AU674255B2

AU674255B2 - Low silicone hair conditioning shampoo and non-silicone hair conditioning/style control shampoo

Info

Publication number: AU674255B2
Application number: AU77575/94A
Authority: AU
Inventors: Amrit Patel; Clarence R. Robbins
Original assignee: Colgate Palmolive Co
Current assignee: Colgate Palmolive Co
Priority date: 1993-11-19
Filing date: 1994-10-31
Publication date: 1996-12-12
Anticipated expiration: 2014-10-31
Also published as: BR9404485A; FR2712490A1; AU7757594A; MY116217A; FR2712490B1; TW388714B; ZA948478B

Description

1-

AUSTRALIA

Patents Act 1990 COLGATE-PALMOLIVE

COMPANY

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT *0

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Invention Title: "Low silicone hair conditioning shampoo and non-silicone hair conditioing/style control1 shaimpoo"l The following statemnent, is a full description of this invention including the best method of performing it known to us:- BACKGROUND OF THE INVENTION s@ o 0 *s Discusion Of the Prior Art So-called two-in-one hair conditioning shampoos which achieve hair conditioning as well as hair cleansing with one product have been formulated to overcome the disadvantages associated with the necessity for sequentially applying separate compositions to the hair to achieve these purposes; 6 The present invention relates to hair conditioning shampoos containing little or no water-insoluble silicone hair l3 conditioning agents.

0066** a Disousaion of the Prior Art So-called two-in-one hair conditioning shampoos which achieve hair conditioning as well as hair cleansing with one product have been formulated to overcome the disadvantages associated with the necessity for sequentially applying separate compositions to th hair to achieve these purposes; one is a shampoo to cleanse the hair and the other is a separate hair conditioner to condition the hair.

Certain cationic compounds and polymers have been found to be excellent hair conditioning agents. However, combining these agents in a shampoo formulation with anionic surfactants which have been found to be the most effective for removing sebum, soil and other atmospheric contaminants gives rise to inherent incompatibility problems between the two types of agents. Contact between a negatively charged anionic surfactant and a positively charged cationic surfactant or cationic polymer produces a precipitate that forms immediately or causes an interaction between the anionic and cationic compounds that significantly reduces their respective cleaning and conditioning properties. The reduction in cleansing and conditioning effectiveness is observed even in compositions wherein the anionic and cationic compounds do not precipitate from the composition, but remain in solution or suspension.

This incompatibility between an anionic surfactant and a 0* cationic conditioning compound is well recognized by those skilled in the art. For example, in Cosetrics, Interscience Publishers, Inc., New York, p. 538 (1957), author Sagarin states that anionic and cationic compounds cannot be used in combination because they react to form insoluble salts.

A partial solution to this incompatibility problem in the formulation of conditioning shampoos lies in substituting nonionic, amphoteric or zwitterionic surfactants for the conventionally employed anionic surfactants in shampoos containing cationic conditioning agents. See, United States Patent Nos. 3,849,348 (Hewitt); 3,990,991 (Gerstein); and 3,822,312 (Sato).

Another difficulty inherent in formulating a conditioning shampoo is an instability problem that results when water-insoluble conditioning agents are also included in the conditioning shampoo composition, such as the non-volatile silicones that are well recognized in the art as providing a degree of softness to the hair.

Silicones in shampoo compositions have been disclosed in a number of prior patents, United States Patent Nos. 2,826,551 (Green); 3,964,500 (Drakoff); 4,364,837 (Pader); 4,741,855 (Grote et al); 4,788,006 (Bolich, Jr. et al); 4,902,499 (Bolich, Jr. et al); 4,704,272 (Oh et al); and British Patent No. 849,433 (Woolston).

A particularly difficult obstacle to overcome in silicone-containing conditioning shampoos is that of main- Staining a dispersed, insoluble, non-volatile silicone material suspended in stable form while retaining the cleansing and 0 conditioning performance of the conditioning shampoo. The stability barrier is particularly prevalent in conditioning shampoos containing an anionic surfactant and a cationic conditioning material which, as outlined above, by themselves tend to interact and present stability dilemmas. A variety of materials have been proposed for inclusion in siliconecontaining conditioning shampoos for purposes of thickening and stabilization u h as xanthan gum, long chain acyl derivatives, long chain amide oxides, and long chain alkanolamides such as those disclosed in, United States Patent Nos. 4,788,006, 4,704,272 and 4,741,855 mentioned hereinabove.

There are also environmental concerns associated with the use of silicones inasmuch as they are not easily biodegraded. Furthermore, processing problems arise when using silicones, particularly high viscosity silicones.

Finally, it is difficult to remove silicones from the hair, thereby reducing the effectiveness of perming and coloring processes.

Numerous attempts have been made to provide so-called three-in-one shampoo compositions, shampoo formulat kons which will provide not only hair cleansing action, but also hair conditioning effects and style control or set and curl retention of the hair following completion of the shampooing and rinsing operations.

Hair conditioning effects are usually described as o softness and smoothness of the hair after washing, a less sticky feeling, easy passage of the comb through the hair, a less hard or rough feeling after shampooing, relief from static electricity or "fly-away" and manageability.

Hair styling, i hair style retention or hold or set and curl retention can be accomplished in two ways.

