Cross-Reference to Related Application

This Application claims the benefit of U.S. Provisional Application Number 60/010,784 filed on January 29, 1996. which is incorporated by reference in its entirety.

Background of the Invention 1. Field of the Invention

This invention relates to conditioning detergent compositions suitable for use in personal cleansing application which not only impart cleansing, wet detangling, dry detangling and manageability properties to hair, but also which are relatively non-irritating and thus suitable for use by young children and adults having sensitive skin and eyes.

2. Description of the Prior Art

In the past, it has been considered desirable to cleanse hair and then to condition it after cleansing. For many years, it was necessary to perform these acts in two separate steps However, with the advent of so-called "two-in-one" conditioning shampoos, it became possible to condition and cleanse simultaneously. Unfortunately, many of these two-in-one conditioning shampoos and body cleansers have proven to be relatively irritating to the eyes and skin and uncomfortable for use with children or sensitive adults. Therefore, it is an object of this invention to create a conditioning shampoo which has good cleansing ability, excellent conditioning properties and has a low degree of ocular and skin irritation. Summary of the Invention

In accordance with this invention, there is provided a detergent composition compπsmg a surfactant portion compπsing-

1. a nonionic surfactant;

2. an amphoteric surfactant; and 3. an anionic surfactant; and a conditioner portion comprising at least two cationic conditioning polymers selected from:

1. a cationic cellulose derivative;

2. a cationic guar derivative; and

3. a homopolymer or copoiymer of a cationic monomer selected from a. a monomer having the formula

- I

wherein

R is H or CH ₃ ,

Y is O or NH, Ri is an alkylene group having from about 2 to about 6 carbon atoms,

R ₂ , R ₃ and RΛ are each independently an alkyl group or hydroxyalkyl group having from about 1 to about 22 carbon atoms, and

X is a monovalent anion selected from halide and alkyl sulfate having from about 1 to about 4 carbon atoms, or b. diallyldimethylammonium chloride.

In accordance with another embodiment of this invention, there is provided a detergent composition comprising, based upon the total weight of the composition: a. a carboxyalkyl alkylpolyamine amphoteric surfactant of the formula:

wherein

I is an alkyl or alkenyl group containing from about 8 to about 22 carbon atoms:

R _H is a carboxyalkyl group having from about 2 to about 3 carbon atoms;

R ₂₁ is an alkylene group having from about 2 (0 about 3 carbon atoms u is an integer of 1 to 4; and b. an anionic surfactant, except those anionic surfactants of the group consisting of

1) an alkyl sulfate of the formula

R-CH ₂ OSO ₃ X'; and

2) an alkylaryl suifonate of the formula

wherein

R' is an alkyl group having from about 7 to about 14 carbon atoms,

R is an alkyl group having from about 1 to about 12 carbon atoms, X' is selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions, and ammonium ions substituted with from about 1 to about 3 substituents, each of the substituents may be the same or different and are selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and hydroxyalkyl groups having from about 2 to about 4 carbon atoms; and c.) optionally a non-ionic surfactant, with the proviso that if the non-ionic surfactant is omitted and the anionic surfactant is an alkyl ether sulfate of the formula

R'(OCH ₂ CH ₂ ) _v OSθ ₃ X', then v is greater than or equal to 3. In accordance with yet another embodiment of this invention, there is provided a detergent composition comprising a. an amidoalkyl sultaine amphoteric surfactant of the formula:

wherein

E is an alkyl group or alkenyl group having from about 7 to about 21 carbon atoms;

Ruand R ₁₅ are each independently an alkyl group or a hydroxyalkyl group having from about 1 to about 4 carbon atoms; r is an integer from about 2 to about 6; and

R ₁₃ is an alkylene or hydroxyalkylene group having from about 2 to about 3 carbon atoms; b. an anionic surfactant, except those anionic surfactants of the group consisting of

- 3

1. an alkyl suifate of the formula

R'-C^OSOsX',

2. an alkyl ether sulfate of the formula

R OCHzCHzivOSOaX'; and

3. an alkylaryl sulfonate of the formula

wherein

R' is an alkyl group having from about 7 to about 14 carbon atoms,

R'ι is an alkyl group having from about 1 to about 12 carbon atoms, X' is selected from the group consisting of alkali metal ions, alkaline earth metal ions, and ammonium ions, and ammonium ions substituted with from about 1 to about 3 substituents: each of the substituents may be the same or different and are selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and hydroxyalkyl groups having from about 2 lo about 4 carbon atoms; and v is an integer from 1 to 5; and c. optionally a non-ionic surfactant.

The composition of this invention, when used in a shampoo or body cleanser, possesses one or more of the following properties: cleansing, wet detangling, dry detangling, manageability, and low degree of ocular irritation. Detailed Description of Preferred Embodiments

In one embodiment of the present invention, the shampoo composition may suitably cornpnse. consist of, or consist essentially of an anionic surfactant, an amphoteπc surfactant, a non-ionic surfactant, and at least two cationic conditioning polymers. The composition is preferably compnsed of, based upon the total weight of the shampoo composition, from about 5 percent to about 20 percent, and more preferably from about 5 percent to about 14 percent of a surfactant portion and, based upon the total weight of the composition, from about 0.01 percent to about 3.0 percent, preferably from about 0 01 percent to about 2 0 percent, more preferably from about 0.01 percent to about 1 0 percent, even more preferably from about 0.01 percent to about 0.5 percent, and most preferably from about 0.01 percent to about 0 3 percent, of a conditioner portion.

