyl-N-(C₁-C₄ alkyl) glucamine sulfate, -N-(C₂-C₄ hydroxyalkyl) glucamine sulfate, and mixtures thereof. More preferably, the anionic sulfate surfactant is a C₁₀-C₁₆ alkyl sulfate which has been ethoxylated with from about 0.5 to about 20, preferably from about 0.5 to about 12, moles of ethylene oxide per molecule.

Alkyl ethoxy sulfate surfactants comprise a primary alkyl ethoxy sulfate derived from the condensation product of a C₁₀-C₁₆ alcohol with an average of from about 0.5 to about 20, preferably from about 0.5 to about 12, ethylene oxide groups. The C₁₀-C₁₆ alcohol itself is commercially available. C₁₂-C₁₄ alkyl sulfate which has been ethoxylated with from about 3 to about 10 moles of ethylene oxide per molecule is preferred. For compositions containing C_10-16 alkyl sulfate which has been ethoxylated with from about 0.5 to about 2.5 moles of ethylene oxide per molecule, a lime soap dispersing agent is added for a stable composition.

Conventional base-catalyzed ethoxylation processes to produce an average degree of ethoxylation of 12 result in a distribution of individual ethoxylates ranging from 1 to 15 ethoxy groups per mole of alcohol, so that the desired average can be obtained in a variety of ways. Blends can be made of material having different degrees of ethoxylation and/or different ethoxylate distributions arising from the specific ethoxylation techniques employed and subsequent processing steps such as distillation.

Anionic sulfate surfactants include the C₉-C₁₇ acyl-N-(C₁-C₄ alkyl) and -N-(C₁-C₂ hydroxyalkyl) glucamine sulfates, preferably those in which the C₉-C₁₇ acyl group is derived from coconut or palm kernel oil. Lime soap dispersing agent can be added, especially to the longer chain length glucamine sulfates for improved product stability (e.g., where C₉-C₁₇ acyl is palm kernel oil). These materials can be prepared by the method disclosed in U.S. Patent 2,717,894, Schwartz, issued September 13, 1955, incorporated herein by reference. Alpha-sulfonated fatty acid alkyl esters disclosed in U.S. Patent 4,118,440, Cutler et al, issued June 2, 1992, having the general formula:

wherein R₁ is on the average a C₈ to C₁₆, preferably a C₁₀ to C₁₄ alkyl; and R₂ is on the average a C₁ to C₆, preferably a C₁ to C₂ alkyl, preferably methyl ester sulfonate is employed.

The counterion ("M") for the anionic surfactant component is preferably selected from calcium, sodium, potassium, magnesium, ammonium or alkanol-ammonium, and mixtures thereof, with calcium and magnesium being preferred for cleaning.

Other anionic surfactants useful for detersive purposes can also be included in the compositions hereof. Exemplary, non-limiting useful anionics include salts (e.g., sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C₈-C₂₂ alkyl sulfates, C₈-C₂₂ secondary alkyl alcohol sulfates, C₈-C₂₄ alkylpolyethersulfates (containing up to 10 moles of ethylene oxide); fatty acyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, secondary C₁₀-C₁₈ alkyl sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, acyl taurates, fatty acid amides, alkyl succinates and sulfosuccinates, acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside, alkyl ether carboxylates, polyethercarboxylates (i.e. alkyl polyethoxy carboxylates), fatty acids esterified with isethionic acid and neutralized with sodium hydroxide, and fatty acids amides of methyl tauride. 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. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference). Calcium

The composition of the present invention may additionally comprise from about 0.08% to about 4%, more preferably from about 0.15% to about 1.6%, most preferably from about 0.2% to about 0.7%, by weight of the composition, of calcium ions. It has been found for compositions containing the present polyhydroxy fatty acid amide and boric acid that the presence of calcium greatly improves the cleaning of greasy soils. Only a moderate level of calcium ions need be added, preferably in a ratio from about 1:8 to 1:4 calcium ion: polyhydroxy fatty acid amide.

