WO1993015711A1

WO1993015711A1 - Shampoo premix compositions

Info

Publication number: WO1993015711A1
Application number: PCT/US1993/000802
Authority: WO
Inventors: Everett Junior Inman
Original assignee: The Procter & Gamble Company
Priority date: 1992-02-10
Filing date: 1993-02-01
Publication date: 1993-08-19
Also published as: JPH07503731A; CN1078631A; AU3598493A; TW266157B; EP0625040A1; CA2129129A1; MA22789A1

Abstract

Disclosed are shampoo premix compositions, shampoo compositions made therefrom, and methods of making such premixes and shampoos thereof. The shampoo premix comprises alkyl ethoxylated sulfate surfactant, a specific type of imidazolinium amphoteric surfactant, polyethylene glycol glyceryl fatty ester nonionic surfactant, a suspending agent that is solubilized and recrystallized in the premix composition at pH less than 7.0, and a sufficient amount of a pH adjustor, i.e., an acid, to adjust pH to less than 7.0 during recrystallisation of the composition. The shampoo premix hereof can be used as an end product, or used as a base from which to add additional shampoo ingredients to form a finished shampoo formulation. The shampoo premix hereof can provide mild, good lathering, pearlescent compositions. The premix compositions hereof are particularly useful for use in conditioning shampoo compositions containing silicone conditioning agents.

Description

SHAMPOO PREMIX COMPOSITIONS

TECHNICAL FIELD

The present invention is related to shampoo premix composi¬ tions as well as finished shampoo compositions comprising the premix and additional shampoo components and/or additional levels of components also included in the premix. The present invention also relates to a method of making said shampoo premix and shampoo compositions.

BACKGROUND OF THE INVENTION

Mild shampoo compositions which provide low irritation to the skin are highly desirable. Conventional shampoos contain high levels of harsh anionic surfactants. These materials can penetrate the skin and destroy its integrity. This results, at the very least, in rough skin, and can ultimately lead to red, irritated skin. Ideal shampoo compositions should provide sufficient lathering and cleaning benefits to cleanse the hair while at the same time causing little or no irritation to the skin. This is particularly essential for shampoo compositions used on babies, small children, or adults with dry or sensitive skin. Furthermore, children can have difficulty if they get shampoo in their eyes during the hair washing or rinsing process. Hence, mild shampoo compositions which also provide reduced eye sting are particularly desirable for use on children.

Mild shampoo compositions, in general, are well known in the art having been taught in, for example, European Patent Application 0250181, published December 23, 1987; U.S. Patent 4,578,216, Fujii et al., issued March 25, 1986; U.S. Patent 4,726,915, Verdicchio, issued February 23, 1988; U.K. Patent Specification 1,508,929, published April 26, 1978; European Patent Application 0160269, published November 6, 1985; U.S. Patent 4,435,300, Guth et al., issued March 6, 1984; U.S. Patent 4,426,310, Vernunica, issued January 17, 1984; U.S. Patent 3,950,417, Verdicchio et al . , issued April 13, 1976; U.S. Patent 4,443,362, Guth et al . , issued April 17, 1984; U.S. Patent 4,654,207, Preston, issued March 31, 1987; U.S. Patent 4,851,154, Grollier et al . , issued July 25, 1989; U.S. Patent 4,292,212, Melby, issued September 29, 1981; and U.S. Patent 4,329,334, Su et al., issued May 11, 1982. These references teach the use of a wide variety of surfactant combinations to achieve mildness. These surfactants include mild anionic surfactants, such as ethoxylated alky! sulfates, a photeric surfactants, nonionic surfactants, and various combinations thereof.

One well-known mild shampoo is Johnson's Baby Shampoo (John¬ son & Johnson). This product contains high levels of nonionic surfactant (PEG-80 Sorbitan Laurate), which is known to provide reduced eye sting. The formula is supplemented by some other mild surfactants to boost its cleaning performance (betaine, ethoxy¬ lated alkyl sulfate, an i idazoline-derived amphoteric, and an ethoxylated alkyl carboxylate) .

The formulation of such mild shampoo compositions, however, generally is an exercise in efficacy and mildness trade-offs, with the resulting composition providing either good cleaning and lathering benefits, or mildness and low eye or skin irritation benefits. In fact, Johnson's Baby Shampoo, while being mild to the skin and eyes, is not a very good cleaner and its lathering profile is not particularly robust.

Hence, it is an object of the present invention to provide a mild shampoo composition which provides good in-use character¬ istics such as lathering, both in terms of abundance of lather and lather stability, and cleaning, while at the same time providing skin mildness benefits, and preferably low eye sting benefits as well. It is also preferable that the shampoo have a pleasing aesthetic appearance which also referred to as pearlescence, in addition to providing the above characteristics.

Also desirable in state of the art shampoo compositions are conditioning benefits inherent in the shampoo compositions. Such products are sometimes termed two-in-one shampoos, meaning the compositions include both cleaning and conditioning ingredients in the same product. Such compositions are difficult to formulate because the cleaning ingredients, in general, tend to be incompat¬ ible with the conditioning ingredients. One highly successful solution to this dilemma has been to use dispersed insoluble non-volatile silicone materials together with certain suspending agents for the silicones in shampoo compositions. Such technology is taught in U.S. Patent 4,704,272, Oh et al . , issued November 3, 1987; U.S. Patent 4,741,855, Grote et al., issued May 3, 1988; and U.S. Patent 4,788,006, Bolich et al., issued June 5, 1984. Another benefit of certain of the suspending agents referred to in these patents is their ability to improve the aesthetic appearance of shampoos by adding pearlescence. However, one problem with the use of silicone materials to deliver hair conditioning from shampoo compositions is that such materials, in general, tend to suppress lathering of the composition. If silicones are used with robust high-lathering surfactants, such as most anionic surfactants, lathering may not be unduly affected. However, if such materials are used with milder, less robust lathering surfactants, lathering may well be suppressed to an unacceptable level from a consumer standpoint.

Hence, it is a further object of the present invention to provide a mild shampoo composition which provides excellent lathering and cleaning benefits while at the same time providing hair conditioning benefits through the use of dispersed insoluble non-volatile silicone conditioning agents.

Alkyl sulfate surfactants tend to be harsh to the skin and are therefore not conducive to formulating mild shampoos. Unfor¬ tunately, in the absence of such alkyl sulfates it is difficult to get the suspending agent into the shampoo in crystalline form. It is when the suspending agent is present in the shampoo in the form of a crystalline network that it is effective in suspending the silicone composition.

The presence of volatile solvents, such as those typically present in perfumes, can under certain circumstances assist in the formulation of shampoos with effective crystalline suspending agent networks. However, that undesirably involves adding the perfume at a stage wherein the composition is subject to high temperatures, i.e., when the suspending agent is being solubilized prior to the subsequent step of cooling it to cause the suspending agent to recrystallize as an effective suspending agent network. Exposure of such volatile components to high temperatures can raise undesirable safety and aesthetic issues.

Improved mild shampoos, i.e., shampoos that are mild and which have both good cleaning and robust lathering have been proposed in U.S. Serial No. 07/681,015* filed April 5, 1991, E. J. Inman, "Mild Shampoo Compositions", wherein particular combina¬ tions of imidazolinium-type amphoteric surfactants and amino- alkanoate and/or i inodialkanoate amphoteric surfactants are required. These compositions can contain suspending agents and dispersed insoluble silicone. Similar compositions are also described in U.S. Serial No. 07/681,016?* iled April 5, 1991, E. J. Inman, "Hair Conditioning Shampoo Compositions With Silicone Conditioning Agent". Whereas these compositions can provide excellent performance, it remains desirable to provide mild, good lathering, good cleaning shampoo compositions which can be pro¬ cessed into shampoos containing highly effective crystalline networks for suspension of silicone without requiring the presence of volatile solvents and/or iminodialkanoate and/or aminoalkanoate surfactants, in addition to the imidazolinium-type surfactants (e.g., cocoamphoglycinate) disclosed therein.

These and other objects will become readily apparent from the detailed description which follows.

Unless otherwise indicated, all percentages are calculated by weight of the total composition and all ratios are calculated on a weight basis.

The compositions and processes herein can comprise, consist essentially of, or consist of any of the critical and optional elements and steps described in this application.

SUMMARY OF THE INVENTION

In one aspect of the invention, the premix compositions hereof comprise:

(^♦Equivalent to W092/17154 publ. 15.10.92; **WO92/04882 publ. 02.04.92) (a) at least about 5%, by weight, of alkyl ethoxylated sulfate anionic surfactant;

(b) at least about 6%, by weight, of an amphoteric surfac¬ tant of the formula:

wherein R¹ is C₈-C₂₂ alkyl or alkenyl, R² is hydrogen or CH₂C0₂M, R³ is CH₂CH₂0H or CH₂CH₂0CH₂CH₂C00M, R⁴ is hydrogen, CH₂CH₂0H, or CH₂CH₂0CH₂CH₂C00M, Z is C0₂M or CH₂C0₂M, n is 2 or 3, and M is hydrogen or a cation;

(c) from about 2% to about 15%, by weight, of a suspending agent recrystallized in said premix composition; and

(d) from about 30% to about 70%, preferably about 30% to about 60%, water; wherein said premix has a weight ratio of (a):(b) of about 1:3 to about 3:1, a weight ratio of (c) to total surfactant present of from about 1:1 to about 1:10, and a weight ratio of (c):(d) of about 1:2 to about 1:15, and said premix composition is substantially free of alkyl sulfate anionic surfactant.

Preferred shampoo premixes for use herein comprise alkyl ethoxylated anionic surfactant, polyethylene glycol glyceryl fatty ester nonionic surfactant, and amphoteric surfactant, and a suspending agent which is present in the premix in solubilized form at an elevated temperature and then crystallized to form a crystalline network by cooling the solution at pH preferably below 7.0 (referred to herein as "recrystallized" suspending agent). As above, the premix composition is substantially free of alkyl sulfates.

