BACKGROUND OF THE INVENTION Field of the Invention

This invention relates to suspending agents for insoluble components of liquid cleaning compositions and also to suspending agents for silicone oil conditioning shampoos, which suspending agents are formed by reacting long-chain alkyl ammonium salts with anionic surfactants. Description of the Related Art

This prior art is replete with emulsions for a myriad of uses. Among the numerous applications for emulsions are fabric softeners, surface cleaners, agricultural chemical mixtures, skin cleansers, creams and lotions, car wax formulations, textile lubricants, and antiperspirant formulations. These emulsions are the type wherein a liquid is dispersed in at least one insoluble liquid. Such emulsions include oil-in-water, water-in-oil, oil-in-water-in-a second oil, water-in-oil-in-a second oil, and oil-in-a second oil emulsions. These emulsions typically include oils such as crude petroleum oil, distilled petroleum oil, heavy paraffinic oil, asphaltene oil, linseed oil, tall oil, soybean oil alkyd, linseed oil alkyd, mineral oil, petrolatum, isopropyl palmitate, isopropyl myristate, caprylic/capric triglyceride, lanolin, acetylated lanolin alcohol, silicone compounds such as dimethicone and cyclomethicone, hydrogenated vegetable oil, sesame oil, safflower oil, avocado oil, glycerine, propylene glycol, sorbitol, C ₁₂ -C ₁₆ alcohol benzoates, cocoa butter, vitamin E acetate, squalene, sodium pyrolidone carboxylic acid, methyl glucose ether, panthenol, melanin, and mixtures thereof.

Exemplary emulsions are shampoo and conditioner compositions. The prior art is also replete with shampoo and conditioner emulsions. Such emulsions are widely used because human hair becomes soiled due to its contact with the surrounding atmosphere and, to a greater extent, from sebum secreted by the head. The build-up of the sebum causes the hair to have a dirty feel and an unattractive appearance.

The soiling of the hair necessitates its being shampooed with frequent regularity.

Shampooing the hair cleans by removing soil and sebum. However, the shampooing process is disadvantageous because the process results in hair that is left in a wet, tangled and generally unmanageable state. A variety of approaches have been developed to alleviate these after-shampoo problems. These approaches range from the inclusion of hair conditioning aids in shampoos to post-shampoo application of hair conditioners, i.e., hair rinses. Post shampoo hair rinses or conditioners typically work by depositing a polymeric film or other material onto the hair. However , the use of solutions of such material as conditioners has not been fully satisfactory. For one thing, hair rinses are generally liquid in nature and must be applied in a separate step following the shampooing, left on the hair for a length of time, and finally rinsed with fresh water. This, of course, is time consuming and inconvenient. Furthermore, hair rinses or the leave-on hair conditioners, in addition to requiring an extra step, are difficult to apply in just the right amount of product and cannot easily be distributed uniformly throughout a head of hair.

Shampoos have been disclosed which contain conditioning aids; however, these shampoos have not been totally satisfactory for a variety of reasons. One reason relates to a lack of compatibility between surfactants which are good cleaning agents and fatty cationic agents which are good conditioning agents. This lack of compatibility caused other surfactants such as nonionics, a photerics and zwitterionics to be examined by workers in the field.

Suspending/emulsifying agents have been used for cationics in shampoo compositions with surfactants and silicone materials. Normally, a suspension system comprising of xanthum gum, glycerol distearate and cetyl alcohol is used. Manufacturing these compositions is extremely complex, costly and time consuming.

The use of silicone material in shampoos has been described in a number of different publications. The manufacture of such compositions is extremely complicated and

requires specialized mixing equipment, high shear pumps, heat exchanger, several manufacturing tanks, etc. Althoug it is desirable to reduce the amounts of silicone compound in cleaning compositions, little success has been evident in this area.

U.S. Patent 4,741,855 describes shampoo compositions which comprise a synthetic surfactant, an insoluble, non¬ volatile silicone, a suspending agent, and water. The described suspending agents include long chain esters of ethylene glycol, esters of long chain fatty amine oxides and many others. There appear to be several key conditioning components in these compositions, including an insoluble, non-volatile, silicone, and a long chain acyl suspending agent such as an ethylene glycol ester of a fatty acid, an alkanolamide, or an alkyl dimethyl amine oxide. Optional components that may be included in these compositions may include cationic surfactants such as di(partially hydrogenated) tallow dimethyl ammonium chloride and cetyltrimethyl ammonium chloride. European patent application No. 89312074.1 teaches hair care compositions comprising from about 0.05% to about 10.0% of a nonrigid silicone gum. Dispersed in the gum is from about 0.01% to about 8.0% of an unsolubilized particulate m a t t e r w h i c h i s p r e f e r a b l y a n octylacrylamide/acrylate/butylaminoethyl methacrylate copolymer. In addition, these compositions include volatile silicone solvents, silicone resins and optional ingredients. Among the optional ingredients are cationic surfactants of the formula

wherein R _j is hydrogen, an aliphatic group of from 1-22 carbon atoms, or an aromatic, aryl or aralkyl group having from 12 to 22 carbon atoms, R ₂ is an aliphatic group having from 1 to

3 carbon atoms, and X is an anion selected from halogen, acetate, phosphate, nitrate and alkylsulfate radicals.

