US3332877A - Detergent composition - Google Patents

Description

y 25. 6 I G. "r. REULAND ETAL 3,332,377

DETERGENT COMPOS IT ION Filed June 30, 1966 Graph Showing Sudsing Synergism Fig. 1

1 100% Detergni (1) Basic Formulation (Weight Basis 11 IOO% Deierqeni (II) 30% Total Active Detergent HI 100% Deiergeni (III) 8% Ethyl Alcohoi 62% Wmer INVENTORS George T. Reulund Todd L. Coward ATTORNEY This is a continuation-in-part patent application of copending patent application Serial No. 524,363, now abandoned, filed December 23, 1965, which is a continuation-in-part of Serial No. 423,007, filed January 4, 1965,

now abandoned.

This invention relates to a novel detergent composition. In particular, it relates to a light-duty detergent composition, preferably liquid, which embodies a synergistic ternary mixture of surface active compounds.

The term light-duty is used in the description of this invention in its usually accepted context, i.e., namely, as a semi-specialty product designed for dishwashing and laundering fine fabrics by hand. The term is also used to differentiate between this class of products and heavy-duty laundering products used in standard and automatic washing machines which substantially depend for their performance on large amounts of various types of additives United States Patent such as suds-boosters, detergency builders, sequestering agents and other ingredients.

In order for a cleaning product to be effective in lightduty applications, it should have the following desirable properties. Such a product should act as a wetting agent to solubilize and emulsify greasy soilsand help remove them from soiled articles, especially from soiled dishes. The cleaning composition should be able to disperse and suspend the soil once it is removed from the articles being washed so that the soil does not 'redeposit on the articles. Moreover, a most important prerequisite for a light-duty dishwashing composition is the capability of rapidly providing a copious amount of stable suds. In applications such as the washing of dishes and fine fabrics, it is important for aesthetic reasons to provide a suds blanket over the surface of the washing solution. Even more important, the suds layer or blanket should be stable enough in order to last throughout the entire washing operation. The cleaning capability of a washing solution is generally gauged by the amount of suds present. In addition, the composition should perform these functions efficiently over the wide range of washing conditions normally encountered in dishwashing and fine fabric washing processes (Water temperature, water hardness, soil type, soil load, type of fabric, etc.). Special precaution is taken to insure that a dishwashing composition should be mild on the skin even through repeated and prolonged exposure. Still further, it is essential that such a composition should provide a physically stable system over a wide range of storage conditions. Economic considerations can also play an important role in the preparation of these types of compositions.

.Few detergent compositions are known which otter each of the foregoing advantages. Those which are known are usually prohibitively expensive as a result of the cost of materials involved.

In the pursuit of compositions which oifer all of the advantages mentioned above, attempts have been made on the one hand to synthesize new compounds with the necessary characteristics. Other avenues of approach have been to combine known detergent compounds in order to try to discover synergistic mixtures of such compounds. In view of the lack of information in theprior art that can serve as a guide to such research efforts with mixtures of detergents, progress in this area, has been slow. The present invention represents a notable exception since the basis for the present invention is a novel synergistic combination of surface active compounds.

It is an overall object of the present invention therefore to provide a light-duty detergent composition, preferably liquid, which offers the foregoing advantages, and which excels in some of them, especially sudsing. Thus, it is a primary object of this invention to provide a lightduty liquid detergent composition which embodies a synergistic mixture of ,surface active compounds whose performance characteristics make it especially valuable as a dishwashing and fine fabric laundering composition. It is another object to provide a high-sudsing light-duty liquid composition which consists essentially of a synergistic mixture of detergents in an aqueous vehicle. These and other objects of the present invention will become apparent from the following description.

FIGURE 1 is a graph presenting data demonstrating the synergistic sudsing'results made possible by the improved light-duty liquid detergent compositions of the present invention.

It has now been discovered, according to the present invention, that an improved detergent composition especially suitable for dishwashing and fine fabric cleaning applications can be prepared which embodies a synergistic ternary mixture of two anionic detergent materials and one zwitterionic surface active compound. The three ingredients are mixed according to critical proportions and percentages. More particularly, the synergistic composi' tiohs of the present invention contain:

Detergent I: From about 12% to about 60% of a Detergent I which is a mixture of from about 30% to about of Component A, from about 20% to about 70% of Component B, and from about 2% to about 15% of Component C, and wherein;

(a) Said Component A is a mixture of double-bond positional isomers of water-soluble salts of alkene-l-sulfonic acids containing from about 12 to about 16 carbon atoms, said mixture of positional isomers including about 10% to about 25% of an alpha-beta unsaturated isomer, about 30% to about 70% of a beta-gamma unsaturated isomer, about 5% to about 25% of a gammadelta unsaturated isomer, and about 5% to about 10% of a delta-epsilon unsaturated isomer,

(b) Said Component B is a mixture of water-soluble salts 1 of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing from about 12 to about 16 carbon atoms, the functional units being hydroxy and sulfonateradicals with the sulfonate radical being attached on the terminal carbon and the hydroxyl group being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atom; and

(c) said Component C is a mixture comprising from 30- Water-soluble salts of alkene disulfonates containing from about 12 to about 16 carbon atoms, and from about 5% to about 70% Water-soluble salts of hydroxy disulfonates containing from about 12 to about 16 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which .is not more than about four carbon atoms removed from the site of. attaohme nt of said second sulfonate group; Detergent II: from about 6% to about 50% of Detergent II which is an alkali metal sulfuric acid ester of an alkyl ethoxylate containing from about to about 14 carbon atoms in the alkyl portion, and from 1 to about 5 moles of ethylene oxide and Detergent III: From about to about 74% of Detergent (III) which is a zwitterionic quaternary ammonium compound selected from the group consisting of compounds having the formula I wherein R is an alkyl radical containing from about 12 to about 14 carbon atoms, R and R are each members selected from the group consisting of methyl, ethyl and hydroxyethyl, R is an alkylene radical having from 1 to about 3 carbon atoms, and 2 is a member selected from the group consisting of hydrogen and hydroxyl, and compounds having the formula wherein R is an alkyl radical containing from about 12 to about 14 carbon atoms, and R and R are each members selected from the group consisting of methyl, ethyl, and hydroxyethyl.

A preferred embodiment of the present invention is a detergent composition containing from about 18% to about 36% of Detergent I, from about 10% to about 36% of Detergent II, and from about 28%, to about 54% of Detergent III.

In a complete liquid detergent formulation, the synergistic ternary mixture is'generally employed in admixture with Water. The active synergistic mixture comprises from about 10% to about 50% by weight of the composition, with the balance of from about 5 0% to about 90% being water. The preferred weight percentage range for the synergistic mixture in a liquid formulation is from about to about 40%, with the remaining 60% to 80% being water.

Two of the members of the synergistic ternary mixture, Detergent I and Detergent II are anionic surface active materials and the third member, Detergent III, is a zwitterionic compound. According to the present invention it is necessary, not only that the preceding enumerated percentages be employed, but it is also essential that there be a critical balance between the combined total of the two anionic compounds and the zwitterionic compound in the complete composition.