For added cleaning benefits additional calcium ions may be used; however, it has been found that formulating such calcium ion-containing compositions in alkaline pH matrices is difficult due to the incompatibility of the calcium ions with hydroxide ions. When both calcium ions and alkaline pH are combined with the surfactant mixture of this invention, grease cleaning is achieved that is superior to that obtained by either alkaline pH or calcium ions alone. Yet, during storage, the stability of these compositions becomes poor due to the formation of hydroxide precipitates. In addition excess calcium ions may form insoluble salt precipitates with free fatty acids and/or boron ions.

Preferably, the calcium ions are added as a chloride, hydroxide, oxide, acetate, formate, or nitrate salt, most preferably formate salt, to compositions containing an alkali metal or ammonium salt of the anionic sulfate, most preferably the ammonium salt. The calcium salts are preferably soluble.

The amount of calcium ions present in compositions of the invention may also be dependent upon the amount of total anionic surfactant present therein. The molar ratio of calcium ions to total anionic surfactant is preferably from about 0.1:1 to about 1:4 for compositions of the invention.

Additional Optional Surfactants

Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, at column 13, line 14 through column 16, line 6, incorporated herein by reference. Exemplary, non-limiting classes of useful nonionic surfactants are listed below. 1. The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols. In general, the polyethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from 6 to 12 carbon atoms in either a straight- or branched-chain configuration with the alkylene oxide. Commercially available nonionic surfactants of this type include Igepal™ C0-630, marketed by the GAF Corporation; and Triton™ X-45, X-114, X-100, and X-102, all marketed by the Rohm & Haas Company.

2. The condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol.

3. The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility.

4. The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine.

5. Alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. U.S. Patent Nos. 4,373,203 and 4,732,704, incorporated herein by reference, also describe acceptable surfactants. Most preferably the surfactant contains less than 10% of alcohol ethoxylates of the formula RO(CH₂CH₂O)XH. R is a C₁₂ to C₁₆ alkyl group, X ranges from 0 to about 10, and the average X is less than 6 and less than 10% soap of the formula RCOO-M+ wherein X is a C₁₁ to C₁₅ alkyl group and M is a cation.

If included in the compositions of the present invention, these optional additional surfactants are typically present at a concentration of from about 1% to about 15%, preferably from about 2% to about 10% by weight.

Suds Booster

Another component which may be included in the composition of this invention is a suds stabilizing surfactant (suds booster) at a level of less than about 15%, preferably from about 0.5% to 12%, more preferably from about 1% to 10% by weight of the composition. Optional suds stabilizing surfactants operable in the instant composition are of five basic types - - betaines , fatty acid amides, amine oxide semi-polar nonionics, and cationic surfactants. Particularly preferred suds boosters are selected from the group consisting of alkyl, amine oxide, alkyldimethylbetaine, alkylamidopropylbetaine, alkylmonoethanol amide, alkyldiethanol amide and mixtures thereof.

The composition of this invention can contain betaine detergent surfactants having the general formula:

R - N⁽⁺⁾(R¹)₂ - R²COO^(-)

wherein R is a hydrophobic group selected from the group consisting of alkyl groups containing from about 10 to about 22 carbon atoms, preferably from about 12 to about 18 carbon atoms, alkyl aryl and aryl alkyl groups containing a similar number of carbon atoms with a benzene ring being treated as equivalent to about 2 carbon atoms, and similar structures interrupted by amido or ether linkages; each R¹ is an alkyl group containing from 1 to about 3 carbon atoms; and R² is an alkylene group containing from 1 to about 6 carbon atoms.

Examples of preferred betaines are dodecyl dimethyl betaine, cetyl dimethyl betaine, dodecyl amidopropyldimethyl betaine, tetradecyldimethyl betaine, tetradecylamidopropyldimethyl betaine, and dodecyldimethyl ammonium hexanoate. Other suitable amidoalkylbetaines are disclosed in U.S. Pat. Nos. 3,950,417; 4,137,191; and 4,375,421; and British Patent GB No. 2,103,236, all of which are incorporated herein by reference.

