AU613545B2 - Detergent composition comprising betaine and ether sulphate - Google Patents

Description

r

AUSTRALIA

PATENTS ACT 1952' r COMPLETE SPECIFICATION r0i Form

(ORIGINAL)

FOR OFFICE USE Short Title: Int. Cl: Application Number: Lodged: Complete Specification-Lodged: Accepted: Lapsed: Published: Priority: Related Art: 04 4 TO BE COMPLETED BY APPLICANT Name of Applicant: Address of Applicant: UNILEVER PLC UNILEVER HOUSE

BLACKFRIARS

LONDON EC4

ENGLAND

Actual Inventor: Address for Service: GRIFFITH HACK CO., 601 St. Kilda Road, Melbourne, Victoria 3004, Australia.

Complete Specification for the invention entitled: DETERGENT COMPOSITION COMPRISING BETAINE AND ETHER SULPHATE.

The following statement is a full description of this invention including the best method of performing it known to me:- 1 C6074 DETERGENT COMPOSITION COMPRISING BETAINE AND ETHER SULFATE BACKGROUND OF THE INVENTION C. Two particularly important characteristics of hand dishwashing detergent liquids are mildness, which is significant due to the exposure of the hands to the detergent formulations, and foamability. Foamability is important because the amount of foam generated during washing is related to the ability of a formulation to clean dishes and eating utensils effectively.

Among the surfactants included to promote mildness in some light duty liquid detergent formulations are certain betaine surfactants and linear ether sulfates. However, such formulations have tended generally to include high levels of total surfactant high levels of the costly betaine surfactants and/or one or more extra surfactants in addition to the betaine and ether sulfates.

2 C6074 Rubin et al., US Patent No. 4 375 421 discloses high viscosity aqueous compositions including alkylamidobetaines and selected salts such as certain sulfates, carbonates, citrates, tartrates and succinates.

The inclusion of micelle-forming anionic surfactants are said to produce a synergistic, viscosity-building effect.

Among the numerous types of anionics mentioned for use in their invention are included sodium, potassium, calcium, I II

I.,

111k -3 C6074 magnesium and ammonium alcohol ethoxy sulfates. In Examples 6-B and 6-C, hand dishwashing preparations are disclosed which include cocoamido betaine, ammonium alcohol ethoxy sulfate, lauryl dimethyl amine oxide and either sodium citrate or sodium sulfate. The ratio of betaine to ether sulfate is much greater than 1:1. Rubin et al. indicate that the particular type of betaine is important and that most betaines are not thickened in the presence of salts. It is said that only alkylamidobetaines are thickened under the described conditions.

00 0 0 0 0 0 ao 0 6 0 0 0 o 0 0 6 0 00 00 0 o a o oo oo a oa o o a Chirash et al., U.S. Patent No. 4,772,425 discloses light duty liquid abrasive-containing dishwashing'compositions which include at least one sulfated or sulfonated anionic surfactant, a betaine, a clay stabilizing agent and a minor amount of a solubilizer such as ethanol as a preferred optional ingredient. Preferably, the formulation includes a ternary surfactant system of an alkyl benzyl sulfonate or alkane sulfonate, an alkyl ethenoxy ether sulfate and a betaine, the clay, and 2 to 9% alcohol Several of the examplified compositions of Chirash include ether sulfate and betaine surfactants and ethanol. For instance, a composition including 17% sodium dodecylbenzene sulfonate, 13% ammonium alkyl triethenoxyether sulfate, 4% cocamidopropyl dimethyl betaine, 5.5% ethanol and water is disclosed. In example 6, 6.5% ether sulfate, 2% amidoalkyl C6074 betaine, 8.5% sodium dodecylbenzene sulfonate and 4% alcohol are included. The examples including ether sulfate and betaine appear to possess ternary surfactant systems.

Verdicchio et al., U.S. Patent No. 3,950,417 discloses high lathering detergent compositions, especially useful as shampoos, which comprise a surfactant betaine, an anionic surfactant and a nonionic surfactant. The preferred molar ratio of surfactant betaine to anionic surfactant falls between about 0.9 and about 1.1. The preferred betaines are said to be surfactant amidocarboxybetaines and amidosulfobetaines. Alcohol ether sulfates are used as anionics and are said to be the preferred "o°o anionics. The examples generally include a nonionic surfactant o 0 o in addition to the betaines and the anionic surfactant such as ether sulfates. In addition to use as shampoos, the compositions 0 0o are said to be useful as cleansers for cleaning other parts of "5 the human body, animals, inanimate objects and the like.

