US2527076A - Detergent composition - Google Patents

Description

Patented Oct. 24, 1950 DETERGENT COMPOSITION Walter 0. Preston, Cincinnati, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Application February 24, 1947, Serial No. 730,559

18 Claims. (Cl. 252-117) The presentinvention relates to detergent compositions, and more particularly to soap-containing compositions which are highly resistant to curd-forming ingredients of hard water.

It is well known that the use of ordinary toilet or household soap in hard water results in the formation and precipitation of insoluble fatty acid salts, more commonly referred to as lime soaps." It is also known that such precipitated lime soaps have a tendency to coagulate and form a sticky curd. This curd is commonly observed in the washstand and bath tub and also in the laundry rinse tub where it rises to the surface of the water as a scum, adheres to the walls of the tub as a ring, and sticks to the clothes during the rinsing operation, thereby giving to the clothes an unsightly dingy appearance, producing spots upon subsequent ironing, and often causing the development of a rancid odor. When soap is used for shampooing the hair, rinsing with hard water results in deposition of the lime soaps on the hair. In applications as divergent as the dyeing of textile fabrics and the plating of metals, the formation of lime soaps has undesirable effects.

' In fact, whenever soap is used in hard water, insoluble lime soap curd forms during the rinsing process when the soap dilution becomes sufliciently great to destroy the foaming and dispersing power of the soap.

The coagulation of the lime soaps to form soap curd is dependent not only on the degree of dilution of thesoap in the hard water, but also on the age of the solution and on the degree of violence of agitation to which it is subjected, in-

creasing age and increasing agitation both being important factors in promoting coagulation.

The primary object of the present invention is to provide a soap composition which forms little or no lime soap curd when used with hard water.

' Another object is to provide a detergent composition which will not form a sticky lime soap curd which will cling to clothes or form the unsightly, difllculty removable soap ring in the washstand or bathtub.

A further object is to increase the resistance of soap-containing detergent compositions to precipitation of lime soap and the coagulation thereof to form curd when such compositions are used in hard water under conditions involving prolonged standing or agitation.

These and other objects of the invention, and how such objects may be realized, will appear from the following detailed description.

It is known that synthetic detergents such as the various organic sulfonates, alkyl sulfates, and other organic sulfuric acid derivatives, when mixed or used with soap in hard water are capable of reducing the formation of lime soap curd. Several such mixtures have been proposed. Some have been commercially produced and designated as hard water soaps, allegedly free of curd forming characteristics when used in hard water. However, according to my investigations and experience, products prepared in accordance with prior art practices, even those which contain more synthetic detergent than soap, frequently form objectionable curd in hard water under normal conditions of use. As the proportion of synthetic detergent increases, the trouble with such hard water curd may decrease in seriousness, but at the same time the cost of the product increases and some of the desirable physical properties found in soap are adversely affected.

As more fully hereinafter described, I have discovered that carboxylic acid amides (although possessing no power to inhibit curd formation when used with soap alone) have a marked power to inhibit lime soap precipitation and curd formation in the case of curd forming detergent compositions comprising essentially a mixture of soap and synthetic detergent in proportions more fully hereinafter described. This power exists even when the compositions are used under conditions wherein the solution is subjected to prolonged standing or to mild or vigorous agitation. I am aware that prior workers in the art have suggested the combination of soap with synthetic detergents (Patents 1,906,484, 2,026,816, and 2,088,308). I am also familiar with recently issued patents covering the use of certain amide type compounds with synthetic detergents to improve the sudsing and detergent power thereof (Patents 2,383,525, 2,383,737, and 2,383,738). None of these patents, however, suggests the use of amide compounds for inhibiting the curd formation when compositions comprising soap and synthetic detergent are employed in hard water.

Amides which come within the scope of the invention are those aliphatic amides of the formula and R" are hydrogen, alkyl, alkylol, or alkylene. joined through an oxygen atom, the total numberof carbon atoms in R, R and R" being from about 9 to about 25.

