US3533955A - Two-phase liquid detergent compositions - Google Patents

Description

United States Patent 3,533,955 TWO-PHASE LIQUID DETERGENT COMPOSITIONS Morton Pader, West Englewood, and Donald Jay Martin, Fair Lawn, N.J., assignors to' Lever Brothers Company, New York, N .Y., a corporation of Maine N0 Drawing. Filed June 15, 1965, Ser. No. 464,217 Int. Cl. A61k 7/06; C11d 3/44, 3/46 US. Cl. 252-153 14 Claims ABSTRACT OF THE DISCLOSURE High foaming two-phase liquid detergent compositions, such as composite shampoo/hair conditioning compositions and composite bubble bath/bath oil compositions, having an upper oily layer made up of a water-immiscible oily material and having a lower aqueous layer made up of an organic detergent system, an emulsion destabilizer and water, which compositions form temporary oil-inwater emulsions when shaken.

The present invention relates to detergent compositions and more particularly to two-phase liquid detergent compositions.

The two-phase liquid detergent compositions of the invention include those compositions designed to provide detergency while simultaneously providing for the deposition of a certain amount of oily material. Typical examples thereof include composite bubble bath/bath oil compositions as well as composite shampoo/hair conditioning compositions. The basic distinction between these two typical examples lies in the proportion of oil. This duality of properties is due to the fact that the compositions exist in the form of an upper oily layer and a lower aqueous layer and form temporary oil-in-water emulsions when shaken. The lower aqueous layer contains a foaming organic detergent system, as well as an emulsion destabilizer, so that it functions as a cleansing and copious foam-producing component. The upper oily layer, as the name implies, furnishes oily material which serves as a hair conditioning and hair grooming aid in the case of the shampoo/hair conditioning formulations and serves as a skin softener or emollient in the case of the bubble bath/ bath oil compositions.

The two-layer physical state of the compositions is essential in order that the compositions will produce a copious foam, in spite of the presence of a substantial quantity of oil, which is a desirable attribute in products designed to have good skin and hair cleansing properties and consumer acceptance and further in order that the compositions in the case of the bubble bath/bath oil compositions will leave a luxurious oily film upon the skin of the bather after bathing and in the case of the shampoo/hair conditioning compositions will leave the proper amount of oil upon the hair so that the hair will be manageable for grooming. This two-layer physical state of the compositions permits them to be colored with a colorant or dye in either one or both layers so that the products can have unusual aesthetic appeal. Thus, an appropriate oil-soluble dye can be incorporated into the upper oily layer and a water-soluble dye can be included in the lower aqueous layer to give the products a pleasing appearance. Moreover, the two-layer physical state of the compositions enables the user to recognize the presence in the compositions of the oil component thereof.

Although the compositions exist in the form of two separate layers, they are shaken prior to use whereupon they form oil-in-water emulsions which are only temporary due to the emulsion destabilizer therein. This emulsion state enables the user to measure out the requisite amount of the composite compositions each time the products are used. By temporary oil-in-water emulsion is meant an emulsion which breaks substantially, i.e., approximately /3 separation, into the original two-layer state within about 30 minutes in the following test.

The test apparatus comprises a horizontal reciprocating shaft having a 13 /2 inch long vertical shaft mounted perpendicularly thereon which is thereby reciprocated through a 40 arc, which are is bisected by the vertical axis of the vertical shaft. A 100 ml. glass stoppered, graduated cylinder having an inside diameter of 1.75 cm. and a height of 24 cm. is centrally clamped at the end of the vertical shaft longitudinally to the shaking motion. The cylinder is filled with 49 to 55 ml. of the product. The cylinder is agitated for 15 cycles. Each cycle lasts 1.5 seconds. The cylinder is then taken oh the apparatus and the phase separation of the product is observed.

The compositions are further characterized by the sharpness of the interface between the two layers in the separted state.

In order that the compositions will have the desirable properties mentioned above, it is essential that they contain four components, namely a water-immiscible oily material making up the upper oily layer and organic detergent system, an emulsion destabilizer and water making up the lower aqueous layer. The nature and amounts of these essential components are discussed below. It will be appreciated that the amounts are dependent upon the nature of the particular components present as well as upon the nature or use for the composition, e.g., as a composite bubble bath/bath oil or as a composite shampoo/hair conditioner.