Nishimura et al., U.S. Patent No. 4,166,048 discloses high foaming detergent compositions which are said to have a very mild action on the skin. The compositions include certain polyoxyethylene alkyl ether su],fate salt mixtures and a betainetype amphoteric surfactant of the.formula Rl(R2)N+(CH2COO-)R3 wherein R1 is alkyl having 8 to 20 carbon atoms. The weight of the betaine type amphoteric surfactant is 0.01 to 2 times, especially 0.03 to 0.5 times the weight of the polyoxyethylene alkyl ether sulfate salt mixture.

5 C6074 The ether sulfate salts of the '048 patent may include monovalent metal ions, preferably Na or K or divalent metal ions, preferably Ca or Mg. Solubilizing agents such as ethanol., propylene glycol, glycerin and xylene sulfonic acid salts may be included. In some of the examples, the composition is tested'for washing power on dishes. Small amounts of ammonium chloride ar included in some of the examples.

The Lonzaine C Product Information Bulletin discloses that Lonzane C is a mild, high foaming surfactant of the amide betaine structure. Lonzaine C is said to contain'5% NaCl.

Lonzaine C is said to have outstanding conditioning, foaming, and viscosity potentiating properties.- Lonzaine C, in combination with most anionic surfactants, is said to potentiate viscosity to permit formulations ranging from viscous liquids to ringing gels.

Shampoo formulations including a 30% solution of Lonzaine C Barlox C, a 40% solution of sodium alpha olefin sulfonate citric acid, water and optionally polymer JR 125 are disclosed. Lonzaine C is said to be useful in light duty liquids and is said to exhibit tolerance toward high levels of builder, electrolytes, alkali and acids.

The Stepan bulletin for Amphosol CA (cocoamidopropyl betaine) gives a shampoo formulation including Amphosol CA, an amine oxide, an alpha olefin sulfonate, citric acid and water.

In three other formulas, the anionic is respectively sodium 6 C6074 lauryl sulfate, another alcohol sulfate salt and alpha olefin sulfonate. It is said that a wide variety of viscositiescan be attained by addition of NaCl (from 0 to a gel).

Pancheri et al., U.S. Patent No. 4,772,423 discloses liquid detergents said to have high sudsing characteristics and said to be suitable for washing tableware. The detergents comprise 5 to 50% anionic surfactant, a polmeric surfactant, detergency builders and water and may also include other surfactants, of which betaine surfactants are highly preferred.

The betaine is present at from 0.5 to 15%, preferably S from 1 to 10%. The ratio of anionic to betaine is from about 1 0O to 80, preferably from 1 to 40 more preferably from about 2 to t001 40. The preferred anionic surfactants are alkylpolyethoxylate S, sulfates having from 0.5 to 10 ethylene oxide groups. The anionics may be salts of sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium and other cations. Alcohols and hydrotropes such as sodium xylene sulfonate may be included, as may water-soluble inorganic builders. Alkyl ether sulfates and alkylamido betaines are included together in various examples, generally with an additional surfactant.

Lamb et. al., U.S. Patent No. 4,671,894 discloses liquid dishwashing detergents comprising 4 to 20% alkyl sulfate, 5 to alkylbenzene sulfonate, 1 to 10% of a nonionic surfactant, S7 C6074 to 24% alkyl ethoxy sulfate, 0.25 to 10% of a zwitterionic surfactant such as an alkyl betaine, an alkylamidobetaine or a sulfobetaine, and a hydrotrope-water system which may include ethanol, urea, and/or a lower alkyl benzene sulfonate. In example D, 9.9% ammonium alkyl ethoxy sulfate, 2.25% amidopropyl betaine, ethanol, alkylbenzene sulfonate, alkyl sulfate and water are included. In comparative Example M, alkylbenzene sulfonate is omitted and a marked decline in suds mileage is said to be obtained.