Amides of this general type which are of especial interest are those aliphatic carboxylic acid alkylolamides oi the formula c (RIRIIRIII) B C O- in which RC0 is the acyl radical of a soap forming carboxylic acid having from about 10 to about 18 carbon atoms, R. and R" are each selected from the group consisting of hydrogen, alkyl, and alkylol radicals, and R' is an alkylol radical, the total number of carbon atoms in R, R" and 3' being from 1 to 7.

Some specific amides coming within the scope of the invention are:

/H O-CHIOH Cu -C 0-- Laurie ethanolamido CHI Dimcthyl lauramide E 011 10 O-N Lam-amide CuHn Lauryl lauramido CHI Cit nC O-N CsHuOH Myristic N-methyl ethanol-snide CiHl Butyl capramide COHIOH Capric butanolsmide CcHl Dibutyl capramide 04H. Dibutyl myristamide CHOH C CHIOH CUBIC ON CHaOH lteu'ic acid amide ct tris (hydrcxymethyl) amino methane n o crron-cmon (Mal Myrhtic glycerylamide OKs-CH:

CHr-Cfi:

N-lsuroyi morpholine H c-cH0H-cmoH C BIG 0- Laurie glycerylamide CHsOH CCH CnHnC0N CH|0H CuHI Lauryl hydroxy-acctamlde CnHD Myristyl formunide 0 01! OH- CH:

Cu O 0- Laurie iaopropanol amide CECIL-CH:

Myristic acid amide of 3-amino-3-methyl-2,4-pentanediol Instead of employing amides 01' single car- 60 boxylic acids as exemplified above, the corresponding amides derived from mixtures of carboxylic acids, especially those mixtures obtainable from oils, fats, and waxes of vegetable and animal origin, may be employed without departing from the spirit of the invention. For example, the amides of fatty acids of oils of the coconut oil group (a group of tropical nut oils characterized by their high content of lauric and myristic acids) such as coconut oil, palm o0 kernel oil and babassu oil are or particular value. Amides derived from other oils and fats such as palm oil, tallow. cottonseed oil, sunflower seed oil, fish oils such as menhaden oil. and the like, as well as from hydrogenated and partially hyll drogenated fats and oils in general may be employed. Corresponding amides of synthetic carbonlic acids having 10 to 20 carbons may also be used. Such carboxylic acids may be obtained, for example, by the oxidation of parafiln hydro- 10 carbons, or petroleum, or they may be obtained directly by hydrogenation of carbon monoxide (the Fischer-Tropsch process) or indirectl by oxidation of the saturated or unsaturated hydrocarbons or oxygenated hydrocarbons resulting 7 from this process.

The kind of soap which is used in preparing my improved detergent compositions is not a limitation of the invention. Any of the watersoluble soaps formulated for industrial, household, and toilet use ma be employed. Thus the character of the soap constitutent may vary widely in its. composition depending on whether the final ternary composition is to be in powdered, spray dried, flake, bar. paste, thread, liquid or other form, and it is to be understood that the specific soaps referred to in the examples given below and prepared from tallow and coconut oil are not to be construed as limining nature. Water-soluble soaps such as the sodium, potassium and other suitable alkali metal or ammonium soaps or soaps of nitrogen bases, such as triethanolamine, derived from other fats and oils such as cottonseed oil, soybean oil, corn oil, olive oil, palm oil, peanut oil, palm kernel, lard, reases. fish oils and the like as well as their hydrogenated derivatives, and mixtures thereof, properly blended to yield the desired soap quality, may be used in compounding the ternary mixtures herein contemplated.

The synthetic detergent constituent of the present detergent compositions may be broadly designated as a detergent of the class consisting of water-soluble salts of organic sulfonic acids and water-soluble salts of aliphatic sulfuric acid esters, that is, water-soluble salts of organic suifuric reaction products having in the molecular structure a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. As indicated above in the designation of the soaps which may be used in compounding the compositions of my invention, the choice of synthetic detergent will depend inter alia on the physical characteristics of the final product, that is, whether the composition is to be in flake, bar, paste, or other form. Obviously if a detergent composition in bar form is desired, it will be impractical to combine ingredients which are too soft to retain their shaped form in use.

