MXPA06008289A - Mild, viscous cleansing composition with versatile compatibility and enhanced conditioning - Google Patents

Abstract

Mild shampoo compositions are described that are economical, have excellent in-use properties, and provide enhanced conditioning benefits. The compositions have low ocular irritation potential and are particularly suitable for use by children. The compositions include a surfactant system composed on an alkyl ethoxy sulfate having at least 3 ethylene oxide groups, a betaine surfactant, and an hydroxysultaine surfactant in specific ratios;and a non-volatile water-insoluble silicone. In-vitro tests are described that allows selection of optional ingredients that do not compromise the mildness or hair conditioning performance of the composition.

Description

CLEANING COMPOSITION SOFT, VISCOSE WITH VERSATILE COMPATIBILITY AND IMPROVED CONDITIONING BACKGROUND OF THE INVENTION The present invention is directed to mild shampoo compositions that are inexpensive, have excellent properties during use, provide improved conditioning benefits. The compositions have low ocular irritation potential and are particularly suitable for use by children. Soft or tear-free shampoos are well known in the art. Many have exceptional softness and their free benefits of tears make them very suitable to apply shampoo to the hair of infants and very young children. However, traditional tear-free compositions do not foam particularly well or provide effective styling and hair conditioning benefits. There is a growing popularity among older children and teenagers for mild, tear-free shampoos that are designed for them but that provide the benefits of copious foam and conditioning / detangling delivered by adult shampoos. This has become especially important in view of the recent trends of fashion towards longer hair and the widely spread use of dryer drying. A second problem encountered with traditional tear-free shampoos concerns the economy in use. Children and teens tend to apply shampoo to their hair more often than adults do. Additionally, because these compositions do not foam particularly well and are frequently watery, they tend to be overdosed to achieve a reasonable level of foam. As a result, traditional tear-free shampoos are not perceived as effective and economical (especially by parents), which tends to limit their use to infants and very young children. An objective of the present invention is a mild, tear-free shampoo composition having excellent properties during use, especially rich bulk foam. Another objective is a gentle, tear-free shampoo composition that provides conditioning and detangling benefits of hair even after drying with a dryer. Yet an additional objective is a gentle, tear-free composition that combines excellent properties during use with effective hair conditioning / detangling benefits, even if it is both thick and efficient, so that it is economical for children and adolescents to use. These and other objects will become clearer from the description of the invention. The following patents and publications have been considered: US 6,489,286 describes compositions including surfactants, two cationic conditioning polymers and a volatile silicone. US 6,495,498 describes compositions including water soluble silicones, a cationic conditioning agent and a detergent.

US Re. 34,584 describes compositions including a surfactant, an insoluble, non-volatile silicone, a suspending agent and water. The suspending agents are long chain acyl derivatives or long chain amine oxide. None of the references cited above shows the specific combination of ingredients in the critical proportions described herein.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides a mild, tear-free shampoo composition, which is economical and has excellent foam, conditioning properties by combining specific anionic and amphoteric surfactants in well-defined proportions, specific conditioning agents, and optionally polymers. compatible cations and highly efficient thickening / suspension agents. More specifically, the mild aqueous shampoo composition comprises the following ingredients in the amounts and proportions indicated: i) an alkyl ethoxy sulfate, wherein the alkyl group has an average of 12-16 carbon atoms and a degree of ethoxylation of at least 3, ii) from about 2% to about 7% of a ine surfactant, iii) from about 2% to about 7% of a hydroxysultaine surfactant, iv) from about 0.1% to about 5% of an insoluble silicone in water, non-volatile, v) at least about 70% by weight of water; wherein the weight ratio of the betaine surfactant to the hydroxysultaine surfactant is in the range of from about 0.5 to about 1.5, and the weight ratio of the alkyl ethoxy sulfate to the sum of the weights of betaine surfactant and hydroxysultaine surfactant it is in the range from about 0.5 to about 1.5.

DETAILED DESCRIPTION OF THE INVENTION As used herein,% or% by weight refers to the weight percentage of an ingredient as compared to the total weight of the composition or component being discussed. The present invention relates to shampoo and conditioner compositions which includes a mild, tear-free and efficient surfactant system, a water-insoluble, non-volatile silicone, and an optional cationic polymer, which is thought desirable, and an effective thickening system . These components are discussed in detail below.

SURFACTANT SYSTEM The surfactant system is composed of a combination of three essential surfactants: one is an anionic surfactant and two are amphoteric surfactants. The anionic surfactant is an alkyl ethoxy sulfate having the general formula R - (O - CH2 - CH2 -) x - O SO3 M wherein R is an alkyl group having a straight or branched alkyl chain. The alkyl group may contain 8-20 carbon atoms, preferably 10-18 carbon atoms and most preferably 12-15 carbon atoms. "X" represents the average ethylene oxide content per molecule of surfactant and can in principle be in the range from about 1 to about 10. However, to achieve adequate softness (ie, low potential for eye irritation), X it should be preferred at least 3 and most preferably between about 3 and about 3.5, since this ethylene oxide content produces compositions having the proper softness without compromising foam performance. "M" represents a cation, preferably a monovalent cation, and most preferably a sodium, ammonium or alkanolammonium ion. The alkyl ethoxy sulfate may be present in the composition in an amount ranging from about 4% to about 15%, preferably 5% to about 10%, and most preferably 6% to 8% based on the total weight of the composition. Higher levels of ethoxysulfate can be accommodated at a given betaine / hydroxysultaine ratio, without compromising ocular irritation as the degree of ethoxylation increases. The second essential component of the surfactant system is a mixture of amphoteric surfactants including a betaine component and a hydroxysultaine component. The betaine component is defined by the following structure: CH3 I R "- N + - CH2 - COO" I CH3 where R "is either an alkyl or an alkyl amidoalkyl group. The alkyl group may in any case be straight or branched chain alkyl group having 8-1 8 carbon atoms, preferably 10-16 carbon atoms and most preferably 1 0-14 carbon atoms.

Available betaines include oleyl betaine, caprylamidopropyl betaine, lauramidopropyl betaine, isostearylamidopropyl betaine, coconut imidaoazolinium betaine. Particularly preferred betaines are lauryl or coco betaine, and lauryl or coco amidopropyl betaine. The third essential component of the surfactant system is a hydroxysultaine (CTFA name for a sulfobetaine having the hydroxypropyl sulfonate group), which is generally formed from the reaction of a tertiary amine with epichlorohydrin and a bisulfite. Its general structure is: CH 0 OH i R * - N * - CH 2 - CH - CH 2 - S 0 3"I CH 3 where R" is either an alkyl or an alkyl amidoalkyl group. The alkyl group may in any case be a straight or branched chain alkyl group having 8-18 carbon atoms, preferably 10-16 carbon atoms and most preferably 1 0-14 carbon atoms. Commercially available sultaines include: lauryl hydroxy sultaine, tallowamidopropyl hydroxy sultaine, erucamidopropyl hydroxy sultaine and alkyl ether hydroxypropyl sultaine. Particularly preferred hydroxysultaines are coconut and lauryl propylhydroxy sultaine and coco amidopropyl hydroxysultaine. The ratio by weight of betaine to hydroxysultaine and the relative proportions of total amphoteric etoxysulfate (betaine plus hydroxysultaine) are critical to achieve a broad formulation compatibility and a high degree of softness. The weight ratio of betaine to hydroxysultaine should be in the range from about 0.5 to about 1.5., preferably from about 0.6 to about 1.0, and most preferably from about 0.7 to about 0.85. The weight ratio of total amphoteric to ethoxysulfate should be in the range of from about 0.5 to about 1.5, preferably from about 0.8 to about 1.2, and most preferably from about 0.9 to about 1.1. Certain optional surfactants may be incorporated at low levels in the composition as long as they do not compromise the softness of the composition especially their eye irritation potential and their hair conditioning performance. This can be assessed via the in vitro tests described in the METHODOLOGY SECTIONS (see Flowease Escape Test and Wet and Dry Combat Strength Test). Examples of acceptable optional surfactants that can be used at low levels, usually below 3% and preferably below 2% are ethoxylated alkyl sulfosuccinates, alcohol ethoxylates having more than 7 ethylene oxide groups, alkylamphoahetates, alkylamphopropionates, alkyl iminodipropionates, alkyl sacrosinate, alkyl ethoxy carboxylates, sorbitan monoesters ethoxylated from fatty acids, polyoxyethylene derivatives of polyol esters. However, certain surfactants should be minimized. These include alkyl sulphates and alkyl or alkyl aryl sulfonates, ethoxylated alkylphenols, ethanolamides of aliphatic acids. If required, these surfactants should be used at a level of less than 2%, preferably less than 1.5% and most preferably less than 1% by weight of the total composition.