First, the hair can be subjected to a permanent chemical alteration to achieve a certain desired shape. Secondly, a temporary alteration of the shape of the hair can be achieved, generally by applying to the hair a third composition following shampooing and/or hair conditioning agent. The materials comprising these temporary style control compositions have traditionally been resins, gums, etc., and are usually applied to the previously shampooed and/or conditioned hair in the form of mousses, gels, lotions or sprays. Drying the thus-treated hair results in a "set" of the resinous or gum material to a stiff condition which temporarily holds the hair in the desired shape.

The temporary style control agents differ from the permanent style control treatments in that the latter are marginally affected by subsequent shampooing operations, whereas the temporary agents are completely removed upon shampooing thereby requiring their re-application after every shampoo operation in order to maintain the desired style control.

One type of temporary style control agent are the adhesive polymers which generally comprise a non-water solvent, and a soluble rigid polymer having a glass transition temperature above the temperature normally reached in styling C operations, blow drying, etc. Examples of such polymers are those described in United States Patent Nos. 3,743,715, 4,165,367 and 4,223,039.

Other polymers heretofore suggested for temporary style control are multi-component polymers which combine up to four or more monomers. Exemplary of these types of style control polymer systems are those disclosed in United States Patent Nos. 3,222,329, 3,577,517, 4,012,501 and 4,272,511.

Block copolymers having multiple glass transition temperatures have also been employed as style control agents, such as those described in United States Patent Nos.

3,907,984, 4,030,512 and 4,283,384.

United States Patent No. 5,104,642 describes the use in a hair styling composition of a polymer comprising up to of a first polymerizable hydrophilic monomer and the remainder a second polymerizable hydrophilic monomer, the resulting polymer having a molecular weight of 5,000 to 1,000,000, a glass transition temperature, Tg, of greater than -20"C and a solubility parameter, 6, of 8.5 to 12.0, International Application No. PCT/US91/02170, published October 17, 0 1991, discloses the incorporation of these types of polymers in a hair shampoo formulation.

Canadian Patent No. 2,033,626 describes a shampoo composition which provides set and curl retention comprising at least one anionic surfactant, a Film-forming polymer Polymer JR, GAFQUAT 755, MERQUAT 550, chitosan or its derivatives, CROQUAT S, LAMEQUAT L or methylvinyl imidazolium chloride/vinyl pyrrolidone copolymer and large amounts of citric acid to enhance the effect of the film-forming polymer.

There is no disclosure in the patent that hair conditioning properties are possessed by the shampoo formulation.

It is an object of the present invention to provide a hair conditioning shampoo which solves the above-noted prior art problems.

It is another object of the invention to provide a hair conditioning shampoo having a high degree of hair conditioning activity and a hair conditioning shampoo which provides style control.

SUMMARY OF THE INVENTION These and other objects are realized by the present invention which relates to an aqueous dispersion of a waterinsoluble lipid phase, an aniohic hair cleansing surfactant and at least one hair conditioning, film-forming, polycationic polymer and 0-6% by weight, based on the weight of the shampoo, of a water-insoluble, non-volatile silicone hair conditioning agent; said polycationic polymer being soluble in said aqueous detergents; said water-insoluble lipid phase com-

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prising at least one lipid-soluble, emulsifiable, monocationic, quaternary ammonium compound or amine solubilized in a water-insoluble, long chain lipid compound, the weight ratio o of monocationic compound to said lipid compound in said lipid phase being in the range of from about 5:1 to about 1:10 and the molar ratio of anionic surfactant to water-insoluble .'20 cationic compound is greater than 2:1, preferably from about 2:1 to about 50:1 and most preferably from about 5:1 to about 30:1.

DETAILED DESCRIPTION OF THE INVENTION The invention is predicated on the discovery that in an aqueous hair conditioning shampoo containing anionic surfactants and detergent-soluble polycationic conditioning agents and relatively low amounts of a water-insoluble, nonvolatile silicone hair conditioning agent, pi .erce in the shampoo of a water-insoluble lipid phas dissolved therein a monocationic, lipid soluble hair co,,ditioning agent results in a hair conditioning shampoo with enhanced hair conditioning and hair cleansing properties, while avoiding many of the instability and reduced effectiveness drawbacks

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associated with conventional two-in-one shampoo formulations.

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It has unexpectedly been found that in the hair

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conditioning shampoo of the invention, the lipid solubilized monocationic compound acts synergistically rather than com- *.!"petitively with the water-soluble polycationic polymeric

*OC

e agents to provide an enhanced hair conditioning effect over that provided by conventional hair conditioning shampoos, while employing very little silicone co-conditioners.

Moreover, it is believed that the presence of the

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lipid phase acts to greatly reduce the inherent instability of

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anionic surfactant/cationic conditioner combinations by limiting contact between the respective oppositely charged species in the formulation. The lipid phase containing the monocationic agent appears to function in the formulation as a water-insoluble conditioner, much like a silicone for oexample, but without the disadvantages associated with typical water-insoluble conditioning agents, such as instability, the tendency to leave an uneven coating on the hair, etc.

