Title of Invention	"A PROCESS FOR PREPARING CLEAR,ULTRA MILD,AQUEOUS FOAMING R CONDITIONING DETERGENT COMPOSITION"
Abstract	Compositions useful as 2-in-1 cleansing products are disclosed that are extremely mild to skin and hair, which use neutralized, essentially chargeless, ionic complexes of fatty amines and fatty acids to deliver various levels of conditioning; neutralized, essentially chargeless, ionic complexes of a detersive surfactant comprising a water soluble cationic surfactant and/or polymer complexed with one or more anionic surfactants; or an amphoteric surfactant complexed with one or more anionic surfactants; or a water soluble cationic surfactant and/or polymer complexed with one or more amphoteric surfactants; or a water soluble cationic surfactant and/or polymer complexed with one or more anionic surfactants and an amphoteric surfactant; detersive surfactant-soluble but water-insoluble silicones or derivatives thereof; and water. These products exhibit true 2-in- conditioning properties, and are lower in cost than current 2 in 1 products. Clear or opacified products can be formulated.

Title of Invention

"A PROCESS FOR PREPARING CLEAR,ULTRA MILD,AQUEOUS FOAMING R CONDITIONING DETERGENT COMPOSITION"

Abstract

Compositions useful as 2-in-1 cleansing products are disclosed that are extremely mild to skin and hair, which use neutralized, essentially chargeless, ionic complexes of fatty amines and fatty acids to deliver various levels of conditioning; neutralized, essentially chargeless, ionic complexes of a detersive surfactant comprising a water soluble cationic surfactant and/or polymer complexed with one or more anionic surfactants; or an amphoteric surfactant complexed with one or more anionic surfactants; or a water soluble cationic surfactant and/or polymer complexed with one or more amphoteric surfactants; or a water soluble cationic surfactant and/or polymer complexed with one or more anionic surfactants and an amphoteric surfactant; detersive surfactant-soluble but water-insoluble silicones or derivatives thereof; and water. These products exhibit true 2-in- conditioning properties, and are lower in cost than current 2 in 1 products. Clear or opacified products can be formulated.

