PT97096B - PROCESS FOR THE PREPARATION OF DETERGENT COMPOSITIONS WITH LOW IRRITATING EFFECT ON THE SKIN - Google Patents

Abstract

Disclosed are novel low skin irritation surfactants and surfactant compositions which are high in foaming properties containing, as an active ingredient, a diamine monoalkyl phosphate salt.

Description

TECHNICAL FIELD The present invention relates to a process for the preparation of new surfactants and surfactant compositions with a low skin irritating effect, which have high foaming properties containing, as an active ingredient, a phosphate salt of monoalkyl diamine.

BACKGROUND OF THE INVENTION

Soaps, detergents and abrasives have long been used to cleanse the body. Surfactants such as alkyl sulfates, polyoxyethylene alkyl sulfates, alkylbenzene sulfonatose a-olefin sulfonates have been widely used as surfactant components for many cleaning articles.

Such anionic surfactants are known to be absorbed and for this reason cause dryness and scaling of the epidermis, as well as cracks and roughness, if used continuously. Thus, skin problems such as hand roughness can be caused by the use of detergents. The roughness of the skin can cause serious skin problems such as evenness. Thus, there is an urgent need to eliminate this disadvantage.

Nonionic surfactants cause little or no skin roughness or dryness. However, they do not have the same advantageous foaming and detergent properties as anionic surfactants. Therefore, it has not been suitable to incorporate nonionic surfactants into cleaning compositions as primary detergent components.

Phosphoric acid esters have been recognized as anionic surfactants, generally as mono or diesters or mixtures thereof. However, its solubility in water is generally not very good.

European Patent No. 265 702 published on May 4, 1988 describes transparent or semitransparent cosmetic compositions containing a monoalkyl phosphate, water, oil and an alcohol for skin treatment. Oils and alcohols are used to obtain clarity. U.S. Patent 4,573,749 issued to Mclntosh, issued June 28, 1988 describes alkyl monamine phosphates with

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antimicrobial activity. US Patent 4,290,904 issued to Poper et al, issued on September 22, 1981, UK Patent Νθ 1,513,053, published on June 7, 1978 and European Patent 023 978, published on February 18, 1981, describe preparations cosmetics and make-up containing alkylene alkoxylated diamines. U.S. Patents 4,476,043, 4,476,044 and 4,476,045 issued to O'Lenick, issued October 16, 1984, describe substantially non-aqueous surfactants containing an organic sulfate, mineral oil and an alkoxylated amine. However, none of these references describes the use of a diamino alkyl phosphate surfactant.

Monoalkyl phosphate salts have also been described as useful surfactants in US Patent 4,139,485 issued to Imokawa et al., Issued February 13, 1979. However, these surfaces form cloudy aqueous solutions unless they contain other solvents (for example, solubilizing agents). In addition, the rheology of these salts limits the variety of formulations that can be made with pleasant aesthetic characteristics.

It has been found that certain new monoalkylamine phosphate salts, as well as certain transparent and stable surfactant compositions containing these salts, easily allow the preparation of stable, aerated and non-pressurized foams. These foams have good washing and detergent power, are smooth and non-irritating and leave little or no residual film on the clean skin surface. These compositions are homogeneous in nature, can be structured to be wet or dry, stable or rapidly decomposable and are aesthetically suitable for use in a wide variety of personal care products.

One of the main objectives of this invention is to describe the preparation of a skin cleansing composition made from the new monoalkyl diamine phosphate salts of the present invention, which will produce a foam that can be used from a hand-held foam device and an aerosol device and which, moreover, do not become useless due device ^at,, © btrução device, for example.

Another object of the present invention is to provide surfactants and surfactant compositions producing

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relatively stable or disintegrable foams. A preferred embodiment of the present invention is to provide low density foams for cleaning the skin.

Another object of the present invention is to provide a surfactant and a smooth surfactant composition that is non-irritating to the skin and eyes and does not require the use of propellants, thus avoiding the danger of explosion or corrosion of the container.

Yet another object of the present invention is to provide a foam-producing composition such that if placed in a manual foam applicator device with deformable walls, the amount of force required to produce the foam is not excessive (that is, less than about 15 psi) and is easily usable by the average user.

These objectives, as well as others apparent to those skilled in the art, are achieved with the compounds and compositions described herein.

SUMMARY OF THE INVENTION the present invention comprises monalkyl diamine phosphate salts having a low human skin irritation effect, of the formula:

OX ^

RO — P ~ 0X ₂

H '

where R is a hydrophobic group or the condensation product of a hydrophobic group with ethylene oxide where preferably R is alkyl or alkenyl with an average of between about 10 to 18 carbon atoms and where X | and X2 are independently selected from the group consisting of hydrogen, alkali metal, ammonium, substituted ammonium (for example, alkoxylated ammonium, alkylammonium, r 3 aliphatic amines, -

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Compositions comprising the phosphate salts of these monoalkyl diamines are also described.

