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Publication numberUS3609090 A
Publication typeGrant
Publication dateSep 28, 1971
Filing dateNov 29, 1968
Priority dateNov 29, 1968
Also published asDE1959103A1, US3627822
Publication numberUS 3609090 A, US 3609090A, US-A-3609090, US3609090 A, US3609090A
InventorsBjorn Sundby, Harold Eugene Wixon
Original AssigneeColgate Palmolive Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Built detergent compositions containing hydroxy ether sulfonates
US 3609090 A
Abstract  available in
Images(9)
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Claims  available in
Description  (OCR text may contain errors)

A, United Stores atent [72] Inventors Bjorn Sundby Highland Park; Harold Eugene Wixon, New Brunswick, both of NJ. [21] Appl. No. 780,172 [22] Filed Nov. 29, 1968 [45] Patented Sept. 28, 1971 [73] Assignee Colgate-Palmolive Company New York, N.Y.

[54] BUILT DETERGENT COMPOSITIONS CONTAINING l-IYDROXY ETl-IER SULFONATES l 1 Claims, No Drawings 52 U.S. Cl 252/138, 252/8.7, 252/121, 252/137, 252/152, 252/161 [51] Int. Cl C lld 3/065, C1 1d 1/12 [50] Field of Search 252/121, 138,137,161,152, 8.7; 260/400, 513

[56] References Cited UNITED STATES PATENTS 2,427,577 9/1947 Smith 260/513 3,082,249 3/1963 Gaertner 260/513 3,267,040 8/1966 Bright 252/161 FOREIGN PATENTS 1,223,831

9/1966 Germany I Primary Examiner-Leon D. Rosdol Assistant Examiner-P. E. Willis Auorneys- Herbert S. Sylvester, Murray M. Grill, Norman Blumenkopf, Ronald S. Cornell, Thomas J Corum and Robert L. Stone ABSTRACT: A detergent composition comprising a comrw lnaymm formula:

(1) R. is a straight or branched higher alkyl group of Ct; to C and preferably Cw to C (2) R is a straight or branched alkyl of C to C and preferably C to C6;

(3) R3 to R1 are, independently, hydrogen or straight or branched alkyl of C to C and preferably hydrogen or lower alkyl of C to C (4) Z is oxygen (O) or sulfur (S);

(5 r and y have the values 0 to 1 and x+y= 1; and

(6) M is a cation such as hydrogen, alkali metal, ammonium, substituted ammonium or amine and preferably a water-solubilizing, salt-forming group. The hydroxy oxa (or thia) s u lfonates of the detergent composition provide both detergency and fabric softening characteristics and are hereinafter referred to generally as hydroxy ether sulfonates.

LUILT DETERGENT COMPOSITIONS CONTAINING HYDROXY ETI-IER SULFONATES The present invention is directed to novel detergent compositions, and more particularly, to novel detergent compositions based upon hydroxy ether sulfonates and water-soluble alkaline detergency builder salts.

In recent years, many detergent compositions have been formulated based upon linear alkyl benzene sulfonates, compounds thought to possess the best detergency characteristics. While such anionic detergents do possess excellent detergency characteristics, the use of linear alkyl benzene sulfonates and other anionic detergents based upon the alkyl aryl sulfonate has certain distinct shortcomings.

Since the alkyl aryl sulfonates or linear alkyl benzene sulfonates do not possess any fabric-softening characteristics, it is necessary to employ an additional fabric softener when employing such anionic detergents. Since however, the best fabric softeners produced to date are of the cationic quaternary ammonium type, such fabric softeners cannot be formulated in the same detergent composition with the anionic detergent. Thus, the conjoint employment of the anionic detergent and the cationic fabric softener is precluded since such fabric softeners and detergents complex and precipitate when employed conjointly thereby eliminating the functional characteristics of each of the materials. Accordingly, it has been found necessary to employ the quaternary ammonium fabric softener in the the rinse cycle of the fabric-washing process so that no contact between the anionic detergent and the cationic fabric softener will occur. This of course provides a great inconvenience in textile washing since it necessitates the addition of active ingredients at two separate points in the washing cycle.

Additionally, conventional anionic detergents based upon linear alkyl benzene sulfonates or alkyl aryl sulfonates in general possess the undesirable characteristics of phase incompatibility with various water-soluble alkaline detergent builders in aqueous systems. Thus, the anionic detergents are incompatible with various phosphate builders generally employed in detergent compositions thereby eliminating the all purpose functionality of the detergents. Accordingly, a clear single-phase liquid detergent composition cannot be prepared from the conventional phosphate builders and the linear alkyl benzene sulfonate detergents since a separation of phases usually results.

Accordingly, it has long been the desire of the detergent industry to develop a detergent composition possessing detergency and fabric-softening characteristics and compatibility with conventional water-soluble alkaline detergency builder salts.

It has now been discovered in accordance with the present invention that detergent compositions comprising certain hydroxy ether sulfonates in conjunction with water-soluble alkaline detergency builder salts possess all of the characteristics desired. Thus, in this respect it has been discovered that the active hydroxy ether sulfonate possesses not only exceptional detergency characteristics, but also possesses fabricsoftening characteristics and is completely compatible with conventional water-soluble alkaline detergency builder salts. Thus, the combination of the present invention comprising the hydroxy ether sulfonates and the conventional water-soluble alkaline detergency builder salts can be produced both as a homogeneous single-phase liquid detergent composition or can be conveniently prepared in the form of bars, flakes, granular r tableted granular compositions.

Accordingly, it is a principal object of the present invention to provide novel detergent compositions which eliminate the inherent deficiencies of previously employed compositions.