Full Text	The present invention relates to a process for preparing clear, ultra mild, aqueous foaming and conditioning detergent composition. The instant invention is generally directed to novel, ultra mild "2-in-1" conditioning aqueous detergent products, including shampoos, antidandruff shampoos, and a variety of body care products, such as shower gels, liquid soaps- with and without antibacterial agents, facial cleansers, baby washes, baby shampoos and the like, having detersive surfactant systems based upon use of balanced molar proportions of the essential anionic detergent, anionic hydrotropic sulfonate or sulfate, amphoteric detergent and cationic conditioner ingredients. The desired balance is achieved by having the sum (on a molar basis) of the anionic detergent and hydrotropic sulfonate/sulfate substantially equal to the sum (on a molar basis) of the amphoteric detergent and any cationic conditioner ingredient. The resultant novel aqueous detergent products deliver excellent cleansing and foaming properties without irritation to skin and hair; provide true 2-in- conditioning properties to the hair and skin; and are lower in cost than current 2-in-1 products. A further benefit is that these detergents are in solution form and are crystal clear, although , if desired, they can be opacified. BACKGROUND OF THE INVENTION Currently, commercially available, 2-in-1" or conditioning shampoos, are optically opaque. This is due to the fact that the conditioning agents incorporated therein are essentially water insoluble. For example, when high-molecular weight silicone derivatives are added to achieve the conditioning benefits, it has been found that H is difficult to formulate silicone-containing shampoos that are stable and do not suffer from the separating out of the silicone ingredient. The most accepted way to incorporate these silicone conditioning agents in such conditioning shampoos is to disperse, suspend, or emulsify them, which results in the opacification of these products and sometimes results in unstable products due to the separation of the emulsified or suspended silicone. While the above-described "2-in-l" conditioning shampoos have achieved a great deal of success in the marketplace, such products suffer, at least among a certain segment of consumers, negative attributes of poor appearance, decreased foam, reduced viscosity, and physical instability because the conditioning materials therein are not completely dissolved. The patent literature relating to detergent compositions which include water-insoluble, hair and skin conditioning matenals reflects a variety of approaches designed to overcome the above mentioned disadvantages. More specifically, the patent literature teaches a vanety of agents that disperse, suspend, or emulsify such conditioning agents. For example, U.S. 4,741,855 to Grote et a! teaches the use of long chain (C16-C22) acyl derivatives, such as ethylene gfycoi distearate or long chain (C16-C22) amine oxides, as suspending agents U.S. 5,152.914 to Forster et al teaches the use of suspending agents chosen from polyethylene gfycoi mono- or diesters of C16-C22 fatty acids having from 2 to 7 ethylene oxide groups. Also, U.S. 4,997,641; U.S. 5,106.613; U.S. 5.213,716; U.S. 5,346,642; and U.S. 5.348.736. all assigned to the assignee of the instant invention, disclose the use of long chain (C24-C45) alcohols and ethoxyiated alcohols as suspending agents. Alternatively, U.S. 4,559.227 to Chandra et al discloses conditioning shampoos in the form of clear solutions where) blends of amme-functionaJ sdoxane polymers and nonioruc surfactants of the aikanoiamide or amine oxide type are dissolved in aqueous solutions containing typical anionic and amphoteric detergents used in shampoos. However, the commercial availability of the latter compositions has not been assessed. Now it has been found that it is possible to formulate aqueous detergent compositions containing balanced molar proportions of anionic, amphoteric and catioc ingredients that are crystal clear (although they can be opacified if desired) which exhibit true '2-in-1 conditioning properties. Furthermore, the resultant compositions are ultra mild and thus do not cause imtation to skin or hair. Additionally, these compositions are high foaming, and can be manufactured in a more cost-effective and lass energy intensive manner than the commercially available silicone-containing conditioning shampoos, which are in emulsion, suspension or dispersion form It is recognized that the pnor art discloses compositions containing essentially equimolar quantities of anionic surfactant and amphoteric surfactant For example, U S 3,950,417 of Verdicchio et al discloses a shampoo containing nonionic surfactant, a surfactant betaine and an anionic surfactant wherein the molar ratio of betaine to anionic is from 0 9 1 to 1 1 1 However, the nonionic detergent is the pnncipal surfactant in the preferred compositions which of necessity exhibit reduced foaming Similarly, U S 4,246,131 of Lohr discloses a low irritant, clear composition containing an equimolar mixture of surfactant betaine and alkonalomine neutralized, anionic, alkyl sulfate detergent However, the poor art composrttons do not indude water-insoluble conditioning agents or anionic hydrotropic sulfonates/sulfates and do not recognize the need for balanced molecular proportions of the anionic, amphoteric and cationic ingredients therein Therefore, said compositions should not provide effective hair and skin conditioning benefits On the other hand, European Application EP 0 294 894 A2 discloses an ion pair complex of an anionic surfactant, an alkyl amine and a wax as a conditioning agent and discloses anionic surfactant based shampoos containing said complex as a conditioning agent However, again there is no recognition of the need for balanced molar proportions of anionic, amphoteric and cationic ingredients in the final composition Thus, the need still exists for a clear, ultra mild, foaming, conditioning composition SUMMARY OFTHF INVENTION As described above, the present invention primary resides in the discovery that foaming and conditioning compositions which are mild can be prepared in the form of clear liquids if balanced molecular proportions of selected anionic detergents, anionic sulfonate/sulfate hydrotropes, amphoteric surfactants and water-insoluble cationic, hair and skin conditioning agents are employed. The present invention relates to process for preparing clear, ultra mild, aqueous foaming and conditioning detergent composition said process comprising admixing by weight of \ 5%, to 40% of a detersive surfactant mixture of (1) 2% to 14% of an anionic detergent selected from the group consisting of C8-C18 alkyl sulfates, C8-C18 alkyl ethenoxy ether sulfates containing 1 to 5 ethenoxy groups in the molecule, C8-C18 acyl lsethionates, C10-Cjn alkyl sulfonates, C10-C22 alkene sulfonates, and mixtures thereof, (2) 0 5% to 5% of an anionic h\drotropic, C1-C3 alkyl benzene sulfonate or C5-CN alkyl sulfate and (3) 2 5% to 21% of an amphoteric surfactant selected from the group consisting of C8-C18 alkyl betames, and sulfobetames, C8-C18s alkyl amido, C2-C3 alkyl betames and sulfobetames, C8-C18, alkyl amphoacetates, C8-C18 alkyl amphopropionates, and mixtures thereof B 0 05% to 9% by weight of a water-insoluble conditioning agent which is soluble in said detersive surfactant mixture and is selected from the group consisting of (1) 0 05% to 5% of a complex of essentially equimolar amounts of a C8-C18 (EtO)i-n) carboxylic acid, and a CVCis alkyl (EtO)0-10 dimethyl amine (2) 0 25% to 3% of a water-insoluble silicone which is soluble in said aqueous detersive surfactant mixture and is selected from the group consisting of polydimethylsiloxane polyether copolymers, polydimethylsiloxanes containing an amino substituent, polydimethylsiloxanes containing at least one ammonia substituent and mixtures thereof and (3) a mixture of B(l) and/or B(2\| with 0 1% to 1 0% of a polyquaternary compound selected from the group consisting of a quatermzed (ellulosic polymer and a mixture of said quatermzed cellulosic polymer with a non-cellulosic quaternary conditioning polymer, and optionally C 05% to 1 0% by weight of either a mono-C10-C22 alkyl tn C1-C4 alkyl ammonium salt or a di(C14-C18 alkyl) (EtO)3-20 di-C1 -C4 alkyl ammonium salt as an anti static agent, D from 0 1% to 4% by weight of an anti-dandruff therapeutic agent, which agent is soluble m the detersive surfactant mixture, E 0 25 % to 3% of an opacifying or pearhzing agent to render the composition opaque or pearhzed, and F the balance being water, the sum of the moles of anionic detergent find anionic benzene sulfonate being equal to the sum of the moles of amphoteric detergent and cationic conditioning agent at a pH in the range at 5 5 to 7 0 and said composition being effective to deliver said conditioning agent m water insoluble form at use concentrations of the composition m water In a preferred aspect, the described invention contains as the conditioning agent a mixture of (a) and quatermzed cellulose polymer, (b) a complex of essentially equimolar amounts of C8-C18 (EtO)i n> carboxylic acid and C8-C18 alkyl (EtOln 10 dimethyl amine and (c) pohdimethylsiloxane potyoxy (C2-C3) aikylene copolymer and, in addition. 0 05 % to 1 0 % of a mono C \ 2-C18 aikyl or di- C12^ 18 akyi (BO)3-20 quaternary ammonium compound The preferred compositions, exhibit enhanced conditioning properties due to the use of the mixture of conditioning agents and also exhibit enhanced anti-static properties due to the inclusion of the mono-alkyi or di-alkyi (ElO) 3.30 quaternary compound. In one further preferred aspect, the inventive compositions enable a manufacturer to market a line of conditioning shampoo products having variable conditioning properties. Mora specifically. by utilizing the specified conditioning materials individually and in mixtures, a iine of conditioning shampoos providing tow. medium and high conditioning effects can be provided. Detailed Description of the Invention Anionic Detergents The suitable anionic detergents are employed in the form of their water-soluble salts and the salt forming cation usually is selected from the group consoling or sodium, potassium, ammonium and mono-, dl- and tri- C2-C3 aJkarttiarnmonnim, with the sodium and arnrnoruum cations bong preferred. The suitable anionic detergents include the following: 1 The CQ-C 18 aikyl ether ethenoxy sulfates of the formula fl(OC2H4)nOS03M where) n is 1 to 5. These sulfates differ from the primary aikyl sulfate detergent in the number of moles of ethylene oxide (1-5) reacted with one mole of afcanoJ in forming the ethoxyiated aikanoi which is sulfated and neutralized to form this anionic detergent. Preferred aikyl ether ethenoxy sulfates contain 12 to 16 carbon atoms in the aikyl group and contain two to three ethylene oxide groups per mole of alkanol. 2. The C8-C18 alkyl sulfates which are usually obtained by sulfating C&-Cis alkanols obtained by reducing the gfycendes of tallow or coconut 01! Preferred aikyl sulfates contain 10 to 16 carbons in the aikyl group. 3. The O-C8-C18 acyl isethionates may be produced by neutralizing the reaction product of a C8-C18 a alkanoic aad with 2-hydroxyethanesuffonic acid. Similar to the sarcosines and taunnes vhe preferred isethionates contain 12 to 14 carbon atoms in an aryl group obtained by reduction of coconut oil. 4 The C10-C20 paraffin sulfonates obtained, for example, by reacting an alpha-olefin with bisulfite. Preferred aikane sulfonates contain 13 to 17 carbon atoms in the alkyl group. 5. The C10-C22 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 aipha-olefin. While mixtures of the foregoing anionic detergents may be employed, the preferred anionic detergents are the alkyl ethenoxy ether sulfates and the alkyl sulfates. The proportion of the anionic detergent in the claimed compositions generally will be in the range of about 2% to about 14% by weight preferably in the range of 4% to 11% by weight ana most preferably in the range of 6% to 8% by weight. Other Anmnm Surfactant In addition to the anionic detergent discussed above, the described inventive compositions include anionic, hydrotropc C1-C3 alkyl substituted benzene sulfonates and C5-C3 alkyl sulfates. These materials are dassrfied as surfactant-hydrotropes and serve to sotubriize the anionic and amphoteric detergent in the aqueous medium. Also, it is believed that these materials assist in removing sod from the substrates being cleaned. Usually, these materials are used in the form of the water soluble sodium, potassium and ammonium salts. Suitable hydrotropic sulfonate and sulfate salts include the salts of toluene sulfonate, xylene sulfonate, cumene sulfonate, C5- C6 alkyl sulfate and mixtures thereof. The proportion of the hydrotropic sulfonate or sulfate material generally will be in the range of about 0.5% to about 5% by weight of the resultant composition Preferably the range of this material will be about 0 5% or 1% to 4% by weight of the final composition Amp Generaily, the amphoteric surfactant components will be selected from the group consisting of C8-C1 8 alkyl betames and suifobetaines, and C8-C18 alkyl amphoacetates and propionates The suitable betames and suifobetaines have the following formula: (Formula Removed) wherein R-i B an alkyl group having 8 to about 18 carbon atoms, preferably 10 to 16 carbon atoms or the amido radical: (Formula Removed) wheretn RCO is an acyl group having 8 to about 18 carbon atoms and a is the nteger 1 to 4: R2 and R3 are each alkyl groups having 1 to 3 carbon atoms and preferably 1 carbon; R4 ts an alkyiene or hydroxyalkylene grc'jp having from 1 to 4 carbon atoms and optionally, one hydroxy! group; and X is an anion selected from the group consisting of SO3* and COO" Typical betames and amido alkyl betames include decyl dimethyl betame or 2-(N-decyl-N,N-dimethylammonio) acetate, cocodimethyl betame or 2-(N-coco-N,N-methylammono) acetate, mynstyl dimethyl betame, palmrtyl dimethyl betaine, lauryl dimethyl betame, cefyl dimethyl betaine. stearyi dimethyl betame, cocoamidopropyl dimethyl betame and laurylmidoethyt dimethyl betaine. Typical suifobetaines or suttames simdany include cooodtmethyt sulfobetaine, or 3- Other suitable amphoteric detergents are the C8-Cl8 alkyl amphoacetates and propionates corresponding to the following formula: (Formula Removed) wherein RC(O) tsa C8 -C18acyl group, R2 is a C1-C2 aikyl group and M is a salt forming group such as sodium or potassium. A substitute for the described amphoacetate or amphopropionate compound is sodium cocoamphohydroxypropyl sulfonate Sodium cocoamphoaetate is a preferred matenai. The proportion of the amphoteric detergent generally will be in the range of about 2.5% to about 21 % by weight 0/ the final composition. Preferably the proportion of amphoteric surfactant will be selected from the range of about 4% to about 13% by weight and most preferably from the range of about 6% to about 10% by weight of the final composition. In the preferred composrtions, the proportion of the detergent mixture will be from about 8% to 28% by weight of the composition; and in the most preferred composrtions the proportion of said detergent mixture will be from 13% to 22% by weight. Conditioning Agonta The essential water-insoluble conditioning agent which is employed in the inventive cornpositions is soluble in the above-described aqueous detersive surfactant mixture and generaly wfl be selected from the group consisting of (1) essentislly equwnolar complexes of C8-C18 alkyl ethoxy carboxysc acids and C8 C18 ethoxy dimethyl amnes; (2) stfcones soluble in the aqueous detergent mixture herein selected from the group consisting of porydimethylsiloxane polyether copolymers, poiydimethyteilaxanes containing an arwno substftutuent and mixtures thereof; and (3) a mature of (1) sno7or (2) with a quatemized ceUutosic polymer or a mixtures of quaterruzed ceHuiosc polymer with rrsnor proportions of non-ceiluiosic quaternary conditioning polymers. The equunotar complexes of C8-C18 alky ethoxy carboxylic acids and C8-C18 alkyl etnoxy dimethyl amines are believed to form amine salts which provide conditioning properties in the described composrtions. Usually, the ethoxytated carboxylic acid will contain from 1 to 10 ethoxyl groups and preferably from 2 to 6 ethoxy groups On the other hand, the higher alkyl dimethyl amine may contain from 0 to 10 ethoxy groups While the amine salts are believed to form when equimolar amounts of said carboxylic acid and said dimethyl amine are present, the presence of excess dimethylamme on a molar basis does not have an adverse effect on the conditioning properties of the amine salt and a slight molar excess of said amine may be preferred Preferred carboxylic acids are the C10-C14 (ElO)2-6 carboxylic aads and preferred amines are the C14-C18 alky I and C14-C18 alkyl amido propyl dimethyl amines. Generally the proportion of the amine salt formed by the complex of C8-C18 alkyl ethoxy carboxylic acid and the C8-C18 aikyi dimethyl amine will be about 0 05% to 5%, preferably 0.1% to 2.5%, and most preferably about 0 15% to 1 5%. by weight of the resultant composition. When this complex is used as sole conditioner, a low level of conditioning is perceived by the user. Surfactant-Soluble. Water-Insoluble Silicones or Silicone-Oenvatives The silicones or silicone-denvatrves that are useful in the present invention are those that are soluble in and compatible with the above described aqueous detersive surfactant mixture, but are insoluble in water. This allows them to be formulated into detergent compositions that are initially transparent, but which, if desired, can be opacified or pea/iized