It will be recognized that the alkyl (and acyl) groups for the above betaine surfactants can be derived from either natural or synthetic sources, e,g., they can be derived from naturally occurring fatty acids; olefins such as those prepared by Ziegler, or Oxo processes; or from olefins separated from petroleum either with or without "cracking".

Examples of the amide surfactants useful herein include the ammonia, monoethanol, and diethanol amides of fatty acids having an acyl moiety containing from about 8 to about 18 carbon atoms and represented by the general formula:

R₁ - CO - N(H)_{m - 1}(R₂OH)₃ - m

wherein R is a saturated or unsaturated, aliphatic hydrocarbon radical having from about 7 to 21, preferably from about 11 to 17 carbon atoms; R₂ represents a methylene or ethylene group; and m is 1, 2, or 3, preferably 1. Specific examples of said amides are mono-ethanol amine coconut fatty acid amide and diethanol amine dodecyl fatty acid amide. These acyl moieties may be derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil, and tallow, but can be derived synthetically, e.g., by the oxidation of petroleum or by hydrogenation of carbon monoxide by the Fischer-Tropsch process. The monoethanol amides and diethanol amides of C_12-14 fatty acids are preferred.

Amine oxide semi -polar nonionic surfactants comprise compounds and mixtures of compounds having the formula

wherein R₁ is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or

3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from about 8 to about 18 carbon atoms, R₂ and R₃ are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl , or 3-hydroxypropyl , and n i s from 0 to about 10. Particul arly preferred are amine oxides of the formul a:

wherein R₁ is a C_12-16 alkyl and R₂ and R₃ are methyl or ethyl. The above ethylene oxide condensates, amides, and amine oxides are more fully described in U.S. Pat. No. 4,316,824 (Pancheri), incorporated herein by reference.

The composition of this invention can also contain certain cationic quarternary ammonium surfactants of the formula:

[R¹(OR²)_y][R³(OR²)_y]₂R⁴N+X- or amine surfactants of the formula:

[R¹(OR²)_y][R³(OR²)_y]R⁴N

wherein R¹ is an alkyl or alkyl benzyl group having from about 6 to about 16 carbon atoms in the alkyl chain; each R² is selected from the group consisting of -CH₂CH₂-, -CH₂CH(CH₃)-, -CH₂CH(CH₂OH)-, -CH₂CH₂CH₂-, and mixtures thereof; each R³ is selected from the group consisting of C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, benzyl, and hydrogen when y is not 0; R⁴ is the same as R³ or is an alkyl chain wherein the total number of carbon atoms of R¹ pl us R⁴ i s from about 8 to about 16 ; each y i s 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 R⁴ is selected from the same groups as R³. The most preferred quaternary ammonium surfactants are the chloride, bromide, and methylsulfate C_8-16 alkyl trimethyl ammonium salts, C_8-16 alkyl di(hydroxyethyl)methyl ammonium salts, the C_8-16 alkyl hydroxyethyldimethyl ammonium salts, C_8-16 alkyloxypropyl trimethyl ammonium salts, and the C_8-16 alkyloxypropyl dihydroxyethylmethyl ammonium salts. Of the above, the C_10-14 alkyl trimethylammonium salts are preferred, e.g., decyl trimethyl ammonium methyl sulfate, lauryl trimethyl ammonium chloride, myristyl trimethylammonium bromide and coconut trimethyl ammonium chloride, and methyl sulfate.

Other useful surfactants may also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight-branched chains. One of the aliphatic substituents contains at least 8 carbon atoms, typically from 8 to 18 carbon atoms, and at lease one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,939,678, Laughlin et al, issued December 30, 1975, (herein incorporated by reference) for examples of such useful ampholytic surfactants.

The suds boosters used in the compositions of this invention can contain any one or mixture of the suds boosters listed above. Other Optional Components

Other desirable ingredients include diluents, solvents, dyes, perfumes, opacifiers, and hydrotropes. Diluents can be inorganic salts, such as sodium and potassium sulfate, ammonium chloride, sodium and potassium chloride, sodium bicarbonate, etc. Diluents useful in the compositions of the present invention are typically present at levels of from about 1% to about 10%, preferably from about 2% to about 5% by weight.