A further object of the present invention is to provide novel detergency compositions wherein the detergent component thereof possesses, in addition to detergency characteristics, fabric-softening characteristics, and is completely compatible with conventional water-soluble alkaline detergency builder salts.

A still further object of the present invention is to provide a novel detergent composition comprising certain detergents and fabric-softening hydroxy ether sulfonates in combination with water-soluble alkaline detergency builder salts. 5 Still further objects and advantages of the novel detergent composition of the present invention will become more apparent from the following more detailed description thereof.

In accordance with the present invention, it has now been discovered that certain hydroxy ether sulfonates possess the unusual characteristics of excellent detergency and fabric-softening ability in addition to complete compatibility with water-soluble alkaline detergency builder saltsconventionally employed in detergent compositions. Accordingly, the present invention is directed to such detergent compositions based upon hydroxy ether sulfonates and water-soluble alkaline detergency builder salts.

THE HYDROXY ETHER SULFONATE COMPONENT wherein:

l. R, is straight or branched higher alkyl group of C to C and preferably C, to C 2. R is a straight or branched alkyl of C to C and preferably C to C 3. R to R-, are, independently, hydrogen or straight or branched alkyl of C, to C,,,, and preferably hydrogen or lower alkyl of C, to C 4. Z is oxygen (O) or sulfur (S);

5. x and y have the values 0 to l and x+y=l and 6. M is a cation such as hydrogen alkali metal, ammonium,

substituted ammonium or amine and preferably a watersolubilizing, salt-forming group. While the sodium salts of the hydroxy ether sulfonates of the present invention are preferred, it is, of course, possible to advantageously employ any water-solubilizing cation e.g. other alkali metals such as potassium or lithium. Additionally, ammonium and amine salts e.g., trialkanolamine salts such as triethanolamine can be advantageously employed with exceptional results.

The novel hydroxy ether sulfonates of the present invention are prepared by reacting an epoxy alkane with an unsaturated aliphatic alcohol with subsequent sulfonation of the reaction product. The epoxy alkane reactants that are useful in the preparation of the hydroxy ether sulfonates of the present invention can be any epoxy alkane having a terminal group i.e., an epoxy alkane having the structure:

n-octyl iso-octyl n-nonyl iso-nonyl n-decyl n-dodecyl tert-dodecyl 2-propylheptyl S-ethylnonyl 2-butyloctyl n-undecyl n-tridecyl n-tetradecyl n-pentadecyl tert-octadecyl 2,6,8 -trimethylnonyl 7 -ethyl-2 -methy]-4 -undecyl n-hexadecyl n-octadecyl eicosyl docosyl tricosyl pentacosyl triacontyl etc.

The alkyl radicals may also include unsaturated alkyl radicals such as hexaryl, oleoyl, dodecenyl, hexadecenyl, and the like.

Illustrative examples of the epoxy alkanes which can be employed as reactants in the process of the present invention to produce the novel hydroxy ether sulfonates of the present invention include:

1,2 epoxyhexane 1,2 epoxyoctane 1,2 epoxydecane ,2 epoxyundecane 1,2 epoxydodecane 1,2 epoxytridecane L2 epoxytetradecane l,2 epoxypentadecane 1,2 epoxyhexadecane 1,2 epoxyoctadecane 7 -ethyl-2-mehtyll ,2-epoxyundecane 2,6,8-trimethyll ,2-epoxynonane l ,l,2-trimethyl-1,2-epoxy decane l.l-dimethyl-2-methyll ,2-epoxytetradecane l,l-diethyl epoxy undecane l, ldiethyl epoxy decane l,l-diisopropyl epoxy octane etc.

Exemplary hydroxy ether sulfonates in accordance with the present invention include:

6-hydroxy-4-oxahexadecyl sodium sulfonate 6-hydroxy-4-oxaheptadecyl sodium sulfonate 6-hydroxy-4-oxaoctadecyl sodium sulfonate 6-hydroxy-4-oxaeicosyl sodium sulfonate 6-hydroxy-4-oxadocosyl sodium sulfonate 6-hydroxy-8 -methyl-l2-ethyl-4-oxapentadecyl sodium sulfonate 6-hydroxy-7,7-dimethyl-4-oxahexadecyl sodium sulfate 6hydroxy-4 -oxahexadecyl potassium sulfonate 6-hydroxy-4-oxanonoadecyl potassium sulfonate 6-hydroxy-4-oxauncosyl potassium sulfonate 6-hydroxy-8 -methyl-l2-ethyl-4-oxapentadecyl potassium sulfonate 6-hydroxy-7,7-dimethyl-4-oxahexadecyl fonate 6-hydroxy-4-oxatetracosyl potassium sulfonate 6-hydroxy-4-oxahexadecyl lithium sulfonate 6-hydroxy-4-oxanonadecyl lithium sulfonate 6-hydroxy-4-oxaheptadecyl ammonium sulfonate 6-hydroxy-4-oxadocosyl ammonium sulfonate 6-hydroxy-8 methyl-l2-ethyl-4-oxapentadecyl ammonium sulfonate triethanol amine salt of 6-hydr0xy-4-oxahexadecyl sulfonic acid potassium sultriethanol amine salt of 6-hydroxy-4-oxaeicosyl sulfonic acid 8-hydroxy-6-oxahexadecyl sodium sulfonate 8-hydroxy-6oxaoctadecyl sodium sulfonate 8-hydroxy-6-oxaeicosyl sodium sulfonate 8-hydroxy-6'oxadocosyl sodium sulfonate 8-hydroxy-8 methyl-l2-ethyl-6-oxapentadecyl sodium suifonate 8-hydroxy-l l,l l,