Thus, the weight ratio of the combined anionic compounds, Detergent I and Detergent II, to the zwitterionic compound, Detergent III, must be within the range of from about 1:3 to about 6:1, and preferably between about 1:1 to about 2.5: 1.

It is also necessary to maintain a critical weight ratio between each of the two anionic members in the synergistic ternary system of the present invention. Detergent I and Detergent II, should be employed within a Weight ratio of Detergent I to Detergent II of from about 10:1

to about 1:4 and preferably within a weight ratio of from about 6:1 to about 1:2.

According to the present invention, if these prescribed weight ratios are not embodied in the complete composition, the synergistic sudsing properties are not obtained.

An example of a high-sudsing light-duty liquid detergent composition embodying the teachings of the present invention is one which comprises from about 10% to about 50% of a synergistic ternary mixture consisting essentially of the following ingredients:

Detergent I: From about 12% to about 60% of a C based Detergent I as described herein;

Detergent II: From about 6% to about 50% of an alkali metal salt of the sulfuric ester of the tri(ethylene oxide) condensate of coconut fatty alcohols; and

Detergent III. From about 15% to about 74% of 3- N,N dimethyl N-alkylammonio)-2-hydroxy-propanel-sulfonate, the alkyl .group being derived from the middle-cut of coconut fatty alcohol,

Permis- Presible ferred Range, Range, Percent Percent CH3(CH2) ;CH2CH2CH2CH=CHSO3M 10-25 15-22 CHa(CH2) r-CHzCHrCH=CHCHzSOaM- 30-70 40-65 OH3(CH;) .CH2CH=CH CH2CH2SOaM 5-25 1020 CH3(CH2)XOH=CHCH2CHZCHXSOSM 5-10 7- 9 In the preceding formulas x is an integer of from about 6 to about 10, preferably about 8 to about 10, and M represents any cation that forms a soluble salt such as alkali metals, e.g., sodium and potassium, and ammonium, and substituted ammonium compounds, e.g., trialkylammonium and trialkylolammonium compounds. Specific examples of substituted ammonium compounds are triethylammonium, trimethylammonium, and triethanolammonium. Others will be apparent to those skilled in the art. The symbols x and M have the same meaning throughout the description of the present invention. There can also be present minor amounts of other double-bond positional isomers. This is the case, for example, when the compositionis prepared by the sulfonation of alpha olefins with uncomplexed sulfur trioxide. Such minor amounts, i.e., less than 10% by weight, do not materially alter the excellent cleaning and sudsing properties of the detergent composition.

Whereas, Component A is a blend or mixture of certain unsaturated isomeric aliphatic compounds, Component B consists of a mixture of certain saturated aliphatic compounds. A minor amount of unsaturation can be included in this mixture but preponderantly the compounds are saturated. The 'bifunctionality of these alkane compounds is due to the presence of a hydroxyl group and a sulfonate radical on the same molecule. It has been discovered that the sulfonate radical must be located on the terminal carbon atom. It also has been discovered that the situs of the hydroxyl group in the compounds that can comprise Component B, is an especially important factor. For example, if the hydroxyl group and the sulfonate radical are attached to adjacent carbon atoms, the valuable detergent and sudsing properties of the Component B compounds are substantially decreased. This is especially true when the alpha and beta carbons are the two sites of attachment. The critical structural arrangement which must exist in order for the compounds to be detergents, is that Permis- Presible ferred Range, Range, Percent Percent CHQ(CH2) XCH2CHQCH(OH) OH2CHzS03M.. -90 25-75 CH3(CHz)XCH2CH(OH)CHzCHzCH2SOaM 10-90 25-75 CHs(CHr) x-CH (OH) CHaUHzCHaCI-IzSOaM--- 10-90 2575 The value for x and M are as previously set forth.

Component B can also include minor quantities, less than about 10%, of compounds wherein the hydroxyl group is attached elsewhere along the carbon chain, e.g., on the sixth carbon atom, without materially altering the overall detergent properties of the compositions. However, at least 90% of the hydroxyl radical substitutions must be in the 3, 4, and 5 positions. The 3- and 4-, and S-hy droxy-n-alkyl sulfonate compounds, illustrated above, however, are preferred ingredients of Component B. In this same connection, it has also been noted that a betahydroxy-n-alkyl-sulfonate compound performs unsatisfactorily as a detergent compound. Not only is it not a good sudsing detergent, but it has been discovered surprisingly that such a compound constitutes an actual load in the present detergency system. For this reason, the level of such a compound or mixture of beta-hydroxy-nalkyl compounds should be held to a minimum. It is noted, however, that minor amounts of beta-hydroxy-nalkyl sulfonate compounds can be tolerated in the syn.- ergistic compositions of this invention provided that Components A, B and C of Detergent II otherwise contain the essential ingredients herein described in the proportions and percentages specified.

The alkene disulfonates should preferably comprise from about 40% to about 80% of the highly polar polyfunctionally substituted aliphatic compounds which make up component C. These alkene disulfonates should preferably contain from about 12 to about 16 carbon atoms. As mentioned above, one sulfonate group is attached to the terminal carbon atom. The second sulfonate group is attached to an internal carbon atom that is not more than about six carbon atoms removed from the terminal carbon. In other words, the second sulfonate functional group can be attached to the second through about the seventh carbon atom. Component C can also include minor amounts of compounds in which the second sulfonate is located more internally than the seventh carbon, such as, for example, on the eighth carbon, etc. There is no apparent advantage in having these latter compounds present in the composition, however. According to a preferred embodiment, the major portion, that is from about 60% to about 95% of the alkene disulfonates, should be 1,2 and 1,3 disulfonates.

The alkene double bond can be distributed between the terminal carbon and about the seventh carbon atom; such unsaturation includes, for instance, alpha-beta, betagamma, gamma-delta, delta-epsilon, epsilon-zeta, and zeta-eta unsaturation. Preferably, the double bond should 6. be distributed between the second to the sixth carbon atom. It should be noted that the alkene double bond can be even more internally located than between the zeta: eta carbons, but again no apparent advantage is gained thereby.

Thus, it can be seen that the alkene disulfonates of Component C contain the polyfunctional combination of a double bond and two sulfonate groups in an important structural relationship. The preferred compounds as ingredients of the alkene disulfonate portion of Component C are 2-alkene-1,2-disulfonate; 3-alkene-1,2-disulfonate; and 4-al-kene-1,2-disulfonate of the 1,2-disulfonate species; and 3-alkene 1,3 disulfonate; 4-alkene-1,3-disulfonate; and 5-alkene-1,3-disulfonate of the 1,3 disulfonate species. The alkene group can contain from about 12 to about 16 carbon atoms and preferably about 14 to 16 carbon atoms. The sodium and potassium salts of these compounds are preferred.