Sesquiaquyl phosphate salts are not within the scope of the present invention.

All parts, percentages and ratios used here are by weight and all measurements are at 252 C, unless otherwise stated.

DETAILED DESCRIPTION OF THE INVENTION

The surfactant compounds of the present invention are of the formula:

OXj

I

RO — P — 0X ₂ where R is a hydrophobic group or a condensation product of a hydrophobic group with ethylene oxide where R is preferably alkyl or alkenyl with an average of between about 10 and 18 carbon atoms, and wherein · X ^ and X ₂ are independently selected from the group consisting of bidrogénio, alkali metal, ammonium, substituted ammonium (e.g., alkoxylated ammonium, alkylammonium, alkoxylated aliphatic amines, polyethoxylated amines) and alkylene diamine. Preferably, R is the condensation product of a hydrophobic group with between about 1 and about 10 moles and preferably between about 1 and about 4 moles of ethylene oxide.

Preferably, the weight ratio of the monalkyl diamine phosphate salt to the dialkyl phosphate salt is between about 99: 1 and about 70:30, respectively, preferably between about 100: 0 and about 90: 10, with a ratio of 100: 0 being most preferred. However, unlike monoamine, alkali, or salts

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Case: 4119R of ammonium phosphate, these diester phosphates of the diester are only soluble in water and, therefore, will not interfere with the devices and formulations described here.

The surfactants of the present invention are particularly useful in detergent products that directly contact the skin for a long time, such as facial cleansers, shampoos and bars of synthetic and solid detergent for makeup because it has an excellent and characteristic power of foam production without causing roughness to the skin. Surfactants can also be used as liquid dishwashing detergent, powder detergent and toothpaste ingredients and are particularly useful compositions where clear, non-cloudy compositions are desired.

The saturated and unsaturated carbon groups with an average carbon atom value of 10-18 (R) are straight, branched or alicyclic hydrocarbons such as decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl and olefinically unsaturated correspondents. These »hydrocarbon groups are contained alone in the compositions or in the form of a combination of several groups. Hydrocarbon groups saturated with a number of carbon atoms of 10 to 14 and unsaturated hydrocarbon groups with an average number of carbon atoms of 16 are particularly preferred. Also useful for this use are the saturated and unsaturated hydrocarbon groups of between about 1 and about 10 units and preferably between about 1 and about 4 units of ethylene oxide per molecule.

The preferred alkali metals for X | and X2 according to the invention are, for example, lithium, sodium and potassium.

alkylammonium or substituted alkylammonium for Xj. and X2 according to the invention, are cations produced from amines used to neutralize the corresponding phosphoric acids by salt formation after the neutralization step in the process of preparing monoalkyl phosphate salts of the present ftBaEBfe). The corresponding amines are primary, secondary and tertiary amines with alkyl groups of 1 to 4 carbon atoms that can still be

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replaced, in particular by hydroxyl groups. As amines may be mentioned, for example, dimethylaminoethanolamine, methyldiethanolamine, trimethylamine, triethylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, isopropyl dimethylamine and isopropylethanolamine. Preferred amines are monoethanolamine, diethanolamine and triethanolamine. A particularly preferred amine is triethanolamine. Other useful amines include arginine, lysine, mono-, di- or tei-isopropanolamine, N, N-tris (hydroxymethyl) aminomethane, diglycolamine, glucamine, aminomethylpropanol and aminomethylpropanediol. Also usable in the present invention are copolymers derived from the addition of ethylene oxide and propylene oxide available as Tetronic® · and Tetronic R® obtainable from BASF Corporation and the polyethoxylated amines available in the form of the Ethomeen® series which is supplied Armak Corporation.

Alkylene diamine according to the present invention has the following general formula:

Rj ^ N — R3 — NR4R5 »where Rj, R2, R4 and R5 are hydrogen independent, an alkyl group with 1 to 4 carbon atoms or a hydroxyalkyl or dihydroxyalkyl group with 1 to 4 carbon atoms or where R4 and R5 together form a saturated 5- or 6-membered heterocyclic ring, which can be replaced by an oxo- or hydroxyalkyl group and R3 represents an alkylene or hydroxyalkylene group having 2 to 4 carbon atoms, provided that at least one of the Rp R2, R3, R4 and R5 contain at least one hydroxy group.

These compounds are fully described in U.K. 1,513,053, published June 7, 1978.

A particular and useful class of amine, in the present case, is an ethylene diamine Ν, Ν-tetrakis (hydroxyalkyl) with the formula:

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R [HO — CH-CH ₂ ] _n

R [CH ₂ —CHOH] _n

N — Rj - N [HO — CH — CH ₂ ] _n [CH ₂ —CHOH] _n where R | is alkylene with two to four carbon atoms, R is hydrogen or an alkyl group with one to six carbon atoms and n is one to four. The foregoing dlamine preferably has a molecular weight of less than about 1700, preferably less than about 1200, even more preferably less than about 800 and most preferably of all less than about 500.