Most unexpectedly, it has been found that the absence of a water-insoluble, non-volatile silicone hair conditioning agent from the above-described formulation imparts style control properties to the shampoo. It was also unexpectedly found that the absence of silicone from the shampoo formulation of the invention results in a high degree of hair damage repair, including split end repairt as well as higher style retention, *A critical feature of the present invention resides in the lipid/lipid-soluble monocationic conditioning agent phase of the hair~ conditioning shampoo.

Suitable lipid-soluble monocationic compounds for inclusion in the lipid phase of the shampoo include any of the aliphatic long chain, monocationic, quaternary ammnonium compounds or amines having at least one long chain aliphatic group, preferably alkyl, having an average of from about 16 to about 40 carbon atoms. Azines having appropriate p~a values, .0 i. e.,f at least about 7.o5 would where the pH of the shampoo formulation is 6 or less, be partially protonated, thereby providing the necessary cationic charge to function as a hair conditioning agent.

The hair conditioning shampoo of the present invention mray include any of t~he conventional adjuvants normally employed in such shampoos such as those disclosed in United States Patent NIo. 5,078,990.

For example, an amphoteric or zwitterionic surfactant may be included in the formulation as a co-surfactant.

In certain preferred shampoo formulations (see Examples 1, and 7 hereinbelow) the amphoteric surf actant is the principal detergent.

F'uitable such amphoter.c surfactants include those corresponding to the formula: R RXOO

I

1 wherein R is a C -cis alkyl or C -C 1 alklanolamido C-C alXyl, 10 R 1 is C 1

-C

3 alkyl, R, is a C -C 4 alkylene or C-C hydroxy alkylene and X is C or SiO. When X is C, the detergent is S4.

called a betaine and when X is 440 the detergent is called a sultaine or sultobetaine. These zwitterionic detergents can be described broadly as derivatives of aliphatic quaternary ammonium or tertiary sulfonium compounds containing aCa-a aliphatic radical which may be straight chained or branch **chained and (containing an anionic group. Preferred betaine and sultaine detergents are tzocoam idopropyl beta in e, lauryl- ~d im4thylallufofioacetate, inyristyldimethylammonioacetate,

CS-C

18 alkanamidopropyldimethylammonicacetate 1- (myriztylcimethy1ammonio) -propane-3-sulf onate and 1- (myrintyldimethylammonio) 2 -hydroxypropane-3 -sul fonate# United States Patent !No4 $1078,990 (Martin et al), tfle disclosure of which is incorporated herein by reference, discloser, that an aqueouin shampoo containing a long chain SlA Us~ alkyl sulfate and/or long chain alkyl ether sulfate anionic surf actant and a cationic di-long chain alkyl quaternary ammonium nitrogen-containing compound unexpectedly increases the ability of the aqueous shampoo to incorporate waterinsoluble conditioning ageints, particularly non-volatile silicone materials, and remove previously applied conditioning agents and other soiled conditioning agents and contaminants from the hair. The patent, however, requires the presence of a water-insoluble conditioning agent and specifies that the molar ratio of anionic surfactant to long chain quaternary ammonium compound is at least about 85:1, and preferably higher. Any of the long chain quaternary ammnonium ionocationic compounds disclosed in United States Patent egO. No. 5,078,990 may be utilized in the practice of the present inventioni.

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Preferred among the monocationic compounds are distearyldimethylammoiiu, d icetyld imethyl ammnonium, tricetylmethylammonium, behenyltrimethylamnoniumi catyltrimethylammionium, hexadecyl 'trimethYlammonium, stearyl benzyl 0:00:20 dimethylamnmonium, cetyl pyridinium salts, chlorides, Sbromides, etc. Suitable alzines include distearylamine, distearylmethylamine# behenyl amine, behenylmethylamino, behenyldimethylamine, dicetylamine, dicetylmethylamine, tricetylamine, etc.

Se-44de-n~ud~g-ha~n~4pM~C Q-C -a.r 11/1 Suitable lipids include long chain aliphatic C 20

-C

5 0 alcohols having an average of 28 to 42 carbon atoms, long chain aliphatic acylated ingredients, esters and amides with at least one long chain greater than about 16 carbon atoms, ethylene glycol distearate, glyceryl tristearate, beeswax, isosteareth-2, isosteareth-lO, petrolatum, isostearyl l.ctate, isopropyl isostearate, isocetyl stearate, ethoxylated alcohols, alcohols having a chain length equal to or greater than 16 carbon atoms wherein the number of ethoxy groups may vary up to a maximum of about 40, and long chain aliphatic acids, e.g,, carboxylic acids having chain lengths of from about 16 to about 40 carbon atoms. Preferably, the lipid ingredient will be a mixture of said C 20

-C

50 alcohol or ethylene glycol distearate with an ethoxylated alcohol. Most preferably, the lipid will be a mixture of said long chain alcohol and isosteareth-2.

0@ 6 0 4 00 000 0e *0

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*0 0 4 0* I- t -24 carbon ata--- yc di--1tAA glyceryl tristearate, beeswax, isosteareth-2, isostee petrolatum, isostearyl lactate, isopropyl i earate, isocetyl stearate, ethoxylated alcohols, alcohols having a chain length equal to or greaty than 16 carbon atoms wherein the number of ethoxy g ps may vary up to a maximum of about and long chan aliphatic acids, carboxylic acids having in lengths of from about 16 to about 40 carbon afoms.

