US3798179A - Granular free-flowing detergent bath composition - Google Patents

Abstract

THERE ARE DISCLOSED GRANULAR, FREE-FLOWING DETERGENT BATH COMPOSITIONS CONSISTING ESSENTIALLY OF A WATER SOLUBLE SYNTHETIC ORGANIC DETERGENT (E.G., AN ALKALI METAL ALKYL GLYCERYL ETHER SULFONATE WHEREIN THE ALKYL HAS FROM 10 TO 18 CARBON ATOMS) AND A MICROENCAPSULATED WATER INSOLUBLE AND/OR WATER-IMMISCIBLE EMOLLIENT (E.G., MINERAL OIL OR A MIXTURE THEREOF WITH ISOPROPYL MYRISTRATE). THE MICRORENCAPSULATED WATER-INSOLUBLE BATH OIL HAS A HYDROLYZED PROTEIN ENCAPSULATING WALL MATERIAL SOLUBLE IN WATER AT A TEMPERATURE OF FROM 75*F. TO 115*F. TO RELEASE THEREFROM EMOLLIENT BATH OIL. THE COMPSTIONS UPON ADDITION TO BATH PROVIDE COMBINED SUDSING AND SKIN EMOLLIENT EFFECTS WITHOUT MUTUAL ANTAGONISM OR INTERACTION, PROVIDING A FLOATING LAYER OF EMOLLIENT BENEATH A LAYER OF SUDS. A WATER-SOLUBLE ALKALINE BUILDER SALT, SUCH AS SODIUM TRIPOLYPHOSPHATE, MAY BE EMPLOYED IN COMBINATION WITH THE WATER-SOLUBLE SYNTHETIC ORGANIC DETERGENT.

Description

United States Patent 3,798,179 GRANULAR FREE-FLOWING DETERGENT BATH COMPOSITION James A. Hellyer, Cincinnati, Ohio, assignor to The Procter 8: Gamble Company, Cincinnati, Ohio No Drawing. Filed June 29, 1971, Ser. No. 158,107

Int. Cl. C11d 1/28, 3/065 US. Cl. 252-535 13 Claims ABSTRACT OF THE DISCLOSURE There are disclosed granular, free-flowing detergent bath compositions consisting essentially of a water soluble synthetic organic detergent (e.g., an alkali metal alkyl glyceryl ether sulfonate wherein the alkyl has from to 18 carbon atoms) and a microencapsulated water insoluble and/or Water-immiscible emollient (e.'g., mineral oil or a mixture thereof with isopropyl myristate). The microencapsulated water-insoluble bath oil has a hydrolyzed protein encapsulating wall material soluble in water at a temperature of from 75 F. to 115 F. to release therefrom emollient bath oil. The compositions upon addition to bath provide combined sudsing and skin emollient effects without mutual antagonism or interaction, providing a floating layer of emollient beneath a layer of suds. A water-soluble alkaline builder salt, such as sodium tripolyphosphate, may be employed in combination with the water-soluble synthetic organic detergent.

This invention relates to detergent bath compositions. More particularly, it relates to detergent compositions efiective to provide in the bathtub a desirable quantity of suds and water-insoluble emollient.

The preparation of compositions adapted to use in bathing has been 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 surface 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 $0 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, attempts 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. The mutually antagonistic properties of foam formation and emolliency are referred to by T. Kaufman in American Perfumer and Cosmetics, vol. 80, pp. 29-31 (February 1965). Also described is the formulation of a foaming hath oil described as a compromise to the attainment of copious foam formation and emolliency.

It is an object of this invention to provide a detergent composition effective to provide a bath having both desirable sudsing and emolliency characteristics.

It is another object of this invention to provide a foaming bath composition exhibiting the capability of delivering to the skin of the bather a quantity of emollient sufficient to impart a noticeably smoother skin feel and to deposit an emollient film barrier to excessive moisture loss from the skin after bathing.

It is a further object of the invention to provide a detergent bath composition in a granular free-flowing form effective upon dissolution in water to simultaneously provide suds formation and emolliency characteristics without mutual antagonism and loss of efiiciency of the foaming and emollient components.