Although other examples are provided below, tetrakis (hydroxyalkyl) ethylene diamine is best identified by the compound N, N, Ν ', N'-tetrakis (2-hydroxypropyl) -ethylenediamine, commercially obtainable under the trademark Quadrol or Neutrol TE (both provided by BASE Wyandotte Company).

Examples of phosphate salts useful in the present invention include, but are not limited to, monococoilfosfato of tetrahidroxipropiletilenodiamina, monolaurllfosfato of tetrahidroxipropiletilenodlamina, monolaurilfosfato of tetrahldropropiletilenodiamlna (monoetoxilado) monoisoestearilfosfato of tetrahidroxipropiletilenodiamina, monostearilfosfato of tetrabidropropiletilenodiamina, monoestearilfosfato of tetrahidroxipropiletilenodiamina (monoetoxilado) monomiristilfosfato of tetrabydroxypropylethylenediamine, tetrabydroxypropylenediamine monooleoylphosphate, tetrahydroxypropylethylenediamine monopalmitylphosphate,

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COMPOSITIONS

The compositions of the present invention comprise:

(a) from about 0.1% to about 99% of one or more monalkyl diamine phosphate salts of the present invention; and (b) from about 1.0% to about 99.0% of a detergent vehicle.

Preferred compositions comprise a mixture of the diamine monoalkyl phosphate salts wherein R is selected from ^the group consisting of Cj.4 alkyl or alkenyl L ^ -C ^ g alkyl or alkenyl (or the condensation product of these portions with between about 1 and about 10 moles of ethylene oxide) and wherein said salts are present in a ratio of between about 80:20 and about 20:80, preferably from about 60:40 to about 40:60 and more preferably from about 55:45 to about 45:55, respectively.

The compositions of the present invention can be administered topically, that is, by direct application in layer or spreading the composition on epidermal or epithelial tissue. Such compositions can be formulated in the form of foams, lotions, creams, greases, solutions, jellies or solids. A highly preferred composition contains the monoalkyl phosphate salt in a soap matrix (i.e., liquid and solid). These topical compositions comprise a safe and effective amount, generally about

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0.1% to about 99% and preferably about 1% and about 10% of the monoalkyl phosphate salt. Bar compositions generally contain very high levels, that is, above 80%, of the monoalkyl diamine phosphate salt. Generally the vehicle is either of an organic nature or an aqueous solution or emulsion and may have the monoalkyl diamine phosphate salt dissolved or suspended therein. The carrier can include pharmaceutically acceptable emollients, skin penetration enhancers, coloring agents, fragrances, emulsifiers, thickening agents and solvents. A more detailed description of such forms follows:

1. Lotions.

Lotions can comprise a safe and effective amount of monoalkyl phosphate salt; from about 0.1% to about 25%, preferably from about 3% to about 15% of an emollient; the balance being water, a C2 or C-j alcohol or a mixture of water and alcohol. Examples of suitable emollients are as follows:

1. Hydrocarbon oils and waxes. Examples are mineral oil, petrolatum, paraffin, ceresin, ozoquerite, microcrystalline wax, polyethylene and perhydrosqualane.

2. Silicone oils, such as polydimethylsiloxanes, methylphenylpolysiloxanes, water-alcohol-soluble silicone-glycol copolymers.

3. Oils and triglyceride fats, such as those derived from plant, animal and marine sources. Examples of this include castor oil, safflower oil, cottonseed oil, corn oil, olive oil, cod liver oil, almond oil, avocado oil, palm oil, sesame oil and soybean oil.

4. Acetoglyceride esters, such as acetylated monoglycerides.

5. Ethoxylated glycerides, such as ethoxylated glyceryl monostearate.

6. Fatty acid alkyl esters with 10 to 20 carbon atoms. Methyl, isopropyl and butyl fatty acid esters are especially useful here. Examples of these include hexyl laurate, isohexyl laurate, isohexyl palmitate,

- 9 4

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J

Mod. 71 - 20,000 ex. - 8/90

J isopropyl, decyl oleate, isodecyl oleate, hexadecyl stearate, decyl stearate, isopropyl isostearate, diisopropyl adipate, diisopropyl adipate, dihexildecyl adipate, diisopropyl sebacate, lactate of lauryl, myristyl lactate and cetyl lactate.

7. Alkenyl esters of fatty acids with 10 to 20 carbon atoms. Examples of these include oleyl myristate, oleyl stearate and oleyl oleate.

8. Fatty acids with 9 to 22 carbon atoms. Suitable examples include pelargonic, lauryl, myristic, palmitic, stearic, isostearic, hydroxy-stearic, oleic, linoleic, ricinoleic, arachidonic, baby and erucic acids.