Solvents useful herein include water and lower molecular weight (C₁-C₄ monohydric) alcohols, such as ethyl alcohol, isopropyl alcohol, etc. Solvents useful in the compositions of the present invention are typically present at levels of from about 1% to about 60%, preferably from about 5% to about 50% by weight.

Hydrotropes such as sodium, potassium, and ammonium xylene sulfonate (preferred), sodium, potassium and ammonium toluene sulfonate, sodium, potassium and ammonium cumene sulfonate (most preferred), and mixtures thereof, and related compounds (as disclosed in U.S. Patent 3,915,903, the disclosure of which is incorporated herein) can be utilized in addition to the boric acid surfactants in the interests of achieving a desired product phase stability and viscosity. Hydrotropes useful in the compositions of the present invention are typically present at levels of from about 1% to about 10%, preferably from about 2% to about 5%, by weight.

Opacifiers such as Lytron (Morton Thiokol, Inc.), a modified polystyrene latex, or ethylene glycol distearate can be added, preferably as a last step. Lytron can be aded directly as a dispersion with mixing. Ethylene glycol distearate can be added in a molten state with rapid mixing to form pearlescent crystals. Opacifiers useful herein, particularly for light duty liquids, are typically present at levels of from about 0.2% to about 10%, preferably from about 0.5% to about 6% by weight.

In a preferred embodiment, the detergent compositions of the present invention are liquid detergent compositions. These preferred liquid detergent compositions comprise from about 94% to about 35% by weight, preferably from about 90% to about 50% by weight, most preferably from about 80% to about 60% by weight of a liquid carrier, e.g., water, preferably a mixture of water and a C₁-C₄ monohydric alcohol (e.g., ethanol, propanol, isopropanol, butanol, and mixtures thereof), with ethanol being the preferred alcohol. A preferred way to make light duty liquids of the present invention is to combine the polyhydroxy fatty acid amide and the anionic surfactant, preferably an alkyl (ethoxy) sulfate with water and ethanol, the pH is adjusted and then calcium and optionally magnesium ions are mixed into the composition as aqueous solutions of chloride salts. The mixture is blended and hydrotrope may be added to adjust the viscosity. Perfume, dye, opacifier, and other optional ingredients may then be added.

Method Aspect

In the method aspect of this invention, soiled dishes are contacted with an effective amount, typically from about 0.5 ml. to about 20 ml. (per 25 dishes being treated), preferably from about 3 ml. to about 10 ml., of the detergent composition of the present invention. The actual amount of liquid detergent composition used will be based on the judgement of user, and will typically depend upon factors such as the particular product formulation of the composition, including the concentration of active ingredient in the composition, the number of soiled dishes to be cleaned, the degree of soiling on the dishes, and the like. The particular product formulation, in turn, will depend upon a number of factors, such as the intended market (i.e., U.S., Europe, Japan, etc.) for the composition product. The following are examples of typical methods in which the detergent compositions of the present invention may be used to clean dishes. These examples are for illustrative purposes and are not intended to be limiting.

In a typical U.S. application, from about 3 ml. to about 15 ml., preferably from about 5 ml. to about 10 ml. of a liquid detergent composition is combined with from about 1,000 ml. to about 10,000 ml., more typically from about 3,000 ml. to about 5,000 ml. of water in a sink having a volumetric capacity in the range of from about 5,000 ml. to about 20,000 ml., more typically from about 10,000 ml. to about 15,000 ml. The detergent composition has a surfactant mixture concentration of from about 21% to about 44% by weight, preferably from about 25% to about 40% by weight. The soiled dishes are immersed in the sink containing the detergent composition and water, where they are cleaned by contacting the soiled surface of the dish with a cloth, sponge, or similar article. The cloth, sponge, or similar article may be immersed in the detergent composition and water mixture prior to being contacted with the dish surface, and is typically contacted with the dish surface for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user. The contacting of the cloth, sponge, or similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the dish surface.