The compositions contain from about 5% to about by weight of one or more Water-immiscible oily materials which form the constituent of the upper oily layer of the compositions. In the composite shampoo/ hair conditioning compositions the amount of oily material is from about 5% to about 20% by weight, while in the composite bubble bath/bath oil compositions the amount of oily material is from about 18% to about 65 by Weight. The oily material serves as a skin softener or emollient and as a hair conditioner or hair grooming aid. Amounts of the oily material less than about 5% are not employed, because one does not obtain the desired emollient or conditioning effect, while amounts thereof greater than about 65 are not utilized in view of the fact that foaming power is inadequate.

Typical suitable oily materials include light to heavy mineral or hydrocarbon oils, such as the light mineral oils having a Saybolt viscosity of 65-75 cps. at F. and a specific gravity of 0.835 to 0.845 at 60 F.; fixed oils or animal and vegetable oils, such as linseed oil, castor oil, olive oil, cottonseed oil, safilower oil, almond oil, peanut oil, coconut oil, coconut oil fractions, and sesame oil; synthetic oils which are fatty acid alkyl esters containing a total of from 16 to 22 carbon atoms, such as isopropyl myristate, isopropyl palmitate and isopropyl stearate; and lanolin compounds, such as the well known lanolin esters and lanolin alcohols. One of the preferred oily materials is mineral or hydrocarbon oil, because of the sharpness of the interface of the two layers. Highly unsaturated triglyceride oils, such as linseed oil and safflower oil, and fatty acid alkyl esters give less sharpness of the interface when used as the sole oily material although they enhance the foaming properies of the compositions when blended in varying amounts with other oily materials, such as mineral or hydrocarbon oil. The final oily layer should be liquid at room temperature.

There is present in the lower aqueous layer from about 5% to about 40% by weight of a foaming organic detergent system which function as a cleansing and foaming agent. In the composite bubble bath/bath oil compositions the amount of the foaming organic detergent system is from about 5% to about 25% by weight, while in the composite shampoo/hair conditioning compositions the amount of the foaming organic detergent system is from about 15% to about 40% by weight. These amounts thereof are utilized because lesser amounts produce insufiicient foam and cleansing action, while substantially greater amounts may cause problems with respect to appearance, irritation, oil detergent balance and too great an emulsion stability.

The foaming organic detergent system is a water-soluble non-cationic surface active agent, i.e., an anionic, nonionic or amphoteric surfactant, which produces acceptable foam or whose foam is supplemented by a suds improver. Preferred anionic detergents are the sodium, magnesium, ammonium, mono-, diand triethanolamine salts of sulfated fatty alcohols as well as these salts of the sulfonated alkylaryl compounds, all of which have a total of from 12 to 21 carbon atoms. Typical anionic detergents include solium lauryl sulate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium lauryl ether sulfate, ammonium lauryl sulfate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, sodium dodecylbenzene sulfonate, triethanolamine dodecylbenzene sulfonate and sodium N-lauroyl sarcosinate. Other anionic detergents include triethanolamine laurate-myristate and triethanolamine oleate.

Nonionic detergents include the alkylene oxide (ethylene oxide and propylene oxile) condensates of a hydrophobic base such as a long chain fatty alcohol or an alkylphenol, and fatty acid alkanolmides. Typicl of the fatty acid alkanolamides are those having a total of from to 21 carbon atoms, such as lauric diethanolamide, coconut oil monoethanolamide and lauric isopropanolamide, the alkylene oxide condensates of long chain fatty alcohols include C to C fatty alcohols condensed with 3 to 20 moles of ethylene oxide, such as the ethylene oxide condensates of lauryl alcohol, myristyl alcohol and palmityl alcohol. The alkylene oxide condensates of alkylphenols include the alkylphenols having a C C alkyl group condensed with 3 to moles of ethylene oxide, such as the octylphenol-8 mole ethylene oxide condensate, the nonyl phenol-10 mole ethylene oxide condensate and the dodecylphenol-IO mole ethylene oxide condensate.