SUMMARY OF THE INVENTION The present invention is based in part upon the discovery that a detergent bath composition elfecti-ve to provide sudsing and emolliency charcteristics can be prepared by admixing a dry microencapsulated water-insoluble emollient material with a dry free-flowing water-soluble detergent component. It has been discovered that the physical separation of emollient and detergent active attained by microencapsulation of the emollient material permits the separate introduction of such materials into bath wa ter without compromise of the desirable attributes of the respective components.

In its composition aspect, the present invention resides in a granular free-flowing detergent bath composition comprising a water-soluble synthetic organic detergent; and a microencapsulated water-insoluble emollient bath oil having an encapsulating wall material soluble in water at a temperature in the range of from F. to F. to release therefrom an emollient bath oil.

DETAILED DESCRIPTION OF THE INVENTION The detergent bath compositions of the present invention, by virtue of physical separation of the respective detergent and emollient components in a granular freeflowing form, permit introduction of the detergent and emollient materials into a bath water in such a manner as to eliminate or at least minimize the mutual antagonistic interaction heretofore expected in the art. The synthetic organic detergent and emollient components are, thus, permitted to perform their intended functions without undesirable competing elfects. Interaction of the detergent and emollient components to result in the formation of an emulsified oil composition is eliminated to provide an elfective detergent bath composition capable of providing the desirable properties described hereinbefore. These properties are attained notwithstanding the rapid watersolubility of the emollient-encapulating wall material which permits the virtually simultaneous introduction of water-soluble emollient and detergent active into a bath solution.

The water-soluble synthetic organic detergent compounds which can be employed in the compositions of this invention are the non-soap anionic, nonionic, ampholytic and zwitterionic synthetic detergents and mixtures thereof which are exemplified as follows:

(a) Anionic synthetic non-soap detergents, a preferred class, can be broadly described as the water-soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. (Included in the term alkyl is the alkyl portion of higher acyl radicals.) Important examples of the synthetic detergents which form a part of the compositions of the present invention are the sodium or potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (Cg-C13 carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, including those of the types described in US. Letters Patent Nos. 2,220,099 and 2,477,383 (the alkyl radical can be a straight or branched aliphatic chain); sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts or sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and about 1 to 6 moles of ethylene oxide; sodium or potassium salts 3f alkyl phenol ethylene oxide ether sulfate 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 acids are derived from :oconut oil; sodium or potassium salts of fatty acid amide at a methyl tauride in which the fatty acids, for examale, are derived from coconut oil; sodium or potassium S-acetoxyor fl-acetamido-alkanesulfonates where the ilkane has from 8 to 22 carbon atoms; and others known 11 the art, a number specifically set forth in US. Letters Patent Nos. 2,486,921, 2,486,922 and 2,396,278. Other mportant anionic detergents, sulfonated olefins, are de- :cribed in US. Pat. 3,332,880, issued July 25, 1967, to Phillip E. Pfiaurner and Adriaan Kessler.

(b) Nonionic synthetic detergents: One class can be )roadly defined as compounds produced by the condensaion of alkylene oxide groups (hydrophilic in nature) with [11 organic hydrophobic compound, which can be aliphatic )1 alkyl aromatic in nature. The length of the hydrophilic )r polyoxyalkylene radical which is condensed with any articular hydrophobic group can be readily adjusted to ield a water-soluble compound having the desired degree f balance between hydrophilic and hydrophobic elenents. Another class has semi-polar characteristics. Preerred classes of nonionic synthetic detergents are as folows:

(1) A class of nonionic synthetic detergents under the rade name of Pluronic. These compounds are formed ly condensing ethylene oxide with a hydrophobic base ormed by the condensation of propylene oxide with proylene glycol. The hydrophobic portion of the molecule lhiCh, of course, exhibits water insolubility, has a moecular weight of from about 1500 to 1800. The addition f polyoxyethylene radicals to this hydrophobic portion ends to increase the water solubility of the molecule as 21 111016 and the liquid character of the product is retained p to the point where the polyoxyethylene content is bout 50% of the total weight of the condensation prod- Lot.