In this embodiment, the surfactant portion of the present invention contains nonionic, amphoteπc and anionic surfactants. Preferably the weight ratio between the amphotenc surfactant and the anionic

surfactant may range from about 3:1 to about 1 3, and preferably from about 2 1 to about 1 2 The weight ratio of the amphoteπc anionic surfactant combination non-ionic surfactant may vary widely, and preferably is about 2.1 to about 1:2. The nomonic surfactant is present in an amount, based upon the total weight of the shampoo composition, of from about 0.1 percent to about 10 percent, preferably from about 1 percent to about 10 percent, and more preferably from about 4 percent to about 8 percent The amphoteπc surfactant is present in an amount, based upon the total weight of the shampoo composition, of from about 0.5 percent to about 10 percent, preferably from about 1 percent to about 8 percent, and more preferably from about 2 percent to about 6 percent. The anionic surfactant is present in the shampoo composition in an amount from about 1.0 percent to about 10 percent, preferably from about 1 percent to about 8 percent and more preferably from about 1 percent to about 6 percent, based on the overall weight of the shampoo composition.

One class of nomonic surfactants useful in the present invention are polyoxyethylene deπvatives of polyol esters, wherein the polyoxyethylene denvative of polyol ester (1) is deπved from (a) a fatty acid containing from about 8 to about 22, and preferably from about 10 to about 14 carbon atoms, and (b) a polyol selected from sorbitol, sorbrtan, glucose, α-methyl giucoside, polyglucose having an average of about 1 to about 3 glucose residues per molecule, glyceπne, pentaerythπtol and mixtures thereof, (2) contains an average of from about 10 to about 120, and preferably about 20 to about 80 oxyethylene units, and (3) has an average of about 1 to about 3 fatty acid residues per mole of polyoxyethylene denvative of polyol ester. Examples of preferred polyoxyethylene deπvatives of polyol esters include, but are not limited to

PEG-80 sorbrtan laurate and Polysorbate 20. PEG-80 sorbrtan laurate, which is a sorbrtan monoester of lauric acid ethoxylated with an average of about 80 moles of ethylene oxide, is available commercially from ICI Surfactants of Wilmington, Delaware under the tradename, Atlas G-4280 " Polysorbate 20, which is the laurate monoester of a mixture of sorbitol and sorbitol anhydπdes condensed with approximately 20 moles of ethylene oxide, is available commercially from ICI Surfactants of Wilmington Delaware under the tradename Tween 20 "

Another class of suitable nomonic surfactants includes long chain alkyl glucosides or polyglucosides, which are the condensation products of (a) a long chain alcohol containing from about 6 to about 22, and preferably from about 8 to about 14 carbon atoms, with (b) glucose or a glucose-containing polymer. The alkyl gluocosides have about 1 to about 6 glucose residues per molecule of alkyl giucoside A preferred giucoside is decyl giucoside, which is the condensation product of decyl alcohol with a glucose polymer and is available commercially from Henkel Corporation of Hoboken. New Jersey under the tradename, Plantaren 2000 "

The compositions of the present invention also contain an amphoteπc surfactant As used herein the term amphoteric" shall mean 1) molecules that contain both acidic and basic sites such as for example, an ammo acid containing both ammo (basic) and acid (e g , carboxylic acid, acidic) functional groups; or 2) zwitterionic molecules which possess both positive and negative charges within the same molecule. The charges of the latter may be either dependent on or independent of the pH of the composition. Examples of zwittenonic mateπals include, but are not limited to alkyl betaines and

amidoalkyi betaines. The amphoteric surfactants are disclosed herein without a counter ion. One skilled in the art would readily recognize that under the pH conditions of the compositions of the present invention, the amphoteric surfactants are either electrically neutral by virtue of having balancing positive and negative charges, or they have counter ions such as alkali metal, alkaline earth, or ammonium counter ions. Commercially available amphoteric surfactants are suitable for use in the present invention and include, but are not limited to amphocarboxylates, alkyl betaines, amidoalkyi betaines, amidoalkyi sultaines, amphophosphates, phosphobetaines, pyrophosphobetaines, carboxyalkyl aikyl polyamines and mixtures thereof.

Examples of suitable amphocarboxylate compounds include those of the formula: A-CONH(CH ₂ ) _x N ^* R ₅ R ₆ R ₇ wherein

A is an aikyl or alkenyl group having from about 7 to about 21. and preferably from about 10 to about 16 carbon atoms; x is an integer of from about 2 to about 6; R ₅ is hydrogen or a cartwxyalkyl group containing from about 2 to about 3 carbon atoms. and preferably is hydrogen;

Re is a hydroxyalkyl group containing from about 2 to about 3 carbon atoms or is a group of the formula: wherein

Re is an alkylene group having from about 2 to about 3 carbon atoms and n is 1 or 2; and

R ₇ is a carboxyalkyl group containing from about 2 to about 3 carbon atoms;

Preferably, the amphocarboxylate compound is an imidazoline surfactant, and more preferably a disodium lauroamphodiacetate, which is commercially available from Mona Chemical Company of Paterson. New Jersey under the tradename, Monateric 949J." When an amphocarboxylate is used in the shampoo composition, it should be present in an amount of about 0.5 percent to about 10 percent, and preferably from about 0.5 percent to about 6 percent, based on the overall weight of the composition.

Examples of suitable alkyl betaines include those compounds of the formula: wherein

B is an alkyl or alkenyl group having from about 8 to about 22. and preferably from about 8 to about 16 carbon atoms,

R ₉ and R1 ₀ are each independently an alkyl or hydroxyalkyl group having from about 1 to about 4 carbon atoms; and p is 1 or 2.

A preferred betaine for use in the present invention is lauryl betaine, available commercially from Albnght & Wilson, Ltd. of West Midlands, United Kingdom as Empigen BB/J." If present, the alkyl betaine should be used in an amount, based on the overall weight of the composition, of from about 0.25 percent to about 10 percent, preferably from about 0.25 percent to about 8 percent, and more preferably, from about 0.25 percent to about 5 percent.