Amphoteric or ampholytic detergents include N-lauryl- N'-carboxymethyl-N'- 2-hydroxyethyl) ethylenediamine, coco-beta-alanine, and the Miranol compounds described in US. Pats. Nos. 2,528,378 and 2,781,354.

An optional component generally present in the lower aqueous layer as a part of the foaming organic detergent system is one or more suds improvers which is utilized in the compositions in an amount from about 2% to about 15% by weight. When a suds improver is present, the amount of water-soluable non-cationic surfactant is then from about 3% to about by weight. The suds improver increases the sudsing power and the foam stability of the suds-producing detergent component even in the presence of the oil ingredient. Preferred suds improvers include tertiary amine oxides having one radical which is an alkyl radical of from 8 to 18 carbon atoms and two other radicals which are alkyl or hydroxalkyl radicals having from 1 to 4 carbon atoms, such as dimethyl dodecyl oxide, dimethyl cocoamine oxide, dimethyl tetradecyl amine oxide, dimethyl hexadecyl amine oxide and his (2- hydroxyethyl) cocoamine oxide. Further preferred suds improvers are C to C acyl amido-propyl-dimethyl-ammonium-acetic acid betaines, such as coconut oil fatty acyl and tallow oil fatty acyl amidopropyl-dimethyl-ammonium-acetic acid betaines, C to C alkyl-dimethylammonuim-acetic acid betaines, such as lauryl, myristyl, palmityl and stearyl-dimethyl-ammonium-acetic acid betaines, C to C acyl dimethyl ammonium propane-sulfonic acid betaines, such as coconut oil fatty acyl and tallow oil fatty acyl dimethyl ammonium propane-sulfonc acid betaines, and C to C alkyl dimethyl ammonium propanesulfonic acid betaines, such as lauryl, myristyl, cetyl and stearyl dimethyl ammonium propane-sulfonic acid betaines. Other suitable suds improvers include fatty acid alkanolamides having a total of from 10 to 21 carbon atoms, such as lauric diethanolamide, coconut oil monoethanolamide and lauric isopropanolamide.

A further essential component of the compositions present in the lower aqueous layer is one or more emulsion destabilizer which is employed in an amount from about 9% to about 45% by weight. In the composite shampoo/ hair conditioning compositions the amount of the emulsion desta-bilizer is from about 9% to about 28% by Weight, while in the composite bubble bath/bath oil compositions the amount of the emulsion destabilizer is from about 10% to about 45%. A minimum of 9% of the emulsion destabilizer is required, because lesser amounts thereof will not satisfactorily destabilize the emulsion which is temporarily formed upon shaking the two-phase liquid detergent compositions.

The preferred emulsion destablizer is an aliphatic monohydric alcohol having from 1 to 7 carbon atoms, such as methyl alcohol, ethyl alcohol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, tertiary butyl alcohol, isoamyl alcohol, hexyl alcohol and heptyl alcohol, and particularly ethyl alcohol and isopropyl alcohol. Other suitable emulsion destablizers include the aliphatic dihydric alcohols having from 2 to 7 carbon atoms, such as ethylne glycol, propylene gylcol and hexylene glycol; the monoalkyl ethers of aliphatic dihydric alcohols having a total of from 3 to about 6 carbon atoms, such as methyl, ethyl and butyl cellosolve; benzyl and phenylethyl alcohols; and dialkyl ketones having a total of from 3 to 5 carbon atoms, such as dimethyl ketone or acetone, methyl ethyl ketone and diethyl ketone.

The remaining essential component of the compositions present in the lower aqueous layer is water which serves as a solvent medium. Water constitutes substantially the balance of the compositions to give a total of by Weight.

While the compositions of the invention contain the above four essential components, other compatible adjuvants can be included therein. Thus the upper oily layer can contain a perfume or essential oil or an oil-soluble dye, while the lower aqueous layer can contain a perfume, water-soluble dye, water-soluble silicones, polyvinyl alcohol and inorganic salts, provided the adjuvants do not increase emulsion stability excessively. However, incompatible adjuvants cannot be incorporated into the compositions. Thus, fatty alcohols having at least 8 carbon atoms, such as decyl alcohol, are excluded, because in sufficient amount they may result in the formation of stable oil-in-water emulsions rather than in two-phase compositions having distinct upper and lower layers or else they can cause gelation of the system.