SILICON INSOLUBLE IN WATER, NOT VOLATILE The shampoo compositions of the present invention further comprise a silicone hair conditioning agent at concentrations effective to provide hair conditioning benefits. Such concentrations range from about 0.01% to about 5%, preferably from about 0.1% to about 5% and most preferably from about 0.2% to about 3%, by weight of the shampoo compositions. The silicone shampoo conditioning agents of the invention are insoluble in water and shampoo compositions and are non-volatile. They will normally be intermixed in the shampoo composition in order to be in the form of a discontinuous, separate phase of insoluble, dispersed particles, also referred to as droplets. These droplets are usually suspended with an optional suspending agent as described hereinafter. The silicone hair conditioning agent phase will comprise a silicone fluid hair conditioning agent, such as a silicone fluid and may also comprise other ingredients, such as a silicone resin to improve the efficiency of silicone fluid deposition or to enhancing hair gloss (especially when using silicone conditioning agents (e.g., highly phenylated silicones) of high refractive index (eg, above about 1.46) .Silicone hair conditioning agents for use in hair Shampoo compositions preferably have a viscosity of from about 20 to about 2,000,000 centistokes, more preferably from about 1,000, to about 1,800,000 centistokes, even more preferably from about 50,000 to about 1,500,000 centistokes, as measured at 25 ° C. The silicone fluids include oils silicone, which are silicone materials capable of flowing having a viscosity of less than 1,000,000 centistokes, preferably between about 5 and 1,000,000 centistokes, more preferably between about 10 and about 1,000,000 centistokes, at 25 ° C. Suitable silicone oils include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers and combinations thereof. Other non-volatile, insoluble silicone fluids having hair conditioning properties can also be used. The viscosity can be measured by means of a glass capillary viscometer as further disclosed in the Dow Corning Corporate Test Method CTM004 July 20, 1970. The average silicone particle size of the silicone emulsified in the shampoo composition is conveniently less than 20 microns, preferably less than 10 microns. Ideally, it varies from 0.15 to 2 microns, optimally from 0.2 to 1 miera. Silicone oils include polyalkyl or polyaryl siloxanes containing substituent groups including alkoxy, aryloxy, alkaryl, arylalkyl, aryalkenyl, alkylamino, and substituted-aryl and ether-substituted, hydroxy-substituted, and halogen-substituted aliphatic groups. Substituent groups can also include cationic amines and quaternary ammonium groups. The aliphatic or substituted aryl groups in the siloxane chain can have any structure, as long as the resulting silicones remain fluid at room temperature, are hydrophobic, are not irritating, toxic or otherwise harmful when applied to hair, are compatible with the other components of the shampoo compositions, are chemically stable under normal use and storage conditions, are insoluble in the shampoo compositions herein, and are capable of being deposited on and conditioned the hair. Preferred alkyl and alkenyl substituents are C ^ Cs alkyls and alkenyls, more preferably from C -? - C4, most preferably from C1-C2. The aliphatic portions of other groups containing alkyl, alkenyl or alkynyl (such as alkoxy, alkaryl and alkanoy) can be straight or branched chains and preferably have from one to five carbon atoms, more preferably from one to four carbon atoms, yet more preferably from one to three carbon atoms, most preferably from one to two carbon atoms. As discussed above, the substituents may also contain amino functionality, for example, amino groups, which may be primary, secondary or tertiary amines or quaternary ammonium. These include mono-, di- and tri-alkylamino and alkoxyamino groups, wherein the chain length of the aliphatic moiety is preferably as described above. Suitable substituent groups in the siloxane chain include methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl. Preferred silicones are polydimethyl siloxane, polydiethylsiloxane and polymethylphenylsiloxane. Polydimethylsiloxane is especially preferred. Other suitable groups include methyl, methoxy, ethoxy, propoxy and aryloxy.

The three R groups in the silicone end caps can also represent the same or different groups. Non-volatile polyalkylsiloxane fluids that can be used include, for example, polydimethylsiloxanes. These siloxanes are available, for example, from General Electric Company in their Viscasil R and SF 96 series, and from Dow Corning in their Dow Corning series. 200. The polyalkylaryl siloxane fluids that can be used also include, for example, polydimethylsiloxanes. These siloxanes are available, for example, from the General Electric Company as SF 1075 methyl phenyl fluid or from Dow Corning as a Fluor 556 cosmetic grade. Polyether siloxane copolymers that can be used include, for example, a polydimethylsiloxane modified with polypropylene oxide (for example, Dow Corning DC-1248), although ethylene oxide or mixtures of ethylene oxide and propylene oxide can also be used . The concentrations of ethylene oxide and polypropylene oxide must be sufficiently wide to prevent solubility in water and in the composition thereof. Suitable alkylamino substituted silicones include those known by the CTFA designation "amodimethicone". An especially preferred cationic polymer is known as "trimethylsilyllamodimethicone". Other silicone fluids are insoluble silicone gums. These gums are polyorganosiloxane materials having a viscosity at 25 ° C of more than or equal to 1,000,000 centistokes. Silicone rubbers are described in US Patent no. 4, 152,416; Noli and Walter, Chemistry and Technology of Silicones, New York: Academic Press 1968; and in the General Electric SE 30, SE 33, SE 54 and SE 76 silicone rubber product data sheets, all incorporated herein by reference. Silicone gums will normally have a mass molecule weight in excess of about 200,000, generally between about 200,000 and about 1,000,000, specific examples of which include polydimethylsiloxane, (polydimethylsiloxane) copolymer (methylvinylsiloxane), poly (dimethylsiloxane) copolymer ) (diphenyl siloxane) (methylvinylsiloxane) and mixtures thereof. Another category of insoluble, non-volatile silicone fluid conditioning agents are the high refractive index silcones, having a refractive index of at least about 1.46, preferably at least about 1.48, more preferably at least about 1.52, most preferably at least about 1.55. The refractive index of the polysiloxane fluid will generally be less than about 1.70, usually less than about 1.60. In this context, the "fluid" of polysiloxane includes oils as well as gums. The high refractive index polysiloxane fluids contain a sufficient amount of aryl containing substituents to increase the refractive index to the desired level, which is described above. The aryl-containing substituents contain five and six membered aryl rings, alicyclic and heterocyclic, and substituents containing five or six membered rings, fused. The aryl rings by themselves can be replaced or not replaced. Substituents include aliphatic substituents, and may also include alkoxy substituents, acyl substiuyenyes, ketones, halogens (e.g., Cl and Br), amines, etc. Exemplary aryl containing groups include substituted and unsubstituted alkenes, such as phenyl, and phenyl derivatives, such as phenyls with alkyl or alkenyl substituents of CT-CS, for example, allyl phenyl, methyl phenyl and ethyl phenyl, finyl phenyls, such as styrenyl, and phenyl alkynes (for example, phenyl C2-C4 alkynes). The heterocyclic aryl groups include substituents derived from furan, imidazole, pyrrole, pyridine, etc. Fused aryl ring substituents include, for example, naphthalene, coumarin and purine. In general, polysiloxane fluids of high refractive index will have a degree of substituents containing aryl of at least about 15%, preferably at least about 20%, more preferably at least about 25%, even more preferably at least about 35% , most preferably at least about 50%. Normally, while not necessarily intended to limit the invention, the degree of aryl substitution will be less than about 90%, more generally less than about 85%, preferably from about 55% to about 80%. Polysiloxane fluids are also characterized by relatively high surface tensions as a result of their aryl substitution. In general, the polysiloxane fluids here will have a surface tension of at least about 24 dynes / cm. sup.2, normally at least approximately 27 dynes / cm. sup.2. Surface tension, for purposes hereinafter, is measured by a Nouy ring tensiometer according to the Dow Corning CTM 0641 Corporate Test Method, November 23, 1971. Changes in surface tension can be measured according to the above test method or in accordance with Method of ASTM D 1331. Preferred high refractive index polysiloxane fluids have a combination of substituents derived from phenyl or phenyl (preferably phenyl), with alkyl substituents, preferably C 1 -C 4 alkyl (most preferably methyl), hydroxy, C 1 -C 4 alkylamine. High refractive index polysiloxanes are available from Dow Corning Corporation (Midland, Mich., US), Huis America (Piscataway, N.J., US) and General Electric Silicon (Waterford, N.Y., US). It is preferred to use high refractive index silicones in solution with a spreading agent, such as a silicone resin or a surfactant, to reduce the surface tension by an amount sufficient to intensify spreading and thereby intensify the gloss (subsequent to drying). ) of hair treated with the composition. In general, a sufficient amount of the spreading agent to reduce the surface tension of the polysiloxane fluid of high refractive index by at least about 5%, preferably at least about 10%, more preferably at least about 15%, even more preferably at least about 20%, most preferably at least about 25%. Reductions in surface tension of the polysiloxane fluid / spreading agent mixture can provide improvement of hair shine. References that describe examples of some silicone fluids suitable for use in shampoo compositions include U.S. Pat. 2,826,551, U.S. Patent No. 3,964,500, U.S. Patent No. 4,364,837, British Patent 849,433 and Silicon Compounds, Petrarch Systems, Inc. (1984), all incorporated herein by reference.