Synthetic detergents of special interest and particular value are the water-soluble salts of higher alkyl sulfuric acids containing from 8 to 18 carbon atoms in the alkyl radical. More speciflcally, the alkali metal salts of sulfuric acid esters of normal primary aliphatic alcohols having 10 to 18 carbon atoms, particularly those whose principal active ingredient is a watersoluble salt of lauryl sulfuric acid or oleyl sulfuric acid, have proved of value in compounding products of the present invention. Thus the sodium salt of alkyl sulfates obtained from the mixed higher alcohols derived by the reduction of coconut oil, palm kernel oil, babassu oil, or other oils of the coconut oil group or the sodium alkyl sulfate derived from sperm oil alcohols may be employed. In addition, water-soluble alkyl sulfates having pronounced detergent power and derived from high molecular branched chain primary alcohols or from high molecular secondary alcohols may be used.

Other aliphatic sulfuric acid esters which may be employed in the preparation of detergent compositions of the present. invention include watersoluble salts of-sulfuric acid esters of polyhydric alcohols incompletely esterified with high molecular weight soap forming carboxylic acids. Such synthetic detergents include the water-soluble salts of sulfuric acid esters of higher molecular weight fatty acid monoglycerides such as sodium salt of the coconut oil fatty acid mono-ester of 1,2-dihydroxy-propane-3-sulfuric acid ester, tri- 8 ethanolamine salt of mono-oleoyl diethylene glycol sulfate, sodium mono-myristoyl ethylene glycol sulfate, and sodium mono-lauroyl diglycerol sulfate.

similarly water-soluble salts of ethers of high molecular weight normal primary alcohols and lower molecular weight hydroxy alkyl sulfuric acid esters may be employed. Specific examples of such synthetic detergents are sodium salt of mono fatty-alcohol-of-coconut-oil ether of glycerol monosulfuric acid and sodium salt of lauryl ether of ethylene glycol monosulfuric acid.

In addition, sulfuric acid ester synthetic detergents such as water-soluble salts of sulfated higher fatty acid alkylolamides, for example the sodium salt of sulfated coconut oil fatty acid ethanolamide and of sulfated babassu oil fatty acid glycerol amide, may be employed in the practice of the invention.

The amides hereinabove mentioned are active also in inhibiting curd formation in the case of those detergent compositions which contain in combination with soap an organic synthetic detergent having a true sulfonate group. These synthetic detergents include salts of higher molecular weight monofatty acid esters of lower molecular weight hydroxy alkyl sulfonic acids such as the sodium salt of the coconut oil fatty acid monoester of 1,2-dihydroxy-propane-3-suli'onic acid, and the oleic acid ester of the sodium salt of isethionic acid. Included also are the higher molecular weight fatty acid amides of lower molecular weight amino alkyl sulfonic acids (for example, potassium salt of oleic acid amide of N-methyl taurine), the water-soluble salts of the higher molecular weight alcohol esters of sulfocarboxylic acids (for example, sodium salt of the lauryl alcohol ester of sulfoacetic acid)-,--

lower molecular weight sulfocarboxylic acid amides of alkylolamine esters of higher molecular weight fatty acids (for example, sodium salt of the sulfoacetamide of amino ethyl laurate) higher alkylated benzene sulfonic acids (for example, potassium salt of the sulfonic acid derived from the condensation product of benzene and a chlorinated kerosene fraction containing predominantly 12 carbon atoms per molecule) and ethers of higher molecular weight alcohols and lower molecular weight hydroxy alkyl sulfonic acids (for example, monolauryl ether of 1,2-dihydroxypropane-3-sodium sulfonate and monolauryl ether of the sodium salt of isethionic acid).

Although the cleansing agent of the compositions of the present invention comprises essentially a ternary mixture of amide, soap, and synthetic detergent, it will be appreciated that the incorporation in the mixture of additional ingredients commonly used with cleansing compositions, such as perfumes, starch, urea, triethanolamine, inorganic salts (silicates, carbonates,

"ortho-, meta-, pyro-, and triphosphates and the like), albuminous substances, glycerin, insecticides, and germicides, and the like, is contemplated as part of the instant invention.

The following examples will illustrate the manner in which the invention may be practiced, but it is to be understood that such details are given merely for exempliiication purposes and are not to be construed as limiting the scope of the appended claims. In all instances the proportions are expressed in parts by weight.