The compositions can be prepared merely by separately blending together the aqueous layer components and the oily layer components and then admixing the two layer formulations prior to use.

As pointed out above the two-phase liquid detergent compositions are shaken prior to use to forma temporary oil-in-water emulsion. An acceptable usage amount of the composite bubble bath/bath oil compositions is approximately 1 ounce per 20 gallons of bath tub water, while a typical usage amount of the composite shampoo/ hair conditioning compositions is approximately from 0.25 to 1 ounce per shampooing.

The compositions of the invention having the properties set forth hereinabove are exemplified by the formulations set forth below in Table I, wherein Examples 1 and 2 are illustrative of the bubble bath/bath oil compositions TABLE III Percent by weight Example No.

5 Components 11 12- 13 14 15 16 Triethanolamine lauryl sulfate 16 19 12 12 12 20 Bls(2-hydroxyethyl) cocoamine oxide 3 3 3 3 3 4 Ethyl alcohol..- 10 10 20 20 20 19 Light mineral oil 14 16 11 10 Cottonseed oil. 14 16 Isopropyl stearate. Olive oil 38 Acetulan (acetylated lanolin fraction) 38 Perfume 2 2 2 2 2 2 Water 41 34 25 25 33 15 Total 100 100 100 100 100 100 TABLE IV Percent by weight Example No Components 17 Ammonium lauryl sulfosuccinate- 19 Sodium lauryl sulfate Sodium lauryl ether sulfate. 10 15 Triethanol ammonium lauryl sulfate Total B Sodium salt of sulfate condensate of about 3 moles of ethylene oxide per mole of mixed alcohols derived from coconut oit.

and Examples 3 through 8 are illustrative of the sham- 35 poo/ hair conditioner compositions.

TABLE I Percent by weight Example No.

Components 1 2 3 4 5 6 7 8 Triethauolamine lauryl sulfate 12 12 18.6 186 Monoethanolamine lauryl lfate Sodium dodecylbeuzene fnn te Sodium N-lauroyl sarcosinate. N-lauryl-N-carboxymethyl-N-(z-hydroxyethyl) ethylenedlamine Dodecyldimethyl amine oxide 3 Bis-(2-hydroxyethyl) cocoamine'oxide 3 Light mineral oil 38 38 Olive oil-- Unsaturated hydroxyester from castor oil and lanolin (Rieilan C) Perfume" 2 2 Isopropyl alcohol- Ethyl alcohol 20 20 Water 25 25 'IotaL. s 100 100 Further examples of the bubble bath/bath oil com- 5 TABLE V positions of the invention are set forth in Tables II Example 29 through V followlng:

Components: Percent by wt. TABLE H Miranol 2MCA modified (dicarboxylic coconut Percent by derivative) 9 Weight Ethyl alcohol 20 Example No. Bis-(2-hydroxyethyl) cocoamine oxide 3 Components 9 10 Light mineral oll 38 N l h 110 l n l d d t 12 Perfume 2 ony p eno mo e et y ene oxi e eon ensa e Laurie diethanolamjde 1o 7 Water 23 gthylglcgllolnihnl.) d 2; 20 l is- 2- y oxye y cocoamine oxi e Light mineraloil 3g 3; Total 100 563 3 31:11:: 25 30 Further examples of the shampoo/hair conditioning 'nv ion ar t forth in ables VI Total i 100 100 COmPOSltlOI'lS Of the 1 6m; 6 SC T and VII following:

TABLE VI Percent by weight Exmple No.

Components 30 31 32 33 34 Lauric-myristic aeid 7. 8 Oleic acid 8. 7 Triethanolaminelauryl sulfate 15.0 18.0 18.0 17.0 Ammonium lauryl sulfate 3. Bis-(Z-hydroxyethyl)cocoamine oxide 4.5 4.5 4.5 4.2 Triethanolamine 10. 0 Protein hydroly Fractionated coconut oil (neobee O) Light mineral oil 6. 4 9. Olive oil. 3.3 5.0 Lanolin alcohol ester (ricilan C) 0. 3 O. 5 Ethyl alcohohol c- 24. 0 18. 0 Water 39.5 44.5

