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Publication numberUS3619115 A
Publication typeGrant
Publication dateNov 9, 1971
Filing dateSep 8, 1967
Priority dateSep 8, 1967
Publication numberUS 3619115 A, US 3619115A, US-A-3619115, US3619115 A, US3619115A
InventorsFrancis L Diehl, Norman R Smith
Original AssigneeProcter & Gamble
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Cool water laundering process
US 3619115 A
Images(11)
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Description  (OCR text may contain errors)

United States Patent [72] Inventors Francis L.D1ehl Continuation-impart of application Ser. No.

581,720, Sept. 26, 1966, now abandoned which is a continuation-impart of application Ser. No. 413,948, Nov. 25,

v 1964, now abandoned which is a continuation-impart of application Ser. No. 163,041, Dec. 29, 1961, now abandoned. The portion of the term of the patent subsequent to Nov. 10, 1987. has been disclaimed.

[54] COOL WATER LAUNDERING PROCESS 5 Claims, No Drawings [52] U.S.CI 8/137, 252/137,252/151, 252/152, 252/355,260/50l [51] 1lnt.Cl D061 [50] Field oISearch 252/137, 152. 151, 355', 8/137; 260/50 [56] Reierences Cited UNITED STATES PATENTS 2,129,264 9/1938 Downing et a1 252/152 UX 2,702,278 2/1955 Cuperctal. 252/152UX 2,739,942 /1961 Drew et a1. 252/138 X 3,213,030 10/1955 Diehl 252/152 FOREIGN PATENTS 1,018,421 10/1952 Germany 252/161 1.051.439 211959 Germany 252/152 751,273 7/1956 Great Britain 252/137 Primary Examiner Mayer Weinblatt Attorneys-Richard C. Witte, Thomas H. OFlaherty and Robert B. Aylor 7 calcium and magnesium ions in hard water.

COOL WATER LAUNDERING PROCESS This application is a continuation-in-part of our copending application, Ser. No. 58l,720, filed Sept. 26, 1966, entitled LAUNDERING PROCESS AND DETERGENT COMPOSI- TION THEREFOR, Now abandoned which was in turn a continuation-in-part of our copending application, Ser. No. 413,948, filed Nov. 25, 1964, entitled LAUNDERING PROCESS AND DETERGENT COMPOSITION THEREFOR, Now abandoned which was in turn, a continuation-in-part of our earlier field application, Ser. No. 163,041, filed Dec. 29, 1961. entitled LAUNDERING PROCESS AND DETERGENT COMPOSITION THEREFOR, 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, it 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 1 l-l50 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 1l0-l50 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 characteristic 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 efficiency 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 waters 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.

With the foregoing considerations in mind, it is an object of the present invention to provide a process nd 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 from 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 i 2 to about 18 carbon atoms, R and R are each selected from the group consisting of methyl, ethyl, propyl, butyl, and ethanol radicals, R is an alkylene chain having from I 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. Branched chain alkylene groups, e.g.,

can be substituted for the group in the above formula.

Compounds which conform to the above general formula 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 chemical name is 3- N,N-dimethyl-NhexadecylammonioI) propanel -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 second carbon atom, the compound can be described as 3- (N,N-dimethyl-N-hexadecylammonio))-2 -hydroxypropanel sulfonate. These compounds are commonly called sultaines or sulfo betaines and can be prepared in the manner disclosed in US. Pat. No. 2,l 29,264 and German Pat. No. l,0l8,42l.

The most preferred compounds of this invention are the ones which have been shown to have cleaning effectiveness at 80 F. which is equivalent to or greater than that exhibited by sodium tetrapropylenebenzenesulfonate at F. These compounds are the sultaine detergents selected from the group consisting of l. 3-( N,N-bibutyl-N-alkylammoniio)propanel -sulfonates wherein the alkyl group contains from about 12 to about 16 carbon atoms;

2. 3-( N ,N-dibutylN-alkylammonio)propancl -sulfonates wherein the alkyl group contains about 12 carbon atoms;

3. 3-(N,N-diemthyl-N-alkylammonio)-2-hydroxypropanel-sulfonates wherein the alkyl group contains from about 12 to about [6 carbon atoms;

4. 3-( N,N-dimethyl-N-alkylammonio)- l ,1 ,3-trimethylpropanc-l-sulfonate wherein the alkyl group contains about 12 carbon atoms;

5. 2-(N,N-dimethyl-N-alkyl)ethane-l-sulfonate wherein the alkyl is coconut oil-derived; and

6. Mixtures thereof.

Within the above preferred compounds there are several compounds which are particularly outstanding. For example, compound 1 is most effective at cleaning fabrics in cool water when the alkyl group contains 16 carbon atoms. Also, when in compound 3, the alkyl group contains 12 carbon atoms or is a mixture of alkyl groups such as those derived from coconut oil (or an equivalent synthetic source) and containing l2, l4, and 16 carbon atoms, the sultaines are especially effective at cleaning fabrics in cool water. Compounds 2, 4 and 5, as disclosed above, are very effective, as hereinafter demonstrated.