The present invention also provides preferred premix compo¬ sitions comprising:

(a) at least about 1%, by weight, preferably at least about 5%, of alkyl ethoxylated sulfate anionic surfactant; (b) from about 3% to about 15%, by weight, of polyethylene glycol glyceryl fatty ester nonionic surfactant;

(c) from about 3% to about 30%, by weight, of an amphoteric surfactant of the formula:

wherein R¹ is C₈-C₂₂ alkyl or alkenyl, preferably C₁₂-C₁₆, R² is hydrogen or CH₂C0₂M, R³ is CH₂CH₂0H or CH₂CH₂0CH₂CH₂C00M, R⁴ is hydrogen, CH₂CH₂0H, or CH₂CH₂0CH₂CH₂C00M, Z is C0₂M or CH₂C0₂M, n is 2 or 3, preferably 2, and M is hydrogen or a cation;

(d) from about 2% to about 15%, by weight, of a recrystallized suspending agent; and

(e) from about 30% to about 70%, by weight, preferably about 30% to about 60%, water; wherein said premix composition is substantially free of alkyl sulfate anionic surfactant, said suspending agent is preferably recrystallized in said premix composition at a pH of less than 7.0, and preferably said premix has a weight ratio of (a):(c) of about from 1:5 to about 3:1, a weight ratio of (d):total surfac¬ tant of about 1:1 to about 1:10, and a weight ratio of (d):(e) of about 1:2 to about 1:15.

In a particularly preferred embodiment, the premix composi¬ tion comprises:

(a) from about 7% to about 12% of said alkyl ethoxylated sulfate anionic surfactant;

(b) from about 5% to about 12%, preferably from about 8% to about 10%, of said polyethylene glycol glyceryl fatty ester nonionic surfactant, said nonionic surfactant having the formula:

RC(0)0CH₂CH(0H)CH₂(0CH₂CH₂)_n0H wherein n is from about 20 to about 100, and RC(0) is an ester wherein R is an aliphatic radical having from about 9 to about 17 carbon atoms; (c) from about 12% to about 20%, more preferably from about 14% to about 18%, by weight, of said amphoteric surfac¬ tant, said amphoteric surfactant preferably having R¹ that is C₁₂-C₁₆ alkyl or alkenyl, n is 2, and is a monocarboxylate or a dicarboxylate, or a mixture thereof;

(d) from about 7% to about 12%, by weight, more preferably from about 8% to about 10% of said suspending agent; and

(e) from about 45% to about 55% water, preferably from about 45% to about 52%.

The present invention also provides shampoo compositions comprising shampoo premixes, as described above, further comprising: additional levels of the required surfactants or optionally other surfactants, though preferably the shampoo remains substantially free of alkyl sulfate or other ingredients that are harsh to the skin; conditioning agents, such as the preferred insoluble, nonvolatile silicone; foam boosters, preferably polyquaternium 10 or other mild-to-the-skin, non-amide foam boosters; color solutions; perfumes; preservatives; or other ingredients useful in shampoo composition; or mixtures thereof.

The present invention also provides a method for making shampoo premix compositions comprising the steps of: (i) preparing a solution comprising:

(a) at least about 5%, by weight, of alkyl ethoxylated sulfate anionic surfactant;

(b) at least about 6%, by weight, of amphoteric surfac¬ tant having the formula

wherein R¹ is C₈-C₂₂ alkyl or alkenyl, R² is hydrogen or CH₂C0₂M, R³ is CH₂CH₂0H or CH₂CH0CH₂CH₂C00M, R⁴ is hydrogen, CH₂CH₂0H, or CH₂CH₂0CH₂CH₂C00M, Z is C0₂M or CH₂C0₂M, n is 2 or 3, and M is hydrogen or a cation; and (c) from about 30% to about 70%, by weight, water; and (ii) adding to the solution from about 2% to about 15%, by weight of the premix, of a suspending agent wherein said solution is heated and said suspending agent is provided in solubilized form; and cooling said composition to provide said suspending agent in crystalline form; wherein said premix has a weight ratio of (a):(b) of from about 1:3 to about 3:1, a weight ratio of (c) to total surfactant of from about 1:1 to about 1:10, and a weight ratio of said sus¬ pending agent:water of about 1:2 to about 1:15, said premix composition is prepared substantially free of alkyl sulfate anionic surfactant, and the pH of said solution is preferably reduced to below 7.0 prior to providing said suspending agent in crystalline form.

In another aspect of the invention, provided is a process for making a preferred premix comprising the steps of: (i) preparing a solution comprising:

(b) from about 3% to about 15%, by weight, of poly¬ ethylene glycol glyceryl fatty ester nonionic surfactant;

(c) from about 3% to about 30%, by weight, of an amphoteric surfactant of the formula;

wherein R¹ is C₈-C₂₂ alkyl or alkenyl, R² is hydrogen or CH₂C0₂M, R³ is CH₂CH₂OH or CH₂CH0CH₂CH₂C00M, R⁴ is hydrogen, CH₂CH₂0H, or CH₂CH₂0CH₂CH₂C00M, Z is C0₂M or CH₂C0₂M, n is 2 or 3, and M is hydrogen or a cation; and

(d) from about 30% to about 70%, by weight, preferably from about 30% to about 60%, water;

(ii) adding to the solution from about 2% to about 15%, by weight of the premix, of a suspending agent wherein said solution is heated and said suspending agent is provided in solubilized form; and cooling said composition to provide said suspending agent in crystalline form; wherein the pH of said solution is preferably adjusted to pH less than 7.0 prior to said cooling step, and said premix composition is prepared substantially free of alkyl sulfate anionic surfactant.

The invention, including preferred embodiments thereof, is described in more detail in the Detailed Description of the Invention, which follows.

DETAILED DESCRIPTION OF THE INVENTION

The essential as well as certain preferred and optimal components of the compositions of the present invention are described below.

Alkyl ethoxylated sulfate surfactants are well known in the art. They typically have the formula R0(C2H40)_XS03M, wherein R is alkyl or alkenyl of from about 8 to about 24 carbon atoms, x is 1 to 12, and M is a water-soluble cation such as ammonium, an alkali metal (e.g., sodium, potassium) alkali earth metal, and tri- ethanola ine. Useful alkyl ethoxylated sulfates are condensation products of ethylene oxide and monohydric alcohols having from about 8 to about 24 carbon atoms. Preferably, R has from about 10 to about 18 carbon atoms. The alcohols can be derived from fats, e.g., coconut oil or tallow, or can be synthetic. Lauryl alcohol and straight chain alcohols derived from coconut oil are preferred herein. Such alcohols are reacted with from about 1 to about 12, preferably from about 2 to about 6, and especially about 3, molar proportions of ethylene oxide and the resulting mixture of molecu¬ lar species having, for example, an average moles of ethylene oxide per mole of alcohol within the above limits, is sulfated and neutralized.

Specific examples of alkyl ethoxylated sulfates which may be used in the present invention are sodium and/or ammonium salts of coconut alkyl triethylene glycol ethoxylated sulfate, tallow alkyl triethylene glycol ethoxylated sulfate, and tallow alkyl hexaoxy- ethylene sulfate. Typically the alkyl ether sulfates will com¬ prise a mixture of individual compounds, said mixture having an average alkyl chain length of from about 12 to about 16 carbon atoms and an average degree of ethoxylation of from about 2 to about 6 moles of ethylene oxide, especially about 3. Especially preferred are narrow range alkyl ethoxylate sulfates such as those having ethoxylation levels primarily in the range of 1 to about 6, especially about 3. Polyethylene Glycol Glyceryl Fatty Ester Nonionic Surfactant

Polyethylene glycol glyceryl fatty ester nonionic surfactant, i.e., PEG glyceryl fatty ester, is a critical element of preferred premixes, shampoos, and processes hereof. They will generally have a degree of polymerization of from about 5 to about 200, and the fatty ester of the surfactant will have an aliphatic hydro- carbyl radical of from about 8 to 20 carbons. The preferred PEG glyceryl fatty esters will generally be of the formula:

0 u RC0CH₂CH(0H)CH₂(0CH₂CH₂)_n0H wherein n is from about 5 to about 200, preferably from about 20 to about 100, more preferably from about 30 to about 85, and

RC(0)- is an ester wherein R comprises an aliphatic radical having from about 7 to 19 carbon atoms, preferably from about 9 to 17 carbon atoms, more preferably from about 11 to 17 carbon atoms, most preferably from about 11 to 14 carbon atoms.

Suitable glyceryl fatty ester portions of these surfactants include glyceryl cocoate, glyceryl tallowate, glyceryl palmate, glyceryl stearate, glyceryl laurate, glyceryl oleate, glyceryl ricinoleate, and glyceryl fatty esters derived from triglycerides, such as palm oil, almond oil, and corn oil.

Preferred glyceryl esters include glyceryl tallowate and glyceryl cocoate.