Total 100.0 100.0

TABLE VII layer which forms a temporary oil-in-water emulsion b h when shaken consisting essentially of (1) from about 5% w to about 65% by weight of a liquid water-immiscible oily Example No. material having skin-softening or emollient and hair-concomponents 36 37 30 ditiomng properties, (2) from about 5% to about 1 1 1m t 18 6 18 6 18 6 by weight of a water-soluble organic detergent selected fit iililil'iffitffifnii:::::::::::::::;:::: 18:0 18:0 1823 from t group consisting f ani n ni nic and am- O w 011 t y k g e y fi m photenc detergents, (3) from about 9% to about fif f?ff j iiii f {ff{ff by weight of an emulsion destabilizer selected from the Coconut oil fatty acyl g p gps g g g 4 5 5 group consisting of alkanols having from 1 to 7 carbon igr l gn ip g afif ???f fflii 5""f6 6' atoms, glycols having from 2 to 7 carbon atoms, monog g 0 alkyl ethers of glycols having a total of from 3 to 6 so iiiil l l gl ilo tfia I8 Carbon atoms, benzyl and phenyl ethyl alcohols, and di- Gorn oil (degummed) Lanolin alcohol ester 0 5 Wild??? 43. 4 41. 4 43. 4

Total 100. 0 100. 0 100. 0

The two-phase physical state of the liquid detergent compositions of the invention is critical as noted above. In a comparative test, more oily material was deposited on hair shampooed with a two-phase composition than with a single-phase composition having the same percentage level of oil. Thus, a representative two-phase composition containing 10% by Weight of a liquid waterimmiscible oily material produced an acceptable foam or lather and deposited 0.03% of oily material on hair (on 100 grams of hair the amount of oily material taken up by the hair was 0.03 grams), whereas a comparable singlephase composition containing 10% by weight of a liquid water-immiscible oily material produced an unacceptable foam or lather and deposited only 0.006% of oily material on hair. When the amount of oily material in the singlephase composition was reduced to only 0.5% by weight in order to produce an acceptable foam or lather, then the single-phase composition deposited only 0.0005 of oily material on hair.

It will be appreciated that various modifications and changes may be made in the compositions of the invention in addition to those set forth above without departing from the spirit thereof and accordingly the invention is to be limited only by the scope of the appended claims.

What is claimed is:

1. A high foaming two-phase liquid detergent composition having an upper oily layer and lower aqueous alkyl ketones having a total of from 3 to 5 carbon atoms, and (4) the balance substantially Water; said amounts being adjusted within said ranges to give said high foaming two-phase liquid composition.

2. The composition as set forth in claim 1 wherein the liquid water-immiscible oily material is a blend of mineral oil and an unsaturated triglyceride oil.

3. A high foaming two-phase liquid composite shampoo/hair conditioning composition having an upper oily layer and lower aqueous layer which forms a temporary oil-in-water emulsion when shaken consisting essentially of (1) from about 5% to about 20% by weight of a liquid water-immiscible oily material having hair-conditioning properties, (2) from about 15% to about 40% by weight of a water-soluble organic detergent selected from the group consisting of anionic, nonionic and amphoteric detergents, (3) from about 9% to about 28% by Weight of an emulsion destabilizer selected from the group consisting of alkanols having from 1 to 7 carbon atoms, glycols having from 2 to 7 carbon atoms, monoalkyl ethers of glycols having a total of from 3 to 6 carbon atoms, benzyl and phenyl ethyl alcohols, and dialkyl ketones having a total of from 3 to 5 carbon atoms, and (4) the balance substantially water; said amounts being adjusted within said ranges to give said high foaming two-phase liquid composition.

4. A high foaming two-phase liquid composite bubble bath/bath oil composition having an upper oily layer and a lower aqueous layer which forms a temporary oilin-water emulsion when shaken consisting essentially of (1) from about 18% to about 65 by weight of a liquid water-immiscible oily material having skin-softening or emollient properties, (2) from about 5% to about 25% by weight of a water-soluble organic detergent selected from the group consisting of anionic, nonionic and amphoteric detergents, (3) from about 10% to about 45% by weight of an emulsion destabilizer selected from the group consisting of alkanols having from 1 to 7 carbon atoms, glycols having from 2 to 7 carbon atoms, monoalkyl ethers of glycols having a total of from 3 to 6 carbon atoms, benzyl and phenyl ethyl alcohols, and dialkyl ketones having a total of from 3 to carbon atoms, and (4) the balance substantially water; said amounts being adjusted within said ranges to give said high foaming two-phase liquid composition.