by adding recognized peartong/opacrfying ingredients such as ethylene glycol dtstearate or polystyrene. Suitable silicones mdude trtnethyisiytamoofrrtetriicone purchased under the trad* name Dow Corning G2-8220 - an amine functional corydirnethytsdoxane; copolymers of polydirnethylsiloxane and a poly C2-C3 alkytane ether purchased under the tradenames Dow Coming 190, Dow Corning 25324 and Dow Corning Q2-5220; and pofydimethyl siioxanes having at least one quaternary ammonium moiety, preferably two quaternary ammonium moieties. The latter siBcone 8 available cornrneraaUy under the tradename A8IL-QUAT 3270 for example. If silicones other than those above are employed, the resultant compositions usually are not dear because part of the pofydimethyisdoxane a present in water insoluble form. The proportion of the surfactant soluble, water insoluble silicone in the inventive composition broadly win be in the range of about 0.25% to about 3%, preferably 0.5% to 2%, most preferably 0.7% to 1.5%, by weight. When said silicone is the sole conditioning agent present, a composition having a low conditioning effect is achieved - a conditioning value of 2.5 for example. However, when a mixture of the described amine salt, cellulose pofyquat and the described silicone is employed as the conditioning agent, the resultant composition exhibits high conditioning properties -- a value of 7.0 or more in the applicable test Cationic Polymers The water-insoluble conditioning complex of carboxylic acid and amine and the water insolubl. silicone conditioning agents are soluble in the described aqueous detergent mature, but are rendered water-insoluble when the resultant detergent compositions are diluted with water dunng use. In addition, either one or both of these conditioning agents may be further employed in admixture with a cationic cellulose polymer. Because the canonic cellulose polymers are water soluble and soluble in the aqueous detergent mixture, clear detergent mixtures can be prepared when the caitonic ceUulosic polymers are employed as the sole conditioning agent. The suitable hair conditioning, cationic polymers are derivatives of natural polymers such as cellulose and gums. These derivatives generally are water-soluble to the extent of at least 0.5% by weight at 20°C. Generally, such polymers have more than 10 monomer units in the* molecules and a molecular weight of about 1000 to about 1,000.000, preferably 2000 to 500.000. Usually, the tower the molecular weight, the higher the degree of substitution by the cationic, usuaJJy quaternary, group. Suitable natural polymers which may be converted into the deeired cationic polymers are hydroxy alkyl celluoses and alkyl hydroxy celluloses. Cationic hydroxy alkyl celluloses and ther preparation are described in B.P. No. 1,166.062 assigned to Union Carbide. These hydroxy ethyl celluloses are marketed under the trade designation JR 125, JR30M and JR 400 and ere believed to have a molecular weight of 150,00 to 400,000 and a degree of substitution of a quaternary group of about 0.3. Akyl hydroxy alky! celluloses having the same formula as hydroxy alkyt cellulose, but wh additional alkyl substituents at other sites on the anhydroglucose unit also are avaiable. More particularly, the ethyl hydroxy ethyl celluloses are available under the tradename 'ModocolP with a molecular weight in the range of about 50,000 to 500,000 and a degree of substitution of about 0.1 to 0.8. Other suitable natural cationic polymers are the galactomannan gums, e.g., guar gum and hydroxy alkylated guar gum The molecular weight of guar gum is believed to be from about 100,000 to 1,000,000 A suitable cationic guar gum carrying the group -CH2CH=CH CH2N (CH3)3C> with a degree of substitution of about 0 2 to 0 8 is commercially available under the tradenames Jaguar C-17 and C-13. The preferred cationic cellulose polymer is Poryquatemium 10 which is a polymeric quaternary ammonium sai! of hydroxyethyl cellulose reacted wrth a trimethyl ammonium substituted epoxide. The proportion of the cationic natural polymer usually will be from about 0 05% to about 1%, preferably 0.1% to 0.8%, most preferably from 0 2% to 0.7%, by weight of the finai composrtion. The cationic polymer provides for enhanced style control and conditioning. When Poryquatemium 10 is employed as the sole conditioning agent, a product wrth moderate conditioning results. When the cationic natural cellulose or gaiactomannan gum polymers are present in the inventive compositions, up to about one half the weight of said natural polymer may be substituted by a second non-catluiosic, cationic polymer, having conditioning properties provided that the non-ceUulosic cationic polymer is soluble in the final composition. Exemplary of such cationic polymers are dtaJkyidlafyl ammonium salt (e.g., halide) homoporymers or copolymers, e.g., dimethyidiaUyl ammonium chloride homoporyrner, dimethyidiaJyl ammonium chlonde/acrylamide copolymer containing at least 60% ammonium chloride monomer, dirnethyidiairyl ammonium chlonde/acryiic aad copolymer containing at least 90% dimethyidiaJfyl arnrnonium chloride monomer, vinyl jnrtazde/vinyi pyrrotidone copolymers containing at least 50% vinyl imidazole and potyethyieneimine. Currently, the preferred cationic polymers are Merquat 100 [a polymer of diaillyldimethyl ammonium chlonde (charge density of 126)) and Luviquat 905 [a 95% vinyl imidazole/5% vinylpyrrolidone copolymer (charge density of 116)J. Other suitable non-ceilulosic cationic polymers are disclosed m the CTFA Cosmetic Ingredient Dictionary under the designation •Polyquatemium* followed by a whole number. OptionaJry. the inventive compositions may include, in addition, a controlled amount of rnono-C14-C18 alkyl quaternary ammonium salt or di-Ci2Ci8 alkyl (EtO) dimethyl ammonium salt to provide enhanced anti static effect. The mono alkyl quaternary salts have the following formula. R9.R10,R11, R12 N+X-wherein at least three of the R groups are C1-C4 alkyl and at least one is a C10-C22 alkyl, with X being a salt-forming anion, such as chlonde, bromide, methosulfate or ethosulfate. Preferably, the lower alkyl groups will contain one to two carbons, the higher alkyl group will contain 14-18 carbon atoms and the water-so/ubilizing group will be chlorine or bromine. Suitable compounds include cetyf trimethyl ammonium chloride and stearyi trimethyl ammonium chlonde. Alternatively a di (C14-C18) alkyl (EtO)3-20 dimethyl ammonium salt may be employed wherein from 3 to 20 ethoxy groups are present with alkyl substitute Preferred compounds are di-stearyl (EtO)5 dimethyl ammonium chlonde and di- stearyl (ElO)is dimethyl ammonium chlonde. If ethoxylated alkyl groups are not present in the di-higher alkyl quaternary salt, the resultant compositions are not clear for example. Generally the proportion of added mono C14-C18 alkyl quaternary sail or di C12-C18 alkyl (EtO)3-20 quaternary salt will be from about 0.05% to about 1%, preferabry from 0.1% to 0.5%, and most preferably 15% to 0.35%, by weight. The anti static effects increase as the proportion of said added quaternary salt increases. The final essential component in the inventive compositions is water which provides an aqueous medium. Generally, the proportion of water wifl range from about 51 % to about 95%, preferably, about 61% to about 92%, and most preferabry about 70% to about 88%, by weight of the resultant composition. An important characteristic of the inventive compositions is that the turn at the moles of anionic detergent and the moles of anionic hydrotrope is substantially equal to the sum of the moles of amphoteric detergent and the moles of cationc conditioning compound including, optionally, the moles at mono alkyl or dialkylethoxy quaternary ano static compound. On a molar basis the ratio of anionic compounds to amphoteric compounds plus cationic compounds wifl be the range of about 0.8:1 to about 1.25:1, preferabry about 0.9:1 to about 1.10:1, most preferably about 0.95:1 to about 1.05:1. It appears that the proportions of afl of the essential ingredients are interrelated and must be controlled in order to achieve compositions having the desired mildness, foaming, cleaning, conditioning, clarity and viscosity characteristics Generally, the viscosity of the inventive compositions will be in the range of about 1000 to 10,000 cps, preferably 2000 to 7000 cps, and most preferably 3500 cps to 5500 cps, at 24°C , as measured with a Brookfield RVT viscometer using a #4 spindle rotating at 20 rpm These inventive compositions are essentially unbuilt liquids, i e , do not contain detergent building proportions of water-soluble inorganic or organic builder ingredients Therefore, the resultant compositions are suitable for use as liquid hand washing detergents, liquid shampoos, liquid shower bath products and light duty fabric washing products Thus, these inventive compositions can contain any of the usual adjuvants found in those compositions provided that they do not interfere with the mildness, performance or clarity characteristics descnbed in the final products. Such additional ingredients include minor proportions of perfumes and cotonng ingredients for aesthetic purposes; opactfiers such as ethylene glycol distearate or polystyrene, sequestering agents such as citrate or ethytenediamine tetreaacetate; preservatives such as formaldehyde or Kathon CG® or monomethyloldimethyl hydantoin; fluorescent agents, acids or bases for adjusting pH; and inert salts such as sodium sulfate. The total concentration of added ingredients usually will be less than 5%, preferably less than 3%, by weight of the total composition. The nventfve compositions are prepared by admixing the cafjonic polymer, if any, with water at a temperature tn the range of about 20°C. to 60°C., usmg sufficient agitation unti a dear, homogeneous mixture is formed. Thereafter, the anionic surfactants, namely, the anionic detergent compound and the anionic hydrotroptc agent are added while continuing the agitation until a homogeneous mixture is formed. Thereafter, the amphoteric detergent and the silicone ingredient, i any, are added wh agitation to the aqueous mature of catiaiic poiyrner ajid amonic surfactants and agitation is continued unti the resultant mixture m homogeneous. Next the diaodium phosphate is added to adjust the pH to 6.0 - 6.5. Next, t the carboxyic aod arrune salt is present, a premix of the ca/boxyiic aod and the desred amine is prepared with agitation at a temperature m the range 20°C. to 60°C. Optionally, the perfume is included in this premix which is mixed until homogeneity is achieved. Thereafter, the prema is added to the aqueous detergent mature with agitation which continues unta homogeneity is achieved. Fmalty the formula amounts of quaternary salt anti-stat, if any, preservative, if any, and color, if any, are added with agitation During the manufactunng process, mixing is controlled to avoid foaming. The resultant composition is clear and has a pH in the range of about 5 5 to 7 0, preferably from about 6.0 to 6 5 In the preferred process, the composition is prepared without the addition of external heat. Thur. the process temperature is controlled in the range of 20°C to 30°C. Using this so-called "cold process' saves energy and the time required to raise or lower the temperature. Normally, the viscosity and pH of the resultant product is checked before the product is filled into containers for saie. If necessary, additional anionic hydrotrope is added to decrease viscosity or polyethylene glycol (PEG) 18-propylene glycol oleale is added to increase viscosity. Also, if necessary, disodium phosphate dibasic or crtnc acid or other acid or base is added to adjust the pH. Preferably, the resultant composition is passed through a 20 mesh or equivalent filter prior to filling same into containers for saie. The foaming properties of the inventive compositions are determined by diluting 15CC of the resultant composition with 85cc of 250 pom water (40% Mg"-1", 60% Ca++), adding 3.0 grams of sebum sod and adjusting the temperature to 25°C. with agitation. Thereafter, the solution is added to a 500 ml graduated cylinder containing a plastic tube fffled with water which has a volume of 25cc The 500 ml glass stoppered cylinder is then rotated through 40 half circles at a speed of 30 rpm. After removing the stepper, trie foam volume is read. The cylinder then is removed from the rotation apparatus and placed on a table top. The time interval in seconds is recorded from the completion of rotation until the liquid level in the cylinder reaches 100 ml (75% of the liquid has drained) and the results are recorded as ml of foam/drainage time in seconds. Ml of Foam and drainage tines are then expressed on a scale of 1 to 10 - 1 poorest 10 best - The conditioning properties are determined by combing hair tresses treated with the product using the fine teeth of the comb when wet and after drying. In this evaluation 3.2 gm tresses of virgin, European brown hair obtained from DeMeo Brothers, Inc. are prepared with the root end of the hair at the top of the tress. The tresses are nnsed with running tap water at 105°F (40.5°C.) and then 1 cc of the test product is worked into the tress with the fingers for one minute The treated tress is rinsed for 30 seconds and a second application of test product is worked into the tress for one minute followed by a 30 second nnsmg. Then each tress is nnsed for 60 seconds with 105°F running tap water and detangled by combing with the wide teeth of the comb The wetted tresses are maintained wet with deionized water and are combed by expert judges using the fine teeth of the comb. The \|udges assign a rating of 1 to 10 for each tress, with 10 being easiest to comb. Each tress is combed by a minimum of 10 judges and the ratings are averaged In the described procedure, the hair tresses are evaluated while wet. The procedure for dry combing is identical except that the hair tresses are dned before being combed. In the test for evaluation of static, the hair tresses are treated with product as described above and dried. The dned tress is then combed by a stalled evaJuator in a forceful, downward manner 20 times usw>g the fine teeth of the comb. The static on each is then evaluated on a scale of 1 to 10 with 10 being excellent. Again, each tress is combed by 10 \|udges and the ratings are averaged. This evaluation is earned out in a constant temperature - constant humidity room. Specific inventive liquid compositions are illustrated in the following examples. AB quantities indicated in the examples or elsewhere in the specification are by weight unless otherwise indicated. A particutenly preferred conditioning shampoo composition according to the described invention is set forth in Example 1 below: 1 6 Example 1 by wl Polyquatemium 10 0 60 Sodium lauryl diethenoxy ether sulfate 7 0 Cocoamidopropyl dimethyl betaine 7 8 Sodium cumene sulfonate 1 3 Disodium hydrogen phosphate 0 3 Dimethylporyoxyethylene sdoxane (DC 5324 fluid) 0.5 Oimethyipotyoxyethylene/ poryoxypropyf lene stk>xane (DC Q-5220 resjn modifief) 0 5 Laureth - 3 - carooxybc aad 0 1 I sostearyrrndopropyl dimethyl amine 0 14 PEG 55 - propylene glycol oleate ± 40 Perfume 0.5 Kathon CG® preservative 0.07 Cethmomum chloride 0.25 Yetow cotor solution 0.14 Water o.s. 100.00 The foregoing shampoo composition is prepared by the preferred cold process at 20°C. - 30°C. without addition of heat In the cold process, the formula weight of Potyquaternwrn 10 is admoced with the formula amount of water with agitation to form a clear homogeneous mixture. Thereafter, the aikyt ether sulfate, the sodium cumene sulfonate, the betaine and the two ssoxane ingredients are added to the aqueous pofyquat solution in sequence with agitation. Mixing m continued after the addition of each ingredient until the resultant mixture e dear and homogeneous. with said agitation being controted to avoid foaming. Next the disodium phosphate basic is added to said aqueous mixture. Then a homogeneous prermx of the formula amounts of laureth-3-carboxyfic acid, the isostearytarrwdc-propyl dimethyl amine and perfume is prepared with agitation at a temperature of 20°C- 30°C. and this premcx is added to the aqueous detergent mixture with agrtation which is continued until the resultant aqueous mixture is clear and homogeneous Finally, the formula amounts of cetnmonium chionde, preservative and color are added to the foregoing mixture with agitation to form the clear, homogeneous shampoo composition The resultant shampoo composition has a viscosity of 4500 cps as measured with a Brookfield Viscometer using an RVT spindle #4 rotating at 20 rpm at 25°C. and a pH of 6.25. When the shampoo composition is tested using the above-descnbed foaming, conditioning and static tests, the following results are obtained: Foarming- 7 0 Conditioning - 9.0 State- 9.0 In the composition of Example 1, the molar proportions of the anionic detergent, anionic benzene sulfonate, amphoteric detergent and catjonic conditioners follow: Sodium iauryi diethenoxy ether sulfate . 