Quaternary ammonium compounds derived from fatty aci amines such as tallow amine and di-tallow amine have been used as conditioners, surfactants and thickeners or emulsifiers in various shampoo and hair care products. For example, European Patent Application No. 0067635A2 discloses conditioning shampoos containing quaternary ammonium compounds of the formula:

wherein the R ¹ and R ² groups contain an average of from about 16 to 22 carbon atoms, most preferably from about 16 to about 18 carbon atoms, R ³ and R ⁴ are C. to C ₄ alkyl or hydroxyalkyl groups, and X is any compatible anion, particularly one selected from the group consisting of halide, hydroxide, ethylsulfate, or acetate anions.

The shampoo compositions of that patent application also contain acyl derivatives which are long chain amides, alkanolamides, esters of ethylene glycol and glycerine, esters of carboxylic acids, esters of thiodicarboxylic acids, and mixtures of these derivatives. The shampoo compositions of that patent application also contain surfactants which are represented by the formula:

wherein R ^l is a long chain alkyl radical having from about 10 to about 18 carbon atoms or an amido radical represented by the formula:

wherein R ⁵ is a long chain alkyl radical, R ² and R ³ ar each alkyl radicals having from about 1 to about 3 carbon atoms, R ⁴ is an alkylene or hydroxy alkylene radical having from about 1 to about 4 carbon atoms, and X is a carboxylate radical.

European Patent Application No. 0 152 194 A2 discloses shampoo compositions containing aminofunctional silicones and quaternary ammonium salts of the formula:

wherein R _! is hydrogen, or an aliphatic group of from 1 to 22 carbon atoms, or an aromatic, aryl or alkaryl group having 6 to 20 carbon atoms; R ₂ is an aliphatic group having from 12 to 22 carbon atoms; R ₃ and R ₄ are each alkyl groups having from 1 to 3 carbon atoms; and X is an anion selected from halogen, acetate, phosphate, nitrate and methyl sulfate radicals.

U.S. Patent No. 4,854,333 discloses shampoo compositions that may contain di(partially hydrogenated tallow) dimethyl ammonium chloride, an alkyl sulfate and a silicone fluid. The alkyl sulfates include the sodium and ammonium alkyl sulfates having 8-22 carbon atoms.

U.S. Patent No. 4,824,602 discloses hair care compositions comprising silicone conditioning agents and compounds of the following formula:

wherein _! and R ₂ are aliphatic groups having from 12-22 carbon atoms, R ₃ and R ₄ may be hydrogen or short chai alkyl groups, and X may be an alkyl sulfate radical.

The preferred quarternary ammonium salts according to this patent are dialkyl dimethyl ammonium chlorides. The alkyl groups include those derived from long-chain fatty acids such as hydrogenated tallow fatty acids. These shampoos may also include anionic surfactants which may be alkyl sulfates having between 10 and 20 carbon atoms where the cation may be ammonium.

U.S. Patent No. 4,788,006 teaches shampoo compositions that include alkyl sulfates such as ammonium lauryl sulfate, a silicone fluid, and, as an optional component, a quaternary ammonium compound such as di(partially hydrogenated tallow) dimethyl ammonium chloride.

U.K. Patent Application No. GB 2196979A discloses hair care compositions comprising silicone conditioning agents and compounds of the following formula:

wherein R _t and R ₂ are aliphatic groups having from 12-22 carbon atoms, R ₃ and R ₄ may be hydrogen or short chain alkyl groups, and X may be an alkyl sulfate radical.

The preferred quarternary ammonium salts according to this patent are dialkyl dimethyl ammonium chlorides. The alkyl groups include those derived from long-chain fatty

acids such as hydrogenated tallow fatty acids. Thes shampoos may also include anionic surfactants which may alkyl sulfates having between 10 and 20 carbon atoms wher the cation may be ammonium.

U.K. Patent Application No. GB 2 196 980A discloses hai care compositions comprising silicone conditioning agents an compounds of the following formula:

wherein _j and R ₂ are aliphatic groups having from 12-2 carbon atoms, R ₃ and R ₄ may be hydrogen or short chai alkyl groups, and X may be an alkyl sulfate radical.

The preferred quarternary ammonium salts according t this patent are dialkyl dimethyl ammonium chlorides. Th alkyl groups include those derived from long-chain fatt acids such as hydrogenated tallow fatty acids. Thes shampoos may also include anionic surfactants which may b alkyl sulfates having between 10 and 20 carbon atoms wher the cation may be ammonium.

U.K. Patent Application No. GB 2124647 A teache quaternary ammonium compounds useful in shampoo compositions The ammonium compounds have the formula:

R2 R2 1-N—R2 x- 0R R1-N-(R3) H X- R2 I

wherein _j is an aliphatic alkyl group containing a average of from about 16 to 22 carbon atoms, mos preferably from about 16 to about 18 carbon atoms, th R ₂ groups are C _j to C ₄ alkyl or hydroxylalkyl groups, th R ₃ groups are alkylene oxide groups, preferably propylen oxide, where y is 1-4 and X is any compatible anion particularly one selected from the group consisting o

halide, hydroxide, methylsulfate, or acetate anions.