The shampoo is formulated such that the weight ratio of monocationic compound to lipid compound is in the range of from about 5:1 to about 1:10, The shampoo should, however, contain at least about 0.7% by weight of the monocationic compound to ensure a sufficiently high degree of hair condi- 15 tioning effect. It has been found that employing less than about 0.7% by weight of monocationic compound results in a shampoo which does not sufficiently condition hair to avoid problems of, "fly-away." Generally, the lipid phase comprises from about *20 1% to about 16% by weight, and preferably from about 4% to about 10% by weight of the shampoo formulation.

Any of the conventionally employed anionic surfactants may be utilized in the shampoo of the present invention.

Typical of these surfactants are those set forth in United States Patent No. 4,554,098, the entire disclosure of which is incorporated herein by reference. Suitable such anionic surfactants include the water-soluble salt of a sulfuric acid L ester of the reaction product of one mole of a CI,-C 1 6 alkanol with 5 to 12 moles of ethylene oxide. These detergents are described in the prior art as alkyl ether sulfates of the following structural formula: R (OC 2

H

4 nOSM wherein R is an alkyl containing about 10 to about 16 carbon atoms, n has an average value of 5 to 12 and M is a cation.

Usually, the cation will be selected from the group consisting of sodium, potassium, ammonium and mono-, di- and tri- 10 ethanolammonium.

a .s 1 Preferably, the alkyl ether sulfates will contain 12 S.to 14 carbon atoms in the alkyl group and will be employed in the form of the sodium or ammonium salt. Examples of suitable alkyl ether sulfates are sodium C 12 -c 14 alkyl ethylenoxy sulfate, ammonium ci 1 -c,4 alkyl ether ethylenoxy sulfate, .sodium CI-C 1 4 alkyl ether ethylenoxy sulfate, sodium

C

1 2-C 1 4 alkyl ether ethylenoxy (11.4) sulfate, potassium C 12

-C

16 alkyl ether ethylenoxy sulfate, ammonium C 12 -C,1 alkyl ether ethylenoxy sulfate and ammonium C 1 2-C 16 alkyl ether ethylenoxy sulfate. Preferred alkyl ether sulfates are the sodium and ammonium C 12 -c 1 3 or C1-C1 alkyl ether ethylenoxy 9) sulfates.

Additional anionic detergents are water-soluble, non-soap, anionic detergents having in their molecular structure a c 7

-C,

2 alkyl, alkenyl or acyl group and a sulfonate, sulfate or carboxylate group. Such detergents are employed in the form of water-soluble salts and the salt-forming cation is usually selected from the group consisting of sodium, potassium, ammonium, and mono-, di- or tri-C 2

-C

3 alkanolammonium, with the sodium and ammonium cations again being preferred.

Suitable such anionic detergents include the following: 1. The C 8

-C

1 alkyl sulfates which are usually obtained by sulfating C 8 -C18 alkanols obtained by reducing the glycerides of tallow or coconut oil. Preferred alkyl sulfates contain 10 to 16 carbons in the alkyl group.

.0 2. The C 9 alkylbenzene sulfonates wherein the V alkyl group is either a straight chain or a branched chain, with the straight chain being preferred for its improved biodegradability.

3. The C 8 olefin sulfonates which may be obtained by sulfating the appropriate olefin. Preferred olefin sulfonates contain from 14 to 16 carbon atoms in the alkyl group and are obtained by sulfonating an a-olefin.

4. The Cg-Cs, alkyl ether ethylenoxy sulfates of 20 the formula: SR (OC2) nOS03M wherein n is 1 to 4. These sulfates differ from the primary alkyl ether sulfate detergent in the number of moles of ethylene oxide reacted with one mole of alkanol in forming the ethoxylated alkanol which is sulfated and neutralized to form this anionic detergent. Preferred alkyl ether ethylenoxy sulfates contain 10 to 16 carbon atoms in the alkyl L I group and contain 2 to 3 ethylene oxide groups per mole of alkanol.

The C,-C 20 paraffin sulfonates obtained, for example, by reacting an a-olefin with bisulfite. Preferred alkane sulfonates contain 13 to 17 carbon atoms in the alkyl group.

6. The C 6

-C

1 phenyl ether polyethylenoxy sulfates containing from 2 to 6 moles of ethylene oxide in the molecule may also be used. These detergents can be prepared by reacting an alkyl phenol with 2 to 6 moles of ethylene oxide and sulfating and neutralizing the resultant ethoxylated alkylphenol. Preferred detergents in this group have 8 to 12 carbon atoms in the alkyl group and contain about 4 ethylene oxide groups in the ,,,olecule.

7. The C 8

-C,

1 alkyl sulfoacetates corresponding to the formula:

ROOCCH

2

SO

3

M

wherein R is a C 8

-C,

8 alkyl which may be prepared by esterifying an alkanol with chloroacetic acid or chloroacetyl 20 chloride and then reacting the chloroester with a sodium or a potassium bisulfite. Preferred sulfoacetates contain 12 to 16 carbon atoms in the alkyl group.