Suitable surfactants of this class are commercially available from Sherex Chemical Co. (Dublin, Ohio, USA) under their Varonic^® LI line of surfactants. These include, for example, Varonic LI 48 (polyethylene glycol (n=80) glyceryl tallowate, alternately referred to as PEG 80 glyceryl tallowate), Varonic LI 2 (PEG 28 glyceryl tallowate), Varonic LI 420 (PEG 200 glyceryl tallowate), and Varonic LI 63 and 67 (PEG 30 and PEG 80 glyceryl cocoates), and from Croda, Inc. (New York, New York, USA) under their Crovol^® line of materials, such as Crovol A-40 (PEG 20 almond glyceride, Crovol A-70 (PEG 60 almond glyceride), Crovol M-40 (PEG 20 maize glyceride), Crovol M-70 (PEG 60 maize glyceride), Crovol PK-40 (PEG 12 palm kernel glyceride), and Crovol PK-70 (PEG-45 palm kernel glyceride). Especially preferred are onotallowate and cocoate fatty ester derivatives of polyethylene glycol, or mix¬ tures thereof, particularly materials such as PEG 82 glyceryl monotallowate and PEG 30 glyceryl cocoate, and mixtures thereof. Imidazoliniurn-Type Amphoteric Surfactant

The imidazolinium-type amphoteric surfactant hereof can be depicted by Formula I:

R³

R¹C0N(CH₂)_nN I+-CH₂Z (I)

R⁴ R² wherein R¹ is C₈ - C₂₂ alkyl or alkenyl, preferably C₁₂-C₁₆, R² is hydrogen or CH₂C0₂M, R³ is CH₂CH₂0H or CH₂CH₂0CH₂CH₂C00M, R⁴ is hydrogen, CH₂CH₂0H, or CH₂CH₂0CH₂CH₂C00M, Z is C0₂M or CH₂C0₂M, n is 2 or 3, preferably 2, M is hydrogen or a cation, such as alkali metal, alkaline earth metal, or ammonium.

Suitable materials of this type are marketed under the tradena e MIRANOL and are understood to comprise a complex mixture of species, and can exist in protonated and non-protonated species depending upon pH with respect to species that can have a hydrogen at R². The amphoteric surfactant hereof can be derived via an imidazoliniurn intermediate, and therefore can be referred to as "imidazolinium-type" amphoteric surfactants. However, it will be recognized by those in the art that the amphoteric surfactant hereof needn't necessarily be derived via an imidazolinium.

Preferred amphoteric surfactants of Formula I are onocar- boxylates and dicarboxylates. Examples of these materials include cocoamphocarboxypropionate, cocoamphocarboxy propionic acid, cocoamphocarboxyglycinate (alternately referred to as cocoa pho- diacetate), and cocoamphoacetate.

Specific commercial products providing the imidazoliniurn derivative component of the present compositions include those sold under the trade names MIRANOL C2M CONC. N.P., MIRANOL C2M CONC. O.P., MIRANOL C2M SF, MIRANOL CM SPECIAL (Miranol, Inc.); ALKATERIC 2CIB (Alkaril Chemicals); AMPHOTERGE -2 (Lonza, Inc.); MONATERIC CDX-38, MONATERIC CSH-32 (Mona Industries); REWOTERIC AM-2C (Rewo Chemical Group); and SCHERCOTERIC MS-2 (Scher Chemicals) . Suspending Agent

Suspending agents useful in the present compositions include those which can exist in the compositions hereof in crystalline form. However, in general, any suspending agent useful for suspending nonvolatile, insoluble silicone fluids and/or particu- late matter (such as particulate antidandruff agents) can be used. Preferred suspending agents are acyl derivatives and amine oxides, especially acyl derivatives, which can be solublized in the shampoo premix solution and then be recrystallized upon cooling. These materials will comprise long chain (e.g., C₈-C₂₂ preferably C₁₆-C₂₂) aliphatic groups, i.e., long chain acyl derivative materials and long chain amine oxides, as well as mixtures of such materials.

In addition to providing a network to support insoluble materials, the suspending agents hereof can also impart pearlescence to the compositions. Whereas it is preferred to include insoluble materials, such as silicone conditioning agents and particulate matter (e.g., antidandruff agents) into the compositions, it is also contemplated that this invention to compositions containing the suspending agents hereof without also containing insoluble materials that need suspending. Such compositions can still benefit by combining mildness and good cleaning and lathering in combination with improved aesthetic appearance, i.e., pearlescence. Examples of suitable suspending agents are described in U.S. Patent 4,741,855, Grote and Russell, issued May 3, 1988, incorpo¬ rated herein by reference. Suitable suspending agents for use herein include ethylene glycol esters of fatty acids preferably having from about 14 to about 22 carbon atoms, more preferably 16-22 carbon atoms. More preferred are the ethylene glycol stearates, both mono and distearate, but particularly the di- stearate containing less than about 7% of the mono stearate. Other suspending agents found useful include alkanol amides of fatty acids, preferably having from about 16 to about 22 carbon atoms, more preferably about 16 to 18 carbon atoms. Preferred alkanol amides are stearic monoethanolamide, stearic diethanol- amide, stearic 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); glyceryl esters (e.g., glyceryl distearate) and long chain esters of long chain alkanol amides (e.g., steara ide diethanolamide distearate, stearamide monoethanolamide stearate). 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, may be used as suspending agents.

Suspending agents also include long chain amine oxides such as alkyl (C₁₆-C₂₂) dimethyl amine oxides, e.g., stearyl dimethyl amine oxide. If the compositions contain an amine oxide or a long chain acyl derivative which is a surfactant, the suspending function could also be provided by such amine oxide or acyl derivative, provided at least a portion of them are present in crystalline form, and additional suspending agent may not be needed.

Other long chain acyl derivatives that can be used include N,N-dihydrocarbyl amido benzoic acid and soluble salts thereof (e.g., Na and K salts), particularly N,N-di(hydrogenated) C₁₆, C₁₈ and tallow amido benzoic acid species of this family, which are commercially available from Stepan Company (Northfield, Illinois, USA).

The suspending agent serves to assist in suspending the silicone material or other particulate matter in shampoo compositions hereof, and may give pearlescence to the product.

The suspending agent can be incorporated into the shampoo premixes hereof by solubilizing it into a solution containing the above described ingredients. The suspending agent is then re¬ crystallized, typically by cooling the solution to a temperature sufficient to induce crystallization. In order to facilitate this, it is highly preferred that the pH of the solution be below 7.0. Preferably the pH is adjusted to levels of from below 7.0 to about 6.0, more preferably from about 6.0 to about 6.5. The pH of the solution, unadjusted, will normally be higher than that, and can be reduced by addition of acids according to known techniques for pH adjustment. Preferably, the pH is adjusted to below pH 7.0 prior to solubilizing the suspending agent, as this can facilitate more rapid solubilization. Suitable pH adjustors include hydro¬ chloric acid, citric acid, sulfuric acid, etc., preferably hydro¬ chloric acid and citric acid. Water

The shampoo premixes hereof will also contain water, typically from about 30% to about 70%, by weight, of the premix, preferably from about 30% to about 60%, more preferably from about 40% to about 55%, most preferably from about 45% to about 52%.

The premix and shampoo compositions hereof are substantially free of alkyl sulfate surfactants. It is recognized that there will generally be some alkyl sulfate present as a result of it being present in commercially available alkyl ethoxylated sulfate raw materials. For purposes hereof, to be substantially free of alkyl sulfate the premix composition and shampoo compositions hereof should have an alkyl sulfate:alkyl ethoxylated sulfate weight ratio of no more than about 0.35 (preferably no more than about 0.30, more preferably no more than about 0.25) for average ethoxylate levels of 2.5 and higher. For alkyl ethoxylated sulfate with an average ethoxylate level of less than 2.5, the ratio should be no more than about 0.40, preferably no more than about 0.5, more preferably no more than about 0.30, most prefer¬ ably no more than about 0.25. It is preferred that no additional amount of alkyl sulfate be added other than that which occurs inherently with the alkyl ethoxylated sulfate. The use of narrow range ethoxylates to lower the alkyl sulfate.-alkyl ethoxylated sulfate weight ratio is preferred. "Narrow range ethoxylate" refers to alkyl ethoxylated sulfate surfactants that have been processed to reduce alkyl sulfates and optionally alkyl ethoxy¬ lated sulfates outside of the desired range of ethoxyulation. The use of narrow range ethoxylates can be used to lower the alkyl sulfate:alkyl ethoxylated sulfate weight ratio to the preferred levels hereof, including to levels as low as about 0.2 or even about 0.1, and less.

It is also preferred that no other ingredients that are harsh to the skin or cause undue eye irritation, such as amide foam boosters (e.g., cocomonoethanolamide, CMEA), be added to the premix or shampoo compositions hereof or be present at levels that significantly increase skin or eye irritation. In general, such ingredients should be absent entirely or be present at levels of less than about 0.5%, by weight, preferably less than about 0.1%, of the composition. Shampoo Premix Compositions and Processing

In one aspect of the invention, the premix compositions hereof comprise:

The above shampoo premixes can be made according to a process comprising the steps of (i) preparing a solution comprising:

(b) at least about 6%, by weight, of amphoteric surfac¬ tant as defined above; and

(c) from about 30% to about 70%, by weight, water; and (ii) adding to the solution from about 2% to about 15%, by weight of the premix, of a suspending agent wherein said solution is heated and said suspending agent is provided in solubilized form; and cooling said composition to provide said suspending agent in crystalline form; wherein said premix has a weight ratio of (a):(b) of about 1:3 to about 3:1, a weight ratio of the suspending agent to total surfac¬ tant present of from about 1:1 to about 1:10, and a weight ratio of the suspending agent to water of about 1:2 to about 1:15, said premix composition is prepared substantially free of alkyl sulfate anionic surfactant, and the pH of said solution is preferably reduced to below 7.0 prior to providing said suspending agent in crystalline form. Optionally, other surfactants can be included in the surfactant solution prior to crystallization of the suspending agent. Especially when no other surfactants, e.g., nonionic surfactants as described below, are added, it is contemplated to utilize about 10% or more alkyl ethoxylated sulfate in the premix. The surfactant added should not be harsh to the skin. Suitable surfactants can include, for example, nonionic surfactants and other amphoteric surfactants.

