CA1046888A

CA1046888A - Foaming and conditioning detergent composition

Info

Publication number: CA1046888A
Application number: CA229,271A
Authority: CA
Inventors: Howard R. Steen; Henry Trainor
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1974-06-14
Filing date: 1975-06-13
Publication date: 1979-01-23
Also published as: FR2274684A1; US4026825A; IT1038932B; FR2274684B1; GB1500719A; DE2525775A1; BE830205A

Abstract

FOAMING AND CONDITIONING DETERGENT COMPOSITION
Howard Robertson Steen Henry Trainor A B S T R A C T
This invention relates to a foaming and conditioning composition, especially a liquid detergent conditioning com-position having a low viscosity and able to provide in the bath tub a desirable quantity of suds and water-insoluble oil material having skin-softening or emollient properties.

Description

BACKGROUND OF THE INVENTION
The preparation of compositions adapted to use in bathing is well known in the art. Such compositions have typically included liquid bath oil compositions which are added to bath water to provide a layer of oily emollient on the sur-face of the bath water. Such compositions provide an anointing or skin softening quality to-alleviate dry skin conditions and to prevent excessive moisture loss from the skin after bathing.
Other bath compositions have included bubble bath formulations comprised of a water-soluble detergent active base to provide a copious quantity of bubbles or foam.
Various attempts have been made in the art to provide bath compositions designed to combine the desirable foaming properties of a bubble bath composition with the emollient properties of a bath oil. Inasmuch as the desirable sudsing, cleaning, wetting, solubilization, emulsification and dispersion properties characteristic of surfactants are mutually antagonistic with the emolliency and deposition properties of oleaginous materials, such attempts have not been entirely satisfactory.
Thus, attemps to provide detergent compositions embodying these desirable properties have been characterized by the attainment of either copious foam formation with little emollient effect or desirable emollient qualities with low levels of foam formation.
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The mutually antagonistic properties of fea~ formation and emolliency ha~e been referred to b~ T. Raufman i~n American Perfumes and Cosmetics, Vol 80, pages 29 to 31 (February, 1965).
The formulation of a foaming bath oil representing a "compromise"
to the attainment of copious foam formation and emolliency is described.
i One approach to the provision of foaming bath oil compositions has involved physical separation of the foaming and emollient components, as by microencapsulation, se as to provide separateointroduction of these components into the bath water and is described in South African Patent 684,784 to Randerbrock et al., granted in January 1969, U.S. Patent 3,533,955 (October 13, 1970) to Pader et al described a two-phase liquid detergent composition having a detergent, emollient, water and emulsion destabilizer. Encapsulation necessarily adds to the cost of foaming bath oils ~hile demulsification properties may depend on the amount of demulsifier employed.
Compositions which are similar to those of the present invention are known and described in British Patent 1,438,081 of Melvin A. Barbera, published Juae 3, 1976, said patent being entitled "Foaming and conditioning detergent compositon".
Fercentages and ratios are by weOEght and temperatures in degrees centrigrade unless otherwise indicated.
SUMMARY OF THE INVENTION
. . . _ The present invention relates to a substantially anhydrous foaming and co~ditionin~ composition providi~g suds a~d a layer of emollient oil upon addition to water; consisting essentially of a mutually insoluble mixture of a water-soluble foaming organic detergent and a water-insoluble oily material having skin-softening or emollient properties, and mutual in-solubility being such that neither the detergent nor the oily material is solub~e in the other in an amount greater than 0.1%

-2-~ 1046888 by ~eig~t of the ~olvent ~aterial, the composition being sub-stantially anhydrous, the v~socosity of the composition being less than 500 centipoises, and t~e organic detergent being `- ~`
present at a level of from about 10 to about 60% by weight of the composition, and being in the fD~m of finely divided particles containing at least 50% by weight of an organic surfactant, selected from the group consisting of anionic, nonionic, Gationic, zwitterionic and amphoteric surfactants, and having a moisture content of less than 5% by weight, at `~--, least 90%, and preferably at least 95~ of the particles being ;-of a size to pass a 100 mesh screen and at least 50% of the . j .
;~ particles being of a size to pass a 200 mesh screen, the particles having a bulk density of at least 0.4g./cc.
r, i DETAILED DESCRIPTION OF THE INVENTION
~ he compositions of this invention have been found to give improved storage stability compared to the compositions of British Patent 1,438,081 and their lower inherent viscosity - permits more flexibility in formulation. The detergent particles are generally faster dissolving than the spray dried particles ;' 20 de~cribed in that patent and may be dispersed almost immediately ~; when the composition is added to water.
The detergent compositions of the invention, by vir-tue of the sm~ll size of the detergent particles and the higher ~` bulk density of ~ld particles, have a low viscosity compared ~' to similar compositions prepared from, e.g., spray dried , ~ detergent granules which have a larger particle size and/or f .
lower bulk density. This results from the higher bulk density which permits incorporation of a greater amount of detergent with less volume. The lower viscosity also results from the very s~ ~11 particle size of the detergent particles.
In order that the compositions of the invention will exhibit the desirable properties described hereinbefore, it is 3_ .