Silicone resins can be included in the silicon conditioning agent. These resins are highly crosslinked polymeric siloxane systems. Cross-linking is introduced through the incorporation of trifunctional and tetrafunctional silanes with monofunctional or difunctional silanes, or both, during the manufacture of the silicone resin. As will be well understood in the art, the degree of crosslinking that is required in order to result in a silicone resin will vary according to the specific silane units incorporated in the silicone resin. In general, silicone materials having a sufficient level of trifunctional and tetrafunctional siloxane monomer units (and hence, a sufficient level of crosslinking), so that they are dried to a rigid, or hard, film are considered as resins of silicone The ratio of oxygen atoms to silicon atoms is indicative of the level of crosslinking in a particular silicone material. Silicone materials having at least about 1.1 atoms of oxygen per silicon atom will generally be silicone resins in the present. Preferably, the ratio of oxygen atoms: Si! Is at least about 1.2: 1 .0. The silanes used in the manufacture of silicone resins include monomethyl-, dimethyl-, trimethyl-, monophenyl-, diphenyl-, methylphenyl-, monovinyl- and methylvinyl-chlorosilanes, and tetrachlorosilane, with the methyl-substituted silanes being very commonly used. Preferred resins are offered by General Electric as GE SS4230 and SS4267. Commercially available silicone resins will generally be provided in a form dissolved in a non-volatile or volatile silicone fluid of low viscosity. The silicone resins for use herein should be supplied and incorporated into the present compositions in such dissolved form, as to be readily apparent to those skilled in the art. The support material on silicones including sections that discuss silicone fluids, gums and resins, as well as the manufacture of silicones, can be found in the Encyclopedia of Polymer Science and Engineering, volume 15, second edition, pp. 204-308, John Wiley & Sons, Inc., 1989, incorporated herein by reference. Silicone materials and silicone resins in particular can be conveniently identified according to a well-known abbreviated nomenclature system for those skilled in the art as "MDTQ" nomenclature. Under this system, the silicone is described according to the presence of several units of siloxane monomer, which form the silicone. Briefly, the symbol M denotes the monofunctional unit (CH3) 3SiO; D was not the difunctional unit (CH3) 2SiO; T denotes the trifunctional unit (CH3) SiO? .5; and Q denotes the quadri- or tetra-functional unit SiO2. The cousins of the unit symbols, for example, M ', D', T 'and Q' denote substitutes other than methyl, and must be defined specifically for each occurrence. Alternative alternating substituents include groups such as vinyl, phenyls, amines, hydroxyls, etc. The molar proportions of the various units, either in terms of subscripts to the symbol indicating the total number of each type of unit in the silicon (or an average thereof) or as proportions specifically indicated in combination with molecular weight, complete the description of the silicone material under the MDTQ system. Higher relative molar amounts of T, Q, T 'and / or Q' to D, D ', M and / or M' in a silicone resin are indicative of higher levels of crosslinking. However, as discussed above, the overall level of reliculation can also be indicated by the ratio of oxygen to silicon. The silicone resins to be used herein, which are preferred, are MQ, MT, MTQ, MDT and MDTD resins. In this way, the preferred silicone substituent is methyl. MQ resins are especially preferred, where the ratio M: Q is from about 0.5: 1 .0 has been approximately 1.5: 1 .0 and the average molecular weight of the resin is from about 1000 to about 10,000. The weight ratio of the non-volatile silicone fluid, having a refractive index below 1.46, to the silicone resin component, when used, is preferably from about 4: 1 to about 400: 1, preferably this ratio is from about 9: 1 to about 200: 1, more preferably from about 19: 1 to about 100.1, particularly when the silicone fluid component is a polydimethylsiloxane fluid or a fluid mixture of polydimethylsiloxane and polydimethylsiloxane gum as It is described before. In terms of the silicone resin, it forms a part of the same phase in the compositions here as the silicone fluid, that is, the active conditioner, the sum of the fluid and resin should be included to determine the level of silicone conditioning agent. in the composition. The silicone component may consist of droplets that are in the normal emulsion size range or may comprise a microemulsion consisting of droplets less than about 0.1 miera. The microemulsified silicones are especially suitable for use in clear shampoo compositions. Additionally, the silicone component may consist of a mixture of emulsified particles of insoluble silicone of specified average silicone particle size and microemulsified particles of insoluble silicone of specified average silicon particle size. The silicones are insoluble in the aqueous maize of the shampoo composition and thus they are present in emulsified and / or microemulsified forms respectively, with the silicones present as dispersed particles. The particle size can be measured by means of a laser light scattering technique, using a 2600 D Particle Sizer from Malvern Instrumenís. The average particle size measurement using this technique is the "D501 1 value." In addition to polydiorganosiloxanes and aminofunctional silicones, the polydiorganosiloxanes can have hydroxyl end groups, which have the designation CTFA dimimeiconol. emulsified insoluble silicones may be of the same type of silicone as the insoluble silicone microemulsified particles, or they may be different.Silicon emulsions and microemulsions suitable for use in the invention are commercially available in a pre-emulsified form. Shaped can be incorporated into the shampoo composition by simple mixing, which is particularly advantageous for ease of processing Pre-formed emulsions are available from suppliers of silicone oils, such as Dow Corning, General Electric, Union Carbide, Wacker Chemie, Shin Etsu, Toshiba, Toyo Beauty Co and Toray Silicone Co. An aqueous emulsion is the preferred form for such preformed emulsion. In such emulsions, it is usual for the emulsion to additionally include at least one emulsifier in order to stabilize the silicone emulsion. Suitable emulsifiers are well known in the art and include anionic and nonionic surfactants. Examples of anionic surfactants used as emulsifiers for the silicone particles are alkylarylsulfonates, for example, sodium dodecylbenzenesulfonate, alkyl sulfates, for example, sodium lauryl sulfate, alkyl ether sulfates, for example, sodium lauryl ether sulfate nEO, where n is from 1 to 20 alkylphenol ether sulfates, for example, octylphenol ether sulfaion nEO, where n is from 1 to 20, and sulfosuccinates, for example, sodium dioctyl sulfosuccinate. Examples of nonionic surfactants used as emulsifiers for the silicone particles are alkylphenol ethoxylates, for example, nonylphenol ethoxylate nEO, where n is from 1 to 50, alcohol efoxylates, for example, lauryl alcohol nEO, where n is from 1 to 50, ethoxylate ester, for example, polyoxyethylene monostearate wherein the number of oxyethylene units is from 1 to 30. Examples of suitable pre-formed emulsions include emulsions DC2-1766, DC2-1784 and DC2-1310, all available from Dow Corning. They are all dimethiconol emulsions. DC2-1766 and DC2-1785 each have an average silicone particle size in the emulsion of less than 2 microns. DC2-1310 has an average silicone particle size in the emulsion of about 8 microns. Cross-linked silicone rubbers are also available in a pre-emulsified form. A preferred example is the material available from Dow Corning as DC X2-1787, which is an emulsion of crosslinked dimethiconol gum having an average silicone particle size in the emulsion of about 0.5 micron. The average silicone particle size of the microemulsified silicone in the shampoo composition is conveniently less than less than 0.075 microns. Ideally, it varies from 0.01 to 0.75 microns, optimally from 0.02 to 0.05 microns. Examples of suitable pre-formed microemulsions include microemulsions DC2-1865 and DC2-1870, available from Dow Corning. Esías are microemulsions of dimethiconol. DC2-1 865 and DC2-1870 each have an average silicone particle size in the microemulsion of less than 0.075 microns. Cross-linked silicone rubbers are also available in a pre-microemulsified form, which is advantageous for ease of formulation. A preferred example is the material available from Dow Corning as DC X2-1391, which is a cross-linked dimethiconol gum microemulsion having an average silicone particle size in the microemulsion of about 0.045 microns. It has been reported in WO9953889, that the performance of silicone conditioning in a surfactant-based shampoo composition can be significantly enhanced by the use of a combination of emulsified silicone and microemulsified silicone in the shampoo composition. The weight ratio of emulsified silicone particles to silicone microemulsified particles conveniently ranges from 4: 1 to 1: 4. Preferably, the ratio of emulsified particles of silicone to microemulsified silicone particles ranges from 3.1 to 1: 3, more preferably from 2: 1 to 1: 1.