Preferably, in the above premix and process, the alkyl ethoxylated sulfate is present at a level of from about 5% to about 30%, more preferably from about 6% to about 25%, even more preferably from about 7% to about 20%. The amphoteric surfactant is preferably present at a level of from about 6% to about 30%, more preferably from about 8% to about 20%. The suspending agent is preferably present at a level of from about 3% to about 15%, more preferably from about 5% to about 12%, most preferably from about 5% to about 10%. The weight ratio of alkyl ethoxylated sulfate to the amphoteric surfactant is preferably from about 1:2 to about 5:2; the weight ratio of suspending agent to total surfactant, from about 1:1 to about 1:8, more preferably about 1:3 to about 1:8; and the weight ratio of suspending agent to water, from about 1:4 to about 1:12, more preferably from about 1:6 to about 1:12.

(a) at least about 1%, by weight, preferably at least about 5%, of alkyl ethoxylated sulfate anionic surfactant;

(b) from about 3% to about 15%, by weight, of polyethylene glycol glyceryl fatty ester nonionic surfactant;

wherein R¹ is C₈-C₂₂ al kyl or al kenyl , preferably C₁₂ -C₁₆ , R² i s hydrogen or CH₂C0₂M, R³ is CH₂CH₂0H or CH₂CH₂0CH₂CH₂C00M, R⁴ is hydrogen, CH₂CH₂0H, or CH₂CH₂0CH₂CH₂C00M, Z is C0₂M or CH₂C0₂M, n is 2 or 3, preferably 2, and M is hydrogen or a cation;

In a corresponding process aspect, the present invention provides a process for preparing the premix comprising the steps of:

(i) preparing a solution comprising:

(a) at least about 1%, preferably at least about 5%, by weight, of alkyl ethoxylated sulfate anionic surfactant;

(c) from about 3% to about 30%, by weight, of an imidazolinium amphoteric surfactant of the formula;

wherein R¹ is C₈-C₂₂ alkyl or alkenyl, R² is hydrogen or CH₂C0₂M, R³ is CH₂CH₂0H or CH₂CH0CH₂CH₂C00M, R⁴ is hydrogen, CH₂CH₂0H, or CH₂CH₂0CH₂CH₂C00M, Z is C0₂M or CH₂C0₂M, n is 2 or 3, and M is hydrogen or a cation; and (d) from about 30% to about 60%, by weight, water; (ii) adding to the solution from about 2% to about 15%, by weight of the premix, of a suspending agent wherein said solution is heated and said suspending agent is provided in solubilized form; and (iii) cooling said composition to provide said suspending agent in crystalline form; wherein said premix composition is prepared substantially free of alkyl sulfate anionic surfactant, the pH of said solution is preferably adjusted (e.g., by addition of an acid) to pH less than 7.0 prior to said cooling step, and preferably the premix has a weight ratio of (a):(b) of about 1:5 to about 3:1, a weight ratio of the suspending agent to total surfactant present of from about 1:1 to about 1:10 and a weight ratio of the suspending agent to water of about 1:2 to about 1:15.

Optionally, other surfactants can be included in the solution prior to crystallization, as previously discussed.

Preferably, in the above premix and process, the alkyl ethoxylated sulfate is present at a level of from about 5% to about 30%, by weight, more preferably from about 6% to about 25%, even more preferably from about 7% to about 15%, most preferably from about 7% to about 12%; the amphoteric surfactant, at a level of from about 5% to about 30%, more preferably from about 12% to about 20%, most preferably from about 14% to about 18%; the PEG glyceryl fatty ester, at a level of from about 5% to about 12%, most preferably from about 8% to about 10%; the suspending agent, from a level of from about 3% to about 15%, more preferably from about 5% to about 12%, even more preferably from about 7% to about 10%, most preferably from about 8% to about 10%. The water level is as described above, more preferably from about 45% to about 55% by weight of the premix, most preferably from about 45% to about 52%. The weight ratio of alkyl ethoxylated sulfate to the amphoteric surfactant is preferably from about 1:3 to about 3:1, more preferably from about 1:2 to about 5:2, most preferably from about 1:2 to about 2:1; the weight ratio of suspending agent to total surfactant, from about 1:3 to about 1:8, more preferably from about 1:5 to about 1:7; and the weight ratio of suspending agent to water, from about 1:5 to about 1:12, more preferably from about 1:7 to about 1:11. Also, the weight ratio of suspending agent:PEG glyceryl fatty ester is preferably at least about 1:2, more preferably about 1:1 or higher.

Typically, the solution will be heated to from about 60°C to about 85°C, preferably from about 65T to about 80^βC, more prefer¬ ably about 65"C to about 75°C, to solubilize suspending agent which has been added in crystalline form. Alternately, the solution can be first heated, and then the suspending agent can be added to it in either solubilized or crystalline form. As used herein "solubilized" suspending agent, suspending agent in "solu¬ bilized form", and "solubilizing" the suspending agent shall include solubilization, emulsification, and/or melting of the suspending agent. The temperature required for solubilization of the suspending agent will vary according to the particular surfac¬ tants and levels chosen, as well as the level of and selection of particular suspending agent. These factors will also affect the temperature to which the premix must be cooled to induce crystal¬ lization. For example, higher levels of alkyl ethoxylated sulfate and lower levels of imidazoliniurn and/or PEG glyceryl fatty ester will generally require lower crystallization temperature. Typi¬ cally, the composition will be cooled to between about 15°C and about 60^βC, preferably between about 20°C and about 55°C, more preferably from about 20"C to about 45°C, most preferably from about 30^βC to about 45^βC.

Preferably, the pH is adjusted prior to solubilization of the suspending agent, as this aids solubilization and can shorten processing time. Shampoo Compositions Containing Shampoo Premix

The shampoo premix compositions hereof can be utilized directly for cleaning purposes, or can be first formulated into shampoo compositions containing additional surfactants of the type included in the premix, other surfactants, and other ingredients useful in the formulation of shampoos. Preferably, the ingredients added do not cause significant harshness to the skin. Preferred compositions have low or essentially zero levels of amide-containing foam boosters (preferably less than about 0.5%, more preferably less than about 0.1%, most preferably 0%).

Preferred shampoo formulations will contain from about 20% to about 95%, more preferably from about 50% to about 80%, most preferably from about 60% to about 85%, by total composition weight, of water.

In general, shampoo formulations hereof will typically comprise at least about 5% to about 30% of alkyl ethoxylated sulfate, preferably from about 5% to about 20%, more preferably from about 5% to about 15%, even more preferably from about 7% to about 12%. In the preferred PEG-glyceryl fatty ester-containing shampoos, the alkyl ethoxylated sulfate level is most preferably present at a level of from about 8% to about 12%. Typical levels of the amphoteric surfactant in shampoo formulations hereof will be at least about 2%, preferably from about 2% to about 10%, more preferably from about 3% to about 8%. Typical PEG glyceryl fatty ester surfactant levels in applicable shampoo formulations will be at least about 2%, preferably from about 3% to about 30%, more preferably from about 5% to about 15%, most preferably from about 5% to about 12%. Typical levels of the crystalline suspending agent will be from about 0.5% to about 15%, preferably from about 1% to about 5%, more preferably from about 1% to about 4%, most preferably from about 1% to about 3%.

A variety of exemplary additional composition ingredients are described below.

Additional ingredients that can be used include other an¬ ionic, nonionic, and amphoteric surfactants, as well as zwitter- ionic and cationic surfactants and additional amounts of the surfactants utilized in the premix. Anionic Surfactants

Optional anionic surfactants include the water-soluble salts of the organic, sulfuric acid reaction products of the general formula:

R1-SO3-M wherein Ri is chosen from the group consisting of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about 24, preferably about 12 to about 18, carbon atoms; and M is a cation. Important examples are the salts of an organic sulfuric acid reaction product of a hydrocarbon of the methane series, including iso-, neo-, and n-paraffins, having about 8 to about 24 carbon atoms, preferably about 12 to about 18 carbon atoms and a sulfonating agent, e.g., SO3, H2SO4, oleum, obtained according to known sulfonation methods, including bleach¬ ing and hydrolysis. Preferred are alkali metal and ammonium sulfonated C12-I8 paraffins.

Additional examples of anionic surfactants which come within the terms of the present invention are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil. Other anionic synthetic surfactants of this variety are set forth in U.S. Patents 2,486,921; 2,486,922; and 2,396,278, incorporated by reference herein.

Still other anionic surfactants include the class designated as succinamates. This class includes such surface active agents as disodium N-octadecylsulfosuccinamate; tetrasodium N-(l,2- dicarboxyethyl)-N-octadecylsulfosuccinamate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of sodium sulfosuccinic acid.

Other suitable anionic surfactants utilizable herein are olefin sulfonates having about 12 to about 24 carbon atoms. The term "olefin sulfonates" is used herein to mean compounds which can be produced by the sulfonation of α-olefins by means of unco plexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sulfones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-al anesulfonates. The sulfur trioxide can be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid SO2, chlorinated hydro¬ carbons, etc., when used in the liquid form, or by air, nitrogen, gaseous SO2, etc., when used in the gaseous form.

The α-olefins from which the olefin sulfonates are derived are ono-olefins having about 12 to about 24 carbon atoms, pre¬ ferably about 14 to about 16 carbon atoms. Preferably, they are straight chain olefins. Examples of suitable 1-olefins include 1-dodecene; 1-tetradecene; 1-hexadecene; 1-octadecene; 1-eicosene and 1-tetracosene.

In addition to the true alkene sulfonates and a proportion of hydroxy-alkanesulfonates, the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportion of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process.

A specific α-olefin sulfonate mixture of the above type is described more fully in the U.S. Patent 3,332,880, Pflaumer and Kessler, issued July 25, 1967, incorporated herein by reference.

Another class of anionic surfactants are the l-alkyloxy alkane sulfonates. These compounds have the following formula:

OR2 H

I I

Rl - C - C - SO3M

I I

H H where Ri is a straight chain alkyl group having from about 6 to about 20 carbon atoms, R2 is a lower alkyl group having from about 1 (preferred) to about 3 carbon atoms, and M is a water-soluble cation as hereinbefore described.