Examples of alkene disulfonate compounds are. the following in which a carbon chain length of 16 was selected as being representative, having sulfonate attachment sites of 1,2 and 1,3;

As mentioned above, Component C contains the afore mentioned and illustrated alkene disulfonates. It also conf tains from about 5% to about and preferably about 20% to about 60%, water-soluble salts of hydroxy disul fonates containing from about 12 to about 16 carbon atoms. The terminal carbon atom has attached to it one of the sulfonate groups. The second sulfonate group can be attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom. The required hydroxy group isattached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group.

The preferred sites of attachment for the hydroxy group on the 1,2 disulfonate species are the fourth and fifth carbon atoms to yield 4-hydroxyalkane-1,2-disulfonates and S-hydroxyalkane-1,2-disulfonates. For the 1,3.- disulfonates the preferred sites of attachment for the hy; droxy group are the fifth and sixth carbon atoms to yield S-hydroxyalkane-l,3-disulfonates and fi-hydroxyalkane- 1,3-disu1fonates. The alkane hydrocarbons as before are those having about 12 to about 16 carbon atoms and preferably about 14 to about 16 carbon atoms. According to a preferred embodiment, the major portion, that is, from about 60% to about'95% of the hydroxy disulfonates should be 1,2 and 1,3 disulfonates.

Thus, for example, the following compounds are contemplated. Again, a 16 carbon 1,2 and 1,3 disulfonate compound is presented as being representative.

It is postulated that a second polar group, as in Components B and C, spaced a critical distance from a terminally attached polar group in a detergent molecule modifies the crystalline lattice structure in such a way as to improve markedly the solubility characteristics of the compound. While this is not known for certain, it is offered as one possible explanation for the exceptional detergent properties of the compositions of the present invention.

Detergent I, as described herein, can be prepared in any suitable manner so long as the above teachings are adhered to. For instance, each of the ingredients can be synthesized separately and then mixed according to the stated proportions. On the other hand, Detergent I, as described herein, can be prepared by a process described in copending patent application Serial No. 516,081, filed December 23, 1965, by Adriaan Kessler and Phillip F. Pflaumer.

If is is desired to synthesize separately the individual components of Detergent I it is possible to do so according to the procedures in the following discussion. Any other suitable methods can be used. The symbol R as used in the following equation represents an aliphatic hydrocarbon radical that would allow for a total of carbon atoms in the molecule between about 12 and about 16. The alpha-beta unsaturated sulfonate containing aliphatic compounds of Component A can be prepared readily by dehydrochlorinating a 2-chlorosulfonic acid derivative. A farily detailed discussion of a suitable preparative route appears in an article in the Journal of the Chemical Society, 1949, page 46, written by J. D. Rose and A. Lambert. The starting step for this synthesis is a reaction between a long chain epoxide and sodium bisulfite to produce a 2-hydroxy-1-sulfonate derivative of the particular long chain epoxide used. This reaction product is condensed with PCl to prepare the aforementioned 2- c'hlorosulfonic acid derivative which in turn is reacted with sodium carbonate to yield an alpha-beta unsaturated compound.

The other preferred double-bond positional isomers of Component A, i.e., the beta-gamma, gamma-delta, and delta-epsilon can be prepared by the thermal dehydration Hno RCH7CH(OH) CHaCHzSOaNB. T

Similarly a reaction mixture of a gamma-delta and a delta-epsilon double-bond isomer compound can be prepared by using a 4-hydroxysulfonate as a starting material:

RCHzCH=CHCHzCHzSOaNa RCH=CHCH2CHzCHzSOaN3 The foregoing synthesis of the double-bond positional isomers follows closely the well known dehydration of an organic alcohol as is mentioned in such standard texts as Whitmores Organic Chemistry, second edition, pages 39-41.

There is no need to separate the reaction product of the two illustrated dehydration reactions. The reaction product can be formulated directly into a detergent com- I position according to the present invention. If, for some reason, it is desired to work with pure ingredients, they can be separated into pure forms.

The hydroxy sulfonates of Component B, such as the preferred 3-, 4-, and S-hydroxy compounds can be prepared by the free radical addition of sodium bisulfite to the corresponding 3-, 4-, or S-hydroxy-l-olefin, respectively:

Free Radical Catalyst RCH(OH)CO=CH1 NaHSOa The hydroxy olefin for use as starting materials in the preceding free radical addition reaction can be prepared by well known organo-metallic reactions, e.g., involving an aldehyde and a Grignard reagent in Which R and R" are organic radicals and X is a halogen. For example:

A discussion of the conversion of hydroxyolefins produced by preceding Equations a and b to hydroxy sulfonates appears in an article written by J. Willens, Bulletin of the Chemical Society of Belgium, vol. 64, page 427 (1955).

It is to be understood that other hydroxy sulfonates as desired can be prepared by using different Grign-ard reagents in the reaction equation set forth above.

The alkene disulfonates and the hydroxy disulfonates which comprise Component C may also be prepared separately by any known manner. For instance, the hydroxy disulfonates may be prepared by epoxidizing olefin sulfonic acid isomers, and then opening the epoxide ring with sodium bisulfite by standard reaction techniques. The hydroxy disulfonates may then be dehydrated by reactions known to those skilled in the art to yield the corresponding isomeric alkene disulfonates.

As mentioned earlier, the Detergent I components should contain from about 12 to about 16 carbon atoms. It is preferred, however, to have the compounds contain from 14 to 16 carbon atoms. It is not necessary that each of the compounds contain the same number of carbon atoms. Mixtures of different chain lengths within the prescribed ranges can be used. I Y

The following compositions are illustrative of Detergent I according to the present invention wherein the percentages are by weight and wherein Components A, B and C total up to 100% of Detergent I. The percentages listed for each ingredient are by weight of that particular ingredient in Detergent I.

Detergent I can be comprised as follows with a chain length of 16 carbons being representative:

Component A: Percent C H CH=CHSO Na C H CH=CHCH SO Na C H CH=CHCH CH SO Na C H CH=CHCH CH CH SO Na 6 Total Component A 65 Component B: Percent C H CH(OI-I)CH CH SO Na C H CI-I(OH)CH CH CH SO Na Total Component B 25 Component C: Percent C13H27CH C(SO3N3.)CHgSOgNB. 1.0 C1 H CH=CHCH(SO Na)CH SO Na 3.0 n zar- =CHCH CH(SO Na)CH SO Na .5 C11H23-CH2-CH =C(SO Na)CH CH SO Na .5 C11H23 'CH CH -CH(SO Na)CH CH SO Na .5 C H -CH=CHCH -CH(SO Na)CH CH SO Na .5 C H -CH(OH)-CHg CH(SO Na)CI-I SO Na 1.5 C H -CH(OH)CH -CH -CH(SO Na)CH SO Na 1.5 C H CH(OI-I)-CH .5 C H -CH(OH)CH CH -CH(SO Na)CI-I --CH SO Na .5

Total Component C 10.0

Detergent I as so comprised has excellent detergent and synergistic sudsing properties when mixed with Detergent II and Detergent III according to the proportions described herein.