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 detergency performance. The carbons in the R,, R,,. and R,, groups must total 14-20 with the R, group being not less than l2 nor more than 18 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 than do those sultaine compounds not so limited and which fall outside the range of the invention.

Convenient sources of the R, component are coconut fatty alcohols. (These normally consist of a mixture of chain lengths, being approximately 0.7 percent C,,, 8.9 percent C,,, 6.8 percent C,,,, 47.2 percent C 18.6 percent C 8.3 percent C and 9.5 percent C,,.,.) and tallow fatty alcohols. (These normally consist of a mixture of chain lengths, being approximately 66 percent C,,,, 30 percent C,,,, and 4 percent C and others.) R, can also be derived from other naturally occurring substances and can also be derived from petroleum fractions, e.g., by polymerizing alkylenes or cracking waxes to form the proper chain lengths, e.g., in the form of olefins. The method of deriving the alkyl chains is immaterial. The alkyl chains can be unsaturated.

Another convenient source of the R, component of the sultaine 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 percent C 66 percent C 23 percent C and 9 percent C Specific sultaine compounds within the general formula set forth above useful in this invention are: 3-(N,N-diemthyl-N- hexadecylammonio)-2-hydroxypropanel 3-( N,N-diemthyl-N- alkylammonio)-2-hydrosypropane-l-sulfonate; the alkyl group derived from tallow fatty alcohol; 3-(N,N-diethyl-N- hexadecylammonio)-2-hydroxypropanel -sulfonate; 3-( N,N- diethyl-N-hexadecylammonio )propanel -sulfonate; 3-( N,N- diethyl-N-tetradecylammonio)propane-Lsulfonate; 3-(N,N- diethyl-N-tetradecylammonio)-2-hydroxypropane-l-sul fonate; 3-N,N-dimcthyl-N,N-tetradecylammonio)-2-hydroxypropane-l-sulfonate, the alkyl group being derived from the middle cut of coconut fatty alcohol; 3-(N,N-dimethyl-N-octadecylammonio )-2-hydroxypropanel -sulfonate; 3-( N2- hydroxyethyl-N-methyl-Ntetradecylammino )propane- 1 -sulfonate; 3-(N-2-hydroxyethyl-N-methyl-N-tetradecylammonio)butane-butane-l-sulfonate; butane-l-sulfonate; 3- (N.N,-dimethyl-N-dodecylammonio)-propane-l-sulfonate; 4- (N-Z-hydroxyethyl-N-methy )-N-tetra-decylammonio )-3- hydroxybutancJ-sulfonate; and 3-[N,Nbis(2-hydroxyethyl), N -tetradecylammonio lpropanel -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 compound is incorporated into the total detergent composition at an active to builder ratio ranging from about 5:l to 1:25, desirably at levels ranging from about 4 percent to about 35 percent of the composition. Below a level of about 4 percent 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 percent usage level (liquid composition) is approximately equal to a concentration of detergent compound in solution of about 0.0088 percent, assuming conventional amounts of water and composition are being used); preferably not more than about 35 percent of the sultaine is used in the detergent composition because the best results are achieved when the remaining 65 percent of the detergent composition comprises substantial amounts of builder salts together with whatever other valuable detergency aids (e.g., antiredeposition agents such as carboxymethylcellulose 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 inorganic builders include sodium and potassium tripolyphosphates and pyrophosphates. Examples of organic alkaline sequestrant builder salts are l alkali metal amino polycarboxylates [e.g., sodium and potassium ethylene diamine-tetraacetates, N-(2- hydroxyethyl)-ethylene diamine triacetates, nitrilotriacetates, and N-(2-hydroxyethyl)-nitrilo diacetates]; 2 alkali metal salts of phytic acid e.g., sodium and potassium phytatessee U.S. Pat. No. 2,739,942); 3 water soluble salts of methylene disphosphonic acid e.g., trisodium and tripotassium methylene diphosphonate and the other diphosphonate salts described in the copending application of Francis L. Diehl, Ser. No. 266,025, filed Mar. 18, 1963, now U.S. Pat. No. 3,213,030 4 water soluble salts of substituted methylene diphosphonic acids e.g., trisodium and tripotassium ethylidene, isopropylidene, benzylmethylidene, and halomethylidene diphosphonates and the other substituted methylene diphosphonates disclosed in the copending application of Clarence H. Roy, Ser. No. 266,055, filed Mar. 18, i963 now U.S. Pat. No. 3,422,02l ,and 5 mixtures thereof.