European Patent Application No. 0294 894 disclose conditioning agents for delivery from shampoos comprisin compounds of the formula:

wherein _j and R ₂ can independently be C _l6 to C^-, alkyl or alkenyl and R ³ is H or CH ₃ , and A is an anionic surfactant selected from the group consisting of alkyl sulfonates, aryl sulfonates, alkylaryl sulfonates, alkyl sulfates, alkyl ethoxylated sulfates, dialkyl sul osuccinates, ethoxylated alkyl sulfonates, alkyl oxybenzene sulfonates, acyl isethionates, acyl alkyl taurates, olefin sulfonates and paraffin sulfonates. A wide variety of surface active (surfactant) compounds are known and widely used. Further, certain relatively specific phthalamate derivatives are at least nominally disclosed in academic and patent literature. Some specific phthalamate derivatives have been suggested as being useful in plant growth regulator formulations, insect repellent formulations, bactericidal, fungicidal, herbicidal formulations, additives for improving low temperature flow characteristics of petroleum distillate fuels, solvent extraction formulations for certain heavy metal ions, catalyst systems for polyurethane foam formulations, additives for thermal recording materials, thickeners for silicone grease and oil-based drilling muds, additives for water-insensitive coatings, plasticizers, etc. Phthalamic acids or phthalamate derivatives have been used as additives for insecticidal compositions; additives for vulcanization activators; additives for rust and corrosion inhibitor formulations; additives to screen-clogging prevention and rust inhibition formulations; additives for improving low temperature flow characteristics of petroleum fuel oils; additives to catalyst systems for polyurethane foam formulations.

Ammonium phthalamates have been used as additives i fuel oil compositions, blending agents for grease lubricating oil additives, and thickening agents fo lubricating oil compositions.

These ammonium phthalamates have the formula

preferably C^-C straight chain alkyl groups of secondary amine, and ma be the same or different.

U.S. Patent No. 5,015,415 discloses formulate conditioning shampoos, surfactant solutions and emulsifie solutions comprising effective amounts of salts of th general formula

and mixtures of the salts and acids of the formula

U.S. Patent No. 2,101,323 discloses compounds of th ormula

in which X is hydrogen or an alkali or alkaline eart

etal, R represents the residue of a dicarboxylic acid preferably an ortho-aromatic radical of the benzen series, R _t is an aliphatic hydrocarbon radical containin eight or more carbon atoms and R ₂ is hydrogen o anorganic radical, and which may be used in water resistant, low-vapor pressure plasticizers for cellulos derivatives, and as wetting and detergent agents.

U.S. Patent No. 2,892,778 teaches grease composition comprising metal soaps of terephthalic acid, terephthalami acid, isophthalamic acid, and amic acids. U.S. Patent No. 2,0915,464 teaches hydrocarbon lubricating oils comprisin salts N-alkylamidophthalic acids where the N-alky substituent contains 8 to 18 carbon atoms.

U.S. Patent No. 2,971,027 discloses the use of diamides of terephthalic acid as grease thickening agents. Thes compounds have the general formula

where R _x and R ₂ are selected from the group consisting of hydrocarbon and substituted hydrocarbon radicals attached to the nitrogen atoms by carbon-nitrogen bonds, and wherein R ₃ and R ₄ are selected from the group consisting of hydrogen, hydrocarbon and substituted hydrocarbon radicals, such hydrocarbon or substituted hydrocarbon radicals being attached to the nitrogen atoms by carbon-nitrogen bonds. U.S. Patent No. 3,095,286 discloses compounds of the general formula

where R is a monovalent aliphatic hydrocarbon radical having between about 4 and 30 carbon atoms as being useful as fuel oil sediment inhibitors, anti-rust

agents, and anti-screen clogging agents.

U.S. Patent No. 3,166,387 teaches pour point depressors for fuel oil compositions comprising salts of a secondary or tertiary monoamine having the formula:

where R, and R ₂ are alkyl groups containing from about 10 to about 22 carbon atoms, and R ₃ and R ₅ are hydrogen or alkyl groups containing from one to about 22 carbon atoms, x and z are each integers of from 1-4 and y is an integer of from 0 to 1.

U.S. Patent Nos. 4,333,082 and 3,544,467 disclose pour point depressants for hydrocarbon fuels and oils comprising succinamic acids of the formula

wherein R is a straight chain aliphatic hydrocarbon group having from 0 to l site of olefinic unsaturation (alkyl or alkenyl) attached at a secondary carbon atom to the succinyl group and is of at least 14 carbon atoms, generally in the range of 15 to 28 carbon atoms and more usually in the range of 15 to 22 carbon atoms. One of X and X ¹ is hydroxyl and the other is: -NYY ¹ wherein N has its normal meaning of nitrogen and Y and Y ¹ are aliphatic hydrocarbyl groups of from 14 to 28 carbon atoms, more usually of from 15 to 22 carbon atoms, having a total of from about 30 to 52 carbon atoms, more usually of from 32 to 48 carbon atoms, and, preferably, of from 32 to 40 carbon atoms, and the salts thereof.

U.S. Patent No. 3,658,453 teaches the use of variou limited solubility wax crystal modifying amides or salt formed from acids with amines or ammonia to improve the col flow properties of distillate fuel oils. Among the salt disclosed are various ammonium salts of fatty acids.

U.S. Patent No. 3,846,481 discloses di-(n-octadecyl) ammonium salts of aromatic carboxylic acids and their use a pour point depressants in hydrocarbon oils.

U.S. Patent No. 3,887,754 teaches the use of phthali acid derivatives of the formula

.CONHR

^• CONHR'

where R and R ¹ are aliphatic hydrocarbon radicals of from 8 to 22 carbon atoms as coating substances for foamed polystyrene articles.

U.S. Patent No. 3,982,909 describes the use of various amides, diamides and ammonium salts of monoamides or monoesters of dibasic acids as wax crystal modifiers and cold flow improves for distillate fuel oils.