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`~ essential that the particle size of t~e detergent particles be such that at least 90% o~ sal~d p~rti~cles ~ill pass through a ~ 100 mesh screen and that at least 50~ of said particles will ; pass a 200 mesh screen. Preferably at least 75% of said par~
ticles will pass through a 200 mesh sceeen and more preferably L' at least 90% of said particles will pass through a 200 mesh screen.
As will be discussed hereinafter the detergent particles of this invention contain at least 50% organic surfactant. In order to obtain the very small particle size~ ;~
required by the compositions of this invention in an economical' manner, it is desirable to resort tb freeze grinding of drum-dried detergent flakes. In freeze grinding the detergent flakes are cooled, e.g., by the application of liquid nitrogen, before being milled or ground to obtain the correct particle f,~. size distribution. Since milling or grinding generates heat and since the surfactants of this invention are plastic mate-rials, it is extremely d~fficult to reduce larger particles to the proper particle size without first chilling the particles. This chilling can be done by any means but a convenient way is to use liquid nitrogen.
O~her methods of size reduction can be used if they s~ result in the proper particle size and the proper bulk density.
~, The bulk density is imp~rtant since the volume of the particles is related directly to the bulk density. The - smaller the volume of the detergent particles, the lower will be the visocosity.
The detergent particles of this invention contain less than S% moisture by weight, preferably less than 2% and most preferably less than 1%. Low moisture is important in order to prevent dissolution of the surfactant in the emol-lient.

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: ' ~ 1046888 The detergent materia~ of this invention must be selected to have t~e correct solub~l~ty characterist~cs.
" The solubility characteristics can be readily ,, determined by resort to known solubility and analytical tech- -, niques, the particular method employed depending upon the ' .,.; particular surfactants or emollients considered, their physic~l '` characteristics and the like. Solid or particulate foaming ~,' surfactants will generally be added to a liquid emollient oil '' , ~ "
~`, at 30C and the amount dissolved expressed as a percentage by weight of the emollient oil. The mutual solubility character-istics of liquid surfactants and emollient oils will normall~,, be determined by measuring the solubility of each material in the other so as to determine the suitability or compatibility of the materials for combination and provi~ion of the desir-able and respective foamingg and emolleency effects.
The detergent particles of this invention contain '~'s at least 50% by weight organic detergent (surfactant), pre-.
ferably the particles oontain at le~8t 75% organic surfactant and most preferably the detergent particles contain at least 90~ organic surfactant.
Detergents suitable herein are water-solub~ foaming ~`, organic detergents selected from anionic, nonionic, cationic, ,' ~, . .
~^,, zwitterionic and amphoteric classes. Suitable detergent ',~ materials are theee which provide copious suds-formation and '; ~ cleansing proper,t~es. It will be appreciated that a g~ven ', surfactant material may provide desirable suds formation and '-' ~ cleansing properties, but may be soluble or insoluble in the : ,.~- , .
,~;', emollient oil, as defined herein~efore, depending on the ;'~
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s particular nature of the emollient considered. Thus, a foaming surfactant may be insoluble in mineral oil and permit the ~' ~, attainment simultaneously of the desired ob~ectives of copious '~
','~", suds- formation and skin depositdon in bath use, but may be .:. .
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soluble, for example, in olive oil and, thus, be unsuited for a composit~on of the invention where it is desirable that ~- olive oil be employed as the emollient component. Compatible combinations of foaming surfactant and emollient, i.e. those ~; which will permit the attainment of both suds formation and skin-oiling effects in bathtub use, can, however, be deter-:.,.
;., mined by the mutual solubility or insolubility characteristics ~ described hereinbefore. Suitable combinations can, thus, be ~ ,~
~ easily determined.
,, , ` 10 Examples of surfactant materials from which the . " ~
foaming and oil-insoluble detergents of the invention can be selected include the water-soluble anionic, nonionic, cationic, zwitterionic and amphoteric detergents described as follows:
(a) Anionic detergents include the synthetic non-soap detergents which can be broadly described as the water-soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in their molecular i'.~ 1 structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consis-ting of sulfonic acid and sulfuric acid ester radicals.
~Included in the term alkyl is the alkyl portion of hi~her acyl radicals.) Important examples of the synthetic deter-gents which form a part of the compositions of the prese~t invention are the alkali metal, e.g. sodium or potassium, alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-~18 carbon atoms) produced by reducing the glycerides of tallow or coconut oil; the alkali metal olefin sulfonates of from 8 to- 24 carbon atoms described, for ;,~ , . .
example, in U.S. Patent 3,332,880 issued July 25, 1967 to ....
'`; 30 Philip E. Pflaumer and Adriaan Kessler; and the alkali metal . ~:

` alkyl glyceryl ether sulfonates, especially those ethers of ., ~ the higher alcohols derived from tallow and coconut oil;
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~, i~ 3, other anionic detergent~ include the alkali metal alkyl-benzene sulfonates, in ~hi~ch t~e al~l group contains from about 9 to ,"` about 15 carbon atoms, încluding those of the types described t:`` in United States Letters Patent Nos. 2,220,099 and 2,477,383 ~,~."ll (the alkyl radical can be a straight or branched aliphatic chain); sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts or sulfuric acid 7~4"~ esters of the reaction product of one mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and about 1 to ; 10 6 moles of ethylene oxide; sodium or potassium salts of alkyl phenol ethylene oxide ether ~u~fate with about 1 to about 10 ~' units of ethylene oxide per molecule and in which the alkyl radicals contain from 8 to about 12 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acid is oleic or derived from coconut oil; sddium or - -`
~' potassium salts of fatty acid amide of a methyl tauride in ~ ~ ^ j . .
which the fatty acids, for example, are derived from coconut oil; soaium or pota~sium ~-acetoxy- or ~-acetamido-alkane-sulfonates where the alkane has ~rom 8 to 22 carbon atoms; and ,~,;~ .~ , .
others known in the art, a number specifically set forth in United States Letters Patent Numbers 2,486,921, 2,486,922, ~, .
~}~ and 2,396,378.
(b) Nonionic synthetic detergents: One class can `$' be broadly defined as componnds produced by the co~densation of ~` alkylene oxide groups ~hydrophilic in nature) with an organic ;~;' hydrophobic compound, which can be aliphatic or alkyl aromatic?,~
in nature. The length of the hydrophilic or polyoxyalkyleneradical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water~soluble compound .
~' ha~ing the desired degree of balance between hydrophilic and ~. . .
~- hydrophobic elements. Another class has semi-polar character-).....
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istics. Classes of nonionic synthetic detergents are as foll~ws.

, ~1) A clas~ of nonionic synt~etic detergents under ~;
the trademark of ~Pluronic". These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits -^' water insolubility, has a molecular weight of from about 1500 to 1800. The addition of polyoxyethylene radicals to th~s hydrophobic portion tends to increase the water solubility of ~; 10 the molecule as a whole and the liquid character of the product , ,~ is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product.

`~ (2) The polyethylene oxide condensates of alkyl ~ phenol~, e.g., the condensation products of alkyl phenols .. : .
having a alkyl group containing from about 6 to 12 car~on ;$~ atoms in either a straight chain or branched chain config~
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uration with ethylene oxide, the said ethylene oxide being present in amounts equ~ to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such com-pounds may be derived from polymerized propylene, diisobutylene, , "
~ octene, or nonene, for example.
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(3) Those nonionic synthetic detergents derived c, from the condensation of ethylene oxide with the product .:
resulting from the reaction of propylene oxide and ethylene diamine. For examp~e, 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 2,500 to 3,000 are satisfactory.

(4) The condensation product of aliphatic alcohols ~ ., ;,.. .
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having from 8 to 22 carbon atoms, in either straight chain or ~rancnes c~ain conf~gur~t~on, ~ith et~ylene oxide, e.g., a coconut alcohol ethylene ox~de condensate hav ng from 5 to ~ -30 moles of ethylene oxide per mole of coconut alc~hol, t~e coconut alcohol fraction having from 10 to 14 carbon atoms.

(5) The ammonia, monoethanol and diethanol amides of fatty acids having an acyl moiety of from about 8 to about 18 carbon atoms. These acyl moieties are normally derived from naturally occurr~ng glycerides, e.g., coconut oil, p~lm oil, soybean oil and tallow, but aan be derived synthetically, ~-e.g., by the oxidation of petrolemm, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process.