8. The N-mono-Cg-C 22 alkyl (includes alkyl groups interrupted by an ether or amido group) sulfosuccinates prepared by reacting, for example, either one mole of Cg-Cla alkanol or a Cg-Cg alkoxy c 2

-C

3 alkanol or a Cs-cg alkanamido C2-c; alkanol with maleic acid and reacting the resultant r a product with an alkali metal bisulfite to form an N-mono-C-C 22 alkyl sulfosuccinate. It should be recognized that the alkyl group of product made from the N-acyl alkanolamine will contain an amido intermediate linkage. Similarly, the alkyl group may be interrupted by an ether linkage or ester linkage if an alkyl ether ethanol or an alkyl ester of ethylene glycol is reacted with maleic acid. Preferred sulfosuccinates are disodium N-mono-Cg-C 18 acylisopropanolaminosulfosuccinate, disodium lauryl sulfosuccinate and N-monooleylisopropanolaminosulfosuccinate.

9. The N-Cs-Cis acyl sarcosines may be produced by neutralizing the reaction product of a C 8

-C

1 8 alkanoic acid with N-methyl glycine. Preferred sarcosinates contain 12 to 14 carbon atoms in an acyl group obtained by l:\iction of 15 coconut oil.

The N-Cg-CIy acyl taurines may be produced by neutralizing the reaction product of a C,-Cg alkanoic acid with aminoethylsulfonic acid. Again, preferred taurates contain 12 to 14 carbon atoms in an acyl group obtained by 20 reduction of coconut oil.

11. The O-C 8

-C

1 8 acyl isethionates may be produced •by neutralizing the reaction product of a C 8 -C1 8 alkanoic acid 4 with 2-hydroxyethanesulfonic acid. Similar to the sarcosines and taurines, the preferred isethionates contain 12 to 14 carbon atoms in an acyl group obtained by reduction of coconut oil.

Cpl r~ C I_ The anionic surfactant is generally present in an amount of from about 3% to about 25%, and preferably from about 7% to about 14% by weight of the shampoo formulation.

Any of the conventional hair conditioning, filmforming polycationic hair conditioning agents used in typical prior art hair conditioning shampoo formulations which are soluble in the aqueous surfactant phase of the composition may be employed in the practice of the present invention.

Exemplary of these agents are Polyquaternium-7 Merquat-550) and mixtures thereof.

Generally, the polycationic quaternary ammonium polymers comprise from about 0.2 to about 3% by weight of the *co shampoo formulation, Any suitable water-insoluble, non-volatile, conventional silicone hair conditioning agent may be employed in the shampoo of the invention and includes, either a polyal-ty siloxane, a polyalkylaryl siloxane or a polyether siloxane copolymer. Mixtures of these fluids may also be used. The silicones should also be insoluble in the shampoo matrix. This is the meaning of "insoluble" as used herein.

The essentially non-volatile polyalkyl siloxanes that may be used include, for example, polydimethyl siloxanes (dioi+hiconas) S ^with viscosities ranging from about 5 to about 100,000 centistokes at 25"C. These siloxanes are available, for example, from the General Electric Company as the Vicasil series and from Dow Corning as the Dow Corning 200 series. The viscosity can be measured by means of a glass capillary viscometer as 17 '"1 t. set forth in Dow Corning corporate Test Method CTMOO04 (July 20, 1970).

The essentially non-volatile polyalkylaryl siloxanes that may be used include, for example, polymethyiphenylsiloxanes ihavinig ~viscosities of about 15 to about 85 centistokes at 250C. These siloxanes are available, for example, from the General Electric company as SF-1075 methyl phenyl fluid or from Dow Corning as 558 Cosmetic Grade Fluid.

The eosentially non-volatile polyether siloxane copolymer that may be used is, for examp e aA 4 etcl ply oxyalkylene ether copolymer fluid having a nominal viscosity of about 1,200 to about 1,500 centistokes at 25*C. This :copolymer is available, for example, from the General Electric Company as SF-1066 organosilicone surfactant. Preferred compounds of this type are polypropylene oxide modified dimethyl- 9.9.polysIloxanes Dow Corning DC-1248) although ethylene ar~ide or mixtures of ethylene oxide and propylene oxide may *also be used.

it is also possible to use siliconen in the present 2 0 :kompositions which have amino-functional groups such as Dow Corninig's X2-8107 material.

@*too: References disc-losing suitable sil~icones include 0* 9 United States Patent Nos. 2#828,551, 3f964,500 and 4,364,837, all of which are incorporated herein by refbrence.

frd lioie-e-iehioead-ies- The polycationic polymers disclosed in the aqueous surfactant phase of the shampoo and the lipid phase of the composition function as the primary stabilizers of the shampoo dispersion. A neutral polymer such as hydroxyethylcellulose may be combined with the polycatio;iic polymer to enhance its stabilizing effect on the dispersion. It is a unique adventage of the present invention that the polycationic polymer, in addition to stabilizing the dispersion, also enhances the hair conditioning properties of the shampoo.

Additional amphoteric surfactants which may be employed in the shampoo of the invention include amine oxides such as the C 8

-C

18 alkyl dimethylamine oxides.

Exemplary of other adjuvants are hydrotrcpes such as sodium cumene sulfonate, sodium xylene sulfonate, sodium .5 benzene sulfonate and sodium hexyls*aferRate.

e*e* The invention is illustrated by the following nonlimiting examples.