U.S. Patent Nos. 4,210,424 and 4,211,534 teach the case of oil-soluble combinations of (A) ethylene polymer of copolymer, (B) normal paraffinic wax composed of normal hydrocarbons whose average molecular weight is within the range of from 300 to 650, and (C) nitrogen compounds, such as amides, amine salts and ammonium salts, of carboxylic acids or anhydrides for use in improving the cold flow properties of distillate hydrocarbon fuel oils.

Journal of Colloid and Interface Science, 139: 381 (1990) describes the use of compounds of the formula

where R is octyl, dodecyl or oleyl as surfactants whic stabilize water-in-oil microemulsions.

Tallow is a fatty acid byproduct of the meat-packin industry obtained by rendering the body fat from cattle an sheep. Tallows from different sources vary in free fatt acid content. The fatty acids normally found in tallow ar myristic acid, palmitic acid, stearic acid, oleic acid, an linoleic acid.

Several methods are known for the preparation of tallo amines, but the most common method in industry is the conversion of a fatty acid to a nitrile by treating with ammonia, followed by catalytic hydrogenation of the nitrile to primary, secondary, or tertiary amine by suitable adjustment in the reaction conditions. Tallow amines, as well as di(hydrogenated tallow) amine, are commercially available; for example, di(hydrogenated tallow) amines are available under the trade name ARMEEN 2HT™ (Akzo Chemicals, Chicago, Illinois) .

Various routes exist for the preparation of phthalamic acids and phthalamic acid salts. In U.S. Patent No. 4,402,708 N,N-diarachidyl phthalamic acid was prepared by adding phthalic anhydride to a 40% solution of amine in toluene in a 1/1 mole ratio at 80°C. The product was recovered by vacuum drying at 50°C, 0.05 mmHg for 20.5 hours. Phthalic anhydride sublimation was observed. This method makes no mention of the presence of any ammonium salt in the resultant product.

U.S. Patent No. 4,402,708 describes a method for preparing N,N-dioctadecyl phthalamic acid dioctadecyl ammonium salt and N,N-diarachidyl phthalamic acid diarachidyl ammonium salt. Phthalic anhydride was added to a 10% solution of amine in toluene in an anhydride to amine mole ratio of 1/2. The product was recovered by filtering and film evaporating a 1/1 toluene/n-heptane solution at 55°C, 40 mmHg.

Phthalamic acids have also been prepared by melting phthalic anhydride at 131°C and subsequent addition of molten

secondary amine. The reactants to be added in an equimola ratio. At the temperature used in this method, 131°C, excessive phthalic anhydride sublimation occurs and increased product degradation is observed. This method makes no mention of the presence of any ammonium salt in the resultant product.

Phthalamic acids have been prepared by addition of a solution of secondary amine in isopropanol at 78°C to a phthalic anhydride/isopropanol slurry at 78°C in a one to one phthalic anhydride/amine molar ratio with subsequent vacuum stripping of the solvent. This method utilizes isopropanol as the solvent for the reaction. Isopropanol, a secondary alcohol, reacts with phthalic anhydride to yield isopropyl mono ester of phthalic acid. At 78°C, as much as 40% of the product may be this ester.

Each of these methods produces a mixture of the desired phthalamic acid and an ammonium phthalamate salt. However, these methods make no mention of the presence of any ammonium salt in the resultant product.

Summarγ of the Invention

It has been unexpectedly discovered that when an alky ammonium salt is added to a liquid cleaning compositio containing an anionic surfactant and the mixture heated abov about 70°C, the resulting composition contains a product whic functions as an excellent suspending agent for insolubl components of the liquid cleaning composition. Thes suspending agents appear as particles that have precipitate in the cleaning composition. Accordingly, the present invention provides suspendin agents for insoluble components of liquid cleanin compositions that are prepared by a process comprising th steps of (a) mixing an alkyl ammonium salt and an anioni surfactant in the cleaning composition; and (b) heating th mixture above about 70°C.

In addition, the present invention provides suspendin agents for silicone oil conditioning agents that are prepare by a process comprising the steps of (a) mixing di(hydrogenated) tallow ammonium salt and a salt of laury sulfate in the shampoo; and (b) heating the mixture at leas about 70°C.

The invention also provides liquid cleaning composition comprising effective amounts of such suspending agents fo suspending insoluble components of liquid cleanin compositions.

The invention further provides networks of th suspending agents and. the insoluble components of liqui cleaning compositions.

The invention also provides shampoo composition containing the suspending agents.

BRIEF DESCRIPTION OF THE DRAWING Figure 1 is a photograph at a magnification of 125 showing spherical droplets of silicone oil conditioning agen (A) adhered to particles of suspending agent (B) .

DETAILED DESCRIPTION OF THE INVENTION It has been unexpectedly discovered that when an alky ammonium salt is added to a liquid cleaning compositio containing an anionic surfactant and the mixture heated abov about 70°C, the resulting composition contains a product whic functions as an excellent suspending agent for insolubl components of liquid cleaning compositions. These suspendin agents appear as particles that have precipitated in th insoluble components of liquid cleaning compositions. Thus the present invention encompasses suspending agent for insoluble components of liquid cleaning compositions, which suspending agents are prepared by a process comprisin the steps of (a) mixing an alkyl ammonium salt and an anioni surfactant in the cleaning composition; and (b) heating th mixture above about 70°C.

The present invention further encompasses suspendin agents for insoluble components of liquid cleanin compositions, which suspending agents are prepared by a process comprising the steps of (a) mixing a di(hydrogenated) tallow ammonium salt and salt of lauryl sulfate in the cleaning composition; and (b) heating the mixture above about 70°C.