fonate 8-hydroxy-6-oxaheptadecyl potassium sulfonate 8-hydroxy-6-oxanonadecyl potassium sulfonate 8-hydroxy-6-oxaeicosyl potassium sulfonate 8-hydroxy-6-oxauncosyl potassium sulfonate 8-hydroxy-l l,l 1-dimethyl-6-oxahexadecyl potassium sulfonate 8-hydroxy-6-oxatetracosyl potassium sulfonate 8-hydroxy-6-oxahexadecyl lithium sulfonate 8-hydroxy-6-oxadocosyl lithium sulfonate 8-hydroxy-6-oxahexadecyl ammonium sulfonate 8-hydroxy-6-oxadocosyl ammonium sulfonate B-hydroxy-S methyl-l2-cthyl-6-oxapentadecyl ammonium sulfonate triethanol amine salt of 8-hydroxy-6-oxahexadecyl sulfonic acid triethanol amine salt of S-hydroxy--oxaelcosyl sulfonic acid triethanol amine salt of 8-hydroxy-9,9-dimethyl-6-oxahexadecyl sulfonic acid 7-hydroxy-5-oxahexadecyl sodium sulfonate 7-hydroxy-5-oxadocosyl sodium sulfonate 7-hydroxy-9,9-dimethyl-5-oxahexadecyl sodium sulfonate 7-hydroxy-5-oxaoctadecyl potassium sulfonate 7-hydroxy-5-oxadocosyl potassium sulfonate 7-hydroxy-9,9-dimethyl-5-oxahexadecyl potassium fonate 7-hydroxy-5-oxanonadecyl lithium sulfonate 7-hydroxy-8 methyl-1Z-ethyl-S-oxapentadecyl ammonium sulfonate triethanol amine salt of 7-hydroxy-7,7-dimethyl-5-oxahexadecyl sulfonic acid l0-hydroxy-8-oxahexadecyl sodium sulfonate lO-hydroxy-S-oxaoctadecyl sodium sulfonate lO-hydroxy-S-oxadocosyl sodium sulfonate lO-hydroxy-7,7-dimethyl-8-oxahexadecyl sodium sulfonate dimethyl-6-oxahexadecyl sodium sulsullO-hydroxy-S-oxahexadecyl potassium sulfonate l0- hydroxy-8-oxadocosyl potassium sulfonate 10-hydroxy-7,7-dimethyl-8-oxahexadecyl potassium sulsulsul-

6-isopropyl-6-hydroxyisopropylidene-S-oxaoctadecyl potassium sulfonate 6-isopropyl-S-hydroxyisopropylidene-5-oxahexadecyl lithium sulfonate 6-hydroxy-S-methyl-4-oxaeicosyl sodium sulfonate 6-hydroxy-S-methyl-4-oxaoctadecyl potassium sulfonate 6-hydroxy-5-methyl-4-oxahexadecyl lithium sulfonate 6-hydroxy-5-methyl-4-oxahexadecyl ammonium sulfonate 6-hydroxy-5-ethyl-4-oxahexadecyl sodium sulfonate -hydroxy-5-ethyl-4-oxahexadecyl lithium sulfonate 6-hydroxy-5-ethyl-8 -methyl-l2-ethyl-4-oxapentadecyl ammonium sulfonate 7-hydroxy-6-isopropyl-S-oxaeicosyl sodium sulfonate 7-hydroxy--isopropyl-S-oxahexadecyl lithium sulfonate triethanol amine salt of 7-hydroxy-6-isopropyl-9,9-

dimethyl-S-oxahexadecyl sulfonic acid 8-hydroxy-7-isopropyl. ll-methyl-6-oxahexadecyl sodium sulfonate 8-hydroxy-7-isopropyl, l l-methyl-9,9-dimethyl-6-oxahexadecyl sodium sulfonate 8-hydroxy-7-isopropyl, ll-methyl-fi-oxadocosyl potassium sulfonate 8-hydroxy-7-isopropyl, l l-methyl-6-oxahexadecyl ammonium sulfonate l-hydroxy-9-t-butyl-8-oxahexadecyl sodium sulfonate l0-hydroxy-9-t-butyl-7,7-dimethyl-8-oxahexadecyl sodium sulfonate lO-hydroxy-9-t-butyl 8-oxahexadecyl lithium sulfonate l0-hydroxy-9-t-butyl-8-oxahexadecyl ammonium sulfonate (B) thia dirivatives (1) wherein y=l and x=0 6-hydroxy-4-thiahexadecyl sodium sulfonate 6-hydroxy-4-thiauncosyl sodium sulfonate 6-hydroxy-4-thiaeicosyl potassium sulfonate 6-hydroxy-4-thiadocosyl lithium sulfonate 6-hydroxy-4-thiadocosyl ammonium sulfonate triethanol amine salt of 6-hydroxy-7,7-dimethyl-4-thiahexadecyl sulfonic acid 8-hydroxy-6-thiaoctadecyl sodium sulfonate 8-hydroxy-6-thianonadecyl potassium sulfonate 8-hydroxy-6-thiaheptadecyl ammonium sulfonate 7-hydroxy-5-thiaoctadecyl sodium sulfonate lO-hydroxy-8-thiaoctadecyl sodium sulfonate lO-hydroxy-8-thianonadecyl lithium sulfonate l l-hydroxy-9-thiahexadecyl sodium sulfonate l l-hydroxy-9-thiahexadecyl lithium sulfonate lZ-hydroxyl O-thiadocosyl potassium sulfonate l-hydroxy-7,7-dimethyll 3-thiahexadecyl sodium fonate l5-hydroxy-8 methyl- 1 Z-ethyl-l 3-thiapentadecyl ammonium sulfonate (2) wherein y=0 and x=l 5-hydroxymethyl-S-thiaeicosyl sodium sulfonate 6-hydroxymethyl-5thiahexadecyl lithium sulfonate 7-hydroxymethyl-6-thiahexadecyl ammonium sulfonate 8-hydroxymethyl-7-thiahexadecyl sodium sulfonate 9-hydroxymethyl-8-thiaoctadecyl potassium sulfonate lO-hydroxymethyl-9-thiahexadecyl sodium sulfonate triethanol amine salt of l0-hydroxymethyl-7,7 -dimethyl-9- thiahexadecyl sulfonic acid 1 l-hydroxymethyl-lO-thiaoctadecyl potassium sulfonate 5-methyl, 5-hydroxymethyl-4-thiahexadecyl sodium sulfonate 6-ethyl, 6-hydroxymethyl-S-thiaeicosyl sodium sulfonate 8-isopropyl, 8-hydroxymethyl-7-thiahexadecyl lithium sulfonate lO-t-butyll O-hydroxymethyl-9-thiaeicosyl fonate 5,( beta-hydroxyethyl )-4-thiahexadecyl sodium sulfonate sulsodium sul- 6,(gamma-hydroxypropyl)-5-thiadecosyl potassium sulfonate 7,(delta-hydroxybutyl)-6-thiahexadecyl ammonium sulfonate 5-hydroxyisopropylidene-4-thiahexadecyl sodium sulfonate 7-(B-hydroxyethylidene)-6-thiaeicosyl sodium sulfonate DETERGENCY BUILDER SALTS In addition to the active detergent and fabric-softening hydroxy ether sulfonate, the novel detergent compositions of the present invention contain one or more water-soluble detergency builder salts either of the organic or the inorganic type and preferably alkaline salts.