OPTIONAL INGREDIENTS Cationic polymer: Cationic polymers are optionally employed to provide enhanced deposition of water-insoluble, non-volatile silicone, as well as conditioning benefits in their own right. The cationic conditioning polymer contains portions containing cationic nitrogen, such as quaternary ammonium or cationic protonated amino moieties. The cationic protonated amine can be primary amines, secondary or tertiary (preferably secondary or tertiary), depending on the particular species and the selected pH of the shampoo composition. The average molecular weight of the cationic conditioning polymers is between about 1.0 million and about 5,000, preferably at least about 100,000, more preferably at least about 200,000, but preferably not more than about 2 million, preferably not more than about 1 .5 million. The polymers also have a cationic charge density ranging from about 0.2 meq / g to about 7 meq / g, preferably at least about 0.4 meq / g, more preferably at about 0.6 meq / g, but also preferably less than about 5 meq / g, more preferably less than about 2 meq / g, at the intended use pH of the shampoo composition, said pH will generally vary from about pH 3 to about pH 9, preferably between about pH 5 and about pH 8 .

Any anionic counterion can be used in association with the cationic coioning polymers, as long as the polymers remain soluble in water, in the shampoo composition, or in a coascervated phase of the shampoo composition, and as long as the conirations are physically and chemically Comparable with the essential components of the shampoo composition or that do not unduly deteriorate the performance, stability or aesthetics of the product in any other way. Non-limiting examples of such counterions include halides (e.g., chlorine, fluorine, bromine, iodine), sulfate, and melilsulfate. The cationic nitrogen containing portion of the cationic polymer is generally present as a substituent in all, or more usually in some, monomer units thereof. In this manner, the cationic polymer for use in the shampoo composition includes homopolymers, copolymers, terpolymers, and so on, of units of monomer substituted with cationic amine or quaternary ammonium, optionally in combination with non-cationic monomers referred to herein as spacer monomers. . Non-limiting examples of such polymers are described in the CTFA Cosmetic Ingredient Dictionary (CTFA Cosmetic Ingredient Dictionary), 3rd edition, edited by Estrin, Crosley and Haynes (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, D.C. (1982)), the description of which is incorporated herein by reference. Particularly suitable cationic polymers for use in the shampoo composition include polysaccharide polymers, such as cationic cellulose derivatives and cationic starch derivatives. Suitable cationic polysaccharide polymers include those that conform to the formula R 1 I A - O -. { - R - N * - R3X ") I R2 wherein A is a residual group of anhydroglucose, such as a cellulose anhydroglucose residue or starch; R is an alkylene oxyalkylene, polyoxyalkylene or hydroxyalkylene group, or combination thereof, R1, R2 and R3 independently are alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl or alkoxyaryl groups, each group containing up to about 18 carbon atoms and the total number of carbon atoms for each cationic portion (i.e., the sum of carbon atoms in R1, R2 and R3), preferably is about 20 or less; and X is an anionic counterion as described hereinabove. Especially preferred cationic coioning polymers are the cationic cellulose polymers especially as those polymers available from Amerchol Corp. (Edison, NJ) in their polymer series Polymer JR and LR, as hydroxyethyl cellulose salts which reacted with epoxide substituted with trimethyl ammonium, referred to in the industry (CTFA) as Polyquaternium 10. Another type of cationic cellulose includes the polymeric salts of quaternary ammonium hydroxyethyl cellulose which recycled with epoxide substituted with lauryl dimethyl ammonium, referred to in the industry (CTFA) as Polyquaternium 24. These materials are available from Amerchol Corp. (Edison, NJ) under the trade name Polymer LM-200. The level of cationic cellulose in the composition may be in the range from about 0.01 to about 2%, preferably from about 0.1 to about 0.6%, and most preferably from about 0.15 to about 0.45%. Although cellulose cationic polymers are preferred, other types of cationic polymers can be incorporated at low levels as optional additives, as long as they do not interfere with stability. Examples of such optional cationic polymers include either modified natural polymers or synthetic polymers. The level of these optional polymers should preferably be incorporated in the range of about 10% to about 25%, based on the weight of the cationic cellulose present in the formulation. Suitable optional modified natural polymers include cationic guar gum derivatives, such as guar hydroxypropyltrimonium chloride, specific examples of which include the Jaguar series commercially available from Celanese Corporation. Other suitable cationic polymers include cellulose ethers containing quaternary nitrone, some examples of which are described in US Pat. 3,962,418, the disclosure of which is incorporated herein by reference. Other suitable cationic polymers include copolymers of etherified cellulose, guar and starch, some examples of which are described in U.S. Pat. 3,958,581, the disclosure of which is incorporated herein by reference. Non-limiting examples of suitable optional synthetic cationic polymers include copolymers of vinyl monomers having quaternary ammonium functionality or cationic protonated amine with water-soluble spacer monomers, such as, acrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylate , allyl methacrylate, vinyl caprolactone vinyl pyrrolidone. The monomers subsituted with alkyl and dialkyl preferably have from C 1 to C 7 alkyl groups, more preferably from C 1 to C 3 alkyl groups. Other suitable spacer monomers include vinyl esters, vinyl alcohol (made by hydrolysis of polyvinyl acetate), maleic anhydride, propylene glycol and ethylene glycol. Other suitable optional synthetic polymers include quaternary ammonium monomers and protonated amino monomers, for inclusion in the cationic polymers of the présenle shampoo composition, include vinyl compounds substituted with dialkylaminoalkyl acrylate, dialkylammoalkyl methacrylate, monoalkylaminoalkyl acrylate, monoalkylaminoalkyl melacrylate , trialkyl methacryloxyalkyl ammonium salt, trialkyl acryloyl ammonium salt, diallyl ammonium quaternary salt and vinyl quaternary ammonium monomers with rings containing cyclic cationic nitride, such as pyridinium, imidazolium and quaternized pyrrolidone, for example, alkyl vinyl imidazolium salts, alkyl vinyl pyridinium, alkyl vinyl pyrrolidone. The alkyl portions of these monomers are preferably lower alkyls, such as d, C2 or C3 alkyls. Other suitable optional synthetic polymers include amino-substituted vinyl monomers for use herein, include dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, dialkylaminoalkyl acrylamide and diacylaminoalkyl methacrylamide, wherein the alkyl groups are preferably hydrocarbyls of C ^ CT-, more preferably CT-CS alkyls. Still other optional synthetic polymers suitable for use in the shampoo composition include copolymers of 1-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salt (eg, chloride salt) (referred to in industry by the Cosmetic, Toiletry, and Fragrance Association, "CTFA", as Polyquaternium-16), such as those commercially available from BASF Wyandotte Corp. (Parsippany, NJ, US) under the trade name LUVIQUAT (for example, LUVIQUAT FC 370); copolymers of 1-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate (referred to in the industry by CTFA as Polyquaternium-1 1), such as those commercially available from ISP Corporation (Wayne, NJ US) under the trade name GAFQUAT (eg, GAFQUAT 755N); cationic polymers containing diallyl quaternary ammonium, including, for example, dimethyldiallylammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride, referred to in the indusry (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively; and salts of amino acid alkyl esters of homopolymers and copolymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms, as described in U.S. Pat. 4,009,256, the disclosure of which is incorporated herein by reference.Thickening Agents and Suspension Agents: The compositions of the present invention preferably further comprise thickening / suspending agents to ensure that insoluble materials are stable. A variety of materials can be used. These include swelling and associative polymers, inorganic and organic, crystalline or amorphous materials, finely divided, forming networks, electrolytes and combinations thereof. Organic polymers include carboxy vinyl polymers, such as the copolymers of acrylic acid crosslinked with polyallylsucrose as described in U.S. Pat. 2,798,053, the disclosure of which is incorporated herein by reference. Examples of these polymers include Carbopol 934, 940, 941 and 956, available from B. F. Goodrich Company and the alkaline swellable acrylic latex polymers sold by Rohm and Haas under the tradenames ARYSOL or ACULYN. Other suitable suspending agents include xanthan gum at concentrations ranging from about 0.35 to about 3%, preferably from about 0.45 to about 1.2%, by weight of the shampoo compositions.