Examples of suitable amidoalkyi betaines include those compounds of the formula D-CC-NHfCHz N'RuR^CHzJ _m CO _? wherein

D is an alkyl or alkenyl group having from about 7 to about 21 , and preferably from about 7 to about 15 carbon atoms;

Rn and Rι ₂ are each independently an alkyl or hydroxyalkyl group having from about 1 to about 4 carbon atoms, q is an integer from about 2 to about 6; and m is 1 or 2

A preferred amidoalkyi betaine is cocamidopropyl betaine, available commercially from Goldschmidt Chemical Corporation of Hopewell, Virginia under the tradename, Tegobetaine L7 " When present in the shampoo compositions of this invention, the amidoalkyi betaine should be used in an amount of from about 0.25 percent to about 10 percent, preferably from about 0.25 percent to about 8 percent, and more preferably from about 0.25 percent to about 5 percent, based on the overall weight of the composition

Examples of suitable amidoalkyi suttaines include those compounds of the formula

wherein E is an alkyl or alkenyl group having from about 7 to about 21 , and preferably from about 7 to about 15 carbon atoms,

R aπd Risare each independently an alkyl, or hydroxyalkyl group having from about 1 to about 4 carbon atoms; r is an integer from about 2 to about 6. and R1 ₃ is an alkylene or hydroxyalkylene group having from about 2 to about 3 carton atoms;

Preferably the amidoalkyi sultaϊne is cocamidopropyf hydroxysultaine, available commercially from Rhone-Poulenc Inc. of Cranbury. New Jersey under the tradename, Mirataine CBS." When present in the shampoo compositions of this invention, it should be used in an amount of from about 0.5 percent to about 10 percent, preferably from about 1.0 percent to about 6 percent, and more preferably from about 1.5 percent to about 5 percent, based on the overall weight of the composition

Examples of suitable amphophosphate compounds include those of the formula

wherein

G is an alkyl or alkenyl group having about 7 to about 21 , and preferably from about 7 to about 15 carbon atoms; s is an integer from about 2 to about 6;

R ₁₆ is hydrogen or a carboxyalkyl group containing from about 2 to about 3 carbon atoms;

R ₁₇ is a hydroxyalkyl group containing from about 2 to about 3 carbon atoms or a group of the formula.

R ₁₉ -0-(CH ₂ ),-C0 ₂ wherein

R1 ₉ is an alkylene or hydroxyalkylene group having from about 2 to about 3 carbon atoms and t is 1 or 2; and

Rιβ is an alkylene or hydroxyalkylene group having from about 2 to about 3 carbon atoms

Preferably the amphophosphate compounds are sodium lauroampho PG-acetate phosphate, available commercially from Mona Industnes of Paterson, New Jersey under the tradename, Monateπc 1023," and those disclosed in U.S. Patent 4,380,637, which is incoφorated herein by reference, with sodium lauroampho PG-acetate phosphate being most preferred.

Examples of suitable phosphobetaines include those compounds of the formula

wherein E, r, R _1t R ₂ and R ₃ , are as defined above. Preferably the phosphobetaine compounds are those disclosed in U.S. Patent Nos. 4,215,064, 4,617,414, and 4,233,192, which are all incoφorated herein by reference.

Examples of suitable pyrophosphobetaines include those compounds of the formula:

wherein E, r, Rι, R ₂ and R ₃ , are as defined above. Preferably the pyrophosphobetame compounds are those disclosed in U.S. Patent Nos. 4,382,036, 4,372,869, and 4,617,414, which are all incorporated herein by reference. Examples of suitable carboxyalkyl alkylpolyamines include those of the formula:

wherein

I is an alkyl or alkenyl group containing from about 8 to about 22, and preferably from about 8 to about 16 carbon atoms; _?2 is a carboxyalkyl group having from about 2 to about 3 ca on atoms:

R ₂ ι is an alkylene group having from about 2 to about 3 carbon atoms and u is an integer from about 1 to about 4.

Preferably the carboxyalkyl alkyl polyamine is sodium carboxymethyl coco polypropylamine, available commercially from Akzo Nobel Surface Chemistry under the tradename, Αmpholak 7CX C." When present in the shampoo composrtions of this invention, it should be used in an amount of from about

0.5 percent to about 10 percent, preferably from about 1 0 percent to about 8 percent, and more preferably from about 2.0 percent to about 6.0 percent, based on the overall weight of the composition

In a preferred embodiment, the amphoteπc surfactant portion of the compositions is compnsed of a mixture of amphoteric surfactants, such as amphocarboxylate and alkyl betaine, or amphocarboxylate and amidoalkyi betaine. In this embodiment, the amphocarboxylate is present in the shampoo composition in an amount, based upon the total weight of the shampoo composition, of from about 0 5 percent to about 9.5 percent and the alkyl betaine or amidoalkyi betaine is present in an amount, based upon the total weight of the shampoo composition, of from about 9.5 percent to about 0.5 percent

The compositions of this embodiment also contain at least one anionic surfactant Preferably, the anionic surfactant is selected from the following classes of surfactants an alkyl sulfate of the formula

R'-CHzOSOjX'; an alkyl ether sulfate of the formula

R'fOCH^^kOSOsX'; an alkyl monoglyceryl ether sulfate of the formula

ROCH ₂ CHCH2θSO ₃ X' ^0H an alkyl monoglyceride sulfate of the formula

R ^, CO ₂ CH ₂ CHCH ₂ OSO ₃ X' ; OH an alkyl monoglyceride suifonate of the formula

an alkyl suifonate of the formula

R'-SO^'; an alkylaryl suifonate of the fonnula

Rϊr Sr S0 ₃ X'

^■ ^χ ^> an alkyl sulfosuccinate of the fonnula:

an alkyl ether sulfosuccinate of the fonnula:

an alkyl suifosuccinamate of the formula:

an alkyl amidosulfosuccinate of the fonnula

an alkyl carboxylate of the formula:

R' — (OCH ₂ CH2)w-OCH ₂ Cθ2X' ,

an alkyl amidoethercarboxylate of the formula:

an alkyl succinate of the fonnula:

a fatty acyl sarcosinate of the formula:

a fatty acyl amino acid of the for ula:

a fatty acyl taurate of the formula.