(2) The polyethylene oxide condensates of alkyl pheols, e.g., the condensation products of alkyl phenols havig an alkyl group containing from about 6 to 12 carbon toms in either a straight chain or branched chain conguration with ethylene oxide, the said ethylene oxide eing present in amounts equal to to 25 moles of ethylne oxide per mole of alkyl phenol. The alkyl substituent 1 such compounds may be derived from polymerized proylene, diisobutylene, octene, or nonene, for example.

(3) Those nonionic synthetic detergents derived from 1e condensation of ethylene oxide with the product reilting from the reaction of propylene oxide and ethylene iamine. For example, compounds containing from about 0% to about 80% polyoxyethylene by weight and havlg a molecular Weight of from about 5,000 to about 1,000 resulting from the reaction of ethylene oxide roups with a hydrophobic base constituted of the reacon product of ethylene diamine and excess propylene xide; said base having a molecular weight of the order 1: 2,500 to 3,000 are satisfactory.

(4) The condensation product of aliphatic alcohols aving from 8 to 22 carbon atoms, in either straight chain r branched chain configuration, with ethylene oxide, e.g.,

coconut alcohol ethylene oxide condensate having from to 30 moles of ethylene oxide per mole of coconut cohol, the coconut alcohol fraction having from 10 to 4 carbon atoms.

(5) The amm ia, monoe hanol and die han l mi of fatty acids having an acyl moiety of from about 8 to about 18 carbon atoms. These acyl moieties are normally derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil and tallow, but can be derived synthetically, e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer- Tropsch process.

(6) Long chain tertiary amine oxides corresponding to the following general formula wherein R is an alkyl radical of from about 8 to about 24 carbon atoms, R and R are each methyl, ethyl or hydroxyethyl radicals, R is ethylene, and n equals from O to about 10. The arrow in the formula is a conventional representation of a semi-polar bond. Specific examples of amine oxide detergents include: dimethyldodecylamine oxide; cetyldimethylamine oxide; bis-(Z-hydroxyethyl) dodecylamine oxide; bis-(2-hydroxyethyl)-3- dodecoxy-l-hydroxypropyl amine oxide.

(7) Long chain tertiary phosphine oxides corresponding to the following general formula RRR"P O wherein R is an alkyl, alkenyl or monohydroxyalkyl radical ranging from 10 to 24 carbon atoms in chain length and R 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 a semi-polar bond. Examples of suitable phosphine oxides are found in US. Pat. 3,304,262 of Feb. 14, 1967 and include: dimethyldodecylphosphine oxide; diethyldodecylphosphine oxide; dimethyl-(2-hydroxydodecyl) phosphine oxide.

(8) Long chain sulfoxides having the formula wherein R is alkyl radical containing from about 10 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 R being an alkyl radical containing 0 ether linkages and containing from about 10 to about 18 carbon atoms, and wherein R 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 sulfoxides; 3-hydroxy tridecyl methyl sulfoxide; 3-methoxy tridecyl methyl sulfoxide; 3-hydroxy4-dodecoxybutyl methyl sulfoxide.

(c) Ampholytic 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 contain 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 can 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 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, phosphate, or phosphono. Examples of compounds falling within this definition are 3-(N,N-dimethyl- N-hexadecylammonio) propane-l-sulfonate and 3-(N,N- dimethyl-N-hexadecylammonio) 2 hydroxy propane-1- sulfonate.

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 curddispersing surfactant in the compositions of the invention is preferred. The presence of hardness in the bath water frequently 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 curdlike material floating on the surface of the water and collecting as a hard-to-remove ring around the bathtub. The use of a detergent component capable of dispersing any such soap curds constitutes a preferred aspect of the present invention. Suitable curd-dispersing surfactants herein include the alkali metal, e.g., sodium, alkyl glyceryl ether sulfonates having from to 18 carbon atoms in the alkyl group, especially those ethers of the higher alcohols derived from tallow and coconut oil; alkali metal salts of sulfuric 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 long-chain tertiary amine oxide and zwitterionic detergents exemplified hereinbefore; the condensation products of aliphatic alcohols having from 8 to 22 carbon atoms with ethylene oxide; the alkali metal B-acetamidoalkane-sulfonates and the fatty acid esters of alkali metal isethionates.