In a typical European market application, from about 3 ml . to about 15 ml., preferably from about 3 ml. to about 10 ml. of a liquid detergent composition is combined with from about 1,000 ml. to about 10,000 ml., more typically from about 3,000 ml. to about 5,000 ml. of water in a sink having a volumetric capacity in the range of from about 5,000 ml. to about 20,000 ml., more typically from about 10,000 ml. to about 15,000 ml. The detergent composition has a surfactant mixture concentration of from about 20% to about 50% by weight, preferably from about 30% to about 40%, by weight. The soiled dishes are immersed in the sink containing the detergent composition and water, where they are cleaned by contacting the soiled surface of the dish with a cloth, sponge, or similar article. The cloth, sponge, or similar article may be immersed in the detergent composition and water mixture prior to being contacted with the dish surface, and is typically contacted with the dish surface for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user. The contacting of the cloth, sponge, or similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the dish surface.

In a typical Latin American and Japanese market application, from about 1 ml. to about 50 ml., preferably from about 2 ml. to about 10 ml. of a detergent composition is combined with from about 50 ml. to about 2,000 ml., more typically from about 100 ml. to about 1,000 ml. of water in a bowl having a volumetric capacity in the range of from about 500 ml. to about 5,000 ml., more typically from about 500 ml. to about 2,000 ml. The detergent composition has a surfactant mixture concentration of from about 5% to about 40% by weight, preferably from about 10% to about 30% by weight. The soiled dishes are cleaned by contacting the soiled surface of the dish with a cloth, sponge, or similar article. The cloth, sponge, or similar article may be immersed in the detergent composition and water mixture prior to being contacted with the dish surface, and is typically contacted with the dish surface for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user. The contacting of the cloth, sponge, or similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the dish surface.

Another method of use will comprise immersing the soiled dishes into a water bath without any liquid dishwashing detergent. A device for absorbing liquid dishwashing detergent, such as a sponge, is placed directly into a separate quantity of undiluted liquid dishwashing composition for a period of time typically ranging from about 1 to about 5 seconds. The absorbing device, and consequently the undiluted liquid dishwashing composition, is then contacted individually to the surface of each of the soiled dishes to remove said soiling. The absorbing device is typically contacted with each dish surface for a period of time range from about 1 to about 10 seconds, although the actual time of application will be dependent upon factors such as the degree of soiling of the dish. The contacting of the absorbing device to the dish surface is preferably accompanied by concurrent scrubbing.

EXAMPLES

The following examples illustrate the compositions of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention. All parts, percentages and ratios used herein are by weight unless otherwise specified.

EXAMPLE I

The following light duty liquid compositions of the present invention are prepared according to the descriptions set forth below.

% By Weight

Component A B C D C_12-14 alkyl N-methyl glucamidel 12.0 12.0 12.0 12.0 Sodium C_13-14 alkyl ethoxy

(1-3) sulfate 17.00 17.00 17.00 17.00

C_9-11 alkyl ethoxy (ave. 10)

alcohol 5.00 5.00 5.00 5.00 C_12-13 alkyl dimethyl amine oxide 2.00 2.00 2.00 2.00 Boric acid 0. 1 0.5 1 .0 1 .5

Sodium cumene sulfonate 2.00 2.00 2.00 2.00 Water and minors - - - - - - - q.s. to 100% - - - - - - -

¹The C_12-14 alkyl N-methyl glucamide contains about 90.5% of C_12-14 alkyl methyl glucamide (less than 0.1% cyclic polyhydroxy fatty acid amide), about 3.3% of C₁₂ alkyl fatty acid, about 5.5% glucamide, and about 0.3 ester amides. A surfactant paste is initially formed by combining any desired surfactants with water and alcohol. The surfactants contained in this surfactant paste include the polyhydroxy fatty acid amides of the present invention. Ideally the surfactant paste should be pumpable at room or elevated temperatures. Separately, in a large mixing vessel having a propeller mixer, three-quarters of the water of the formulated product, one-half of the alcohol of the formulated product, one-half of the alcohol of the formulated product, and any optional hydrotropes (e.g. xylene, cumene, toluene sulfonates) and boric acid are combined with mixing to give a clear solution. The surfactant paste is added and the pH of the mixture is adjusted to 7.0 - 7.5, before any calcium ions, if needed, are added.