Klisch et al., U.S. Patent No. 4,554,098 discloses good foaming liquid detergents having reduced skin irritating properties which include 8 to 30% alkyl ether sulfate, a supplementary, non-soap anionic detergent, 1 to 8% of a zwitterionic surfactant which may be a betaine, an amidobetaine or a sulfobetaine and a solubilizer which is selected from a group including alcohols, lower alkyl benzene sulfonate salts, urea and mixtures thereof.

The formulations are said to be suitable as hand dishwashing liquids.

Example 5 of Klisch includes 16% ammonium alkyl ether sulfate salt, 6% sodium alkyl ether sulfate salt, 4% amidobetaine, 3% monoethanolamide, 5.4% sodium xylene sulfonate and 9.5% ethanol. Example 35 includes 13% ammonium alkyl ether sulfate, 2% ammonium lauryl sulfate, 4.5% amidobetaine, monoethanolamide, 9.2% ethanol, and 4.2% sodium xylene sulfonate.

8 C6074 Bissett et. al., U.S. Patent No. 4,558,360 discloses mild, foaming detergent compositions comprising 5 to 99% of a mild, foaming anionic surfactant selected from a group including alkyl ether sulfates, 1 to 30% of a surfactant which may be a betaine or an amidobetaine and 0.5 to 20% of an amine oxide suds booster. The ratio of anionic detergent to the betaine is from 1:1 to 20:1, preferably 3:1 to 10:1. Detergency builders, solvents such as ethanol and water, and hydrotropes such as sodium xylene sulfonate may be included. In Example III, 27% alkyl ether sulfate, 5% amine oxide, and 10% cetyl dimethyl betaine are present.

Carter et. al., U.S. Patent No. 4,088,612 discloses compositions which include certain sulfobetaines and an anionic surfactant in a molar ratio of not less than 1 to 2 parts. Among 1 1 the anionics listed are ether sulfates. In Table II a formulation including hexadecyl pyridino sulfobetaines and sodium lauryl ethylene oxide (BEC) ether sulfate in a 1:1 molar ratio is given.

Compositions including sulfobetaines and ether sulfates are also given in Table I. Hydrotropes such as alkali metal aryl 2C sulfonates, organic solvents such as lower alcohols, and salts such as sodium sulfate may be included.

European Patent Application 036,625 discloses liquid cleaning compositions said to be useful for washing dishes by hand. The compositions include by weight 4-20% of a mixture of 9 C6074 sulfated ethylene oxide/alkanol adducts, and oadiionally 2-5% surface active betaines in addition to one or more anionic tensides, optionally nonionic tensides, solvents and other ingredients.

Example 4 appears to include 9% alkylbenzene sulfonate, 9% alkyl ether sulfate, 2% alkyamidopropyldimethylcarboxymethylbetaine and ethanol. Example 6 appears to include alkylbenzenesulfonate, 10% alkylsulfonate, 5% alkyl ether sulfate, 5% amidobetaine and 8% isopropanol. Example 9 appears to include 5% alkyl ether sulfate, 2% betaine, 3% alkylsulfate, 5% nonionic and 4% isopropanol.

It has now been found that light duty liquid detergent formulations having a ratio of amido- and/or amido sulfobetaine surfactants to linear ether sulfate within the range defined below exhibit excellent mildness and foaming without the need for additional surfactants or excessive amounts of betaine or of total surfactant.

SUMMARY OF THE INVENTION The invention comprises aqueous light duty liquid detergent formulations, especially suitable for use in hand dishwashing, which include a) an essentially-binary active system consisting essentially of i) a betaine surfactant which may be an alkylamidobetaine or a amidosulfob- 'ne or mixtures thereof and ii) an alkyl ether sulfate surfact- erein the weight ratio of i) to ii) is in the range of .o 1:1, b) from 1 to .12% of a sm~ r~pasurPs~ la~pmr 10 C6074 hydrotrope and c) from 0 to 12% of electrolytes. Preferably the range of i) to ii) is from 1:3 to 1:1, even more preferably 1:2 to 1:1.5.

The light duty liquid detergent of the invention has been found to have excellent mildness and foaming properties, and is particularly suitable for use as a hand dishwashing liquid.