9. Fatty alcohols with 10 to 20 carbon atoms. Lauryl, myristyl, cetyl, hexadecyl, stearyl, isostearyl, hydroxystearyl, oleyl, ricinoleyl, behenyl, reucyl and 2-octyl dodecyl are examples of suitable fatty alcohols.

10. Fatty alcohol esters. Ethoxylated fatty alcohols with 10 to 20 carbon atoms include the lauryl, cetyl, stearyl, isostearyl, oleyl and cholesterol alcohols that have between 1 to 50 ethylene oxide groups or 1 to 50 propylene oxide groups or its a mixture.

11. Ether esters such as the fatty acid esters of ethoxylated fatty alcohols.

12. Lanolin and its derivatives. Lanolin, lanolin oil, lanolin wax, lanolin alcohols, lanolin fatty acids, isopropyl lanolate, ethoxylated lanolin, ethoxylated lanolin alcohols, ethoxylated cholesterol, propoxylated lanolin alcohols, acetylated lanolin, acetylated lanolin alcohols, acetylated lanolin alcohols lanolin, lanolin alcohol ricinoleate, lanolin acetate alcohol ricinoleate, ethoxylated alcohol esters acetate, lanolin hydrogenolysis, ethoxylated hydrogenated lanolin, ethoxylated sorbitol lanolin and liquid lanolin absorption bases and liquid derivatives are illustrative. of lanolin.

13. Derivatives of polyhydric and polyether etherols. Propylene

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14. Polyhydric alcohol esters, ethylene glycol mono- and di-fatty esters, diethylene glycol mono- or di-fatty esters, polyethylene glycol mono- and di-fatty esters (PM 200-6000) , propylene glycol mono and di-fatty acid esters, propylene glycol 2000 monoleate, propylene glycol 2000 monostearate, ethoxylated propylene glycol monostearate, glyceryl mono and di-fatty acid esters, poly-fatty acid esters polyglycerol, ethoxylated glyceryl monostearate, 1,3-butylene glycol monostearate, 1,3-butylene glycol distearate, polyoxyethylene fatty acid ester, sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters are satisfactory alcohol esters polyhydric.

15. Wax esters, such as beeswax, spermaceti, myristyl myristate, stearyl stearate.

16. Beesphere derivatives, for example, polyoxyethylene sorbitol from beeswax. These are reaction products of beeswax with ethoxylated sorbitol with a varied content of ethylene oxide, which form a mixture of ether-esters.

17. Vegetable waxes, including carnauba and candelaria waxes.

18. Phospholipids, such as lecithin and its derivatives.

19. Sterols. Cholesterol, cholesterol fatty acid esters are examples of them.

20. Starches, such as fatty acid starches, ethoxylated fatty starches, fatty acid alkanolamides

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solid.

Lotions further comprise between about 1% and about 10%, preferably between about 2% and about 5% of an emulsifier. Emulsifiers can be non-ionic, anionic or cationic. Satisfactory examples of non-ionic emulsifiers include fatty acid alcohols with 10 to 20 carbon atoms, fatty alcohols with 10 to 20 carbon atoms condensed with 2 to 20 moles of ethylene oxide or propylene oxide, alkyl phenols with 6 to 12 carbon atoms in the alkyl chain condensed with 2 to 20 moles of ethylene oxide, esters of mono- and di-fatty ethylene oxide, esters of mono- and di-fatty acids of ethylene glycol in which the fatty acid contains between 10 to 20 carbon atoms, diethylene glycol, polyethylene glycols of molecular weight 200 to 6000, propylene glycols of molecular weight 200 to 3000, glycerol, sorbitol, sorbitan, polyoxyethylene sorbitol, polyoxyethylene sorbitan and hydrophilic wax esters. Suitable anionic emulsifiers include soaps and fatty acids, for example sodium, potassium and triethanolamine soaps, wherein the fatty acid portion contains between 10 to 20 carbon atoms. Other suitable anionic emulsifiers include alkali metal, ammonium or substituted alkyl ammonium sulfates, alkyl aryl sulfonates and alkyl ethoxy ether sulfonates having 10 to 30 carbon atoms in the alkyl portion. Ether alkyl ethoxy sulfonates contain between about 1 to 50 ethylene oxide units. However, it is recognized that certain anionic emulsifiers can result in a cloudy solution and that is why anionic emulsifiers are the least preferred for use in the present case.

rest of the lotion consists of water or a Cg or Cg alcohol, or a mixture of water and alcohol. The solutions are formulated by simply mixing all the components. Preferably, the monoalkyl phosphate salt is dissolved in the mixture. Optional conventional components can also be included. One of these additives is a thickening agent at a level of between about 1% and about 10% of the composition. Examples of suitable thickening agents include; crosslinked polymers of carboxypolymethylene (sufficiently neutralized), aluminum magnesium silicate, carboxymethylcellulose, hydroxyethylcellulose, $ 91

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acrylic acid polymers (eg Acrysol ICS-I, produced by

Rohm & Haas Corporation), polyethylene glycols, tragacanth gum, caraia gum, xanthan and bentonite gums. Cationic polymers, such as guar cationic gum, are not preferred for use in the present case.