The calcium ions may be added directly to the mixing vessel as calcium chloride, calcium formate, or as calcium oxide or hydroxide powder. The calcium oxide or hydroxide powder is added to the acid form of the surfactant salts (e.g. alkyl benzene sulfonates, alkyl sulfates, alkyl ethoxylated sulfates, methyl ester sulfonates, etc.) in the surfactant paste. When calcium is added as a oxide or hydroxide powder, a less than stoichimometrically required amount is added with mixing to ensure complete dissolution. The pH of the calcium-containing surfactant paste is then adjusted by using NaOH or KOH solutions.

The mixture is mixed until a homogenous, clear solution product is obtained. Additional water, alcohol, and any desired additional hydrotropes (added as a solution) may then be added to trim the solution product viscosity to the desired level, ideally between 50 and 1000 cps, as measured by a Brookfield viscometer at 70°F. The pH of the final product is then adjusted with either HCl or NaOH to a level of 7.0 ± 0.7 for formulas containing ammonium ions, and 8.5 + 1.5 for formulas which do not contain ammonium ions (pH measurements of a 1% solution of the formula).

Perfume, dye and other ingredients, e.g., opacifying agents such as Lytron and ethylene glycol distearate, are added as the last step. Lytron can be added directly as a dispersion with mixing. Ethylene glycol distearate must be added in a molten state with rapid mixing to form the desired pearlescent crystals. The following procedures show how the above formulations are evaluated in terms of how well they maintain their pH stability.

The method used to evaluate pH stability of the compositions of this invention involves storing a portion of the product without opacifier at 40°F (4.4°C), room temperature, and 120°F (48.9°C) for several days. At the end of the period a 10% solution of the product in water is evaluated for pH stability using a pH meter. Representative results are shown in Table 1.

Table 1

Composition

A B C D

Initial 7.02 7.14 7.02 6.91 Week 1 Δ pH

Room Temp. 0. 14 0. 10 0.09 0.04 120ºF (48.9ºC) 0.35 0.23 0. 18 0.13 Week 2

Room Temp. 0.14 0.10 0.08 0.04 120ºF (48.9ºC) 0.46 0.30 0.21 0. 16

All of the above formulations of the present invention demonstrated that improved pH stability (i.e. significantly less pH drift) can be achieved by the addition of boric acid to the compositions of this invention.

EXAMPLE II

The following compositions are prepared according to Example I.

% By We ight

Component A B

C₁₂ alkyl N-methyl glucamide¹ 16.3 16.3 C_12-13 alkyl ethoxy (ave. 3) sulfate,

sodium 16.3 16.3

C_12-13 alkyl amine oxide 3.7 3.7

C_9-11 alkyl ethoxy (ave. 8) alcohol 0.75 0.75

Cumene sulfonate, sodium 4.0 4.0 Boric acid 0 1.3

Others (water, ethanol, dye, perfume

etc. ) - - - - - - -balance - - - - - - - pH (10% solution) 7-7.2 7-7.2

¹The C_12-14 alkyl N-methyl glucamide contains about 90.5% of C_12-14 alkyl methyl glucamide (less than 0.1% cyclic polyhydroxy fatty acid amide), about 3.3% of C₁₂ alkyl fatty acid, about 5.5% glucamide, and about 0.3 ester amides.