Examples of water-soluble inorganic detergency builder salts are alkali metal carbonates, phosphates, polyphosphates, sulfates, and silicates, etc. Specific examples of such salts are sodium, potassium and lithium tripolyphosphates, carbonates, pyrophosphates, orthophosphates and hexamethaphosphates, sodium, potassium and lithium sulfates and sodium, potassium O and lithium silicates. Examples of organic alkaline detergency builder salts are (l) alkali metal aminopolycarboxylates {e.g., sodium and potassium ethylenediaminetetraacetates, N-(Z- hydroxyethyl)-ethyl-enediarninetriacetates, nitrilo triacetates, and N-(2-hydroxyethyl)-nitriol diacetates]; (2) alkali metal salts of phytic acid (e.g., sodium and potassium phytates-see US Pat. No. 2,739,942); (3) water-soluble salts of ethane-lhydroxyl l-diphosphonate (e.g., the trisodium and tripotassium salts-see U.S. Pat. No. 3,159,581); (4) water-soluble salts of methylene diphosphonic acid (e.g., trisodium and tripotassium methylene diphosphonate and the other salts described in U.S. Pat. No. 2,2l 3,030); (5) water-soluble salts of substituted methylene diphosphonic acids (e.g., trisodium and tripotassium ethylidene, isopropylidene, benxylmethylidene, and halomethylidene diphosphonates); (6) water-soluble salts of polycarboxylate polymers and copolymers (e.g., homopolymers of itaconic acid, aconitic acid; maleic acid; mesaconic acid; fumaric acid; methylene malonic acid; and citronic acid and copolymers thereof with other compatible copolymerizable monomers such as ethylene); and mixtures thereof.

DETERGENT COMPOSITION In the detergent compositions of the present invention the active hydroxy ether sulfonate is generally employed in an amount of from about 1 to about percent by weight of the total composition, while the water-soluble detergency builder salts comprise from about ID to about 99 percent by weight of the total composition. Preferably, the hydroxy ether sulfonate Comprises about 5 -50 percent by weight while the detergent builders comprise from 15-90 percent of the total composition. Generally, the ratio of the water-soluble detergency builder salts to the total detergent is in the range of 1:3 to 20:1.

The compositions of this invention may be formulated as liquids, solids, pastes, gels, etc. As liquids using water or the vehicle, the compositions are unexpectedly, characterized by unique clarity and homogeneity i.e. the compositions are single-phase systems.

The detergent compositions of this invention can contain any of the usual compatible adjuvants, diluents and additives including other detergents, for example, anionic nonionic, ampholytic, cationic or zwitterionic detergents; perfumes, antitarnishing agents, antiredeposition agents, bacteriostatic agents, dyes, fluorescers, suds builders, suds depressors, and

the like, without detracting from the advantageous properties of the composition.

Suitable anionic surface active agents include those surfaceactive or detergent compounds which contain an organic hydrophobic group and an anionic solubilizing group. Typical examples of anionic solubilizing groups are sulfonate, sulfate, carboxyiate, phosphonate and phosphate. Examples of suitable anionic detergents which fall within the scope of the invention include the soaps, such as the water-soluble salts of higher fatty acids or rosin acids, such as may be derived from fats, oils and waxes of animal, vegetable or marine origin, e.g. the sodium soaps of tallow, grease, coconut oil, tall oil and mixtures thereof; and the sulfated and sulfonated synthetic detergents, particularly those having about eight to 26, and preferably about 12-22, carbon atoms to the molecule.