Another illustrative example of Detergent I is as follows:

Component A: Percent (3 I'I29(:I'I (:I'IS()3 1a. 9 C 31'1 7CI'I CI'ICI'I2S()g l a C H CH=CHCH CH SO Na C H CH=CHCH CH CH S0 Na 10 Total Component A 65 Component B: Percent C H CH(OH)CH CH SO Na C H CH(OH)CH CH CH SO Na 10 C H CH(OH)CH CH CH CH SO Na 3.

Total Component B 23 1 0 Component C: Percent C H CH -CH -CH CH C(SO Na)CH (SO Na) 1.0 C oHg -CH(SO Na)-CH SO Na 3.5 C 3H2 1.0 1o 21 2.-CH; a

-CH CH -SO N8. .5 C H CH CH -CH CH -CH- CHSO NE1 .5 C1oH2 -CH2CH2-CH2C .5 C H CH CH -CH OH) -CH CH(SO Na)CH SO Na 3.0 C H -CH CH (OH) CH CH CH(SO Na)-CH SO Na 1.0 C H --CH CH(OH)CH CH(SO Na)CH CH SO Na 1.0

Total Component C 12.0

This Detergent I composition offers excellent detergent properties of cleaning and synergistic sudsing in admixturewith Detergents II and III as described herein.

The following are other illustrative examples of Detergent I with 12, 14 and 16 carbon lengths and are referred to as a C -Based Detergent I, a C -Based Detergent I, and a C -Based Detergent I. Hereinafter these compositions will be referred to for simplicity by these terms rather than reproducing all of the ingredients.

(1) An active detergent composition referred to herein as C -Based Detergent I, having the following composition, percentages by weight.

(2) A detergent active composition referred to herein as C -Based Detergent I and having the following composition, percentages being by weight.

Component A: Percent C H CH=CHSO Na C1 H CHCHCH SO Na 3 3 C H CHCHCH CH SO Na$ C H CH=CHCH CH CH SO Na 6 Total Component A "E Component B: Percent C11H23CH(OH) CH2CH2SO3 Nfl C1H21CH(0H)CH2cH2CH2SO3 Na 5 Total Component B 25 11 Component C: Percent v C H CH =CHCH(SO Na)CH CH (SO Na) 1.5

CH (SO Na) 3.0 C H CH(OH)CH CH(SO Na) CH CH (SO Na) 1.0

Total Component C 10.0

(3) A detergent composition referred to herein as C Based Detergent I and having the following composition, percentages being by weight. This was the composition of Detergent I employed in the tests described below, the results of which are presented in FIGURE 1.

Component A: Percent C H CH=CHSO N21 C1 H 7CH CHCH2SO Na C H CH=CHCH CH SO Na 13 C1IH23CH CHCH2CHZCHZSO3Na 6 Total Component A 65 Component B: Percent C H CH(OH)CH CH SO Na 20 C H CH(OH)CH CH CH SO Na Total Component B 25 Component C: Percent C H CH=CHCH(S0 Na)CH (SO Na) 4.5 n zs :CHCH (SO Na) CH CH (SO Na) 1.5 C H CH(OH)CH CH(SO Na) CH (SO Na) 3.0 C11H23CH OH) CH CH SO Na) CH CH (SO Na) 1.0

Total Component C 10.0

The second anionic species Detergent II which can be employed in the present invention in critical admixture with the previously described anionic member Detergent I, is represented by the formula R'(OC H SO M, wherein R represents an alkyl radical containing from about to about 14 carbon atoms, preferably about 12, and y ranges from 1 to about 5. M represents any cation which forms a water soluble salt but preferably sodium, potassium, ammonium and substituted ammonium salts.

The long chain aliphatic radical, R, can contain from about 10 to about 14 carbon atoms, compounds having mixed chain lengths within this range can be used. Thus, the alkyl radical can be derived from a natural source such as the middle-cut of distilled coconut fatty alcohol which consists of a mixture of various chain lengths be ing approximately 2% C 66% C 23% C and 9% C The important requirement is that the compounds must have the preponderant chain length within the C C range and preferably C It is to be understood that minor amounts of compounds whose carbon chain length is less than 10 and greater than 14 can be tolerated without upsetting the desirable synergistic properties. The coconut alkyl species described above represents a preferred embodiment of the present invention. These compounds can be characterized as the sulfated product of the reaction between one mole of a higher fatty alcohol containing the requisite number of carbon atoms and 1 to about 5 moles of ethylene oxide. The unbalanced equation for the preparative route is:

These compounds can also be made by sulfating and neutralizing alkyl ethoxylates made by reacting an alkyl bromide with sodium glycolate in an excess of an ethylene glycol.

The value for y in the formula RO(CH CH O) is understood to represent an average number of ethylene oxide units in the reaction product, and not an absolute value.

Examples of such compounds which can be used in the present invention are the sodium salt of the sulfuric ester of the tri(ethylene oxide) condensate of a mixture of coconut fatty alcohols; the sodium salt of the sulfuric ester of the di(ethylene oxide) condensate of dodecanol, the potassium salt of the sulfuric ester of the tetra (ethylene oxide) condensate of a mixture of coconut fatty alcohols; the sodium salt of the sulfuric ester of the mono (ethylene oxide) condensate of tetradecan'ol; the sodium salt of the sulfuric ester of the penta(ethylene oxide) condensate of coconut fatty alcohols.

Examples of the zwitterionic detergent compound which can be used as Detergent III in admixture with the blend of the two anionic detergent compounds described above to provide synergistic cleaning and sudsing results are as follows:

3-(N,N dimethyl N dodecylammonio) 2 hydroxyprop anel -sulfonate 3-(N,N dimethyl N dodecylammonio) propane lsulfonate 3-(N,N diethyl N dodecylammonio) 2 hydroxypropane-l-sul-fonate 3-(N,N-di(hydroxyethyl)-N-dodecylammonio) 2 hydroxypropane-l-sulfonate 3-(N,N-dimethyl N tetradecylammonio) 2 hydroxypropane-l-sulfon ate 3-(N,N-diethy1 N tetradecylammonio) 2 hydroxypropane-l-sulfonate 3-[N,N-di(hydroxyethyl) N tetradecylammonio] 2 hydroxypropane-l-sulfonate 3-(N,N-dimethyl-N-alkylammonio) 2 hydroxypropanel-sulfonate, the alkyl group being derived from the middle-cut of coconut fatty alcohol 2-(N,N-diethyl-N-alkylammonio) 2 hydroxypropanel-sulfonate, the alkyl group being derived from the middle-cut of coconut fatty alcohol 2-(N,N-diethyl-N alkylammonio) 2 hydroxyethanel-sulfonate, the alkyl group being derived from the middle-cut of coconut fatty alcohol 3- [N,N-di (hydroxyethyl -N-alkylammonio] -2 hydroxypropane-l-sulfonate, the alkyl group being derived from the middle-cut of coconut fatty alcohol 4-[N,N-di(hydroxyethyl)-N-alkylammonio]-2 hydroxybutane-l-sulfonate, the alkyl group being derived from the middle-cut of coconut fatty alcohol The foregoing sulfonate compounds are illustrative of the class of sultaine compounds which can usefully be employed in the synergistic compositions of the present invention. These sultaine compounds represent the preferred zwitterionic compounds.