(6) Long chain tertiary amine oxides corresponding to the following general formula R2 , -. -Rl _ XoR4)n - l~o R

wherein Rl is an alkyl radical of from about 8 to about 24 carbon atoms, R2 and R3 are each methyl, ethyl or hydroxyethyl radicals, R4 is ethylene, and n equals from 0 to about 10.
The arrow ia the formula is a conventional representation of a semi-polar bond. Specific examples of amine oxide detergentx include: dimethyldodecylamine oxide; cetyldimethylamine oxide;
bis-(2-hydroxyethyl) dodecylamine oxide; and bis-X2-8ydroxyethyl) -3-dodecoxy-1-hydroxypropyl amine oxide.

(7) Long chain tertiary phosphine oxides corresponding to the following geneeal formula RR'R"P ~ O wherein R is an alkyl, alkenyl or monohydroxyalkyl radical ranging from 10 to 24 carbon atoms in chain length and Rl and R" are each alkyl or monohydroxyalkyl groups containing from 1 to 3 carbon atoms.

The arrow in the formula is a conventional representation of _g_ ..... ' ' .
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a semi~polar bond. Examples of su~table phosp~l~ne oxi~des are found in U.S. Patent 3,304,262 of ~ebruary 14, 1967 and i~nclude:
~methyldodecylphosphine oxide; diethyldodecylphosphine oxide;
dimethyl-(2-hydroxydodecyl) phosphine oxide.

(8) Long chaim sulfoxides having the formula wherein R5 is an alkyl radical containing from about 1~ to about 28 carbon atoms, from 0 to about 5 ether linkages and from 0 to about 2 hydroxyl substituents, at least one moiety of R5 being an alkyl radical containing 0 ether linkages and ~ containing from about 10 to about 18 carbon atoms, and wherein R6 is an alkyl radical containing from 1 to 3 carbon atoms and from one to two hydroxyl groups. Specific examples of these sulfoxides are: dodecyl methyl sulfoxide; 3-hydroxy tridecyl methyl sulfoxide; 3-methoxy tridecyl methyl sulfoxide;

j and 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.
I- (c) Amphoteric synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents - contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato, or phosphono. Examples of compounds falling within this definition are sodium-3-dodecylaminopropionate and sodium-3-dodecylaminopropane sulfonate.

(d) Zwitterionic synthetic detergents ca~ be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radical may be straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 13 carbon -10~

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atom~ and one contains an anionic water solubilizing group, e.g., ca~-oxy, sul~o, sul~ato, p~o~phato, or phospnono~ Examples of compounds falling within this definition are 3- ~,N-dimethyl-N
hexadecylammonio)propane-l-sulfonate and 3-(~,N-dimethyl-N-hexadecylammonio)-2-hydroxy propane-l-sulfonate.
(e) Cationic detergents include those naving the formula -R - N(R2)3(+)X( ) wherein R iS an alkyl chain containing from about 8 to about 20 carbon atoms, each R2 is selected from the group consisting of alkyl and alkanol groups containing from 1 to 4 carbon atoms and benzyl groups there being normally no more than one benzyl group and two R groups can be joined by either a carbon-car- ;
bon ether, or imino linkage to form a ring structure, and X -represents a halogen atom, sulfate group, nitrate group or -~
other pseudohalogen group. Specific examples are coconut alkyl trimethyl amine chloride, dodecyl dimethyl benzyl bromide, and - ~ -dodecyl methyl morpholino chloride.
Especially preferred herein are water-soluble synthetic detergents which exhibit desirable scum-dispersing properties. Inasmuch as bar soaps are usually employed for cleansing the skin while bathing, the presence of a curd-dispersing surfactant in the composition of the invention is preferred. The presence of hardness in the bath water fre-quently causes the formation of soap curd which, in combination `~
with an emollient bath oil and body soils or lipids, can result in the formation of unsightly curd-like material floating on the surface of the water and collecting as hard to-remove ring around the bathtub. The use of a detergent component capable of dispersing any such sepp curds const~tutes a preferred aspect of the present învention. Preferred curd~dispersing surfactants herein include the alkali metal, e.g., sodium, .
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alkyl glxceryl etner sulfonates havi~n~ f~ 10 to 18 carbon atoms in the alRyl group, especially th`os~ et~ers of the higher alcohols derived from tallow and coconut oil; and the long~
chain tertiary amine oxide detergents exemplified ~ereinBefore.
These curd-dispersing detergents provide copious foam formation in bathtub use and are virtually insoluble in a preferred emollient, mineral oil. Other curd-dispersing detergents include the condensation products of aliphatic alcohols having from 8 to 22 carbon atoms with ethylene oxide; the alkali metal ~-acetamido-alkanesulfonates and the fatty acid esters of alkali metal isethionates and the alkali mètal salts of sul-furic acid esters of the reaction product of one mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) with about 1 to 6 moles of ethylene oxide.
The water-soluble synthetic detergent of the composi-tions of the invention is employed in an amount sufficient to provide desired suds formation under normal usage conditions.
In some instances copious suds formation will be desired while in others a bathing composition providing less sudsing effects may be preferred by the user. Depending upon the faaming capacity and amount of the particular detergent employed, desirable variations can be obtained. Normally the detergent component will comprise from about 10% to 60% by weight of the composition. Preferably, the detergent comprises from 20% to 50% by weight of the composition. While some users will tend to use more or less of the compositions of the invention than others, the use of a sufficient amount to provide about 0.4 g of a copious foaming detergent per gallon of hbth tub water will normally be sufficient to provide desired suds formation.
Mixtures of detergent compounds can be employed ~here desired. A preferred detergent com~ination comprises an al~ali metal alkyl glyceryl ether sulfonate ~av~ng from 10 to ~12_ ,.. .