Example 1.5.5 parts of the coconut oil fatty acid amide of monoethanolamine, 67.2 parts of flaked sodium soap derived from a mixture of 75% tallow and 25% coconut oil and containing about 3% moisture, and 27.3 parts of a commercial alkyl sulfate containing about 88% synthetic detergent (the sodium salt of alkyl sulfuric acids derived from coconut oil alcohols) were combined, mixed with about 3 parts of water, and run over a seal milling roll. The milling operation was continued until a. homogeneous mixtureof ingedients was obtained, and until the moisture content of the soap was reduced to about 3 or 4%. The soap was removed from the rolls in the form of thin ribbons which were allowed to dry and then broken up into suitable flake form. In the composition thus prepared, the ratio of soapzsynthetlc was about 2.7: 1 and the ratio of synthetic: amide was about 4.4:1. When used in 21 grain water (molar ratio of CaCl2:MgCl:=2.9:1) to wash dishes, no sticky curd was formed.

Example 2.The same amide, soap flakes, and synthetic detergent employed in Example 1 were used in the preparation of the product of this example. 5 parts amide, 60.5 parts soap, and 24.5 parts commercial alkyl sulfate were combined and mixed with parts sodium sulfate. The mixture was treated substantially in accordance with the procedure of Example 1 and converted into flake form. The ratio of soapzsynthetic was about 27:1 and the ratio of syntheticzamide was about 4.311. The product produced no sticky soap curd when used in 21 grain water.

Instead of employing the coconut oil fatty acid amide of monoethanolamine as set forth in EX- ample 2, the corresponding simple amide, dimethyl amide, glycerylamide, isopropanolamide, morpholine amide, or other carboxylic acid amides specifically mentioned hereinabove may be substituted.

Example 3.A detergent flake was prepared substantially in accordance with Example 1 from a mixture of 5 parts of the babassu oil fatty acid amide of monoethanolamine, 75 parts soap (as used in Example 1), and 27.4 parts Nacconol LA" containing as the active synthetic detergent ingredient about 73% of the sodium salt of coconut oil higher alcohol ester of sulfoacetic acid, the remaining fraction of the Nacconol LA being essentially sodium chloride. The ratio of soapzsynthetic was about 3.6:1 and the ratio of syntheticzamide was 4:1. The product was used in hard water without the formation of objectionable sticky curd.

An efficient detergent flake may be produced by substituting 20 parts of sodium oleyl sulfate or of the sodium salt of the sulfuric acid ester of coconut oil fatty acid glyceryl amide for the 27.4 parts of Nacconol LA used in this example.

Example 4.-This example illustrates the preparation of a detergent bar coming within the scope of the invention. Six parts of coconut oil fatty acid amide of monoethanolamine, 70 parts of sodium soap derived from a mixture of 80% tallow and 20% coconut oil and containing about moisture, and 24 parts of the alkyl sulfate employed in Example 1 were mixed with about 2-3 parts water and milled in accordance with accepted procedure to produce a homogeneous product. The product resulting from the milling was then plodded and cut and stamped in the form of a bar. The ratio of soapzsynthetic was 2.821 and the ratio of syntheticzamide was 3.521. The detergent bar may be employed in the washstand or bathtub for toilet use without the formation of the objectionable soap ring.

In an ancillary example the amide of monoethanolamine and a mixture of Clo-C carboxylic acids obtained by the oxidation of paraflin wax is used; instead of the coconut oil fatty acid amide of monoethanolamine.

Additional examples of compositions coming within the scope of my invention and possessing excellent curd resisting qualities when employed in hard water are given below.

Example 5.In accordance with the procedure of Example 4, a detergent bar was prepared from 5 parts of coconut oil fatty acid amide of monoethanolamine, 74 parts of soap containing 15% moisture, and 28.8 parts of the "Nacconol LA" used in Example 3 (73% active synthetic detergent). The ratio of soapzsynthetic was 3.011 and the ratio of syntheticzamide was 4.2:1.