Moreover, the liquid of the invention does not require large amounts of the betaine or of total surfactant and uses an essentially binary active system, thus eliminating the need for additional surfactants.

1. 1 DETAILED DESCRIPTION OF THE INVENTION t I The betaine surfactants useful in the invention are S. zwitterionic surfactants and are either alkylamidobetaines or alkylamidosulfobetaines.

The alkylamidobetaines useful in the present invention are given by the following formula: 0 (CHi)y(CH 3 11 I

CNH(CH

2 )xN(+)CH 2

CO

2

(CH

2 )z(CH 3 where R is an alkyl or alkenyl chain containing 9 to 17 carbon ?0 atoms, x is an integer of 2 to 4, y is an integer of 0 to 3, and z is an integer of 0 to 3. The preferred value of x is 3. The preferred values of y and z are both 0. R is preferably.a fatty' 1_1 ~_O 11 C6074 group which contains 11 to 13 carbon atoms, moSL preferably in a straight chain. The preferable source of the R group is coconut oil. The preferred amidobetaine may be represented by the following formula: 0 CH3 11 I

RCNH(CH

2 3

N(+)CH

2

CO

2 CH3 wherein R is an alkyl or alkenyl group containing 9 to .13 carbon atoms.

Examples of the alkylamidobetaines useful in the present invention include cocoamidomethylbetaine, laurylamidopropylbetaine, and cetylamidomethylbetaine.

Alkylamidobetaines useful in the present invention are commercially available from, Lonza Incorporated under the trademark Lonzaine C; from the Miranol Chemical Company under the tr-demark Mirataine CB; and from the Stepan Chemical Co. under the trademark Amphosol CA.

The alkylamidosulfobetaines useful in the invention have the following formula: 0 R2

R

5 -C-NHR4-N CH-Rl-SO3 S I

R

3 Y X wherein R1 is an alkylene radical having from 1 to about 3 carbon atoms, X is hydrogen, methyl or hydroxy, Y is hydrogen or methyl, 91-~ S12 C6074

R

2 and R 3 are independently selected from methyl, ethyl and hydroxyethyl radicals, R 4 is an alkylene radical having from about 2 to about 6 carbon atoms and R 5 is an alkyl radical having from about 10 to about 18 carbon atoms.

Representative amidosulfobetaine surfactants include cocoamidomethylsulfopropylbetaine, stearylamidodimethylsulfopropylbetaine, and laurylamidobis-(2-hydroxyethyl)-sulfopropylbetaine.

In preferred sulfobetaine surfactants, R 2 and R 3 are methyl. R 1 is preferably ethylene. R4 is preferably an alkylene radical having 2 to 4 carbon atoms. R 5 preferably is a straight chain. Convenient sources of alkyl radicals having from 10 to 18 carbon atoms are tallow fatty alcohol and coconut fatty alcohol.

Particularly preferred amidosulfobetaines are hydroxysultaines such as cocamidopropyl hydroxysultaine, the formula of which is 0 CH3 RC-NH(CH2) 3 -N(+)CH2CHCH2SO3(-) CH3 OH 2) whereRCO represents the coconut acid radical. Cocamidopropylhydroxysultaine is available from'Lonza Inc. as Lonzaine CS and Lonzaine JS and from Miranol as Mirataine CBS.

The betaine surfactants will gen' :ally be present in the compositions of the inventions at levels ranging from 2-13% by weight, preferably 3-9%.

t 13 C6074 By essentially binary active system it is meant that no more than about 1% of surfactants other than the ether sulfate and amidobetaine or amidosulfobetaine are included.

The alkyl ether sulfate surfactants used in the present formulations have the formula: RO(CnH2nO)qS03X RO(CnH(2n+1)0)qSO 3

X

t4 0 0 00 04.1 200 where R is an alkyl or hydroxyalkyl group containing about 8 to about 18 carbon atoms, n is 2 or 3 and q can vary; from 1 to about 30. Ether sulfates wherein R is from C 12 to C 15 are preferred.

Preferably q ranges from 1 to 3, especially 3. n is preferably 2. X is a cation preferably selected from the group consisting of alkali metal, especially sodium and potassium, ions, alkaline earth metal, calcium and magnesium, ions, ammonium or substituted ammonium ions such as mono-, di- or triethanolammonium cations. Mixtures of cations may be used. Ammonium ions are especially preferred. The alkyl ether sulfates will generally be present in the compositions of the invention at levels of from 6 to 22%, preferably 6 to 20%, and especially 10 to 18%.

