US3539521A - Detergent composition - Google Patents

Description

United States Patent US. Cl. 252-137 9 Claims ABSTRACT OF THE DISCLOSURE A detergent composition for cool water washing comprising a combination of specific sulfobetaines and specific builders.

This application is a continuation of copending application Ser. No. 163,042 filed Dec. 29, 1961, now abandoned.

The present invention relates to the laundering of textile fabrics in cool aqueous media employing a composition containing a specific type of synthetic detergent compound. More particularly, if relates to a process of, and product for, laundering fabrics in cool water using products containing specific sulfo betaine (sultaine) detergent compounds as hereinafter more fully described.

At the present time the synthetic detergent Washing compounds used in laundering clothes and other textile fabrics are utilized in home and commercial operations at water temperatures ranging from 110-150 F., with the usual washing temperature being at a median of about 120 to 130 F. It is within this temperature range that the most effective washing action is achieved for the common laundry fabrics such as cottons, woolens, and synthetic fabrics, using the conventional detergent materials.

However, it is well known that some fabrics have a pronounced tendency to shrink, wrinkle, or draw up when washed in water at temperatures ranging from 110 150 F. Such fabrics are the new wash-wear materials like Dacron, Creslan, resin treated cotton, cloth made from Kodel polyester fibers, and several other additional ones. It is also well known that sweaters, blankets, and other articles made from natural wool shrink considerably when washed at the normal temperatures. The shrinkage not only alters the size of the article but also changes the characteristics and feel of it, making it less soft and pleasant to the touch. Because of these facts, these fabrics are washed in lukewarm or cool water where shrinkage and drawing up is kept at a minimal level.

Below the normal washing temperature range of 110 to 150 F., the efficacy of the commonly used detergent compositions such as those containing sodium dodecyl benzene sulfonate, the dodecyl group being derived from tetrapropylene, (currently the most commonly used active ingredient), higher alkyl sulfates, sulfated and sulfonated amides and amines as the active detergent compound, is reduced considerably. In some instances, sudsing ability of such detergent compounds in cool water is also reduced, necessitating the addition of organic enhancing agents to the detergent composition to increase sudsing; whiteness maintenance is poor and in general, conventional detergent compounds simply have a marked lower level of detergency performance at lower temperatures. Therefore, it can readily be seen that when fabrics are washed in cool water to avoid shrinkage and other problems, the housewife will usually pour more detergent composition than normal into the washing solution in an attempt to achieve the same cleaning level as would be obtained at normal temperatures. This is both wasteful and uneconomical because there is little indication that the same cleaning level could be achieved in cool water by the addition of excess detergent composition as is obtained in washing clothes at the normal temperatures using normal amounts of detergent composition in the solution.

Additionally, in many of the economically less well developed areas of the world, particularly the South American and Asian countries, clothes washing and other laundry tasks are commonly performed at temperatures below 100 F. using comparatively crude methods. At these cool water temperatures, as previously mentioned, the most commonly used synthetic detergent compositions have only moderate detergency power, and as a result it tends to promote wastefulness for the reason that excess detergent material is then used in an effort to achieve higher cleaning performance.

It can be appreciated too that considerable savings in fuel bills would be realized over a period of time if an effective way were to be found to wash clothes in cool water because it takes considerably less fuel to heat water to a temperature of about F. than it does to heat it to the higher temperatures at which clothes are normally washed.

Wih the foregoing considerations in mind, it is an object of the present invention to provide a process and a product for washing fabrics using a detergent composition that will clean as efficiently in cool water as conventional compositions do at normal Washing temperatures. The term cool water as used herein is defined to mean water which is at a temperature ranging about 40 F. to about F.

It is a further object of the present invention to provide a process and a product for washing fabrics which will minimize the amount of shrinking, drawing up, or wrinkling of fabrics that occurs under normal washing conditions.

Other objects and advantages of the invention will be apparent during the course of the ensuing description.

It has been found that these objects can be accomplished by a washing process comprising the step of washing fabrics in cool aqueous solution, the solution containing a detergent composition consisting essentially of a builder salt and a quaternary ammonium compound having the general formula wherein R represents an alkyl radical having from about 12 to about 18 carbon atoms, R and R are each selected from the group consisting of methyl, ethyl, and ethanol radicals, R is an alkylene chain having from 1 to about 3 carbon atoms, and X is selected from the group consisting of hydrogen and hydroxyl radicals, wherein the sum of the R R and R radicals total 14-20 carbon atoms.