Example 6.'Ihe following mixture of ingredients was converted into a detergent bar in accordance with the procedure outlined in Example 4: four parts of coconut oil fatty acid amide of monoethanolamine, 56 parts soap containing 15% moisture, 27.4 parts "Nacconol LA" used in Examples 3 and 5, and 20 parts urea. The ratio of soapzsynthetic was about 2.4:1 and the ratio of synthetic amide was 5.0: 1.

Example 7.-In accordance with the procedure of Example 1, the following mixture was converted into a flake composition: 5 parts of coconut oil fatty acid amide of monoethanolamine, 70 parts soap containing 3% moisture, and 25 parts of the sodium salt of the coconut fatty acid monoester of 1,2-dihydroxy-propane-3-sulfonic acid, sometimes referred to as the sodium salt of coconut oil monoglyceride sulfonate. The ratio of soap:sulfonate was about 2.711 and the ratio of sulfonatezarnide was about 5:1.

Example 8.In accordance with previous examples dealing with a detergent composition in flake form, 5. parts of coconut oil fatty acid amide of monoethanolamine, 84 parts of soap containing 3% moisture, and 73.4 parts of Igepon T gel containingabout 15% of the synthetic detergent, oleic acid amide of the sodium salt of methyl taurine, and about 85% moisture were combined and processed to yield a flake containing a ratio of soap:synthetic of about 74:1 and a ratio of syntheiczamide of about 2.2:1.

Another example involves repeating the above, but substituting N-lauroyl morpholine for the coconut oil fatty acid amide of monoethanolamine.

Example 9.In accordance with the procedure of Example 1, flakes are prepared from the following mixture of ingredients: 5 parts of the stearic acid amide of tris (hydroxymethyl) amino methane, parts of soap containing 3% moisture, and 32.6 parts Igepon A containing 46% of the oleic acid ester of sodium isethionate as the synthetic detergent, the balance being essentially inorganic salts. The ratio of soapzsynthetic is about 5.2:1 and the ratio of syntheticzamide is about 3: 1.

Another example ancillary to the above involves the palmitic acid amide of 2-amino-2- methyl-1,3-propane-diol in place of the stearic acid amide of tris (hydroxymethyl) amino methane. Example 10.In accordance with the procedure of Example 1, flakes are prepared from the following mixture of ingredients: 3 parts of coconut fatty acid amide of monoethanolamine,!!!) parts soap containing 3% moisture, 17 parts of the sodium salt of the coconut oil fatty acid mono-ester of 1,2-dihydroxy-propane-B-sulfuric acid, sometimes referred to as the sodium salt of the sulfuric acid mono-ester of coconut oil monoglyceride as synthetic detergent. The composition contains a ratio of soapzsynthetic of about 4.6:1 and a ratio of syntheticzamide of about 5.7:1, and can be used in 21 grain water for cleansing purposes without the formation of objectionable soap curd.

As an auxiliary example the above is repeated substituting the sodium salt of lauryl ether of ethylene glycol monosulfuric acid or the sodium salt of the suli'oacetamide of amino ethyl laurate for the synthetic detergent used.

Example 11.The following ingredients are mixed in accordance with the procedure outlined in Example 1 and processed to produce a detergent composition in flake form: 7 parts of coconut oil fatty acid amide of monoethanolamine, 51 parts soap containing 3% moisture, 52.5 parts of "Nacconol NRSF containing 80% of the sodium salt of the sulfonic acid derived from the condensation product of benzene and a chlorinated kerosene fraction containing predominantly 12 carbon atoms per molecule as the synthetic detergent and about 20% inorganic salts. The ratio of soap:synthetic is about 1.2:1 and the ratio of synthetic to amide is about 6: 1.

Additional examples showing the usage figures for essential ingredients in the manufacture of detergent products of the invention are given below. The soap employed is the same soap used in Example 4, the synthetic detergent is the sodium salt of the sulfuric acid ester of mixed higher alcohols derived by the reduction of coconut oil, and the amide is the coconut oil fatty acid ethanolamide. The addition of small amounts of water is commonly desirable in order to plasticize milled mixtures.

In some of the above examples, reference has been made to use in water of 21 grains of hardness per gallon. It is to be understood, however, that 21 grainwater is referred to only as being representative of hard waters in general. According to my experience and investigations, my ternary detergent composition is effective in water of any municipal water system or any domestically used water source of which I am aware.