The invention also encompasses liquid cleaning compositions formulated to include an effective amount of such suspending agents for suspending insoluble components of liquid cleaning compositions.

The alkyl ammonium salts of the invention may be represented by the formula:

R,R ₂ R ₃ R ₄ N+ X- where

R _j , R ₂ , R ₃ and R ₄ are the same or different and represent aralkyl, alkyl or alkenyl having 1 to 40 carbon atoms; or

R _j and R ₂ are the same or different and represent alkyl or alkenyl having 8 to 40 carbon atoms when

R ₃ and R ₄ are hydrogen, or a C _j to C ₈ alkyl polyoxyethylene; and X is

halogen, acetate, nitrate, hydroxide, phosphate; aklyl sulfate where the alkyl portion has 1-2 carbon atoms; mono- or di-alkyl phosphate where each alky portion has 1-22 carbon atoms; an anion of the formula

R _j -CO ^' _j where R ₅ is straight or branched chain alkyl having 1-22 carbon atoms; or

where R _H and R ₁₂ are the same or different and represent alkyl or alkenyl having 1-40 carbon atoms; and

Y is ortho, para or meta substituted phenyl, or alkylene or alkenylene having 0-6 carbon atoms, or cycloalkene having 5-7 carbon atoms.

The salts of the alkyl sulfate may be represented by the formula:

M ⁺ O _I1 W-R ₆ where

W is sulfur or phosphorous n is 3 or 4;

Re i ^s alkyl or alkenyl having from 10-16 carbon atoms; aryl, aralkyl or alkylaryl where each alkyl portion has 1-16 carbon atoms; alkyl polyoxyalkylene where the alkyl portion has

1-8 carbon atoms and each alkylene has 2-5 carbon atoms; or alkyl alkanoate where the alkyl portion has 1-6 carbon atoms and the alkanoate portion has 2-6 carbon atoms; and M is sodium, potassium, or N y g gR^ where R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different

and represent hydrogen or straight or branche chain alkyl groups having 1-8 carbon atoms.

By alkyl in the present invention is meant straight o branched chain alkyl groups. By alkenyl is meant straight o branched chain alkenyl groups having at least one carbon carbon double bond. When the alkenyl groups have a pluralit of double bonds, the double bonds may be conjugated or no conjugated.

By aryl in the invention is meant aromatic groups suc as, for example, phenyl and naphthyl. By aralkyl is mean radicals which may be represented by the formulas:

where R may be hydrogen or an alkyl group having from 1-1 carbon atoms. By alkylaryl is meant radicals which may b represented by the formula:

where R' represents an alkylene group having 1-16 carbo atoms.

By alkyl polyoxyalkylene is meant radicals of th formula:

R ^« [0(CH ₂ ) _z ] _s -

when R" represents an alkyl group having 1-8 carbon atoms, is an integer from 2-5; and s is an integer from 1-20.

By alkyl alkanoate is meant radicals of the formulas:

R ^, ' ^, 0 ₂ C(CH ₂ ) _q , or R ^,, 0 ₂ CCH(CH ₂ ) _t CH ₃ where R'" is an alkyl group having 1-6 carbon atoms, q is a integer from 1-20, and t is 0 or an integer from 1-18.

The preferred alkyl ammonium salts for utilization i the present invention are di(hydrogenated) tallow ammoniu salts. These di(hydrogenated) tallow ammonium salts may b represented by the forumula:

{R ^j m ₂ ^+x' where R _t and R ₂ are the same or different and represen straight or branched chain alkyl groups having 16-2 carbon atoms; and X is halogen, acetate, nitrate, hydroxide, phosphate; aklyl sulfate where the alkyl portion has 1-22 carbon atoms; mono-or di-alkyl phosphate where each alkyl portion has 1-22 carbon atoms; an anion of the formula

R ₅ -CO- ₂ where R ₅ is straight or branched chain alkyl having 1-22 carbon atoms; or

- where R _π and R ₁₂ are the same or different and represent alkyl or alkenyl having 1-40 carbon atoms; and

Y is ortho, para or meta substituted phenyl, or alkylene or alkenylene having 0-6 carbon atoms, or cycloalkene having 5-7 carbon atoms.

By Y in the above formulas is meant an ortho, meta, or para substituted phenyl group, or methylene, ethylene, propylene, butylene, pentylene, hexylene, etheneylene, propenylene, 1-, or 2-butenylene, 1-, 2-, or 3-pentylene, or 1-, 2-, or 3-hexenylene, cyclohexylene or cyclohexenylene. The amic acid anions resulting from the variation of Y groups include phthalamate, isophthalamate, terephthalamate, oxalamate, malonamate, glutaramate, adipamate, pimelamate, suberamate, maleamate, succinamate, 1,2-cyclohexanamate, 1,3- cyclohexanamate, and 1,4 cyclohexanamate anions.

Mixtures of various alkyl ammonium salts. and anionic surfactants may be utilized in the present invention to achieve different suspending properties as desired.