The water-soluble synthetic detergent of the compositions of the invention is employed in an amount sufiicient 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 particular detergent and amount employed, desirable variations can be obtained. Normally the detergent component will comprise from about 4% to 20% by weight of the composition. Preferably, the detergent comprises from 7% to 10% 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 suificient amount to provide about 0.1 g. of detergent component per gallon of bathtub water is normally sufiicient to provide desired suds formation.

The water-soluble detergent component can be employed as a free-flowing powder or granule prepared by spraydrying, agglomerating or other methods known in the art. Preferably, the water-soluble detergent component is employed in a granular or agglomerated form in combination with a water-soluble organic or inorganic builder salt. Builder salts serve as a convenient carrier for the Watersoluble detergent component, serve as a desirable moisture sink in maintaining free-flowing properties, in some cases help stabilize suds or foam against collapse when soap is dissolved in the bath Water and minimize the formation of sticky lime soaps or curds.

Suitable water-soluble inorganic alkaline builder salts that can be employed alone or in admixture are the alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. The ammonium or substitutedammonium salts can also be employed. Specific examples of suitable builder salts include sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, sodium acid pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, potassium pyrophosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium monoand di-orthophopshate and potassium 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 potassium et-hyplenediaminetetraacetate, sodium and potassium N-(2-hydroxyethyl)ethylenediaminetriacetates, sodium and potassium nitrilotriacetates and sodium, potassium and triethanolammonium, N-(2- hydroxyethyl) nitrilodiacetate. Other organic alkaline sequestrant builder salts which can be used are: hydroxyethylethylenediaminetriacetates; 2 hydroxyethyliminodiacetates, diethylenetriarninepentaacetates; 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. Pat. 2,739,942).

The detergent granules utilized herein, alone or in combination with a water-soluble builder or carrier salt, are preferably formed by the well-known spray-draying process. The particle sizes of these granules should range from about 0.1 mm. to about 1.5 mm. and the densities should range from about 0.1 to about 0.8 gram/cc. to avoid segregation of the granules from the microencapsulated emollient and other components of the compositions of the invention.

Inasmuch as the compositions of the invention will be in contact with the skin of the user the detergent granules will be formulated to provide a pH within the range of from about 5 to about 10, depending upon the particular builder or carrier material employed. Preferably, they provide a pH in the range of 7 to 9.

In a preferred composition of the invention, spraydried or agglomerated detergent granules consisting essentially of water-soluble synthetic organic detergent and water-soluble alkaline builder salt in a ratio of detergent to builder salt of from 2:1 to 1:10 are employed. A preferred ratio is from 1:1 to 1:6. Such granules comprise from 20 to of preferred detergent bath compositions of the invention. Amounts of less than 20% tend to provide insufiicient foaming action under normal usage conditions While amounts substantially greater than 90% tend to detract from the amount of emollient component that may be accommodated. Preferably, the detergent granules are employed in an amount of from 40% to 60%.

The microencapsulated emollient component of the compositions of the invention comprises a water-insoluble and/or water-immiscible oily material encapulsated with a suitable wall material in the form of minute capsules. Suitable emollient materials which can be employed herein in microencapsulated form include any of the large variety of oils having an emollient or anointing effect and known in the bath oil arts. These include 1ight-toheavy mineral or hydrocarbon oils, vegetable oils, such as olive oil, arachid oil, sesame oil, castor oil, peanut oil, almond oil, sunflower oil, safflower oil, cottonseed oil, coconut oil, synthetic esters such as isopropyl myristate, isopropyl palmitate, isopropyl stearate, decaglycerol, decalinoleate and the lanolin and cholesterol derivatives such as the lanolin alcohols and esters and silicone oils. Especially preferred is a mixture of mineral oil and isopropyl myristate.

