US3876563A

US3876563A - Liquid detergent compositions

Info

Publication number: US3876563A
Application number: US291508A
Authority: US
Inventors: Jerome H Collins
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1972-09-22
Filing date: 1972-09-22
Publication date: 1975-04-08
Anticipated expiration: 1992-04-08
Also published as: CA1012029A

Abstract

Concentrated heavy-duty liquid detergent compositions containing a mixture of a nonionic surfactant, a zwitterionic surfactant, an ethanolamine, and a solvent and being especially adapted to stain and soil removal from fabrics, either applied directly to such fabrics before washing or employed as detergent compositions especially effective under hard water conditions for conventional fabric laundering.

Description

United States Patent Collins 1 1 Apr. 8, 1975 LIQUID DETERGENT COMPOSITIONS FOREIGN PATENTS OR APPLICATIONS [75] Inventor: Jerome H. Collins, Cincinnati. Ohio 708 147 4/1965 Canada [73] Assignee: The Procter & Gamble Company, OTHER PUBLICATIONS Cincinnati, Ohio Defensive Publication T903009, Phosphorous Free Filed: p 1972 Cleaning Formulation, Kastra 9-1971.

[21] Appl. No.: 291,508

Primary Examiner-Mayer Weinblatt 52 us. c1. 252/545; 252/526; 252/546;

252/548; 252/D1G. 1 1511 1111.61 Clld 1/18; C11d 1/38;C11d 1/62; 1 1 ABSTRACT C] M 1/835 Concentrated heavy-duty liquid detergent composi- [58] held of Search 252/548- tions containing a mixture of a nonionic surfactant, a 252/526- zwitterionic surfactant, an ethanolamine, and a solvent and being especially adapted to stain and soil removal [56] References Cned from fabrics, either applied directly to such fabrics be- UNITED STATES PATENTS fore washing or employed as detergent compositions 3.537.993 11/1970 Coward 61111. 252/548 especially effective under hard Water Conditions for 3.557.002 11/1967 McCarty 252/D1G. 12 conventional fabric laundering. 3.634.266 1/1972 Theile et al..... 252/DIG. l2 3.663.445 5/1972 Augustin 252/117 9 Clams, N0 Drawmgs LIQU ID DETERGENT COMPOSITIONS BACKGROUND OF THE INVENTION The present invention relates to concentrated heavyduty liquid detergent compositions. Such compositions contain a nonionic surfactant component, a zwitterionic surfactant component, an ethanolamine component, and a solvent.

Heavy-duty liquid detergent compositions are well known in the art. Usually such compositions (see, for example, U.S. Pat. Nos. 2,908,651, 2,920,045, 3,272,753, 3,393,154, and Belgian Patent Nos. 613,165 and 665,532) contain a synthetic organic detergent component which is generally anionic, nonionic or mixed anionic-nonionic in nature; an inorganic builder salt; and a solvent usually water and/or alcohol. These compositions frequently contain a hydrotrope or solubilizing agent to permit the addition of sufficient quantities of detergent and builder salt to provide a reasonable volume usage/performance ratio. While such liquid detergent compositions have been found effective for some types of home laundering, the presence of inorganic builder salts in such compositions may be undesirable from an ecological standpoint if such compositions are employed on a broad scale.

Several attempts have been made to formulate builder-free, hydrotrope-free liquid detergent compositions. Most of these formulations employ mixtures of anionic and nonionic surfactants as the active ingredients. (For example, see U.S. Pat. Nos. 2,543,744; 2,875,153; and 3,528,925 and the copending U.S. Pat. application of Collins, Ser. No. 222,363, filed Jan. 31, 1972.) While detergent compositions of this type are effective for certain types of washing operations, the presence of an ionic surfactant species therein renders most compositions of this type relatively susceptible to performance variation when utilized in hard water.

Attempts have been made to formulate detergent compositions (not necessarily liquid) containing no anionic surfactant species. Such systems have been disclosed, for example, in U.S. Pat. Nos. 2,702,279 and 2,999,069; British Pat. Nos. 1,021,017, 1,092,149 and 1,115,300 and Belgian Pat. No. 774,607, all of which disclose certain zwitterionic compounds in combination with certain nonionic surfactants. While these compositions are likewise effective to some degree for fabric laundering operations, none of them are hydrotrope-free, builder-free liquid detergent compositions especially adapted for use in hard water as both stain removal and heavy-duty laundering agents.

Accordingly, it is an object of the present invention to provide concentrated heavy-duty liquid detergent compositions especially adapted for use in hard water laundering solutions.

It is a further object of the instant invention to provide such heavy-duty liquid detergent compositions which are free of inorganic builders and conventional hydrotropes.

It is a further object of the instant invention to formulate heavy-duty liquid detergent compositions which are effective on all types of fabrics both as stain pretreatment agents and as laundry washing agents.