Besides possessing resistance to curd formation in hard water, products of the present invention dissolve at a desirable rate in the water. suds profusely, and cleanse emciently. Addition of the amide to the soap-synthetic detergent mixtures, as specified in the application, tends in general to increase the sudsing power of the composition. However, excessive additions of amide are to be avoided, as they may decrease sudsing power, harm the desired physical properties of the soap bar, flake or other product, and interfere with handling in some of the common soap manufacturing processes.

It is especially noteworthy that the bar products of my invention have a definite advantage over bars composed predominantly of synthetic detergent in that they do not dissolve too rapidly, do not become soft, are more soap-like in appearance and feel, behave more like soap in processing operations, and produce a lather which is 10 generally similar in structure and feel to that of soap, being unlike that produced by the synthetic alone.

The amount of amide that can advantageously be used decreases with increasing molecular weight of the amide and is also to a degree dependent upon the nature and amount of synthetic detergent present in the composition, but it has been found that the'most useful products result when the amount of amide exceeds one sixth of, but is not greater than, the amount of synthetic detergent present and constitutes at least 2 per cent of the combined weights of soap, synthetic, and amide.

Most of the above examples cover compositions in which the ratios of essential ingredients come within preferred ranges: that is, a ratio of soapzsynthetic from about %:1 to about 4:1 and a ratio of syntheticzamide from about 1 /2:1 to about 6:1. The advantages of my discovery, however, are to be realized in compositions falling outside the above preferred ranges of proportions and accordingly compositions coming within the ratios of soap2synthetic from about 1/2I1 to about 8:1 and of synthetic:amide from about 1:1 to about 10:1 are contemplated as a part of the broad invention, the amide constituting at least two per cent of the combined weights of soap, synthetic, and amide. Optimum results in the case of each composition may be realized by adiustment of the ratios used depending on the types of soap, synthetic detergent, and amide employed.

As indicated above, the physical form of the compositions is not a limitation of the invention I and may be varied in well known manner. In

now abandoned.

some instances, however, it may be necessary to adjust temperature conditions or moisture content of the mixture to give a product of the desired consistency for handling in the various processing operations required in the development of the desired physical form. Such adjustments of course are well within the scope of those skilled in the art.

The manner of mixing the ingredients is not a limitation of the invention. Any suitable mixing device such as a series of milling rolls ordinarily used in mixing plastic soa with added ingredients 0r crutching mechanism of high mixing efficiency as employed in mixing more-fluid constituents may be employed to effect homogeneity-in the mixture .of amide, soap, and synthetlc detergent.

j'I'his application is a continuation-in-part of application Serial No. 685,384, filed July 22, 1946,

Having thus described my invention, what I claim and desire to secure by Letters Patent is:

1. A detergent composition, characterized by reduced tendency to form sticky lime soap curd when used in hard water at rinsing dilutions, comprising essentially a ternary mixture of a watersoluble soap, a water-soluble salt of an organic sulfuric reaction product having pronounced detergent properties and having in its molecular structure a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals, and an aliphatic carboxylic acid amide having the formula wherein R is selected from the group consisting of hydrogen, alkyl, and alkylol and R and R" are selected from the group consisting of hydrogen, alkyl, alkylol, and alkylene joined through an oxygen atom, the total number of carbon atoms in R, R and R" being from about 9 to about 25 and the ratio of soapzsulfuric reaction product salt being from about /2:1 to about 8:1, the ratio of sulfuric reaction product saltzamide being from about 1:1 to about 10:1 and the amount of amide constituting at least 2 per cent of the combined weights of soap, sulfuric reaction product salt, and amide.

2. A detergent composition, characterized by reduced tendency to form stick lime soap curd when used in hard water at rinsing dilutions,

wherein R is selected from the group consisting of hydrogen, alkyl, and alkylol, and R and R" are selected from the group consisting of hydrogen, alkyl, alkylol, and alkylene joined through an oxygen atom, the total. number of carbon atoms in R, R and R being from about 9 to about 25 and the ratio of soapzsulfuric reaction product salt being from about %:1 to about 4: 1, the ratio of sulfuric reaction product saltzamide bein from about 1 /2:1 to about 6:1, and the amount of amide constituting at least 2 per cent of the combined weights of soap, sulfuric reaction product salt, and amide.