Compounds which conform to the above general for mula are characterized by the presence of both positive and negative charges which are internally neutralized (i.e., zwitterionic). Where R is 16 carbon atoms, R and R are methyl groups, and R is an ethylene group, the technical name is 3-(N,N-dimethyl-N-hexadecylammonio) propane-l-sulfonate. Where R is 16 carbon atoms, R and R are methyl groups and R is an ethylene chain with a hydroxy radical attached to the 2nd carbon atoms, the compound can be described as 3-(N, N-dimethyl N hexadecylammonio) 2 hydroxypropane-l-sulfonate. These compounds are commonly called sultaines or sulfo betaines and can be prepared in the manner disclosed in U.S. Pat. 2,129,264 and German Pat. 1,018,421.

The sum of the carbon chain lengths of the R R and R component groups of the compounds have been found to be a critical factor in achieving good cool water detergency performance. The carbons in the R R and R groups must total 14-20 with the R group being not less than 12 nor more than 1-8 carbon atoms because it has surprisingly been found that the sultaine compounds having such chain length combinations have a significantly greater cool water cleaning performance and whiteness maintenance (e.g., prevention of yellowing) than do those sultaine compounds not so limited and other detergent compounds which fall outside the range of the invention. The most outstanding cool water detergency is achieved when the R group in the sultaine is a hexadecyl radical, however, it has been found that a mixture of sultaines having an R component of 16 and 14 carbon atoms shows approximately the same efficiency in cleaning as does the purse hexadecyl R group compound. Preferred cool water detergency results are obtained when R is 16 carbons, R and R are methyl groups and R is a 2 carbon alkylene or hydroxy alkylene group.

While the preferred sultaine compounds incorporated into the compositions of this invention have an R chain length of 16 carbon atoms, a more convenient source of the R component is tallow fatty alcohol which consists of a mixture of various chain lengths, being approximately 66% C 30% C plus 4% C and others.

Another convenient source of the R components of the sutlaine where R is to average about 12 carbon atoms is that obtained from the middle cut of distilled coconut fatty alcohol which also consists of a mixture of various chain lengths, being approximately 2% C 66% C C14 and C15.

Specific sultaine compounds within the general formula set forth above useful in this invention are: 3-(N,N-dimethyl N hexadecylammonio)-2-hydroxypropane-l-sulfonate; 3-(N,N-dimethyl N alkylammonio)-2-hydroxypropane-l-sulfonate, the alkyl group derived from tallow fatty alcohol; 3-(N,N diethyl-N-hexadecylammonio)-2- hydroxypropane-l-sulfonate; 3-(N,N-dimethyl-N-hexadecylammonio) propane-l-sulfonate; 3-(N,N dimethyl-N- tetradecylammonio) propane-l-sulfonate; 3-(N,N-diethyl- N tetradecylammonio-2-hydroxypropane-l-sulfonate; 3- (N,N-dimethyl N alkylammonio)-2-hydroxypropane-1- sulfonate, the alkyl group being derived from the middle cut of coconut fatty alcohol; (3-N,N-dimethyl-N- octadecylammonio)-2-hydroxypropanel-sulfonate; 3-(N- 2-hydroxyethyl, N-methyl, N-tetradecylammonio) propane-l-sulfonate; 3-(N-2-hydroxyethyl N-methyl, N-tetradecylammonio) butane-l-sulfonate; 3-(N,N-dimethyl-N- dodecylammonio)-propane-I-sulfonate; 4 (N-Z-hydroxyethyl, N-methyl, N-tetradecylammonio)-3-hydroxybutanel-sulfonate; and 3-[(N,N bis (2-hydroxyethyl), N-tetradecylammonio]propane-l-sulfonate. Specific reference to the above compounds is given only for the purpose of illustration and it will be appreciated that many other similar variations may be used in this invention so long as the important R R R and R requirements described above are observed.