01862 Sodium cumene sulfonate 0058 Cocoainidopropyl dimethyl beuune 02281 Poryquatermium 10 (monomer raw. -504) .0012 Based upon the foregoing analysis, the ratio of the sum of the motes of anionic detergent and benzene sulfonate to the sum of the moles of betame and catione conditioner a .02493 to 02478 or 0.99:1.0. When the 7% of anionic alky! diethenoxy ether sulfate is replaced by 5.6% by weight of sodium tetradecyl aBcane sulfonates or 5.8% by weight of sodium C14-C16 alkene sulfonate or 5.3% by weight of ammonium lauryl sulfate - each being equimolar to said ether sulfate -, the resultant cornposalons have svndar characteristics. Examples 2 -4 The composition of Example 1 is repeated with exceptions that the concentration of Pofyquat #10 is reduced to 0.25%, 0 35% and 0.5% by weight respectively and the percentage of PEG - 55 propylene glycol oleate is increased to 0.8%, 0.8% and 0.6% by weight respectively, with any balance being water The resultant clear homogeneous ultramild shampoo compositions yield the foaming, conditioning, static, viscosity and pH results set forth in Table A below: Table (Table Removed) Examples 5-8 The compositions of Examples 1 -4 are repeated with the exceptions that 2% by weight of an opacifying agent which is a mixture of ethylene glycol distearate (0 6%) and stearyt alcohol ethoxamer (4) and 0.2% by weight of distearyl dimethyl polyoxyethyiene (5) ammonium methyl sulfate are substituted for a like proportion of water. The resultant products are homogeneous, but opaque due to the inclusion of the opacifying agent. Furthermore, the conditioning/static properties are modified due to the inclusion of the added quaternary ammonium salt The properties of said cornpositions are shown in Table B below: (Table Removed) The addition of the distearethoxy (5) dimethyl ammonium methyl sulfate reduces the molar ratio of anionic compounds to the sum of amphoteric and cationic compounds to 0.98:1. Examples 9- 12 The condrttoning effects of iiie mixture of laureth-3 carboxylic acid and isostearamidopropyi dimethylamine are set forth in Examples 9-12 % bY YYt. A 1Q II 12 Sodium lauryl diethenoxy ether sulfate 7 0 70 70 70 Cocoamidopropyl dimethyl betaine 78 78 78 78 Sodium cumene sulfonate 13 13 1.3 1.3 Disodium hydrogen phosphate 0.3 0.3 0.3 0.3 Laureth-3 carboxylic aad 0.1 0.3 1 0 2.0 Isostearamidopropyi dimethyl amine 0.14 0.42 14 2.8 PEG 55 propylene glycol oleate 0.2 0.2 0.2 0.2 Perfume, color, preservative and water o>5 £Lfi 33 35 100.0 100.0 100.0 100.0 Conditioning 2 2.5 3 3.5 Foaming 8 8.0 7 6 CJarty Viscosity 2500 3050 4100 4780 These examples illustrate that the amine-acid complexes - amine salts - provide conditioning propertiee and that the conditioning properties increase as the proportion of the amine-acid complex - amine sal - increases. However, even at the highest concentration of the amine salt, i.e., 4% by weight because excess amine is present, the conditioning rating is 3.5 which is low. Further, as the level of ethoxylation increases in the carboxylic acid component, the conditioning value decreases because the motor amount of the amine salt produced therefrom decreases. When stearamidopropyl dimethyl amine is substituted for isosteararnidopropyl dimethyl amine in Examples 9-12. the conditioning properties and foaming properties of the final compositions are not changed. FxamplPS 13 and 14 The conditioning effects of cationic cellulosic poiyquats in the inventive composition are illustrated in Examples 13 and 14 wherein Polyquatemium 10 is the sole conditioning agent present. %t?ywL 12. 14 Poryquaternium 10 0.3 0.6 Sodium lauryl diethenoxy ether sulfate 7 0 7 0 Cocoamidopropyi dimethyl betaine 7 8 7.8 Sodium cumene sulfonate 13 1.3 Disodium hydrogen phosphate 0.3 0.3 PEG 55 propylene glycol oleate 0 2 0.2 Perfume, color, preservative and water 05 32 100.0 100,0 Conditioning 4.0 6.75 Foaming 8.0 9.0 Static 5.0 4.0 danty dear ciear The foregoing conditioning results show that medium conditioning is obtained when a cationic cellulose potyquat is the sole conditioning agent. Example 15 and 16 The compositions of Examples 13 and 14 are repeated with the exceptions that 0.24% by weight and 0.48% by weight respectively of Polyquatemium 7 (Merquat 550«) is substituted for the amounts of Polyquatemium 10 and the amine salt produced from 0.1% of laureth-3 carboxylic aod and 0.14% of isostearamidopropyl dimethyl amine is included, with any balance being deducted from the amount of water present. The conditioning, foaming and clanty properties of the resultant compositions are set forth in Table C below: (Table Removed) Because the compositions are not clear, Polyquaterruum 7 as the sole polyquat is not satisfactory When Example 16 is repeated using a mixture of 0 3% by weight of Poryquatemium 10 and 0 24% by weight of Polyquatemium 7 in place of 0 48% of Poryquatemium 7, a clear shampoo resuts having a conditioning rating of 7, a foaming value of 8 5, and a static value of 4 0 This result indicates that a minor proportion - up to about 50% by weight of Poryquatemium i o may be substituted by Polyquatemium 7 - a non cellulosic pofyquat without adversefy affecting the clanty of the inventive compositions. Furthermore, the mixture of a cellulose pofyquat with a non-cellulostc pofyquat results m a slight increase in conditioning effects. Examples 17 and 18 When the compositions of Examples 15 and 16 are repeated using 0.3% and 0 6% of Poryquatemium 11 (Celquat 200) - a cellulose pofyquat - substituted for 0.24% and 0 48% of Potyquatemium 7, respectively, shampoos having the properties set forth in Table 0 are obtained. Table D (Table Removed) Poiyquaternium 11 results in compositions having slightly lower conditioning than Poryquatemium 7. The compositions of Examples 13-18 above are not within the scope of the claimed invention, but are included herein to further define said invention Samples 19 and 20 The conditioning properties or polymethylsiioxane in the inventive compositions is illustrated by the following compositions wherein the composition of Example 19 is a control because it contains no conditioning agent. %by wt. 12 2J2 Sodium lauiyl diethenoxy ether sulfate 7 0 7 0 Cocoarrudopropyl dimethyl betaine 7 8 7 8 Sodium cumene sulfonate 1-3 1.3 Dimethylporyoxyehtylene sdoxane (DC 5324 fluid) - 0.5 Oimethylpolyoxyethyiene/ potyoxypropyslene siloxane (DC Q-5220 ream modifier) - 0.5 Oisodtum hydrogen phosphate 0.3 0.3 PEG 55 - propylene glycol oleate 0.2 0.2 Perfume, color, preservative, water 15 02* 100.00 100.00 Conditioning 1 0 2.5 Foaming 7 4 7.5 Static 2.0 3.0 Viscosity 5200 cps 1100 ops CJanty ' clear clear The foregoing compositions demonstrate a conditioning agent must be present in the compositions in order to achieve any conditioning of the hair when shampooed using the inventive composition. When the composition of Example 20 is repeated with the exception that Silicone DC 5324 is omitted, the resultant composition exhibits a conditioning value of 2.0, a static value of 2.5 end a viscosity of 4000 cps at 25°C. using the Viscometer RVT. 23 Examples The compositions which follow are preferred compositions containing a mixture of three condrtioning agents, each with a different porymethyl siioxane component. %by wt 21 22. 23. 24 Poryquaternium 10 0.6 0 6 0.6 0.6 Sodium lauryl diethenoxy ether sulfate 7.0 70 70 70 Cocoamidopropyl dimethyl betaine 78 78 78 78 Sodium cumene sulfonate 17 13 13 1.3 Disodjum hydrogen phosphate 0.3 0 3 0.3 0.3 Laureth - 3 - carboxybc aad 0.1 0 1 0.1 0.1 Isostearyrrudopropyl dimethyl amine 0 14 0.14 0.14 o 14 TrenethytsilytarncKJirnetrucone (DC Q2-8220) 0.5 - SBicone quatemtum 2 (Silquat 100) - 0.5 - SScone quaterntum 2 (Silquat 300) - - 0.5 - Dknethicone copoiyol amine (SBamine50) 0.5 PEG 55 • propylene glycol oleate Perfume, color, preservative, water OJ q-s. g.s. a.^, 100.00 100.00 100.00 100 00 Conditioning 8.0 8.0 8.0 8.0 Foammg 8.0 7 0 7 0 7 0 Static 4.0 4.0 4.0 4.0 Clanty dear dear dear clear Viscosity (cps) 1000 4000 4000 4000 Examples 25 and 26 When the composition of Example 21 8 repeated with the exceptions that the amount of sodium cumene sulfonate is reduced to 1 3% by weight and 0.1% and 0.25%, respectively, of centrimonium chlonde is added, with any difference being water, shampoo composrtions having the properties shown in Table E are obtained Table E (Table Removed) Examples 27 and 28 These examples show other compositions which are within the scope of the described invention and their properties. % by wt 21 23. Polyquatemium 10 0.9 0.3 Sodium lauryi diethenoxy ether sulfate 10-S 3.5 Cocoarnidopropyi dimethyl betame 11.7 3.9 Sodium cumene sulfonate 1.95 0.65 Disodium hydrogen phosphate 0.45 0.15 Laureth - 3 carboxyfc aod 0.15 0.05 Isostearyrmdopropyl dimethyl amine 0.21 0.07 Silicone DC 5220 0.75 0.25 Sicone DC 5324 0.75 0.25 PEG 55 • propylene glycol oleate 0.6 0.2 Cetyttrirnethyl ammonium chJonde 0.375 0.125 Water O^ 0£» 100.00 100.00 Conditioning 9.0 6.0 Foaming 8.0 4.0 Static 9.0 9.0 Clanty dear dear Viscosity 10000 1900 pH 6.2 6.35 Example 28 illustrates that foaming is reduced when a proportion of 8% by weight of the detersive surfactant is employed. Further, as expected, good foaming is achieved when the proportion of detersive surfactant is increased to 24 2% by weight of the composition. Examples 29 and 30 The following compositions illustrate the importance of the presence of the anionic hydrotropc sulfonate/sulfate in the descnbed compositions. rafrwL 22. 20. Sodium lauryl diethenoxy ether sulfate 7 0 9.2 Cocoamidopropyl dimethyl betaine 7 8 7 8 DisodJum hydrogen phosphate 0.3 0.3 Water g^fi q.s. 100.00 100.00 Conditioning 1.0 1.0 Foarrang 4.5 4.0 Static Control 2.0 2.0 Ctenty dear dear Viscosity 10050 10100 Example 30 differs from Example 29 in that the molecular proportion of anionic detergent a increased to be equivalent to the sum of the molar proportion of anionic detergent and anionic hydrotropic sulfonate shown in the control formulation of Example 19. Comparison of Examples 27 and 28 compositions with the Example 19 composition illustrates that omission of the anionic hydrotrope ingredient from the inventive compositions results in a significant reduction in foaming and a doubling in viscosity. In these examples, the applicable molar ratios of anionic compounds to amphoteric plus cationic compounds are 0.78:1 and 1.03:1 respectively. Thus, the presence of the anionic hydrotrope sulfonate/sulfate ingredient is essential in the claimed detersive surfactant mixture of the inventive compositions. When like molar proportions of cocyl isethionate anionic detergent, hydrotropic sodium xylene sulfonate, hydrotropic hexyl sulfate, lauryl trimethyl betaine, sodium cocoyl amphopnonate and lauryiamidoethyl suttaine are substituted for the corresponding components in the above examples, compositions having similar performance and physical characteristics are obtained. The resultant products are effective for conditioning hair and skin and, therefore, are useful for cleansing the hair and skin. Although the need for substantially balanced molar proportions of anionic materials - detergent plus hydrotropic sulfonate/sulfate - and amphoteric plus cationic ingredients is not understood, it is believed that the anionic ingredients and the amphoteric plus cationic materials form a complex - possibly two complexes. The existence of at least one complex is suggested by the improved mildness and the increased viscosity of the resultant mixtures. It is further suggested by the improved conditioning properties when conditioning agents are included. While the actual mechanism is not understood, the efficacy of the resultant compositions is apparent at use concentrations thereof. The dear ultra mild compositions of the present invention can also be formulated as anti- dendruff shampoos, by employing therein about 0.10% to about 4% by weight of a conventional anti-dandruff therapeutic agent which is soluble n the detersive surfactant mixture. Such agents include: 1-imidazolyl-chiorophenoxy)-3,3-dimethylbutan-2-one (Ctimbazole); acetytealicytic acid; salicylic acid; 2,4,4,,-tnchloro-2'-hydroxy diphenyi ether (tnclosan); 1-acetyl-4-(4-{(2-(2.4- dichlorophenyl)-2-{1 H-imidazoly-l ,3-dioxolanl)methoxy)phenyl)-paperazina (ketoconazoie); 1-hydroxy-4-methyl-6,4,4-trimethylpentyl)-2-pyridone monoethonolamine salt (picrotone otamine); and mixtures thereof. Climbazole is the preferred anti-dandruff therapeutic agent. Examples 31 and 32 These examples illustrate clear antidandruff corrposrtions which are within the scope of the described invention. %bvwL 21 32 Poryquaternium 10 0 6 0.6 Sodium lauryl diethenoxy ether sulfate 7 0 7 0 Cocoamidopropyl dimethyl betaine 78 7 3 Sodium cumene sulfonate 13 2.17 Disodium hydrogen phosphate 0.1 0.3 Laureth - 3 carboxylic aad 0.1 0.1 Isc^eajvrnidopropyi dimethyl amine 0.14 0.14 Silicone DC 5220 0.24 Silicone DC 5324 0.44 SBicone DC Q2-8220 0.5 PEG 55 • propylene glycol oleate 0.36 PEG 18 • glyceryl glycol dioieococoate 0.2 Cetyltrimethyt ammonium chloride 0.25 0.25 C&mtazoie 0.5 0.5 Color, perfume, preservative, water a-fi U»S«. 100.00 100.00 The invention has been described with respect to various examples and illustrations thereof but is not to be limited to these because it is clear that one of skill in the art, with the present descnption before him, wii be able to utilize substitutes and equivalents without departing from the invention. WE CLAIM: 1. A process for preparing clear, ultra mild, aqueous foaming and conditioning detergent composition said process comprising admixing A. 5% to 40% of a detersive surfactant mixture of: (1) 2% to 14% of an anionic detergent selected from the group consisting of C8-C18 alkyl sulfates, C8-C18 alkyl ethenoxy ether sulfates containing 1 to 5 ethenoxy groups in the molecule, C8-C18 acyl isethionates, C10-C20 alkyl sulfonates, C10-C22 alkene sulfonates, and mixtures thereof; (2) 0.5% to 5% of an anionic hydrotropic, C1-C3 alkyl benzene sulfonate or C5-C3 alkyl sulfate: and (3) 2.5% to 21% of an amphoteric surfactant selected from the group consisting of C8-C18 alkyl betaines, and sulfobetaines, C8-C18 alkyl amido, C2-C3 alkyl betaines and sulfobetaines, C8-C18 alkyl amphoacetates, C8-C18 alkyl amphopropionates, and mixtures thereof: B. 0.05% to 9% by weight of a water-insoluble conditioning agent which is soluble in said detersive surfactant mixture and is selected from the group consisting of: (1) 0.05% to 5% of a complex of essentially equimolar amounts of a C8-C18 (EtO)1-10 carboxylic acid, and a C8-C18 alkyl (EtO)0-10 dimethyl amine: (2) 0.25% to 3% of a water-insoluble silicone which is soluble in said aqueous detersive surfactant mixture and is selected from the group consisting of polydimethylsiloxane polyether copolymers, polydimethylsiloxanes containing an amino substituent, polydimethylsiloxanes containing at least one ammonia substituent and mixtures thereof: and (3) a mixture of B(l) and/or B(2) with 0.1% to 1.0% of a polyquaternary compound selected from the group consisting of a quaternized cellulosic polymer and a mixture of said quaternized cellulosic polymer with a non-cellulosic quaternary conditioning polymer; and optionally C) .05% to 1.0% by weight of either a mono-C10-C22 alkyl tri C1-C4 alkyl ammonium salt or a di(C14-C18 alkyl) (EtO)3-20 di-C1 -C4 alkyl ammonium salt as an anti static agent; D) from 0.1% to 4% by weight of an anti-dandruff therapeutic agent, which agent is soluble in the detersive surfactant mixture; E) 0.25 % to 3% of an opacifying or pearlizing agent to render the composition opaque or pearlized; and F) the balance being water; the sum of the moles of anionic detergent and anionic benzene sulfonate being equal to the sum of the moles of amphoteric detergent and cationic conditioning agent at a pH in the range at 5.5 to 7.0 and said composition being effective to deliver said conditioning agent in water insoluble form at use concentrations of the composition in water. 2. A process as claimed in claim 1 wherein the mole ratio of the sum of the moles of anionic detergent and the moles of anionic hydrotrope to the sum of the moles of amphoteric detergent and the moles of cationic conditioning agent is in the range of 0.8:1 to 1.25:1. 3. A process as claimed in claim 1 having: A. from 8% to 28% of a detersive surfactant mixture of: (1) from 4% to 11% of an anionic detergent selected from the group consisting of water soluble salts of C8-C18 alkyl sulfates and C8-C18 alkyl (ethenoxy) 1-5 ether sulfates. (2) from 1% to 4% of a water soluble salt of an anionic hydrotropic C1-C3 alkylbenzene sulfonate: and (3) from 4% to 13% of an amphoteric surfactant selected from the group consisting of C8-C18 alkyl betaines and C8-C18 alkylamido C2-C3 alkyl betaines; B. from 0.05 % to 9.0% of a water-insoluble conditioning agent selected from the group consisting of: (1) from 0.1% to 2.5% of a complex of essentially equimolar amounts of a C8-C18 (EtO)2- carboxylic acid, and a C8-C18 alkyl (EtO)o- dimethyl amine; (2) from 0.5% to 2% of a water-insoluble silicone; and (3) a mixture of B(l) and/or B(2) with 0.1% to 0.8% of polyquaternary compound; and C. from 61% to 92% of water; the molar ratio of the sum of the moles of anionic detergent and anionic benzene sulfonate to the sum of the moles of amphoteric detergent and cationic conditioning agent at a pH in the range of 6 to 6.5 being from 0.9:1 to 1.1:1, said composition being effective to deliver said conditioning agent in water-insoluble form at use concentrations of the composition in water. 4. A process as claimed in claims 1 wherein said anti-dandruff therapeutic agent is selected from the group consisting of: 1-imidazolyl- l-(4-chlorophenoxy)-3,3-dimethylbutan-2-one (climbazole); acetyl salicylic acid; salicylic acid; 2,4,4,'-trichloro-2'-hydroxy diphenyl ether (triclosan); 1 -acetyl-4-(4-((2-(2,4-dichlorophenyl)-2-( 1 H-imidazolyl-1-methyl)-1, 3- dioxolan) methoxy) phenyl) piperazine (ketoconazole); l-hydroxy-4- methyl-6-(2,4,4-trimethylpentyl)2-pyridone monoethonolamine salt (picrotone olamine); and mixtures thereof. 5. A process as claimed in claim 1 wherein said opacifying or pearfizing agent is selected from the group consisting of ethylene glycol distearate, polystyrene and mixtures thereof. 6. A process for preparing clear, ultra mild, aqueous, foaming and conditioning detergent composition substantially as herein described with reference to the foregoing examples.