A hair conditioning shampoo having the followinq *0 formulation was prepared: I I I I- Part 1 Ingredient Delonfzed Water Amnoiun LaLryt Sulfate Sodfun Deceth.3 Sulfate Sodium Cumene Sultpate Na 4

EDTA

N

2 HPQ3 CocoamldopyLW Setatne W3 supplier Tradename Henkel's Standapol A, 2OX Vistas NoveL 10'44 Ma, 30% Stepn's Stepenate SCS, 43X Rh.%e-Pout's Cheelox V-78 Sodlum PhosFate Dibasic GoLdschmidt's Tego Betaine L-7, 3OX Anerchok's PoLymr JR-304 Catgon's Merquat-550, 8% Shere,'s Varonle 66-EZ (1.5 E) PetroLttC's C-7138 Potyner .erex's ArosLrf TA-100 wt.* 13,750 16,000 15.000 7.000 tO,100 0,200 30.000 5,000 01500 2 Delonized Water Po I yqua tern i un* 10 3 Polyquaternlu7 4 Isosteareth*2* Compount 90go DIftearyl Dimoniun ChLoride 5 Yel(oW Color (X solution) Prtu Preservative, 50X aqueo solution Sodlits Cunee Sulfonate 2,500 2.000 4,000 11000 0,250 1,200 0t S i1e

J.

I SO Stepan's Stepanate SCSI 43X 1.000 t0500 tOTAL 100,000 Isosteartth-2 Is othoxytated Isostearyt alcohol (1.5 EQ uits), crqond 909 is 0 C 20

C

40 MfphatIc alcool, 25 *es 0 0S a *4,655 54

S

The main mixing vessel is stainless steel equipped with a variable speed Lightnin' Mixer and heating and cooling faclities. A separate stainless steel or plastic Vessel was used for the Part 2 premix. A separate stainless steel Vessel equipped with heating facilities and minimal mixing is employed for the Part 4 oil phase.

To the main mixing vessel was charged Part I formula.

amount of deionized water and mixing begun. In order, Part 1 formula amounts of amonium lauryl sulfate, sodium dornth sulfater sodium cumeno sulfonatet Na 4 EDTA, sodium phosphate ~L1~L' dibasic and cocoamidopropyl betaine were added to the main mixing vessel, allowing sufficient time for each ingredient to completely dissolve before adding the next and taking care not to promote foam formation. The batch was mixed for at least 15 minutes before continuing. The batch was heated with miing to 85-87'C.

To a separate, dry, clean container, Part 2 formula amount of deionized water was charged. With mixing, Part 2 formula amount of Polyquaternium-10 was dispersed in the deionized water and mixed well until the premix was free of lumps, but not longer than 5 minutes just prior to addition, to avoid gelling. Part 2 premix was added to the main mixing vessel with mixing, taking care not to promote foam formation.

9.

The batch was nixed for at least 15 minutes before continuing.

4q 4 9 1is Mixing was continued with heating to 85-87'C.

Part 3 formula amount of Polyquaternium-7 was added

S

tz the main mixer with mixing, taking care not to promote foam formation. The batch was mixed for at least 15 minutes before continuing. Mixing was continued with heating to 85-87'C.

a To a third, separate, beatable container, the S* formula amounts of all ingredients of the Part 4 oil phase were charged and heating begun. The ijigredients were mixed well until all the material was melted and uniform at a temperaturo of 90-920C. When liquid and uniform, the mixture will not necessarily be clear; it may be translucent, When batch was 65-87'C, Part 4 premix was added to the main mixing vessel with high-speed mixing, taking care not to promote foam formation. Heating was discontinued and the batch was mixed at temperature for at least 15 minutes. Then the batch was cooled with mixing, Part 5 colors were added at any time during the cooling of the batch. When batch was at 52'C, Part 5 formula amount of perfume was added to the batch and mixing and cooling were continued. When batch was at or below 38'C, Part formula amount of preservative was added to the batch with continued mixing and cooling.

Specifications were checked on a batch sample cooled to 25'C and, if neceosary, sodium cumene sulfonate was added to the main mixing vessel to reduce viscosity.

In the formulation of Example 1, two polycationic conditioners were employed at a total active concentration of 15 0.6% by weight Polyquaternium-10 (Amerchol's Polymer and 0.3% Polyquaternium-7 (Calgon's Merquat-550, In the following tests, a variety of different polycationic conditioners were employed in the formulation of Example 1 at an active concentration of 0.6% by weight. The hett 20 polycationics and the test results are set forth belo,: ee*** 9* 9* 9 9 Polcationids Polycationics of Example 1 Q.6 Meruat-550 0.6% Polymer JR-20M 0.60 Polymer JR-400 0.0t Meqat-100 Relative wet-Com2 nci scorR i- The higher wt cobng scores Indicate a higher Lvel ctf conditfoning, A score of 4,5 Is apprfmAteWy equIValent to CnrcolLo two'in-oo conditioning shmpos contlining siticoQm conclitiocrs.