It is a further object of the instant invention to formulate such heavy-duty liquid detergent compositions which are chemically and physically stable.

It has been discovered that by employing nonionic and zwitterionic surfactants in certain essential ratios in mulated which are unexpectedly superior to liquid detergent compositions presently known to the prior art.

SUMMARY OF THE INVENTION The present invention provides liquid detergent compositions consisting essentially of (a) from about 25 to about by weight of a nonionic surfactant produced by the condensation of alkylene oxide with an organic hydrophobic compound; (b) a zwitterionic surfactant in an amount sufficient to provide a weight ratio of nonionic surfactant to zwitterionic surfactant within the range of from about 1:1 to about 8:1; (c) from about 1 to about 30% by weight of the composition of an ethanolamine compound; and (d) from about 4 to about 50% by weight of the composition of a water or water-alcohol solvent.

DESCRIPTION OF THE INVENTION The components of the instant detergent composition are discussed in detail as follows:

THE NONIONIC SURFACTANT From about 25 to about 80% by weight of the liquid detergent compositions of the present invention, preferably from about 40 to 65%, consists of a nonionic surfactant derived by the condensation of an alkylene oxide (hydrophilic in nature) with an organic hydrophobic compound, which is usually aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene moiety which is condensed with any particular hydrophobic compound can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements. Examples of suitable nonionic surfactants are:

l. the polyethylene oxide condensates of alkyl phenols. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived, for example, from polymerized propylene, diisobutylene, octene, or nonene. Examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol, dodecyl phenol condensed with about 12 moles of ethylene oxide per mole of phenol, dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol, di-isooctylphenol condensed with about 15 moles of ethylene oxide per mole of phenol. Commerciallyavailable nonionic surfactants of this type include Igepal CO-63O marketed by the GAF Corporation; and Triton X-45, X-l 14, X- and X-102, all marketed by the Rohm and Haas Company.

2. The condensation products of aliphatic alcohols with ethylene oxide. The alkyl chain of the aliphatic alcohol may either be straight or branched and generally contains from about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of about 6 moles of ethylene oxide with 1 mole of tridecanol, myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of myristyl alcohol, the condensation product of ethylene oxide'with coconut fatty alcohol wherein the coconut alcohol is a mixture of fatty alcohols with alkyl chains varying from to 14 carbon atoms in length and wherein the condensate contains about 6 moles of ethylene oxide per mole of alcohol, and the condensation product of about 9 moles of ethylene oxide with the above-described coconut alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol l5-S-9 marketed by the Union Carbide Corporation, Neodol 23-65 marketed by the Shell Chemical Company and Kyro EOB marketed by the Procter & Gamble Company.

3. The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds has a molecular weight of from about 1500 to 1800 and of course exhibits water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tendsto increase the water-solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product. Examples of compounds of this type include certain of the commercially available Pluronic surfactants marketed by the Wyandotte Chemicals Corporation.

4. The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. The hydrophobic base of these products consists of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of from about 2,500 to about 3,000. This base is condensed with ethylene oxide to the extent that the condensation product contains from about 40 to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 1 1,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic compounds marketed by the Wyandotte Chemicals Corporation.

For use in the detergent compositions of the instant invention, it is preferred that the particular nonionic surfactant or nonionic surfactant mixture employed have a hydrophilic-lipophilic balance (HLB) of from about 8 to about 15. A highly preferred nonionic surfactant having an HLB within this range is the condensation product of 6 moles of ethylene oxide with coconut fatty alcohol. (HLB 12).

The presence of the nonionic surfactant in the instant liquid detergent compositions in the essential specified concentration provides the necessary oily stain removal in both pre-treatment application and wash water utilization of the instant invention. Such nonionic surfactant also contributes to the physical stability of the liquid detergent compositions.

THE ZWlTTERlONlC SURFACTANT Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The cationic atom and the quaternary compounds can be part of a heterocyclic ring. In all of these compounds there is at least one aliphatic groups, straight chain or branched, containing from about 3 to 18 carbon atoms 4 and at least one aliphatic substituent containing an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfato, pliosphato or phosphono. Examples of various classes of Zwitterionic surfactants operable herein are described as follows:

1. Compounds corresponding to the general formula wherein R is alkyl, alkenyl or a hydroxyalkyl containing from about 8 to about 18 carbon atoms and containing if desired up to about 10 ethylene oxide moieties and/or a glyceryl moiety; Y is nitrogen, phosphorus or sulfur, R is alkyl or monohydroxyalkyl containing 1 to 3 carbon atoms; x is 1 when Y, is S, 2 when Y, is N or P; R, is alkylene or hydroxyalkylene containing from 1 to about 5 carbon atoms; and Z is a carboxy; sulfonate, sulfate, phosphate or phosphonate group. Examples of this class of Zwitterionic surfactants include 3-( N,N-dimethyl-N-hexadecylammonio)-propanel sulfonate; 3-(N,N-dimethyl-N-hexadecylammonio)-2- hydroxypropanel -sulfonate; 2-( N,N-dimethyl-N- dodecylammonio )acetate; 3-( N,N-dimethyl-N- dodecylammonio)propionate; 2-(N,N-dimethyl-N- octadecylammonio)ethane-l-sulfate; 3-(P,P-dimethyl- P-dodecylphosphonio )propanel -sulfonate; 2-( S- methyl-S-tert-hexadecylsulfonio)ethane-l-sulfonate; 3-(S-methyl-S-dodecylsulfonio)propionate; 4-(S- methyl-S-tetradecylsulfonio )butyrate; 3-( N ,N- dimethyl-N-4-dodecenylammonio )propanel sulfonate; 3-(N,N-dimethyl-N-2- diethoxyhexadecylammonio )propane- 1 -phosphate; and 3-(N,N-dimethyl-N-4-glyceryldodecylammonio)- propionate.

Preferred compounds of this class from a commercial standpoint are 3-(N,N-dimethyl-N- hexadecylammonio)-2-hydroxypropane-l-sulfonate; 3-(N,N-dimethyl-N-alkylammonio)-2- hydroxypropane-l-sulfonate, the alkyl group being derived from tallow fatty alcohol; 3-(N,N-dimethyl-N- hexadecylammonio )propane- 1 -sulfonate; 3-( N ,N- dimethyl-N-tetradecylammonio )propane- 1 -sulfonate; 3-( N,N-dimethyl-N-alkylammonio )-2- hydroxypropanel-sulfonate, the alkyl group being derived from the middle cut of coconut fatty alcohol; 3- (N,N-dimethyldodecylammonio)-2-hydroxypropanel-sulfonate; tetradecylammonio )butanel -sulfonate; 4-( N,N- dimethyl- N-hexadecylammonio )butanel -sulfonate; 4-(N,N-dimethyl-hexadecylammonio)butyrate; 6- (N,N-dimethyl-N-octadecylammonio )hexanoate; 3- (N,N-dimethyl-N-eicosylammonio )-3-methylpropanel-sulfonate; and 6-(N,N-dimethyl-N- hexadecylammonio)hexanoate.

Means for preparing many of the surfactant compounds of this class are described in US. Pat. Nos.

2,129,264, 2,774,786, 2,813,898, 2,828,332 and 3,529,52l and;German Pat. No. l,0l8,421 all incorporated herein by reference.

2. Compounds having the general formula:

4-(N,N-dimethylwherein R is an alkyl, cycloalkyl, aryl. aralkyl or alkaryl group containing from to carbon atoms; M is a bivalent radical selected from the group consisting of aminocarbonyl, carbonylamino, carbonyloxy, aminocarbonylamino, the corresponding thio groupings and substituted amino derivatives; R and R are alkylene groups containing from 1 to 12 carbon atoms; R,, is alkyl or hydroxyalkyl containing from 1 to 10 carbon atoms: R is selected from the group consisting of R,, groups R M-R,-,, and R,,COOMe wherein R R R and R are as defined above and Me is a monovalent salt-forming cation. Compounds of the type include N,N-bis(oleylamidopropyl)-N-methyl-N-carboxymethylammonium betaine; N,N-bis(stearamidopropyl)-N-methyl-N-carboxymethylammonium betaine; N-(stearamidopropyl)-N-dimethyl-N-carboxymethylammonium betaine; N,N,-bis(oleylamidopropyl)-N-2-hydroxyethyl)-N-carboxymethylammonium betaine; and N-N-bis-(stearamidopropyl)-N- (2-hydroxyethyl)-N-carboxymethylammonium betaine. Zwitterionic surfactants of this type are preparing in accordance with methods described in U.S. Pat. No. 3,265,719 and D.A.S. 1,018,421.

3. Compounds having the general formula:

Rio

I 9 R G1I(Cl-I2)nCll'S 0;

l e R11 R12 Rm wherein R is an alkyl group, R is a hydrogen atom or an alkyl group, the total number of carbon atoms in R and R10 being from 8 to 16 and )1? R11 R12 Rm represents a quaternary ammonio group in which each group R". R and R is an alkyl or hydroxyalkyl group or the groups R R and R are conjoined in a heterocyclic ring and n is 1 or 2. Examples of suitable Zwitterionic surfactants of this type include the 'y and 5 hexadecyl pyridino sulphobetaines, the y and 8 hexadecyl 'y-picolino sulphobetaines, the y and 8 tetradecyl pyridino sulphobetaines and the hexadecyl trimethylammonio sulphobetaines. Preparation of such zwitterionic surfactants is described in South African patent application No. 69/5788.