The wall material of the microencapsulated emollients herein is a material which permits the preparation of cap sules which are durable against forces such as those encountered in processing, packaging and shipping and which rapidly dissolve in aqueous solution. Suitable wall materials include gelatin, gelatin/gummi/arabicum, succinated gelatin, gelatin/ sodium alginate and like hydrolyzetlprotein materials. These wall materials comprise from about 10 to 30% by weight of the microcapsules.

Suitable microencapsulated emollients are those having a wall material that permits rapid dissolution upon addition to bath water. Such microcapsules are those which release substantially all of their emollient content immediately upon addition to bath Water at a temperature suitable for bathing, i.e., from about 75 F. to about F. Preferably, they dissolve within 2 minutes, especially within /2 minute. It has been found quite surprisingly, that notwithstanding immediate release of the emollient to provide a layer of emollient upon the surface of the bath water, that no appreciable effect on sudsing is observed and emulsification of the emollient component does not occur to any appreciable extent. 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 detergent granules 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.

Particle sizes of the microencapsulated emollient can vary widely and will depend upon processing conditions employed in their preparation and on the nature of the particular emollient and wall materials employed. Generally, the microcapsules have diameters within the range of from to 2000 microns. Preferred capsules herein are those which can be suitably admixed with detergent granules without product segregation and settling and which have a bulk density nearly equal to that of the detergent granules.

The microencapsulated emollient component of the compositions of the invention can be prepared by methods known in the art. Typically, such microencapsulated materials are prepared by a coacervation process involving the establishment of a three-phase system of liquid vehicle continuous phase, coating or wall material and emollient as dispersed phases, deposition of a liquid polymeric wall material around the material to be coated and gelation of the polymeric coating or wall material. Suitable microencapsulation process for preparing microencapsulated emollients suitable herein are described in US. Pats. 2,800,457 and 2,800,458 to Green (July 23, 1957) and in Kirk-Othmer Encyclopedia of Chemical Technology, 2nd ed., vol. 13, pp. 436-456 (1967), incorporated herein by reference.

The microencapsulated component will normally be admixed with the detergent granules described hereinbefore in an amount of from to about 80%. Use of less than about 10% of the component tends to provide an insufiicient amount of emolliency under normal usage levels while amounts greater than about 80% provide little additional benefit and minimizes the amount of detergent that may be accommodated. The amounts of microencapsulated emollient and detergent granules can be varied according to the relative degrees of emollient deposition on the skin, sudsing and curd-dispersion properties desired. The microcapsules are preferably employed in an amount of from 40% to about 60% of the compositions of the invention.

An essential aspect of the compositions of the present invention is that they be formulated so as to have substantially no free or uncombined moisture. Inasmuch as the microcapsules are prepared so as to relase their emollient immediately upon addition to water, it is essential that free moisture in the compositions of the invention be controlled so as to prevent or minimize dissolution of the microcapsule wall of the composition. Free moisture in the compositions of the invention permits dissolution of microcapsule walls, release of the emollient contained :herein, dissolution of the water-soluble organic detergent and emulsification of the emollient by the detergent. The affect of excess free moisture is manifested by a tacky, ;ticky and/or caking composition or viscous liquid or gel product characterized by a loss of emollient and dezerging effects. The compositions of the invention are charlcterized by having a free moisture content, not in excess )f about 5% of the composition and sufiiciently low as :o minimize rupture of the capsule walls, release and :rnulsification of the emollient contained therein. Preferred from the standpoint of assuring free-flowing prop- :rties is a free moisture content of about 3% or less.