18 carbon atoms ~n the alk~l group and an a~ine oxide deter~ ;
gent having one al~yl of from 8 to 24 carbon atoms and two short-chain alkyl groups. Such a com~ination is virtually ~nsoluble in mineral oil. Dispersed in min~ral oil, it pro-vides desirable suds formation and permits the formation of a stable viscous composition exhibiting uniform viscosity upon storage.
A further preferred detergent composition comprises a water-soluble, scum-dispersing synthetic detergent, for instance, an alkali metal alkyl glyceryl ether sulfonate -having from 10 to 18 carbon atoms in the alkyl group, together with a fatty acid mono- or di-alkanolamide, or a mixture of the two. The fatty acid alkanolamides act to increase the initial level and the stability of suds formed when a sample of the composition is dispersed in water. Preferably, the composition comprises a mixture of lauric monoethanolamide and lauric diethanolamide, this combination giving good initial suds height and suds stability in bo~h soft and hard water.
The amides are generally used in a q-ight ratio lying between 10 to 1 to 1 to 1, but a ratio of 2 to 1 has been found to be particularly effective. The alkali metal alkyl glyceryl ether sulfonate by itself is also a preferred detergent.
It will be recognized that some of the above deter-gents will be liquids in the pure form. In such instances, a sufficient amount of an inorganic material will be added to ;
the detergent to make the mixture a solid at room temperature. ;-As stated hereinbefore, the water-soluble detergent component is admixed or distributed through the emollient continuum in the form ~f very small particles. These particles can contain a water-soluble organic or inorganic builder salt.
Builder salts s~rve as a convenient carrier or vehicle for the water-soluble detergent component and serve as a des;rable . .
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moisture s~n~. In some cases they ~elp sta~llze suds or f~a~
aga~nst collapse when soap is dissolved l`n the bath w~ter and minimize the formation of sticky lime soap bar curds.
Suitable water-soluble inorganic alkaline builder salts that can be emp~oyed alone or ~n adm~xture are the alkali~
metal carbonates, borates, phosphates, pol~phosp~ates, b~i`car~
bonates and silicates. The ammonium or suDstituted~ammonium salts can also be employed. Specific examples of suitable --builder salts incl~de sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, sodium acid pyro-phosphate, sodium bicarbonate, potassium tripolyphosphate, potsasium~ pyrophosphate, sodium hexametaphosphate, sod;um sesquicarbonate, sodium mono-and di-orthophosphate and potessium bicarbonate.
Examples of water-soluble organic alkaline sequestrant builder salts used alone or in admixture are alkali metal, ammonium or substituted-ammonium, aminopolycarboxylates, e.g., sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-~2-hydroxyethyl)-ethylenediaminetri-acetates, sodium and potassium nitrilotriacetates and sodium, potassium and triethanolammonium, N-(2-hydroxyethyl)nitrilodiacetate.
Other organic alkaline sequestrant builder salts which can be used are: hydroxyethylenediaminetriacetates; 2-hydroxy- -ethyliminodiacetates, diethylenetriaminepentaacetates; 1,2-diaminocyclohexanetetraacetates and the alkali metal citrates.
Mixed salts of these polycarboxylates are also suitable. The alkali metal salts of phytic acid e.g. sodium phytate are also suitable as organic alkaline sequestrant builder salts (see U.S. Patent 2,739,942 Inasmuch as the compositions of the invention will -~
be in contact with the skin of the user the detergen component will be formulated to provide a pH in use within the range of .: ; ' ', ' , , ~.