2. Creams.

The compositions of the present invention can also be formulated in the form of a cream. These comprise effective amounts of the monoalkyl sulfate salt; between about 0.1% to 95% of an emollient, preferably from about 10% to about 25%; the rest being water. The emollients described above can also be used in cream compositions. Optionally, the cream form contains a suitable emulsifier, as previously described. When an emulsifier is included, the composition is at a level of between about 3% and about 50%, preferably between about 5% and about 20%.

3. Solutions.

The compositions of the present invention can also be formulated as a solution. This comprises an effective amount of the monalkyl phosphate salt, generally at least about 0.01% to about 50% and preferably about 0.1% to about 10%; the remainder consisting of water or a suitable organic solvent. Suitable organic materials and useful as solvents or parts of a solvent system are the following: propylene glycol, polyethylene glycol (PM 200-1000), polypropylene glycol (PM 425-2025), butylene glycol, glycerin, sorbitol esters, 1 , 2,6-hexanethriol, ethanol, isopropanol, diethyl tartrate, butanediol and mixtures thereof.

These solutions can be applied to the skin as is, or they can be formulated in tightening devices, as described or as an aerosol and sprayed on the skin from an aerosol container, or as a mouth wash composition and used as a oral rinse. Aerosol compositions further comprise between about 25% and about 80%, preferably between about 30% and about 50% of suitable propellants. Examples of such propellants are chlorinated, fluorinated and hydrocarbons

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low molecular weight chlorofluorides. Nitrous oxide, carbon dioxide, butane and propane can also be used as gaseous propellants. These propellants are used at a level sufficient to expel the contents of the container.

Foam squeeze packs are well known, as exemplified by the descriptions of the following patents incorporated herein by reference. U.S. Patent Nos. 3,709,437, Wright, issued Jan. 9, 1973; 3,937,364, Wright, issued Feb. 10, 1976; 4,022,351, Wright, issued May 10, 1977; 4,147,306, Bennett, issued Apr. 3, 1979; 4,184,615, Wright, issued Jan. 22, 1980; 4,598,862, Rice, issued July 8, 1986; and 4,615,467, Grogan et al., issued on Oct. 7, 1986; and French Patent 2,604,622, Verhulst, published Apr. 8, 1988.

The aforementioned containers (packaging) do not use any propellant and are therefore safe for the consumer and the environment. They create a foam from any surfactant composition. Although there is no need to add foam expanders for the sole purpose of stabilizing it, such materials may be desirable. In some compositions, the use of foam expanders can even be counterproductive, since the foam has to break in order for the container to function properly. The composition is placed in the container reservoir (tight and plastic bottle). By compressing the container by hand, the composition is forced to pass through a foaming head or other foaming means, in which the composition is mixed with air and then through homogenizing means that cause the foam more homogeneous and that control the consistency of the foam. The foam is then discharged in the form of a uniform, non-pressurized aerated foam.

The minimum pressure to activate the squeeze foam maker is about 1 psig to about 2 psig. The minimum pressure is related to the size of the channels in the applicator, the viscosity of the composition, etc.

In general, the density of the foam should be between about 0.002 and about 0.25 g / cc, preferably between about

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liquid vehicle in a nozzle washing preparation is generally a mixture of ethanol and water. The amount of ethanol is generally between about 5% to about 60%, preferably between about 5% and about 25% by weight of the vehicle. These mouthwash compositions may also contain other optional components such as emulsifying agents as described above, flavoring agents, sweeteners and humidifiers. Other formulations and methods for creating mouthwash products useful in the present invention are described in U.S. Patent 4,323,551 issued to Parran, issued April 6, 1982, which is incorporated herein by reference.

4. Jellies.

These compositions can be formulated in a jelly form by simply mixing a thickening agent suitable for the solution compositions as described above. Examples of suitable thickening agents have been described previously when referring to lotions.

The gelled compositions comprise a safe and effective amount of the monoalkyl phosphate salt, from about 0.5% to about 20%, preferably from about 1% to about 10% of the thickener; the rest being water.

5. Solids.

The compositions of the present invention can also be formulated in a solid form, for example, a cylinder type composition. Such compositions comprise an effective and safe amount of the monoalkyl phosphate salt and between about 0.01% and about 99%, preferably between about 60% and about 90%, of the emulients described above. This composition can further comprise between about 0.1% and about 20%, preferably between about 5% and about 15% of a suitable thickening agent and, optionally, emulsifiers and water. The thickeners described above for lotions are also suitable for this case.