Specific examples of J-alkyloxy-alkane-1-sulfonates, or alternatively 2-alkyloxy-alkane-l-sulfonates, having low hardness (calcium ion) sensitivity useful herein include: potassium-J- methoxydecanesulfonate, sodium 2-methoxy-tridecanesulfonate, potassium 2-ethoxytetradecyl sulfonate, sodium 2-isopropoxyhexa- decyl sulfonate, lithium 2-t-butoxytetradecyl -sulfonate, sodium J-methoxyoctadecylsulfonate, and ammonium J-n-propoxydodecyl- sulfonate.

Many additional synthetic anionic surfactants are described in McCutcheon's, Emulsifiers and Detergents, 1989 Annual, pub¬ lished by M. C. Publishing Co., which is incorporated herein by reference. Also U.S. Patent 3,929,678, Laughlin et al . , issued December 30, 1975, discloses many other anionic as well as other surfactant types and is incorporated herein by reference. Soaps, of course, also fall within the scope of anionic detersive surfactants that can be used. Nonionic Surfactants

Nonionic surfactants in addition to the PEG glyceryl fatty esters can be used as detersive surfactants. They are preferably used in combination with an anionic, amphoteric, or zwitterionic surfactant, or mixtures thereof. Nonionic surfactants include those broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. Examples of classes of nonionic surfactants are:

1. The polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 20 carbon atoms, preferably from about 6 to about 12, in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to from about 10 to about 60 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octane, or nonane, for example.

2. Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine products which may be varied in composition depending upon the balance between the hydrophobic and hydrophilic elements which is desired. For example, compounds containing from about 40% to about 80% polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of about 2,500 to about 3,000, are satisfactory.

3. The condensation product of aliphatic alcohols having from about 8 to about 18 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, e.g., a coconut alcohol ethylene oxide condensate having from about 10 to about 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from about 10 to about 14 carbon atoms.

4. Long chain tertiary amine oxides corresponding to the following general formula:

R1R2R3N > 0 wherein Ri contains an alkyl, alkenyl or monohydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties, and from 0 to about 1 glyceryl moiety, and R2 and R3 contain from about 1 to about 3 carbon atoms and from 0 to about 1 hydroxy group, e.g., methyl, ethyl, propyl, hydroxyethyl , or hydroxypropyl radicals. The arrow in the formula is a conventional representation of a semipolar bond. Examples of amine oxides suitable for use in this invention include dimethyl- dodecylamine oxide, oleyldi(2-hydroxyethyl) amine oxide, dimethyl- octylamine oxide, dimethyl-decylamine oxide, dimethyl-tetradecyl- amine oxide, 3,6,9-trioxaheptadecyldiethylamine oxide, di(2- hydroxyethyl)-tetradecylamine oxide, 2-dodecoxyethyldimethylamine oxide, 3-dodecoxy-2-hydroxypropyldi(3-hydroxypropyl) amine oxide, dimethylhexadecylamine oxide.

5. Long chain tertiary phosphine oxides corresponding to the following general formula:

RR'R"P > 0 wherein R contains an alkyl, alkenyl or monohydroxyalkyl radical ranging from about 8 to about 18 carbon atoms in chain length, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety and R' and R" are each alkyl or monohydroxyalkyl groups containing from about 1 to about 3 carbon atoms. The arrow in the formula is a conventional representation of a se ipolar bond. Examples of suitable phosphine oxides are: dodecyldimethylphosphine oxide, tetradecyldimethylphosphine oxide, tetradecylmethylethylphosphine oxide. 3,6,9,-trioxaoctadecyldi- ethylphosphine oxide, cetyldimethylphosphine oxide, 3-dodecoxy-2- hydroxypropyldi(2-hydroxyethyl) phosphine oxide, stearyldimethyl- phosphine oxide, cetylethylpropylphosphine oxide, oleyldiethyl- phosphine oxide, dodecyldiethylphosphine oxide, tetradecyldiethyl- phosphine oxide, dodecyldipropylphosphine oxide, dodecyldi(hy- droxymethyl)phosphine oxide, dodecyldi(2-hydroxyethyl)phosphine oxide, tetradecylmethyl-2-hydroxypropylphosphine oxide, oleydi- methylphosphine oxide, 2-hydroxydodecyldimethylphosphine oxide.

6. Long chain dialkyl sulfoxides containing one short chain alkyl or hydroxy alkyl radical of from about 1 to about 3 carbon atoms (usually methyl) and one long hydrophobic chain which include alkyl, alkenyl, hydroxy alkyl, or keto alkyl radicals containing from about 8 to about 20 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety. Examples include: octadecyl methyl sulfoxide, 2-ketotridecyl methyl sulfoxide, 3,6,9,-trixaoctadecyl 2-hydroxyethyl sulfoxide, dodecyl methyl sulfoxide, oleyl 3-hydroxypropyl sulfoxide, tetra¬ decyl methyl sulfoxide, 3-methoxytridecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

7. Other nonionic surfactants can also be used in the compositions hereof. Polysorbates, e.g., sucrose esters of fatty acids. Such materials are described in U.S. Patent 3,480,616, e.g., sucrose cocoate (a mixture of sucrose esters of a coconut acid, consisting primarily of monoesters, and sold under the tradenames GRILLOTEN LSE 87K from RITA, and CRODESTA SL-40 from Croda).

Alkyl polysaccharide nonionic surfactants are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group. The polysaccharide can contain from about 1.0 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Op¬ tionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6-positions on the preceding saccharide units.

Optionally, and less desirably, there can be a polyalkylene- oxide chain joining the hydrophobic moiety and the polysaccharide moiety. The preferred alkyleneoxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 18, preferably from about 10 to about 16, carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group can contain up to about 3 hydroxy groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkylene moieties. Suitable alkyl poly- saccharides are octyl, nonyldecyl, undecyldodecyl , tridecyl, tetradecyl, pentadecyl , hexadecyl , heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lacto- sides, glucoses, fructosides, fructoses and/or galactoses. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentagluscosides and tallow alkyl, tetra-, penta-, and hexagluco¬ sides.

The preferred alkyl polysaccharides are alkylpolyglycosides of the formula

R 0(C_nH_2n0)(glycosyl)_x wherein R² is selected from the group consisting of alkyl, alkyl- phenyl, hydroxyalkyl , hydroxyalkylphenyl , and mixtures thereof in which alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from 1.3 to about 10, preferably from 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpoly- ethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position. Zwitterionic and Amphoteric Surfactants

Zwitterionic surfactants are exemplified by those which can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfoniu compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. A general formula for these compounds is:

(R³)x

R2 - γ(+) - CH2 - R⁴Z(") wherein R2 contains an alkyl, alkenyl, or hydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety; Y is se¬ lected from the group consisting of nitrogen, phosphorus, and sulfur atoms; R- is an alkyl or monohydroxyalkyl group containing about 1 to about 3 carbon atoms; X is 1 when Y is a sulfur atom, and 2 when Y is a nitrogen or phosphorus atom; R^ is an alkylene or hydroxyalkylene of from about 1 to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.

Examples of such surfactants include: 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carboxy¬ late; 5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1- sulfate;

3-[P,P-diethyl-P-3,6,9-trioxatetradexocylphosphonio]-2-hydroxy- propane-1-phosphate;

3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropylammonio]-propane-1- phosphonate;

3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate;

3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-l-sulfonate;

4-[N,N-di(2-hydroxyethyl)-N-(2-hydroxydodecyl)ammonio]-butane-1- carboxylate;

3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-1- phosphate;

3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate; and

5-[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxy-pentane-

1-sulfate.

Other zwitterionics such as betaines can also be useful in the present invention. Examples of betaines useful herein include the high alkyl betaines, such as coco dimethyl carboxymethyl betaine, cocoamidopropyl betaine, cocobetaine, lauryl amidopropyl betaine, oleyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alphacarboxyethyl betaine, cetyl dimethyl carboxy¬ methyl betaine, lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, stearyl bis-(2-hydroxypropyl) carboxymethyl betaine, oleyl di¬ methyl gamma-carboxypropyl betaine, and lauryl bis-(2-hydroxy- propyl)alpha-carboxyethyl betaine. The sulfobetaines may be represented by coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxyethyl) sulfopropyl betaine and the like; amido- betaines and amidosulfobetaines, wherein the RC0NH(CH2)3 radical is attached to the nitrogen atom of the betaine are also useful in this invention. Preferred betaines for use in the present compo¬ sitions are cocoamidopropyl betaine, cocobetaine, lauryl amido¬ propyl betaine, and oleyl betaine.

Examples of amphoteric surfactants which can be used in the compositions of the present invention are those which are broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples of compounds falling within this defini¬ tion are sodium 3-dodecyl-aminopropionate, sodium 3-dodecylamino- propane sulfonate, sodium lauryl sarcosinate, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium ise- thionate according to the teaching of U.S. Patent 2,658,072, N-higher alkyl aspartic acids such as those produced according to the teaching of U.S. Patent 2,438,091, and the products sold under the trade name "Miranol" and described in U.S. Patent 2,528,378.

Other amphoteric surfactants include sultaines and amidosul- taines. Sultaines and amidosultaines can advantageously be utilized as foam enhancing surfactants that are mild to the eye in partial replacement of anionic surfactants. Sultaines, including amidosultaines, include for example, cocodimethylpropylsultaine, stearyldimethylpropylsultaine, lauryl-bis-(2-hydroxyethyl) pro- pylsultaine and the like; and the amidosultaines such as coco- amidodimethylpropylsultaine, stearylamidododi ethylpropylsultaine, laurylamidobis-(2-hydroxyethyl) propylsultaine, and the like. Preferred are amidohydroxysultaines such as the C₁₂-C₁₈ hydro- carbyl amidopropyl hydroxysultaines, especially C₁₂-C₁₄ hydro- carbyl amido propyl hydroxysultaines, e.g., laurylamidopropyl hydroxysultaine and cocamidopropyl hydroxysultaine. Other sul¬ taines are disclosed in U.S. Patent 3,950,417, issued April 13, 1976, incorporated herein by reference.