The use of xanthan gum as a suspending agent in silicone-containing shampoo compositions is described, for example, in U.S. Pat. 4,788,006, the description of which is incorporated herein by reference. Combinations of long chain acyl derivatives and xanían gum can also be used as a suspension agent in shampoo compositions. Such combinations are described in U.S. Pat. 4,704,272, the disclosure of which is incorporated herein by reference. Other suitable polymeric suspending agents can be used in shampoo compositions, including those that can impart a gel-like viscosity to the composition, such as water-soluble or water-soluble polymers colloidally as cellulose ethers (eg, methylcellulose, hydroxybutyl methylcellulose, hydroxypropylcellulose, hydroxypropyl methylcellulose, hydroxyethyl ethyl cellulose and hydroxyethylcellulose), guar gum, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl guar gum, starch and starch derivatives and other thickeners, viscosity modifiers, gelling agents, etc. Mixtures of these materials can also be used. Optional crystalline organic suspension agents include acyl derivatives, long chain amine oxides or combinations thereof, concentrations of which range from about 0.1% to about 5.0%, preferably from about 0.5% to about 3.0%, in weight of the shampoo compositions. When used in shampoo compositions, these suspending agents are present in crystalline form. These suspending agents are described in U.S. Pat. 4,741, 855, the description of which is incorporated herein by reference. These suspending agents include ethylene glycol esters of fatty acids, preferably having from about 16 to about 22 carbon atoms. Examples include silica glycol esters, monoanthene as distearate, but in particular distearate containing less than about 7% of the monostearate. Other suitable suspending agents include alkanol fatty acid amides, preferably having from about 16 to about 22 carbon atoms, more preferably about 16 to 18 carbon atoms, preferred examples of which include stearic monoethanolamide, spheroid diefanolamide, spherical monoisopropanolamide and stearic monoethanolamide stearate. Other long chain acyl derivatives include long chain esters of long chain fatty acids (e.g., stearyl stearate, cetyl palmitate, etc.); glyceryl esters (eg, glyceryl distearate) and long chain esters of long chain alkanol amides (e.g., stearamide diethanolamide distearate, stearamide monoethanolamide stearate). The long chain acyl derivatives, ethylene glycol esters of long chain carboxylic acids, long chain amine oxides and alkanol amides of long chain carboxylic acids in addition to the preferred materials listed above, can be used as suspending agents. For example, it is contemplated that suspending agents may be used with long chain hydrocarbyls having C8-C22 chains. Examples of long chain amine oxides suitable for use as suspending agents include (C 6 -C 22) alkyl dimethyl amine oxides, for example, stearyl dimethyl amine oxide. Another useful crystalline suspending agent is trihydroxystearin sold under the tradename THIXCIN R. Inorganic network forming materials include, but are not limited to, clays and silicas. Examples of clays include smectite clay selected from the group consisting of bentonite and hectorite and mixtures thereof. Synthetic hectorite clay (laponite) is often used with an electrolyte salt capable of causing the clay to thicken (alkaline and alkaline-earth salts, such as halides, ammonium salts and sulfates). Bentonium is a colloidal aluminum clay sulfate. Examples of silica include amorphous silica and include fumed silica and precipitated silica and mixtures thereof. Associative polymers are those that incorporate hydrophobic groups, which can form labile crosslinks alone or with the participation of surfactant micelles. An example of associative polymers are the hydrophobically modified crosslinked polyacrylates sold by Noveon under the trade name PEMULEN. Another example are hydrophobically modified cellulose ethers and hydrophobically modified polyurethanes. A particularly preferred class of thickening and suspending agent in the present invention are non-ionic, water-soluble, hydrophobically modified polyols. The hydrophobically modified water-soluble nonionic polyols for use herein are methyl glucoside dioleate PEG 120 (available from Amercol under the tradename GLUCAMATE DOE 120), pentearyl PEG-150 tetratearate (available from Croda under the tradename) CROTHIX, dioleate of PEG-75 (available from Kessco under the trade name PEG-4000 DIOLEATE) and distearate of PEG-150 (available from Witco under the trade name WITCONAL L32) .The long chain fatty esters of polyethylene glycol, for example, PEG-150 distearate are especially preferred thickening and suspending agents in the present invention Although PEG fatty esters can be used alone, it has been found that their effectiveness and efficiency can be vastly improved when combined with certain electrolytes. especially preferred for use in combination with distearazole of PEG-150, are sodium citrate and sodium chloride, since They provide a synergistic thickening system that allows adequate thickening at low levels of inclusion in the composition having a low total concentration of surfactant, for example, less than about 15% by weight. This is important to achieve tear-free, mild formulations that provide excellent conditioning properties and are economical.

The above thickening and structuring agents can be used alone or in mixtures and can be present in an amount from about 0.1% by weight to about 10% by weight of the composition. When mixtures of PEG-150 distearate / electrolyte are employed as the thickening system, the level of organic thickener can be substantially reduced to a level between about 0.1 to about 0.5% by weight, preferably between 0.2% by weight and 0.4% by weight. weight.

Aesthetic and auxiliary ingredients: A wide variety of optional ingredients can be incorporated into the formulation as long as they do not interfere with the softness and hair conditioning benefits provided by the composition. These include but are not limited to: perfumes, pearlizing and opacifying agents such as higher fatty alcohols, fatty acids, solid esters, pearlescent "interference pigments" such as TiO2 coated micas, dyes and dyes, agents perceived by the senses such as menthol, preservatives including antioxidants and chelating agents, emulsion stabilizers, auxiliary thickeners and mixtures thereof. , Additional hair and skin benefit agents: A variety of optional ingredients may be incorporated into the compositions of the present invention to promote hair and scalp health. However, these ingredients should be chosen as consistent with the tear-free softness of the composition. Potential beneficial agents include, but are not limited to: lipids such as cholesterol, ceramides and pseudoceramides, additional non-silicone hair conditioning agents, such as synthetic hydrocarbon esters, humectanis such as glycerol, antimicrobial agents such as zinc pyridinethione, sun blockers and mixtures thereof.

METHODOLOGY OF EVALUATION In vitro fluorescein leakage test The in vitro model referred to as fluorescein leakage test is used to assess the potential of eye irritation and is ideal to discriminate against or qualify the eye softness of products such as shampoo. The assay, which is known in the art, involves a culture of monolayer cells which mimic the tight junctions found in the cornea of the eye. In this test, which is described below, the greater the leakage of sodium fluorescein through cell culture, which is caused by a particular composition, the greater the potential to cause ocular irritation by that composition. The fluorescein leakage assay uses a cell culture system consisting of Madin-Darby canine kidney cells (MDCK). As these cells proliferate, they form tight junctions analogous to those found in the outermost epithelium of human corneal tissue. The cells are cultured in cell culture inserts until they are confluent and fed with nutrient media for a period of 7 days. The test maferial can be applied pure or with varying degrees of dilution for a certain period. The test material is rinsed and 0.01% sodium fluorescein was applied for 30 minutes. The amount of sodium fluorescein that permeates through the cell junctions is collected, measured and calculated as% permeability or leak (amount of damage). In addition, cells can continue to be maintained for up to 5 days and fluorescein can be re-applied daily to measure the degree of cell recovery. The in vitro fluorescein leakage assay was used to evaluate the compositions of the invention as well as to compare their irritation potential with competitive comparison brands. In this test, a shampoo is typically tested in triplicate at a 5% dilution in water, applied topically to the MDCK monolayer for 30 seconds. The effect of the treatment is assessed as the% permeability of sodium fluorescein to the monolayer after the initial exposure and after a recovery period of 24 h. The results are expressed as% permeability of fluorescein leak through the cell layer. The compositions of this invention should be, preferably, a leakage permeability% of fluorescein through the cell layer of less than about 10%, and more preferably less than about 8%. Compositions with this level of fluorescein leakage are classified as having minimal to mild ocular iridium.