The compositions of the invention can be maintained n a substantially dry and free-flowing state by assuring hat the detergent and microencapsulated emollient com- Jonents are substantially dry and free-flowing. In this regard, detergent or detergent/builder mixtures having a 'ree or uncombined moisture content of 5% or less are :uitable herein. The compositions of the invention can :ontain components having hydratability characteristics to as to provide a moisture sink for free moisture that may come into contact with the compositions of the invention during processing, packaging, storing or the like. Suitable materials include the water-soluble carbonates and phosphates such as sodium tripolyphosphate, sodium metaphosphate, sodium sesquicarbonate and the like described hereinbefore. Other examples are described at column 2, line 65 to column 4, line 40 in US. Pat. 3,451,935, issued June 24, 1969 to Roald et al. and incorporated herein by reference. In addition, minor amounts of from about 1% to 2% of anti-caking agents such as tricalcium phosphate or colloidal silica to provide desirable free-flowing characteristics can be employed.

The compositions of the invention can optionally contain adjuvants, diluents or additives which provide desirable aesthetic qualities or render the compositions more elfective. Perfume, for example, can be employed and can be suitably incorporated into the detergent or microencapsulated 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. Filler 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 alkanolamides, suds suppressors and the like can be employed herein without detracting from the ad vantageous properties of the compositions of the invention.

The compositions of the invention can be packaged in containers well known in the art or can be packaged in moisture-proof or wax-lined cartons to ensure the flowability of the compositions of the invention and to minimize the possible influences of excessive humidity conditions. The use of bottles, water-soluble plastic pouches or capsules or other protective devices can also be suitably employed.

The following are examples illustrative but not limitative of the compositions of the present invention.

EXAMPLE I C14; 9% C15) 12-5 Sodium tripolyphosphate 25-8 Sodium acid pyrophosphate 2.9 Sodium sulfate 19.1 Water 2.7

The encapsulated emollient, having a bulk density of about 0.4 g./cc. and a particle size distribution such that all passes through a 14 mesh US. Standard screen (1410 microns), was admixed with the spray-dried detergent granules in a rotating mixer and blended to uniform distribution. The encapsulated emollient contained the following ingredients in parts by weight:

Parts Mineral oil 25 Isopropyl myristate 3 Perfume 1 Wall material (water-soluble gelatin/gum arabic) 8 The bath composition had a bulk density of 0.43 and was free-flowing. Analysis showed a total moisture content of 6.5% including 1.7% free moisture. This composition combined desirable sudsing and emollient effects in the bath. Addition of 3 tablespoons of the composition (19.1 g.) to about 25 gallons bath water provides 2.5 g. of curddispersing sodium alkyl glyceryl ether sulfonate and 3 g. of emollient. The composition releases the emollient within one minute at 105 F. and the emollient floats to the water surface. The use of a conventional bar soap with use of the bath composition of the invention in hard water (13 gr./ gal.) does not cause the formation of floating curdli-ke material or its deposition around the bathtub. Addition of the bath composition to the running stream of a filling bathtub results in the formation of a layer of suds over a floating emollient layer with impairment of neither curd dispersion nor emollient deposition.

Results similar to those obtained in the previous example are obtained when the following builder salts are substituted, either wholly or in part, for sodium tripolyphosphate in that bath compositions effective to provide foaming and emollient action are obtained: sodium, potassium, ammonium, monoethanol ammonium, diethanol ammonium and triethanol ammonium salts of the following acids:

ethylenediaminetetraacetic acid; N-(Z-hydroxyethyl)-ethylenediaminetriacetic acid; N-(2-hydroxyethyl)-nitrilodiacetic acid; diethylenetriaminepentaacetic acid; nitrilotriacetic acid; ethylene diphosphonic acid; ethane-l-hydroxy-l,l-diphosphonic acid; ethane-l,1,2-triphosphonic acid; ethane-Z-carboxy-l,1-diphosphonic acid; hydroxymethane-diphosphonic acid; carbonyldiphosphonic acid; ethane-l-hydroxy-l,1,2-triphosphonic acid; ethane-2-hydroxy-1,1,2-triphosphonic acid; propane-1,1,3,3-tetraphosphonic acid; propane-1,l,2,3-tetraphosphonic acid; and propane-1,2,2,3-tetraphosphonic acid and potassium tripolyphosphate;

and salts of polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid and citraconic acid and copolymers with themselves and/or ethylene and/or acrylic acid in, e.g., 1:1 molar ratios and having molecular weights of 75,000; 100,000; and 125,000 (the copolymers with ethylene and/ or acrylic acid having equivalent weights, based on the acid form of 65, 70 and 75); in the form of their sodium, potassium, triethanolammonium, diethanolammonium and monoethanolammonium salts.