Suitable di(hydrogenated) tallow ammonium salts ar easily prepared and/or commercially available. The alky ammonium salts derived from tallow amine include various ami acid ammonium salts. In certain embodiments of th invention, R _1# R ₂ , R ₃ , and R ₄ , are derived from hydrogenate tallow. Because tallow is a mixture of C-14 to C-18 fatt acids, and amines derived from tallow are a mixture of tallo amines, the amic acid ammonium salts thereof used in th present invention may, therefore, have R groups that are th same or different. Preferred amic acid ammonium salt according to the present invention include, for example di(hydrogenated) tallow ammonium di(hydrogenated) tallo succinamate, di (hydrogenated) tallow ammoniu di(hydrogenated) tallow cyclohexamate, di(hydrogenated tallow ammonium di(hydrogenated) isophthalamate di(hydrogenated) tallow ammonium di(hydrogenated) tallo maleamate, di(hydrogenated) tallow ammonium di(hydrogenated) tallow oxalamate, di(hydrogenated) tallow ammoniu di(hydrogenated) tallow malonamate, di(hydrogenated) tallo ammonium di(hydrogenated) tallow glutaramate di(hydrogenated) tallow ammonium di(hydrogenated) tallo adipamate, di(hydrogenated) tallow ammonium di(hydrogenated) tallow pimelamate, and di(hydrogenated) tallow ammoniu di(hydrogenated) tallow subaramate. A particularly preferre alkyl ammonium salt is di(hydrogenated) tallow ammoniu di(hydrogenated) tallow phthalamate.

Similarly, anionic surfactants are easily prepare and/or commercially available. Among the anioni surfactants suitable for use in the present invention are alkyl polyalkoxy sulfates and sulfonates; aralkyl sulfates sulfonates, and phosphates; alkyl ryl sulfates an sulfonates; α-olefin sulfates and sulfonates; α-sulfo-alky alkanoates; and alkyl sulfates, sulfonates and phosphates.

The preferred anionic surfactants that may be used i the invention are salts of lauryl sulfate. These salts o lauryl sulfate may be represented by the formula

M ⁺ O ₄ S-R< _; where R_- is an alkyl group having from 10-16 carbo atoms; and

M is sodium, potassium, or UR-,R _S R^R_ ₀ where R ₇ , R ₈ , Rg and R ₁₀ are the same or differen and represent hydrogen or straight or branche chain alkyl groups having 1-8 carbon atoms. A particularly preferred salt of lauryl sulfate is ammoniu lauryl sulfate.

Suitable amounts of alkyl ammonium salt are from abou 0.5% to about 20% of a cleaning composition. Preferre amounts are from about 2-10%. More preferred amounts of th alkyl ammonium salts are from about 3-7%.

In a cleaning composition such as, for example, shampoo, the anionic surfactant may be used in an amount i excess of the alkyl ammonium salt. Suitable amounts o anionic surfactants are from about 1% to about 50% of a cleaning composition. Preferred amounts are from about 5- 30%. More preferred amounts of anionic surfactants are from about 8-20% of a cleaning composition.

After preparation of a formulated shampoo including a suspending agent according to the invention, the preparation was filtered, and particles collected. Chemical analysis of the particles indicated the particles are the product of a reaction between the cationic portion of the alkyl ammonium salt and the anionic portion of the surfactant.

Upon preparation of a formulated conditioning shampoo including a silicone oil conditioning agent and a suspending agent according to the invention, the preparation was filtered, and particles collected. Microscopic analysis of these particles reveals that the silicone oil conditioning agent and suspending agent particles are a network of the silicone oil adhered to the particles of the suspending agent. Figure 1 shows the larger silicone oil droplets (A) adhered to the smaller particles (B) of a suspending agent prepared from a tallow ammonium compound and lauryl sulfate. The network effectively maintains silicone conditioning agents in suspension in cleaning compositions such as shampoo formulations.

By network is meant an arrangement or complex of silicone oil conditioning agent droplets adhered to suspending agent particles to form an interconnected system

of silicone and suspending agent.

The compostitions and shampoos of the invention may be prepared to comprise from about 0.05% to 35% by weight of the network formed by silicone oil droplets adhered to particles of the suspending agent. Preferred amounts of the network are from about 2-30% by weight of the composition. More preferred amounts are from about 3-25% by weight of the compostion.

The silicone compounds which may be used in the formulations of the present invention are well known and have been generally taught to be useful in a variety of emulsions, suspensions, and non-aqueous systems. These silicone compounds include silicones such as dimethicone and cyclomethicone. Generally such silicone compounds may be represented by the formula:

wherein R is a 1 to 3 carbon alkyl group, n is a number from 3 to 10, preferably from 3 to 7, and the unsatisfied valences on the oxygen and silicon atoms at the ends of the chain may be joined to one another to form a cyclic structure. Suitable silicone compounds are, for example, U.C.C. Y-7207, sold by Union Carbide Corporation in which each R is methyl and which typically comprises by weight 99.4% tetramer, 0.6% trimer and traces of the pentamer and hexamer; SWS-03314, sold by SWS Silicones, a Division of Stauffer Chemical Company, in which R is methyl and which is substantially all tetramer; and Dow Corning 344 fluid, sold by Dow Corning, Inc. , in which R is methyl and which typically comprises by weight about 88% tetramer, about 11.8% pentamer and traces of trimer and hexamer. Typical vapor pressures of silicones are shown below. These vapor pressures were determined using Dow Corning 344 fluid at various temperatures.