3. The composition of claim 1, in which the amide has the formula wherein RC is the acyl radical of a soap-forming carboxylic acid having from about 10 to about 18 carbon atoms, R and R" are each selected from the group consisting of hydrogen, allcyl and alkylol radicals, and R' is an alkylol radical, the total number of carbon atoms in R, R", and R' being from 1 to 7.

4. The composition of claim 1, in which the amide has the formula CHa-CHzOH RCO-N wherein RC0 is the acyl radical of a soap-forming carboxylic acid having from about 10 to about 18 carbon atoms.

5. The composition of claim 1, in which the amide consists of the amide 0f monoethanolamine and a mixture of fatty acids consisting predominantly of fatty acids containing 12 to 14 carbon atoms.

6. The composition of claim 1, in which the amide consists of the amide of monoethanolamine and a mixture of fatty acids of coconut I 12 oil consisting predominantly of lauric and myriatic acids.

7. The composition of claim 1, in which the amide consists of lauric ethanolamide.

8. The composition of claim 1, in which the organic sulfuric reaction product salt is a watersoluble salt of an alkyl sulfuric acid having 10 to 18 carbon atoms in the alkyl radical.

9. The composition of claim 1, in which the sulfuric reaction product salt is a water-soluble salt of alkyl sulfuric acids of higher alcohols derived from an oil of the group consisting of coconut, palm kernel and babassa oils.

10. The composition of claim 1, in which the sulfuric reaction product salt consists of a, watersoluble salt of dodecyl sulfuric acid, and in which the amide is of lauric ethanolamide.

11. The composition of claim 1, in which the amide has the formula CHr-CHOH-CH1 RCON wherein RC0 is the acyl radical of a soap-forming carboxylic acid having from about 10 to about 18 carbon atoms.

12. The composition of claim 1, in which the amide consists of the amide of isopropanolamine and a mixture of fatty acids containing 12 to 14 carbon atoms in the molecule.

13. The composition of claim 1, in which the amide consists of the amide of isopropanolamine and a mixture of fatty acids of coconut oil consisting predominantly of lauric and myristic acids.

14. The composition of claim 1, in which the sulfuric reaction product salt consists of a watersoiuble salt of a higher alkylated aryl sulfonic acid.

15. The 'product of claim 1, in which the amide has the formula CHe-CHQH-CHaOH RCON wherein RC0 is the acyl radical of a soap-forming carboxylic acid having from about 10 to about 18 carbon atoms.

16. The composition of claim 1, in which the amide consists of the amid of glycerylamine and a mixture of fatty acids containing 12 to 14 carbon atoms.

17. The composition of claim 1, in which the amide consists of the amide of glycerylamine and a mixture of fatty acids of coconut oil and consisting predominantly of lauric and myristic acids.

18. The composition of claim 1, in which the sulfuric reaction product is a water-soluble salt of the coconut oil fatty acid monoester of 1,2-dihydroxy-propane-3-sulfuric acid ester.

WALTER. C. PRESTON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,026,816 Bertsch Jan, '7, 1936 2,303,212 Kise et al. Nov. 24, 1942 2,383,737 Richardson Aug. 28, 1945

Claims (1)

1. A DETERGENT COMPOSITION, CHARACTERIZED BY REDUCED TENDENCY TO FORM STICKY LIME SOAP CURD WHEN USED IN HARD WATER AT RINSING DILUTIONS, COMPRISING ESSENTIALLY A TERNARY MIXTURE OF A WATERSOLUBLE SOAP, A WATER-SOLUBLE SALT OF AN ORGANIC SULFURIC REACTION PRODUCT HAVING PRONOUNCED DETERGENT PROPERTIES HAVING IN ITS MOLECULAR STRUCTURE A RADICAL SELECTED FROM THE GROUP CONSISTING OF SULFONIC ACID AND SULFURIC ACID ESTER RADICALS, AND AN ALIPHATIC CARBOXYLIC ACID AMIDE HAVING THE FORMULA