' 4. Compounds having the general formula 6 sulfonate; 3-(N-hexadecylbenzyl-NN- dimethylammonio )propanel -sulfonate; 3-( N- dodecylbenzyl-N,N-dimethylammonio)propionate; 4- (N-hexadecylbenzyl-N,N-dimethylammonio )butyrate; 3-( N-tetradecylbenzyl-N,N-dimethylammonio)propanel -sulfate; 3-(N-dodecylbenzy1-N,N-

dimethylammonio)-2-hydroxypropane-l-sulfonate; 3-

wherein R is an alkylphenyl, cycloalkylphenyl or alkenylphenyl group containing from 8 to 20 carbon atoms, in the alkyl, cycloalkyl or alkenyl moiety; R and R are each aliphatic groups containing from 1 to 5 carbon atoms; R and R are each hydrogen atoms, hydroxyl groups or aliphatic groups containing from 1 to 3 carbon atoms and R is an alkylene group containing from 2 to 4 carbon atoms.

Examples of Zwitterionic surfactants of this type include 3-(N-dodecylphenyl-N,N- dimethylammonio )prop anel-sulfonate; 4-( N- 'hexadecylphenyl-N,N-dimethyl )butanel -sulfonate;

3-(N-tetradecylphenyl-N,N-dimethylammonio)-3,3- dimethylpropane-l-sulfonate and 3-(N-dodecylphenyl- N,N-dimethylammonio)-3-hydroxypropane-lsulfonate. Compounds of this type are described more fully in British Pat. Nos. 970,883 and 1,046,252, incorporated herein by reference.

Of allthe above-described types of Zwitterionic surfactants, preferred compounds include 3(N,N- dimethyl-N-alkylammonio)-propanel -sulfonate and 3(N,N-dimethyl-N-alkylammonio)-2-hydroxypropanel-sulfonate wherein in both compounds the alkyl groups averages 14.8 carbon atoms in length; 3(N,N- dimethyl-N-hexadecy1ammonio )-propanel -su1fonate; 3(N,N-dimethyl-N-hexadecylammonio)-2- hydroxypropane- 1 -sulfonate; 3-(N-dodecylbenzy1- N,N-dimethy1ammonio)-propane-1-sulfonate; 3-( N- dodecylbenzyl-N,N-dimethylammonio )-2- hydroxypropane-l-sulfonate; (N-dodecylbenzyl-N,N- dimethy1ammonio)acetate; 3 -(N-dodecyl-benzyl-N,N- dimethylammonio)propionate: -(N-dodecylbenzyl- N,N-dimethylammonio)hexanoate; and (N,N- dimethyl-N-hexadecylammonio)acetate. Highly preferred Zwitterionic surfactants include 3(N,N- dimethyl-N-hexadecylammonio )-propane- 1 -sulfonate and 3(N,N-dimethy1-N-alky1ammonio)-2- hydroxypropane-l-sulfonate wherein the alkyl group is derived from coconut fatty alcohol.

Zwitterionic surfactant is present in the instant heavy-duty laundry detergent compositions in an amount sufficient to provide a weight ratio of nonionic surfactant to Zwitterionic surfactant of from about 1:1 to about 8:1, preferably from about 3:1 to about 6:1.

A third essential component of the liquid detergent compositions of the present invention is an ethanolamine compound. The ethanolamine useful herein is selected from the group consisting of monoethanolamine. diethanolamine, triethanolamine, and mixtures thereof. Mixtures of these three ethanolamine compounds are produced by the reaction of ethylene oxide with ammonia. The pure compounds can be separated from this mixture by standard distillation procedures.

The ethanolamine component of the present invention serves several purposes. First, ethanolamine acts as a solvent which reduces the viscosity and improves the stability of the liquid detergent compositions. Secondly, ethanolamine acts as a buffering agent to maintain the pH of washing solutions containing the instant composition within the range of from about 7 to about 9.5. Thirdly, the ethanolamine component surprisingly counteracts detergency performance diminution which has come to be expected from utilization of wash water containing a high concentration of dissolved minerals (primarily calcium), i.e. hard water. Even more surprisingly detergency performance of the instant preferred compositions containing ethanolamine actually improves with increasing wash water hardness. The ethanolamine compound is present in the instant detergent composition to the extent of from about 1 to about 30% by weight, preferably from about 8 to about 12% by weight.

THE SOLVENT COMPONENT Although the liquid detergent compositions of the instant invention need only contain the above-described three active components in order to provide excellent stain removal and detergency, compositions of the present invention must additionally contain a solvent selected from the group consisting of water and wateralcohol mixtures to provide physical stability. Generally, such solvents comprise from about 4 to 50% by weight of the total detergent composition. In preferred compositions the solvent comprises from about 25 to about 50% by weight.