Grease removal benefits of the above formulations are assessed by measuring interfacial tension (IFT) at the oil/water interface. IFT is a measure of the amount of energy needed to emulsify grease. The lower number, the better the grease cleaning ability of the product. IFT is determined using a University of Texas Model 500 Spinning Drop Interfacial Tensionmeter, under conditions representative of those encountered by consumers using light duty liquid or gel dishwashing composition. Thus, measurements were made at a sample temperature of about 115'F (46.1ºC) using a product concentration of about 0.2% to about 15% in from about 0.5 to about 15 grain water. The soil is animal fat. A narrow capillary tube is filled with solution of the compositions and a drop of the melted animal fat is carefully added via a syringe. An IFT reading is taken immediately upon insertion of the sample into the tensionmeter and again at five and ten minutes. Results are shown in Table 2.

Table 2

Avg. IFT¹ dyne/cm

Hardness gpg A B

0.5 0.85 0.50

7 0.62 0.47

15 0.44 0.29

1 Avg. IFT = (clean solution IFT) + (soiled solution IFT)

2

The results of Table 2 show improved IFT values for a composition in which boric acid is added as an ingredient (Composition B) over a composition where no boric acid is added (Composition A).

EXAMPLE III

The following compositions are prepared according to Example

I. % By Weight

Component A B C

C₁₂ al kyl N-methyl glucamide¹ 16.3 16.3 16.3

C_{12 - 13} al kyl ethoxy (ave. 3) sul fate,

sodium 16.3 16.3 16.3

C_{12- 14} al kyl amine oxide 3.7 3.7 3.7

C_{9- 11} al kyl ethoxy (ave. 8) alcohol 0.75 0.75 0.75

Boric acid 0 1.3 1.3

Ca⁺⁺ ions (added as calcium formate) 0.2 0.2 0.5 Others (water, ethanol, dye, perfume

etc.) - - - - - - - - - balance - - - - - - - - -

¹The C_12-14 alkyl N-methyl glucamide contains about 90.5% of

C_12-14 alkyl methyl glucamide (less than 0.1% cyclic polyhydroxy fatty acid amide), about 3.3% of C₁₂ alkyl fatty acid, about 5.5% glucamide, and about 0.3 ester amides.

An alternate method for grease removal is a determination of the amount of solid animal fat removed from polypropylene cups

(PPC) under soil situation. Between 3 and 8 grams of animal fat is solidified onto the bottom of polypropylene cups and from about 0.2 to about 0.4% of the product is added. The % of fat removed after about 4 hours of storage is a gauge for the grease cleaning efficiency of the compositions. Results are shown in Table 3.

Table 3

% soil removal

Hardness gpg A B C

0.5 4.0 0.7 16.8

7 16.8 14.4 16.2

Results in Table 4 demonstrate that calcium ions improve grease cleaning in soft water of compositions containing glucamide and boron. However, higher levels of clacium ions are needed in boron containing compositions than a composition without boron.

EXAMPLE IV

The following clear, stable, concentrated liquid compositions are formulated. The compositions are prepared in the same manner as the compositions of Example I. % By Weight

Component J K

C₁₂ alkyl N-methyl glucamide 11.1 9.0

Sodium C_13-14 alkyl ethoxy (ave 0.8)

sulfate 19.1 9.0

Sodium C_13-14 alkyl ethoxy (ave 3)

sulfate 3.1 8.0 C₁₁ alkyl ethoxy (ave. 10) alcohol - - 5.0 C_i0 alkyl ethoxy (ave. 8) alcohol 4.6 - - Dodecyl dimethyl betaine 2.6 3.0

C_12-14 alkyl dimethyl amine oxide 1.6 2.0

Calcium formate 0.15 0.6

Magnesium chloride hexahydrate 0.75 0.3

Aluminum hydroxide 0.5 0.5 Aluminum trichloride 0.5 0.5

Water and minors q.s. to 100% q. s. to 100 pH of a 10% solution about 6.0

Claims

What is Claimed is:

1. A liquid or gel dishwashing detergent composition comprising, by weight:

(a) from 3% to 40% of polyhydroxy fatty acid amide having the formula:

wherein R¹ is hydrogen, C_1-4 hydrocarbyl, 2- hydroxyethyl, 2-hydroxypropyl, or mixtures thereof; R² is C₅-C₃₁ hydrocarbyl; and Z is a polyhydroxy-hydrocarbyl having a linear hydrocarbyl chain with at least three hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof;