Any of the above builders can be used in the form of their ammonium, triethanolammonium,dicthanolammonium, monoethanolammonium, sodium, and potassium salts, and mixtures thereof.

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.

The above designated builders are employed at a ratio of builder to detergent compound of from about l:5 to about 25: l desirably at levels from about 8 percent to about percent 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, anti-redeposition 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 clectroyltes, 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 Krafft 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. lf a nonbuilt composition is desired, then sufficient inorganic or organic electrolytes must be added to insure solubility of the sultaines in aqueous solution. Suitable electrolytes may be, for example, NaCll, liCll, Na SO,,, and NAT.

The discovery that the sultaine-type compounds described in this invention show exceptional cool water detergency was unpredictable in view of the fact that there is no published theory or background information on the mechanics of cool water detergency. Moreover, those conventional compounds such as dodecyl benzene sulfonate which are good hot water (130 F.-l40 1F.) 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 such 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 0.06 percent sodium tripolyphosphate builder in solution decreases only slightly as the concentration of the detergent compound in solution is substantially decreased from 0.03 percent to 0.01 percent. Other common detergent compounds lose their effectiveness at such low concentrations. The concentration of a detergent compound in solution usually employed is conventional household washing situations ranges from about 0.45 percent for granules to 0.026 percent 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 pl-l being 10.5 to 1 L5. Using normal amounts of water for washing, a pill of l l of the solution can be obtained by incorporating into the compositions of this invention a normal amount of silicate, i.e., up to 8 percent 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 contacts cool water at a temperature ranging from about 40 F. to about 100 F. The detergent product concentration in solution can range from about 0.05 percent to 0.50 percent by total weight, and should be added in sufficient amount to provide a sultaine detergent compound concentration of at least 0.005 percent.

The sultaine detergent compound concentration can be as high as about 0.175 percent based upon the use of a 0.5 percent concentration of a detergent composition containing 35 percent of said sultaine detergent compound. The detergency builder is present in the washing solution in an amount from about 0.004 percent to about 0.45 percent, these figures corresponding respectively to 0.05 percent of a detergent composition containing 8 percent detergency builder and 0.5 percent of a detergent composition containing 90 percent detergent builder. 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 then 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 an 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 sufficient 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 and 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 l0 minutes in an aqueous solution of a. detergent composition containing the sultaine compound to be tested and a builder (0.03 percent detergent compound concentration and 0.06 percent builder concentration in the wash solution at a pH of IO, water at 7 grains per gallon hardness at F. or l40 F.). No fluorescers, bleaches, or antiredeposition agents were used. After washing, rinsing and drying the percent oflipid 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, lnterscience Publishers, Inc. 1954) page 60.)

WHITE SHIRT DETERGENCY 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 percent organic surface active agent and 0.06 percent 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 standard 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 agitatingntype washer, for a period of 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 (H5 percent. (No fluorescers 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 in dividual. 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 ofeach 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 I0 is clean, with the remaining numbers representing intermediate values of these conditions.

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 cool water temperatures as compared to compositions containing other commonly used commercially available synthetic detergent com pounds. 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 ofthe 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 efficacy in cleaning. The standardized commercial detergent composition is:

percent detergent compound 50 percent sodium tripolyphosphate 6 percent silicates 1:2.45 ratio of Na OzSiO 0.4 percent sodium carboxymethylcellulose 23 percent l la SO 3.6 percent water and miscellaneous Cleaning Grade Lt) dilTerence is statistically significant Detergent Compound (active ingredient A. 3-(N,N-dimethyl-N-hexadecyl ammonio propane-l-sulhonate l0.() B. Condensation product of tetra ropylene benzene and ll moles of ethylene oxide 6.95

C. Sodium tallow alkyl sulfate 5.47

D. Sodium tetrapropylene benzene sulfonatc 3.87 E. Potassium coconut oil soap 0.33

The alkyl chain length distribution of tallow alkyl sulfate is approximately 66 percent C1, percent Cu, and 4 percent other.