Assay in solubility of zein The solubility of zein provides a simple directional indication of softness and is widely used in the art to test the softness of both surfactant raw materials and shampoos. Zein is a protein (amino acid mixtures derived from corn), which swells and denatures in response to surfactants in a similar way to skin keratin proteins. This procedure was developed on the basis that while more zein is solubilized by a given surfacid composition under standardized test conditions, greater is the irritation of the composition. The solubility of zein is not intended as a replacement for clinical studies, or the more biologically based in vitro fluorescein leak assay, even when a reasonable correlation has been demonstrated. Therefore, the principle application for zein solubility is for initial classification where it provides a good prediction of potential irritation potential. Under the test conditions employed and described below, a solubility of zein of less than 1% is a good indicator of potentially mild compositions, while a solubility of zein greater than 1% is a good indication that the composition will be safe for the eyes.

APARA TO Analytical balance, 100 ml beaker, agitation bars, medium agitation plate, 10 ml syringe, 20 ml scintillation vials, conventional oven, set at 75 ° C.

PROCEDURE 1. Weigh 6.25 g of shampoo in a 100 ml beaker and dilute it to 50 g with DI water. 2. Mix the solution on a shaking plate @ 300 rpm (fix disc to 4 on the stir plate) until the solution looks uniform 0 the complete sample is dissolved. 3. Record the pH of the solution. 4. Remove 6 ml of solution using a syringe. 5. Filter the solution through a 0.45 micron syringe filter over a scintillation vial. 6. Cover the vial and mark it as white. A white is necessary to correct for any soluble material. 7. Add 2 g of zein to the remaining solution and equilibrate for 1 hour at constant agitation speed (300 rpm). After 10 minutes of agitation, if all or most of the zein is dissolved, add 1 g of additional zein. Keep adding more zein in increments of 1 g every 5-10 minutes until the undissolved zein floats in the solution. 8. After 1 hour of constant agitation, allow the solution to settle for 5 minutes. 9. Remove 6 ml of the supernatant solution using a syringe and filter it through a 0.45 micron syringe filter over a scintillation vial. 10. Cap the vial and mark it as a sample. 1 1. Perform non-voilafiles in both samples using a conventional oven set at 75 ° C. Allow the samples to dry overnight. 12. Calculate the percentage of dissolved zein.

CALCULATION% solubilized zein =% non-volatile sample -% non-volatile white In vitro test of wet and dry combing force As shown in the García y Dias document (Combability measurements on human hair, J. Soc. Cosmet. Chem., Vol 27 379-398 (1976)), incorporated by reference herein, the ease of combing can be measured instrumentally by monitoring the forces of friction that result as hair passes through a comb. These combing forces are measured as a function of the distance traveled through the loops. The parameters such as the maximum combing force, the average combing force and / or the combing energy can then be used to evaluate the performance. Product distinctions are easier to detect during wet combing experiments. The procedure listed below is specifically related to wet combing experiments, with a final section underlining method modifications which are used for dry combing.

Apparatus Stress test equipment (preferably an Instron equipped with a 500 g load cell, or alternatively a Diasfron Mini-Tensile Tester), 2 g standard loops, hard rubber combs and an "iníellifaucet".

Procedure Loop preparation: First the loops are deeply washed. Eight standard 2 g loops are used in the evaluation of each product. The sensitivity of styling experiments can be significantly improved through the use of damaged hair loops. The bleached loops can be used in the evaluation of conditioning effects of shampoo compositions. Sample application: 0.2 ml of product is applied to a 2 g loop. The product is left in contact with the hair for 1 minute. At the end of this time, the loop is rinsed for 30 seconds using standard tap water at 40 ° C and a flow rate of 2l / min. Instrumental conditions: The treated loops are manually pre-combed to remove any matting / obstacle inside the hair. The loops are then mounted on the instrument and combed at a speed of 101.6 cm / min (40 in / min). Seven combing curves are measured per loop. The first combing race is often longer than the others because it still contains a considerable contribution to disentangling. For this reason, the first combing curve is discarded. Any other combing curve which contains unusually alose spikes as a result of knot, obstacles, etc. they are also omitted. Calculations: From these combing curves, it is then possible to extract parameters such as the maximum combing force, the average combing force and / or combing energy. The maximum combing force is the highest load recorded during the experiment, the average energy is a value averaged between two predetermined points, while the combing energy is the energy under the curve. When using the Instron 5500, experimental conditions and generation of the calculated parameters can be obtained automatically by using the "COMBING2" method pre-set. Statistical analysis of data: The data is analyzed using the Tukey HSD test at the 95% confidence limit. Modifications to the procedure for dry combing: For dry combing, the looped loops are allowed to dry in the air and are conditioned overnight at 60% relative humidity. The dry combing experiments are performed in the same way as indicated above, except that the humidity during the experiment is also regulated at 60%.

In vitro silicone retention assay Silicone polymers, such as dimethicone and some amino functional silicones, can be extracted from loops treated with hair care formulations using organic solvents. Loops brought with reactive or crosslinked silicone resins may require chemical treatment, such as aminolysis with anhydrous amines, before silicone extraction is possible. Hexane is a good extractor for most silicone polymers from hair. However, if a simple loop extraction is to be used as a sample preparation for a variety of analyzes, including the measurement of ionic surfactants by mass spectrometry, chloroform is the solvent of choice. A heavy amount of hair is extracted twice with organic solvent using an ultrasonic bath to aid extraction. Extracts are combined, concentrated and analyzed by silicon using an inductively coupled plasma spectrometer (ICP) that has been standardized with a solution containing dimethicone, for which the silicon fraction is known. Apparatus: Atomic emission spectrometer of plasma coupled inductively (ICP-AES); wide-mouth jars, 248.82 g (8 oz); scissors; balance - analytical, accurate for ± 0.01 g; ultrasonic bath; Graduated cylinder - 50 mi, pipette, - class A, TD, 10 ml. Reagents: Hexane - spectrophotometric grade, chloroform - spectrophotometric grade, dimethicone - a siloxane polymer that contains 37.9 percent by weight of silicon. Procedure Loop Extraction: Two 2 g loops of hair that were brought with the same test shampoo composition were coried in approximately 3.81 cm (1.5 in) long pieces. These cut samples were mixed to make a composite sample and 1 .0 to 1.25 g of each was weighed in a jar of 248.82 g (8 oz). 50 ml of organic solvent was added to each jar and shaken to wet the hair. The jars are tightly capped and placed in an ultrasonic bath for 30 minutes. The solvent is then decanted in a clean jar and the solvent is allowed to evaporate in a hood. To perform a second extraction in duplicate, 50 ml of organic solvent is added to the hair in the original jar, it is capped and again placed in an ultrasonic bath for 30 minutes. This second sample is decanted in the jar containing the residue from the first extracfo and again allowed to evaporate in the hood. Sample preparation and standard: The residue of the combined extracts is dissolved in 10 ml of chloroform using sonication to aid in the removal of all the residue from the jar surfaces. A standard calibration solution is prepared by dissolving the dimethicone in chloroform, so that the concentration of silicon is at a level slightly higher than that expected in the sample. Spectrophotometric measurement: A 1 .0 mm centimeter pipe is installed in the ICP torch, which is used to analyze samples in organic solvent and the 251.6 nm line is selected for silicon analysis. The insfrumenfo is sequenced by sequentially aspirating a chloroform target and then the dimethicone standard. The samples are then aspirated and the concentration value of silico is recorded. Calculation: The micrograms (μg) of silicon per gram of hair are calculated from the following equation: μg silicon (10 ml sample solution) μg silicon / g hair = ml hair sample solution g To convert μg of silicon to silicone polymer as dimethicone: Dimethicone contains 37.9 weight percent silicon. μg dimethicone / g hair = μg silicon / g hair 37.9 100 Ease of in vitro panel testing of wet combing qualification order This test is a forced choice shared rating of the combing facility provided by a given set of shampoo compositions under in vitro conditions that are representative of normal use. Pureba uses human evaluation for ease of combing hair loops that have been treated with test and control compositions using a forced-choice rating system. The test provides a good indication of the comparative level of detangling benefits provided by a composition relative to well-defined control compositions or without composition (untreated).