The concentration of silicone oil conditioning compoun in the formulations and shampoos of the invention may rang from about 0.05% to about 15% by weight of the composition. More preferred amounts are from about 0.5 to 10% of the formulation. By suspension is meant a mixture of particles or solid particulate of matter or droplets of an insoluble liquid evenly distributed throughout a liquid system in which the particles or droplets are insoluble. The particles or droplets may be of any composition, i.e., they may be organic or inorganic compounds. In addition, various organometallic compounds, such as the solid, insoluble, active antiperspirant aluminum and zirconium salts, may be included in the formulations of the invention. These aluminum and zirconium salts include aluminum chloride, aluminum chlorhydroxide, basic aluminum bromide, zirconyl chloride, zirconyl hydroxide, complexes of aluminum hydroxide, zirconyl chloride and aluminum chlorhydroxide, complexes of aluminum hydroxide, zirconyl hydroxychloride and aluminum chlorhydroxide, complexes of dihydroxyaluminum glycinate, zirconyl chloride and/or zirconyl hydroxychloride and aluminum chlorhydroxides, complexes of zirconyl chloride and/or zirconyl hydroxychloride with aluminum chlorhydroxide and an amino acid, such as glycine (as a buffering agent) . The liquid systems may be aqueous, nonaqueous, or an emulsion as described below.

By emulsion is meant a mixture of the type wherein a liquid is dispersed in at least one insoluble liquid. Those skilled in the art will recognize a variety of emulsions

where the compounds of the present invention may be used The emulsions of the invention include emulsions such as, fo example, oil-in-water, water-in-oil, oil-in-water-in-a secon oil, water-in-oil-in-a-second oil, and oil-in-a second oi emulsions.

The shampoos of the present invention are readil manufactured using a conventional single-phase, hot process The manufacture of the conditioning shampoos using a single phase, hot process is simple and, therefore, preferred ove multi-phase processes.

The shampoos of the present invention are prepared b incorporating the alkyl ammonium salt and anionic surfactan in typical shampoo bases. The shampoo formulations of th invention may also include pearling agents, emollients humectants, proteins, amino acids, and polymers. Thos skilled in the art will recognize that desired properties ma be attained by adding certain ingredients to thes formulations. A representative list of such ingredients ma be found in the Cosmetic, Toiletry and Fragrance Associatio (CTFA) Dictionary. For example, thickeners and viscosit modifiers such as a diethanolamide of a long-chain fatty aci (e.g., cocomide diethanolamine) may be added to th formulations of the present invention.

Because tallow is a mixture of fatty acids of variou chain lengths, predominantly C-14 to C-18, and amines derive from tallow are a mixture of tallow amines, the tallo ammonium salts used in the present invention may, therefore have alkyl groups that are the same or different.

Laboratory and salon results indicate that th suspending agents for silicone oil conditioning compounds a prepared according to the invention, when combined wit silicone oils, exhibit excellent flow properties and lon term stability at a variety of storage temperatures. Th finished formulations retain their conditioning, flow an storage properties after at least three freeze-thaw cycle an are easily preserved using common preservatives.

The present invention also encompasses methods fo preparing the suspending agents of the invention.

The invention is illustrated further by the followin

examples which are not to be construed as limiting th invention in scope or spirit to the specific procedure described in them.

EXAMPLE 1

Preparation of a mixture of N,N-di(hydrogenated tall amic acid and N,N-di(hydrogenated tallow) amic acid (hydroσenated tallow) ammonium salt One mole (148.Og) of flaked phthalic anhydride (PA) charged into a 4-neck 5-liter round bottomed flask reac equipped with a mechanical stirrer, a thermocou temperature controller and a heating mantle. A charge 650g of isopropyl alcohol (USP grade) was added to reactor to achieve a slurry of about 50% solids. One m (about 502g) of molten di(hydrogenated tallow) amine slowly added to the slurry in the reactor with continu stirring. The temperature of the reaction mass was allo to stabilize at about 45-55°C with gradual addition of amine and cooling of the reactor flask. Amine addition completed in about 0.5 to 1 hours. Thereafter the reac was maintained at about 60°C until the PA flakes dissipa and IR spectroscopic analysis showed no detectable amounts PA in the reaction mass. Isopropyl alcohol was then remo under vacuum (about 1-50 mmHg) On analysis, about 62 mole acid and about 38 mole % salt were found with an avera molecular weight of about 782.

EXAMPLE 2

Maleic anhydride (0.25 ol) was added to a flask heated to about 80°C. To the liquid maleic anhydride added 0.338 mol of liquid di(hydrogenated) tallow amine. resulting mixture was stirred for 150 minutes at 80°C a after workup, yielded a mixture of di(hydrogenated) tal ammonium di(hydrogenated) tallow maleamate a di(hydrogenated) tallow maleamic acid.

EXAMPLE 3 Preparation of a Conditioning Shampoo Water (70.Og) was first added into a suitable vesse equipped with agitation, heating and cooling capabilities While the water was agitated and heated slowly, tetrasodiu EDTA (0.2g), STEPANOL® AM-V (ammonium lauryl sulfate 2g) an NINOL® 40 CO (cocomide diethanolamine 2g) were added. A about 60°C a 70:30 mixture of N, N-di(hydrogenated tallow) phthalamic acid and N,N-di(hydrogenated tallow) phthalami acid N,N-di(hydrogenated tallow) ammonium salt (5g) , followe by silicone DC 200 (dimethicone (2g)) were added to th mixture. The mixture was heated to 70-75°C and emulsified fo 20-30 minutes at high speed while maintaining the temperatur between 70-75°C. The mixture was slowly cooled with agitation set at medium speed. When the temperature of the mixture cooled to about 45°c, 1,3,5,5-tetramethyl hydantoin (O.lg) and ammonium chloride (O.lg) were added. The pH was checked and adjusted as necessary with ammonium hydroxide or citric acid to a value between about 4.5 to 6.5. The viscosity was checked and adjusted as necessary with ammonium chloride to a value between 2000 and 6000 cps. (Formulation 1)

EXAMPLE 4

Formulation 2 was prepared to contain a mixture of di(hydrogenated) tallow ammonium di(hydrogenated) tallow maleamate and di(hydrogenated) tallow maleamic acid esentially according to the procedure described above in

Example 3.