Full Text

The present invention relates to a process for preparing clear, ultra mild, aqueous foaming and conditioning detergent composition.
The instant invention is generally directed to novel, ultra mild "2-in-1" conditioning aqueous detergent products, including shampoos, antidandruff shampoos, and a variety of body care products, such as shower gels, liquid soaps- with and without antibacterial agents, facial cleansers, baby washes, baby shampoos and the like, having detersive surfactant systems based upon use of balanced molar proportions of the essential anionic detergent, anionic hydrotropic sulfonate or sulfate, amphoteric detergent and cationic conditioner ingredients. The desired balance is achieved by having the sum (on a molar basis) of the anionic detergent and hydrotropic sulfonate/sulfate substantially equal to the sum (on a molar basis) of the amphoteric detergent and any cationic conditioner ingredient. The resultant novel aqueous detergent products deliver excellent cleansing and foaming properties without irritation to skin and hair; provide true 2-in- conditioning properties to the hair and skin; and are lower in cost than current *2-in-1 products. A further benefit is that these detergents are in solution form and are crystal clear, although , if desired, they can be opacified.
BACKGROUND OF THE INVENTION
Currently, commercially available, *2-in-1" or conditioning shampoos, are optically opaque. This is due to the fact that the conditioning agents incorporated therein are essentially water insoluble. For example, when high-molecular weight silicone derivatives are added to achieve the conditioning benefits, it has been found that H is difficult to formulate silicone-containing shampoos that are stable and do not suffer from the separating out of the silicone ingredient. The most accepted way to incorporate these silicone conditioning agents in such conditioning shampoos is to disperse, suspend, or emulsify them, which results in the opacification of these products and sometimes results in unstable products due to the separation of the emulsified or suspended silicone.
While the above-described "2-in-l" conditioning shampoos have achieved a great deal of
success in the marketplace, such products suffer, at least among a certain segment of consumers,
negative attributes of poor appearance, decreased foam, reduced viscosity, and physical instability
because the conditioning materials therein are not completely dissolved. The patent literature relating
to detergent compositions which include water-insoluble, hair and skin conditioning matenals reflects a
variety of approaches designed to overcome the above mentioned disadvantages. More specifically,
the patent literature teaches a vanety of agents that disperse, suspend, or emulsify such conditioning
agents. For example, U.S. 4,741,855 to Grote et a! teaches the use of long chain (C16-C22) acyl
derivatives, such as ethylene gfycoi distearate or long chain (C16-C22) amine oxides, as suspending
agents U.S. 5,152.914 to Forster et al teaches the use of suspending agents chosen from
polyethylene gfycoi mono- or diesters of C16-C22 fatty acids having from 2 to 7 ethylene oxide groups.
Also, U.S. 4,997,641; U.S. 5,106.613; U.S. 5.213,716; U.S. 5,346,642; and U.S. 5.348.736. all
assigned to the assignee of the instant invention, disclose the use of long chain (C24-C45) alcohols
and ethoxyiated alcohols as suspending agents. Alternatively, U.S. 4,559.227 to Chandra et al
discloses conditioning shampoos in the form of clear solutions where*) blends of amme-functionaJ
sdoxane polymers and nonioruc surfactants of the aikanoiamide or amine oxide type are dissolved in
aqueous solutions containing typical anionic and amphoteric detergents used in shampoos. However,
the commercial availability of the latter compositions has not been assessed.
Now it has been found that it is possible to formulate aqueous detergent compositions
containing balanced molar proportions of anionic, amphoteric and catioc ingredients that are crystal
clear (although they can be opacified if desired) which exhibit true '2-in-1 conditioning properties.
Furthermore, the resultant compositions are ultra mild and thus do not cause imtation to skin or hair.
Additionally, these compositions are high foaming, and can be manufactured in a more cost-effective
and lass energy intensive manner than the commercially available silicone-containing conditioning
shampoos, which are in emulsion, suspension or dispersion form
It is recognized that the pnor art discloses compositions containing essentially equimolar
quantities of anionic surfactant and amphoteric surfactant For example, U S 3,950,417 of Verdicchio
et al discloses a shampoo containing nonionic surfactant, a surfactant betaine and an anionic surfactant
wherein the molar ratio of betaine to anionic is from 0 9 1 to 1 1 1 However, the nonionic detergent is
the pnncipal surfactant in the preferred compositions which of necessity exhibit reduced foaming
Similarly, U S 4,246,131 of Lohr discloses a low irritant, clear composition containing an equimolar
mixture of surfactant betaine and alkonalomine neutralized, anionic, alkyl sulfate detergent However,
the poor art composrttons do not indude water-insoluble conditioning agents or anionic hydrotropic
sulfonates/sulfates and do not recognize the need for balanced molecular proportions of the anionic,
amphoteric and cationic ingredients therein Therefore, said compositions should not provide effective
hair and skin conditioning benefits
On the other hand, European Application EP 0 294 894 A2 discloses an ion pair complex of an anionic surfactant, an alkyl amine and a wax as a conditioning agent and discloses anionic surfactant based shampoos containing said complex as a conditioning agent However, again there is no recognition of the need for balanced molar proportions of anionic, amphoteric and cationic ingredients in the final composition Thus, the need still exists for a clear, ultra mild, foaming, conditioning composition
SUMMARY OFTHF INVENTION
As described above, the present invention primary resides in the discovery that foaming and conditioning compositions which are mild can be prepared in the form of clear liquids if balanced molecular proportions of selected anionic detergents, anionic sulfonate/sulfate hydrotropes, amphoteric surfactants and water-insoluble cationic, hair and skin conditioning agents are employed.
The present invention relates to process for preparing clear, ultra mild, aqueous
foaming and conditioning detergent composition said process comprising
admixing by weight of
\ 5%, to 40% of a detersive surfactant mixture of
(1) 2% to 14% of an anionic detergent selected from the group consisting of C8-C18 alkyl sulfates, C8-C18 alkyl ethenoxy ether sulfates containing 1 to 5 ethenoxy groups in the molecule, C8-C18 acyl lsethionates, C10-Cjn alkyl sulfonates, C10-C22 alkene sulfonates, and mixtures thereof,
(2) 0 5% to 5% of an anionic h\drotropic, C1-C3 alkyl benzene sulfonate or C5-CN alkyl sulfate and
(3) 2 5% to 21% of an amphoteric surfactant selected from the group consisting of C8-C18 alkyl betames, and sulfobetames, C8-C18s alkyl amido, C2-C3 alkyl betames and sulfobetames, C8-C18, alkyl amphoacetates, C8-C18 alkyl amphopropionates, and mixtures thereof
B 0 05% to 9% by weight of a water-insoluble conditioning agent which is
soluble in said detersive surfactant mixture and is selected from the group consisting of
(1) 0 05% to 5% of a complex of essentially equimolar amounts of a C8-C18 (EtO)i-n) carboxylic acid, and a CVCis alkyl (EtO)0-10 dimethyl amine
(2) 0 25% to 3% of a water-insoluble silicone which is soluble in said aqueous detersive surfactant mixture and is selected from the group consisting of polydimethylsiloxane polyether copolymers, polydimethylsiloxanes containing an amino substituent, polydimethylsiloxanes containing at least one ammonia substituent and mixtures thereof and
(3) a mixture of B(l) and/or B(2| with 0 1% to 1 0% of a polyquaternary compound selected from the group consisting of a quatermzed (ellulosic polymer and a mixture of said quatermzed cellulosic polymer with a non-cellulosic quaternary conditioning polymer, and
optionally
C 05% to 1 0% by weight of either a mono-C10-C22 alkyl tn C1-C4 alkyl
ammonium salt or a di(C14-C18 alkyl) (EtO)3-20 di-C1 -C4 alkyl ammonium salt as an anti static agent,
D from 0 1% to 4% by weight of an anti-dandruff therapeutic agent, which
agent is soluble m the detersive surfactant mixture,
E 0 25 % to 3% of an opacifying or pearhzing agent to render the
composition opaque or pearhzed, and
F the balance being water, the sum of the moles of anionic detergent find
anionic benzene sulfonate being equal to the sum of the moles of amphoteric detergent and cationic conditioning agent at a pH in the range at 5 5 to 7 0 and said composition being effective to deliver said conditioning agent m water insoluble form at use concentrations of the composition m water
In a preferred aspect, the described invention contains as the conditioning agent a mixture of (a) and quatermzed cellulose polymer, (b) a complex of essentially equimolar amounts of C8-C18 (EtO)i n> carboxylic acid and C8-C18 alkyl (EtOln 10 dimethyl amine and (c) pohdimethylsiloxane
potyoxy (C2-C3) aikylene copolymer and, in addition. 0 05 % to 1 0 % of a mono C \ 2-C18 aikyl or di-
C12^ 18 a*kyi (BO)3-20 quaternary ammonium compound The preferred compositions, exhibit enhanced conditioning properties due to the use of the mixture of conditioning agents and also exhibit enhanced anti-static properties due to the inclusion of the mono-alkyi or di-alkyi (ElO) 3.30 quaternary compound.
In one further preferred aspect, the inventive compositions enable a manufacturer to market a line of conditioning shampoo products having variable conditioning properties. Mora specifically. by utilizing the specified conditioning materials individually and in mixtures, a iine of conditioning shampoos providing tow. medium and high conditioning effects can be provided.
Detailed Description of the Invention Anionic Detergents The suitable anionic detergents are employed in the form of their water-soluble salts and the salt forming cation usually is selected from the group consoling or sodium, potassium, ammonium and mono-, dl- and tri- C2-C3 aJkarttiarnmonnim, with the sodium and arnrnoruum cations bong preferred.
The suitable anionic detergents include the following:
1 The CQ-C 18 aikyl ether ethenoxy sulfates of the formula
fl(OC2H4)nOS03M where*) n is 1 to 5. These sulfates differ from the primary aikyl sulfate detergent in the number of moles of ethylene oxide (1-5) reacted with one mole of afcanoJ in forming the ethoxyiated aikanoi which is sulfated and neutralized to form this anionic detergent. Preferred aikyl ether ethenoxy sulfates contain 12 to 16 carbon atoms in the aikyl group and contain two to three ethylene oxide groups per mole of alkanol.
2. The C8-C18 alkyl sulfates which are usually obtained by sulfating C&-Cis alkanols
obtained by reducing the gfycendes of tallow or coconut 01! Preferred aikyl sulfates contain 10 to 16 carbons in the aikyl group.
3. The O-C8-C18 acyl isethionates may be produced by neutralizing the reaction
product of a C8-C18 a alkanoic aad with 2-hydroxyethanesuffonic acid. Similar to the sarcosines and taunnes vhe preferred isethionates contain 12 to 14 carbon atoms in an aryl group obtained by reduction of coconut oil.
4 The C10-C20 paraffin sulfonates obtained, for example, by reacting an alpha-olefin
with bisulfite. Preferred aikane sulfonates contain 13 to 17 carbon atoms in the alkyl group.
5. The C10-C22 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 aipha-olefin.
While mixtures of the foregoing anionic detergents may be employed, the preferred anionic detergents are the alkyl ethenoxy ether sulfates and the alkyl sulfates.
The proportion of the anionic detergent in the claimed compositions generally will be in the range of about 2% to about 14% by weight preferably in the range of 4% to 11% by weight ana most preferably in the range of 6% to 8% by weight.
Other Anmnm Surfactant In addition to the anionic detergent discussed above, the described inventive compositions include anionic, hydrotropc C1-C3 alkyl substituted benzene sulfonates and C5-C3 alkyl sulfates. These materials are dassrfied as surfactant-hydrotropes and serve to sotubriize the anionic and amphoteric detergent in the aqueous medium. Also, it is believed that these materials assist in removing sod from the substrates being cleaned. Usually, these materials are used in the form of the* water soluble sodium, potassium and ammonium salts. Suitable hydrotropic sulfonate and sulfate salts include the salts of toluene sulfonate, xylene sulfonate, cumene sulfonate, C5- C6 alkyl sulfate and mixtures thereof.
The proportion of the hydrotropic sulfonate or sulfate material generally will be in the range of about 0.5% to about 5% by weight of the resultant composition Preferably the range of this material will be about 0 5% or 1% to 4% by weight of the final composition
Amp Generaily, the amphoteric surfactant components will be selected from the group consisting of C8-C1 8 alkyl betames and suifobetaines, and C8-C18 alkyl amphoacetates and propionates The
suitable betames and suifobetaines have the following formula:
(Formula Removed)
wherein R-i B an alkyl group having 8 to about 18 carbon atoms, preferably 10 to 16 carbon atoms or
the amido radical:
(Formula Removed) wheretn RCO is an acyl group having 8 to about 18 carbon atoms and a is the nteger 1 to 4: R2 and R3 are each alkyl groups having 1 to 3 carbon atoms and preferably 1 carbon; R4 ts an alkyiene or hydroxyalkylene grc'jp having from 1 to 4 carbon atoms and optionally, one hydroxy! group; and X is an anion selected from the group consisting of SO3* and COO" Typical betames and amido alkyl betames include decyl dimethyl betame or 2-(N-decyl-N,N-dimethylammonio) acetate, cocodimethyl betame or 2-(N-coco-N,N-methylammono) acetate, mynstyl dimethyl betame, palmrtyl dimethyl betaine, lauryl dimethyl betame, cefyl dimethyl betaine. stearyi dimethyl betame, cocoamidopropyl dimethyl betame and laurylmidoethyt dimethyl betaine. Typical suifobetaines or suttames simdany include cooodtmethyt sulfobetaine, or 3- Other suitable amphoteric detergents are the C8-Cl8 alkyl amphoacetates and propionates
corresponding to the following formula: (Formula Removed)