As examples of suitable synthetic anionic detergents there may be cited the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from to 16 carbon atoms in the alkyl group in a straight or branched chain, e.g., the sodium salts of higher alkyl benzene sulfonates or of the higher alkyl toluene, xylene and phenol sulfonates; alkyl naphthalene sulfonate, ammonium diamyl naphthalene sulfonate, and sodium dinonyl naphthalene sulfonate. 1n one preferred type of composition there is used a linear alkyl benzene sulfonate having a high content of 3- (or higher) phenyl isomers and a correspondingly low content (well below 50 percent of 2- (or lower) phenyl isomers; in other terminology, the benzene ring is preferably attached in large part at the 3 or higher (e.g. 4, 5, 6 or 7) position of the alkyl group and the content of isomers in which the benzene ring is attached at the 2 or 1 position is correspondingly low. Particularly preferred materials are set forth in US. Pat. No. 3,320,174, May 16, 1967, OH. Rubinfeld.

The mixtures containing linear alkylbenzene sulfonates and the detergent compounds of this invention have unexpectedly good properties, particularly with respect to softening power. These mixtures are the invention of Harold Wixon.

Other anionic detergents are the olefin sulfonates, including long-chain alkene sulfonates, long-chain hydroxy-alkane sulfonates or mixtures of alkenesulfonates and hydroxyalkanesulfonates. These olefin sulfonate detergents may be prepared, in known manner, by the reaction of SO with long chain olefins (of 8-25, preferably 12-21 carbon atoms) of the formula RCH=CHR", where R is alkyl and R" is alkyl or hydrogen, to produce a mixture of sultones and alkenesulfonic acids, which mixture is then treated to convert the sultones to sulfonates. Examples of other sulfate or sulfonate detergents are paraffin sulfonates, such as the reaction products of alpha olefins and bisulfites (e.g. sodium bisulfite), e.g., primary paraffin sulfonates of about 10-20, preferably about 15-20, carbon atoms; sulfates or higher alcohols; salts of a-sulfofatty esters (e.g. of about 10-20 carbon atoms, such as methyl orsulfomyristate or a-sulfotallowate).

Examples of sulfates of higher alcohols are sodium lauryl sulfate, sodium tallow alcohol sulfate, Turkey Red Oil or other sulfated oils, or sulfates of monoor di-glycerides of fatty acids (e.g. stearic monoglyceride monosulfate), alkyl poly (ethenoxy) ether sulfates such as the sulfates of the condensation products of ethylene oxide and lauryl alcohol (usually having one to five ethenoxy groups per molecule); lauryl or other higher alkyl glyceryl ether sulfonates; aromatic poly (ethenoxy) ether sulfates such as the sulfates of the condensation products of ethylene oxide and nonyl phenol (usually having one to six oxyethylene groups per molecule).

The suitable anionic detergents include also the acyl sarcosinates (e.g. sodium lauroylsarcosinate) the acyl esters (e.g. oleic acid ester) of isethionates, and the acyl N-methyl taurides (e.g. potassium N-methyl lauroylor oleyl tauride).

The most highly preferred water soluble anionic detergent compounds are the ammonium and substituted ammonium (such as mono-, diand triethanolamine), alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts or the higher alkyl benzene sulfonates, olefin sulfonates, the higher alkyl sulfates, and the higher fatty acid monoglyceride sulfates. The particular salt will be suitably selected depending upon the particular formulation and the proportions therein.

Nonionic surface active agents include those surface active or detergent compounds which contain an organic hydrophobic group and a hydrophilic group which is a reaction product of solubilizing group such as carboxylate, hydroxyl, amide or amino with ethylene oxide or with the polyhydration product thereof, polyethylene glycol.

As examples of nonionic surface active agents which may be used there may be noted the condensation products of alkyl phenols with ethylene oxide, e.g., the reaction product of isooctyl phenol with about six to 30 ethylene oxide units; condensation products of alkyl thiophenols with Wm 15 ethylene oxide units; condensation products of higher fatty alcohols such as tridecyl alcohol with ethylene oxide; ethylene oxide addends of monoesters of hexahydric alcohols and inner ethers thereof such as sorbitan monolaurate, sorbitol monooleate and mannital monopalmitate, and the condensation products of polypropylene glycol with ethylene oxide. Other nonionics include amine oxides, e.g. lauryl dimethyl amine oxide; sulfoxides and the like.

Cationic surface-active agents may also be employed. Such agents are those surface active detergent compounds which contain an organic hydrophobic group and a cationic solubilizing group. Typical cationic solubilizing groups are amine and quaternary groups.

As examples of suitable synthetic cationic detergents there may be noted the diamines such as those of the type RNHC PLHN wherein R is an alkyl group of about 12 to 22 carbon atoms, such as N-2-aminoethyl stearyl amine and N-2- aminoethyl myristyl amine; amide-linked amines such as those of the type RCONl-IC I-LNH wherein R is an alkyl group of about nine to 20 carbon atoms, such as N-Z-amino ethylstearyl amide and N-amino ethyl myristyl amide; quaternary ammonium compounds wherein typically one of the groups linked to the nitrogen atom is an alkyl group of about 12 to 18 carbon atoms and three of the groups linked to the nitrogen atom are alkyl groups which contain one to three carbon atoms, including such one to three carbon alkyl groups bearing inert substituents, such as phenyl groups, and there is present an anion such as halogen, acetate, methosulfate, etc. Typical quaternary ammonium detergents are ethyl-dimethyl-stearyl ammonium chloride, benzyl-dimethyl-stearyl ammonium chloride, benxyl-dirnethyl-stearyl ammonium chloride, trimethyl stearyl ammonium chloride, trimethyl-cetyl ammonium bromide, dimethyl-ethyl dilauryl ammonium chloride, dimethyl-propylmyristyl ammonium chloride, and the corresponding methosulfates and acetates.