Another specific class of amphoteric surfactants is defined by the aminoalkanoates of the formula:

R-NH(CH₂)_nC00M ; and

the iminodial kanoates of the formul a: R-N[(CH₂)_mC00M]₂

and mixtures thereof; wherein n and m are numbers from 1 to 4, R is C₈ - C₂₂ alkyl or alkenyl, and M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkanolammonium.

Examples of amphoteric surfactants falling within the a inoalkanoate formula include n-alkylamino-propionates and n-alkyliminodipropionates. Such materials are sold under the tradename DERIPHAT by Henkel and MIRATAINE by Miranol, Inc. Specific examples include N-lauryl-beta-amino propionic acid or salts thereof, and N-lauryl-beta-imino-dipropionic acid (DERIPHAT 160C) or salts thereof, and mixtures thereof. Conditioning Agent

A preferred optional component hereof is a conditioning agent suitable for conditioning hair or skin. Especially preferred are silicone conditioning agents, particularly nonvolatile, insoluble silicone conditioning agents. The shampoo compositions, in parti¬ cular, will preferably comprise from about 0.01% to about 10%, by weight, of such silicone conditioning agent, more preferably from about 0.05% to about 5%, even more preferably from about 0.05% to about 3%, and most preferably from about 0.1% to about 2.5%. The silicone conditioning agent comprises a nonvolatile, insoluble silicone fluid. The silicone conditioning agent for use herein in shampoo compositions will preferably have average viscosity of from about 1,000 to about 2,000,000 centistokes at 25^βC, more preferably from about 10,000 to about 1,800,000 centistokes, even more preferably from about 100,000 to about 1,500,000 centistokes. Lower viscosity nonvolatile silicone conditioning agents, however, can also be used. Viscosity can be measured by means of a glass capillary visco eter as set forth in Dow Corning Corporate Test Method CTM0004, July 20, 1970.

As used hereinafter, the term "insoluble" in reference to the silicone conditioning agent shall mean that the silicone material is not soluble in water. The term "nonvolatile" in reference to the silicone conditioning agent as used herein shall be interpreted according to the meaning well understood to those skilled in the art, i.e., the silicone fluid exhibits very low or no significant vapor pressure at ambient conditions. The term "silicone fluid" shall mean flowable silicone materials having a viscosity of less than 1,000,000 centistokes at 25^βC. Generally, the viscosity of the fluid will be between about 5 and 1,000,000 centistokes at 25^βC, preferably between about 10 and about 100,000 centistokes. The silicone conditioning agent hereof can also comprise silicone gums, which are also nonvolatile and insoluble, Silicone gums are later described. The term "silicone", as used herein, shall be synonomous with the term "polysiloxane".

Suitable nonvolatile silicone fluids for use in hair condi¬ tioning agents include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymer and mixtures thereof. However, other silicone fluids having hair conditioning properties may be used. The nonvolatile polyalkyl siloxane fluids that may be used include, for example, polydimethylsiloxanes. These siloxanes are available, for example, from the General Electric Company as a Viscasil series and from Dow Corning as the Dow Corning 200 series. Preferably, the viscosity ranges from about 10 centistokes to about 100,000 centistokes at 25^βC.

The polyalkylaryl siloxane fluids that may be used, also include, for example, polymethylphenylsiloxanes. These siloxanes are available, for example, from the General Electric Company as SF 1075 methyl phenyl fluid or from Dow Corning as 556 Cosmetic Grade Fluid.

The polyether siloxane copolymer that may be used includes, for example, a polypropylene oxide modified dimethylpolysiloxane (e.g., Dow Corning DC-1248) although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used. The ethylene oxide and polypropylene oxide level must be sufficiently low to prevent solubility in water and the composition hereof.

Silicone fluids hereof also include polyalkyl or polyaryl siloxanes with the following structure:

wherein R is alkyl or aryl, and x is an integer from about 7 to about 8,000 may be used. "A" represents groups which block the ends of the silicone chains.

The alkyl or aryl groups substituted on the siloxane chain (R) or at the ends of the siloxane chains (A) may have any structure as long as the resulting silicones remain fluid at room temperature, are hydrophobic, are neither irritating, toxic nor otherwise harmful when applied to the hair, are compatible with the other components of the composition, are chemically stable under normal use and storage conditions, and are capable of being deposited on and of conditioning hair.

Suitable A groups include methyl, methoxy, ethoxy, propoxy, and aryloxy. The two R groups on the silicone atom may represent the same group or different groups. Preferably, the two R groups represent the same group. Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl . The pre¬ ferred silicones are polydimethyl siloxane, polydiethylsiloxane, and polymethylphenylsiloxane. Polydimethylsiloxane is especially preferred.

References disclosing suitable silicone fluids include U.S. Patent 2,826,551, Geen; U.S. Patent 3,964,500, Drakoff, issued June 22, 1976; U.S. Patent 4,364,837, Pader; and British Patent 849,433, Woolston. All of these patents are incorporated herein by reference. Also incorporated herein by reference is Silicon Compounds distributed by Petrarch Systems, Inc., 1984. This reference provides an extensive (though not exclusive) listing of suitable silicone fluids.

Another silicone material that can be especially useful in the silicone conditioning agents is insoluble silicone gum. The term "silicone gum", as used herein, means polyorganosiloxane materials having a viscosity at 25^βC of greater than or equal to 1,000,000 centistokes. Silicone gums are described by Petrarch and others including U.S. Patent 4,152,416, Spitzer et al . , issued May 1, 1979, and Noll, Walter, Chemistry and Technology of Si l i¬ cones, New York: Academic Press 1968. Also describing silicone gums are General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76. All of these described references are incorporated herein by reference. The "silicone gums" will typically have a mass molecular weight in excess of about 200,000, generally between about 200,000 and about 1,000,000. Specific examples include polydimethylsiloxane, (polydimethylsiloxane) (methylvinylsiloxane) copolymer, poly(dimethylsiloxane) (diphenyl siloxane)(methylvinylsiloxane) copolymer and mixtures thereof.

Preferably the silicone hair conditioning agent comprises a mixture of a polydimethylsiloxane gum, having a viscosity, at 25°C, greater than about 1,000,000 centistokes and polydimethyl¬ siloxane fluid having a viscosity, at 25^βC, of from about 10 centipoise to about 100,000 centistokes, wherein the ratio of gum to fluid is from about 30:70 to about 70:30, preferably from about 40:60 to about 60:40.

Cationic silicone fluids and gums may be used, although nonionic silicone fluids and gums are preferred. Optional Components

The compositions herein can contain a variety of non-essen¬ tial optional components. Such optional ingredients include, for example, preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea; cationic conditioning agents, including both cationic conditioning surfactant and cationic conditioning polymers; fatty alcohols; block polymers of ethylene oxide and propylene oxide such as Pluronic F88 offered by BASF Wyandotte; sodium chloride; sodium sulfate; ammonium xylene sulfonate; propylene glycol; polyvinyl alcohol; ethyl alcohol; foam boosters such as Polyquaternium-10 (an industry term desig¬ nated by The Cosmetic, Toiletry and Fragrance Association (CTFA) for the polymeric quaternary ammonium salt of hydroxyethyl cellu¬ lose reacted with trimethyl ammonium substituted epoxide), commercially available from Union Carbide Corp. (Danbury, Connecticut, USA) under their UCARE POLYMER JR series of materials, e.g., UCARE POLYMER JR-30M, JR-125 and JR-400; additional pH adjusting agents for the final shampoo composition such as citric acid, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate, etc.; perfumes; dyes; and sequestering agents such as disodium ethylenediamine tetraacetate. These optional ingredients are typically used at levels of from about 0.01% to about 10% of the composition. This list of optional ingredients is not meant to be inclusive, and other optional components can be utilized.

Other optional materials include antidandruff agents such as pyridinethione salts, specifically those in platelet form, as disclosed in U.S. Patents 4,379,753 and 4,345,080, incorporated herein by reference. Included, for example, are heavy metal (e.g., zinc), magnesium, and aluminum salts of 1-hydroxy-2-pyridi- ethione. Other antidandruff agents include selenium compounds such as selenium disulfide. Antidandruff agents are normally used at levels of from about 0.1% to about 4% of the composition, preferably from about 0.2% to about 2%.

Pediculicides can also be included in the compositions hereof to provide control of lice infestations. Suitable pediculicides are well known in the art and include, for example, pyrethrins such as those disclosed in U.S. Patent 4,668,666, Allan, incorpo¬ rated herein by reference. Optional Thickeners and Suspending Agents

Another type of suspending agent that can be used is carboxyvinyl polymer. Preferred polymers are copoly ers of acrylic acid crosslinked with polyallylsucrose as described in U.S. Patent 2,798,053, Brown, issued July 2, 1957, incorporated herein by reference. These polymers are provided by B. F. Goodrich Company as, for example, Carbopol 934, 940, 941, and 956.

A carboxyvinyl polymer is an interpolymer of a monomeric mixture comprising a monomeric olefinically unsaturated carboxylic acid, and from about 0.1% to about 10% by weight of the total monomers of a polyether of a polyhydric alcohol, which polyhydric alcohol contains at least four carbon atoms to which are attached at least three hydroxyl groups, the polyether containing more than one alkenyl group per molecule. Other onoolefinic monomeric materials may be present in the monomeric mixture if desired, even in predominant proportion. Carboxyvinyl polymers are substan¬ tially insoluble in liquid, volatile organic hydrocarbons and are dimensionally stable on exposure to air.