In this invention the active sultaine detergent compounds is incorporated into the total detergent composition at an active to builder ratio ranging from about :1 to 1:25, desirably at levels ranging from about 4% to about 35% of the composition. Below a level of about 4% it has been found that the total amount of composition needed in the wash solution to utilize the detergent compounds described in the present invention to full advantage is inconveniently large. (A 4% usage level (liquid composition) is approximately equal to a concentration of detergent compound in solution of about .OO88%, assuming conventional amounts of water and composition are being used); preferably not more than about 35% of the sultaine is used in the detergent composition because the best results are achieved when the remaining 65% of the detergent composition comprises substantial amounts of builder salts together with whatever other valuable detergency aids (e.g., antiredeposition agents such as carboxy methyl cellulose or anticorrosive agents such as sodium silicate) are desired.

An essential component of the composition utilized in this invention is a water-soluble inorganic alkaline builder salt or an organic alkaline sequestrant builder salt. Suitable builders include, for example, soluble polyphosphate salts such as sodium or potassium pyrophosphate and tripolyphosphate, alkali metal salts of phytic acids such as sodium phytate (described by Eckey in U.S. Letters Patent 2,739,942; granted Mar. 27, 1956'), and salts of aminopolycarboxylic acid (such as sodium or potassium ethylenediamine tetraacetate). These alkaline compounds serve to complex the calcium and magnesium ions present in hard water and they also serve to increase the level of detergency obtainable with synthetic detergent compounds. Other compounds such as sodium or potassium orthophosphate, sodium silicate, sodium carbonate and sodium borate can be added to increase detergency although they do not complex the calcium and magnesium ions present in hard water. Potassium pyrophosphate, sodium tripolyphosphate, sodium phytate, sodium or potassium ethylene diamine tetraacetate and nitrilotriacetate and mixtures thereof are especially preferred builders in the practice of this invention.

The above designed builders are employed at a ratio of builder to detergent compound of from about 1:5 to about 25:1, desirably at levels from about 8% to about by weight of the total composition. The balance of the composition, in addition to the detergent compound as mentioned previously, can consist of water, sodium sulfate, and other additives valuable as detergency aids, as, for example, antiredeposition agents, anticorrosion agents, perfume and the like.

It is believed that the sultaine detergent compounds of this invention, when used alone in a composition without the presence of builders and other electrolytes, are not good cool water detergents because they do not possess the essential solubility characteristics for such use. The builders are added, not only to improve detergency as is ordinarily the case with most synthetic detergent compounds but also to act as an electrolyte in reducing the Kraft point of the sultaine compounds of this invention to such an extent that they are soluble in cool water and are capable of acting as outstanding detergent compounds. If a non-built composition is desired, then suflicient inorganic or organic electrolytes must be added to insure solubility of the sultaines in aqueous solution. Suitable electrolytes may be, for example, NaCl, KCl, Na SO and NaI.

The discovery that the sultaine type compounds described in this invention show exceptional cool water detergency was unpredicable in view of the fact that there is no published theory or background information on the mechanics of cool water detergency. Moreover, those con ventional compounds such as dodecyl benzene sulfonate which are good hot water F. F.) detergent compounds show a minimum of activity in cool water. From the published literature one would be led to assume that these compounds of the invention would be, comparatively speaking, as poor as any other conventional detergent compounds when used in cool water; however, as has been discovered, the sultaines described in the present invention are far more effective in cool water than many of the commonly used commercially available detergent compounds are in hot water. It can therefore be seen that the structure of a given detergent compound effective in hot water has little or no relation to the effectiveness of compounds in cool water.

It has also surprisingly been found that the compounds used in this invention exhibit good detergent properties when used in wash water at very low concentrations. For example, it was found that the cleaning ability of the preferred 3-(N,N-dimethyl-N-hexadecylammonio) propane-l-sulfonate in the presence of .06% sodium tripolyphosphate builder in solution decreases only slightly as the concentration of the detergent compound in solution is substantially decreased from .03% to .01%. Other common detergent compounds lose their effectiveness at such low concentrations. The concentration of a detergent compound in solution usually employed in conventional household washing situations ranges from about .045 for granules to .026% for liquids.