Examples of suitable amphoteric detergents are those containing both an anionic and a cationic group and a hydrophobic organic group, which is advantageously a higher aliphatic radical, e.g. of 10-20 carbon atoms. Among these are the N- long chain alkyl aminocarboxylic acids (e.g. of the formula the N-long chain alkyl iminodicarboxylic acids (e.g. of the formula RN(RCOOM) and the N-long chain alkyl betaines (e.g. ofthe formula where R is a long chain alkyl group, eg of about 10-20 carbons, R is a divalent radical joining the amino and carboxyl portions of an amino acid (e.g. an alkylene radical of l-4 carbon atoms), M is hydrogen or a salt-forming metal, R is a hydrogen or another monovalent substituent (e.g. methyl or other lower allryl), and R and R are monovalent substituents joined to the nitrogen by carbon-to-nitrogen bonds (e.g. methyl or other lower alkyl substituents). Examples of specific amphoteric detergents are N-alkyl-beta-aminopropionic acid; N-alkyl-beta-iminodipropionic acid, and N-alkyl, N,N- dimethyi glycine; the alkyl group may be, for example, that derived from coco fatty alcohol, lauryl alcohol, rnyristyl alcohol (or a lauryl-myristyl mixture), hydrogenated tallow alcohol, cetyl, stearyl, or blends of such alcohols. The substituted aminopropionic and iminodipropionic acids are often supplied in the sodium or other salt forms, which may likewise be used in the practice of this invention. Examples of other amphoteric detergents are the fatty imidazolines such as those made by reacting a long-chain fatty acid (e.g. of 10 to 20 carbon atoms) with diethylene triamine and monohalocarboxylic acids having two to six carbon atoms, e.g. l-coco-5-hydroxethyl-5-carboxylmethylimidazoline; betaines containing a sulfonic groups instead of the carboxylic group; betaines in which the longchain substituent is joined to the carboxylic group without an intervening nitrogen atom, e.g. inner salts of 2- trimethylamino fatty acids such as 2-trimethylaminolauric acid, and compounds of any of the previously mentioned types but in which the nitrogen atom is replaced by phosphorus.

While the detergent compositions of the present invention are excellent compositions for all types of cleaning operations, they are extremely effective for the cleaning of textiles in a conventional laundry or washing machine. Thus, the detergent compositions of the present invention can be effectively used for laundering fabrics in water having a temperature from about 60 F. to about 212 F., the detergent composition of the present invention exhibiting unusually effective detergency and fabric softening characteristics in both cold and hot water. Preferably, the step of the present invention is followed by rinsing and drying of the fabric. The detergent composition concentration in the wash solution should range from about 0.05 percent to about 0.5 percent by total weight, and the detergent composition should be added so as to provide an effective detergent and softening amount of the hydroxy ether sulfonate component of at least 0.002 percent.

In washing fabrics, the addition of the fabrics and the detergent composition can be conducted in any suitable conventional manner. Thus, for example the fabrics can be added to the container or washer either before or after the washing solution is added. The fabrics are then agitated in the detergent solution for varied periods of time, a wash cycle of from 8 to 15 minutes being generally used in the washing cycle of an automatic agitator type washer. As stated above, following the washing of the fabrics the detergent composition is drained off and the fabrics are rinsed in substantially pure water. Here again, as a matter of choice, the fabrics can be rinsed as many times as desired. After rinsing of the fabrics, they are dried, first by spinning, and then by contact with the air as in a conventional hanging of the fabrics on a clothesline or in an automatic dryer type system.

In the preparation of the novel detergent compositions of the present invention, generally, the organic detergent and fabric-softening component as well as the builders and any minor ingredients are incorporated into the composition prior to its conversion into the final product form e.g. detergent granuied, flakes, bar etc. However, the individual components of the novel detergent composition of the present invention can be added in the form of particles or directly as a liquid to produce a liquid detergent composition.

A particularly preferred detergent composition of the present invention comprises the hydroxy ether sulfonate detergent and softener component in combination with sodium xylene sulfonate and potassium pyrophosphate in a clear, aqueous single-phase liquid form. ln such a liquid detergent composition the water generally comprises from about 30 to about 70 percent of the total composition while the hydroxy ether sulfonate comprises from about 5 to 15 percent by weight; the sodium xylene sulfonate from 5 to 15 percent by weight and the potassium pyrophosphate or similar alkaline detergency builder salt from about 10 to 30 percent by weight.

While the above description of the present invention has been described primarily with respect to the combination of the hydroxy ether sulfonate detergent and fabric softening component with a water soluble alkaline detergency builder salt, it is important to note that where the washing of very fine fabrics is to be encountered, the detergency builder salts can be eliminated from the composition. Thus, with respect to the preferred composition noted above a composition adapted for the washing of fine fabrics can comprise the hydroxy ether sulfonates with or without sodium xylene sulfonate in an aqueous, single phase system.

The following specific examples illustrate various embodiments of the present invention. it is to be understood however, that such examples are presented for purposes of illustration only and the present invention is in no way to be deemed as limited thereby.

EXAMPLE I An experiment is conducted in order to demonstrate the compatibility of the hydroxy ether sulfonate detergent and fabric softener with water soluble alkaline detergency builder salts.

A composition comprising 15 percent by weight of 6- hydroxy-4-oxaeicosyl sodium sulfonate, 35 percent sodium tripolyphosphate, and 50 percent sodium sulfate is prepared by mixing respectively 3.75 grams, 8.75 grams, and 12.50 grams of the individual components. 25 grams of a powdered composition is prepared.