Procedure Preparation of loops: First the loops are deeply washed. Standard 2 g loops are used in the evaluation of each product. The sensitivity of styling experiments can be significantly improved through the use of damaged hair loops. The bleached loops can be used in the evaluation of conditioning effects from shampoo composition. Sample application: 0.2 ml of product is applied to a 2 g loop. The product is styled in the hair with twenty runs over 20 seconds. At the end of this time, the loop is rinsed for 30 seconds using standard tap water at 40 ° C and a flow rate of 2 l / min. Hairstyle evaluations: Treated and still wet loops are pre-combed to remove any large matting / obstacle within the hair. A loop treated with each product under evaluation is marked blindly and suspended in a grid to create a set for comparison. A loop in the set is left untreated. Multiple combing panels comparing a set of treatments can be prepared with the order of random panel-to-panel treatments. Within each panel an individual then combs each loop and qualifies his hairstyle. For example, in a panel containing four loops, the subject would qualify the loop that exhibits the easiest hairstyle with a value of 1, while the loop that exhibits the most difficult hairstyle would have a value of 4. The multiple raters comb and qualify the loops within of each panel and its rating results are tabulated then. Statistical data analysis: Data are analyzed using the Tukey HSD test at the confidence limits of 90% and 95%.

In vitro tests as means to evolve optional ingredients The fluorescein leakage, zein solubility, wet comb and silicone deposition assays described above are also very useful for assessing the potential impact of optional ingredients on the performance of the composition and this way they classify which optional ingredients are suitable for inclusion.

For example, as will be shown in the examples below, a highly effective composition combining high softness (low ocular irritation potential) and excellent conditioning performance essentially consists of the alkyl ethoxy ether sulfate (> 3EO), betaine and hydroxysultaine surfactants in the proportions specified herein; a cationic cellulose polymer; a silicone insoluble in water, non-volatile; PEG-150 distearate; and an electrolyte, such as sodium chloride. Numerous optional and auxiliary ingredients of shampoos and esyetics can be included at low levels in this composition, for example, less than 5% by weight in ioíal. Most of these ingredients will be suitable for inclusion and are within the scope of the invention because they have negligible impact on the key properties of eye irritation and conditioning performance. Nevertheless, some ingredients may adversely affect the ocular irritation potential of the composition and even the conditioning performance, for example, alkyl sulfates and alkyl aryl sulfates used at more than a small percentage, solvents, high levels of anionic polymers. As long as the leakage permeability% of fluorescein through the cell layer remains less than 10%, (or alternatively the solubility of zeia is less than 1% in the in vitro assay of less preferred zein solubility) ) and the maximum styling force in the in-vitro wet combing test is below about 25 g force, preferably below 22 and most preferably below 20, the optional ingredient is suitable for inclusion.

EXAMPLES The following examples are shown as illustrations of the invention, the paticularities but are not intended in any way to limit its scope.

EXAMPLE 1 . This example illustrates the combination of softness and excellent conditioning performance of the present compositions.

Examples 1 A and 1 B, whose compositions are given in Table 1A were prepared as follows: Preparation of ei 1A (clear 2-in-1 composition) A container was charged with water. The Polymer JR 30M was dispersed in water by mixing at approximately 250 rpm, followed by cocamidoropil betaine. The resulting clear mixture was heated to about 60-63 C and PEG-150 distearate was added and mixed until dissolved. The heating was discontinued and cocamidoopyl hydroxysultaine was added, while stirring was maintained. Sodium lauryl ethoxy (3EO) was added and mixed until dissolved. At 50 ° C or less, the silicone microemulsion (DC2-1870HV) was added and mixed until dissolved. The remaining ingredients consisting of sodium citrate, preservatives, fragrance, dyes and citric acid to adjust the pH to about 6.5, were added sequentially and mixed until it was clear and uniform.

Preparation of E1 1 B (opaque 2-in-1 composition) A container with approximately 2/3 amounts of water was charged. Polymer JR 30M was dispersed in water by mixing at approximately 250 rpm followed by cocamidopropyl betaine. The resulting clear mixture was heated to about 60-63 C and Peg-150 distearate was added and mixed until dissolved. The heating was discontinued and cocamidopropyl hydroxysultaine was added while stirring was maintained. Sodium lauryl ethoxy (3EO) was added and mixed until dissolved. Although the surfactants were being mixed, Carbopol 980 was dispersed using the remaining water in a separate vessel using alpha agitation of approximately 700 rpm. This Carbopol paste was then added and mixed until it dispersed. At 50 ° C or less, a premix of mica and titanium dioxide was prepared and added with the silicone macroemulsion (DC 1786). The remaining ingredients consisting of preservatives, fragrance, dyes and sodium hydroxide to adjust the pH to about 6.5, were added sequentially and mixed until uniform.

Table 1A. a) as silicone The performance of Ej 1A and Ej 1 B in in vitro tests of softness, silicone deposition and wet combing are summarized in Table 1b and are also compared to several commercialized shampoo products that serve as comparative examples. These tests are described earlier in the METHODOLOGY OF EVALUATION section. The results in Table 1 b indicate that the compositions of the present invention which combine an alkyl ethoxy sulfate (EO> 3), a betaine and a hydroxysultaine in the claimed proportions with a non-volatile water-insoluble silicone, and include polymer cationic and optional but preferred thickening system, actually provide a gentle formulation with low potential for eye irritation and excellent hair conditioning properties.

Table 1 B C1 is L'Oreal Kids Fasí Dry 2-in 1 C2 is Salon Seleclives (varianle "Don'l fade on me") C3 is L'Oreal Extra Conditioning 2-in-1 The performance of Shampoo Ej 1A was also evaluated in a classroom test. A half-head saloon test was conducted on 39 children aged 3-8 with hair at least 7.62 cm (3 in) on the crown. The product was applied by the stylist and dried with evaluation of the father by attributes of wet stage and dry stage. In addition to this, the children were asked if they noticed a difference in the sides for combing / pulling, knotting and fragrance. Half of each child's head was washed with 1 A Shampoo while the other half was washed with a commercially available shampoo for children, C4. In evaluations by parents, it was found that Ej 1A is directionally easier to untangle wet and left hair less straight. It was perceived that Ej 1A was significantly softer and was also perceived as having a greater aroma. The children perceived a significant difference from side to side in combing / brushing.

EXAMPLE 2. This example demonstrates that a water-insoluble, non-volatile silicone provides better performance than a volatile silicone or water-soluble silicone, non-volatile in the present composition. Comparative examples C4 and C5, and Ej 2 whose compositions are given in Tables 2, were prepared by the procedure of Example 1A. These compositions differ only in the type of silicone that was used. C4 includes a volatile silicone (D5), C5 uses a water-soluble silicone (BIOSIL BASICS SPQ), while Ej 2 contains the non-volatile, water-insoluble silicone of the present invention.

The results in Table 2 demonstrate that the non-volatile water-insoluble silicone microemulsion delivers a higher level of conditioning to wet hair (lower maximum load and lower total energy) than a similar composition using either volatile silicone or a silicone soluble in water. Table 2 Note: a) as silicone EXAMPLE 3. This example compares a cationic cellulose polymer of the present invention with other types of cationic polymers. Comparative Examples C6 and C7 and Example 3, whose compositions are given in Table 3, were prepared by the method used in the Example 1 to with the appropriate substitution made for the Polymer JR 30M. The results in Table 3 indicate that when the preferred cationic cellulose polymer of the present invention is replaced by a cationic guar, the composition becomes ineffective and flocculates and loses its clarity. When the cationic cellulose is replaced by a synthetic cationic polymer, SALCARE, the composition also loses clarity. Example Ex 3 (cationic cellulose) was also compared to comparative example C7 (SALCARE-C60, a synthetic polymer comprising acrylamide and acrylamidopropyl-iorimonium chloride) in silicone deposition (in vitro test) as a wet combing facility (test of room) as described above in the METHODOLOGY SECTION. It is seen from the results in Table 3, that cationic cellulose not only provides a clear stable composition in the present invention, compared to the cationic synthetic polymer, but also silicon deposition is surprisingly higher, which translates in practice at a significant perceptible benefit in wet combability.

TABLE 3 EXAMPLE 4. This example illustrates the greatly improved thickening efficiencies by combining long chain fatty esters of propylene glycol and electrolytes. Examples 4A to 4H, whose compositions are given in Tables 4, were prepared by the methods described in Example 1. The example compositions in Table 4B demonstrate unexpected synergistic thickening at low levels of inclusion in compositions having a low total concentration of surfactants of the type and in the proportions specified in the present invention (compare Ex 4F-4H with Ex 4A-4E ). The stability of these clear compositions has been demonstrated by storage at 49 ° C for 12 weeks.