It has also been found that the maximum detergency of the compositions of this invention is achieved when the pH of the washing solution, at cool water temperatures, is within a range of about 8 to about 12 with the preferred pH being 10.5 to 11.5. Using normal amounts of water for washing, a pH of 11 of the solution can be obtained by incorporating into the compositions of this invention a normal amount of silicate, i.e., up to 8% by weight. The silicate acts as a buffer and also as a corrosion inhibitor.

The washing step in the laundering method of this invention can be practiced in a number of different, but conventional, ways so long as the essential detergent composition is used. Preferably the step of washing is followed by rinsing and drying the fabrics. For example, the washing solution to be used in the washing step can be prepared by adding the detergent composition of this invention to a tub or automatic washer or any other container which contains cool water at a temperature ranging from about 40 F. to about 100 F. The detergent composition concentration in solution can range from about .05% to .50% by total weight, and should be added in sufficient amount to provide a sultaine detergent compound concentration of at least 0.005%. The fabrics can be added to the container or washer before or after the washing solution is added. As is usual in a washing step, the fabrics are than agitated in the detergent solution for varying periods of time, but sufficient to obtain the desired amount of cleaning. With an automatic agitator type washer, it has been found that good cleaning can be achieved using a washing cycle which ranges from 8 to 15 minutes.

After the desired level of cleaning is achieved in the washing step, the washing liquor is then drained off or the fabrics are separated from the liquor and thereafter the fabrics are rinsed in substantially pure water. The fabrics can be rinsed as many times as desirable in order to insure that all of the washing liquor and other undissolved material is separated from them. Using an automatic washer, it has been found that six spray rinses and one deep rinse is usually sufiicient for this purpose. Between and after rinsing steps, the bulk of the rinse water is usually drawn from, or spun out of the fabrics. After rinsing the fabrics can be dried by conventional means, using a machine dryer or simply hanging them on a line. Although rinsing and drying are usual and desirable steps, the important advantage of the invention is achieved in the washing step.

In the following described examples there will be mentioned three different methods of testing the effectiveness of the detergent compositions used. These tests will be described herein, and are termed, respectively, the Cloth Swatch Test, the White Shirt Detergency Test, and the Regular Wash-Wear Test.

CLOTH SWATCH TEST In a cloth swatch test the detergency effectiveness of the sultaine compounds of this invention were determined by washing naturally soiled cloth (desized print cloth) for 10 minutes in an aqueous solution of a detergent composition containing the sultaine compound to be tested and a builder (0.03% detergent compound concentration and 0.06% builder concentration in the wash solution at a pH of 10, water at 7 grains per gallon hardness and at F. or F.). No fluorescers, bleachers, or antiredeposition agents were used. After washing, rinsing and drying the percent of lipid soil removed from the swatch during the washing process was calculated. The percentage of soil removed by the sultaine test composition was then compared with the percentage of lipid soil removed by washing with a known standard (sodium tetrapropylene benzene sulfonate) and in that way the relative effectiveness of the compound was determined. A Tergotometer was used for the washing operation. (Tergotometer testing is described in Detergency Evaluation and Testing, By J. C. Harris, Interscience Publishers, Inc. (1954), p. 60.)

WHITE SHIRT DETER'GENCY TEST In addition to the Cloth Swatch Test described above, the detergency of the sultaine compounds utilized in compositions of this invention was evaluated by washing naturally soiled white dress shirts. Shirts are worn by male subjects under ordinary conditions for two normal working days. The degree to which the detergent composition containing a detergent compound to be tested cleans the collars and cuffs of the soiled shirts, relative to the cleaning degree of a similar composition containing a standard detergent compound is considered a measure of the detergency effectiveness of the test compound.

The washing solution used in the test contains 0.03% organic surface active agent and 0.06% sodium tripolyphosphate. (No fluorescers, bleaches, or antiredeposition agents were used.) The pH of the washing solution is 10 and water of 7 grains per gallon hardness is used. A conventional agitator type washer is used. The detergent compound in the standard detergent composition was sodium tetrapropylene benzene sulfonate, the most commonly used organic detergent compound in heavy duty laundry detergent compositions. The test detergent composition contains the detergent compound to be tested, i.e., compared with the stardard composition.