This powdered composition comprising the hydroxy ether sulfonate, sodium tripolyphosphate and sodium sulfate is added to grams of water thereby preparing a total of 200 grams of solution. This solution is a clear single phase liquid at room temperature.

An attempt is made to prepare a clear single-phase liquid detergent composition employing a linear tridecyl benzene sulfonate detergent slurry in lieu of the hydroxy ether sulfonate above. A homogeneous single-phase liquid detergent can not be prepared but the composition produced is opaque with granular detergent particles which separate rapidly. Dilution of the composition to 500 grams with additional water does not change the composition and detergent particles still separate rapidly.

This therefore clearly shows the unusual and unexpected compatibility of the hydroxy ether sulfonate detergent and fabric softener with water-soluble alkaline detergency builder salts.

A further detergent composition in accordance with the present invention is prepared from the following components.

Component Percent By Weight fi-hydroxyJ-oxaeicesyl sodium sulfonate 10.0 potassium pyrophosphate solution, 60% 25.0 water 65.0

EXAMPLE ll The detergency of the compositions of the present invention compared with a conventional detergent composition is tested in a Spangler Soil (Sebum) detergency test in a tergotometer having normal reciprocating agitation. The test conditions employ three soiled swatches of fabric with 1000 milliliters of detergent solution, the detergent concentration being 0.15 perequivalent amount of linear dodecyl benzene sulfonate, a conventional anionic detergent, in lieu of the 6-hydroxy-4-oxaeicosyl sulfonate, sodium salt of the present invention. Here again, because of the incompatibility of the anionic detergent cent in all cases. 5 with the water-soluble alkaline detergency builder salts, the

The tests are run in both hard and soft water and both under System is Produced as p rate phases. c ld-wate d hop ater conditions A fabric softening test is conducted by washing a terry-cloth In all cases, the detergent composition contains 50 percent towel in 17 gallons of N43 p water at employing 140 sodium sulfates, 35 percent sodium tripolyphosphate, and 15 grams 9 the liquid detergent P 1 on a Scale of f percert of the sulfonate detergent. Three tests are made em- 10 wherein 1 designates no Softening and 1 designates exploying a hydroxy ether sulfonate while a present run is made cellem Foftening, the composition of the p invention employing a linear tridecyl benzene sulfonate, a conventional P ?Y hydroxy ether sulfonate of example I in Conanionic detergent. JUIICUOI! with the alkaline detergency builder salts provides a After washing, rinsing and drying the amount of lipid so softness rat1ngof9, while the comparable system containing a remaining on the Swatches is determined this amount being conventional linear dodecyl benzene sulfonate detergent rates measured against the amount of soil on the swatches prior to washing Accordingly higher positive values indicate greater This test therefore indicates the exceptional fabric softening washing efficiency abrl|ty of the hydroxy ethersulfonate detergents employed in The detergent compositions embodied y the present inven 2 the built detergent compositions of the present invention. tion are prepared as in example i above by the mere addition EXAMPLE W of the three active components to an aqueous system, the compatibility of the components providing a clear single phase The follqwins are typical detergent compositions in liquid detergent composition. A dual-phase system is prepared cordance the P inventionin order to provide a liquid detergent composition comprising SOLID a linear tridecyl benzene sulfonate as the active detergent a component since, such anionic detergent is found to be incompatible with the alkaline detergency builder salts and thus a clear single phase solution can not be prepared. Accordingly, the control system is prepared by providing ggggzg 'ti z iz'f separate aqueous solutions of l) the linear tridecyl benzene Sodium fi z 08p a e 318 Fluumsccm sulfonate, xylene and water, and (2) sodium tripolyphosphate, dye 0.18 sodium xylene sulfonate, and water. Perfume The results of the detergent tests are shown in table 1 below:

TABLE I 6-hydroxy-4- 6-hydr0xy4- 6-hydroxy-4- Linear trioxahexadecyl oxaeicosyl oxadocosyl decyl benzene sulfonate, Na sulfonate, Na sulfonate, Na sulfonate, Na

70 F., NB tap water +17.6 +20.5 +19.6 +18.l 70 F., 300 p.p.m. water +11.2 +16. 0 +14 9 +9.5 120 F., NB tap water. +17.4 +20.2 +20.8 +20.1 120 F., 300 p.p.rn. Water +12. 8 +16. 1 +15.9 +11.4

The results above clearly show that the hydroxy ether sul- SOLID fonates of the present invention exhibit unusually good detergency in both hard and soft water under both hot and cold conditions. Accordingly, the compatible hydroxy ether sulmp n Percent fonate detergents and fabric softeners employed in the detergent compositions of the present invention not only possess v mxy -4- ducosyl sodium sulfonate 1 the desirable detergency and fabric-softening characteristics ll gg 3g 8 as well as the compatibility with water soluble alkaline detersodium silica, (Namsim: [.235] gency builder salts, but, in addition, possess detergency Brightener M characteristics substantially equal to or better than a conven- 2:12; tional anionic detergent. 1O

EXAMPLE Ill SOLID A novel detergent composition of the present invention is tested for softening ability against a conventional anionic build detergent system. The composition of the present inven- .60 Perm" tion employed in the softening test is as follows:

6-hydroxy-4-oxahexadecyl potassium sulfonate 30 o-h drox -4-oxueicos l sulfonate, sodium suit 10.01 l l f pymphosphaw Sotliuin x ylcnu sult'onztc. 40' Al solution 20.0% 0 Potassium pyrosphute, 1 Al solution 25.0% Sodium curhmmc m Witter 45.0;

mom i' M "IL od uvuuth llnlunct- The composition is prepared as in example 1 by blending the individual components and heating until a clear single SOLID phase liquid composition is formed. The clarity and homogeneity of the systems are maintained upon cooling to room temperature. The single-phase liquid composition has a Component Percent specific gravity of 1.19, a'pH of 9.9, and a viscosity of 20 cps.