It can be seen that the cool water cleaning efficiency of the sultaine compound contained in a standard composition is pound to be superior to the other commercial compositions overall cleaning effectiveness at lOO" F. yet as indicated in l ample l above, the sultaine detergent composition is market superior to a composition containing sodium tetrapropyle benzene sulfonate at F.

A White Shirt Detergency Test, previously described, \I conducted using several commercially available detergt compounds in a formulation (containing the detergent co pound to be tested and a builder) in comparison with the tergent compounds utilized in this invention. The washi solution contained 0.03 percent detergent compound a 0.06 percent sodium tripolyphosphate. (No fluoresce blcaches or antiredeposition agents were used.) The washi solution had a pH of 10 and the water was 7 grains per gall hardness. The detergent compounds used in this test were (N,N-dimethyl, N-hexadecylammonio)propane-l-sulfonate (N,N-dimethyl,N-hexadecylammonio)2-hydroxypropane-lsulfonate, (two of the preferred compounds of this invention dimethyldodecylamine oxide, sodium tetrapropylene benze sulfonate, and sodium tallow alkyl sulfate. Under the test cc ditions, the detergency effectiveness of 3-(N,N,-diemthylhexadeylammonio) propane-l-sulfonate and 3-(N, diemthyl-N-hexadecylammonio)-2-hydroxypropane-l-sulfonate in wash water of 80 F. was quite superior to the dett gency effectiveness of dimethyldodecylamine oxide at 80 and tetrapropylene benzene sulfonate at F., and a greatly superior to the detergency efi'ectiveness of sodium t low alkyl sulfate and sodium tetrapropylene benzene sulfonz at 80 F. If the pH of the washing solution at 80 F. l Hequivalent to the hydroxyl ion concentration in solution pH =l0 at 140 F). the margin of superiority of the sultai compounds is increased.

Similar comparative results are obtained if, in the Wh Shirt Detergency Test, an organic alkaline sequestrant builc salt, sodium ethylene diamine tetraacetate or potassit nitriloacetate, is used instead ofthe sodium tripolyphosphatt EXAMPLE ll. Here a Cloth Swatch Test, previously described, was conducted under the following conditions: water at a temperature of 80 F. or l40 F. and 7 grains per gallon hardness, 0.03 percent detergent compound and 0.0 percent sodium tripolyphosphate builder concentration in tl washing solution (NO fluorescers, bleaches, or antiredeposition agents were used.) The detergent washing solution had a pH of IO.

Lipid Tom; removal, l att [)vtvrgont agent percent A. 3-t I,Nxlimt-tliyl N -lioxadecylammouio) -2- liydroxypropauc-l-sulfouatv 66. 2 B. Sodium tallow alkyl sulfate 66.0 Sodium tvtrapropylvuv Iu-nzcuu sultouatc. 6-1. I) l). 3- (N,N -dimethyl -N -hvxudecylammouio) propaue-l-Sulfouatc 61!. 5| E. Sodium tallow alkyl sulfntt- 56. .I F. (undonsatiou product of tallow alcohol and 17 molt-s vthylouo oxide 5t .5 (i. 3- l I.N -tllllltlllyl-N ()tfltttlotfylttlll[1101110) propzuiu-l-sullouatv 54. 5 ll. Sodium tt-trapropylvue lit-uzt-no sull'ouale. 50. T

1 Based on cloth swatches.

It can be seen that the sultaine compounds of the present i vention, A & D exhibit superior lipid soil removing properti in cool water as compared to the commonly used hot wat commercial detergent compounds, and in cool water a about equal to commercial detergent compounds used in 14 F. The octadecyl homolog, while not as effective as t preferred hexadecyl compounds, is superior to SOClll. tetrapropylene benzene sulfonate in cool water.

Substantially the same performance advantages are c served by the housewife when doing the home laundry water ranging from 40 to l00 F., using conventior procedures. Woolens and synthetic fibers washed in the same manner are cleaned as efficiently when washed according to the process ofthis invention and using the compositions ofthis 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 l F., the temperature range in which the most outstanding results are seen is about 60 F. to 90 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 composi tions are useful in automatic washers and conventional type washers as well as hand washing operations.

Solid:

B-(N,N-rlimcthyl-Ntctradocylannnonio)-2-hydroxypropanc-l-sulfonato.