As noted, the physical stability of the detergent compositions is improved by such solvents in that clear points are thereby lowered to provide compositions which do not cloud at lower temperatures which might be encountered during shipping or storing of commercially marketed detergent compositions. Furthermore, detergent compositions of the instant type containing such solvents in the preferred amounts are desirable from the standpoint of several safety considerations. More dilute solutions tend to be less toxic and tend to produce less eye irritation than more concentrated or anhydrous detergent compositions containing the three active components.

When an alcohol-water mixture is employed as a solvent, the weight ratio of water to alcohol preferably is maintained above about 3:1, more preferably from about 4:1 to about 7:1. Alcohol (particularly ethanol) concentrations higher than this in water-alcohol mixtures used in the instant invention are preferably avoided because of flammability problems which arise at higher alcohol levels.

Preferably, an alcohol containing from i to about carbon atoms is employed in the water-alcohol mixture if such a mixture is utilized in the instant detergent compositions. Examples of such operable alcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, and pentanol. From a toxicological standpoint, ethanol is highly preferred.

OPTIONAL COMPONENTS The liquid detergent compositions can contain minor amounts of various performance-enhancing additives. Such additives include, for example, electrolyte salts. Electrolyte salts serve to lessen gel formation which tends to occur upon aqueous dilution of the instant detergent compositions. When used in combination with a water-alcohol solvent, from about 0.5 to 5% by weight of an electrolyte salt can completely eliminate gel formation without utilization of alcohol levels which exceed the flammability safety levels discussed above.

Suitable electrolyte salts include the alkali metal chlorides, sulfates and carbonates, and the salts formed from the reaction of ethanolamines with formic, acetic, propionic, butyric, citric or sulfuric acid. Specific examples of such salts include sodium chloride, potassium chloride, sodium carbonate. potassium carbonate, potassium sulfate, sodium sulfate, triethanolamine sulfate, triethanolamine citrate, triethanolamine acetate, triethanolamine formate, monoethanolamine propionate and diethanolamine butyrate. Potassium chloride is preferred and is preferably added to the instant compositions to the extent of from about 1 to 3% by weight.

Other optional non-essential, non-interfering components may be added to the instant composition to provide improved performance or aesthetic appeal. These optional components include, for example, brighteners, fluorescers, enzymes, bleaching agents, anti-microbial agents, corrosion inhibitors and coloring agents. Such non-electrolyte optional components preferably comprise no more than about 3% by weight of the total composition.

The above-described compositions containing nonionic, zwitterionic, ethanolamine and solvent and other non-essential components can be formulated by preparing each component separately and then thoroughly mixing such components together in any order. Compositions of the instant invention are used in two different ways for fabric cleaning. They may be used as pretreatment agents which are applied in concentrated form directly onto fabric stains prior to fabric washing.

The instant compositions are also useful as detergents for conventional fabric laundering operation. Both stain removal and soil removal are obtained when the instant compositions are dissolved in washing solution to the extent of from about 0.90 to 0.12% by weight (approximately one-fourth cup per 17-19 gallons of wash water).

The following examples illustrate the liquid detergent compositions of the instant invention:

EXAMPLE 1 A heavy-duty liquid detergent composition was prepared having the following composition:

Component Weight Percent Condensation product of about 42.3% 9 moles of ethylene oxide with a secondary fatty alcohol containing about l5 carbon atoms -Continued Component Weight Percent Dimethyl-alkylammonio-hydroxy 16.9 propane-sulfonate wherein the alkyl group is derived from 5 coconut fatty alcohol Triethanolamine l(). I

Water and Minors 30.7

In the above composition the weight ratio of nonionic surfactant to zwitterionic surfactant is 2.5: 1. Such a composition is a stable clear liquid detergent which is relatively nontoxic, which is stable to freeze thaw, which is nonflammable, and which provides stain removal from cotton, polyester and polyester-cotton fabrics when utilized directly on stains prior to fabric laundering and excellent wash water detergency when employed in a concentration of approximately one-third cup per 18 gallons of hard water (7 grains/gallon) at 70F.

Compositions of substantially similar stability and performance are obtained when the zwitterionic surfactant is replaced with 3-(S-methyl-S-dodecylsulfonio )propionate; 'y-hexadecylpyridino-sulfobetaine; 3-( N- 10 dodecylphenyl-N,N-dimethylammonio)propane-lsulfonate; 3( N,N-dimethyl-N-alkylammonio)-propanel-sulfonate and 3(N,N-dimethyl-N-alkylammonio)-2- hydroxypropane-l-sulfonate wherein in both compounds the alkyl group averages 14.8 carbon atoms in length; 3(N,N-dimethyl-N-hexadecylammonio)-2- hydroxypropanel -sulfonate; 3-( N-dodecylbenzyl- N,N-dimethylammonio)-propane-l-sulfonate; 3-(N- dodecylbenzyl-N,N-dimethylammonio)-2- hydroxypropane-l-sulfonate; (N-dodecylbenzyl-N,N- dimethylammonio)-acetate; 3-(N-dodecylbenzyl-N,N- dimethylammonio)propionate; o-(N-dodecylbenzyl- N,N-dimethylammonio)hexanoate; or (N,N-dimethyl- N-hexadecylammonio)acetate, and the triethanolamine is replaced with monoethanolamine or diethanolamine.