- I I

a fatty alkyl sulfoacetate of the formula:

an alkyl phosphate of the formula:

R— (OCH ₂ CH ) _w -0— ? P— OX'.

OH wherein

R' is an alkyl group having from about 7 to about 22, and preferably fom about 7 to about 16 carbon atoms,

R'ι is an alkyl group having from about 1 to about 18, and preferably from about 8 to about 14 carbon atoms,

R' _? is a substituent of a natural or synthetic l-amιno acid,

X' is selected from the group consisting of alkali metal ions, alkaline earth metal ions. ammonium ions, and ammonium ions substituted with from about 1 to about 3 substituents, each of the substituents may be the same or different and are selected from the group consisting of aikyl groups having from 1 to 4 carbon atoms and hydroxyalkyl groups having from about 2 to about 4 carbon atoms and v is an integer from 1 to 6, w is an integer from 0 to 20, and mixtures thereof. Preferably the anionic surfactant is compnsed of sodium tndeceth sulfate, sodium laureth sulfate, disodium laureth sulfosuccinate. or mixtures thereof Sodium tπdeceth sulfate is the sodium salt of sulfated ethoxylated tridecyl alcohol that conforms generally to the following formula Ci ₃ H ₂₇ (OCH ₂ CH ₂ ) _n OS0 ₃ Na, where n has a value between 1 and 4, and is commercially available from Stepan Company of Northfield, Illinois under the tradename. Cedapal TD-403M " Sodium laureth sulfate is available from from Albright & Wilson, Ltd. West Midlands, United Kingdom under the tradename

Empicol 0251 70-J." Disodium laureth sulfosuccinate is available commercially from Albnght & Wilson Ltd. of West Midlands, United Kingdom under the tradename, Empicol SDD "

In this embodiment, the shampoo composition of the present invention also contains a conditioner portion which is comprised of at least two cationic conditioning polymers Preferred cationic conditioning polymers are selected from the following:

1. a cationic cellulose denvative;

2. a cationic guar denvative; and

3. a homopolymer or copoiymer of a cationic monomer selected from a. a monomer having formula I

wherein

R is H or CH _3l

Y is O or NH,

Ri is an alkylene group having from about 2 to about 6 and preferably from about 2 to about 3 carbon atoms

R ₂ , R ₃ and R ₄ are each independently an alkyl group having from about 1 to about 22, and preferably from about 1 to about 4 carbon atoms and

X is a monovalent anion selected from haiide and alkyl sulfate, or b. diallyldimethylammonium chloπde. The amount of each conditioner component may range, based upon the total weight of the composition, from about 0.01 percent to about 1 0 percent, preferably from about 0 01 percent to about 0 5 percent, and more preferably from about 0 01 to about 02 percent

Preferably, the cationic cellulose denvative is a polymenc quaternary ammonium salt denved from the reaction of hydroxyethyl cellulose with a tnmethylammonium substituted epoxide The mateπal known as Polyquatemιum-10, commercially available from Amerchol Coφoration of Edison New Jersey as Polymer JR-400,"is especially useful in this regard

- I3 -

The cationic guar derivative is preferably a guar hydroxypropyltπmoπium chionde, available commercially from Rhone-Poulenc Inc., of Cranbury, New Jersey under the tradename, Jaguar C-17 "

Another preferred cationic polymer includes those compounds denved from acrylamidopropyl trimonium chloride which has the formula:

and more preferably is the copolymer of this monomer with acrylamide, the latter of which is available commercially from Allied Colloids, of Suffolk, Virginia under the tradename, Salcare SC60."

Other preferred cationic conditioning polymers are those derived from the monomer diallyldimethylammonium chloride. The homopolymer of this monomer is Polyquatemιum-6, which is available commercially form Allied Colloids of Suffolk, Virginia under the tradename, Salcare SC30." The copolymer of diallyldimethylammonium chloride with acrylamide is known as Polyquatemιum-7, and is also available from Allied Colloids under the tradename Salcare SC10."

In a preferred embodiment, the conditioner portion is a combination of cationic cellulose denvative with a cationic guar derivative. In this embodiment, the cationic cellulose denvative is present in the composition in an amount, based on the overall weight of the shampoo composition, of from about 0.01 percent to about 2 percent, preferably from about 0.05 percent to about 1.0 percent, and more preferably from about 0.05 percent to about 0.3 percent, and the cationic guar denvative is present in an amount, based on the overall weight of the shampoo composition, of from about 0.01 percent to about 1.0 percent, preferably from about 0.05 percent to about 1.0 percent, and more preferably from about 0.05 percent to about 0.3 percent.

In another preferred embodiment, the conditioner portion is compnsed of cationic cellulose derivative or cationic guar derivative and a homopolymer or copolymer of the cationic monomer having formula I. In this embodiment, the cationic cellulose denvative or cationic guar denvative is present in an amount, based on the overall weight of the composition, of from about 0.01 percent to about 0.5 percent, and preferably from about 0.01 percent to about 0.2 percent, and the homopolymer or copolymer of the above monomer is present in an amount, based on the overall weight of the composition, of from about 0.01 percent to about 0.5 percent, preferably from about 0.01 percent to about 0.2 percent.