Results similar to those obtained in the previous example are obtained when the following organic detergents are substituted, either wholly or in part, for the sodium alkyl glyceryl ether sulfonate in that bath compositions providing combined foaming and emollient action are obtained: sodium linear dodecyl benzene sulfonate, the condensation product of 1 mole of dodecyl phenol with moles of ethylene oxide, dimethyldodecylamine oxide, dimethyldodecylphosphine oxide, 3- (N,N-dimethyl-N- hexadecylammonio) 2-hydroxypropane-1-sulfonate and sodium-3-dodecylaminopropane sulfonate.

EXAMPLE H A granular and free-flowing bath composition suitable for providing a bathing solution having foaming and emollient properties is prepared by dry-mixing 54 parts by weight of detergent granules having the following ingreclients:

Parts Sodium alkyl glyceryl ether sulfonate (where the alkyl is derived from middle-cut coconut oil having the following approximate composition: 2% C 66% C12; C14; C16) Sodium citrate 16 Sodium sulfate 18 Water 1 with 44.5 parts encapsulated emollient having the following ingredients:

Parts Isopropyl palmitate- 36 Perfume 1.2 Wall material (water-soluble gelatin/ gum arabic) 7.3

EXAMPLE III A granular and free-flowing bath composition providing foaming, curd-dispersing and emollient properties was prepared by dry blending 54.2 parts of spray-dried detergent granules having the following composition:

Parts Sodium alkyl glyceryl ether sulfonate (Where the alkyl was derived from middle-cut coconut alcohols from coconut oil and had the following approximate composition: 2% C 66% C 23% 14 9% C16) 19 Sodium sulfate 18.4 Sodium chloride 15.7 Water 1.1

with 45.8 parts of encapsulated oil (through 20 mesh US. Standard, 841 microns) having the following composition:

Parts Mineral oil 33.6 Isopropyl myristate 3.7 Perfume 1.2 Wall material (water-soluble gelatin/ gum arabic) 7.3

The composition was free-flowing, had a bulk density of 0.35 g./cc. and provides sudsing, curd-dispersing and emollient properties on dissolution in water.

EXAMPLE IV The replacement of 37.3 parts of mineral oil and isopropyl myristate of the composition of Example III with 37.3 parts of a 50/50 by weight mixture of mineral oil/ isopropyl myristate and addition of 1.3 parts of fumed colloidal silica resulted in the preparation of a granular and free-flowing bath composition having foaming, curddispersing and emollient properties.

1 1 EXAMPLE v A powdered and free-flowing detergent bath composition is prepared by drymixing 49 parts of a powdered detergent composition containing the following ingredients:

Parts Potassium alkyl sulfate (where the alkyl is derived from middle-cut coconut alcohols from coconut alcohol and has the following approximate comwith 2 parts pyrogenic silica and 49 parts of encapsulated emollient having a particle size such that all passes through a US. Standard mesh screen and having the following composition:

Parts Mineral oil 36.0 Isootyl myristate 4.0 Perfume 1.2 Wall material (water-soluble gelatin/gum arabic) 7.8

What is claimed is:

1. A granular free-flowing detergent bath composition providing sudsing and skin emollient effects upon addition to bath water and consisting essentially of from about 4% to 20% by weight of a water-soluble synthetic organic detergent; and from about 10% to about 80% of a microencapsulated water-insoluble emollient bath oil having a hydrolyzed protein encapsulating wall material soluble in water at a temperature of from 75 F. to 115 F. to release therefrom an emollient bath oil; said granular free-flowing detergent bath composition being characterized by having substantially no free or uncombined moisture.

2. The detergent bath composition of claim 1 wherein the water-soluble synthetic organic detergent is an anionic, nonionic, ampholytic or zwitterionic detergent.