The following zwitterionic compounds are also useful in the present invention and, although they are less preferred than the sultaines, they still provide valuable synergistic sudsing properties in the detergent compositions described herein.

(N,N dimethyl-N-dodecylammonio)methane carboxylate (N,N-dimethyl-N-tetradecylammonio)methane carboxylate (N,Ndimethyl-N alkylammonio)methane carboxylate, the alkyl group being derived from the middle cut of coconut fatty alcohol As noted above in the specific examples of suitable zwitterionic quaternary ammonium compounds, the long chain aliphatic radical can be a C (dode'cyl) or C (tetradecyl) radical or alternatively can be derived from a natural source such as the middle-cut of distilled coconut fatty alcohol which consists of a mixture of various chain lengths being approximately 2% C 66% C 23% C and 9% C Thus, it has been found essential to have the preponder-ant chain length be C and C It is to be understood, that minor amounts of ingredients whose chainlength is less than 10 and greater than 14 can be tolerated withoutupsetting the desirable properties of the composition. The coconut alkyl species of the zwitterionic quaternary ammonium compounds described above are preferred compounds of this type for use in admixture with the anionic detergent according to the present invention.

The quaternary ammonium compounds which are useful in terms of the present invention can be prepared by any known method. The way in which these compounds are prepared forms no part of the present invention. One acceptable synthesis route which is described in detail in German Patent 1,018,421, comprises reacting an aliphatic tertiary amine such as dodecyldimethyl amine with a propane sultone. A corresponding hydroxy compound such as 3-(N,N-dimethyl-N-dodecylammonio)-2- hydroxypropane-l-sulfonate can be prepared readily by reacting glycerol-monochlorohydrin sulfonic acid with a suitable tertiary amine such as dodecyl dimethyl amine. This process is described in German Patent 651,733. Use of a coconut alkyl dimethyl amine or tetradecyl dimethyl amine will result in the corresponding desired quaternary compounds. I

The following examples of liquid detergent compositions are given by way of illustrating the present invention. It is not intended to limit the invention thereto, for modifications will be readily apparent to those skilled in the, art from a careful reading of the preceding and following descriptions. Percentages are all by weight, unless otherwise indicated.

Example I 18% C -Based Detergent I having the composition given above 6% Sodium salt of the sulfuric ester of the tri(ethylene oxide) condensate of dodecanol 6% 3-(N,N-dimethyl-N-alkyl ammonio) 2 hydroxypropane-l-sulfonate, the alkyl radical being derived from the middle-cut of coconut fatty alcohol 8% Ethyl alcohol 62% Water Example II 20% C -Based Detergent I having the composition given above 20% Sodium salt of the sulfuric acid ester of the di(ethylene oxide) condensate of a mixture of coconut fatty alcohols 10% 3-(N,N-dimethyl-N-dodecylammonio)-propane 1- sulfonate 10% Ethyl alcohol 40% Water Example 111 15% O -Based Detergent I as described above 5% Potassium salt of the sulfuric ester of the tetra(ethylene oxide) condensate of a mixture of tallow fatty alcohols 3-(N,N-dimethyl-N-tetradecylammonio) 2 hydroxypropane-l-sulfonate 5% Ethyl alcohol 50% Water Example IV 4% C -Based Detergent I as described above 1% Sodium salt of the sulfuric ester of the rnono(ethylene oxide) condensate of tetradecanol 15% 3-[N,N-di(hydroxyethyl)-N-akylammonio]-2 hydroxy-propane-l-sulfonate, the alkyl group being derived from the-middle-cut of coconut fatty alcohol 80% Water 1 4' Example V 7.5% C -Based Detergent I described above 2.5% Sodium salt of the sulfuric ester of penta(ethylene oxide) condensate of hexadecanol 20 2-(N,N-diethyl-N-dodecylammonio)ethane-1 sulfonate 7% Ethyl alcohol 63% Water Example VI 14% C -Based Detergent I as described above 6% Sodium salt of the sulfuric ester of tri(ethylene oxide) condensate of dodecanol 20% 3-(N,N-dimethyl-N-dodecylammonio)-propane lsulfonate 60% Water Example VII 6.6% C -Based Detergent I as described above 6.6% Potassium salt of the sulfuric ester of tri(ethylene oxide) condensate of dodecanol 6.6% 4-(N,N-dimethyl-N-tetradecylammonio) 2 hydroxypropane-l-sulfonate 802% Water Example VIII 7.5 C -Based Detergent I as described above 15 Potassium salt of the sulfuric ester of di(ethylene oxide) condensate of a mixture of coconut fatty alcohol-s 7.5% 3-(N,N-dimethyl-tetradecylammonio)-2 hydroxypropane-l-sulfonate 70% Water Example IX 8% C -Based Detergent I as described above 24% Sodium salt of the sulfuric ester of the tri(ethylene oxide) condensate of dodecanol 8% 3-(N,N-diethyl-N-tetradecyl amomnio)-2 hydroxypr'opane-l-sulfonate 60% Water Example X 4% G -Based Detergent I as described above 16% The potassium salt of the sulfuric ester of the tetra (ethylene oxide) condensate of a mixture of coconut fatty alcohols 5% 3-[N,N-di(hydroxyethyl)-N tetradecyl amomnio] propane-l-sulfonate 8% Ethyl alcohol 67% Water Example XI 15% C -Based Detergent I as described above 15% Sodium salt of the sulfuric ester of tri(ethylene oxide) condensate of dodecanol 5% 3-(N,N-dimethyl-N-tetradecyl ammonio)-Z-hydroxypropane-l-sulfonate 65% Water Each of the preceding examples provide excellent dishwashing and fine fabric laundering compositions which have remarkably hig-h-sudsing and cleaning properties.

While liquid detergent compositions are the preferred embodiment of the present invention, solid forms, e.g. granular products, can also be prepared. Such solid particulate products having synergistic sudsing properties have the following compositions.

Example XII 3% C -Based Detergent I :as described above 3%Sodium salt of the sulfuric ester of tri(ethylene oxide) condensate of a mixture of coconut fatty alcohols 3 3 (N,N-dimethyl-N-tetradecylammonio -2-hydroxypropane-l-sulfonate 91% Sodium sulfate 1 5 Example XIII 8% C -Based Detergent I as described above 16% Sodium salt of the sulfuric ester of the tri(ethylene oxide) condensate of dedecanol 8% 3-[N,N-di(hydroxyethyl)-N tetradecyl ammonio]- propane-l-sulfonate 68% Sodium sulfate Example XIV This is an example of a liquid dishwashing composition that besides offering synergistic sudsing is outstandingly mild to the skin.

18% C -Based Detergent I as described above 4.5% Sodium salt of the sulfuric ester of the tri(ethylene oxide) condensate of middle-cut coconut fatty alcohol 7.5% (N,N-dimethyl-N-dodecylammonio)methane carboxylate 70% Water The following standardized liquid formulation was used to demonstrate the synergistic properties of the novel ternary mixtures of the present invention. Percentages are by weight.