In another preferred embodiment, the conditioner portion is composed of cationic guar denvative and a homopolymer or copolymer of diallyldimethylammonium chionde In this embodiment, the cationic guar derivative is present in an amount, based on the overall weight of the shampoo composition, of from about 0.01 percent to about 0.5 percent, preferably from about 0.01 percent to about 0.2 percent, and the homopolymer or copolymer of diallyldimethylammonium chionde is present in an amount, based on the overall weight of the shampoo composition, of from about 0.01 percent to about 0.5 percent, preferably from about 0.01 percent to about 0.2 percent.

- I4 -

In accordance with another embodiment of this invention, there is provided a composition suitably comprised of, consisting of, or consisting essentially of an amphoteπc surfactant and an anionic surfactant, with the total amount of surfactants ranging, based upon the total weight of the composition, from about 4 percent to about 20 percent, preferably from about 4 percent to about 15 percent, and more preferably from about 4 percent to about 10 percent. Examples of suitable amphoteric surfactants include those described above and preferably include the above-described carboxyalkyl alkylpolyamines, the amidoalkyi sultaines, and mixtures thereof. Examples of suitable anionic surfactants include those described above and preferably include those anionic surfactants except the anionic surfactant compounds of the group consisting of: 1) the above-described alkyl sulfates or alkylaryl sulfonates when the amphoteric surfactant is the above described carboxyalkyl alkylpoiyamine; and 2) the alkyl sulfates. alkyl ether sulfates, and alkylaryl sulfonates when the amphoteric surfactant is the above-descπbed amidoalkyi suttaine.

In this embodiment, the amount of each of the amphotenc surfactant and anionic surfactant used in the composition may range, based upon the total weight of the composition, from about 2 percent to about 10 percent, and preferably from about 2 percent to about 6 percent, respectively. The weight ratio of amphoteric surfactant:anionic surfactant may range from about 3:1 to about 1 :3, preferably from about 2:1 to about 1 :2, and most preferably from about 1.5:1 to about 1 :1 5. Optionally, the composition of this embodiment may contain one or more of the above-mentioned non-ionic surfactants and/or one or more of the above-mentioned cationic conditioners. Preferably, the non-ionic surfactant , if used, is a polyoxyethylene derivative of a polyol ester, more preferably Polysorbate 20, and the preferred cationic conditioner is Polyquartemium 10, guar hydroxypropyltriammonium chionde, acrylamidopropyl tπmonium chioride/acrylamide copolymer, and mixtures thereof. The amount of nomonic surfactant used in the composition may range, based upon the total weight of the composition, of from about 0 to about 5 percent, and preferably from about 0.5 percent to about 1 percent. When the nomonic surfactant is used, the weight ratio of amphoteric/anionic surfactant: nonionic surfactant is from about 40 1 to about 2.1 and preferably from about 20:1 to about 10:1. The amount of each cationic conditioner used in the composition may range, based upon the total weight of the composition, from about 0 to about 0 5 percent, and preferably from greater than about 0 percent to about 0.3 percent, and more preferably from greater than about 0 percent to about 0.2 percent. The composition of the present invention may also include one or more optional ingredients nonexclusively including a peariescent or opacifying agent, a thickening agent, secondary conditioners, humectants, chelating agents, and additives which enhance their appearance, feel and fragrance, such as colorants, fragrances, preservatives, pH adjusting agents, and the like. The pH of the shampoo compositions of this invention is preferably maintained in the range of from about 5 to about 7 5, and more preferably from about 5.5 to about 7.0.

Commercially available peariescent or opacifying agents which are capable of suspending water insoluble additives such as silicones and/or which tend to indicate to consumers that the resultant product is a conditioning shampoo are suitable for use in this invention. The peariescent or opacifying agent is present in an amount, based upon the total weight of the composition, of from about 0 percent to about 3

percent, preferably from about 0.25 percent to about 2.5 percent, and more preferably, from about 0.5 percent to about 1.5 percent. Examples of suitable peariescent or opacifying agents include, but are not limited to mono ordiesters of (a) fatty acids having from about 16 to about 22 carbon atoms and (b) either ethylene or propylene glycol; mono or diesters of (a) fatty acids having from about 16 to about 22 carbon atoms (b) a polyalkylene glycol of the fonnula

HO-(JO) _a -H wherein

J is an alkylene group having from about 2 to about 3 carbon atoms; and a is 2 or 3; fatty alcohols containing from about 16 to about 22 carbon atoms; fatty esters of the formula

KCOOCH ₂ L wherein K and L independently contain from about 15 to about 21 carbon atoms; inorganic solids insoluble in the shampoo composition, and mixtures thereof.

In a preferred embodiment, the peariescent or opacifying agent is introduced to the shampoo composition as a pre-fonned, stabilized aqueous dispersion, such as that commercially available from Henkel Corporation of Hoboken, New Jersey under the tradename. Euperian PK-3000." This material is a combination of glycol distearate (the diester of ethylene glycol and steaπc acid), Laureth-4 {CH ₃ (CH ₂ )ιoCH ₂ (OCH ₂ CH ₂ ) ₄ OH) and cocamidopropyl betaine and preferably is in a weight percent ratio of from about 25 to about 30: about 3 to about 15: about 20 to about 25, respectively. Commercially available thickening agents which are capable of imparting the appropπate viscosity to the conditioning shampoo compositions are suitable for use in this invention. If used, the thickener should be present in the shampoo compositions in an amount sufficient to raise the Brookfield viscosity of the composition to a value of between about 500 to about 10,000 centipoise Examples of suitable thickening agents πonexclusively include: mono or diesters of 1) polyethylene glycol of formula HO-(CH ₂ CH ₂ 0)*H wherein z is an integer from about 3 to about 200. and 2) fatty acids containing from about 16 to about 22 carbon atoms; fatty acid esters of ethoxylated polyols; ethoxylated derivatives of mono and diesters of fatty acids and glyceπne, hydroxyalkyl cellulose, alkyl cellulose; hydroxyalkyl alkyl cellulose; and mixtures thereof. Preferred thickeners include polyethylene glycol ester, and more preferably PEG-150 distearate which is available from the Stepan Company of Northfield, Illinois or from Comiel, S.p.A. of Bologna, Italy under the tradename, PEG 6000 DST