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I

6. Soaps.

The compositions of the present invention can also be formulated in a liquid or solid soap mold (for example, bar). Such compositions comprise a safe and effective amount of the monoalkyl phosphate salts ranging from about 0.1% to about 99%; and between about 1% and about 99% of an excipient such as those described above. Optionally, the soap contains a suitable emulsifier, as previously described. When an emulsifier is included, it is in the composition at a level of between about 10% and about 50%.

7. Toothpaste.

The compositions of the present invention can also be formulated as toothpaste. Such toothpastes, especially toothpaste, comprise a safe and effective amount of the monoalkyl phosphate salt ranging from about 0.1% to about 20% by weight of the composition. Conventionally, toothpaste compositions contain abrasive materials, foaming agents, binders, wetting agents, flavoring agents and sweeteners.

_n ~, tr. ,, ^and processes „,,.

Denture compositions suitable for their manufacture usable in the present invention are fully described in U.S. Patent 3,535,421, issued to Briner et al., Issued October 20, 1970, which is incorporated herein by reference.

8. Shampoos.

Compositions of the present invention can also be formulated in a shampoo form. Shampoos comprise a safe and effective amount of the monoalkyl phosphate diamine salt ranging from about 0.1% to about 99%; from about 5% to about 60% of a synthetic surfactant; and the rest in water. A secondary surfactant can also be used. However, such a secondary surfactant should be neutralized by a diamine as described above.

These shampoos can · contain a variety of optional non-essential components. Such optional conventional ingredients are well known in the art and are, for example, preservatives, such as benzyl alcohol, ethyl paraben,

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Additional minor components can be added to the compositions of the present invention in order to increase their attractiveness, versatility and storage. Pharmaceutically acceptable water-soluble perfumes and dyes or food dyes can be added to make these compositions more attractive. Antifungal and antimicrobial agents are useful to prevent contamination by molds or bacteria and to increase the storage of the compositions. Conventional anti-bacterial agents can be included in the present compositions at levels of between about 0.1% and about 4%, preferably between about 0.2% and about 1%. Antibacterial agents suitable for use are 3,4-die 3,4 ', 5-tribromosalicylanides; 4,4'-dichloro-3 (trifluoromethyl) carbanilide; 3,4,4'-trichlorocarbanilide; phenoxy ethanol or propane; chlorhexidene salts; hexamidine salts; Irgasan DP 300 (Triclosan); salicylic acid;' parachloromethoxylenol; Octopirox and mixtures of these materials. For general purposes, skin cleansing compositions with a pH range of about 5.0 to about 8.0 are desirable. If necessary, the pH of these compositions can be adjusted downwards using citric or lactic acid. For skin cleansers that treat more sensitive skin surfaces, such as vaginal or perineum cleaners,

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Case: a pH of about 6.5 is desirable. These and other minor modifications can be made without changing materially or departing from the basic concept of this invention.

The nature of the foam produced determines the usefulness of the present compositions. For a foam to be useful as a skin cleansing agent, it must have a uniform consistency, good spreadability and good cleansing ability.

The characteristics of foaming and moistening are guided by the surface tension of the skin cleansing composition. The surface tension for the compositions of the present invention varies between about 20 and about 70 dynes / cm. For general skin cleansing compositions, a range of about 23 to about 50 dynes / cm is preferred. Liquid compositions with a surface tension lower than these limits have greater spreading characteristics and better wetting with improved foam formation. Compositions capable of foaming with higher tensile surfaces generally provide more stable foams, but are also more difficult to foam and require more strength to extrude the foam.

The foam-producing skin cleansing compositions of the present invention are particularly advantageous in that they leave a minimal amount of surfactant residue on the skin surface. This has been achieved, in part, through the use of a low percentage of total surfactants in the skin cleansing compositions themselves and by preparing foams with an abnormally low density. The present compositions provide foam densities that give a good cleaning capacity and more importantly leave a negligible amount of surfactant residue on the skin surface after rinsing or rubbing, thus preserving the skin's elasticity and reducing transepidermal moisture losses .

The cleaning capacity of these aerated foams is a direct function of the cleaning capacity of the surfactant itself in the solution that produces the foam.

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Case: 4119R

The following non-limiting examples follow the embodiments of the invention in question, in which both the essential and optional ingredients are combined. It should be understood that these examples are for illustrative purposes only and are not to be considered as limiting the scope of the invention.

EXAMPLE 1 mole of monolauryl acid phosphate is heated under a steam bath at about 50 ° C, until it melts. 1 mole of Ν, Ν, Ν ', N'-tetrakis (2-hydroxypropyl) -ethylenediamine (available according to Table 1 from BASF Corporation) is heated in a separate beaker at 50 ° C until it can be poured.

Fused phosphate is slowly added to ã, Ν, Ν ’, Ν’-tetrakis (2-hydroxypropyl) -ethylenediamine. The phosphate is added until a pH of 5.0 to 9.0 (preferably 7.0) is reached. The resulting Ν, Ν, Ν *, N'-tetrakis (2-hydroxypropyl) -ethylenediamine monolauryl phosphate is then cooled to a clear, yellow solid.