wherein RC(O) tsa C8 -C18acyl group, R2 is a C1-C2 aikyl group and M is a salt forming group such as
sodium or potassium. A substitute for the described amphoacetate or amphopropionate compound is
sodium cocoamphohydroxypropyl sulfonate Sodium cocoamphoaetate is a preferred matenai.
The proportion of the amphoteric detergent generally will be in the range of about 2.5% to about 21 % by weight 0/ the final composition. Preferably the proportion of amphoteric surfactant will be selected from the range of about 4% to about 13% by weight and most preferably from the range of about 6% to about 10% by weight of the final composition.
In the preferred composrtions, the proportion of the detergent mixture will be from about 8% to 28% by weight of the composition; and in the most preferred composrtions the proportion of said detergent mixture will be from 13% to 22% by weight.
Conditioning Agonta
The essential water-insoluble conditioning agent which is employed in the inventive cornpositions is soluble in the above-described aqueous detersive surfactant mixture and generaly wfl be selected from the group consisting of (1) essentislly equwnolar complexes of C8-C18 alkyl ethoxy carboxysc acids and C8 C18 ethoxy dimethyl amnes; (2) stfcones soluble in the aqueous detergent mixture herein selected from the group consisting of porydimethylsiloxane polyether copolymers, poiydimethyteilaxanes containing an arwno substftutuent and mixtures thereof; and (3) a mature of (1) sno7or (2) with a quatemized ceUutosic polymer or a mixtures of quaterruzed ceHuiosc polymer with rrsnor proportions of non-ceiluiosic quaternary conditioning polymers.
The equunotar complexes of C8-C18 alky ethoxy carboxylic acids and C8-C18 alkyl etnoxy dimethyl amines are believed to form amine salts which provide conditioning properties in the described composrtions. Usually, the ethoxytated carboxylic acid will contain from 1 to 10 ethoxyl groups and preferably from 2 to 6 ethoxy groups On the other hand, the higher alkyl dimethyl amine may contain from 0 to 10 ethoxy groups While the amine salts are believed to form when equimolar amounts of said carboxylic acid and said dimethyl amine are present, the presence of excess dimethylamme on a molar basis does not have an adverse effect on the conditioning properties of the amine salt and a slight molar excess of said amine may be preferred Preferred carboxylic acids are the
C10-C14 (ElO)2-6 carboxylic aads and preferred amines are the C14-C18 alky I and C14-C18 alkyl
amido propyl dimethyl amines.
Generally the proportion of the amine salt formed by the complex of C8-C18 alkyl ethoxy
carboxylic acid and the C8-C18 aikyi dimethyl amine will be about 0 05% to 5%, preferably 0.1% to
2.5%, and most preferably about 0 15% to 1 5%. by weight of the resultant composition. When this
complex is used as sole conditioner, a low level of conditioning is perceived by the user.
Surfactant-Soluble. Water-Insoluble Silicones or Silicone-Oenvatives
The silicones or silicone-denvatrves that are useful in the present invention are those that are soluble in and compatible with the above described aqueous detersive surfactant mixture, but are insoluble in water. This allows them to be formulated into detergent compositions that are initially transparent, but which, if desired, can be opacified or pea/iized by adding recognized peartong/opacrfying ingredients such as ethylene glycol dtstearate or polystyrene. Suitable silicones mdude trtnethyisiytamoofrrtetriicone purchased under the trad* name Dow Corning G2-8220 - an amine functional corydirnethytsdoxane; copolymers of polydirnethylsiloxane and a poly C2-C3 alkytane ether purchased under the tradenames Dow Coming 190, Dow Corning 2*5324 and Dow Corning Q2-5220; and pofydimethyl siioxanes having at least one quaternary ammonium moiety, preferably two quaternary ammonium moieties. The latter siBcone 8 available cornrneraaUy under the tradename A8IL-QUAT 3270 for example. If silicones other than those above are employed, the resultant compositions usually are not dear because part of the pofydimethyisdoxane a present in water insoluble form.
The proportion of the surfactant soluble, water insoluble silicone in the inventive composition broadly win be in the range of about 0.25% to about 3%, preferably 0.5% to 2%, most preferably 0.7% to 1.5%, by weight. When said silicone is the sole conditioning agent present, a composition having a low conditioning effect is achieved - a conditioning value of 2.5 for example. However, when a mixture of the described amine salt, cellulose pofyquat and the described silicone is employed as the conditioning agent, the resultant composition exhibits high conditioning properties -- a value of 7.0 or more in the applicable test
Cationic Polymers The water-insoluble conditioning complex of carboxylic acid and amine and the water insolubl*. silicone conditioning agents are soluble in the described aqueous detergent mature, but are rendered water-insoluble when the resultant detergent compositions are diluted with water dunng use. In addition, either one or both of these conditioning agents may be further employed in admixture with a cationic cellulose polymer. Because the canonic cellulose polymers are water soluble and soluble in the aqueous detergent mixture, clear detergent mixtures can be prepared when the caitonic ceUulosic polymers are employed as the sole conditioning agent.
The suitable hair conditioning, cationic polymers are derivatives of natural polymers such as cellulose and gums. These derivatives generally are water-soluble to the extent of at least 0.5% by weight at 20°C. Generally, such polymers have more than 10 monomer units in the* molecules and a molecular weight of about 1000 to about 1,000.000, preferably 2000 to 500.000. Usually, the tower the molecular weight, the higher the degree of substitution by the cationic, usuaJJy quaternary, group.
Suitable natural polymers which may be converted into the deeired cationic polymers are
hydroxy alkyl celluoses and alkyl hydroxy celluloses. Cationic hydroxy alkyl celluloses and ther
preparation are described in B.P. No. 1,166.062 assigned to Union Carbide. These hydroxy ethyl celluloses are marketed under the trade designation JR 125, JR30M and JR 400 and ere believed to have a molecular weight of 150,00 to 400,000 and a degree of substitution of a quaternary group of about 0.3. Akyl hydroxy alky! celluloses having the same formula as hydroxy alkyt cellulose, but w*h additional alkyl substituents at other sites on the anhydroglucose unit also are avaiable. More particularly, the ethyl hydroxy ethyl celluloses are available under the tradename 'ModocolP with a molecular weight in the range of about 50,000 to 500,000 and a degree of substitution of about 0.1 to 0.8.
Other suitable natural cationic polymers are the galactomannan gums, e.g., guar gum and hydroxy alkylated guar gum The molecular weight of guar gum is believed to be from about 100,000 to 1,000,000 A suitable cationic guar gum carrying the group -CH2CH=CH CH2N (CH3)3C>* with a degree of substitution of about 0 2 to 0 8 is commercially available under the tradenames Jaguar C-17
and C-13. The preferred cationic cellulose polymer is Poryquatemium 10 which is a polymeric quaternary ammonium sai! of hydroxyethyl cellulose reacted wrth a trimethyl ammonium substituted epoxide.
The proportion of the cationic natural polymer usually will be from about 0 05% to about 1%, preferably 0.1% to 0.8%, most preferably from 0 2% to 0.7%, by weight of the finai composrtion. The cationic polymer provides for enhanced style control and conditioning. When Poryquatemium 10 is employed as the sole conditioning agent, a product wrth moderate conditioning results.
When the cationic natural cellulose or gaiactomannan gum polymers are present in the inventive compositions, up to about one half the weight of said natural polymer may be substituted by a second non-catluiosic, cationic polymer, having conditioning properties provided that the non-ceUulosic cationic polymer is soluble in the final composition. Exemplary of such cationic polymers are dtaJkyidlafyl ammonium salt (e.g., halide) homoporymers or copolymers, e.g., dimethyidiaUyl ammonium chloride homoporyrner, dimethyidiaJyl ammonium chlonde/acrylamide copolymer containing at least 60% ammonium chloride monomer, dirnethyidiairyl ammonium chlonde/acryiic aad copolymer containing at least 90% dimethyidiaJfyl arnrnonium chloride monomer, vinyl jnrtazde/vinyi pyrrotidone copolymers containing at least 50% vinyl imidazole and potyethyieneimine. Currently, the preferred cationic polymers are Merquat 100 [a polymer of diaillyldimethyl ammonium chlonde (charge density of 126)) and Luviquat 905 [a 95% vinyl imidazole/5% vinylpyrrolidone copolymer (charge density of 116)J. Other suitable non-ceilulosic cationic polymers are disclosed m the CTFA Cosmetic Ingredient Dictionary under the designation •Polyquatemium* followed by a whole number.
OptionaJry. the inventive compositions may include, in addition, a controlled amount of rnono-C14-C18 alkyl quaternary ammonium salt or di-Ci2*Ci8 alkyl (EtO) dimethyl ammonium salt to provide enhanced anti static effect. The mono alkyl quaternary salts have the following formula.
R9.R10,R11, R12 N+X-wherein at least three of the R groups are C1-C4 alkyl and at least one is a C10-C22 alkyl, with X being a salt-forming anion, such as chlonde, bromide, methosulfate or ethosulfate. Preferably, the lower alkyl groups will contain one to two carbons, the higher alkyl group will contain 14-18 carbon atoms and the
water-so/ubilizing group will be chlorine or bromine. Suitable compounds include cetyf trimethyl
ammonium chloride and stearyi trimethyl ammonium chlonde. Alternatively a di (C14-C18) alkyl
(EtO)3-20 dimethyl ammonium salt may be employed wherein from 3 to 20 ethoxy groups are present
with alkyl substitute Preferred compounds are di-stearyl (EtO)5 dimethyl ammonium chlonde and di-
stearyl (ElO)is dimethyl ammonium chlonde. If ethoxylated alkyl groups are not present in the di-higher
alkyl quaternary salt, the resultant compositions are not clear for example.
Generally the proportion of added mono C14-C18 alkyl quaternary sail or di C12-C18 alkyl
(EtO)3-20 quaternary salt will be from about 0.05% to about 1%, preferabry from 0.1% to 0.5%, and
most preferably 15% to 0.35%, by weight. The anti static effects increase as the proportion of said
added quaternary salt increases.
The final essential component in the inventive compositions is water which provides an
aqueous medium. Generally, the proportion of water wifl range from about 51 % to about 95%,
preferably, about 61% to about 92%, and most preferabry about 70% to about 88%, by weight of the
resultant composition.
An important characteristic of the inventive compositions is that the turn at the moles of anionic
detergent and the moles of anionic hydrotrope is substantially equal to the sum of the moles of
amphoteric detergent and the moles of cationc conditioning compound including, optionally, the
moles at mono alkyl or dialkylethoxy quaternary ano static compound. On a molar basis the ratio of
anionic compounds to amphoteric compounds plus cationic compounds wifl be the range of about
0.8:1 to about 1.25:1, preferabry about 0.9:1 to about 1.10:1, most preferably about 0.95:1 to about
1.05:1. It appears that the proportions of afl of the essential ingredients are interrelated and must be
controlled in order to achieve compositions having the desired mildness, foaming, cleaning,
conditioning, clarity and viscosity characteristics Generally, the viscosity of the inventive compositions
will be in the range of about 1000 to 10,000 cps, preferably 2000 to 7000 cps, and most preferably
3500 cps to 5500 cps, at 24°C , as measured with a Brookfield RVT viscometer using a #4 spindle
rotating at 20 rpm
These inventive compositions are essentially unbuilt liquids, i e , do not contain detergent
building proportions of water-soluble inorganic or organic builder ingredients Therefore, the resultant
compositions are suitable for use as liquid hand washing detergents, liquid shampoos, liquid shower
bath products and light duty fabric washing products Thus, these inventive compositions can contain
any of the usual adjuvants found in those compositions provided that they do not interfere with the
mildness, performance or clarity characteristics descnbed in the final products. Such additional
ingredients include minor proportions of perfumes and cotonng ingredients for aesthetic purposes;
opactfiers such as ethylene glycol distearate or polystyrene, sequestering agents such as citrate or
ethytenediamine tetreaacetate; preservatives such as formaldehyde or Kathon CG® or
monomethyloldimethyl hydantoin; fluorescent agents, acids or bases for adjusting pH; and inert salts
such as sodium sulfate. The total concentration of added ingredients usually will be less than 5%,
preferably less than 3%, by weight of the total composition.
The nventfve compositions are prepared by admixing the cafjonic polymer, if any, with water at
a temperature tn the range of about 20°C. to 60°C., usmg sufficient agitation unti a dear,
homogeneous mixture is formed. Thereafter, the anionic surfactants, namely, the anionic detergent
compound and the anionic hydrotroptc agent are added while continuing the agitation until a
homogeneous mixture is formed. Thereafter, the amphoteric detergent and the silicone ingredient, i
any, are added w*h agitation to the aqueous mature of catiaiic poiyrner ajid amonic surfactants and
agitation is continued unti the resultant mixture m homogeneous. Next the diaodium phosphate is
added to adjust the pH to 6.0 - 6.5. Next, t the carboxyic aod arrune salt is present, a premix of the
ca/boxyiic aod and the desred amine is prepared with agitation at a temperature m the range 20°C. to
60°C. Optionally, the perfume is included in this premix which is mixed until homogeneity is achieved.
Thereafter, the prema is added to the aqueous detergent mature with agitation which continues unta
homogeneity is achieved. Fmalty the formula amounts of quaternary salt anti-stat, if any, preservative, if
any, and color, if any, are added with agitation During the manufactunng process, mixing is controlled
to avoid foaming. The resultant composition is clear and has a pH in the range of about 5 5 to 7 0,
preferably from about 6.0 to 6 5
In the preferred process, the composition is prepared without the addition of external heat.
Thur. the process temperature is controlled in the range of 20°C to 30°C. Using this so-called "cold
process' saves energy and the time required to raise or lower the temperature.
Normally, the viscosity and pH of the resultant product is checked before the product is filled
into containers for saie. If necessary, additional anionic hydrotrope is added to decrease viscosity or
polyethylene glycol (PEG) 18-propylene glycol oleale is added to increase viscosity. Also, if necessary,
disodium phosphate dibasic or crtnc acid or other acid or base is added to adjust the pH. Preferably, the
resultant composition is passed through a 20 mesh or equivalent filter prior to filling same into
containers for saie.
The foaming properties of the inventive compositions are determined by diluting 15CC of the
resultant composition with 85cc of 250 pom water (40% Mg"*-1", 60% Ca++), adding 3.0 grams of sebum
sod and adjusting the temperature to 25°C. with agitation. Thereafter, the solution is added to a 500 ml
graduated cylinder containing a plastic tube fffled with water which has a volume of 25cc The 500 ml
glass stoppered cylinder is then rotated through 40 half circles at a speed of 30 rpm. After removing
the stepper, trie foam volume is read. The cylinder then is removed from the rotation apparatus and
placed on a table top. The time interval in seconds is recorded from the completion of rotation until the
liquid level in the cylinder reaches 100 ml (75% of the liquid has drained) and the results are recorded
as ml of foam/drainage time in seconds. Ml of Foam and drainage tines are then expressed on a scale
of 1 to 10 - 1 poorest 10 best -
The conditioning properties are determined by combing hair tresses treated with the product
using the fine teeth of the comb when wet and after drying. In this evaluation 3.2 gm tresses of virgin,
European brown hair obtained from DeMeo Brothers, Inc. are prepared with the root end of the hair at
the top of the tress. The tresses are nnsed with running tap water at 105°F (40.5°C.) and then 1 cc of
the test product is worked into the tress with the fingers for one minute The treated tress is rinsed for
30 seconds and a second application of test product is worked into the tress for one minute followed by
a 30 second nnsmg. Then each tress is nnsed for 60 seconds with 105°F running tap water and
detangled by combing with the wide teeth of the comb The wetted tresses are maintained wet with
deionized water and are combed by expert judges using the fine teeth of the comb. The |udges assign
a rating of 1 to 10 for each tress, with 10 being easiest to comb. Each tress is combed by a minimum of
10 judges and the ratings are averaged In the described procedure, the hair tresses are evaluated
while wet. The procedure for dry combing is identical except that the hair tresses are dned before
being combed.
In the test for evaluation of static, the hair tresses are treated with product as described above and dried. The dned tress is then combed by a stalled evaJuator in a forceful, downward manner 20 times usw>g the fine teeth of the comb. The static on each is then evaluated on a scale of 1 to 10 with 10 being excellent. Again, each tress is combed by 10 |udges and the ratings are averaged. This evaluation is earned out in a constant temperature - constant humidity room.
Specific inventive liquid compositions are illustrated in the following examples. AB quantities indicated in the examples or elsewhere in the specification are by weight unless otherwise indicated. A particutenly preferred conditioning shampoo composition according to the described invention is set forth in Example 1 below:
1 6 Example 1
by wl
Polyquatemium 10 0 60
Sodium lauryl diethenoxy ether sulfate 7 0
Cocoamidopropyl dimethyl betaine 7 8
Sodium cumene sulfonate 1 3
Disodium hydrogen phosphate 0 3
Dimethylporyoxyethylene
sdoxane (DC 5324 fluid) 0.5
Oimethyipotyoxyethylene/
poryoxypropyf lene stk>xane
(DC Q-5220 resjn modifief) 0 5
Laureth - 3 - carooxybc aad 0 1
I sostearyrrndopropyl dimethyl amine 0 14
PEG 55 - propylene glycol oleate ± 40
Perfume 0.5
Kathon CG® preservative 0.07
Cethmomum chloride 0.25
Yetow cotor solution 0.14
Water o.s.
100.00
The foregoing shampoo composition is prepared by the preferred cold process at 20°C. -
30°C. without addition of heat In the cold process, the formula weight of Potyquaternwrn 10 is
admoced with the formula amount of water with agitation to form a clear homogeneous mixture.
Thereafter, the aikyt ether sulfate, the sodium cumene sulfonate, the betaine and the two ssoxane
ingredients are added to the aqueous pofyquat solution in sequence with agitation. Mixing m
continued after the addition of each ingredient until the resultant mixture e dear and homogeneous.
with said agitation being controted to avoid foaming. Next the disodium phosphate basic is added to
said aqueous mixture. Then a homogeneous prermx of the formula amounts of laureth-3-carboxyfic
acid, the isostearytarrwdc-propyl dimethyl amine and perfume is prepared with agitation at a temperature
of 20°C- 30°C. and this premcx is added to the aqueous detergent mixture with agrtation which is
continued until the resultant aqueous mixture is clear and homogeneous Finally, the formula amounts
of cetnmonium chionde, preservative and color are added to the foregoing mixture with agitation to form
the clear, homogeneous shampoo composition The resultant shampoo composition has a viscosity of
4500 cps as measured with a Brookfield Viscometer using an RVT spindle #4 rotating at 20 rpm at
25°C. and a pH of 6.25.
When the shampoo composition is tested using the above-descnbed foaming, conditioning and static tests, the following results are obtained:
Foarming- 7 0
Conditioning - 9.0
State- 9.0
In the composition of Example 1, the molar proportions of the anionic detergent, anionic benzene sulfonate, amphoteric detergent and catjonic conditioners follow:
Sodium iauryi diethenoxy ether sulfate . 01862
Sodium cumene sulfonate 0058
Cocoainidopropyl dimethyl beuune 02281
Poryquatermium 10 (monomer raw. -504) .0012
Based upon the foregoing analysis, the ratio of the sum of the motes of anionic detergent and benzene
sulfonate to the sum of the moles of betame and catione conditioner a .02493 to 02478 or 0.99:1.0.
When the 7% of anionic alky! diethenoxy ether sulfate is replaced by 5.6% by weight of sodium tetradecyl aBcane sulfonates or 5.8% by weight of sodium C14-C16 alkene sulfonate or 5.3% by weight of ammonium lauryl sulfate - each being equimolar to said ether sulfate -, the resultant cornposalons have svndar characteristics.
Examples 2 -4
The composition of Example 1 is repeated with exceptions that the concentration of Pofyquat #10 is reduced to 0.25%, 0 35% and 0.5% by weight respectively and the percentage of PEG - 55 propylene glycol oleate is increased to 0.8%, 0.8% and 0.6% by weight respectively, with any balance being water The resultant clear homogeneous ultramild shampoo compositions yield the foaming, conditioning, static, viscosity and pH results set forth in Table A below:
Table (Table Removed)