Commercially available secondary conditioners such as volatile silicones which imparts additional attributes such as gloss to the hair are suitable for use in this invention. Preferably, the volatile silicone conditioning agent has an atmospheric pressure boiling point less than about 220 C. The volatile silicone conditioner is present in an amount of from about 0 percent to about 3 percent, preferably from about 0.25

percent to about 2.5 percent, and more preferably from about 0.5 percent to about 1.0 percent, based on the overall weight of the composition. Examples of suitable volatile silicones nonexclusively include polydimethylsiloxane, polydimethylcyclosiloxane, hexamethyidisiloxaπe, cyclomethicone fluids such as polydimethyicyclosiloxane available commercially from Dow Coming Coφoration of Midland, Michigan under the tradename, DC-345"and mixtures thereof, and preferably include cyclomethicone fluids.

Commercially available humectants which are capable of providing moistunzation and conditioning properties to the shampoo composition are suitable for use in the present invention. The humectant is present in an amount of from about 0 percent to about 10 percent, preferably from about 0.5 percent to about 5 percent, and more preferably from about 0.5 percent to about 3 percent, based on the overall weight of the composition. Examples of suitable humectants nonexclusively include: 1 ) water soluble liquid polyols selected from the group comprising glycerine, propylene glycol, hexylene glycol butylene glycol, dipropylene glycol, and mixtures thereof; 2)polyalkylene glycol of the fonnula

HO-(RD) „-H wherein R"is an alkylene group having from about 2 to about 3 carbon atoms and b is an integer of from about 2 to about 10 ;

3) polyethylene glycol ether of methyl glucose of formula

CH _r C ₆ H ₁₀ θ ₅ -(OCH ₂ CH ₂ ) _c -OH wherein c is an integer from about 5 to about 25;

4) urea; and 5) mixtures thereof, with glycenne being the preferred humectant. Examples of suitable chelating agents include those which are capable of protecting and preserving the compositions of this invention. Preferably, the chelating agent is EDTA, and more preferably is tetrasodium EDTA available commercially from Dow Chemical Company of Midland. Michigan under the tradename, Versene 100XL"and is present in an amount, based upon the total weight of the composition, from about 0 to about 0.5 percent, and preferably from about 0.05 percent to about 0.25 percent. Suitable preservatives include Quatemιum-15. available commercially as Dowicil 200" from the Dow Chemical Corporation of Midland. Michigan, and are present in the composition in an amount, based upon the total weight of the composition, from about 0 to about 0.2 percent, and preferably from about 0.05 percent to about 0.10 percent.

The above described composition may be prepared by combining the desired components in a suitable container and mixing them under ambient conditions in any conventional mixing means well known in the art, such as a mechanically stirred propeller, paddle, and the like. Although the order of mixing is not critical, it is preferable to pre-blend certain components, such as the fragrance and the nonionic surfactant before adding such components into the mam mixture.

When a cationic guar conditioner is used, it is also preferable to preblend the cationic guar conditioner with glycerin under ambient conditions, then allow the guar conditioner to be wet-out" by the glycerin. Although the time to Wet-out" may vary, typically this time penod may range from about 5 minutes to about 30 minutes. Preferably, the guar conditionerglycenn weight ratio is from about 1 100 to

about 1:1, and more preferably from about 1:50 to about 1:5, and most preferably from about 1 15 to about 1:7. The resulting suspension is mixed with water under ambient conditions at a suspension: water weight ratio of from about 1:5 to about 1:20. The resulting water-suspension mixture is then acidified with an amount of acid, preferably citric acid, effective to reduce the pH of the overall composition to a value of about 4.

When using a thickener component, it is also preferable to preblend the desired thickener with from about 5 percent to about 20 percent, based upon the total weight of the composition, of water and preferably at a temperature of from about 60°C to about 80°C. When processing with a thickener, it is also preferable to reduce the temperature of the overall composition to less than about 45°C before any pre- formed peariizer is added thereto.

The detergent composition of the present invention is preferably used in personal cleansing applications nonexclusively including shampoos, gels such as shower gels, baths such as baby baths, and the like.

The invention illustratively disclosed herein suitably may be practiced in the absence of any component, ingredient, or step which is not specifically disclosed herein. Several examples are set forth below to further illustrate the nature of the invention and the manner of carrying it out However, the invention should not be considered as being limited to the details thereof.

Examples

All amounts of materials are given in parts by weight based on 100 parts of the overall formulation. unless stated otherwise. The following test procedures were used in the following Examples.

1. Hair Conditioning Properties: Conditioning properties of shampoos are determined by measunng the average energy and force required to comb hair in the wet and dry state after the hair has been washed with a particular shampoo formulation in accordance with the method set forth as follows: a) Preparation of Hair samples: Human hair tresses are prepared by weighing out about 10-12 grams of virgin brown hair, and binding the cuticle end with a cable tie and hot melt glue The cuticle end of the bundle is positioned in a binder clip. The hair is fanned out evenly over the width of the binder clip. Hot melt glue is applied along the edge of the binder clip, joining the clip and the hair Glue is applied to the inside of the clip for further strength. A rubber band is applied to the outside of the clip, to keep the jaws of the clip from separating. The glue is allowed to dry thoroughly. The tress is washed to remove contaminants such as dust or shampoo residue by immersing the tress in methanol for ten seconds and removing the tress and allowing it to air dry. Loose hair is removed. Tangles are removed by combing the tresses with a standard comb or brush. Static charge buildup is removed using a static reducing gun

The number of trials required for the test is equal to the number of formulations (and suitable controls) under test. The formulations are randomized such that each product is applied to each tress at some point in time. Two shampooings each using about 1 cc of shampoo composition are required The tress is thoroughly wet under running, 100 F tap water. About 1 cc of a given shampoo composition is applied evenly from top to bottom of the tress. Using the fingers of both hands, the shampoo is rubbed into

the hair for approximately 30 seconds to produce lather. The tress is then rinsed thoroughly under running, 100 F water. The tress is then again washed and rinsed using a second 1 cc sample of product. The tress is then allowed to drip dry for 5 minutes.