Gelling tendency of all the above-described compositions is substantially lowered by the addition to such compositions of 1.5% by weight of sodium chloride, potassium chloride, sodium carbonate, potassium carbonate, potassium sulfate, sodium sulfate, triethanolamine sulfate, triethanolamine citrate, triethanolamine acetate, triethanolamine formate, monoethanolamine proonate or diethanolamine butyrate.

Several heavy duty liquid detergent compositions are formulated having compositions as set forth in Table 1.

Table 1 Example Number Component V VI VII VIII IX X Butanol Potassium Chloride l Minors (Brighteners. color stabilizers, perfume colormg agents) Water Weight ratio of nonionic surfactant to zwitterionic surfactant lOOzl Balance 2.75:1 Z.75:l 3.95zl 3.45:] 3.00:! 5.25:1

Ethoxylated fatty alcohol 2 Condensation product of ethylene oxide with a hydrophobic hase formed by condensing propylene oxide with propylene glycol Condensation product of ethylene oxide with the compound resulting from the reaction of pro ylene oxide and ethylene dianiine Examples II, III, IV, VIII and IX represent typical compositions of the instant invention containing only a water solvent. Examples V, VI and X represent compositions of the instant invention utilizing a water-alcohol mixture as a solvent.

Compositions IV, V and VII containing the potassium chloride electrolyte salt are especially resistant to gel formation upon aqueous dissolution in wash water. Compositions II, VII and X having relatively large nonionic to zwitterionic weight ratios are especially effective as stain pretreatment agents when applied directly to stained fabrics before laundering.

WASH-WEAR TEST Wash water detergency performance for several of the compositions of the instant invention was compared with that of commercially available built granular laundry detergents in a wash and wear test. The test employed was conducted in the following manner: Light-colored dress shirts, cotton T-shirts and other fabrics were distributed among various individuals. Each dress shirt and T-shirt was worn for one normal working day under uniform conditions, and the other articles were used for their generally intended purposes. The soiled clothes and fabrics were then washed in an automatic agitating type washer, for a period of minutes, with detergent solutions at 70F. The detergents employed were the compositions of Examples I and II at a concentration of one-third cup per 17 gallons of water, Tide, a commercially available built granular detergent marketed by The Procter & Gamble Company, used at concentrations of both 1% cup and 0.9 cup per 17 gallons of water, and Cheer, a commercially available built granular cool water detergent marketed by the Procter & Gamble Company at a concentration of 1% cups per 17 gallons of water. Fluorescers had been removed from the Tide and Cheer formulations. The wash water solutions of the liquid detergents had a pH of about 7.2 and for the Tide and Cheer solutions about 9,5. Wash water hardness was about 7 grains per gallon. After washing, the clothes were rinsed (six spray rinses and one deep rinse) and then dried.

Direct visual comparisons were made by a panel of expert graders between pairs of shirts and fabrics worn and soiled by the same individual. The dress shirts, T- shirts and other fabrics used were graded on the degree of whiteness and the degree of cleaning obtained, paying particular attention on this latter feature to the dress shirt collars and cuffs. For purposes of this invention, the term cleaning" or cleanliness measures the ability of a washing composition to remove actual soil lines or deposits such as at crease lines of collars and cuffs where the soil has had an opportunity to become deeply embedded. Whiteness, on the other hand, is a more general concept which measures the ability of a cleaning composition to whiten areas which are only slightly or moderately soiled. The relative cleaning effectiveness of each detergent composition in each area was graded visually on a 9 point scale under artificial light wherein the highest grade was assigned to the relatively best performance obtained.

Based upon such comparisons, it was found that the two liquid detergent compositions of the instant inven tion provided cleaning comparable to l A cups of Tide and l A cups of Cheer. Further, all compositions of the instant invention provided combined cleaning and whiteness performance comparable to 1% cups of Tide and 1% cups of Cheer. Further, all compositions of the instant invention provided combined cleaning and whiteness performance comparable to l A cups of Tide and l A cups of Cheer.

The effectiveness of the instant composition in removing lipid soil from various fabrics was ascertained utilizing the following test. An artificial lipid soil consisting of equal weight parts of oleic acid, octadecane and triolein was prepared simulating the composition of natural lipids. The artificial lipid utilized was radiolabeled by employing the carbon-l4 radioisotope for each substituent of the soil formulation.

This artificial lipid soil was applied to 50/50 polyester/cotton test swatches by dissolving the soil in carbon tetrachloride and pipetting this solution dropwise onto 1% X 1% swatches to provide a 5% by weight soil level on the cloth. Swatches were aged about 48 hours at F. Uniform distribution of the soil on the cloth was confirmed by microscopy and by radio-assay of sections of the swatches.