WASH-WEAR TEST The standard Wash-Wear test mentioned in the examples is conducted as follows:

White dress shirts, cotton T-shirts and other fabrics are distributed among various male individuals and each shirt and T-shirt is worn for one normal working day under uniform conditions. The soiled shirts and fabrics are then washed in an automatic agitating-type washer, for a period of 10 minutes, with detergent solutions at 80 F. temperature. After washing the clothes are rinsed (six spray rinses and one deep rinse) and then dried. The water has a hardness of 7 grains per gallon and the detergent composition concentration in solution is 0.15%. (No fiuorescers or bleaches are used.) Direct comparisons are made by a panel of 3 skilled graders between pairs of shirts and fabrics worn and soiled by the same individual. The shirts and fabrics are graded on the degree of cleanness and whiteness maintenance obtained, paying particular attention to the collars and cuffs. The relative cleaning effectiveness of each detergent composition is graded on a raw score under simulated U.V.free light and simulated north daylight, averaged, and then translated onto a 1-10 scale wherein on the scale 1 is filthy, 5 is acceptable, and 10 is clean, with the remaining numbers representing intermediate values of these conditions.

Having described the various methods of testing the cleaning effectiveness of the sultaine compounds used in this invention, the following described examples will serve to illustrate their detergent power.

EXAMPLE I The following test was conducted to illustrate the cleaning efficacy of a detergent composition containing the preferred sultaine compound of the invention at 7 cool water temperatures as compared to compositions containing other commonly used commercially available synthetic detergent compounds. The cleaning grade of these detergent compounds described hereafter was established by conducting a standardized Wash-Wear test as previously described.

In this example the detergency effectiveness of the sultaine compounds of this invention in cool water (80 F.) is determined by a comparison test in which the sultaine compounds and several well known and commonly used hot water detergent compounds are substituted for the active compound in a commercial detergent formulation which has excellent detergent power (in hot water) and the results are graded on a comparative basis for efiicacy in cleaning. The standardized commercial composition is:

Percent Detergent compound 17 Sodium tripolyphosphate 50 Silicates (1:2.45 ratio of Na ozsiO 6 Sodium carboxymethylcellulose .4 N32804: 2 Water and miscellaneous 3.6

Cleaning grade 1.0 difference is statistically Detergent compound (active ingredient) 1 The alkyl chain length distribution of tallow alkyl sulfate is approximately 66% C15, 30% C and 4% other.

It can be seen that the cool water cleaning efficiency of the sultaine compound contained in a standard composition is markedly and surprisingly superior to the other commonly used hot water detergent compounds, When used under the same test conditions.

Another Wash-Wear Test was conducted using five well known detergent compositions available commercially. The tests showed the detergent composition utilizing sodium tetrapropylene benzene sulfonate as the active detergent compound to be superior to the other commercial compositions in overall cleaning effectiveness at 100 F. yet as indicated in Example I above, the sultaine detergent composition is markedly superior to a composition containing sodium tetrapropylene benzene sulfonate at 80 F.

A White Shirt Detergency Test, previously described, was conducted using several commercially available detergent compounds in a formulation (containing the detergent compound to be tested and a builder) in comparison with the detergent compounds utilized in this invention. The washing solution contained 0.03% detergent compound and 0.06% sodium tripolyphosphate. (No fluorescers, bleaches or antiredeposition agents were used.) The washing solution had a pH of 10 and the 'water was 7 grains per gallon hardness. The detergent compounds used in this test were 3-(N,N-dimethyl, N- hexadecylammonio) propane 1 sulfonate, 3-(N,N-dimethyl, N-hexadecylammonio) 2 hydroxypropane-lsulfonate (two of the preferred compounds of this invention), dimethyldodecylamine oxide, sodium tetrapropylene benzene sulfonate, and sodium tallow alkyl sulfate. Under the test conditions, the detergency effectiveness of 3 (N,N-dimethyl-N-hexadecylammonio( propane 1 sulfonate and 3-(N,N-dimethyl-N-hexadecylammonio) 2 hydroxypropane-l-sulfonate in wash water of 80 F. was quite superior to the detergency effectiveness of dimethyldodecylamine oxide at 80 F. and tetrapropylene benzene sulfonate at 140 F., and

Here a Cloth Swatch Test, previously described, was conducted under the following conditions: water at a temperature of F. or 140 F. and 7 grains per gallon hardness, 0.03% detergent compound and 0.06% sodium tripolyphosphate builder concentration in the washing solution. (No fluorescers, bleaches, or antiredeposition agents were used.) The detergent washing solution had a pH of 10.