The tresses are then suspended from a sturdy ring stand such that they hang freely and have several inches of clearance between the bottom of the tress and the top of the bench. b) Wet Dβtanalina Energy. A Combing Force Device (CFD), which is a hand held. electromechanical instrument which measures the amount of force or energy required to pass a comb through the hair, is held horizontally in the one hand and tangles are removed from the tresses by starting at the lower portion of the tress and moving the CFD downward. Each successive stroke is started at a point which is higher than the previous stroke. This measurement continues until the CFD passes freely through the entire length of the tress. Once all tangles have been removed, three top-to-bottom strokes complete the detangling measurement. The cumulative energy to detangle the hair tresses is reported as wet detangling energy, in units of gram-seconds (g/sec). c) Wet Comb Force: After the detangling energy measurement is completed on all tresses, the tresses are measured for wet comb force. A sensor attached to a curling iron measures the twisting, or torsional force of the curling iron as the instalment is moved though the hair. The instrument is passed through the detangled tresses about 25 times. Comb force, expressed in grams, is the median force required to pass the comb through the detangled tress. d) Dry Detangling Energy. After the tresses are blow-dried until they are no longer damp, the detangling procedure set forth in b is repeated using the dry tresses. e) Dry Comb Force: After the tresses are blow-dried until they are no longer damp and dry detangling energy is determined, the combing procedure set forth in c) is repeated using the dry tresses

2.) Ocular Irritation Properties: Irritation to the eyes expected for a given formulation is measured in accordance with the Invittox Protocol Number 86, the "Trans-epithelial Permeability (TEP) Assay" as set forth in Invittox Protocol Number 86 (May 1994). in general, the ocular irritation potential of a product can be evaluated by determining its effect on the permeability of a cell layer, as assessed by the leakage of fluorescein through the layer. Monolayers of Madin-Darby canine kidney (MDCK) cells are grown to confluence on microporous inserts in a 24-well plate containing medium or assay buffer in the lower wells The irritation potential of a product is evaluated by measunng the damage to the permeability bamer in the cell monolayer following a 15 minute exposure to dilutions of the product Bamer damage is assessed by the amount of sodium fluorescein that has leaked through to the lower well after 30 minutes, as determined spectrophotometrically. The fluorescein leakage is plotted against the concentration of test mateπal to determine the EC50 (the concentration of test material that causes 50% of maximum dye leakage, i e . 50% damage to the permeability bamer). Exposure of a layer of MDCK cells grown on a microporous membrane to a test sample is a model for thafirst event that occurs when an irritant comes in contact with the eye. In vivo, the outermost layers of the cornea! epithelium form a selectively permeable bamer due to the presence of tight junctions between cells. On exposure to an imtant, the tight junctions separate, thereby removing the permeability

- I9 -

barrier. Fluid is imbibed to the underlying layers of epithelium and to the stroma, causing the collagen lamellae to separate, resulting in opacity. The TEP assay measures the effect of an irritant on the breakdown of tight junctions between cells in a layer of MDCK cells grown on a microporous insert. Damage is evaluated spectrophotometrically, by measuring the amount of marker dye (sodium fluorescein) that leaks through the cell layer and microporous membrane to the lower well. Generally, a passing score is reflected in an EC ₅₀ of 2.2% or higher.

Example 1: Compounding of Shampoo Composition

The following pre-blends were prepared: Preblend A: 1.5 parts of PEG 6000 DS were mixed with 20 parts deionized water at 65*C in a mixing vessel until a homogeneous mixture was obtained.

Preblend B: 1.00 part glycerine was added to a mixing vessel. 0.1 part Jaguar C17 was added slowly with agitation and the agitation was continued for 15 minutes. 10.0 parts water were added, 20% citric acid solution was added to adjust the pH of the blend to 4.0, and agitation was continued for an additional 15 minutes.

Preblend C: 1.0 part Atlas G-4280 was mixed with 0.25 parts fragrance.

Preblend D: 0.05 parts Dowicil 200 were blended with 0.15 parts water and the mixture was stirred until solution was obtained.

After charging 25.75 parts water to a mixing vessel, 0.19 parts of Polymer JR-400 was added thereto with maintained agitation until a clear solution was obtained. 12.16 parts Tegobetaine L7, 9.50 parts Cedepal TD-403M, 2.85 Monateric 949J and 5.5 parts Atlas G-4280 were added sequentially to the solution with agitation. After Preblend A, which was maintained at a temperature of 65'C, was added with agitation to the solution, Preblend C was then added thereto with agitation. An additional 1.14 parts of Tegobetaine L7 was then added thereto. 0.18 part Versene 100 XL, 3.21 parts of dye solution, preblend D, 4.00 parts Euperian PK 3000 and 0.75 parts DC 345 were then added sequentially with agrtation thereto. Citric acid solution was added in an amount to adjust the pH of the solution to 6.0. Preblend B was then added with agitation. The pH was then checked and adjusted to 6.0 with additional citric acid solution. The amounts of the ingredients used to make the composition of Example 1 are shown in Table 1 below.