Examples 5-8 The compositions of Examples 1 -4 are repeated with the exceptions that 2% by weight of an opacifying agent which is a mixture of ethylene glycol distearate (0 6%) and stearyt alcohol ethoxamer (4) and 0.2% by weight of distearyl dimethyl polyoxyethyiene (5) ammonium methyl sulfate are substituted for a like proportion of water. The resultant products are homogeneous, but opaque due to the inclusion of the opacifying agent. Furthermore, the conditioning/static properties are modified due to the inclusion of the added quaternary ammonium salt The properties of said cornpositions are shown in Table B below:
(Table Removed)
The addition of the distearethoxy (5) dimethyl ammonium methyl sulfate reduces the molar ratio of
anionic compounds to the sum of amphoteric and cationic compounds to 0.98:1.

Examples 9- 12
The condrttoning effects of iiie mixture of laureth-3 carboxylic acid and isostearamidopropyi
dimethylamine are set forth in Examples 9-12
% bY YYt.
A 1Q II 12
Sodium lauryl diethenoxy ether sulfate 7 0 70 70 70
Cocoamidopropyl dimethyl betaine 78 78 78 78
Sodium cumene sulfonate 13 13 1.3 1.3
Disodium hydrogen phosphate 0.3 0.3 0.3 0.3
Laureth-3 carboxylic aad 0.1 0.3 1 0 2.0
Isostearamidopropyi dimethyl amine 0.14 0.42 14 2.8
PEG 55 propylene glycol oleate 0.2 0.2 0.2 0.2
Perfume, color, preservative and water o>5 £Lfi 3*3 3*5
100.0 100.0 100.0 100.0
Conditioning 2 2.5 3 3.5
Foaming 8 8.0 7 6
CJarty Viscosity 2500 3050 4100 4780
These examples illustrate that the amine-acid complexes - amine salts - provide conditioning propertiee and that the conditioning properties increase as the proportion of the amine-acid complex - amine sal - increases. However, even at the highest concentration of the amine salt, i.e., 4% by weight because excess amine is present, the conditioning rating is 3.5 which is low. Further, as the level of ethoxylation increases in the carboxylic acid component, the conditioning value decreases because the motor amount of the amine salt produced therefrom decreases.
When stearamidopropyl dimethyl amine is substituted for isosteararnidopropyl dimethyl amine in Examples 9-12. the conditioning properties and foaming properties of the final compositions are not changed.
FxamplPS 13 and 14 The conditioning effects of cationic cellulosic poiyquats in the inventive composition are illustrated in Examples 13 and 14 wherein Polyquatemium 10 is the sole conditioning agent present.
%t?ywL
12. 14
Poryquaternium 10 0.3 0.6
Sodium lauryl diethenoxy ether sulfate 7 0 7 0
Cocoamidopropyi dimethyl betaine 7 8 7.8
Sodium cumene sulfonate 13 1.3
Disodium hydrogen phosphate 0.3 0.3
PEG 55 propylene glycol oleate 0 2 0.2
Perfume, color, preservative and water 0*5 3*2
100.0 100,0
Conditioning 4.0 6.75
Foaming 8.0 9.0
Static 5.0 4.0
danty dear ciear
The foregoing conditioning results show that medium conditioning is obtained when a cationic
cellulose potyquat is the sole conditioning agent.
Example 15 and 16
The compositions of Examples 13 and 14 are repeated with the exceptions that 0.24% by weight and 0.48% by weight respectively of Polyquatemium 7 (Merquat 550«) is substituted for the amounts of Polyquatemium 10 and the amine salt produced from 0.1% of laureth-3 carboxylic aod and 0.14% of isostearamidopropyl dimethyl amine is included, with any balance being deducted from the amount of water present. The conditioning, foaming and clanty properties of the resultant compositions are set forth in Table C below:

(Table Removed)
Because the compositions are not clear, Polyquaterruum 7 as the sole polyquat is not satisfactory
When Example 16 is repeated using a mixture of 0 3% by weight of Poryquatemium 10 and
0 24% by weight of Polyquatemium 7 in place of 0 48% of Poryquatemium 7, a clear shampoo resuts
having a conditioning rating of 7, a foaming value of 8 5, and a static value of 4 0 This result indicates
that a minor proportion - up to about 50% by weight of Poryquatemium i o may be substituted by
Polyquatemium 7 - a non cellulosic pofyquat without adversefy affecting the clanty of the inventive
compositions. Furthermore, the mixture of a cellulose pofyquat with a non-cellulostc pofyquat results m
a slight increase in conditioning effects.
Examples 17 and 18
When the compositions of Examples 15 and 16 are repeated using 0.3% and 0 6% of
Poryquatemium 11 (Celquat 200) - a cellulose pofyquat - substituted for 0.24% and 0 48% of
Potyquatemium 7, respectively, shampoos having the properties set forth in Table 0 are obtained.
Table D
(Table Removed)