This solid can be used as a solid bar or as a material to produce a liquid cream or jelly.

The application on the skin of approximately 0.5 grams, will provide a foam cleaning product that has a cleaning and detergent power, which is smooth and non-irritating and leaves little, if any, residual film on the clean surface. skin.

Substantially similar results are obtained when the monolauryl phosphate acid is replaced with an equivalent amount of monocollolephosphate acid, monolauryl phosphate acid, mono isostearyl phosphate acid, monomyristyl phosphate acid, monoleyl phosphate acid, monopalmityl phosphate acid, monopalmityl phosphate acid, monopalmityl phosphate monoundecylenylphosphate acid, monotridecylenylphosphate acid, mono (methylmiristyl) phosphate acid, mono (isopropylauryl) phosphate acid, mono (isodecylneopentyl) phosphate, monethylphosphate acid and its mono (isopropyl) phosphate and its monohydrate.

63292

Case: 4119R

EXAMPLE II

Face cleansing composition for topical administration is prepared by combining the following ingredients:

Ingredients Percentage P / P

Ν, Ν, Ν ’, Ν’-tetrakis (2-hydroxypropyl).

ethylenediamine monolaurylphosphate 2,500

2,500 Butylene Glycol

Methylparaben 0.250

Propylparaben 0.150

Coconut potassium (hydrolyzed animal protein) ¹ 0.032

Glycerin 2,000

Aloe Vera 0.500

Fragrance 0.050

Color 0.170

0.050 xanthan gum

Water q.s.

Sold as Lamepon S by Henkel Corporation

Sold as Keltrol T by Kelco Corporation

EXAMPLE III ’

A cream facial cleansing composition for topical administration is prepared by combining the following ingredients:

Ingredients

Ν, Ν, Ν ’, Ν’-tetrakis (2-hydroxypropyl) ethylenediamine monolaurylphosphate lauric acid

Ν, Ν, Ν ’, Ν’-tetrakis (2-hydroxypropyl) ethylenediamine

Carboxyvinyl polymer

Glycerin

Percentage P / P

27,000

4,000

4,000

0.200

8,000 (cont.)

63292

Case: 4119R

Sorbitol

Water

Sold as Quadrol by BASE-Wyandotte

Sold as Carbopol 941 by B.E.Goodrich Company .2,000

q.s.

EXAMPLE IV

A facial cleansing composition for topical administration is prepared by combining the following ingredients:

Ingredients

Ν, Ν, Ν ’, N'-tetrakis (2-hydroxypropyl) ethylenediamine monolaurylphosphate Lauric acid

Coconut potassium (hydrolyzed animal protein)

Hydroxyethyl cellulose

Methyl paraben

Propyl Paraben

Glycerin

Fragrance

Color water

P / P Percentage

3,000

1,000

0.500

2,000

0.100

0.100

3,000

0.100

0.000

q.s.

EXAMPLE V

A jelly facial cleansing composition for topical administration is prepared by combining the following ingredients:

Ingredients Percentage P / P

Ν, Ν, Ν ’, N'-tetrakis (2-hydroxypropyl) ethylenediamine monolaurylphosphate 10,000 Acrylic acid polymer 0.500 Ν, Ν, Ν’, N'-tetrakis (2-hydroxypropyl) ethylenediamine 1,000 Glycerin 5,000 lauric acid 2,000 Water q.

- 21 63292

Case: 4119R 9

EXAMPLE VI

A shaving foam composition for topical & prepared administration by combining the following ingredients

Ingredients P / P Percentage Ν, Ν, Ν ', Ν’-tetrakis (2-hydroxypropyl) - ethylenediamine monolaurylphosphate 7,000 Ν, Ν, Ν ’, Ν’-tetrakis (2-hydroxypropyl) - ethylenediamine monopalmityl phosphate Lauric acid 7,000 1,500 Palmitile acid Ν, Ν, Ν ’, Ν * -tetrakis (2-hydroxypropyl) - ethylenediamine 1,500 1,500 Fragrance 0.100 Aloe Vera 2,000 Water q.s. EXAMPLE VII

A facial cleansing composition for topical administration is prepared by combining the following ingredients:

Ingredients. P / P Percentage Ν, Ν, Ν ’, N’-tetrakis (2-hydroxypropyl) - ethylenediamine (1 mole ethoxylated) - monolaurylphosphate 2,500 Butylene Glycol 2,500 Methylparaben 0.250 Propylparaben Potassium coconut (hydrolyzed animal protein) ¹ 0.150 0.032 Glycerin 2,000 Aloe Vera 0.500 Fragrance Color - 2 Eat xanthan 0.050 0.170 0.050 Water q.s. 1 Sold as Lamepon S by Henkel Corporation 2 Sold as Keltrol T by Kelco Corporation