Lipid Detergent agent removal 1 Temp., F

(A)... 3-(N,N-dimethyl-N-hexadecylam- 66.2 80

monio)-2-hydroxypropane-l-sulionate.

(B) Sodium tallow alkyl sulfate 66. 0 140 (C)... Sodium tetrapropylene benzene 64.0 140 sulfonate.

(D)-.. 3-(N,N-dirnethyl-N-hexadeeylam- 62. 9 80 monio)-propane-1-sulionate.

(E) Sodium tallow alkyl sulfate 56. 9 80 (F) Condensation product of tallow alcohol 56. 3 80 and 17 moles ethylene oxide.

(G)... 3-(N,N-dimethyl-N-octadecylammonio) 54. 3 80 propane-l-sullonate.

(H) Sofdium tetrapropylene benzene sul- 50. 7 80 (mate.

1 Percent removal, based on cloth swatches.

It can be seen that the sultaine compounds of the present invention, A and D, exhibit superior lipid soil removing properties in cool water as compared to the commonly used hot water commercial detergent compounds, and in cool water are about equal to commercial detergent compounds used in 140 F. The octadecyl homolog, while not as effective as the preferred hexadecyl compounds is superior to sodium tetrapropylene benzene sulfonate in cool water.

Substantially the same performance advantages are observed by the housewife when doing the home laundry in water ranging from 40 to 100 F., using conventional procedures. Woolens and synthetic fibers washed in the same manner are cleaned as efiiciently when washed according to the process of this invention and using the compositions of this invention as they would be if they were washed in conventional detergent compositions at hot water temperatures, yet a minimum of shrinkage and wrinkling takes place and the feel of the wool is preserved to a greater extent.

While the compositions of this invention are outstandingly effective in water at a temperature ranging from 40 F. to 100 F., the temperature range in which the most outstanding results are seen is about 60 F. to F. Below about 60 F. it has been found that the granular detergent compositions of this invention are slow to dissolve, consequently it is preferred to use the liquid compositions at the lower temperatures.

The following compositions will illustrate the manner in which the product invention can be practiced. Included are both liquid and granular formulations. It will be understood, however, that the examples are not to be construed as limiting the scope of conditions claimed hereinafter. These compositions are useful in automatic washers and conventional type washers as well as hand washing operations.

Solid: Percent 3 (N,N-dimethyl-N-hexade cylammonio propane-l-sulfonate 7 Sodium tripolyphosphate 50 Sodium xylene sulfonate 5 Sodium silicate (Na- O:SiO =1:2.5) 7 Fluorescent dye .16 Perfume .2 Benzothiazole .02 Sodium sulfate 20.62 Water and minor amounts of miscellaneous 10 Liquid: Percent 3- (N,N-dimethyl-N-alkylammonio -2-hydroxy-propanel-sulfonate l 2 Tetrapotassium pyrophosphate Sodium silicate (Na O:SiO =1:1.6) 3.8 Potassium toluene sulfonate 8.5 Sodium carboxymethyl hydroxy ethyl cellulose .3 Fluorescent dye .12 Perfume .15 Benzotriazole .02 Water 55.11

Alkyl referring to the R1 group derived from the middle cut of coconut alcohol (2% C10, 66% C12, 23% C14, 9% Cm).

Liquid: Percent 3-(N,N-dimethyl-N-tetradecylammonio)-2- hydroxypropane-l-sulfonate 22 Tetrapotassium pyrophosphate 19 Sodium silicate (Na O:Si0 =1:l;6) 3.8 Potassium toluene sulfonate 8.5 Sodium carboxy methyl hydroxy ethyl cellulose .3 Perfume .2 Benzotriazole .02 Water and minor amounts of miscellaneous 46.18

Liquid Percent 3- N,N-dimethyl-N-alkylammonio 2 -2- hydroxypropane-l-sulfonate 12 Tetrapotassium pyrophosphonate 19 Sodium silicate (Na O:SiO =1:1.6) 3.8 Potassium toluene sulfonate 8.5 Sodium carboxy methyl cellulose .3 Perfume .2 Water 56.20

Alkyl referring to the R1 group obtained from talloW fatty alcohol (66% Cm, C10, 4% C14 and others).