1~46888 from about 4 to about 10, depending u~on the particular deter~
gent or ~aterl'al employed. Preferably, a p~ ~n t~e range of 5 to 8 is provided.
The emollient component of the compositions of the invention comprises a ~ater-insoluble and/or water immiscible oily material having skin softening or conditioning properties.
Suitable emollient materials which can be employed herein are those which combine with a foaming surfactant in a relation of mutual insolubility and include emollîent materials known ~n the bath oil arts. These include light-to-heavy mineral or hydrocarbon oils, vegetable oils, such as olive oil, arachid oil, sesame oil, castor oil, peanut oil, almond oil, annflower oil, safflower oil, cottonseed oil, coconut oil, synthetic esters such as isopropyl myristate, isopropyl palmitate, isopropyl stearate, decaglycerol, decalinoleate and the lanolin and chloresterol derivatives such as the lanolin alcohols and esters and silicone oils. Preferred emollients include mineral oil having a viscosity of from about 20 cp to 200 cp and isppropyl myristate which are readily available and in which preferred foaming surfactants such as alkyl glyceryl ether sulfonates, amine oxides and olefin sulfonates are virtually insoluble. Especially preferred are mixtures of mineral oil and isopropyl myristate, e.g. 20% mineral oil/80% isopropyl myristate.
The emollient component will normally be admixed with the foaming surfactant described hereinbefore in an amount of from 40% to about 90%. Use of less thah about 40% tends to ~ive a product which is not sufficiently fluid, while amounts greater than about 90% provide little additional benefit and limit the amount of the detergent component that may be accom-modated. The relative amounts of emollient and detergent com-ponent can, however, be varied according to the relative degrees .. . . . . . .
- .

~046888 of emollient deposition on the skin, suds$ng and curd.disper-s~on properties desi`red and the inherent foaming and skin-deposit;ng or conditioning properties of the particular materials employed. The emollient will preferably ~e empolyed in an a~ount of from 50% to about 80% of the compositions of the invention.
The extent to which the compositions of the inven~ion will provide foaming and skin depositing or conditioning prop-erties.,will.. dépend..up~n.~the degree to~,which.~the~-respectiv.e-~ ~
foaming and e~ollient compounds exhibit their respective prop- ..
erties in the absence of incompatible or antagonistic material and upon the degree of incompatibility or solubili~ when employed in combination. Combinations of foaming surfactant and emollient material will permit maximmm realization of the ' inherent properties of the respective components where the ,.
materials are mutually insoluble as defined hereinbefore. Best '.
results are achieved where the solubility is less than 0.01%. ~`.,, Combinations of surfactants which exhibit low orders of mutual ~.
solubility include the following at a 50/50 by weight pro-~. , portion: sodium coconut-alkyl glyceryl ether sulfonate and. ' mineral oil; lauric diethanolamide and mineral oil; dimethyl ~
coconut-alkyl amine oxide and mineral oil; olein acid ester , :.
of sodium isethionate and olive oil; sodium ~-olefin sulfonate and mineral oil; potassium coconut-alkyl sulfate and mineral -:.
oil; and potassium coconut-alkyl sulfate and isopropyl .. -myristate. :-Preferred combinations of the invention are those ' which include a surfactant which exhibits a high intrinsic ~.
capacity for foam formation in a~ueous solut~on and which is infiol~le'..in-the emollient oil. .~ ~uch ~combination~ ar~.pr~ red from the standpoints of their copious foaming properties and ~ ~ .

1~46888 their emolliency e~ects and include com~ositions compris~ngc frcm 20~ to 60% of a ~ater~oluble foamlng organic deter~ent selected from the group consisting of al~ali metal alkyl glyceryl ether sulfonates having from 10 to 18 carbon atoms in the alkyl group; ~ong-chain tertiary amine oxides having the formula ~2 Rl _ (oR4)n- N ~ O

wherein R' is alkyl of from 8 to 24 carbon atoms, R2 and R3 are each methyl, ethyl or hydroxyethyl, R4 is ethylene and n is 0 to 10; and alkali metal olefin sulfonates of from 8 to 24 carbon atoms; mixtures thereof; and from 40% to 80% mineral oil; neither the water-soluble foaming organic detergent nor mineral oil being soluble in the other to an extent greater than about 0.1% and the composition having a free moisture content of up to 2%.
These preferred compositions are illustrated, for example, by homogeneous and mutually-insoluble admixtures ~50/50 by weight) of sodium coconut-alkyl glyceryl ether sulfonate and mineral oil; dimethylhexadecyl amine oxide and mineral oil; sodium salt of sulfonated l-tetradecene and mineral oil.
An~-essential aspect of the compositions of the present invention is that they be formulated so as to be substantially anhydrous. For purposes of the present invention, substantially anhydrous compositions are those which have substantially no free or uncombined moistu~e. Such compositions will h~ve an amount of free or uncombined moisture of less than about 2% by weight of the composition and are considered herein as being substantially anhydrous. Preferably the compositions have less than about 1% free moisture. The presence of free or uncombined 17~