Neodol 25-3A (ex Shell), which includes an ether sulfate wherein R is a mixture of C 12

-C

15 alcohol, X is ammonium and the alcohols are ethoxylated with 3EO groups may be used as a source j 14 C6074 of the ether sulfates. Other sources of alkyl ether sulfates suitable for use in the compositions of the invention include Pareth 23-3 (ex Shell) which includes ammonium alkyl ether sulfates in which R is a mixture of C12 and C13 alcohols and wherein the alcohols are ethoxylated with 3 EO groups.

The total percent by weight of surfactants in the formulations of the invention is preferably no higher than more preferably no higher than 25%, especially up to 21%. Preferably the surfactants comprise at least 16% of the composition.

The hydrotropes used herein are preferably selected from the group consisting of alkanols and lower alkyl (C 1

-C

3 benzene' sulfonates and mixtures thereof. Alkanols containing from one to six carbon atoms, particularly ethyl alcohol, and mixtures thereof can be used as solvents. Isopropanol is another appropriate alcohol. The preferred lower alkyl benzene sulfonates are sodium and potassium xylene, toluene, and cumene sulfonates and mixtures thereof. Especially preferred hydrotrope systems for alkylamidobetaines comprise mixtures of ethyl alcohol and sodium xylene sulfonate. The preferred hydrotrope for alkylamidosulfobetaines is ethanol.

23 The hydrotropes can tota'l from 1 to 12% by weight of the formulation. For sodium xylene sulfonate and other lower alkyl benzene sulfonate hydrotropes, the preferred range is from 0.5 to 15 C6074 wt%, preferably 1.5 to The preferred range for ethanol is from 1 to 10%, especially 3 to 8%.

Among the optional ingredients which may be present in the light duty liquid detergent compositions of the invention are neutral salts. Particularly preferred neutral salts include the alkali metal sulfates, particularly sodium sulfate, and the alkali metal chlorides, particularly sodium chloride. The neatral salts comnprise from 0 to 12%, preferably from 0.5 to 12% of the present compositions. Sodium chloride is preferably present within the range of 0.25 to 2 wt% whereas sodium sulfate will generally be present at from 0 to 5 wt%, especially 0.25 to wt Compositions may include both sodium chloride and sodium I t sulfate. Other examples of neutral salts which may be included t4a in the formulations of the invention are sodium, potassium, S ammonium, zinc, monoethanolammonium, diethanolammonium and triethanolammonium sulfates, chlorides, bromides, iodides, fornates, oretates, citrates, succinates and tartrates.

The compositions of the invention are formulated generally to have a viscosity of from 150 to 3500 cps. Where less ciscous liquids are desired, the viscosity will range from 150 up to 1000 cps, preferably 300-400 cps. The viscosity of high viscosity liquids will preferably be within the range of 1000-2500 cps, preferably about 2500 cps. The present invention yields an clear, stable, highly viscous liquid within the 1000-2500 cps /ie C6074 range. Such higher viscosity formulations can be used advantageously in direct application washing wherein the liquid is applied to the dishware or utensil itself (e.g.

squirted onto the utensil or onto a sponge and applied to the utensil) instead of after dilution with dishwater. In general, the viscosity of the compositions is adjusted by varying the levels of neutral salts and hydrotropes.

Water will generally comprise from 40 to 80% by weight 10 of the compositions, preferably 49 to 77%.

2.Tbi'2^rton s ,&he invention may include various her ingredients typically fouid in light duty detergents including colorants and dyes such as D&C Yellow #fIO and FD&C Green perfumes and preservatives.

The pH of the compositions will generally range from 6 to 7.5, preferably about 7.

The compositions of the invention are stable and generally clear, although they may be opacified if desired.

0 The light duty liquid detergent of the invention does not generally include cationic polymers, a clay or an abrasive, although inclusion of such ingredients may be appropriate in certain circumstances. Also, the detergent of the invention does not generally include polymeric surfactants, alkanolamide or amine oxide surfactants. The amount of surfactant (if any) other than the specified betaine and alkyl ether sulfate is anyway not more than 1% by weight.