Percent Total active detergent 30 Ethyl alcohol 8 Water 62 Total standardized formulation 100 The ethyl alcohol was used as a solubilizer and a viscosity control measure. Although ethyl alcohol is usually employed in liquid detergent formulations as a solvent to reduce viscosity and to lower the chill temperature, its .use herein is not considered essential to the present invention. Its presence has no substantial bearing on the sudsing properties of the compositions.

Several compositions were tested using the procedure outlined below. The compositions differed from each other only in the make up of the active detergent portion. Each of the members of the ternary system were tested as the sole detergent active in a formulation. Then, each of the three possibly binary systems were also evaluated. Thereafter, ternary mixtures were evaluated in which different percentage levels of each of the three ingredients were used. The results for each composition tested were plotted 0n the triangular graph, presented as FIGURE 1, and the points were then connected by graph lines. The triangular diagram is of the conventional type with each corner representing 100% of one of the three necessary active detergents of the present invention as indicated as FIG- URE 1. The straight lines on the diagram each represent by weight. In this manner it was possible to delimit the areas in which synergistic sudsing results were obtained.

The procedure used to discover the synergistic mixtures of the present invention is a standardized procedure which is performed in the following manner.

A dishpan was prepared containing one gallon of water with a hardness of 7 grains, a temperature of 115 F. and a pH of 7. To this solution was added 7.25 cc. of the detergent compositions being tested. The solution containing the detergent composition was mechanically agitated and the maximum suds level was measured. This was referred to as the original suds level.

After this original suds level was obtained, a series of five ordinary dinner plates soiled with about 2 grams of standardized fatty soil (a triglyceride shortening) were washed in the prepared test solution. The suds height was again measured. The procedure was repeated a fixed number of times. A measurement of the suds height was taken after each set of five dishes were washed. An average was then obtained for the several suds height measurements, and the average was then expressed in terms of a percent of the original suds height. This percentage figure represents a relative measure of the initial suds volume produced and even more important, of the stability of the suds formed by each composition in the presence of increasing soil load. The results are dependable and reproducible. Those skilled in performing this evaluation know from experience that a difference in suds height of from about 3% to about 5% is considered significant.

The results of these evaluations are presented in FIG- URE 1. The detergent used as Detergent I was that referred to above as C -based Detergent I.

The detergent used as Detergent II was the sodium salt of the sulfuric ester of the tri(ethylene oxide) condensate of a mixture of coconut fatty alcohols.

The detergent used as Detergent III was 3-(N,N-dimethyl N alkylammonio) 2 hydroxypropane 1- sulfonate, the alkyl group being derived from the middlecut of coconut fatty alcohols.

It will be seen from FIGURE 1 that when each of the members of the ternary system are used as the sole active,

average sudsing performance figures were less than 40% in the instance of Detergent I, and 35% in the instance of Detergent II and Detergent III. For a binary mixture of Detergents I and II, the highest average values were between 40% and 45%; a binary mixture of Detergents I and III gave highest average values between 35% and 40%; and a binary mixture of Detergents II and III resulted in highest average values between 40% and 45 On the other hand, the synergistic ternary compositions of the present invention were those which fell into the superior performance areas designated within the 45% closed graph line. The preferred embodiments of the present invention are those synergistic ternary mixtures which are included in the area enclosed by the 50% graph line, approximately in the center of the triangular graph.

It should be noted that the performance results in FIGURE 1 were obtained with a C based Detergent I. With a different chain length, e.g., 12 or 14 carbon atoms, the graph lines can be expected to deviate slightly from those in FIGURE 1. In any event, however;

when the three detergents are mixed according to the proportions and ratios described herein synergistic performance results are obtained and the advantages of the present invention can be utilized.

The synergistic active detergent compositions of the present invention also can be used with other materials to form detergent compositions, particularly light-duty liquid compositions, Such complete composition can contain from about 5% to 50% of the detergent mixtures of this invention with the remaining 50% to being made up of water soluble inorganic alkaline builder salts, organic sequestering agents, or mixtures thereof, hydro tropes, solubilizing agents, anti-tarnishing agents and water.

The builders and sequestrants are employed at levels of from about 4% to about 30% and preferably from about 8% to about 25%. Water soluble inorganic alkaline builder salts which can *be used alone or in admixture are alkali metal carbonates, borates, phosphates,- polyphosphate, bicarbonates and silicates. Specific examples of such salts are sodium and potassium, tripolyphosphate, sodium and potassium carbonate, sodium and potassium tetraborate, sodium and potasium pyrophosphate, sodium bicarbonate, sodium hexametaphosphate, sodium, sesequicarbonate, sodium monoand diorthophosphate and potassium bicarbonate. Such inorganic builder salts.

monium or substituted ammonium, aminopolycarboxylates, e.g., sodium and potassium N-(Z-hydroxyethyD- ethylenediamine triacetates, sodium and potassium nitrilotriacetates and sodium, and potassium and triethanolammonium N-(2-hydroxyethyl)-nitrilodiacetates. Mixed salts of these polycarboxylates are also suitable. Other valuable polycarboxylate builder compounds are the sodium and potassium salts of polymaleate, polyitaconate and polya-crylate. The alkali metal salts of phytic acid, e.g., sodium phytate, are also suitable as organic alkaline builder salts (see U.S. Patent 2,739,942).

Polyphosphonates are also valuable builders in terms of the present invention including specifically sodium and potassium salts of ethane-l-hydroxy-1,1-diphosphonate,

sodium and potassium salts of methylene diphosphonate, sodium and potassium salts of ethylene diphosphonate, and sodium and potassium salts of ethane-1,1,2-triphosphonate. Other examples include the alkali metal salts of ethane-Z-carboxy-l,l-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-l hydroxy-1,1,2 triphosphonic acid, ethane-Z-hydroxy-l,1,2-triphosphonic acid, propane-1,l,3,3-tetraphosphonic acid, propane-1,1,2,3-tetraphosphonic acid, and propane-1,2,2,3-tetraphosphonic acid.

Hydrotropes can be added if desired to increase the compatibility of the ingredients of the formulations of this invention in lightly built systems. Preferred hydrotrope anions are benzene sulfonate, xylene sulfonate, and toluene sulfonate. They are preferably use-d as their soluble salts such as: ethanol-ammonium, diethanolammonium, and triethanol-ammonium, and especially as the alkali metal, potassium, or sodium salts. Sodium or potassium toluene sulfonate is especially preferred. The hydrotrope is added at levels of from about to about 10%. Levels of from about 2% to 8% are preferred. The upper limit of'about 10% is set by increasing dilution of the product by an ingredient substantially inert so far as sudsing and detergency are concerned. The lower limit is the amount required to achieve a homogeneous solution. It will be appreciated that it is necessary that the formulations of this invention should be liquid at somewhat higher and at somewhat lower temperatures than usual room temperature. The amount of hydrotrope salt used is preferably the minimum amount which will hold the ingredients in solution at the temper-ature to which it is desired that the formula can be cooled without phase separation.