EXAMPLE 5

Preparation of an Anti-dandruff/ Conditioning Shampoo

Water (70.Og) was first added into a suitable vesse equipped with agitation, heating and cooling capabilities

While the water was agitated and heated slowly, tetrasodiu

EDTA (0.2g), STEPANOL® AM-V, (ammonium lauryl sulfate, 2g) and NINOL® 40 CO (cocomide diethanolamine) were added. A about 60°C, a 70:30 mixture of N, N-di(hydrogenated tallow) phthalamic acid and N,N-di(hydrogenated tallow) phthalami acid N,N-di(hydrogenated tallow) ammonium salt (5g) , followe by silicone DC 200 (dimethicone 0.2g) and ZPT (zin pyrithione, 48% dispersion, 0.6g) were added to the mixture.

The mixture was heated to 70-75°C and emulsified for 20-3 minutes at high speed while maintaining the temperatur between 70-75°C. The mixture was slowly cooled with agitatio set at medium speed. When the temperature of the mixtur cooled to about 45°C, 1,3,5,5-tetramethyl hydantoin (O.lg) an ammonium chloride (O.lg) were added. The pH was checked an adjusted as necessary with ammonium hydroxide or citric aci to a value between about 4.5 and 6.5. The viscosity wa checked and adjusted as necessary with ammonium chloride t a value between 2000 and 6000 cps. (Formulation 3)

Formulation 4 was prepared to contain a mixture o di(hydrogenated) tallow ammonium di(hydrogenated) tallo maleamate and di(hydrogenated) tallow maleamic aci essentially according to the procedure set forth in Exampl

5.

EXAMPLE 6 Preparation of a conditioning shampoo Water (108.0 g) was first added into a suitable vesse equipped with agitation, heating, and cooling capabilities To the agitated water was added α-sulfo-methyl laurate (81. g) , a 70:30 mixture of N,N-di(hydro-genated tallow phthalamic acid and N,N-di(hydrogenated tallow) phthalami acid N,N-di(hydrogenated tallow) ammonium salt (10g.0), an silicone DC200 (12,500 cps, l.Og) . The mixture was heated t about 90°C and was mixed for an additional 10-15 minutes. Th temperature of the mixture was slowly cooled and the p adjusted to about 4.5 to 6.0 with sulfuric acid and/or sodiu hydroxide. The mixture was then cooled to room temperature.

EXAMPLE 7 Preparation of a conditioning shampoo

Water (163.0g) was first added into a suitable vesse equipped with agitation, heating and cooling capabilities. To the water was added a mixture of Cg_ ₁₀ polyethoxy phosphate. The pH was subsequently adjusted to 1.5 to 2.0, if necessary, with sulfuric acid (50%) . The mixture was agitated and heated to about 90°C. At about 90°C, di(hydrogenated tallow) amine (6.0g) and silicone DC 200 (12,500cps, l.Og) were added to the mixture. The resulting mixture was then agitated for 20 minutes at 200°F, after which it was cooled to about 90°F pH. The pH was then adjusted to 4.5 to 6.0 with ammonium hydroxide (28%) and the mixture cooled to room temperature.

EXAMPLE 8 Preparation of a conditioning shampoo Water (89.0 g) was first entered into a suitable vessel equipped with agitation, heating, and cooling capabilities. To the agitated water was added sodium lauryl sulfate (100.0 g) , a 70:30 mixture of N,N-di(hydrogenated tallow) phthalamic acid and N,N-di(hydrogenated tallow) phthalamic acid N,N- di(hydrogenated tallow) ammonium salt (lOg) , and silicone DC200 (12,500 cps, l.Og). The mixture was heated to about 90°C and was mixed for an additional 10-15 minutes. The temperature of the mixture was slowly cooled and the pH adjusted to about 4.5 to 6.0 with citric acid (50%) and/or sodium hydroxide. The mixture was then cooled to room temperature.

EXAMPLE 9

Preparation of a conditioning shampoo Water (113.0 g) was first added into a suitable vessel equipped with agitation, heating, and cooling capabilities. To the agitated water was added sodium C ₁₇ . ₁₉ α-olefin sulfonate (38%, 80.0 g) , a 70:30 mixture of N,N-di(hydrogenated tallow) amine (6.0g), and silicone DC 200 (l.Og). The mixture was heated to about 90°C and mixed for about an additional 20 minutes. The temperature of the mixture was slowly cooled and the pH adjusted to about 4.5 to 6.0 with sulfuric acid (50%) and/or sodium hydroxide (50%) . The mixture was then cooled to room temperature.

EXAMPLE 10 Preparation of a conditioning shampoo Water (117.0 g) was first added into a suitable vesse equipped with agitation, heating, and cooling capabilities To the agitated water was added sodium dodecylbenzen sulfonate (75.Og), a 70:30 mixture of N,N-di(hydrogenate tallow) amine (6.0g), and silicone DC200 (2.0g). The mixtur was heated to about 90°C and was mixed for about an additiona 20 minutes. The temperature of the mixture was slowly coole and the pH adjusted to about 4.5 to 6.0 with sulfuric aci (50%) and/or sodium hydroxide. The mixture was then coole to roomtemp.

From the foregoing it will be appreciated that, althoug specific embodiments of the invention have been describe herein for purposes of illustration, various modification may be made without deviating from the spirit and scope o the invention.