5. A high foaming two-phase liquid detergent composition having an upper oily layer and a lower aqueous layer which forms a temporary oil-in-water emulsion when shaken consisting essentially of (1) from about 5% to about 65% by weight of a liquid water-immiscible oily material having skin-softening or emollient and hair-conditioning properties, (2) from about 3% to about 25% by weight of a water-soluble organic detergent selected from the group consisting of an anionic, nonionic and amphoteric detergents, (3) from about 2% to about by weight of a suds improver, (4) from about 9% to about 45 by weight of an emulsion destabilizer selected from the group consisting of alkanols having from 1 to 7 carbon atoms, glycols having from 2 to 7 carbon atoms, monoalkyl ethers of glycols having a total of from 3 to 6 carbon atoms, benzyl and phenyl ethyl alcohols, and dialkyl ketones having a total of from 3 to 5 carbon atoms, and (5) the balance substantially water; said amounts being adjusted within said ranges to give said high foaming two-phase liquid composition.

6. A high foaming two-phase liquid detergent composition having an upper oily layer and lower aqueous layer which forms a temporary oil-in-water emulsion when shaken consisting essentially of (1) from about 5% to about 65% by weight of a liquid water-immiscible oily material selected from the group consisting of mineral oils, fixed oils, fatty acid alkyl esters containing a total of from 16 to 22 carbon atoms and lanolin, (2) from about 3% to about by weight of a synthetic organic anionic nonsoap detergent selected from the group consisting of sulfonated and sulfated anionic detergents, (3) from about 2% to about 15% by weight of a suds improver selected from the group consisting of tertiary amine oxides having one radical selected from the group consisting of alkyl radicals having from 8 to 18 carbon atoms and the other two radicals selected from the group consisting of alkyl and hydroxyalkyl radicals having from 1 to 4 carbon atoms, fatty acid alkanolamides having a total of from 10 to 21 carbon atoms, a C to C acyl amidopropyl-dimethyl-ammonium-acetic acid betaine, a C to C alkyl dimethyl-ammonium-acetic acid betaine, a C to C acyl dimethyl-ammonium-propanesulfonic acid betaine and a C to C alkyl dimethyl-ammonium propanesulfonic acid betaine, (4) from about 9% to about by weight of an emulsion destabilizer selected from the group consisting of alkanols having from 1 to 7 carbon atoms, glycols having from 2 to 7 carbon atoms, monoalkyl ethers of glycols having a total of from 3 to 6 carbon atoms, benzyl and phenylethyl alcohols, and dialkyl ketones having a total of from 3 to 5 carbon atoms, and (5) the balance substantially water, said amounts being adjusted within said ranges to give said high foaming two-phase liquid composition.

7. A high foaming two-phase liquid detergent composition having an upper oily layer and lower aqueous layer which forms a temporary oil-in-water emulsion when shaken consisting essentially of (1) from about 5% to about by weight of a mineral oil, (2) from about 3% to about 25 by weight of a synthetic organic anionic nonsoap detergent selected from the group consisting of sulfonated and sulfated anionic detergents, (3) from about 2% to about 15% by weight of a tertiary amine oxide suds improver having one radical selected from the group consisting of alkyl radicals having from 8 to 18 carbon atoms and the other two radicals selected from the group consisting of alkyl and hydroxyalkyl radicals having from 1 to 4 carbon atoms, (4) from about 9% to about 45% by weight of an alkanol having from 1 to 7 carbon atoms, and (5 the balance substantially water, said amounts being adjusted within said ranges to give said high foaming two-phase liquid composition.