As mentioned previously solubilizing agents also can be added, if necessary, and those preferred are lower alcohols such as methyl, ethyl and propyl alcohols. They are generally employed ata level of from about 0% to about 25 by weight of the composition and preferably between about to 15% by weight.

Various minor ingredients can also be added to the compositions of the present. invention. Such normal and desirable additives include perfumes, viscosity control agents, opacifiers, and pigments. In addition, inert materials such as water-soluble inorganic salts can also be present in minor amounts, generally as impurities from the various ingredients or as opacifier stabilizers. For example, ethylene glycol distearate or polystyrene can be used as opacifiers in amounts of up to 3% by weight of the composition.

While liquid detergent compositions represent a preferred embodiment of the present invention, the synergistic compositions can also be embodied in other forms including solids such as granules, flakes, powders and other particulate materials. Such compositions can be prepared as lightly built, medium built or heavily built detergent compositions using the builder compounds described herein or equivalents thereof.

While the synergistic ternary detergent composition described herein finds special application in so-called light duty or lightly built detergent compositions, it can also be used in heavily built liquid and solid detergent compositions where it is desired to take advantage of the synergistic sudsing properties of mixtures described herein. An example of such acomposition contains about 17.5% of the novel ternary mixture of the present invention, about 50% of sodium tripolyphosphate, about 24% sodium sulfate and about 8.5% sodium silicate.

It has also been discovered that the synergistic sudsing properties of the novel ternary detergent composition described herein can be even further enhanced by adding to said composition from about 0.1% to about-0.3% by weight of a water hardness salt suchas magnesium sulfate, magnesium chloride, calcium sulfate and calcium chloride, or mixtures thereof. Other well known water hardness salts can also be used such as iron salts and the like. Preferably from about 0.15%- to 0.25% by weight of the inorganic salt should be present in the product. j

The suds building effect is more pronounced in relatively soft water but it is also effective in so-called medium hard water or hard water. A surprising aspect of this discovery is that the marked improvement in sudsing is not obtained-if theequivalentamount ofwater hardness salts is added to the water solution instead of being present in the detergent product.

It should be understood that the foregoing detailed description and specific examples, while indicating general and preferred embodiments of the present invention, are given by way of illustration only since-warious changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

What is claimed'is:

1. A synergistic ternary detergent composition consisting essentially of the following ingredients:

(I) from about 12% to about 60% of a Detergent I which is a mixture of from about 30% to about 70% of Component A, from about 20% to about 70% of Component B, and from about 2% to about 15%-of Component C, wherein:

(a) said Component A is a mixture of double-bond positional isomers of water soluble salts of alkene-l-sulfonic acids containing from about 12 to about 16 carbon atoms, said mixture of positional isomers including about 10% to about 25% of an alpha-beta unsaturated isomenabout 30% to about 70% of a beta-gamma unsaturated isomer, about 5% to about 25 of a gammadelta unsaturated isomer, and about 5% to about 10% of a delta-epsilon unsaturated isomer;

(b) said Component B is a mixture of water s-oluble salts of bifunctionally-substituted sulfurcontaining saturated aliphatic compounds containing from about 12 to about 16 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hydroxyl radical being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atom, at least of the hydroxyl radical substitutions being in the 3, 4 and 5 positions; and

(c) said Component C is a mixture comprising from 30-95% water-soluble salts of alkene di-' sulfonate containing from about 12 to about 16 carbon atoms, and from about 5%. to about 70% water-soluble salts of hydroxy disulfonates containing from about 12 to about 16 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds having-a sulfonate radicabattached to,'a terminal carbon, a second sulfonategroup attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group; (II) from about 6% to about 50% of Detergent II which is an alkali metal sulfuric acid ester of an alkyl ethoxylate containing from about to about "-14 carbon atoms in the alkyl portion, and from 1 to about 5 moles of ethylene oxide; and (III) from about to about 74% of Detergent III which is a zwitterionic quaternary ammonium compound selected from the group consisting of com: pounds having the formula RE; i I

R3 Z I. wherein R is an alkyl radical containing from about 12 to about 14 carbon atoms, R and R are each members selected from the group consisting of methyl, ethyl and hydroxyethyl, R is an alkylene radical having from 1 to about 3 carbon atoms, and Z is a member selected from the group consisting of hydrogen and hydroxyl; and compounds having the formula RiI I-oH2o 0 0- lie wherein R is an alkyl radical containing from about 12 to about 14 carbon atoms and R and R are each members selected from the group consisting of methyl, ethyl and hydroxy ethyl; wherein the combined weightratio of Detergent I plus Detergent II to Detergent III is within the range of from about 1:3 to about 6:1 and wherein the ratio, by weight, of Detergent I to Detergent II is from about 10:1 to about 1:4.

2. The synergistic ternary detergent composition of claim 1 wherein Detergents I, II, and III are present in the following percentages: from about 18% to about 36% of Detergent I; from about 10% to about 36% of Detergent II; and from about 28% to about, 54% of Detergent III, wherein the combined weight ratio of Detergent I plus Detergent II to Detergent III is within the range of from about 1:1 to about 2.521 and wherein the ratio, by weight, of Detergent I to Detergent II is from about 6:1 to about 1:2.

3. A high-sudsing light-duty liquid detergent composition consisting essentially of from about 10% to about 50% by Weight of the synergistic ternary mixture of claim 1 and from about 50% to about 90% water.

4. A high-sudsing light-duty liquid detergent composition comprising essentially of from about to about 40% by weight of the synergistic ternary mixture of claim 1 and from about 60% to about 80% water.

5. A high-sudsing light-duty liquid detergent composition comprising from about 10% to about 50% of a synergistic ternary mixture consisting essentially of the following ingredients:

Detergent I: from about 12% to about 60% of a C -based Detergent I which is a mixture of from about 30% to about 70% of Component A, from about 20% to about 70% of Component B, and from about 2% to about 15% of Component C, wherein:

(a) said Component A is a mixture of doublebond positional isomers of water soluble salts of alkene-l-sulfonic acids containing 14 carbon atoms, said mixture of positional isomers including about 10% to about of an alpha-beta unsaturated isomer, about to about 70% of a beta-gamma unsaturated isomer, about 5% to about 25% of a gamma-delta unsaturated isomer, and about 5% to about 10% of a deltaepsilon unsaturated isomer;

(b) said Component B is a mixture of water soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing 14 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hydroxyl radical being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atom; and

(c) said Component C is a mixture comprising from 3095% water-soluble salts of alkene disulfonate containing 14 carbon atoms, and from about 5% to about 70% water-soluble salts of hydroxy disulfonates containing 14 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group;

Detergent II: from about 6% to about 50% of an alkali metal salt of the sulfuric ester of the tri ethylene oxide) condensate of coconut fatty alcohols; and

Detergent III: from about 15 to about 74% of 3 (N,N-dimethyl-N-alkylammonio) 2 hydroxypropane-l-sulfonate, the alkyl group being derived from the middle-cut of coconut fatty alcohol, wherein the combin ed weight ratio of Deteregnt I plus Detergent II to Detergent III is within the range of from about 1:3 to about 6: 1, and wherein the ratio, by weight, of Detergent I to Detergent II is from about 10:1 to about 1:4; and'50% to water.