44 *4 4 4*4 9 .4 04# 4 9 44 4 identical placce of folowing The foa.'dlation of Example 1 was varied to include 10Vcl~ Of nofnQunQtinal cationic conditioners in the diotoaryldimethylammonium compound with tha results! M* n 9P-0AU 9 P Distearyidizethylammo~lu Trcaylmethyl mzoni.m 01catydimthylammonium aohenythimytammonium Catyltrmethylmmonium Relati4veW~t Combirict score 34$ Goo* 4 9 Il~INII-.~~iii 1IIYI The formulation of Example I. was also varied to include other lipids in place of isosteareth-2 with the following results: LIr.,idM Isosteareth-2 Isosteareth-O Petrolatum Isostearyl lactate Isopropyl isostearate Tsocetyl stearate RelAtive lat_2CombUiz qqp 445 ge S. S

S.

SS

S

5.9 9.

@9*i 69 5.94 .9 5* 9 **9S 0

S

EXAMPLE 2 The following shampoo formulation was prepared accorcding to the procedure of Example 2.: ingredient Tradenamo, Ami lie r PartA Filtered OnionIzed Irradiated Water Hydroxyethyt Cellulose

QS

Aqia ton 0,200 Natrosol. 250-HHR 9 *999 9 .9 9 9*9 9 9.

*tst 99 9999 20 9 9*9* 9999 9* 99 9 9 Part 8 Amiiu Lauryl sulfate Sodiuii Phosphate Monobasic godim, Phosphate Dibasic Soditai Cum~ne sutonate Cocomnldopropyl Betaine poirt C Propylene Glytol USP PQlyquaternfua'10 Quaternf~ed Guar Gun part Q Paraffin Wax ia8'r

C

20 40 Alcohol $tearyl AlcoWo VricetYl Ansonitm Chloride Distearvl D~mimu chloride Beh"yl C 2 2 quat Laureth-4 Hydrogenate4 Castor Oil Pert une Preservative Blue Color tolUtion) Green Color 01% solution) stanciapol. A, 289 NaH 2 P0 4 Ma 2

HPO

4 Naxonate SC, 98% T090 Betaine L-7, 30% Propylene QtycoL USP Poliymer JR-30M Cosmedi a Guar C-261 Bolar 1070 Unilln 425 Adol 62 TC.90'V Arosurf TA4100 Ceriamin KOMF Bri P30 Cremophor RH-40 Henkel 14T. Baker 14,. Baker Reutgors.-iease Qoldschmidt Amerchol Henkel Boler Petroleun PetroL ite Sherex Sherex Sherex

BASF

ICI

BASF

67.85a 0,200 0,200 1.000 13.33.4 1,0000 0.300 0.3m0 1.000 2.000 200 24000 0.500 0.500 04500 04500 1.200 0.750 0,021 0,168 100,000 TOMA EXAMPLE 3 The following formulation was prepared according to the prccedure of Example 1: PArt Izigredient *9 4 9 9 9.

9 9.

~5 .9 9 .4 4999 4 *919 999 9 99 .9 9 9990 9 Sb I Deionized Water sodfun Deceth-3 Sulfate Sodfus Laurvh,2 EO Sulfate Sodium Laureth-13 Carboxytate Cocoy( Sarcosine Na 4

EOTA

Sodium Tride~eth Sulfate 2 Cocoaffoiiodacetate Cocoaidopropyt Betafre No. 3 3 PEG-B0 Sorbf tan Laurate Polyquatorniune10 Peionized Water Sodiuus Cufene Sulfonate PotyquaterniLn- 4 lostsarethv2 Cwpoud 909 Distearyl Dimoniisn Chloride Buvplier, Tradaname Vista's Novel 10,44 E.s. Na, 30% Henkel 'a Standaspol ES-2 LVt 2.5% Sandoz's Sandopari L-24, 70% Hanpshire's Hiwposyl C-Acid, 100% Rhone-Poulenc's Cheetox OF-78 Rhone'Poutencs Rhodo-ex EST-300 Hiranoils C2M4 38% Goldschmidt's Tego Bacaine 30% iCt's Atlas G-4280 Amerchot's Polymer JR'304 Stepan's Ste"anate SC$, 43% Sherex's Varonlc 66-E2 (1,5 EO) Patrotite's Polymner C-7138 Sherex's Arosurf TA-100 0s 6.000O 6.518 2.750 0,090 9,200 13,750 91000 0.275 3.000 2.500 1.850 4,100 0.M0 colors Perfume Preser-vative, equeous solution

QS

1.200 1,000 100,000 TOTAL EXAMPLE 4 The following formulations were prepared according to the above procedure and tested: so 0* 0 *00 a a a a. a S S a *r S S a. S *Oa S a a a S S S S S S Ingredlent Part 1 Deionized Water ALS (28X) SDES (30%) Ua 4 %57-jA Part 2 Betaine L-7 (30%) Part 3 Deionized Water Part 4 SCS (43%) Polyquaternium-7 Part Isosteareth-2 corpound 909 Distearyl DMAC Part 6 Color, Perfune Preservative wet Conbing Dry Coming Static Flyaway Body Style Control