'Ictrapotassinni pyrophosphatc.)

. Sodium silicate fNugOiSiOz=l2l0).

. Potassium tolucmsulfonatc.

Sodium carlmxy methyl hydroxy cthyl cellulose.

Water and minor amounts of misccllancous.

3-(N,N-dimcthyl-N-alkylamm0nio )-2-hydroxypropaiii-- l-sulfonatc.

Tetrapotassium pyrophosphonatc.

. Sodium silicate (NazO:SiO:=l:l.6).

. Potassium toluene sulfouatc.

. Sodium carboxy methyl ccllulosc.

Water.

3-(N,N-dimcthyl-N-alkylammoni0 )'2-hydroxypropancl-sulfonate.

Sodium tripolyphosphate.

. Sodium silicate (Nfl2OISiO:=1Z2.5).

Sodium tolucnc sulfonatc.

Sodium carboxy mcthyl cellulose.

Sodium sulfate.

. Fluorescent dyv.

Water.

Miscellaneous.

3-(N,N-dlmethyl-N-alkylammonio )-.2-hydroxypropanotd-sulfonate. l h t 60 So ium yrop iosp a e. 6 2? Sodium silicate (NBzO2slOg=lI2.5). 2% Sodium toluene sulfonatc. 3%.. Sodium carboxy methyl cellulose. 11.3% H Water. Balancm Miscellaneous (fluoresccrs, perfume, anti-tarnish agents,

sodium sulfate, etc.).

3(N,N-dimethyl-N-alkylammonio )-2-hydroxypropanet-sulfonate.

Sodium tripolyphosphate.

Sodium silicate (N8:O.'SiOz=122.5).

Sodium tolutnio sulfonato.

Sodium carboxy methyl ccllulosc.

Sodium sulfate.

Water.

Miscellaneous.

3 (N,N-dimethyl-N-alky1ammon.io propane-l-sulfonatn. Sodium tripolyphosphate. 6% Sodium silicate (Na2O:Si0:=1:2.5)v

till

.. Sodium caruoxy mvthyl t'vllulosv.

. odlum sulfatv.

. Watt-r.

. Mlsccllanoons.

1 Alkyl rt-ft-rring to tho it; group dcrivt-d front the middle cut of t'Ut'tlnut fatty alcohol (3) C t, till"; 2, 232'; Cu. '.l (I

Alkyl rt-ft-rriug to tho it. group ohtninvd from tallu fatty alcohol old"; (15. 30); Cu, 4"; Cu and others) 3 Alkyl referring to tln R group tlll'iVt'tl front tlnmiddle (ill of coconut fatty alcohol (2Q 0. 66% (11. 23";- C 'J'I, (J 5).

It will be appreciated that the sultaine compounds used in the present invention can be incorporated into liquid or granular detergent compositions with suitable adjustments being made in the other components.

EXAMPLE Ill 1 Based on cloth swatches. Aver-ago of two tests. 3 Average of three tests.

It can be seen from this data that detergent agents A, B, D, E, F, H, l and J are superior in cool water detergency effectiveness to C and G. They are also markedly superior in cool water to K in hot water, K being the longtime standard organic detergent compound. The variation in effectiveness within the preferred compounds can be seen in the above results.

When, in detergent agents B and D in tetradecyl group is substituted for the hexadecyl and dodecyl groups, respectively substantially equivalent results are obtained in that the detergent agents are effective cleaning agents at F.

When, in the above example, mixtures of any and all of detergent agents A, B, D, E, F, H, l and J, are substituted for any or all of detergent agents A, B, D, E, F, H, l or J, substantially equivalent results are obtained in that effective cool water cleaning is obtained.

Llt

LII

EXAMPLE IV Here a Cloth Swatch Test, previously described, was conducted under the following conditions: water at a temperature of 80 F. or l40 F. and 7 grains per gallon hardness, 0.03 percent detergent compound and 0.06 percent 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. Seven cycles ofsoiling and cleaning were used.

LIPID REMOVAL BASED ON CLOTH SWA'lCHlzS Percent Removal Temper .llUYL' Detergent Agent A. Sodium coconntalkyl beta ainmonio ummoniol-I-hydnnyprn ane-l-sulfonatc 44 II x I D. Sodium tetrapromlene benzene Sulfonate 3x 5 I40 I As can be seen from the above table. detergent agent C is clearly superior to any of the other detergent agents but that detergent agent B is clearly superior to both detergent agents A and D. it will be noted that detergent agent A at 80 F. cannot approach the performance ofdetergent agent D at 140 F. The performance of detergent agent D at 140 F. is a standard criteria for adequate cleaning.