8. A high foaming two-phase liquid detergent composition having an upper oily layer and lower aqueous layer which forms a temporary oil-in-water emulsion when shaken consisting essentially of (1) from about 5% to about 65% by weight of a light mineral oil, (2) from about 3% to about 25% by weight of a synthetic organic anionic sulfated nonsoap detergent having from 12 to 21 carbon atoms, (3) from about 2% to about 15 by weight of a tertiary amine oxide suds improved having one radical selected from the group consisting of alkyl radicals having from '8 to 18 carbon atoms and the other two radicals being selected from the group consisting of alkyl and hydroxyalkyl radicals having from 1 to 4 carbon atoms, (4) from about 9% to about 45% by weight of ethyl alcohol, and (5) the balance substantially water, said amounts being adjusted within said ranges to give said high foaming two-phase liquid composition.

9. The composition as set forth in claim 1 wherein the upper oily layer consists essentially of component (1) and the lower aqueous layer consists essentially of components (2), (3), and (4).

10. The composition as set forth in claim 5 wherein the water-soluble organic detergent is a syntheic organic anionic sulfated nonsoap detergent having from 12 to 21 carbon atoms and the suds improver is a tertiary amine oxide having one radical selected from the group consisting of alkyl radicals having from 8 to 18 carbon atoms and the other two radicals selected from the group consisting of alkyl and hydroxyalkyl radicals having from 1 to 4 carbon atoms.

11. The composition as set forth in claim 5 wherein the water-soluble organic detergent is a synthetic organic anionic sulfated nonsoap detergent having from 12 to 21 carbon atoms and the suds improver is a C to C acyl dimethyl-ammonium propanesulfonic acid betaine.

12. The composition as set forth in claim 5 wherein the water-soluble organic detergent is a synthetic organic anionic sulfated nonsoap detergent having from 12 to 21 carbon atoms and the suds improver is a C to C alkyl dimethyl ammonium propanesulfonic acid betaine.

13. A high foaming two-phase liquid composite shampoo/hair conditioning composition having an upper oily layer and a lower aqueous layer which forms a temporary oil-in-water emulsion when shaken consisting essentially of the following components in the approximately indicated weight proportions:

Percent Light mineral oil 9.5 Olive oil 5 Triethanolamine lauryl sulfate 18.6 bis-(Z-hydroxyethyl) cocoamine oxide 4.5 18

Ethyl alcohol Balance substantially water.

Percent Light mineral oil 9.5 Olive oil 5 Triethanolamine lauryl sulfate 18.6

Coconut oil fatty acyl amido-propyl dimethyl ammonium acetic acid betane Ethyl alcohol Balance substantially water.

References Cited UNITED FOREIGN PATENTS OTHER REFERENCES STATES PATENTS Streatfield: Soap, Perfumery and Cosmetics, v01. 24,

Rider et a1 252-312 XR P 809, August 1951,

Lang et a1. 252152 Stewart. 5 LEON D. ROSDOL, Primary Examiner E32 XIII: D. L. ALBRECHT, Assistant Examiner US. Cl. X.R.

Canada. 10 42470; 252-118, 152, 161

Great Britain.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3:533: 955 Dated October 3, 97

Inventor(s) Morton Pader and Donald Jay Martin It is certified that error appears in the aboveidentified patent and that said Letters Patent are hereby corrected as shown below:

Column 3, line 39, "solium lauryl sulate" should be sodium lauryl sulfate ----a line 50, "alkanolmides' should be alkanolamides and 'Typicl" should be Typical --5 line 5 "amide the" should be amide. The line 7A, "water-soluable should be water-soluble Column lines 7 and 8, after "dodecyl" and before "oxide" (first occurrence, line 8), insert amine --5 line 19 propanesulfonc" should be propane-sulfonic --5 line 18, "ethylne" should be ethylene Column 5, line 6, "forma" should be form a Column 6, last line of Table IV, "coconut oit" should be coconut oil Column 7, line 12,

"(neobee 0)" should be (Neobee 0% line 15, (ricilan C) should be (Ricilan C) line 1 "Ethylalcohohol" should be Ethyl alcohol line 5 of Table VII under Example 37, the figure "18.3" should be 18.0 -3 line 11 of Table VII under Example 37, the figure "9.0" should be 9.5 Column lO line 1? "improved" should be improver --5 line 31 'syntheic should be synthetic -5 line 73, "betane should be betaine SIGNED mm smsn M9 1971 m1 1:. an.

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