The resulting composition was tested for detangling energy and comb force, and the results are provided in Table 2 below: Ocular Irritation of the resulting composition was also measured, and the data are presented in Table 3.

Table 1

Example 2: Compounding of Shampoo Composition without cyclomethicone

The procedure of Example 1 was repeated using the ingredients as set forth in Table 1 The resulting composition was tested for detangling energy and comb force, and the results are provided in Table 2 below:

Comparative Example 1: Compounding of Shampoo Composition without guar cationic conditioner or cyclomethicone:

The procedure of Example 1 was repeated using the ingredients as set forth in Table 1. The resulting composition was tested for detangling energy and comb force, and the results are provided in

Table 2 below:

Comparative Example 2: Compounding of Shampoo Composition without Polvouatemium-10 or cyclomethicone

The procedure of Example 1 was repeated using the ingredients as set forth in Table 1. The resulting composition was tested for detangling energy and comb force, and the results are provided in

Table 2 below:

Table 2 - Detangling Energy and Comb Force Measurements

As indicated by the data in Table 2, the formulations of Examples 1 and 2, which contain both Polyquatemium-10 and Guar hydroxypropyftrimonium chloride, exhibit significantly improved wet detangling force (lower detangling energy) than either of Comparative examples 1 or 2, each of which contains only one of the conditioners. In accordance with prior experience, Polyquatemium-10, when used as the sole conditioner in a shampoo formulation, was known to have imparted dry hair managability benefits to the composrtions. Similarly, cationic guar compounds have been known to impart wet detangling benefits. Due to the cationic nature of both of these compounds, it was thought that these compounds, when used mixed together, would have competed for the anionic sites on the hair and would thus not have resulted in a shampoo composition exhibiting both improved wet and dry detangling benefits. However, we have unexpectedly found that the combination of cationic cellulose derivatives and cationic guar derivatives in the compositions of this invention imparts superior wet and dry detangling properties to the compositions. More specifically, the wet and dry detangling energy is much lower when using the combination of conditioners of this invention, i.e., cationic guar derivatives and Polyquatemium-10, than if either of the conditioners are used alone.

Example 1 differs from Example 2 in the presence of volatile silicone in formulation. As seen from the data in Table 2, the presence of volatile silicone in Example 1 results in a further reduction in dry detangling energy. Thus, it can be seen that the combination of cationic polymer conditioners and volatile silicone of the compositions of this invention afford both excellent wet detangling and dry detangling benefits.

Table 3 - TEP Ocular Irritation Results

As indicated above, formulations which exhibit a mean EC ₅₀ value of 2.2 or higher are deemed to pass the ocular irritation test while those exhibiting an EC5 ₀ value below 2.2 are deemed to fail the test. As shown in Table 3, the formulation of Example 1 exhibits a passing value, which is on par with Johnson's Baby Shampoo, a commercial shampoo known for its ocular mildness. In contrast, other commercial shampoos, i.e., the Pert Plus products marketed by the Proctor & Gamble Company, fail the test.

Thus, it can be seen from the above Examples that the compositions of the present invention possess superior wet and dry detangling capabilities while retaining low ocular irritation values.

Examples 3 - 15: Preparation of Cleansing Compositions

T e following preferred formulations, as shown in Tables 4 - 7, were made in accordance with the procedure described in Examples 1 and 2.

Table 4

Table 5

* Genapol 437-X is a commercial product containing about 20% ethylene glycol distearate, about β% cocamidopropyl betaine and about 5% cocamide monoethanolamide/diethanotamide available from Hoechst AG, Frankfurt, Germany.

Table 6

Table 6

Table 7

Selected compositions from Tables 4 - 7 were evaluated for hair and skin cleansing on human subjects, where the compositions were evaluated for their cleansing, conditioning and irritancy properties. Selected compositions were also evaluated by manual washing and combing of tresses. The compositions were found to be satisfactory conditioning personal cleansing compositions.

Examples 18 - 54 Preparation of Cleansing Compositions

Additional compositions are prepared in accordance with the procedure set forth in Examples 1 and 2 using the components as set forth in Tables 8 - 13 below.

Table s

ro

PEG 6000 DS added in quantity sufficient to adjust viscosity to between 500 and 10,000 centipoise

Table 9

ro oo

PEG 6000 DS added in quantity sufficient to adjust viscosity to between 500 and 10,000 centipoise

Table 10

ro

PEG 6000 DS added in quantity sufficient to adjust viscosity to between 500 and 10,000 centipoise

Table 11

O o

PEG 6000 DS added in quantity sufficient to adjust viscosity to between 500 and 10,000 centipoise

Table 12

I O

* PEG 6000 DS added in quantity sufficient to adjust viscosity to between 500 and 10,000 centipoise

Table 13

co ro

* PEG 6000 DS added in quantity sufficient to adjust viscosity to between 500 and 10,000 centipoise

Example 55: In VrtroTests

Samples of shampoo compositions shown in Table 14 were evaluated in in vitro tests. In general, members of a test panel were given a blind sample of each respective formulation in Table 14, as well as a blind sample of commercially available Pert Plus for Kids conditioning shampoo ("Pert Plus ^* ). The members were asked to independently use the samples, in approximately equivalents amounts, to shampoo and condition their hair for a given period of time.

The results of the in vitro tests revealed that formulations of Examples 1 and 5 were rated as parity to Pert Plus with respect to ease of conditioning of hair in the dry and wet states. However, the formulation of Example 1 was prefeπed relative to Pert Plus for the attribute of speed of detangling. By contrast, the formulation of Comparative Example 3, containing only a single cationic polymeric conditioner, was less preferred than Pert Plus with respect to these attributes. These results further illustrated that the formulations of the present invention containing at least two conditioning polymers demonstrated performance superior to shampoos containing only a single conditioning polymer.

Table 14