6. A high-sudsing light-duty liquid detergent composition according to claim 5, containing from about 20% to about 40% of the synergistic ternary mixture.

7, A high-sudsing light-duty liquid detergent composition according to claim 5 wherein the combined weight ratio of Detergent I plus Detergent II to Detergent III is within the range of from about 1:1 to about 25:1 and wherein the ratio, by weight, of Detergent I to Detergent II is from about 6:1 to about 1:2.

8. A synergistic ternary detergent composition according to claim 1 which also contains from about 0.1% to about 0.3% by weight of a water hardness salt selected from the group consisting of magnesium sulfate, magnesium chloride, calcium sulfate and calcium chloride.

9. A synergistic ternary detergent composition according to claim 8, wherein the Water hardness salt is present at a percentage of from about 0.15% to about 0.25% by weight.

References Cited UNITED STATES PATENTS 2,061,617 11/1936 Downing et al. 2,061,618 11/19-36 Downing et al. 2,061,620 Il/ 1936 Downing et al. 2,477,383 7/1949 Lewis. 3,072,618 1/1963 Turbak.

(Other references on following page) 21 FOREIGN PATENTS 651,783 8/1964 Belgium.

OTHER REFERENCES Alpha-Olefine in the surfactant Industry, J. Amer. Oil Chem. Society November 1963T. H. Liddicoet; 631- 636.

Aikene Sulfonates Made by New Method-Chemical and Engineering News Apr. 15, 1963, R. F. Turbak, pp. 96-98.

The Reactions of Sulfur Trioxido and of Its Adducts with Organic Compounds, Chemical Review 62, #6, December 1962, pp. 549-589.

Chem. Ber., 97, #10, 2903-13 October Molecular Aliphatic Sulfonic Acids. I. 2-HydroXy-1-n-alkanesulfonic Acids, F. Puschel and Claus Kaiser.

Chem. Ber. 97, #10, 2916-25 October 1964, Higher Molecular Aliphatic Sulfonic Acids. II 3-Hydroxy-1-n Alkanesulfonic Acids and Their Inner Esters (1,3-Sultones), F. Puschel and Claus Kaiser.

Chem. Ber. 97, #10, 2926-33 October 1964, Higher Molecular Unsaturated Sulfonic Acids and the Hydrolysis of 1,3-Alkanesu1tones, F. Puschel and Claus Kaiser.

Chem. Ber. 98, 735-742 1965, Higher Molecular Aliphatic Sulfonic Acids. IV. Sulfonation of Unbranched Alpha-Olefins with S0 F. Puschel and Claus Kaiser.

LEON D. ROSDOL, Primary Examiner.

1964, Higher 15 S. E. DARDEN, Assistant Examiner.

Claims (1)

1. A SYNERGISTIC TERNARY DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF THE FOLLOWING INGREDIENTS: (I) FROM ABOUT 12% TO ABOUT 60% OF A DETERGENT I WHICH IS A MIXTURE OF FROM ABOUT 30% TO ABOUT 70% OF COMPONENT A, FROM ABOUT 20% TO ABOUT 70% OF COMPONENT B, AND FROM ABOUT 2% TO ABOUT 15% OF COMPONENT C, WHEREIN: (A) SAID COMPONENT A IS A MIXTURE OF DOUBLE-BOND POSITIONAL ISOMERS OF WATER SOLUBLE SALTS OF ALKENE-1-SULFONIC ACIDS CONTAINING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS, SAID MIXTURE OF POSITIONAL ISOMERS INCLUDING ABOUT 10% TO ABOUT 25% OF AN ALPHA-BETA UNSATURATED ISOMER, ABOUT 30% TO ABOUT 70% OF A BETA-GAMMA UNSATURATED ISOMER, ABOUT 5% TO ABOUT 25% OF A GAMMADELTA UNSATURATED ISOMER, AND ABOUT 5% TO ABOUT 10% OF A DELTA-EPSILON UNSATURATED ISOMER; (B) SAID COMPONENT B IS A MIXTURE OF WATER SOLUBLE SALTS OF BIFUNCTIONALLY-SUBSTITUTED SULFURCONTAINING SATURATED ALIPHATIC COMPOUNDS CONTAINING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS, THE FUNCTIONAL UNITES BEING HYDROXY AND SULFONATE RADICALS WITH THE SULFONATE RADICAL ALWAYS BEING ON THE TERMINAL CARBON AND THE HYDROXYL RADICAL BEING ATTACHED TO A CARBON ATOM AT LEAST TWO CARBON ATOMS REMOVED FROM THE TEMRINAL CARBON ATOM, AT LEAST 90% OF THE HYDROXY RADICAL SUBSTITUTIONS BEING IN THE 3, 4 AND 5 POSITIONS; AND (C) SAID COMPONENT C IS A MIXTURE COMPRISING FROM 30-95% WATER-SOLUBL SALTS OF ALKENE DISULFONATE CONTAINING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS, AND FROM ABOUT 5% TO ABOUT 70% WATER-SOLUBLE SALTS OF HYDROXY DISFULFONATES CONTAINING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS, SAID ALKENE DISULFAONTES CONTAINING A SULFONATE GROUP ATTACHD TO A TERMINAL CARBON ATOM AND A SECOND SULFONATE GROUP ATTACHED TO AN INTERNAL CARBON ATOM NOT MORE THAN ABOUT SIX CARBON ATOMS REMOVED FROM SAID TERMINAL CARBON ATOM, THE ALKENE DOUBLE BOND BEING DISTRIBUTED BETWEEN THE TERMINAL CARBON ATOMS AND ABOUT THE SEVENTH CARBON ATOM, SAID HYDROXY DISULFONATES BEING SATURATED ALIPHATIC COMPOUNDS HAVING A SULFONATE RADICAL ATTACHED TO A TERMINAL CARBON, A SECOND SULFONATE GROUP ATTACHED TO AN INTERNAL CARBON ATOM NOT MORE THAN ABOUT SIX CARBON ATOMS REMOVED FROM SAID TERMINAL CARBON ATOM, AND A HYDROXY GROUP ATTACHED TO A CARBON ATOM WHICH IS NOT MORE THAN ABOUT FOUR CARBON ATOMS REMOVED FROM THE SITE OF ATTACHMENT OF SAID SECOND SULFONATE GROUP; (II) FROM ABOUT 6% TO ABOUT 50% OF DETERGENT II WHICH IS AN ALKALI METAL SULFURIC ACID ESTER OF AN ALKYL ETHOXYLATE CONTAINING FROM ABOUT 10 TO ABOUT 14 CARBON ATOMS IN THE ALKYL PORTION, AND FROM 1 TO ABOUT 5 MOLES OF EHTYLENE OXIDE; AND (III) FROM ABOUT 15% TO ABOUT 74% OF DETERGENT III WHICH IS A ZWITTERIONIC AUATERNARY AMMONIUM COMPOUND SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS HAVING THE FORMULA

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