1~46888 moisture, as opposed to that w~ch ~a~ ~e pxesent as water of hydration or water of crystallization, w~ll permit emNls~f~'cat~on of the emollient by the detergent component and t~ereby reduce the efficiency of the detergent/emollient system. Free moisture permits emulsification within the composit~on itself thereby reducing ~he amount of oil available for delivery in bath use in the form of a floating layer of oil which can ~e deposited upon the skin of the bather. It has been found that careful control of both mutual solubility and free moisture content permits dellvery of emollient in bath tub use to provide a layer of emollient upon the surface of the bath water. While ~-applicant does not wish to be bound by any theory as to the ;
mechanism by which desirable foaming and formation of a layer of emollient on the water surface is obtained, it is believed that the rapid dissolution of the foaming detergent component to provide a dilute solution of detergent active prevents dispersion or emulsification of the emollient component and thereby permits the emollient to form a film layer on the surface of the bath water and beneath a layer of suds.
The compositions of the invention can be maintained in a substantially anhydrous state by assuring that the detergent and emollient components are themselves substantially anhydrous.
The compositions can, however, be maintained in an anhydrous condition by the incorporation of desiccant materials to serve as a moisture sink and thereby prevent moisture pick-up that might tend to promote emulsification within the composition.
Thus, the compositions of the invention can contain components having hydratability characterist~cs so as to provide a moisture sink for free moisture that may come into contact with the ~ -compositions of the invention during pro~es~ , packaging, storing or the like. Suitable materials in~lude sodium sulfate, magnesium sulfate, the water-soluble carbonates and phosphates such as sodium tripolyphosphate, sodium metaphosphate, sodium ses~uicarbonate and t~e l~e descr~Bed hereinbefore. Other examples are described at column 2, line 65 to column 4, line 40 in U.S. Patent 3,451,935 issued June 24, 1969 to Roald et al, The compositions of the invention can optionally contain adjuvants, diluents or additives which provide desirable aesthetic qualities or render the compositions more effective.
Perfume, for example, can be employed and can be suitably incorporated into the detergent or emollient or added to compositions of the invention in the form of an admixture of perfume oils and inert absorbent powder such as bentonite, - -starch or powdered milk to minimize contact of the perfume with alkaline components of the compositions. F~ller or diluent materials such as urea, sugars, soaps, sodium chloride, sodium ~ -sulfate, talc or the like can also be employed. Antimicrobial agents, bacteriostatic agents, dyes, sunscreens, suds builders such as long-chain alkyl amine oxides and fatty acid alkanol-amides, suds suppressors and the like can be employed herein without detracting from the advantageous properties of the compositions of the invention.
While the foaming and conditioning compositions of t~e invention have been described for the most part in connection with their suitability as foaming and s~in-conditioning com-positions intended for bathing use, the compositions can also be employed as shampoos. Thus, they can be employed for the cleaning of haif so as to effect simultaneously hair conditioning or emollient effects and thereby improve manageability of the hair for grooming. The shampoo compositions will be employed in use by direct application to the scalp but upon addition b~
water will provide a layer of oil beneath a layer of suds.
Accordingly, such compositions are intenaed as being within the scope of the appended claims.

,....

The following are examples illustrative but not limitative of the compos~tions of t~e present invent~on.
EX~MPLE