3. The detergent bath composition of claim 2 wherein the water-soluble synthetic organic detergent is present as a granular mixture of said detergent and a water-soluble alkaline builder salt in a ratio of synthetic organic detergent to builder salt of from 2:1 to 1:10.

4. The detergent bath composition of claim 3 wherein the ratio of synthetic organic detergent to builder salt is from 1:1 to 1:6.

5. The detergent bath composition of claim 4 wherein the mixture of synthetic organic detergent and builder salt is in the form of granules ranging in size from about 0.1 mm to about 1.5 mm.

6. The detergent bath composition of claim 5 wherein the detergent granules amount to from 20% to of the bath composition.

7. The detergent bath composition of claim 6 wherein the detergent compound of the detergent compound of the detergent granules is an alkali metal alkyl glyceryl ether sulfonate wherein the alkyl has from 10 to 18 carbon atoms.

8. The detergent bath composition of claim 7 wherein the free moisture content is about 5% or less by weight of the bath composition.

9. The detergent bath composition of claim 8 wherein the free moisture content is up to 3%.

10. The detergent bath composition of claim 9 wherein the microencapsulated embollient has a wall material selected from the group consisting of gelatin, gelatin/gummi/arabicum, succinated gelatin and gelatin/sodium alginate, said wall material being soluble in water at a temperature of from 75 F. to F. within two minutes, thereby to release the emollient content.

11. The detergent bath composition of claim 10 wherein the emollient is a mineral oil.

12. The detergent bath composition of claim 10 wherein the embollient is a mixture of mineral oil and isopropyl myristate.

13. The bath oil composition of claim 10 wherein the wall material is of gelatin and gum arabic.

References Cited UNITED STATES PATENTS 3,574,120 4/1971 Siebert et a1. 252 X 3,705,102 12/1972 Mast 252316 X 3,091,567 5/1963 Wurzburg et a1 424-35 3,150,049 9/1964 Emory 424-28 2,800,457 7/1957 Green et a1. 252-316 3,520,971 7/1970 Benford 252316 X 3,533,955 10/1970 Pader et al. 252--153 FOREIGN PATENTS 424,596 2/1935 Great Britain 252-554 4,784 2/1969 Republic of South Africa OTHER REFERENCES Soap, Perfumery & Cosmetics, 42, #12, p. 871 (December 1969).

RICHARD D. LOVERING, Primary Examiner U.S.Cl. X.R.

252-89, 121, 316, 531, 550, 554, Dig. 11; 424-37 Inventofls) f UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Dated March, 19, 1974 Jamee A. Hellyer It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown. below:

Colu n Column Column 2, line 46,

lin 5 f er waterdelete "soluble" and insert therefor insoluble delete "contain" and insert therefor con ins ll' line lfi,

i2, line 8,

delete "ethyplenediaminet raaoe-"and inseam" ther efor'-- ethylenediaminetetraace I delete "relase" endinsert therefor rlielease et filsootyl" and insert therefior delete "of the detergentcompoflnds" Signed and sealed this 2nd clay of July 1974,

(SE L) Attest:

EDWARD M. FLETCHERJR. Li Attesting Officer C.MARSHALL DANN Commissioner of Patents Patent No. 3,798.17

1nventor(s) 9 Dated March 19, 1974 James A. Hellyer It is certified that error appears in the aboveddentified patent and that said Letters Column 2, line 46) column 7, li e 4-8,

Column 1.1;, line 26,

Column 12, line 8,

delete "conqain" and Patent are hereby corrected as shown below:

after water-- delete "soluble" and insert therefor insoluble insert therefo;

"- contains delete "ethyplen diaminetetreaoeand in iw-"t' I therefor ethyiLenediaminetetraaoe delete "relase" andinsert therefor r .felease de letefilsootyl" and insert therefio'r -flsoqc yl.

delete "Qf the detergent compounds Signed and sealed this Zrid-day of July 1974.

(SEAL) Attest:

EDWARD M. F L ting Officer C.MARSHALL DANN Commissioner of Patents