Solid: Percent 3-( N,N-dimethylN-alkylammonio 3 -2- hydroxypropane-l-sulfonate 17 Sodium tripolyphosphate 50 Sodium silicate (Na O:SiO =1:2.5) 6 Sodium toluene sulfonate 2 Sodium carboxy methyl cellulose .3 Sodium sulfate 13 Fluorescent dye .16 Water 8 Miscellaneous Balance *Alkyl referring to the R1 group obtained from tallow fatty alcohol (66% C18, 30% Cm, 4% C14 and others).

Solid: Percent 3-(N,N-dimethyl-N-alkylammonio -2- hydroxypropane-l-sulfonate 10 Sodium pyrophosphate 60 Sodium silicate (Na O:SiO =1:2.5) 6 Sodium toluene sulfonate 2 Sodium carboxy methyl cellulose .3 Water 11.3 Miscellaneous (fluorescers, perfume, antitarnish agents, sodium sulfate, etc.) Balance Alkyl referring to the R1 group obtained from tallow fatty alcohol (66% Cu, 30% Cm, 4% Cn and others).

Alkyl referring to the R1 group derived from the middle cut of coconut fatty alcohol (2% C10, 66% C12, 23% C11, 9%

Solid Percent 3- N,N-dimethyl-N-dialkylammonio propane-l-sulfonate 17 Sodium tripolyphosphate 45 Sodium silicate (Na O:SiO =l:2.5) 6 Sodium carboxy methyl cellulose .3 Sodium sulfate 28 Water 3.5 Miscellaneous Balance Alkyl referring to the R1 group derived from the middle cC1ut)of coconut fatty alcohol (2% C10, 66% C12, 23% Cu, 9%

Liquid: Percent 3- (N ,N-dimethyl-N-hexadecylamrnonio) -2- hydroxypropane-l-sulfonate 12 Sodium nitrilo triacetate 19 Sodium silicate (Na O:SiO =1:1.6) 3.8 Sodium carboxy methyl cellulose .3 Water 63 Miscellaneous Balance It Will be appreciated that the sultaine compounds used in the present invention can be incorporated into liquid or granular detergent compositions with sutable adjustments beng made in the other components.

Materials which are considered normal and desirable additives in liquid or granule detergent compositions can also be added to the compositions of this invention without substantially modifying the basic characteristics of the sultaine detergent surfactants. For example, a tarnish inhibitor such as benzotriazole or ethylene thio-urea may be added in amounts up to about 1%. Fluorescers, perfume, color, antiredeposition agents, thickening agents, opacifiers, other detergent compounds, and blending or viscosity control agents, While not essential in the compositions of this invention, may also be added.

Since certain chainges may be made in the process and composition without departing from the scope of the invention, it is intended that the description shall be interpreted as illustrative and not in a limiting sense.

What is claimed is:

1. A synthetic detergent composition, for the effective laundering of fabrics in water having a temperature of from about 60 F. to about F., consisting essentially of:

(A) from about 4% to about 35% of a zwitterionic quaternary ammonium compound selected from the group consisting of (1) 3 (N,N-dimethylN-alkylammonio)-propane-1-sulfonates and (2) 3-(N,N-dimethyl N -alkylammonio) 2 hydroxypropane-lsulfonates, wherein said alkyl radicals are selected from the group consisting of (a) hexadecyl radicals; (b) mixtures of alkyl radicals containing 14 and 16- carbon atoms; (c) alkyl radicals derived from tallow, and (d) alkyl radicals derived from coconut oil;

(B) from about 8% to about 90% of a detergency builder selected from the group consisting of pyrophosphates, tripolyphospates, phytates, ethylenediaminetetraacetates and nitrilo triacetates, wherein the cation of said detergency building is selected from the group consisting of sodium and potassium, and wherein the ratio of (A) to (B) by parts ranges from about 5: 1 to about 1:25; and

11 (C) from 0% to about 88% of an additive selected from the group consisting of water, sodium sulfate and mixtures thereof.