Preferred polyhydric alcohols used to produce carboxyvinyl polymers include polyols selected from the class consisting of oligosaccharides, reduced derivatives thereof in which the car- bonyl group is converted to an alcohol group, and pentaerythritol ; more preferred are oligosaccharides, most preferred is sucrose. It is preferred that the hydroxyl groups of the polyol which are modified be etherified with allyl groups, the polyol having at least two allyl ether groups per polyol molecule. When the polyol is sucrose, it is preferred that the sucrose have at least about five allyl ether groups per sucrose molecule. It is preferred that the polyether of the polyol comprise from about 0.1% to about 4% of the total monomers, more preferably from about 0.2% to about 2.5%.

Preferred monomeric olefinically unsaturated carboxylic acids for use in producing carboxyvinyl polymers used herein include monomeric, polymerizable, alpha-beta monoolefinically unsaturated lower aliphatic carboxylic acids; more preferred are monomeric monoolefinic acrylic acids of the structure

where R is a substituent selected from the group consisting of hydrogen and lower alkyl groups; most preferred is acrylic acid.

Preferred carboxyvinyl polymers used in formulations of the present invention have a molecular weight of at least about 750,000; more preferred are carboxyvinyl polymers having a mole¬ cular weight of at least about 1,250,000; most preferred are carboxyvinyl polymers having a molecular weight of at least about 3,000,000.

Other materials can also be used as suspension agents, including those that can impart a gel-like viscosity to the composition, such as water soluble or colloidally water soluble polymers like cellulose ethers (e.g., hydroxyethyl cellulose), 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.

Such optional suspending agent thickeners, and viscosity modifiers, etc., in general, are used at a level of from about 0.1% to about 10%, most commonly from about 0.3% to about 5.0% by weight of the total composition.

Another type of suspending agent that can be used is xanthan gum. Shampoo compositions utilizing xanthan gum as a suspending agent for the silicone hair conditioning component are described in U.S. Patent 4,788,006, Bolich and Williams, issued November 29, 1988, incorporated herein by reference. Xanthan gum is bio- synthetic gum material that is commercially available. It is a heteropolysaccharide with a molecular weight of greater than 1 million. It is believed to contain D-glucose, D-mannose and D-glucuronate in the molar ratio of 2.8:2.0:2.0. The polysac¬ charide is partially acetylated with 4.7% acetyl . This informa¬ tion and other is found in Whistler, Roy L. Editor Industrial Gums - Polysaccharides and Their Derivatives New York: Academic Press, 1973. Kelco, a Division of Merck & Co., Inc. offers xanthan gum as Keltrol^®. The gum, when used as the silicone hair conditioning component suspending agent, will typically be present in pourable, liquid formulations at a level of from about 0.3% to about 3%, preferably from about 0.4% to about 1.2%, in the compositions of the present invention.

The pH of the compositions for direct use for cleaning applications is not generally critical and may be in the range of from 2 to about 10, preferably from about 3 to about 9, more preferably from about 4 to about 8, most preferably from about 6 to about 8.

In preferred formulations, the present invention provides a shampoo comprising shampoo premix and insoluble, nonionic silicone conditioning agent, a mild-to-the-skin foam booster, or a combination thereof; it is also especially preferred to include the silicone. Typically for such preferred compositions, the shampoo composition comprises about 15% to about 50%, by total weight, of a shampoo premix hereof, more preferably from about 15% to about 25%, and from about 0.05% to about 5% of said silicone. In a particularly preferred shampoo composition, the shampoo comprises:

(a) from about 5% to about 15%, by weight, preferably from about 5% to about 12% alkyl ethoxylated sulfate anionic surfactant;

(b) from about 5% to about 15%, by weight, preferably from about 5% to about 12%, of polyethylene glycol fatty ester nonionic surfactant;

(c) about 2% to about 10%, by weight, of imidazolinium surfactant having the formula

wherein R¹ is C₈-C₂₂ alkyl or alkenyl, R² is hydrogen or CH₂C0₂M, R³ is CH₂CH₂0H or CH₂CH0CH₂CH₂C00M, R⁴ is hydrogen, CH₂CH₂0H, or CH₂CH₂0CH₂CH₂C00M, Z is C0₂M or CH₂C0₂M, n is 2 or 3, and M is hydrogen or a cation; and (d) from about 60% to about 85%, by weight, water.

METHOD OF USE The present compositions are used in a conventional manner for cleaning hair. An effective amount of the composition for cleaning hair, typically, from about 1 g to about 20 g of the composition, is applied to hair that has preferably been wetted, generally with water, and then rinsed out. Application to the hair typically includes working the composition through the hair such that most or all of the hair is contacted with the composition.

EXAMPLES The following Examples further describe and demonstrate the preferred embodiments within the scope of the present invention. The Examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention as many variations thereof are possible without departing from its spirit and scope.

EXAMPLES I-V

Carbide Corporation. ² A 40/60 blend of SE-76 silicone gum available from GE Sili¬ cones and a silicone fluid having a viscosity of about 350 centistokes.

³ Available under the tradename MIRANOL C-2M from Miranol, Inc. in a 38% active solution.

⁴ Available under the tradename MIRANOL CM CONC from Miranol, Inc. in a 37% active solution.

⁵ Available under the tradename VARONIC LI-48 from Sherex Chemical Company as a 100% active solution.

⁶ Available under the tradename VARONIC LI-63 from Sherex Chemical Company as a 100% active solution.

⁷ Available commercially as a 28.5% active solution.

The compositions are prepared as follows. A silicone premix is first prepared by adding a small portion (e.g., about 0.2% by weight of the finished product) of the sodium laureth-3 sulfate to the premix tank and heating to 71"C. The sodium chloride is added. The dimethicone is added and mixed until an emulsion is formed.

A portion of the sodium laureth-3 sulfate, the Varonic LI-63, and the cocoamphodiacetate are placed in a tank. The mixture (the "main premix") is agitated and heated to 71°C. The citric acid in the form of a 50% active solution is added to adjust pH. The ethylene glycol distearate is then added and allowed to melt. The premix has a weight ratio of ingredients, in the order listed in this paragraph, of about 4:4:7:1:4. The main mix is passed through a heat exchanger where it is cooled to 38^βC and collected in a finishing tank. As a result of this cooling step, the ethylene glycol distearate has crystallized to form a crystalline network in the product. The silicone premix is collected in the same finishing tank, where the main premix and the silicone premix are mixed until homogeneous. Finally, the remainder of the ingredients are added and mixed into the shampoo composition. The composition comprises about 22%, by weight, of the main premix. The final pH is adjusted by the citric acid to within the range of 6.3 - 6.8. The compositions of the Examples can provide excellent in-use hair cleaning and conditioning, along with high silicone hair conditioning agent efficiency.

EXAMPLES VI-X

The following examples exemplify shampoo compositions of the present invention.

UCARE Polymer JR-30M, commercially available from Union Carbide Corporation.

A 50/50 blend of SE-76 silicone gum available from GE Sili¬ cones and a silicone fluid having a viscosity of about 350 centistokes.

Available under the tradename MIRANOL C-2M from Miranol, Inc. in a 38% active solution.

Available under the tradename MIRANOL CM CONC from Miranol, Inc. in a 37% active solution. ⁵ Available under the tradename GENAGEN CAB from Hoechst Celanese as a 30% active solution.

⁶ Available under the tradename DERIPHAT from Henkel Corp. as a 30% active solution.

⁷ Available commercially as a 28.5% active solution.

⁸ "TCMAC" Available commercially from Akzo-Chemie as ARQUAD-316 as a 90% suspension.

The compositions are prepared as follows. A silicone premix is first prepared by adding a small portion (e.g., about 0.2% by weight of the finished product) of the sodium laureth-3 sulfate to the premix tank and heating to 71°C. The cetyl and stearyl alcohols, as applicable, are added. The dimethicone is then added and mixed until an emulsion is formed.

For Examples VI and IX, about one-third of the sodium laureth-3 sulfate, the cocoamphodiacetate and/or cocoamphoacetate, the CAPB and TCMAC, as applicable, are placed in a tank. The mixture (the "main premix") is agitated and heated to 71°C. The ethylene glycol distearate is then added and allowed to melt. The citric acid in the form of a 50% active solution is added to adjust pH. The main mix is passed through a heat exchanger where it is cooled to 32^βC and collected in a finishing tank. As a result of this cooling step, the ethylene glycol distearate crystallizes to form a crystalline network in the product. The Polyquaternium 10, if applicable, is then added as a solid or predissolved in water to the main premix. For Examples VII, VIII, and X, the CAPB is mixed into the main premix after the ethylene glycol distearate has been crystallized instead of being added at the above-indicated earlier stage. The silicone premix is col¬ lected in the same finishing tank after being cooled to about 30^βC, where the main premix and the silicone premix are mixed until homogeneous. Finally, the remainder of the ingredients are added and mixed into the shampoo composition. The final pH is adjusted as desired by the addition of citric acid and/or NaOH. The final viscosity is adjusted as desired by the addition of ammonium xylene sulfonate and/or NaCl, The compositions of the Examples can provide excellent in-use hair cleaning, lather, mildness, conditioning and dandruff control (where applicable), and pearlescence.

Claims

CLAIMS:

1. A mild shampoo premix composition characterized in that it comprises:

(a) at least 5%, by weight, of alkyl ethoxylated sulfate anionic surfactant;

(b) from 3% to 15%, by weight, of polyethylene glycol glyceryl fatty ester nonionic surfactant;

(c) from 3% to 30%, by weight, of an amphoteric surfactant of the formula:

(d) from 2% to 15%, by weight, of a suspending agent recrystallized in said composition at pH below 7.0; and

(e) from 30% to 60% water; wherein said premix composition is substantially free of alkyl sulfate anionic surfactant.