With reference to example 111. it will be noted that the detergent agents of this invention are all better in performance at 80 F. than the performance ofdetergent agent D at 140 F.

When examples Ill and 1V pyrophosphates; ethylene diaminetetraacetates; N-(Z-hydroxyethyl)-ethylenediamine triacetates; nitrilo triacetates; N-( Z-hydroxyethyl nitrilodiacetates; phytates; methylenediphosphonates; ethylidene diphosphonates; isopropylidene diphosphonates; benzylmethylidene diphosphonates; chloromethylidene diphosphonates; and mixtures thereof in the form of their sodium potassium. triethanolammonium diethanolammonium, and monoethanolammonium salts and mixtures thereof are substituted, either wholly or in part. e.g.. a 50 percent substitution, for the sodium tripolyphosphate builder substantially equivalent results are obtained in that for each builder substitution the detergent agents used in the process ofthis invention are effective cleaning agents at temperatures of about 80 F. and the above detergency building agents provide their buildingfunction with such agents. The surprising cool water superiority of these combinations of such agents and builders is found on a relative basis throughout the cool water range of 60 F.-90 F.

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 lpercent. Fluorescers. perfume. color antiredeposition agents, germicides, thickening agents opacifiers, blending or viscosity control agents, suds boosters and depressants and other detergent compounds, while not essential in the composition of this invention, can also be added.

All parts, percentages. and ratios herein are by weight unless otherwise specified.

Since certain changes can 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:

l. The process of washing wash-wear fabrics in a washing solution having a temperature of from about 60 F. to about F. and consisting essentially of A. from about 0.005 percent to about 0.175 percent of a /\\'itterionic quaternary ammonium compound selected from the group consisting of l 3-(N.N-dimethyl-N-alkylammonio) propane-l-sulfonates wherein the alkyl group contains from about 12 to about 16 carbon atoms; 3-(N.N-dibutyl-N-alkylammonio) propane-lsulfonates wherein the alkyl group contains about 12 carbon tttomS;

3. 3-(N.N-dimethyl-N-alkylammonio)-2-hydroxypropane-l-sulfonates wherein the alkyl group contains from about 12 to about 16 carbon atoms;

4. 3-(N,N-diemthyl-N-alkylammonio)1,1.3-trimethylpropane-l-sulfonate wherein the alkyl group contains about 12 carbon atoms;

. 2-(N.N -dimethyl-N-coconutalkylammonio)ethane-lsulfonates; ethane-l-sulfonates; and

6. mixtures thereof;

B. from about 0.004 percent to about 0.45 percent of a detergency builder selected from the group consisting of pyrophosphates;

.ethylenediaminetetraacetates;

N-(2-hydroxyethyl)-ethylenediamine-triacetates;

nitrilotriacetates N-(Z-hydroxyethyl)-nitrilodiacetates;

. phytates;

. tripolyphosphates; and

. mixtures thereof in the form of their sodium, potassi' um; triethanolammonium. diethanolammonium, and monoethanol-ammonium salts and mixtures thereof; and

C. water wherein the ratio of A to B by parts ranges from about 5:1 to about 1:25 all percentages herein being by weight.

2. The process of claim I wherein Compound (A) is 3- (N,N-dimethy1-N-hexadecylamminio)propane-1-sulfonate.

3. The process of claim 1 wherein Compound (A) is 3(N,N- dimethyl-N-dodecylammonio)-2-hydroxypropane-l-sulfonate.

4. The process of claim wherein Compound (A) is 3-(N,N- dimethyl-N-coconutalkylammonio)-l-sulfonate.

5. The process of claim 1 wherein Compound (B) consists essentially of tripolyphosphates.

'" UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,619,115 mud November 9, 1971 humor) Francis L. Diehl and Norman R. Smith It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

[Column 1, line 52, "waters" should read -water is--- Column 2 line 10, "nd" should read --and--.

Column 2 line 73, "3-(N,Nbibutyl-N-alkylammonio) propane-lsulfona tes" should read --3-(N,N-dimethylN-alkylammonio) propane-l-sulfonstes--.

Column 3, line 3, "3-(N,N-diemthyl-N-alkylanunonio)-2-hydroxypropane l-sulfonates" should read .3(N,N-dimethyl-N-alkylammonio) -2- hydroxypropane-l-sulEonates-.