Swatches were washed together on a miniature Tergotometer containing about 200 ml. of solution at 50C for 10 minutes. Solution composition and washing conditions are set forth in Table 2. The swatches were drained and then rinsed for 1 minute at the same temperature and hardness of the wash. After draining again, the swatches were air dried on stainless steel plates.

Percent Lipid Removal= 100 (Count of Unwashed Swatch Count of Washed Swatch X100) Table 2 demonstrates lipid soil removal performance of 0.1 1% by weight aqueous solutions (Solutions A and C) of representative compositions of the instant invention in comparison with comparable solutions (Solutions B and D) containing the same surfactant components but no triethanolamine. Sodium hydroxide was used to adjust the initial pH of the triethanolamine-free washing solution to 7.2, the initial pH of the triethanolamine containing solutions. Performance at two different wash-water hardness levels was tested.

Table 2 Surfactant Weight Ratio (Nonion ic/ zwitterionic Solution Grains/ Gal. C a-H- 0.0833% Coconut Alcohol Hexaethoxylate 0.016771 Dimcthylhexadecylammonio-propane sulfonatc 0.01% Triethanolamine 0.083371 Coconut Alcohol Hexaethoxylate 0.016771 Dimethylhcxa- B dccylammoniopropane sulfonatc Sodium hydroxide to pH 7.2

0.05% Coconut Alcohol Hcxacthoxylate 0.05% Dimethylhcxadecylammonio propane sulfonatc 0.01% 'lricthanolaminc 0.05% Coconut Alcohol Hexacthoxylatc 0.05% Dimethylhcxadccylammonio-propanc sulfonatc Sodium Hydroxide to pH 7.2

Table 2 clearly demonstrates that with compositions of the instant invention containing the three essential components within the specified ratios, no loss in lipid soil removal occurs as water hardness increases. Analogous compositions, however, not containing the essential triethanolamine component demonstrate poorer lipid soil removal performance especially under hard water conditions. The preferred composition of the instant invention utilizing a nonionic to zwitterionic surfactant ratio of 5:1 (Solution C) actually shows improvement in lipid soil removal as water hardness increases.

What is claimed is:

l. A liquid laundry detergent composition, consisting of:

a. from about to about 80% by weight of a nonionic surfactant produced by the condensation of ethylene oxide with an organic hydrophobic compound, said nonionic surfactant having a hydrophilic lipophilic balance of from about 8 to about b. a zwitterionic surfactant present in a quantity sufficient to provide a weight ratio of nonionic surfactant to the zwitterionic surfactant offrom about 1:1 to about 8:1;

c. from about 1 to by weight of an ethanolamine selected from the group consisting of monoethanolamine. diethanolamine. triethanolamine and mixtures thereof: and

d. from about 4 to about 50% by weight of a solvent selected from the group consisting of water and mixtures of water and lower monohydric alkanols.

2. A composition in accordance with Claim 1 which contains from about 25 to 50% by weight of water.

3. A composition in accordance with claim 1 which contains from about 25 to about 50% of a solvent consisting of a mixture of water and an alcohol containing from 1 to about 4 carbon atoms; said mixture having a water to alcohol weight ratio greater than about 3: 1.

4. A composition in accordance with claim 3 wherein the alcohol is ethanol.

5. A composition in accordance with claim 4 which contains in addition from about 0.5 to about 5% by weight of an electrolyte salt selected from the group consisting of alkali metal chlorides, sulfates and carbonates, and the ethanolamine salts of formic, acetic, propionic, butyric. citric and sulfuric acids.

6. A composition in accordance with claim 5 wherein the electrolyte salt is potassium chloride.

dimethylammonio)hexanoate; and (N,N-dimethyl-N- hexadecylammonio)acetate; the solvent is a waterethanol mixture having a water to ethanol weight ratio from about 4:1 to about 7:1; the solvent comprises from about to about 50% by weight of the composition; and the potassium chloride electrolyte salt comprises from about 1 to about 3% by weight of the composition.

8. A liquid laundry detergent composition consisting of:

a. from about 40 to about 65% by weight of a nonselected from the group consisting of monoethanolamine, diethanolamine, triethanolamine and mixtures thereof; I

d. from about 4 to about 50% by weight of a solvent consisting of a water-ethanol mixture having a water to ethanol weight ratio of from about 4:1 to about 7:1; and

e. from about 0.5 to about 5% by weight of an electrolyte salt selected from the group consisting of sodium chloride, potassium chloride, sodium carbonate, potassium carbonate, potassium sulfate, sodium sulfate, triethanolamine sulfate, triethanolamine citrate, triethanolamine acetate, triethanolamine formate, monoethanolamine propionate and diethanolamine butyrate.