2. A premix composition according to Claim 1, wherein said suspending agent is selected from the group consisting of acyl derivatives having C₈-C₂₂ hydrocarbyl chains and long chain amine oxides having C₁₆-C₂₂ hydrocarbyl chains, and mixtures thereof, preferably said suspending agent is selected from acyl derivatives having C₈-C₂₂ hydrocarbyl chains, most preferably said suspending agent is selected from ethylene glycol esters of C₁₄-C₂₂ acids.

3. A premix composition according to Claim 1 or 2 comprising:

(a) from 5% to 15% of said alkyl ethoxylated sulfate anionic surfactant; (b) from 5% to 12% of said polyethylene glycol glyceryl fatty ester nonionic surfactant;

(c) from 12% to 20% of said amphoteric surfactant;

(d) from 3% to 15% of said suspending agent; and

(e) from 40% to 55% water.

4. A premix composition according to Claim 1, 2, or 3, wherein said imidazolinium amphoteric is a monocarboxylate or a dicarboxylate, or a mixture thereof, preferably said imidazolinium amphoteric surfactant comprises cocoamphocarboxyglycinate, cocoamphoacetate, cocoa phocarboxypropionate, or cocoamphocarboxypropionic acid, or a mixture thereof.

5. A premix composition according to Claim 3 or 4, comprising:

(a) from 7% to 12% of said alkyl ethoxylated sulfate anionic surfactant;

(b) from 8% to 10% of said polyethylene glycol glyceryl fatty ester nonionic surfactant, said nonionic surfactant having the formula:

RC(0)0CH₂CH(0H)CH₂(0CH₂CH₂)_n0H wherein n is from 20 to 100, and RC(0) is an ester wherein R is an aliphatic radical having from 9 to 17 carbon atoms;

(c) from 14% to 18% of said amphoteric surfactant, wherein R¹ is C₁₂-C₁₆ alkyl or alkenyl, and said amphoteric surfactant is a monocarboxylate or a dicarboxylate, or a mixture thereof;

(d) from 8% to 10% of said suspending agent; and

(e) from 45% to 52% water.

6. A premix composition according to Claim 1, 2, 3, 4, or 5, wherein for said polyethylene glycol glycerol fatty ester nonionic surfactant, n is from 30 to 85 and R is an aliphatic radical having from 11 to 14 carbon atoms. 7. A shampoo composition characterized in that it comprises: (i) from 15% to 25%, by weight, of said premix composition of Claim 1, 2, 3, 4, 5, or 6; and (ii) from 0.05% to 5%, by weight, of a dispersed, insoluble silicone; wherein said shampoo composition comprises:

(a) from 5% to 15%, by weight, alkyl ethoxylated sulfate anionic surfactant ;

(b) from 5% to 15% of polyethylene glycol fatty ester nonionic surfactant;

(c) 2% to 10%, by weight, of amphoteric surfactant having the formula

wherein R¹ is C₈-C₂₂ alkyl or alkenyl, R² is hydrogen or CH₂C0₂M, R³ is CH₂CH₂0H or CH₂CH0CH₂CH₂C00M, R⁴ is hydrogen, CH₂CH₂0H, or CH₂CH₂0CH₂CH₂C00M, Z is C0₂M or CH₂C0₂M, n is 2 or 3, and M is hydrogen or a cation; and

(d) from 60% to 85% water.

8. A process for making a shampoo premix composition characterized in that it comprises the steps of:

(i) preparing a solution comprising:

(a) at least 5%, by weight, of alkyl ethoxylated sulfate anionic surfactant;

(c) 3% to 30%, by weight, of surfactant having the formula

wherein R¹ is C₈-C₂₂ alkyl or alkenyl, R² is hydrogen or CH₂C0₂M, R³ is CH₂CH₂0H or CH₂CH0CH₂CH₂C00M, R⁴ is hydrogen, CH₂CH₂0H, or CH₂CH₂0CH₂CH₂C00M, Z is C0₂M or CH₂C0₂M, n is 2 or 3, and M is hydrogen or a cation; and (d) from 30% to 60%, by weight, water; (ii) adding to the solution from 2% to 15%, by weight of the premix, of a suspending agent wherein said solution is heated and said suspending agent is provided in solubilized form; and cooling said composition to provide said suspending agent in crystalline form; wherein the pH of said solution is adjusted by addition of an acid to pH less than 7.0 prior to said cooling step and said premix composition is prepared substantially free of alkyl sulfate anionic surfactant.

9. A premix composition according to Claim 1, 2, 3, 4, 5, or 6 wherein said premix has a weight ratio of (a):(c) of from 1:5 to 3:1, a weight ratio of (d):total surfactant of from 1:1 to 1:10, and a weight ratio of (d):(e) of from 1:2 to 1:15.

10. A premix composition according to Claim 5 or 6, wherein said premix has a weight ratio of (a):(c) of from 1:2 to 2:1, a weight ratio of (d):total surfactant of from 1:3 to 1:8, and a weight ratio of (d):(e) of from 1:7 to 1:11.

11. A shampoo composition as in Claim 7, wherein said premix has a weight ratio of (a):(c) of from 1:5 to 3:1, a weight ratio of (d):total surfactant of from 1:1 to 1:10, and a weight ratio of (d):(e) of from 1:2 to 1:15.

12. A shampoo composition as in Claim 11, wherein said premix has a weight ratio of (a):(c) of from 1:2 to 2:1, a weight ratio of (d):total surfactant of from 1:3 to 1:8, and a weight ratio of (d):(e) of from 1:7 to 1:11. 13. A premix composition as in Claim 1, 2, 3, 4, 5, 6, 9, or 10 wherein said suspending agent is recrystallized in said premix at pH below 7.0.

14. A mild shampoo premix composition characterized in that it comprises:

(a) at least 5%, by weight, of alkyl ethoxylated sulfate anionic surfactant;

(b) at least 6%, by weight, of an amphoteric surfactant of the formula:

(c) from 2% to 15%, by weight, of a suspending agent recrystallized in said premix composition; and

(d) from 30% to 70% water; wherein said premix has a weight ratio of (a):(b) of 1:3 to 3:1, a weight ratio of (c) to total surfactant present of from 1:1 to 1:10, and a weight ratio of (c):(d) of 1:2 to 1:15, and said premix composition is substantially free of alkyl sulfate anionic surfactant.

15. A premix composition according to Claim 14, wherein said suspending agent is selected from the group consisting of acyl derivatives having C₈-C₂₂ hydrocarbyl chains and long chain amine oxides having C₁₆-C₂₂ hydrocarbyl chains, and mixtures thereof said suspending agent is selected from acyl derivatives having C₈-C₂₂ hydrocarbyl chains more preferably said suspending agent is selected from ethylene glycol esters of C₁₄-C₂₂ acids most preferably said suspending agent is ethylene glycol distearate. 16. A premix composition according to Claim 14 or 15, wherein said amphoteric surfactant is a monocarboxylate or a dicarboxylate, or a mixture thereof.

17. A premix composition according to Claim 14, 15, or 16, wherein said imidazolinium amphoteric surfactant comprises cocoamphocarboxyglycinate, cocoamphoacetate, cocoamphocarboxypropionate, or cocoamphocarboxypropionic acid, or a mixture thereof.

18. A shampoo composition comprising the premix composition of Claim 1, 2, 3, 4, 5, 6, 9, 10, 13, 14, 15, 16, or 17, and a hair conditioning agent, said hair conditioning agent preferably comprises insoluble nonvolatile silicone dispersed in said composition.

19. A shampoo composition comprising the premix composition of Claim 1, 2, 3, 4, 5, 6, 9, 10, 13, 14, 15, 16, or 17 and a foam booster.

20. A shampoo composition comprising the premix composition of Claim 1, 2, 3, 4, 5, 6, 9, 10, 13, 14, 15, 16, or 17 and a foam booster and a hair conditioning agent.

21. A shampoo composition according to Claim 20 wherein said foam booster is a quaternary ammonium salt of hydroxyethylcellulose reacted with trimethyl ammonium-substituted epoxide and said hair conditioning agent is an insoluble, nonvolatile silicone.

23. A shampoo composition comprising the premix composition of Claim 1, 2, 3, 4, 5, 6, 9, 10, 13, 14, 15, 16, or 17 and a foam booster and said shampoo is substantially free of amide-containing foam boosters. 24. A process for making a mild shampoo premix composition characterized in that it comprises the steps of

(i) preparing a solution comprising:

(a) at least 5%, by weight, of alkyl ethoxylated sulfate anionic surfactant;

(b) at least 6%, by weight, of amphoteric surfactant having the formula

wherein R¹ is C₈-C₂₂ alkyl or alkenyl, R² is hydrogen or CH₂C0₂M, R³ is CH₂CH₂0H or CH₂CH0CH₂CH₂C00M, R⁴ is hydrogen, CH₂CH₂OH, or CH₂CH₂0CH₂CH₂C00M, Z is C0₂M or CH₂C0₂M, n is 2 or 3, and M is hydrogen or a cation; and

(c) from 30% to 70%, by weight, water; and

(ii) adding to the solution from 2% to 15%, by weight of the premix, of a suspending agent wherein said solution is heated and said suspending agent is provided in solubilized form; and (iii) cooling said composition to provide said suspending agent in crystalline form; wherein said premix has a weight ratio of (a):(b) of 1:3 to 3:1, a weight ratio of suspending agent to total surfactant present of from 1:1 to 1:10, and a weight ratio of suspending agent:water of

1:2 to 1:15, said premix composition is prepared substantially free of alkyl sulfate anionic surfactant.

25. A process according to Claim 24, wherein the pH of said solution is reduced to below 7.0 prior to providing said suspend¬ ing agent in crystalline form.

26. A process as in Claim 8, wherein said premix has a weight ratio of (a):(c) of from 1:5 to 3:1, a weight ratio of (d):total surfactant of from 1:1 to 1:10, and a weight ratio of (d):(e) of from 1:2 to 1:15.