-I 17 C6074 While the light duty liquid detergent compositions of the invention are primarily adapted to use as hand dishwashing detergents, their use is not limited thereto. For instance, it may be appropriate to utilize the formulations as shampoos, bubble bath compositions, liquid soaps and the like.

The compositions of the invention may be prepared in the following manner. The required amount of alkyl ether sulfate active solution is poured into a mixing vessel fitted with an overhead stirrer. With the mixer operating at high speed, any 1 sodium xylene sulfonate solution is slowly added. Once the soluo* U S tion is homogeneous, water is slowly added to the center of the S vortex to minimize gelation. If electrolyte is required in the formulation, it should be dissolved in the water beforehand.

Once all the water has been added, mixing is continued until no gel particles are visible. The betaine solution is then added with mixing, followed by any color and fragrance. The entire process is carried out at room temperature.

Unless otherwise indicated, all percentages given herein are by weight.

-Jql 18 ;i C6074

EXAMPLES

Example 1 The following dishwashing liquid was prepared in accordance with the process described above.

Component by weight Ammonium C 12

-C

15 alcohol ethoxylated with 15.4% 3 moles ethylene oxide, sulfated Cocoamidopropylbetaine 8.6% Ethanol 3.9% Sodium chloride 1.4% Sodium xylene sulfonate Water, color, fragrance to 100% The viscosity of the product was 2000-2500 cps. The product was clear and stable.

1 9 Example 2 it Mildness An occlusive patch test was cpnducted to evaluate formulations for mildness potential. Ivory Liquid Dishwashing detergent was used as a standard. In the occlusive patch test, 2% solutions of a formulation are attached to the forearm using plastic discs. The discs are left on the arm for 24 hours, then the skin is evaluated 24 hours after removal of the discs. The lower the score, the less irritating the formulation. The following formulations were tested.

S19 C6074 Component A B C D E Sodium lauryl sulfate 14 Ammonium C12-C15 13.5 19 15 19 alcohol 3 EO, Sulfated (from Neodol 25-3A) Cocoamidopropylbetaine 8 7.5 6 Cocoamidopropylhydroxy- 6 sultaine Ethanol 3.4 4.75 3.75 4.75 Sodium Chloride 1.3 1.25 1.0 1.67 0.85 Sodium xylene sulfonate 1.5 1.5 1.5 1 Water 75.2 72.85 67.75 68.08 69.40 Formulation Irritation A (Comparison) 1.233 o' B 0.6 C 0.6 D 0.633 E 0.6 Ivory Liquid 0.7 There are no significant differences between formulations B,C,D and E in accordance with the invention and Ivory Liquid.

Example 3 Dispersibility A six foot clear tygon tube with an internal diameter of 3 cm was suspended vertically. The tube was calibrated, its end capped and filled with 40 degree C tap water. A 75 ul aliquot of 20 C6074 light duty liquid was injected onto the water surface using a positive displacement pipette. The LDL droplet was followed visually and the point where the drop could no longer be seen was recorded. Three trials were performed for each LDL. Fresh degree C tap water was used for each formulation. The larger the distance reported, the poorer the dispersability.

Formulation: Component 1 2 3 4 Ammonium C12-C15 13.5 13.5 13.5 13.5 13.5 alcohol ethoxylated with 3 moles Ethylene oxide, sulfated cocoamidopropyl betaine 7.5 7.5 7.5 7.5 t Ethanol 3.4 3.4 3.4 3.4 8.2 Sodium chloride 1.25 1.25 11.25 1.25 1.25 Sodium sulfate 4.0 8.0 Sodium xylene sulfonate 0.5 2.5 Water 73.85 67.85 64.35 66.35 69.55 Viscosity (cps) 2000 2000 2000 2000 2000 Formulation Dispersion Distance (inches) 1 32 2 3 did not disperse 4 did not disperse Commercial Dishwashing Liquid I 33 Commercial Dishwashing Liquid II 49 Viscosities were measured with a Brookfield viscometer using a 25 number 3 spindle. This example demonstrates the preferred embod-

I-

21 C6074 iment of a high viscosity LES/betaine mixture uhich possesses dispersability equal to that of marketed products. The higher viscosity provides an advantage in direct application washing.