Column 3, line 52, "3-(N,NdiemthylN-" should read --3-(N,N-

dimethyl-N-- Column 3, line 53, after "hydroxypropane-l" should read ---sulfonate:--.

Column 3, line 53, "3-(N,N-diemthyl-N- should read --3-(N,N-

dimethylN- Column 3, line 54, "hydrosypropane" should read --hydroxypropane--.

Column 3, line 60, "3-N,N-dimethyl-N,N-tetradecylammonio) should read --3-(N,N-dimethyl-N-alkylammonio)-- Column 3, line 64, "tetradecylamino" should read --tetradecylammonio Column 3, line 66, "monio)butsnebutane-l-sulfonate: butane-lsulfonatm" should read --monio)butane-l-su1onate:-.

Column 3, line 68, (N-Z-hydroxyethyl-N-msthy) should read --(N-2- hydroxyethylN-methyl)--.

Column 4, line 26, "1'' should read --(1)--.

Column 4, line 29, the second "2" should read --(2) Column 4, line 30, "mg. should read --(e.g.

Column 4 line 31, the second "3" should read --(3)--.

Column 4, line 35, "4" should read --(4)--.

Column 4, line 37, "e.g. should read --(e.g.,--.

Column 4, line 42, "3,422,021: and 5 mixtures thereof" should read --3,422,021) and (5) mixtures thereot. J

m3" UNITED STATES PATENT omen CERTIFICATE OF CORRECTION a n 3,619,115 p November 9, i971 Inventor) Francis L. Diehl and Norman R. Smith It is certified that error appears in the above-identified patent and that said letters Patent are hereby corrected as shown below:

Page 2 Column 4, line 51, "sodium, silicate should read -sodium -1 silicate-.

a Column 5, line 33, "is" should read --Tn--.

Column 5, line 34, "0.45" should read --.O45--. Column 6, line 6, "an" should read --and--. Column 7, line 2, "agltetingntype" should read --agitatingtype. Column 7, line 55, "sulbonate" should read --sulfonat'e--. Column 8, end or line 1, should read --1n--.

Column 8, end of line 2, should read --Ex---.

Column 8, end of line 3, should read --markedly--.

Column 8, end of line 4, should read --tetrapropylene--. Column 8, end of line ,6, should read was. Column 8, end of line 7, should read --detergent-. :olumn 8, end of line 8, should read --com---'.

Zolumn 8, end of line 9, should read -:-de--.

201mm 8, end of line 10, should read --waeh1ng--.

:olumn 8, end of line ll, should read --and--.

tolumn 8, end or line 12, should read --luoresoers,--. :olumn 8, end of line 13, should read --washing--.

.olumn 8, end or line 14 or 15, should read --ga1lon--. olumn 8, end of line 16, should read --3---.

rolumn 8, end of line 17, should read 3---.

olumn 8, end or line 19, should read --inventlon) olumn 8, end of line 20, should read --benzene--.

olumn 8, end or line 21, should read --con---.

olumn 8, end of line 22, should read --N---.

olumn 8, end of line 23, should read --N---.

olumn 8, end or line 25, should read --deter---.

olumn 8, end of line 26, should read --80'F.--.

olumn 8, end of line 27, should read --was--.

PO-IOSO Patent No.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Dated Francis L. Diehl and Norman R. Smith and that said Letters Patent are C olumn Colunm Column Column Column Column Column Column Column Column Column Column Column Column Column Column Column Column Column Column Column Column Column Column Column Column Column Column Colunm ll, line 14,

end end end end end end end end end end end end end end end end end end end end end end end end end of of of of of of of of of of of of of of of of of of or of of of of of 11, line Column ll, line Eolumn 11, line 2e, 29, so, 31, 32, 34, as, as, 37, 42, 43,

line line line line line line line 71, line 73, line' 74, line 75,

as, 66, e7, 68, 69, 10,

Page

read read read the above-identified patent herebg corrected as shown below:

--tal---. -sulfonate-. --is--.

--dt-" s --sultaine--. --White-. --builder-. --potassium--. --tripolyphosphate.--. --o.os--. --the--.

-Temperature, F.- --80--.

& 55, should read --l40-. lines 56-60, should read --80-.

read read read read read read read read read read should should should should should should should should should should line 53, "pyrophosphate.)" line 59, the second "in" should read should read should read should read --ln---. --properties-. --water--.

--are--. --l40'--. --the-. --sodium--. --ob---.