9. A composition in accordance with claim 8 wherein a. the nonionic surfactant is the condensation product of ethylene oxide with coconut fatty alcohol, said condensation product containing about 6 moles of ethylene oxide per mole of coconut fatty alcohol;

b. the ethanolamine is triethanolamine; and

c. the electrolyte salt is potassium chloride present to the extent of from about 1 to about 3% by weight.

Claims

1. A LIQUID LAUNDRY DETERGENT COMPOSITION, CONSISTING OF: A. FROM ABOUT 25 TO ABOUT 80% BY WEIGHT OF A NONIONIC SURFACTANT PRODUCED BY THE CONDENSATION OF ETHYLENE OXIDE WITH AN ORGANIC HYDROPHOBIC COMPOUND, SAID NONIONIC SURFACTANT HAVING A HYDROPHILIC - LIPOPHILIC BALANCE OF FROM ABOUT 8 TO ABOUT 15; B. A ZWITTERIONIC SURFACTANT PRESENT IN A QUANTITY SUFFICIENT TO PROVIDE A WEIGHT RATIO OF NONIONIC SURFACTANT TO THE ZWITTERIONIC SURFACTANT OF FROM ABOUT 1:1 TO ABOUT 8:1; C. FROM ABOUT 1 TO 30% BY WEIGHT OF AN ETHANOLAMINE SELECTED FROM THE GROUP CONSISTING OF MONOETHANOLAMINE, DIETHANOLAMINE, TRIETHANOLAMINE AND MIXTURES THEREOF; AND D. FROM ABOUT 4 TO ABOUT 50% BY WEIGHT OF A SOLVENT SELECTED FROM THE GROUP CONSISTING OF WATER AND MIXTURES OF WATER AND LOWER MONOHYDRIC ALKANOLS.

3. A composition in accordance with claim 1 which contains from about 25 to about 50% of a solvent consisting of a mixture of water and an alcohol containing from 1 to about 4 carbon atoms; said mixture having a water to alcohol weight ratio greater than about 3:1.

4. A composition in accordance with claim 3 wherein the alcohol is ethanol.

5. A composition in accordance with claim 4 which contains in addition from about 0.5 to about 5% by weight of an electrolyte salt selected from the group consisting of alkali metal chlorides, sulfates and carbonates, and the ethanolamine salts of formic, acetic, propionic, butyric, citric and sulfuric acids.

7. A composition in accordance with claim 6 wherein the zwitterionic surfactant is selected from the group consisting of 3(N,N-dimethyl-N-alkylammonio)-propane-1-sulfonate wherein the alkyl group averages about 14.8 carbon atoms in length; 3(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-1-sulfonate wherein the alkyl group averages about 14.8 carbon atoms in length; 3(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate; 3(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)-propane-1-sulfonate; (N-dodecylbenzyl-N,N-dimethylammonio)acetate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)propionate; 6-(N-dodecylbenzyl-N,N-dimethylammonio)hexanoate; and (N,N-dimethyl-N-hexadecylammonio) acetate; the solvent is a water-ethanol mixture having a water to ethanol weight ratio of from about 4:1 to about 7:1; the solvent comprises from about 25 to about 50% by weight of the composition; and the potassium chloride electrolyte salt comprises from about 1 to about 3% by weight of the composition.

8. A liquid laundry detergent composition consisting of: a. from about 40 to about 65% by weight of a nonionic surfactant produced by the condensation of ethylene oxide with an organic hydrophobic compound, said nonionic surfactant having a hydrophilic-lipophilic balance of from about 8 to about 15; b. a zwitterionic surfactant selected from the group consisting of 3(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate and 3(N,N-dimethyl-N-alkylammonio)2-hydroxypropane-1-sulfonate wherein the alkyl group is derived from coconut fatty alcohol, present in an amount sufficient to provide a nonionic surfactant to zwitterionic surfactant weight ratio of from about 3:1 to 6:1; c. from about 8 to 12% by weight of an ethanolamine selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine and mixtures thereof; d. from about 4 to about 50% by weight of a solvent consisting of a water-ethanol mixture having a water to ethanol weight ratio of from about 4:1 to about 7:1; and e. from about 0.5 to about 5% by weight of an electrolyte salt selected from the group consisting of sodium chloride, potassium chloride, sodium carbonate, potassium carbonate, potassium sulfate, sodium sulfate, triethanolamine sulfate, triethanolamine citrate, triethanolamine acetate, triethanolamine formate, monoethanolamine propionate and diethanolamine butyrate.

9. A composition in accordance with claim 8 wherein a. the nonionic surfactant is the condensation product of ethylene oxide with coconut fatty alcohol, said condensation product containing about 6 moles of ethylene oxide per mole of coconut fatty alcohol; b. the ethanolamine is triethanolamine; and c. the electrolyte salt is potassium chloride present to the extent of from about 1 to about 3% by weight.