Formulations 1, 2 and 5 containing sufficient hydrotrope such that the LDL is dispersed in this test are preferred. It is especially preferred that the LDL disperse within 40, preferably within 35, inches in this test.

Example 4 Piston Plunger Test The piston plunger is used to determine the relative abilities of LDLs to resist foam depletion in the presence of food soil. In the test, foam is generated and food soil is added in 10 gram increments. The agitation/soil addition cycles continue until the foam is depleted. The weight of the soil added is then determined and used as a relative measure of LDL efficacy.

I I 22 C6074 Crisco Shortening Soil agu Spaghetti Soil A Food Soil Including A Food Soil Including Crisco Shortening Ragu Spaghetti Sauce Example of Cleaning Performance

I

The piston plunger method using the Ragu spaghetti soil was utilized to determine the performance of the following formulations. The experiments were conducted at 400C.

Component 1 2 Ammonium C 12

-C

15 alcohol 13.5% 19.3% 3EO, sulfated Cocoamidopropylbetaine 7.5 10.7% Ethanol 3.40% 4.9% Sodium chloride 1.25% 1.8% Sodium xylene sulfonate 0.5 0.7% Water 73.85% 62.9% Formulation Trial 1 Trial 2 Trial 3 1 384g 428g 356g 2 435g 533g 405g Commercial Dishwashing Liquid I 363g 380g 289g Commercial Dishwashing Liquid II 422g 463g 371g The performance of formulation 1 (21% total active) is superior to that of Commercial Dishwashing Liquid I. The performance of formulation 2 (30% total active) is superior to that of Commercial Dishwashing Liquid II. Both Commercial Dishwashing Liquid I and Commercial Dishwashing Liquid II Liquids contain greater than 30% total actives.

23 C6074 Cleaning Performance

II

Effect of LES/betaine Ratio Evaluation was via piston plunger using Rague spaghetti sauce soil. The experiment was conducted at 40 0

C.

Component 1 2 3 4 Ammonium C 12

-C

15 alcohol 3 EO, sulfated 19.5% 16.5% 13.5% 10.5% Cocoamidopropylbetaine 1.5% 4.5% 7.5% 10.5% Ethanol 4.9% 4.15% 3.4% 2.6% Sodium chloride 0.25% 0.75% 1.25% 1.75% Sodium sulfate 4.0% 4.0% 4.0% Sodium xylene sulfonate 1.5% 1.5% 1.5% Water 68.35% 68.6% 68.85% 69.15% Formulation Trial 1 Trial 2 Trial 3 1 246g 280g 264g 2 317g 351g 342g 3 339g 341g 386g 4 321g 362g 372g Ivory Liquid Detergent 383g 429g 425g Commercial Dishwashing Liquid II 370g 403g 413g Commercial Dishwashing Liquid I 313g 320g 326g SAt a ratio of 4 LES/1 betaine and a total of 21% actives, equal performance to Commercial Dishwashing Liquid I is attained. At smaller ratios of LES/betaine (below and a total actives content of 21%, superior performance to Commercial Dishwashing Liquid I was observed.

24 C6074 Cleaning Performance

III

Comparison of 24% total active formulations to Ivory Liquid (33-34% total actives). The piston plunger test using the Crisco shortening soil at 40 degrees C was used.

o Oc 0O 0000 0 04 101 Component Ammonium C 12

-C

1 5 alcohol 3 EO, sulfated Cocoamidopropylbetaine Cocoamidopropylhydroxysultaine Ethanol Sodium chloride Sodium sulfate Sodium xylene sulfonate Water Viscosity (cps) 1 15.4% 8.6% 3.8% 1.4% 4.6% 1.7% 64.5% 2000 2 18.0% 4.6% 1.15% 4.0% 64.75% 2000 3 15.4% 3.8% 70.2% 2000 Formulation Weight of 1 2 3 Ivory Liquid Detergent Soil to Deplet' Foam 247g 239g 237g 250g Cleaning Performance IV The plates washing test was used to evaluate the examples from "Cleaning Performance III".