--in--. --conventional--.

should read --pyrophosphate should read --a-.

'" UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION mm No. 3,619,115 mm November 9,1911

Inmgr(.) Francis L. Diohl and Norman R. Smith It in cottiiiod that ortot oppooro in tho obovo-idontitiod potoot and that aid Lotta-o Paton: no horoby ootrootod no shown bolov:

Pogo 4 olumn 12, lino 24, "3-(N,N-diomthyl-N-olkylamonio)1,1,3-trimethblohould road --3-(N,N-dimothyl-N-olkylomonio)-l,l,3-trimothyl- Column 12, lino 25, propono-l-oultonoto" should read --propaneloulfonatoo--. Column 12, lino 28, tho oooond "othono-l-oulfonatoa ohould be dolotod. Column 12, lino 47, (N,N-dimothyl-N-hoxodocylominio) should road --(N,N-dimothyl-N-hoxodooylamaonio)--. column 12, lino 53, alto: "claim" and botoro "whoroin" ohould road --l--. column 12, lino 54, "dimothyl-R-coconutolkyloumonio)-l-oulfonate" ohould road --dimothyl-fl-coconutolkylomaonio) -2-hydroxypropanel-ou1onoto-.

Signod and ooolod thio 13th on] 0! ul! 97 (SEAL) Attoot:

EDHARD HJLBTOHKRJR. ROBERT OO'I'I'SOHAIK Attooting crum- Oomiooionor or Potonto

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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3912662 *Nov 28, 1973Oct 14, 1975Modokemi AbLiquid detergent composition containing an ampholytic betaine-type detergent
US3984335 *Jan 16, 1975Oct 5, 1976Basf Wyandotte CorporationCompositions for souring and softening laundered textile materials and stock solutions prepared therefrom
US4000091 *Apr 2, 1975Dec 28, 1976The Procter & Gamble CompanyBuilt detergent compositions
US4000092 *Apr 2, 1975Dec 28, 1976The Procter & Gamble CompanyZwitterionic surfactants
US4083813 *Jan 31, 1977Apr 11, 1978The Procter & Gamble CompanyProcess for making granular detergent composition
US4144093 *Aug 4, 1977Mar 13, 1979Henkel Kommanditgesellschaft Auf AktienProcess for machine washing of soiled articles using a water-insoluble cation-exchange polymer
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US6313084 *May 16, 2001Nov 6, 2001Colgate Palmolive Co.Composition comprising alpha-olefin sulfonate surfactant, magnesium salt of alkylbenzenesulfonate surfactant, sultaine surfactant, lauroyl ethylene diamine triacetate, solubilizing agent, lactic acid, water
US6376456Apr 16, 1999Apr 23, 2002Unilever Home & Personal Care Usa, Division Of Conopco, Inc.Wrinkle reduction laundry product compositions
US6403548Apr 16, 1999Jun 11, 2002Unilever Home & Personal Care Usa, Division Of Conopco, Inc.Sulfated vegetable oils, sulfonated vegetable oils, polyalkyleneoxide modified polydimethylsiloxane, linear aminopolydimethylsiloxane polyalkyleneoxide copolymers;
US6426328Sep 10, 1999Jul 30, 2002Unilever Home & Personal Care, Usa Division Of Conopco Inc.Wrinkle reduction laundry product compositions
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US6495500 *Jul 15, 2002Dec 17, 2002Colgate-Palmolive CoEthoxylated alkyl ether sulfate, magnesium and sodium alkyl benzene sulfonates, an amine oxide, a polyalkylglucoside, zinc salt and water; high foaming and degreasing
US6500793Apr 24, 2002Dec 31, 2002Unilever Home & Personal Care Usa Division Of Conopco, Inc.Sulfonated vegetable oils
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US6624131Nov 27, 2001Sep 23, 2003Unilever Home & Personal Care Usa Division Of Conopco, Inc.Inclusion of one or more wrinkle reducing ingredients in a laundry detergent product. The benefits are delivered to the laundered item during the cleaning step and, therefore, reduces the need for further wrinkle reducing steps when the
US6759379May 16, 2002Jul 6, 2004Unilever Home & Personal Care Usa, Division Of Conopco, Inc.Wrinkle reduction laundry product compositions
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Classifications
U.S. Classification8/137, 516/DIG.500, 510/357, 510/359, 510/495, 510/337
International ClassificationC11D1/92
Cooperative ClassificationY10S516/05, C11D1/92
European ClassificationC11D1/92