2. The composition of claim -1, in which the compound (A) is 3-(N,N-dimethyl-N-l1exadecylammonio)-2-hydroxypropane-l-sulfonate.

3. The composition of claim 1 in which compound (A) is 3-(N, N-dimethyl-N-hexadecylammonio)-propane l-sulfonate.

4. The composition of claim 1 in which compound (A) is 3 (N,N-dimethy1-N-alkylammini0)-propane- 1-su1- fonate, wherein the alkyl group is a mixture of alkyl radicals containing from 14 to 16 carbon atoms.

5. The composition of claim -1 in which compound (A) is 3-(N,N-din1ethyl-N-alkylammonio)-2-hydroxypropane-tl-sulfonate wherein the alkyl radical is a mixture of alkyl radicals containing from 14 to 16 carbon atoms.

6. The composition of claim 1 in which compound (A) is 3-('N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-l-sulfonate, wherein the alkyl radical is derived from coconut oil.

7. The composition of claim 6 in which compound (B) is sodium tripolyphosphate.

-8. The composition of claim 4 in which compound (B) is sodium tripolyphosphate.

9. The composition of claim 5, in which compound (B) is sodium tripolyphosphate.

References Cited UNITED STATES PATENTS 10/1966 Ernst 252,355 X 9/1938 =Downin=g et a1. 252-152 2/1955 Cupery et a1 2'52152 3/1956 Eckey 252F452 8/ 19-60 Goff 252152 8/1961 Drew et al 252-138 12/1964 Diehl 252-137 FOREIGN PATENTS 10/ 1952 Germany. 2/1959 Germany.

7/ 1956 Great Britain.

OTHER REFERENCES Soap and Sanitary Chemicals, October 1950, p. 81, Products and Processes (copy in Sci. Lib

LEON D. ROSDOL, Primary Examiner M. HALP-ERN, Assistant Examiner US. Cl. X.R.

2% UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No- 3,539,52l Dated November 10,1970

Inventor-(a) Arnon 0 Snoddy, Francis L. Diehl Norman R. Smith Joseph E. Caller It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2 line 26, "Wih" should read With- Column 2 lines 32 and 33, after "ranging" and before "about" insert --from- Column 2, line 49, "R N CH R 50 should read R N CH2 R4 s0 Column 3, line 21, "purse" should read --pure-- Column 3, lines 43 and 44, "3-(N,N-dimethyl-N-hexadecylammonio) propane-l-sulfonate" should read 3-(N,Ndiethyl-N- hexadecylammonio) propanel-sulfonate Column 3, lines 44 and 45, "3-(N,NdimethylNtetradecyl ammonio) propane-l-sulfonate" should read 3-(N,Ndiethyl-N tetradecylammonio) propanelsulfonate Column 3, lines 49 and 50, (3N,N-dimethyl-N-octadecylammonio)-2-hydroxypropane-l-sulfonate" should read -3-(N,N dimethyl-N-octadecylammonio)-2hydroxypropane-lsulfonate-- Column 3, lines 63 and 64, "com-pounds" should read ---com-pound-.

Column 4, line 30, "designed" should read -designated--. Column 4, line 47, "Kratt" should read Krafft- Column 5, line 39, "than" should read then-.

Column 6, line 2, "bleachers" should read -bleaches.

Column line 16, after "is:" and before "Percent" insert the heading -Detergent.

13333 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 2atent No. 3,539,521 Dated November 10,1970

Arnon O. Snoddy, Francis L Diehl, Norman R. smith a Page 2 Joseph E. Callen It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 7, lines 70 and 71, "3-(N,N-dimethyl-N-hexadecylammonio(propane-l-sulfonate" should read --3(N,Ndimethyl-N- hexadecylammonio) propane-l-sulfonate- Column 9, line ll, "Benzothiazole" should read -Benzotria2 Column 9, line 27, after "coconut" and before "alcohol" insert -fatty-- Column 10, lines 15 and 16, "3-(N,N-dimethyl-N-dialkylammonio propane-l-sulfonate" should read -3-(N,N-dimethyl-N- alkylammonio propanel-sulfonate- Column 10, line 36, "sutable" should read -suitable Column 10, line 49, "chainges" should read --changes-- SIGNED I MIMJP mom 50mm, l Islonar of Patent