Plates Washing Test Soiled dishes are prepared by spreading 5 mls of Crisco (R) shortening soil on each dish with a spatula. They are then stacked. Meanwhile, water containing the appropriate amount of hardness is heated to 115 degrees F.

25 C60711 One gallon of the warm water is added to a was basin along with the appropriate amount of LDL. Foam is then generated by using a Mixette electric hand mixer at high speeds for 20 seconds.

Plates washing then proceeds using a standard wash cloth and washing regime. The operator submerges the plate and washes the front surface with six circular stokes. The plate is inverted, and the back surface is washed with three circular strokes. The plate is then removed from the wash solution, tipped against the Sasin's edge at a 45 degree angle for 3 seconds (to allow foam l;r and stacked. The process continues until half the wZt.- surface is no longer covered with foam, as judged by an independent observer. The number of plates washed is then counted and used as a relative measure of performance.

Formulation Plates Washed 1 36 2 33 3 31 Ivory Liquid 34 Both the piston plunger and plates washing test demonstrate that the preferred embodiment at 24% total actives level provides parity performance to a leading product containing 34% total actives.

Claims (7)

1. An aqueous liquid detergent comprising a) an essentially binary active system consisting of a betaine surfactant selected from: A) alkylamidobetaines having the formula: O .(CH 2 )y(CH 3 R-CNH (CH2)xN -CH2CO 2 I (CH 2 )zCH 3 where R is an alkyl or alkenyl chain containing 9 to 17 carbon atoms, x is an integer of 2 to 4, y is an integer of 0 to 3 and z is an integer of 0 to 3 and B) alkylamidosulfobetaines of formula: O R 2 5 4 1 i R CNH-R N(+)CH-R -SO 3 1 3 R Y X 1 wherein R is an alkylene radical having from 1 to 3 carbon atoms, X is hydrogen, methyl or hydroxy, Y is hydrogen or methyl, R 2 and R are each independently selected from methyl, ethyl and hydroxyethyl radicals, R 4 is an alkylene radical having from about 2 to about 6 carbon atoms and R is an alkyl radical having from 10 to 18 carbon atoms, and mixtures thereof and IL 7 \p~eL 27 C6074 (ii) an alkyl ether sulfate surfactant of formula: RO(CnH2nO)q-SO3X RO(CnH(2n+l)O)q-SO3X wherein R is higher alkyl or hydroxy alkyl group of from 8 to 18 carbon atoms, X is a member selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions and ammonium ions substituted with from one to three lower alkyl or alkenol groups, n is 2 or 3, and q is from 1 to 30, and mixtures thereof, the weight ratio of (i) Sto (ii) being in the range of 1:4 to 1:1, said detergent S\ containing no more than 1% by weight of surfactants other than and (ii); b) from 1 to 12% by weight of a hydrotrope, c) from 0 to 12% by weight of electrolytes and d) water.

2. A composition as claimed in claim 1, wherein the alkyl ether sulfate salt is an ammonium salt. I 3. A composition as claimed in claim 1 or claim 2 wherein the hydrotrope is selected from ethanol, isopropanol, C 1 and C 3 aromatic sulfonates and urea.

4. A composition as claimed in any one of claims 1 to 3 wherein the alkyl ether sulfate is a liner alkyl ether sulfate. 7 28 C6074 A composition as claimed in any one of claims 1 to 4 wherein the weight ratio of to (ii) is from about 1:3 to about 1:1.5.

6. A composition as claimed in any one of claims 1 to wherein the betaine surfactant is present at from 2 to 13% by weight.

7. A composition as claimed in any one of claims 1 to 6 wherein the alkyl ether sulfate is present at from 6 to 22% by weight.

8. A composition as claimed in any one of claims 1 to 7 comprising no greater than 30% total surfactant. o

9. A composition as claimed in any one of claims 1 to 8 wherein the electrolytes are selected from neutral salts of the group of sodium chloride, sodium sulfate and mixtures thereof. A method for the preparation of a composition according to any one of claims 1 to 9 which comprises E mixing together the surfactants, hydrotrope and an appropriate quantity of water. i DATED THIS 8TH DAY OF DECEMBER 1989 I UNILEVER PLC By its Patent Attorneys: GRIFFITH HACK CO. Fellows Institute of Patent Attorneys of Australia