FORMULA

5 6 T J L 9 PP as as as OS as Os Qs as Os as Os 16.00 16.00 16.00 16.00 16.00 16.00 16.00 32.00 16.00 16-0 25.00 15.00 15.00 15.00 15.00 15.00 15.00 30.00 15.00 15.00 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 60.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 0.30 0.30 0.30 0.30 0.30 0.30 0.30 1.05 0.30 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 3.75 3.75 3.75 3.75 3.75 3.75 3.75 7.50 3.75 2.00 2.00 2.00 2.00 200 2.00 2.00 2.00 4.00 4.00 4. 4.00 400 400 4.00 4.00 4.00 0.90 0.90 0.90 0.90 0.90 0.90 8.90 0.90 0.90 Os Os as as Qs Os as as as QS OS 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Results of Lab Evaluatioa of Preceding formutae on Virgin Europeon Hair 4.50 1.75 1.75 2.75 3.75 4.00 3.00 3.00 5.00+ 4.50 3.00 4.00 2.00 1.00 3.50 5.00 4.00 3.50 3.00 5.00 4.50 3.00 No No Yes Yes No No No No No No No OK OK OK OK Less COK OK OKC Less Less OK Good Exc. Good

I

Those formulations that provide a high degree of style retention, such as Formulae Nos. 4, 8 and 9 of Example 4, were also found to be capable of repairing hair damage.

EXI.MPLE The following shampoo compositions were prepared according to the above-described procedure:

S.

S S

S

9.

S

S.

5* *5

S

*SSS*@

S

.55.5.

S* S S S TnarA~i~tq a a.

a S a a.

Level 12 .3 4 Part 1 Filtered Irradiated Deionized Water Hydroxyethyl Cellulose No. 2 Ammonium Lauryl Sulfate, 28% Sodium Deceth-3 Sulfate, 30t Ka. EDTA Sodium Cumene Sulfonate, 43.3% Cocoamidopropyl Betaine, 30% Sodium Phosphate Dibasic Part 2 Filtered Irradiated Deionized Water Polyquaternium-lo Part 3 Isosteareth-2 Compound 909 (Unilin) Distearyl Dimonium Chloride

QS

0.7 12.0 15.0 0.1 4.5 30.0 +0.2

QS

0.7 12.0 15.0 0.1 4.5 30.0 ±0.2 3.0 0.3 0.8 4.0 1.0

QS

0. 5 12.0 15.0 0.1 4.5 30.0 ±0.2 5.0 0.3 0.8 4.0 1.0

QS

0.3 12.0 15.0 0.1 5.0 30.0 ±0.2 8.0 0.6 0.8 4.0 1.0

QS

12.0 15.0 0.1 30.0 +0.2 10.0 0.9 0.8 3.0 0.2 0.8 it. 0 1.0 Part 4 Dinethicone.(Polydimethyl Siloxane) 1.0 2.25 3.5 4.0 Part Blue color aqueous solution) Green Color (1t aqueous solutioh) Perfume Preservative (50t aqueous solution) Sodium Cunene Sulfonate, 93% 0.021 0.168 1.2 1.0 +0.5 0.021 0.168 1.2 1.0 +0.5 0.021 0.168 1.2 1.0 +0.5 0.021 0.168 1.2 1.0 +0.5 0.021 0.168 1.2 TOTALS: TOALS:100% EACH Each formulation was found to impart a high degree of hair conditioning and style, control to hair shampooed therewith.

:**too 0 CC to" *see%.

Claims

19. The shampoo of claim 1 wherein said water- 2 insoluble lipid phase comprises from about 1% to about 16% by 3 weight of said shampoo.

20. The shampoo of claim 1 wherein said anionic 4eoee* 2 surfactant comprises from about 3% to about 25% by weight of sid shampoo. 1 21. The shampoo of claim 1 wherein said hair 2 conditioning cationic polymer comprises from about 0.7% to 3 about 3% by weight of said shampoo. I rP

22. The shampoo of claim 1 additionally containing shampoo adjuvants.

23. an amphoteric 24, surfactaot in a hydrotrope. The shampoo of claim 1 additionally containing surfactant, The shampoo of claim 23 wherein said amphoteric cocoamidopropyl betaine. The sharfioo of claim 1 additionally containing 4 .4i S 404 Si *0S Si

26. The shamnpoo of claim 25 wherein said hydrotrope is sodium cumene sulfonate, sodium xylene sulfonateo sodium benzene sulfonate or sodium hexyl sulfate. DOTD T1i1 31 DAY OV OCTOEWR 1994 COGA-F>PAMOLIVE COMANY Patont Attoreyua for thee A.Rplitcantt F~tb:RTM.* MO 0*4* 4 MEj~T OfTh D8COSm A hair conditioning shampoo coir,'"ising an aqueous dispersion of a vatsr-41nooilUa lipid phase, An anionic hair- cleansing surFactant and at least one hair conditioning, film- forming, polycationic polymer soluble ir iha aqueous disper- 59 sion and C-6% by wight, based on 'the weight of the rnhazpoo of a water-insolubleg non-volatile hair conditioning silicone, the water-.ingoluble lipid phase comprising at least one lipid- soluble, emulsifiable$, rQnocatoni, quaternary ammnfium com- 0 pound or amine solubilized in a water-insoluble long chain .00::.Io lipid compound, tle weight ratio of monocationic compound to 06:4 the lipid compound in the lipid phase being in the range of from about 5:1 to about 1110 and the molar rtlo of anionic surfactant to water-insoluble cationic compound is greater than 2:1. The uahazpoo having no silicone poseses a high degree of style control proportieon The shampoo o:ontaining ailicone has a high degree of hair c ;ditioning properties.