. , A composition containing alkyl glyceryl ether sulfonate paste t96 parts), anhydrous sodium sulfate (3.92 parts) and dye (0.08 parts) was dried by drum drying to a solid flake contain~ng 0.8% of moisture. The flake, in the drum dried form of 2~3cm.
rolls, was further treated by freeze grinding with liquid nitrogen to yield a fine free flowing powder of 0.9~ moisture content. The freeze gri~d~ng technique involved pre-co~ling -the surfactant flake with liquid nitrogen prior to mechanical milling by a conventional hammer mill. By this technique the consumption of liquid nitrogen was 1 part per 1 part of flake processed and a grinding temperature of -150C was reached. The -~
embrittling effect thereby achieved allowed production of a finely -d~vided powder having no materi~ greater than 100# size and a proportion of 80 wt. % finer than 200#. The bulk density of this powder was 0.45 gm/cc.
A blend of mineral oil (20 p,ar~s), ~so~ropyl myristate (44 parts) and the freeze ground sur~actan~-p~Wder ~3~ ~A~Ei was made with the powder evenly dispersed through the oil phase.
The blend was passed onç through a colloid mill to jive a visually homogeneous prod~ct to which perfume`(~ parts) was added.
Final product visocosity was 130 cp.
The product made by freeze grinding was tested for disperaability against product made to the same formulation but ~ -in which the detergent powder was ~pray dried. In the freeze ~ -ground product the detergent particles had a bulk density of O.45 gm~cc and were of such size ~at 92% by weight passed a 100 mesh screen and 80~ passed through a 200X ~creen. The spray dried particles had a hulk density of 0.3 gm/cc and were of such size that 82% of the particles passed through a 100# screen . . ' ,~'' '' 1()46888 and 30% passed through a 200# screen.
A 2cm diameter glas~ tu~e was f~lled to 150 cm depth with water at 110T, 2 cc of the spray dried product was - -~ntroduced into the base of the column of water. Some dispersion of the oil and surfactant components was observed to take place but some particulate aggregates of surfactant rose the full length of the tube and settled on the free surface. -When 2 cc of the freeze ground product was introduced into a fresh column of water at the same temperature there were no d~scernible particulate aggregates rising above 30 cm from the base of the column.
The above show the superiority of freeze dried particles having a particle size predominantly sl~ller than that corresponding to a 200 mesh screen as opposed to a representative spray-dried product having a larger particle size and a lighter density.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A foaming and conditioning composition providing suds and a layer of emollient oil upon addition to water consisting essentially of a mutually, insoluble mixture of a water-soluble foaming organic detergent and a water-insoluble oily material having skin-softening or emollient properties, neither the detergent nor the oily material being soluble in the other in an amount greater than about 0.1% by weight of the solvent material, the composition being substantially anhydrous, the viscosity of the composition being less than 500 centipoises, and the organic detergent being present at a level of from about 10 to about 60% by weight of the composition, and being in the form of finely divided particles containing at least 50% by weight of an organic surfactant selected from the group consisting of anionic, nonionic, cationic, zwitterionic and amphoteric surfactants, and having a moisture content of less than 5% by weight, at least 90% of said particles being of a size to pass a 100 mesh screen and at least 50% of said particles being of a size to pass a 200 mesh screen, and said particles having a bulk density of at least 0.4 gm./cc.

2. The composition of claim 1 wherein the detergent particles contain at least 75% by weight of organic surfactant.

3. The composition of claim 1 wherein the detergent particles contain at least 90% by weight of organic surfactant.

4. A composition according to claim 2 wherein at least 70% of the particles pass through a 200 mesh screen.

5. A composition according to claim 4 wherein the moisture content of the detergent particles is less than 2%.

6. A composition according to claim 5 wherein the moisture content of the detergent particles is less than 1%.

7. A composition according to claim 2 wherein the detergent particles are prepared by freeze-grinding.

8. A composition according to claim 2 wherein the organic surfactant is selected from the group consisting of anionic, nonionic, amphoteric and zwitterionic surfactants.

9. A composition according to claim 8 wherein the water-soluble foaming organic detergent constitutes from 20 to 50% by weight of the composition.

10. A composition according to claim 8 wherein the organic surfactant is selected from the group consisting of alkali metal alkyl glyceryl ether sulfonates wherein the alkyl group has from 10 to 18 carbon atoms; amine oxides having a long-chain alkyl radical of from 8 to 24 carbon atoms; alkali metal olefin sulfonates of from 8 to 24 carbon atoms; and mixtures thereof.

11. A composition according to claim 10 wherein the water-soluble foaming organic detergent includes a surface-active material selected from the group consisting of fatty acid monoalkanolamides, fatty acid dialkanolamides and mixtures of fatty acid monoalkanolamides and fatty acid dialkanolamides.

12. A composition according to claim 11 wherein the water-soluble foaming organic detergent includes a mixture of lauric monoethanolamide and lauric diethanolamide in a weight ratio lying between 10 to 1 and 1 to 1.

13. A composition according to claim 2 wherein the oily material having skin-softening or emollient properties is a mineral oil.

14. A composition according to claim 13 wherein the organic surfactant is an alkali metal alkyl glyceryl ether sulfonate wherein the alkyl group has from 10 to 18 carbon atoms.