A similar liquid composition is prepared by employing an 6-hydroxy-4-oxaoctadecyl lithium sulfonate Table -Zb riti nued Sodium sulfate 20.8 Tetrasodiurn pyrophosphate 50 Sodium toluene sulfonate 2.8 Fluorescent dye 0.6 Water l2 Miscellaneous Adjuvants Balance LIQUID Component Percent 6-hydroxy-4-oxanonadecyl potassium sulfonate 15 Sodium ethylcncdiamine tetracetate 13.6 Potassium phytate 3.8 Sodium silicate (Na,0:Si0,= 1:1.6) 2.4 Sodium carboxy methyl cellulose 0.5 Water Balance LIQUID Component Percent 6-hydroxy-4-oxaeicosyl ammonium sulfonate 22 Sodium nitrilotriacetate 17 Sodium silicate (Na,O:Si0,- l:l.6) 4.2 Sodium sulfate 6.7

Water 50 Miscellaneous Adjuvants Balance SOLID Component Percent 6 hydroxy-4-oxahexadccyl sodium sulfonate 6.4 Potassium ethylene diamine tctracetate 16.2 Sodium silicate M 0510 l:2.35) 10.0 CMC 0.5 Fluorescent dye 0.8 PVA 0.5

Perfume 0.6

Sodium sulfate 53,4 \Vater Balance In each case the detergent composition, whether solid or liquid, was found to have an exceptional fabric-softening ability and detergent characteristics.

EXAMPLE V sul- EXAMPLE VI Novel detergent compositions of the present invention were formulated as in Example IV employing as the hydroxy either sulfonate;

IS-hydroxyl 3-oxahexadecyl sodium sulfonate Shydroxy methyl-S-methyl l2-ethyl-4-oxapentadecylammonium sulfonate o-hydroxymethyl-5oxahexadecyl lithium sulfonate S-hydroxymethyl-T-oxahexadecyl sodium sulfonate 5- methyl-S-hydroxymethyl-4-oxadocosyl potassium sulfonate l-t-buty1-lO-(hydroxymethyl)-9-oxahexadecyl sodium sulfonate 5 6-gamma-hydroxypropyl-5-oxahexadecyl sodium sulfonate 7-( delta-hydroxybutyl )-6-oxahexadecyl sodium sulfonate 6-isopropyl-5-hydroxyisopropylidene In each case the detergent composition, whether solid or liquid, was found to have an exceptional fabric-softening abili- 10 ty and detergent characteristics.

EXAMPLE VII is J.

wherein:

1. R is a straight or branched higher alltyl group of C to 2. R is a straight or branded alkylene of C to C 3R to R are, independently, hydrogen. straight or branched alkyl of C to C 4. Z is oxygen or sulfur;

5. x and y have the values of 0 to l and x+y=l; and

6 when x equals 0 the depicted OH group is attached directly to C*;

7. M is a water-solubilizing salt-forming cation, and

B. a water soluble detergency builder salt the ratio of (A) to (B) ranging from 3:l to I120.

2. The detergent composition of claim I wherein R contains from about 10 to about 22 carbon atoms.

3. The detergent composition of claim I wherein R contains from three to six carbon atoms.

4. The detergent composition of claim 1 wherein the hydroxy ether suifonate is present in an amount of from about I to about 90 percent by weight.

5. The detergent composition of claim 4 wherein the hydroxy ether sulfonate is present in an amount from about 5 to about percent by weight.

6. The composition of claim 1 wherein the hydroxy ether sulfonate is 6-hydroxy-4-oxaeicosyl sodium sulfonate.

7. The composition of claim I wherein the builder is potassium pyrophosphate.

8. The detergent composition of claim 1 including a hydrotrope.

9. The composition of claim 8 wherein the hydrotrope is xylene sulfonate.

T ifle composition of dais /E the builder salt is potassium pyrophosphate.

11. The composition of claim 10 wherein the hydroxy ether sulfonate is -hydroxy-roxaeicosyl sodium sulfonate.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2427577 *Mar 1, 1945Sep 16, 1947Colgate Palmolive Peet CoProduction of ether sulphonates
US3082249 *May 13, 1958Mar 19, 1963Monsanto ChemicalsSodium 3-tridecyloxy-2-propanol-1-sulfonate
US3267040 *Mar 8, 1965Aug 16, 1966Lever Brothers LtdSynergistic combinations of alkane sulfonates and alkoxy hydroxy propane sulfonates
DE1223831B *May 18, 1965Sep 1, 1966Basf AgVerfahren zur Herstellung der Alkali- und Erdalkalisalze von in beta-Stellung durch eine AEthergruppe substituierten Alkansulfonsaeuren
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3950276 *May 22, 1972Apr 13, 1976Colgate-Palmolive CompanySulfonate detergent compositions
Classifications
U.S. Classification510/327, 510/324, 510/495, 510/325, 510/328, 510/357, 510/337, 510/359
International ClassificationC11D3/00, C11D1/00, C11D1/12, C07C33/025, C07C309/08, B01J8/00
Cooperative ClassificationB01J8/003, C11D1/12, C07C323/66, C11D3/001, C11D1/002, C07C309/10
European ClassificationC07C323/66, C07C309/10, B01J8/00F6, C11D1/12, C11D1/00B, C11D3/00B3