(b) from 0.001% to 2% of one or more elements selected from the group consisting of aluminum, gallium, boron, silicon and mixtures thereof; preferably added to said composition as a compound selected from the group consisting of boric acid, boron trihalides, alkali metal borates, aluminum hydroxide, aluminum trichloride, silicic acid, silicon tetrachloride and mixtures thereof; and

(c) from 3 to 95% of an anionic surfactant preferably selected from the group consisting of alkyl sulfate, alkyl ether sulfate, polyethercarboxylate, secondary olefin sulfonates, acylsarcosinates, methyl ester sulphonates, alkylglycerol ether sulphonates, and mixtures thereof; wherein said composition has a pH in a 10% solution in water at 20ÿC of between 6 to 11.

2. A composition according to Claim 1 further comprising from 0.08% to 4% of calcium ions added to said composition as a salt selected from the group consisting of calcium chloride, calcium hydroxide, calcium oxide, calcium acetate, calcium formate, calcium nitrate and mixtures thereof; from 0.5% to 12% suds booster selected from the group consisting of alkyl amine oxide, alkyl diethylbetaine, alkylamidopropylbetaine, alkylmonoethanol amide, alkyldiethanol amide and mixtures thereof; and having a pH in a 10% solution in water at 20ÿC of between about 7 and about 10.

3. A composition according to Claim 1 or 2 further comprising nonionic surfactant selected from the group consisting of polyethylene, polypropylene and polybutylene oxide condensates of alkyl phenols; the alkyl ethoxylate condensation products of aliphatic alcohols with ethylene oxide; the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol; the condensation product of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine; alkylpolysaccharides; and mixtures thereof.

4. A composition according to any one of the preceding claims comprising from 5% to 30% of said polyhydroxy fatty acid amide, wherein R¹ is C₁-C₄ alkyl and R² is a straight-chain C₇-C₁₉ alkyl or alkenyl group or mixture thereof and Z is selected from the group consisting of - CH₂ - (CHOH)_n - CH₂OH, - CH(CH₂OH) - (CHOH)_n-1 - CH₂OH, -CH₂ - (CHOH)₂ (CHOR¹) (CHOH) - CH₂OH, where n is an integer from 3 to 5, inclusive, and R1 is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof.

5. A composition according to any one of the preceding claims comprising from 6% to 60% of said anionic surfactant which is selected from the group consisting of C₁₀-C₁₆ alkyl sulfate which has been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule, C₉-C₁₇ acyl-N-(C₁-C₄ alkyl) glucamine sulfate, -N-(C₂-C₄ hydroxyalkyl) glucamine sulfate, preferably C₁₂-C₁₄ alkyl sulfate which has been ethoxylated with from about 3 to about 10 moles of ethylene oxide per molecule and mixtures thereof.

6. A composition according to any one of the preceding claims comprising from 0.1% to 0.8% boron wherein said boron is added to said compositions as a compound selected from the group consisting of boric acid, boron trihalides, alkali metal borates and mixtures thereof; and wherein said composition has a boron to polyhydroxy fatty acid amide ratio of from 0.25:1 to 1:2.

7. A liquid detergent composition according to any one of the preceding claims comprising from 6% to 65% of said anionic surfactant and further comprising from 94% to 35% of a liquid carrier comprising a mixture of water and a C₁-C₄ monohydric alcohol, preferably from 90% to 50% of a mixture of water and ethanol.

8. A liquid detergent composition according to any one of the preceding claims comprising from 0.3% to 1.5% of calcium ions, said ions added to said composition as calcium chloride or calcium formate and said composition, said boron is added to said composition as boric acid having a pH in a 10% solution in water at 20ÿC of between about 7 and about 9.

9. A gel detergent composition according to any one of the preceding claims comprising from 10% to 40% of said anionic surfactant and from 0.3% to 1.5% of calcium ions added to said composition as calcium formate.