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Claims (2)

= CLAIMS = wool- Process for the preparation of a detergent composition with a low irritating effect presented in the form of soaps, creams, solutions, mouthwashes, toothpastes and shampoos, comprising: a) between about 1% and about 99% of one or more of a surfactant compound with the formula RO — Ρ — OX! T 0 where R is a hydrophobic group or the condensation product of a hydrophilic group with ethylene oxide and where X ^ and 2. ^ are independently selected from the group consisting of hydrogen, alkali metal, ammonium substituted and alkylene diamine; provided that at least one of X ^ and X ^ is an alkylene diamine; and b) between about 99% and about 1% of a detergent vehicle. Process according to claim 1, characterized in that R is alkyl or alkenyl with an average of between about 10 and about 18 carbon atoms and in which said substituted ammonium is selected from the group consisting of alkoxylated ammonium, alkylammonium, amines alkoxylated aliphatics and polyethoxylated amines. Process according to Claim 2, characterized in that R is alkyl or alkenyl with an average of between about 10 and 14 carbon atoms and in which said alkali metal is selected from the group consisting of sodium, potassium and lithium and their mixtures. 4. A process according to claim 3, characterized in that said alkylammonium is selected from the group consisting of trimethylammonium, triethylammonium, dibutylammonium, butyldimethylammonium. and isopropyl dimethylammonium and mixtures thereof and wherein said substituted alkylammonium is hydroxyalkylammonium. Process according to claim 4, character 23 63292 Case: 4119R characterized by at least one of X ^ and X ^ is a fully hydroxyalkylated alkylene diamine in which R is a condensation product of a hydrophobic group having about 1 and about 10 ethylene oxide springs. 6. A process according to claim 5, characterized in that at least one of X X and X £ is a hydroxyalkylated alkylene diamine wherein said alkylene contains between 2 and about 6 carbon atoms, said alkylene diamine having been oxyalkylated with an alkylene oxide containing at least 2 carbon atoms or a mixture, -,,,. ' containing. , of alkylene oxides between 2 and more carbon atoms. 7. A process according to claim 6, characterized in that one of X ^ and X ^ is Ν, Ν, Ν ', N'-tetrakis (2-hydroxypropyl) -ethylene-diamine. 8ê- process according to claim 1, said composition compreen bering a mixture of diamine monoalkyl phosphate salts wherein R is selected from the group consti tuted by ^a ^ 4 alkyl or alkenyl and C ^ g alkyl or alkenyl and wherein said salts are present in a ratio of between about 60:40 and about 40:60. 95- Process according to claim 8, Compreen bering said composition a mixture of the diamine monoalkyl phosphate salts wherein R is selected from the group cons títuido the condensation product of a C ^ ^a alkyl or alkenyl with between about 1 and about 10 moles of ethylene oxide and the condensation product of one to C 1 g alkyl or alkenyl with between about 1 and about 10 moles of ethylene oxide and in which said salts are present in a ratio of between about 60:40 to about 40:60 respectively. 10a ^- Process for the preparation of a composition with low irritation effect, according to the preceding claims, comprising: a) one or more of a surfactant compound with the formula la: RO - P — 0X. II q - 24 63292 Case: 4119R 2; wherein R is a hydrophilic group or the condensation product of a hydrophilic group with ethylene oxide in which X4 and s ^are independently selected from the group consisting of hydrogen, alkali metal, ammonium, substituted ammonium and alkylene diamine, provided that at least one of X ^ and X ^ is an alkylene diamine; and b) one or more surfactant compounds with the formula: RO — P - OR II wherein R is a hydrophilic group or the condensation product of a hydrophilic group with ethylene oxide and in X X and selected from the group consisting of hydrogen, alkali metal, ammonium, substituted ammonium and alkylene diamine; characterized in that the ratio of (a) to (b) is between about 99: 1 and about 70:30. Process according to claim 10, characterized in that R is an alkyl or alkenyl with an average of between about 10 to 18 carbon atoms or R is the condensation product of an alkyl or alkenyl with an average of between about 10 to 18 carbon atoms with between about 1 to 10 moles of ethylene oxide, in which the substituted ammonium is selected from the group consisting of alkoxylated ammonium, alkylammonium, alkoxylated aliphatic amines, polyethoxylated amines and at least one of X ^ and X ^ is Ν, Ν, Ν ', N'-tetrakis (2-hydroxypropyl) -ethylene-diamine. Process according to claim 1, characterized in that one of the X X is alkylammonium and said alkylammonium is selected from the group consisting of trimethylammonium, triethylammonium, dibutylammonium, butyldimethylammonium, isopropyl dimethylammonium, diglycolamines, glucamines and their compounds mixtures and in which said substituted alkylammonium is hydroxyalkylammonium and declares that it has interlaced the processes and containing 2;