TABLE 4 A 1 fifteen 00 TABLE 4B EXAMPLE 5. This example illustrates how the level of ethoxylation of the ethoxy sulfate alcohol and the ratio of ethoxy sulfate alcohol to betaine and total hydroxysultaine are critical for the smoothness and deposition of silicone. Examples 5 and comparative C8 and C9, whose compositions are given in Table 5, were prepared according to the methods of Example 1. A comparison of Ex 5 with C9 shows that when the ratio of ethoxy sulfate alcohol to betaine and total hydroxysultaine is greater than the preferred range, the in vitro softness and the level of silicone deposition fall precipitously. In this example, the drop in softness occurs at a tofal level of 10% ethoxyl sulfate. Higher levels of ethoxysulfafo can be present when the average degree of eryoxylation is greater than 3, provided that the proportion of this component to the photoallergic is within the required range. Experience has shown that when the solubility of zein exceeds approximately 1% as measured by the procedure described in the METHODOLOGY section., the composition does not have adequate softness. Similarly, a comparison of Ex 5 with comparative example C8 indicates that when the degree of ethoxylation of the ethoxy sulfate alcohol is less than 3, the solubility of zein exceeds 1% and the composition is not greater than the objective smoothness profile .

TABLE 5 EXAMPLE 6. This example illustrates the synergy in silicone deposition that arises when combining the surfactant of betaine and hydroxysultaine in relation to any component used alone. Comparative examples C10 and C1 1 and Example 6, whose compositions are given in Table 6, were prepared using the procedure for Example 1. The silicone deposition was measured by the in vitro silicone deposition test and the wet combability was measured by the wet comb panel test both described above in the EVALUATION METHODOLOGY section. The results in Table 6 clearly demonstrate the surprising synergy in silicone deposition on hair that arises when the betaine and hydroxysultaine surfactants are combined in the proportions specified in the present invention. Even more importantly, this synergism also results in a highly significant benefit in the ease of wet combing (untangled) provided by the synergistic mixture of betaine and hydroxysultaine in the proportions described herein (see last row of Table 6). ). Furthermore, as can be seen from a comparison of silicone deposition provided by Ex 6 with comparative example C9 (shown in Table 5), this synergy in deposition is lost when the ratio of alkyl ether sulfate to betaine plus hydroxysultaine tofal is outside the required combination ratio specified in the present invention.

TABLE 6 EXAMPLE 7. This example illustrates a shampoo composition containing a mixture of optional ingredients that does not compromise the potential for low eye irritation or conditioning benefits of the shampoo.

TABLE 7 Shampoo composition EXAMPLE 8. This example illustrates shampoo compositions containing various proportions of surfactane mixtures of alkyl eioxy sulfate, betaine and hydroxysultaine.

TABLE 8 Shampoo composition 15 ^ 4

Claims (10)

1 . An aqueous shampoo composition having excellent detangling and conditioning properties, comprising: (i) an alkyl efoxy sulfafo surfactant, wherein the alkyl group has an average of 12-16 carbon atoms and an ethoxylation degree of at least 3, (ii) from 2% to 7% of a betaine surfactant, (iii) from 2% to 7% of a hydroxysulfaine surfactant, (iv) from 0.1% to 5% of a water-insoluble, non-volatile silicone , (v) at least 70% by weight of water; wherein the weight ratio of the betaine surfactant to the hydroxysultaine surfactant is in the range of 0.5 to 1.5, and the weight ratio of the alkyl ethoxy sulfate surfactant to the sum of the weights of betaine surfactant and hydroxysultaine surfactant it is in the range from 0.5 to 1.5. The composition according to claim 1, wherein the alkyl ethoxy sulfate surfactant is present at a level from 5% to 10% by weight of the composition. 3. The composition according to claim 1, wherein the betaine is selected from the group consisting of lauryl betaine, coco betaine, cocoamidobetaines, cocoamidopropyl beiraine, oleyl betaine, caprylamidopropyl betaine, lauramidopropyl betaine, isosphearylamidopropyl beine, coconut imidoazolinium befain and mixtures thereof. 4. The composition according to claim 1, wherein the hydroxysultaine is selected from the group consisting of C8-C? 8 alkylamidopropyl hydroxysultaine, lauryl hydroxysultaine, seboamidopropl hydroxysultaine, erucamidopropyl hydroxysultaine and a C8-C18 alkyl ether amidopropyl hydroxysultaine and mixtures thereof. same. The composition according to claim 1, wherein the water-insoluble, non-volatile silicone is a microemulsion. The composition according to claim 1, wherein the non-volatile, water-insoluble silicone has a viscosity greater than 10,000 CST and is selected from the group consisting of dimethicone, dimethiconol, a dimethicone or cross-linked dimethiconol, a gum silicon, an organomodified silicone and mixtures thereof. The composition according to claim 1, wherein the weight% ratio of the betaine surfactant to the hydroxysultaine surfactant is in the range of 0.75 to 1.25. The composition according to claim 1, wherein the weight% of the alkyl ethoxy ether sulfate to the sum of the betaine surfactant and the hydroxysuitaine surfactant is in the range of 0.7 to 1.3. 9. The composition according to claim 1, further comprising a cationically modified cellulose. 10. The composition according to claim 9, wherein the cationically modified cellulose is selected from Polyquaternium-10. eleven . The composition according to claim 1, further comprising a polyethylene glycol fatty diester selected from the group consisting of PEG 120 methyl glycoside dioleate, PEG-150 pentaerythrityl, PEG-75 dioleate, PEG-150 distearate and mixtures thereof. same. The composition according to claim 1, wherein the polyethylene glycol fatty diester is PEG 150 distearate. The composition according to claim 1, further comprising an electrolyte selected from the group consisting of sodium and sodium citrate, sodium sulfate, sodium bromide, sodium iodide and mixtures thereof. The composition according to claim 1, wherein the composition has either a solubility of zein of less than 1% as measured by the in vitro assay of zein solubility or a fluorescein leakage permeability% less than 10% as measured by the fluorescein leak test; and wherein the composition has a wet combing force of less than about 25 grams force as measured by in vitro wet and dry combing strength testing. 15. The composition according to claim 1, which further comprises cosmetic and auxiliary shampoo ingredients selected from the group consisting of perfumes, aperollers and opacifiers, interference pigments, dyes, colorants, sense-sensing agents, preservatives, thickeners, emulsion stabilizers and mixtures thereof. 16. The composition according to claim 1, further comprising skin and hair benefit agents selected from the group consisting of cholesterol, ceramides and pseudoceramides, non-silicone hair conditioning agents, humectanols, antimicrobial agents, sunscreens, chelating agents, botanical extracts and mixtures thereof. 17. An aqueous shampoo composition having excellent detangling and conditioning properties, comprising: i) from 5% to 12% of an alkyl ethoxy sulfate, wherein the alkyl group has an average of 12-16 carbon atoms and the degree of ethoxylation is at least 3. ii) from 2% to 7% of a betaine surfactant selected from the group consisting of alkylamido betaine, alkyl betaine and alkyl amidoalkyl betaine, iii) from 2% to 7% of an alkylamido hydroxysultaine , iv) from 0.05% to 2% of a cationically modified cellulose, v) from 0.1% to 5% of a water-insoluble silicone, non-volatile, vi) from 0.02% to 1.0% of a polyethylene glycol fatty diester, vii) from 0.1% to 1.0% of an electrolyte selected from the group consisting of sodium chloride, sodium citrate, sodium sulfate, sodium bromide, sodium iodide and mixtures thereof, viii) at least 70% in weight of water; wherein the weight ratio of betaine surfactant to alkylamido hydroxysultaine is in the range of 0.5 to 1.5, and the weight ratio of alkyl ethoxy ether sulfate to the sum of the weights of surfactant components of betaine and alkylamido hydroxysultaine it is in the range from 0.5 to 1.5; wherein the shampoo composition has either a solubility of zein of less than 1% as measured by the in vitro test for solubility of zein or a% fluorescein leakage permeability of less than 10% as measured by the test of fluorescein leak; and wherein the composition has a wet combing force of less than about 25 grams force as measured by in vitro wet and dry combing strength testing. 18. A method for applying shampoo to children's hair to achieve clean, knot-free and conditioned hair without irritation of the eyes, said method comprising the step of treating the hair with the shampoo composition according to claim 1.