Poiyquaternium 11 results in compositions having slightly lower conditioning than Poryquatemium 7.
The compositions of Examples 13-18 above are not within the scope of the claimed invention,
but are included herein to further define said invention
Samples 19 and 20 The conditioning properties or polymethylsiioxane in the inventive compositions is illustrated by the following compositions wherein the composition of Example 19 is a control because it contains no conditioning agent.
%by wt.
12 2J2
Sodium lauiyl diethenoxy ether sulfate 7 0 7 0
Cocoarrudopropyl dimethyl betaine 7 8 7 8
Sodium cumene sulfonate 1-3 1.3
Dimethylporyoxyehtylene
sdoxane (DC 5324 fluid) - 0.5
Oimethylpolyoxyethyiene/
potyoxypropyslene siloxane
(DC Q-5220 ream modifier) - 0.5
Oisodtum hydrogen phosphate 0.3 0.3
PEG 55 - propylene glycol oleate 0.2 0.2
Perfume, color, preservative, water 15 0*2*
100.00 100.00
Conditioning 1 0 2.5
Foaming 7 4 7.5
Static 2.0 3.0
Viscosity 5200 cps 1100 ops
CJanty ' clear clear
The foregoing compositions demonstrate a conditioning agent must be present in the compositions in order to achieve any conditioning of the hair when shampooed using the inventive composition.
When the composition of Example 20 is repeated with the exception that Silicone DC 5324 is omitted, the resultant composition exhibits a conditioning value of 2.0, a static value of 2.5 end a viscosity of 4000 cps at 25°C. using the Viscometer RVT.
23 Examples
The compositions which follow are preferred compositions containing a mixture of three condrtioning agents, each with a different porymethyl siioxane component.
%by wt
21 22. 23. 24
Poryquaternium 10 0.6 0 6 0.6 0.6
Sodium lauryl diethenoxy ether sulfate 7.0 70 70 70
Cocoamidopropyl dimethyl betaine 78 78 78 78
Sodium cumene sulfonate 17 13 13 1.3
Disodjum hydrogen phosphate 0.3 0 3 0.3 0.3
Laureth - 3 - carboxybc aad 0.1 0 1 0.1 0.1
Isostearyrrudopropyl dimethyl amine 0 14 0.14 0.14 o 14
TrenethytsilytarncKJirnetrucone (DC Q2-8220) 0.5 -
SBicone quatemtum 2 (Silquat 100) - 0.5 -
SScone quaterntum 2 (Silquat 300) - - 0.5 -
Dknethicone copoiyol amine (SBamine50) 0.5
PEG 55 • propylene glycol oleate
Perfume, color, preservative, water OJ q-s. g.s. a.^,
100.00 100.00 100.00 100 00
Conditioning 8.0 8.0 8.0 8.0
Foammg 8.0 7 0 7 0 7 0
Static 4.0 4.0 4.0 4.0
Clanty dear dear dear clear
Viscosity (cps) 1000 4000 4000 4000
Examples 25 and 26 When the composition of Example 21 8 repeated with the exceptions that the amount of sodium cumene sulfonate is reduced to 1 3% by weight and 0.1% and 0.25%, respectively, of centrimonium chlonde is added, with any difference being water, shampoo composrtions having the properties shown in Table E are obtained
Table E
(Table Removed)
Examples 27 and 28
These examples show other compositions which are within the scope of the described
invention and their properties.
% by wt
21 23.
Polyquatemium 10 0.9 0.3
Sodium lauryi diethenoxy ether sulfate 10-S 3.5
Cocoarnidopropyi dimethyl betame 11.7 3.9
Sodium cumene sulfonate 1.95 0.65
Disodium hydrogen phosphate 0.45 0.15
Laureth - 3 carboxyfc aod 0.15 0.05
Isostearyrmdopropyl dimethyl amine 0.21 0.07
Silicone DC 5220 0.75 0.25
Sicone DC 5324 0.75 0.25
PEG 55 • propylene glycol oleate 0.6 0.2
Cetyttrirnethyl ammonium chJonde 0.375 0.125
Water O^ 0£»
100.00 100.00
Conditioning 9.0 6.0
Foaming 8.0 4.0
Static 9.0 9.0
Clanty dear dear
Viscosity 10000 1900
pH 6.2 6.35
Example 28 illustrates that foaming is reduced when a proportion of 8% by weight of the
detersive surfactant is employed. Further, as expected, good foaming is achieved when the proportion
of detersive surfactant is increased to 24 2% by weight of the composition.
Examples 29 and 30
The following compositions illustrate the importance of the presence of the anionic hydrotropc
sulfonate/sulfate in the descnbed compositions.
rafrwL
22. 20.
Sodium lauryl diethenoxy ether sulfate 7 0 9.2
Cocoamidopropyl dimethyl betaine 7 8 7 8
DisodJum hydrogen phosphate 0.3 0.3
Water g^fi q.s.
100.00 100.00
Conditioning 1.0 1.0
Foarrang 4.5 4.0
Static Control 2.0 2.0
Ctenty dear dear
Viscosity 10050 10100
Example 30 differs from Example 29 in that the molecular proportion of anionic detergent a increased
to be equivalent to the sum of the molar proportion of anionic detergent and anionic hydrotropic
sulfonate shown in the control formulation of Example 19.
Comparison of Examples 27 and 28 compositions with the Example 19 composition illustrates that omission of the anionic hydrotrope ingredient from the inventive compositions results in a significant reduction in foaming and a doubling in viscosity. In these examples, the applicable molar ratios of anionic compounds to amphoteric plus cationic compounds are 0.78:1 and 1.03:1 respectively. Thus, the presence of the anionic hydrotrope sulfonate/sulfate ingredient is essential in the claimed detersive surfactant mixture of the inventive compositions.
When like molar proportions of cocyl isethionate anionic detergent, hydrotropic sodium xylene sulfonate, hydrotropic hexyl sulfate, lauryl trimethyl betaine, sodium cocoyl amphopnonate and
lauryiamidoethyl suttaine are substituted for the corresponding components in the above examples,
compositions having similar performance and physical characteristics are obtained. The resultant
products are effective for conditioning hair and skin and, therefore, are useful for cleansing the hair and
skin.
Although the need for substantially balanced molar proportions of anionic materials - detergent
plus hydrotropic sulfonate/sulfate - and amphoteric plus cationic ingredients is not understood, it is
believed that the anionic ingredients and the amphoteric plus cationic materials form a complex -
possibly two complexes. The existence of at least one complex is suggested by the improved
mildness and the increased viscosity of the resultant mixtures. It is further suggested by the improved
conditioning properties when conditioning agents are included. While the actual mechanism is not
understood, the efficacy of the resultant compositions is apparent at use concentrations thereof.
The dear ultra mild compositions of the present invention can also be formulated as anti-
dendruff shampoos, by employing therein about 0.10% to about 4% by weight of a conventional
anti-dandruff therapeutic agent which is soluble n the detersive surfactant mixture. Such agents
include: 1-imidazolyl-chiorophenoxy)-3,3-dimethylbutan-2-one (Ctimbazole); acetytealicytic
acid; salicylic acid; 2,4,4,,-tnchloro-2'-hydroxy diphenyi ether (tnclosan); 1-acetyl-4-(4-{(2-(2.4-
dichlorophenyl)-2-{1 H-imidazoly-l ,3-dioxolanl)methoxy)phenyl)-paperazina
(ketoconazoie); 1-hydroxy-4-methyl-6,4,4-trimethylpentyl)-2-pyridone monoethonolamine salt
(picrotone otamine); and mixtures thereof. Climbazole is the preferred anti-dandruff therapeutic
agent.
Examples 31 and 32
These examples illustrate clear antidandruff corrposrtions which are within the scope of the
described invention.
%bvwL
21 32
Poryquaternium 10 0 6 0.6
Sodium lauryl diethenoxy ether sulfate 7 0 7 0
Cocoamidopropyl dimethyl betaine 78 7 3
Sodium cumene sulfonate 13 2.17
Disodium hydrogen phosphate 0.1 0.3
Laureth - 3 carboxylic aad 0.1 0.1
Isc^eajvrnidopropyi dimethyl amine 0.14 0.14
Silicone DC 5220 0.24
Silicone DC 5324 0.44
SBicone DC Q2-8220 0.5
PEG 55 • propylene glycol oleate 0.36
PEG 18 • glyceryl glycol dioieococoate 0.2
Cetyltrimethyt ammonium chloride 0.25 0.25
C&mtazoie 0.5 0.5
Color, perfume, preservative, water a-fi U»S«.
100.00 100.00
The invention has been described with respect to various examples and illustrations thereof but is not to be limited to these because it is clear that one of skill in the art, with the present descnption before him, wii be able to utilize substitutes and equivalents without departing from the invention.

WE CLAIM:
1. A process for preparing clear, ultra mild, aqueous foaming and conditioning detergent composition said process comprising admixing
A. 5% to 40% of a detersive surfactant mixture of:
(1) 2% to 14% of an anionic detergent selected from the group consisting of C8-C18 alkyl sulfates, C8-C18 alkyl ethenoxy ether sulfates containing 1 to 5 ethenoxy groups in the molecule, C8-C18 acyl isethionates, C10-C20 alkyl sulfonates, C10-C22 alkene sulfonates, and mixtures thereof;
(2) 0.5% to 5% of an anionic hydrotropic, C1-C3 alkyl benzene sulfonate or C5-C3 alkyl sulfate: and
(3) 2.5% to 21% of an amphoteric surfactant selected from the group consisting of C8-C18 alkyl betaines, and sulfobetaines, C8-C18 alkyl amido, C2-C3 alkyl betaines and sulfobetaines, C8-C18 alkyl amphoacetates, C8-C18 alkyl amphopropionates, and mixtures thereof:
B. 0.05% to 9% by weight of a water-insoluble conditioning
agent which is soluble in said detersive surfactant mixture
and is selected from the group consisting of:
(1) 0.05% to 5% of a complex of essentially equimolar amounts of a C8-C18 (EtO)1-10 carboxylic acid, and a C8-C18 alkyl (EtO)0-10 dimethyl amine:
(2) 0.25% to 3% of a water-insoluble silicone which is soluble in said aqueous detersive surfactant mixture and is selected
from the group consisting of polydimethylsiloxane polyether copolymers, polydimethylsiloxanes containing an amino substituent, polydimethylsiloxanes containing at least one ammonia substituent and mixtures thereof: and
(3) a mixture of B(l) and/or B(2) with 0.1% to 1.0% of a polyquaternary compound selected from the group consisting of a quaternized cellulosic polymer and a mixture of said quaternized cellulosic polymer with a non-cellulosic quaternary conditioning polymer; and optionally
C) .05% to 1.0% by weight of either a mono-C10-C22 alkyl tri C1-C4 alkyl ammonium salt or a di(C14-C18 alkyl) (EtO)3-20 di-C1 -C4 alkyl ammonium salt as an anti static agent;
D) from 0.1% to 4% by weight of an anti-dandruff therapeutic agent, which agent is soluble in the detersive surfactant mixture;
E) 0.25 % to 3% of an opacifying or pearlizing agent to render
the composition opaque or pearlized; and
F) the balance being water; the sum of the moles of anionic
detergent and anionic benzene sulfonate being equal to the sum of the
moles of amphoteric detergent and cationic conditioning agent at a pH in
the range at 5.5 to 7.0 and said composition being effective to deliver
said conditioning agent in water insoluble form at use concentrations of
the composition in water.
2. A process as claimed in claim 1 wherein the mole ratio of the sum of the moles of anionic detergent and the moles of anionic hydrotrope to the sum of the moles of amphoteric detergent and the moles of cationic conditioning agent is in the range of 0.8:1 to 1.25:1.
3. A process as claimed in claim 1 having:
A. from 8% to 28% of a detersive surfactant mixture of:
(1) from 4% to 11% of an anionic detergent selected from the
group consisting of water soluble salts of C8-C18 alkyl
sulfates and C8-C18 alkyl (ethenoxy) 1-5 ether sulfates.
(2) from 1% to 4% of a water soluble salt of an anionic
hydrotropic C1-C3 alkylbenzene sulfonate: and
(3) from 4% to 13% of an amphoteric surfactant selected from
the group consisting of C8-C18 alkyl betaines and C8-C18
alkylamido C2-C3 alkyl betaines;
B. from 0.05 % to 9.0% of a water-insoluble conditioning agent
selected from the group consisting of:
(1) from 0.1% to 2.5% of a complex of essentially equimolar amounts of a C8-C18 (EtO)2- carboxylic acid, and a C8-C18 alkyl (EtO)o- dimethyl amine;
(2) from 0.5% to 2% of a water-insoluble silicone; and
(3) a mixture of B(l) and/or B(2) with 0.1% to 0.8% of polyquaternary compound; and
C. from 61% to 92% of water; the molar ratio of the sum of the
moles of anionic detergent and anionic benzene sulfonate to the
sum of the moles of amphoteric detergent and cationic conditioning
agent at a pH in the range of 6 to 6.5 being from 0.9:1 to 1.1:1,
said composition being effective to deliver said conditioning agent
in water-insoluble form at use concentrations of the composition in water.
4. A process as claimed in claims 1 wherein said anti-dandruff
therapeutic agent is selected from the group consisting of: 1-imidazolyl-
l-(4-chlorophenoxy)-3,3-dimethylbutan-2-one (climbazole); acetyl salicylic
acid; salicylic acid; 2,4,4,'-trichloro-2'-hydroxy diphenyl ether (triclosan);
1 -acetyl-4-(4-((2-(2,4-dichlorophenyl)-2-( 1 H-imidazolyl-1-methyl)-1, 3-
dioxolan) methoxy) phenyl) piperazine (ketoconazole); l-hydroxy-4-
methyl-6-(2,4,4-trimethylpentyl)2-pyridone monoethonolamine salt
(picrotone olamine); and mixtures thereof.
5. A process as claimed in claim 1 wherein said opacifying or pearfizing agent is selected from the group consisting of ethylene glycol distearate, polystyrene and mixtures thereof.
6. A process for preparing clear, ultra mild, aqueous, foaming and conditioning detergent composition substantially as herein described with reference to the foregoing examples.

Documents:

1710-del-1996-abstract.pdf

1710-del-1996-assignment.pdf

1710-del-1996-claims.pdf

1710-del-1996-complete specification (granted).pdf

1710-del-1996-correspondence-others.pdf

1710-del-1996-correspondence-po.pdf

1710-del-1996-description (complete).pdf

1710-del-1996-form-1.pdf

1710-del-1996-form-13.pdf

1710-del-1996-form-19.pdf

1710-del-1996-form-2.pdf

1710-del-1996-form-3.pdf

1710-del-1996-form-6.pdf

1710-del-1996-gpa.pdf

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Patent Number

195850

Indian Patent Application Number

1710/DEL/1996

PG Journal Number

31/2009

Publication Date

31-Jul-2009

Grant Date

21-Apr-2006

Date of Filing

31-Jul-1996

Name of Patentee

COLGATE-PALMOLIVE COMPANY

Applicant Address

300 PARK AVENUE, NEW YORK, NEW YORK 10022, USA.

Inventors:

#	Inventor's Name	Inventor's Address
1	AMRIT MANILAL PATEL	35 WETHERHILL WAY, DAYTON, NEW JERSEY 08810, USA.

PCT International Classification Number

A 61 K 7/50

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA