CA2078442C

CA2078442C - Novel surfactants and surfactant compositions

Info

Publication number: CA2078442C
Application number: CA 2078442
Authority: CA
Inventors: Joseph Albert Ehrhard, Jr.; George Endel Deckner
Original assignee: Richardson Vicks Inc
Current assignee: Richardson Vicks Inc
Priority date: 1990-03-27
Filing date: 1991-03-11
Publication date: 1995-12-05
Anticipated expiration: 2011-03-11
Also published as: PT97096A; JPH05506018A; AU7581791A; NZ237587A; CN1055385A; WO1991014693A1; EP0521980A4; IE911002A1; PT97096B; EP0521980A1; CA2078442A1; CN1029912C

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. It has the formula:

Description

P ~ /US9l/01622 W 0,~1/14693 ~ 2 ~ 7 8 ~ 4 2 NOVEL SURFACTANTS AND SURFACTANT COMPOSITIONS

TECHNICAL FIELD
The present invention relates to novel low skin irritation surfactants and surfactant compositlons wh k h are high in foaming properties containing, as an active ingredient, a diamine monoalkyl phosphate salt.
BACKGROUND OF THE INVENTION
Soaps, detergents and abrasives have long been used to cleanse the sktn on various portions of the body. An~onic surfactants such as alkyl sulfates, polyoxyethylene alkyl sulfates, alkylbenzene sulfon-ates and ~-olefin sulfonates have been widely used as the surfactant component for many cleansers.
It is known that such anionic surfactants are adsorbed and thereby remain on the s~in surface to cause dryness and scaling of the epiderm1s, or sktn chapping and roughness, if they are used continual-ly. Thus, skin troubles such as roughness of hands are apt to be caused by the use of detergents. Skin roughntss can be a precursor of more severe skin troubles such as eczema. Thus, there is an urgent need to eliminate this dlsadvantage.
Nonionic surfactants, on the other hand, cause llttle or no skin dryness or roughness. However, they do not h~ve the same advantageous properties of foa~ing and detergency as anionic surfactants. It has, therefore, not been suitable to incorpor-te nonionic surfactants into cleansing compos1tions as the primary detergent component.
Phosphortc ~ctd esters have been known as anionic surfactants, gen~rally as mono- and diesters, or mi%tures thereof. However, in gener~l, thetr water solubilities and foaming properties are not very goot.
European Patent No. 265 702 published May 4, 1988 discloses transparent or semi-transptrent cosmetic composittons containing a monoalkyl phosphate, water, oil and alcohol for skin treatment. The oils and alcohols are used to obtain clarity. U.S. Patent 4,573,749 to McIntosh, issued June 28, 1988 discloses monoamine alkyl phosphates having antimicrobial activity. U.S. Patent 4,290,904 to Poper et al.
issued September 22, 1981, U.K. Patent No. 1,513,053, published June 7, 1978 and European Patent 023 978, published February 18, 1981 disclose cosmetic and toiletry preparations containing alkoxylatea w o 91/14693 2 Q 7 8 ~ ~ ~ 2 - P ~ /US9l~016 ~alkyl~ne dl~ ~nes. U.S. Patent ~,~76,043, ~,~76,0~ and 4,47 5 to O'L~ntck, all issued October 9, 198~ and U.S. Patent 4,477,372 to O'Len~ck, issued October 16, 198~ disclose substantially non-aqueous surfactants containing an organic sulfate, mineral oil and an alkox~l-ated amine. I' .leve~, none of these references disclose the use of adiamine alkyl phosphate surfactant.
Monoalkyl phosph~te salts h~ve also been disclosed as useful surfactants in U.S. Patent 4,139,~85 to Imokawa et al., issued Febru-ary 13, 19~9. However, these surfactants form turbid aqueous solu-tions unless they contain other solvents (e.g., solubilizing agents).Further, the rheology of these salts limits the variety of formula-tions which can be made with aesthet k ally pleasing characteristics.
It has been discovered that certain novel diamine monoalkyl phosphate salts as well as certain transparent and stable surfactant compositions containing these salts readily enable the preparation of stable non-pressurized, aerated foams. These foams possess good cleansing power and detergency, are mild and non-irritating, and leave little, if any, residual film rem~ining on the cleansed surface of the skin. These compositions are homo3eneous in nature, can be structured to be wet or dry, st~ble or fastbretking, and are aesthetical7y suit-able for use in a w1de varlety of personal care products.
One of the prtncip~l purposes of this invent~on is to describe the preparation of an aqueous skin cleansing composition made from the novel diamine monoalkyl phosphate salts of the present invention which will prodùce ~ usable foa~ from a hand-held, squeezable foam dispens-ing device, as well as from an aerosol device and further which will not render the d~vtcc unusable by, for ex~mple, clogging the device.
Another ob~ect of this invention is to provide surfactants and foa~-produclng surfactant compositions wh~ch produce relatively stable or collapsible fou~s. A preferred embod1ment of th1s invention is to provide sk1n cleansing foams of low density.
Another object of this invention is to provide surfactants and foaming composit~ons w~th creamy lather, good skin feel and good rinsability and which retains skin elasticity.
Another ob~ect of this invention is to provide a surfactant and surfactant composition which is mild and non-irritating to skin and eyes and which does not require the use of propellants, thereby avoiding the danqer of explosion or corrosion of the containerO

W O 91/lq693 3 P¢~r/ussl/o~6~ ~8~4 Still another object of this invention is to provide a foam produclng co~position such that if placed in a hand-held, foam dis-pensing device having deformable walls, the amount of force required to produce the foa~ is not excessive (i.e., less than about 15 psi) and is readily usable by the average person.
These ob~ectives as well as others apparent to those skilled in the art are obtained with the compounds and compositions described herein.
SUMMARY OF THE IHVENTION
This invention comprises diamine monoalkyl phosphate salts having low irritation effect to human skin of the formula:
OX~
RO--P--0% 2 o wherein R is a hy~rophobic group or the condensation product of a hydrophobic group wtth ethylene oxide, preferably R is alkyl or alkenyl having an average of from about 10 to 18 carbon atoms, and wherein Xl and X2 are independently selected from the group consisting of hydro~en, alkall metal, ammonium, substituted ammonium (e.g., alkoxylated ammonium, alkylammonium, alkoxylated allphattc amines, polyethoxylated amines) and alkylene diamine, provided that at least one of X! and X is a tQtally hydroxyalkylated alkyl2r,e d~amine.
Also disclosed are compositions comprising these diamine monoalkyl phosphate salts.
Sesquialkyl phosphate salts are not within the scope of the present invent1on.
All parts, percentages and ratios used herein are by weight and all measure~ents are at 25'C unless otherwise indicated.
DETAILED DESCRIPTION OF T~E INVENTION
The surfactant compounds of the present invention are of the formula:
OX~

o wherein R is a hydrophobic group or the condensation product of a hydrophobic group with ethylene oxide, preferably R is alkyl or alkenyl having an average of from about lO to 18 carbon atoms, and wherein Xl and X2 are independently selected from the group consisting of hydrogen, alkali metal, ammonium, substituted ammonium (e.g., W O 91/14693 2 Q 7 ~ 4 4 ~ 4- P~/US91/01622 alkoxyl~ted a~ontum, alkylammon~um, alkoxylated al1phatic ~lnes, polyethoxyl~ted amines) and alkylene diamine, provided that at least one of X1 and X2 is a totally hydroxy alkylatedalkylene diamine.
Monoalkyl phosphate salts in the present invention can be pre-pared, for example, by a known process wherein a long chain al iphatic alcohol (or the condensation product of a long chain aliphatic alcohol with ethylene oxide) is reacted with a phosphatizing agent such as phosphoric anhydride or phosphorus oxychloride. It is recognized that the dialkyl phosphate can be by-produced by this process and which possess poor water-solubility or foaming properties. Such dialkyl phosphates have the formula:

RO--P--OR
a wherein R is a hyd~ophobtc ~roup or the condensation product of a hydrophob1c group with ethylene oxide, preferably R is alkyl or alkenyl having an a~erage of from about lO to 18 carbon atoms, and wherein X3 iS selected from the group consisting of hydrogen, al kal i metal, ammonium, substituted ammonium (e.g., alkoxylated amm,onium, alkylammonium, alkoxyl~ted aliphatic amines, polyethoxylated amines) and alkylene diamine. Preferably, R is the condensation product of a hydrophob~c group w~th from about 1 to about 10 moles and preferably from about 1 to about 4 moles of ethylene oxide.
Preferably, the weight ratio of the diamine monoalkyl phosphate salt to the dialkyl phosphate salt is from about 99:1 to about 70:30, respectively, preferably from about 100:0 to about 9O:10, most prefer-red is a r~t~o of sùbstantially 100:0. However, unlike monoamine, alk~li, or a~monium phosphate salts, these diamine phosphates of the diester are unlquely water-soluble and, therefore, will not interfere as much ~ith the devlces and formulations described herein.
The surfactants of the present invention are particularly useful in detergent products whlch are directly contacted with the skin for a long time such as facial cleansers, shampoos, and solid synthetic detergent toilet bars, because they have a characteristic, excellent foaming power and skin roughness is not caused. The surfactants can also be used as ingredients of dish-washing liquid detergents, powder detergents and dentifrices and are particularly useful compositions where a clear and non-turbid composition is desirable.

~ ~ ~ Pt~r/US9l/01622 W 0 91/14693 ~ 2 ~ 7 8 ~ ~ 2 The satur~ted and unsaturated hydroc~rbon groups having an aver~ge carbon number of 10-18 (R) are straight chain, branched or al~cyclic hydrocarbons such as decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl grou~s and correspondtng olefinicallY unsaturated groups. Those hydrocarbon groups are contained in the compositions singly or in the form of a combinat~on of several groups. 5aturated hydrocarbon groups of an average carbon number of 10 to 14 and unsaturated hydrocarbon groups of an average carbon number of 16 are particularly preferred. Also preferred for use herein are the saturated or unsaturated hydrocarbon groups wherein said hydrocarbon groups possess from about 1 to about lO units and preferably from about l to about 4 units of ethylene oxide per molecule.
The preferred alkali metals for Xl and %2 according to the invent~on, are, for example, lithium, sodium and potassium.
The alkylammonium or substituted alkylammonium for Xl and X2 according to the inventlon, are cations produced from amines used for neutralization of the corresponding phosphoric acids by salt formation after the neutralizatlon step in the process for preparing monoalkyl phosphate salts ~n the present invention. The corresponding amines are prtmary, secondary and tertiary amines having alkyl qroups of 1 to 4 ~arbon atoms whieh ean be further substttuted, part kularly by hydroxyl groups. As the amines, there can be mentioned, for example, dtmethylmonoethanola~ine, methyldiethanolamine, trimethylamine, trtethylamine, dibutylamine~ butyld~methylamine, monoethanolamine.
diethanolamine, triethanolamine, isopropyldimethylamine and isopropyl-ethanol~ne. Preferred am~nes are monoethanolamine, diethanolamine and triethanola~ine. A particularly preferred amine is triethanol-a~ne. Other us~ful amines include arg~nine, lysine, mono-, di- or triisopropanolamine, N,N-tris(hydroxymethyl)aminomethane, diglycol-amine, glucamine, am~nomethylpropanol, and aminomethylpropanediol.
Also useful in the present invention are the copolymers derived from the addition of ethylene oxide and propylene oxide available as Tetronic~ and Tetronic R~ available from BASF Corporation and the 3~ polyethoxylated amines available as the Ethomeen~ series available from Armak Corporation.

W o 91/14693 2 0 7 8 ~ ~ 2 6 P ~ IUS91/01622Th~ alkylene diamtne, according to the present invention ~ the general for~ula:
RlR2N--R3--NR,R~, in wh kh Rl, R2, R~ and R5 are independently hydrogen, an alkyl group having 1 to 4 carbon atoms or a hydroxylalkyl or dihydroxyalkyl group having l to 4 carbon atoms or R, and R5 jointly form a saturated 5 or 6 membered heterocycltc ring, which can be substltuted 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 R1, R2, R3, R~ and R~ contain at least one hydroxy group.
These compounds are fully disclosed in U.K. Patent 1,513,053, published June 7, 1978.
A part kular am~ne class that is useful herein is an N,N-tetrakis (hydroxyalkyl) ethylene diamine having the formula:

~HO--CH--CH2]n ~ ,~CH2--CHOH]n N--R~--N
[HO--cH--cH2]n ~ ~cH2--cHoH3n R R
wherein R1 is alkylene having two to four carbon atoms, R is hydrogen or an alkyl group having one to six carbon atoms and n is from one to four. The foregoing diamine preferably has a mQlecUlar weight cf under about 1700, preférably under about 1200, even more preferably under about 800 and most preferably under about 500.
Although other examples w~ll also be given hereinafter, the tetrakls (hydroxyalkyl) ethylene diamine is best exemplified by the compound N,N,N',H'-tetrakis(2-hydroxypropyl)-ethylenedlamine, obtain-able co~merc1ally under the trademark Quadrol or Neutrol ~E (both ava11able from BASF ~yandotte Company).
Examples of diamine monoalkyl phosphate salts useful in the present invention include, but are not limited to, tetrahydroxypropylethylenediamine monococoylphosphate.
tetrahydroxypropylethylenediamine monolaurylphosphate, tetrahydroxypropylethylenediamine (monoethoxylated) monolaurylphosphate, tetrahydroxypropylethylenediamine monoisostearylphosphate, tetrahydroxypropylethylenediamine monostearylphosphate, tetrahydroxypropylethylenediamine (monoethoxylated) monostearylphosphate, i` ` PCI/US91/01622 tetrakydt~x~.opylethylenediamine monomyrtstylphosph~te, 8 ~ ~ 2 tetrahyJ~oxy~ropylethylenediamine (monoethoxylated) monomyristglphosphate, tetrahydroxypropylethylenediamine monooleoylphosphate, tetrahydroxypropylethylenediamine monopalmiltylphosphate, tetrahydroxypropylethylenediamine (monoethoxylated) monopalmiltylphosphate, tetrahydroxypropylethylenediamine monocaprylphosphate, tetrahydroxypropylethylenediamine (monoethoxylated) monocaprylphosphtte, tetrahydroxypropylethylenediamine monoundecylenylphosphate, tetrahydroxypropylethylenediamine monotridecylenylphosphate, tetrahydroxypropylethylened~amine mono(methylmyristyl)phosphate, tetrahydroxypropylethylenediamine mono(isopropyllauryl)phosphate, tetrahydroxypropylethylenediamine mono(isodecylneo~entyl)phosphate, tetrahydroxypropylethylenediamine monocetylphosphate, and tetrahydroxypropylethylenediamine mono(isopropylmyristyl)phosphate.
COMPOSITIONS
The compositions of the present invention compr~se:
(a~ from about 0.1% to about 9gX of one or more of a diamine monoalkyl phosphate salt of the present invention; and ~b~ from abou~ 1.Q% to ahout 9g.~% o~ ~ detergent carrier.
Preferred compositions comprise a mixture of the diamine mono-alkyl phosphate salts wherein R is selected from th~ group consisting of C12 to C~ alkyl or alkenyl and C1~ to C1~ alkyl or alkenyl (or the condensation porduct of these moieties with from about 1 to about 10 moles of ethylene ox1te) and wherein said salts are present in a ratio of from about 80:20 to about 20:80, preferably from about 60:40 to about ~0:60 and most preferably from about 55:45 to about 45:55, respecttvely.
The compositions of the present invention can be administered topically, i.e., by the direct laying on or spreading of the composi-tion on epidermal or epithelial tissue. Such compositions can be formulated as foams, lotions, creams, ointments, solutions, gels or sol~ds. A highly preferred composition contains the monoalkyl phos-phate salt in a soap màtrix (i.e., liquid and solid). These topical compositions comprise a safe and effective amount, usually from about 0.1% to about 99%, and preferably from about 1% to about 10%, of the W O 91/14693 2 ~ 7 ~ ~ 4 ~ 8 - P~/US91/016Z2 mono~lkyl phQsphate salt. Bar composit1Ons gener-lly conta ~ very htgh levels i.e., above 80%, of the d~amine mono~lkyl phosphate salt.
Generally, the carrler is either or~anic in nature or a solution or an aqueous emulsion and is capable of having the diamine monoalkyl 5 phosphate salt dispersed. dtssolved 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:
I0 I. Lotions.
The lot~ons can comprise a safe and effective amount of the monoalkyl phosphate salt; from about 0.1% to about 25%, preferably from about 3% to about 15%, of an emollient; the b~lance being water, a C2 or C3 alcohol, or a mixture of water and the alcohol. Examples I5 of suitable emollients are as follows:
I. Hydrocarbon oils and waxes. Examples are mineral oil, petrolatum, paraffin, ceresin, ozokerite, microcrystalline wax, polyethylene, and perhydrosqualane.

2. Sllicone oils, such as polydimethylsiloxanes, methylphenyl-polysiloxanes, water-soluble and alcohol-soluble silicone~glycol copolymers.

3. Trtglycer~de fats ant oils, such ~s those derived from vegetable, antmal and marine sources. Examples include castor oil, safflower oil, cotton seed 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 mono-stearate.

6. Alkyl esters of fatty acids having I0 to 20 carbon atoms.
Methyl, lsopropyl and butyl esters of fatty acids are especially useful herein. Examples include hexyl laurate, isohexyl laurate.
isohexyl palmltate, isopropyl palmitate, decyl oleate, isodecyl oleate, hexadecyl stearate, decyl stearate, isopropyl isostearate, diisopropyl adipate, diisohexyl adipate, dihexyldecyl adipate, diiso-propyl sebacate, lauryl lactate, myristyl lactate, and cetyl lactate.

7. Alkenyl esters of fatty acids having I0 to 20 carbon atoms.Examples thereof include oleyl myristate, oleyl stearate, and oleyl oleate.

. P ~ /US91/01622 W O 91/14693 9 2 ~ 2 8. Fatty ac1ds having 9 to 22 carbon atoms. Suitable examples include pelargonic. laurtc, myristtc, palmttic, stearic, isostearic, hyJ.o~ysteartc, oleic, linoleic, ricinoleic, arachtdonic, behenic, and eructc actds.

9. Fatty alcohols having 10 to 22 carbon atoms. Lauryl, myris-tyl, cetyl, hexadecyl, stearyl, isostearyl, hydroxystearyl, oleyl, ricinoleyl, behenyl, erucyl, and 2-octyl dodecyl alcohols are examples of suitable fatty alcohols.

10. Fatty alcohol ethers. Ethoxylated fatty alcohols of 10 to 20 carbon atoms include the lauryl, cetyl, stearyl, ~sostearyl, oleyl, and cholesterol alcohols having attached thereto from 1 to 50 ethylene oxide groups or 1 to 50 propylene oxide groups, or a mt%ture thereof.

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

12. Lanolin and tts dertvatives. Lanolin, lanolin oil, lanolin wax, lanolin alcohQls~ lanolin fatty acids, isopropyl lanolate, ethoxylated lanolin, ethoxylated lanolin alcohols, ethoxylated choles-terol, propoxylated lanol~n alcohols, acetylated lanolin, acetylated lanoltn alcohols, lanoltn alcohols linoleate, lanolin alcohols rtcinoleate, acetate of lanolin alcohols rictnoleate, acetate of ethoxylated alcohols-esters, hydrogenolysis of lanolin, ethoxylated hyd?ogenated lanc~, ethoxy~ated sorbttol lanolin, and liquid and semisoltd lanoltn absorption bases are illustrative of emollients dertved from lanoltn.

13. Polyhydric alcohols and polyether derivatives. Propylene glycol, dtpropylene glycol, polypropylene glycol (M.~. 2000-4000).
polyoxyethylene potyoxypropylene glycols, polyoxypropylene polyoxy-ethylene glycols, glycerol, ethoxylated glycerol, propoxylated gly-cerol, sorb~tol, ethoxylated sorbitol, hydroxypropyl sorbitol, poly-ethylene glycol (M.~. 200-6000), methoxy polyethylene glycols, poly-tethylene oxide~ homopolymers (M.W. 100,000-5,000,000), polyalkylene glycols and derivatives, hexylene glycol (2-methyl-2,4-pentanediol), 1,3-butylene glycol, 1,2,6-hexanetriol, ethohexadiol USP (2-ethyl-1,3-hexanediol), Cl5-CI~ vicinal glycol, and polyoxypropylene deriva-tives of trimethylolpropane are examples thereof.

14. Polyhydric alcohol esters. Ethylene glycol mono- and di-fatty acid esters, diethylene glycol mono- and di-fatty acid esters, polyethylene glycol (M.~. 200-6000) mono- and di-fatty acid esters, propylene glycol mono- and di-fatty acid esters, polypropylene W o 91/14~93 2 0 7 ~ o- P ~ /US91/01622 glycol 2000 monooleate, polypropylene glycol 2000 monos rate, ethoxylated propylene propylene glycol monostearate, glyceryl mono-and d~-fatty acid esters, polyglycerol poly-fatty acid esters, eth-oxylated gylceryl monostearate, 1,3-butylene glycol monosteara~e, 1,3-butylene glycol distearate, polyoxyethylene polyol fatty acid ester, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters are satisfactory polyhydric alcohol esters.

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

16. Beeswax derivatives, e.g., polyoxyethylene sorbitol beeswax.
These are reaction products of beeswax with ethoxylated sorbitol of varying ethylene oxide content, forming a mlxture of ether-esters.
1~. Vegetable waxes including carnauba and candelilla waxes.
18. Phospholipids, such as lecithin and derivatives.
19. Sterols. Cholesterol, cholesterol fatty acid esters are examples thereof.
20. Amides, such as fatty acid amides, ethoxylated fatty acid amides, solid fatty acid alkanolamides.
The lotions further comprise from about 1% to about 10%, prefera-bly from about 2% to about 5%, of an emulsifier. The emulslfiers can be nonionic, anionic or cattonic. Examples of satisfactory nonionic emul~tfiers ~noiude ratty acid alcohols hav~ng 10 to 20 carbon atoms, fatty alcohols hav~ng 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, mono- and di-fatty acid esters of ethylene oxide, mono- and di-fatty ac1d esters of ethylene glycol wherein the fatty ac1d moiety cont~tns from 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 sorbltol, polyoxyethylene sorbitan and hydrophilic wax esters. Suitable anionic emulsifiers include the fatty acid soaps.
e.g. sodium, potassium and triethanolamine soaps, wherein the fatty acid moiety contains from 10 to 20 carbon atoms. Other suitable anionic emulsiflers include the akali metal, ammonium or substituted ammonium alkyl sulfates, alkyl arylsulfonates, and alkyl ethoxy ether sulfonates having 10 to 30 carbon atoms in the alkyl moiety. The alkyl ethoxy ether sulfonates contain from 1 to 50 ethylene oxlde PC~r/US91/01622 W O gl/14693 2078442 _ units. Ho~ever, it is recognized that certain anion1c emulsifiers can result in a turbid formulatiOn~ and hence, anionic emulsifiers are - less preferred for use herein.
The ba~an~e of the lotion is water or a C2 or C~ alcohol, or a - 5 mixture of water and the alcohol. The lotions are formulated by simply admtxing all of the components together. Preferably the monoalkyl phosphate salt is dissolved in the mixture. Conventional optional components can be included. One such additive is a thicken-ing agent at a level from about ll~ to about 10% of the composition.
Examples of suitable thic~ening agents include: cross-linked carboxy-polymethylene polymers (sufficiently neutralized), magnesium aluminum si1lcate, car~oxymethylcellulose, hydroxyethylcellulose, acrylic acid polymers (e.g., Acrysol~ ICS-I, ava~lable from Rohm ~ Haas Corpora t~on), polyethylene glycols, gum tragacanth, gum kharaya, xanthan gums and bentonite. Cation1c polymers, such as cationic guar gum, are not pr~ferred for use herein.
2. Creams.
Compositions of the present invention also can be formulated in a cream form. The crea~s comprise safe and effective amounts of the monoalkyl phosphate salt; from about 0.1% to g5~/0, preferably from about 10% to about 2~%, of an emollient; the balance being water. The e~71~erts ~bove d~seribed can aiso be used in the cream compositions.
Optionally, the cre~m form contains a su1table emulsifier, as previ-ously described. When an emulsifier ls included, it is is the compo-sition at a level from about 3D/~ to about 50~/~, preferably from about 57.
to a~out 20~.
3. Solut1ons.
The co~poslt10ns of this invention can also be formulated as a solut10n. The solution form comprises a safe and effective amount of 3Q the mano~lkyl phosphate salt, usually at least about O.Ol~/o up to about 50% and preferably about 0.1% to about lO~; the balance being water or a suitable organic solvent. Suitable organic materials useful as the solvent or a part of a solvent system are as follows: propylene glycol, polyethylene glycol (M.~. 2~0-1000), polypropylene ~lycol (M.~. 425-2025), butylene glycol, glycerine, sorbitol esters, l,2,6-hexanetriol, ethanol, isopropanol, diethyl tartrate, butanediol, and mixtures thereof.

t, ~

2 0 7 8 4 4 2 l2 PC~r~US91/016~

~These solutions can be applied to the skin as is~ or else can be - for~ul~ted into, for ex~mple, sque~7e devices descrtbed below or as an aerosol and sprayed onto the s~in from an aerosol container, or as a mouth~ash composition and used as an oral rinse. The aerosol composi-tions further comprise from about 25% to about 80%~ preferably from about 30% to about 54~, of suitable propellants. Examples of such propellants are the chlorinated, fluorinated and chlorofluorinated lower molecular weight hydrocarbons. Nitrous oxide, carbon dioxide, butane, and propane can also be used as propellant gases. These propellants are used at a leYel sufficient to expel the contents of the container.
Squeeze foamer packages are well known as exemplified by the disclosures of the following patents: U.S. Pat. Nos. 3,709,437, Wright, issued Jan. 9, 1973; 3,937,364, lSWright, 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; 4,598,8~2, Rice, issued July 8, 1986; and 4,615,467, Grogan et al., issued Oct. 7, 1986; and French Pat.
2,604,622, Verhulst, published Apr. 8, 1988.
The above containers (packages) do not use any propellant and are therefore safe for the consumer and the enYironmænt. They create a foam from almost any surfactant compos1tion. Altho~gh there is no need to add foa~ boosters merely for the purpose of stabil izing the foam, such materials can be desirable. In some compositions the use of foam boosters can eYen be counterproductive since the foam has to 2~ break in order for the container to work properly. The composition is placed in the cont~tner reservoir (plastic squee~e bottle~. Squee ing the Containe! wtth the hand forces the composition through a foamer head, or other foam producing means, where the composition is mixed with air and then through a homogenizing means that makes the foam more homogeneous and controls the consistency of the foam. The foam is then discharged as a uniform, non-pressurizéd aerated foam.
The minimum pressure to activate the squeeze foamer is about 1 psig, typically from abo~t 2 psig to about 7 psig. The m i nimum pressure is related to the size of the channels in the dispenser, 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 0.01 and about 0.12 g~cc, ànd more preferably between about 0.02 and about 0.07 g/cc.

W o 91/14693 2 0 7 8 4 4 2 -13- P ~ /US91/0162Z
The c~rrter liquld in a ~outh~sh is generally a mixture of eth~nol and ~ater. The amount of ethanol is generally from about 5%
to a~out 6~X, preferably from about 5% to about 25X by weight of the carrier. ~ater then constltutes the remainder of the carrier liquid 5 mixture. These ~outhwash compositions can also contain other optional components such as emulsifying agents as preYiously descrtbed, flavor-ing agents, sweeteners. and humectants. Other mouthwash formulations and methods for making mouthwashes useful in the present invention are dtsclosed in U.S. Patent 4,323,5~1 to Parran, issued April 6, lg82.

4. Gels.
Compositions herein can be formulated into a gel form by simply admixing a suitable thickening agent to the previously described solutton compositions. ~xamples of suitab~e thickening agents have been preYiously described with respect to the lottons.
The gelled compositions comprise a safe and effective amount of the monGalkyl phosphate salt, fro~ about 0.5X to about 2~%, prefera~ly fro~ about lX to about l~X, of the thlc~ening agent; the balance being water.
5. Solids.
The compositions of th~s invention can also be formulated in a solid form1 etg.7 2 stic~-type c~pasit,on. Sucn compositions com-prise a safe and effect he amount of the monoa1kyl phosphate salt and from about 0.01% to about 9gX, preferably from about 60X to about 90%, of the prev10usly described emollients. This composition can further comprise from about O.lX to about 20X, preferably from about 5% to about l~X, of a sultable thie~ening agent, and opttonally emulsifiers and ~ater. Th~c~ening agents previously described with respect to lotions ar~ als~ suitable herein.
6. So~ps.
The co~positions of this in~ention can also be formulated into a liquid or solid (e.g., bar) soap matrix. Such compositions comprise a safe and effectiYe amount of the monoalkyl phosphate salt ranging from abaut 0.1% to about 99%; and from about 1% to about ggX of an excipi-ent such as those previously described. Optionally, the soap contains a suitable emulsifier as previously described. ~hen an emulsifier is included, it is in the composition at a leYel from abuut 10% to about 5~X.

,:

.

PC~r/US9l/016Z~
w 0 9l/14693 7. OentifrtcPs. 207~442 The c~oosittons of thts inventlon can also be formulated as dentifric~s. Such dentifrices, espectally toothpaste, comprise a safe and effective a~ount of the monoalkyl phosphate salt ranging frcm about 0.1% to about 20X by weight of the composition. Toothpaste compositions conventic-ally contain abrasive materials, sudsing agents, binders, humectants, flavoring and sweetening agents.
Suitable dent1frice compositions and the methods of their manufacture useful in the present invention are fully set forth in U.S. Patent 3,535,4Zl to Briner et al., issued October 20, 1970.
-8. Shampoos.
Composit10ns of this invention also can be formulated in ashampoo for~. The shampoos comprise a safe and effective amount of lS the dia~ine monoalkyl phosphate salt ranging from about 0.1% to about %; from about 5% to about 6~% of a synthetic surfactant; and the balance ~te~. A secondary surfactant can also ~e utilized, however, such secondary surfactant shoùld be neutralized by a diamine as descrtbed above.
These shampoos can contain a variety of nonessential optional components. Such conventional optional ingredients are we71 known to those skilled in the art, e.g., preservatives, such as benzyl alcohol, ethyl paraben, propy7 paraben and imidazolidinyl urea; cationic surfactants, such as cetyl trimethyl a~on1u~ chloride, stearyldi-methyl benzyl a~oniu~ chloride, and di(partially hydrogenated tallow) dimethylam~oniu~ chloride; thickeners and viscosity modifiers such as diethanolamide of a long-chain fatty acid (e.g. PE~ 3 lauramide), block poly~srs of eth~lene oxide and propylene oxide, sodium chloride.
sodium sulfate, polyvinyl alcohol, and ethyl alcohol; pH adjustina agents, such as citric acid, succinic acid, phosphoric acid, sodium carbonate; perfu~es; dyes; and, sequestering agents, such as disodium ethylenediamine tetraacetate. Such a~ents generally are used indivi-dually at a level of from about 0.01% to about 1C%, preferablY from about O.5% t~ ~bout 5.0% by weight of the composition.
'S Additional minor components can be added to the compositions o;
this invention in order to increase their attractiveness, versatility and shelf-life. Perfumes and water soluble, pharmaceutically acce~t-able dyes or food colors can be added to enhance the attractiveness of W o 91/14693 2 0 7 8 4 4 2 -15- PCT/US~1/0162~
these co~posttions. Antifungal and anttmtcrobtal agents are useful in preYenttng ~old or bacterial contamtnatton and in increastng the - shelf-life of the composttlons. Conventional anttbacterial agents can be included in the present compositions at levels of from about 0.1,.
to about 4%, prefe~ably from about 0.2X to about 1%. Typical antibac-terial agents whtch are suitable for use herein are ~,4-di- and 3,~',5-tribromosaltcylanildes; 4,4'-dichloro-3-(trifluoromethyl)car-banilide; 3,4,4'-trichlorocarbanilide; phenoxy ethanol or propanol;
chlorhexidene salts; hexamidine salts; Irgasan~ DP 300 (Triclosan);
salicylic acid; parachlorometaxylenol; Octopirox, and mixtures of these materials. For general purposes skin cleansing compositions having a pH range from about 5.0 to about 8.0 are desirable. rf necessary, the pH of these composittons can be adjusted downward using cttric or lacttc acid. For sktn cleansers whtch deal with more sensittve skin surfaces, such as in vaginal and perianal cleansers, a pH of about 6.; ts desirable. These and other minor modifications can be made wtthout materlally altertng or departtng from the bastc concept of this invention.
The nature of the fo~ produced determtnes the usefulness of the present compostttons. In order for a foa~ to be useful as a skin cleansing agent, tt must have a uniform consistency, good spreadabil-ity, and good cle~nsing ability.
The foa~abtltty and wettabiltty characteristtcs are governed by the surface tenston of the s~1n cleansing comp~s1tion. The surface tenston for the composittans of thts invention vartes from about 20 to 70 dynes/cm. For general skin cleansing compositions a range of from about 23 to about 50 dynes/cm is preferred. Liquid compositions having a surface tenston in the lower portion of this range possess gre~t~r spread1ng and better wettinq characteristics with increased foa~blltty. Foa~tble composttions naving htgher surface tensions gene~ally provide ~ore stable foams but are also more difficult to cause to foam and re~uire more force to extrude the foam.
The foam-productng s~tn cleansing compositions of thts invention are particularly advantageous in that they leave a minimum amount of surfactant residue on the surface of the skin. This has been achievea in part by utiltzing a low percentage of total surfactants in the s~in cleansing composittons itself, and by preparing foams with unusuall~
low density. The present compositions provide foam densities provia~

' , 16 2 0 ~ a PCT/~'S91/01622 w O 91/14693 good cleansing ab~tity and more importantly, leave a nesligible amount of surfact~nt residue on the surface of the skin upon rinsing cr flattening, thereby preserving skin elasticity, and reducing transepi-- der~al moisture loss.
S The cleansing ability of these aerated foams is a direct function of the cleansing ability of the surfactant solution itself which produces the foam.
The following non-limiting examples illustrate embodiments of tne subject invention wherein both essential and optional ingredients are combined. It is to be understood that these examples are for illus-trative purposes only and are not to be construed as limiting the scope of the lnvention thereto.
EXAMPLE I
1 male of monolauryl phosphate acid is heated over a steam bath to about 50-C until molten. 1 mole of ~,N,H',N'-tetrakis(2-hydroxy-propyl)-ethylenediamine (available as Quadrol~ from BASF Corporation) is heated in a separate beaker to 50~C until pourable.
The ~olten phosphate is slowly added to the H,H,N',N'-tetrakis(2-hydroxypropyl)-ethylenediamine. The phosphate is added until a pH of 5.0 to 9.0 is reached (preferably 7.0). The resulting N,H,~',N'-tetrakis(2-hydroxypropyl)-ethylenediamine monolaurylphosphate is then cooled to for0 a clear. yellow solid.
This solid can be used as a solid bar or as a material to produce liquid cream or gel product.
z5 Application of approximately O.S grams to the skin will provide a foaming cleanser possessing good cleansing power and detergency, which is ~ild and non-irrttating, and leaves little, if any, residual film re~aintng on the cleansed surface o~ the skin.
Substantially similar results are obtained when the monolauryl phosphate acid is replaced with an equivalent amount of monococoyl-phosphate acid, monolaurylphosphate acid, monoisostearylphosphate acid, monostearylphosphate acid, monomyristylphosphate acid, mono-oleoylphosphate acid, monopalmitylphosphate acid, monocaprylphosphate acid, monoundecylenylphosphate acid, monotridecylenylphosphate acid.
,5 mono(methylmyristyl)phosphate acid, mono(isopropyllauryl)phosphate acid, mono(isodecylneopentyl)phosphate acid, monocetylphosphate aci~.
and mono(isopropylmyristyl)phosphate acid and mixtures thereof.

p~

W O 91/146932 0 7 ~ 4 4 2 -17- PC~r/US9l/0l62 EXAHP~E II
~A factal cleansing compositton for topical administration is - prepared by combining the fol7Owing ingredients:
In~redtents Percent w/w H N H H -tetrakis(2-hydroxypropyl)-ethylenediamine monolaurylphosphate 2.500 Butylene Glycol 2.500 Methylparaben 0.250 Propylparaben 0.l50 iO - Potasstum coco(hydrolysed animal protein)l 0.032 Glycertn 2.000 Aloe Vera 0 500 Fragrance 0 050 Color 0.l70 Xanthan ~um2 o . oso ~ater q.s.
I Available as Lamepon~S from Henkel Corporation 2 Available as Keltrol~T from Kelco Corporatton EXA~P~E III
20A facial cleansing cream composition for topical administration is prepared by combtning the following ingredients:
Tn~redtents Per~ent w/w H N N N -tetrakis(2-hydroxypropyl)-ethylenediamine monolaurylphosphate 27.000 Laur1c actd 4 0OO
H H H H -tetrakis(2-hydroxypropyl)-ethylenediamtnel 4 ooo C~rboxyvinyl polymer2 0.200 Glycertne 8.000 Sorbttol 2.000 ~ater q.s.

l Available as Quadrol from BASF-~yandotte 2 Available as Carbopol 941 from B.F. Goodrich Company 3~

W O 91/14693 -18- P ~ /US91/01622 = - - 207~44~ EYAMPLE IV
A facial cleansing composition for topical admtnistration is prepared by combintng the following ingredients:
Inaredients Percent w/w H,N,N',N'-tetrakis(2-hydroxypropyl)-ethylenediamine monolaurylphosphate 3.000 Laurtc actd l.000 Pottssium coco(hydrolysed animal protein) 0.500 Hydroxyethyl cellulose z ooo Methyl paraben O.lO0 Propyl paraben O.lO0 Glycerin 3.000 Fragrance 0.100 Color O.OOl ~ater q.s.
EXAMPLE V
A factal cleanstng gel composttton for toptcal administration is prepared by combining the following ingredients:
Inaredtents Percent w/w N,H,N',N'-tetrak1s(2-hydroxypropyl)-ethylenediam1ne monolaurylphosphate lO.000 Acryltc acid polymer o.~oo N,H,N',N'-tetrakis(2-hydroxypropyl)-ethylened1amine 1.000 Glycertn 5 ooo Lauric acid 2.000 ~ater q.s.

",~ , WO 91/14693 1~ PCI`/US91/01622 ~ FXAMPLE VI 2078~42 A facial shaving foam composition for topical administration is prep~red by comblning the following ingredients:
In~re~ientsPercent w/w N N N N -tetrakis(2-hydroxypropyl)-ethylenediamine monolaurylphosphate 7.000 N N N N -tetrakis(2-hydroxypropyl)-ethylenediamine monopalmityl phosphate 7.000 Lauric acid 1.500 Palmityl acid 1.500 N N N N -tetrakis(2-hydroxypropyl)-ethylenediamine1.500 Fragrance 0.100 Aloe Vera 2.000 Water q.s.

EXAMPLE V~I
A faclal cleanstng composition for topical administration is prepared by combining the followinq ingredients:
Inqredients Percent w/w N N N N -tetrdkts(2-hydroxypropyl)-ethylenediamine (1 mole ethoxylated ) monolaurylphosphate 2.500 Butylene Glycol 2.500 Methylparaben 0.250 Propylparaben 0.150 Potassiu~ coco(hydrolysed animal protein)'0.032 Glycerin 2.000 Aloe Vera 0.500 Fragrance 0.050 Color 0.170 Xanthan gum2 o.oso Water q.s.
1 Available as Lamepon S from Henkel Corporation 2 Available as Keltrol T from Kelco Corporation WHAT IS CLAIMED IS:

Claims

Claims:

1. A surfactant compound having low irritation effect to human skin of the formula:

wherein R is alkyl or alkenyl having an average of from about 10 to 18 carbon atoms or R is the condensation product of an alkyl or alkenyl having an average of from about 10 to 18 carbon atoms with from about 1 to 10 moles of ethylene oxide, and wherein X1 and X2 are independently selected from the group consisting of hydrogen, alkali metal, ammonium, substituted ammonium and alkylene diamine, provided that at least one of X1 and X2 is a totally hydroxyalkylated alkylene diamine.

2. A compound according to Claim 1 wherein R is alkyl or alkenyl having an average of from about 10 to about 18 carbon atoms and wherein said substituted ammonium is selected from the group consisting of alkoxylated ammonium, alkylammonium, alkoxylated aliphatic amines and polyethoxylated amines.

3. A compound according to Claim 2 wherein R is alkyl or alkenyl having an average of from about 10 to 14 carbon atoms, and wherein said alkali metal is selected from the group consisting of sodium, potassium and lithium and mixtures thereof.

4. A compound according to Claim 3 wherein one of X1 and X2 is alkylammonium and said alkylammonium is selected from the group consisting of trimethyl-ammonium, triethylammonium, dibutylammonium, butyldimethylammonium, isopropyldimethylammonium, diglycolamines, glucamines and mixtures thereof and wherein said substituted alkylammonium is a hydroxyalkylammonium.

5. A compound according to Claim 4 wherein R is a condensation product of a hydrophobic group with from about 1 to about 10 moles of ethylene oxide.

6. A compound according to Claim 5 wherein at least one of X1 and X2 is a totally hydroxyalkylated alkylene diamine wherein the alkylene moiety contains from about 2 to about 6 carbon atoms, said totally hydroxyalkylated alkylene diamine having been oxyalkylated with an alkylene oxide containing at least about 2 carbon atoms or a mixture of alkylene oxides containing 2 or more carbon atoms.

7. A compound according to Claim 6 wherein at least one of X1 and X2 is N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine.

8. A detergent composition having low irritation effect comprising:
(a) from about 1% to about 99% of one or more of a surfactant compound having the formula:

wherein R is alkyl or alkenyl having an average of from about 10 to 18 carbon atoms or R is the condensation product of an alkyl or alkenyl having an average of from about 10 to 18 carbon atoms with from about 1 to 10 moles of ethylene oxide, and wherein X1 and X2 are independently selected from the group consisting of hydrogen, alkali metal, ammonium, substituted ammonium and alkylene diamine, provided that at least one of X1 and X2 is a totally hydroxyalkylated alkylene diamine; and (b) from about 99% to about 1% of a detergent carrier.

9. A detergent composition according to Claim 8 wherein R is alkyl or alkenyl having an average of from about 10 to about 18 carbon atoms and wherein said substituted ammonium is selected from the group consisting of alkoxylated ammonium, alkylammonium, alkoxylated aliphatic amines and polyethoxylated amines.

10. A detergent composition according to Claim 9 wherein R is alkyl or alkenyl having an average of from about 10 to 14 carbon atoms and wherein said alkali metal is elected from the group consisting of sodium, potassium and lithium and mixtures thereof.

11. A detergent composition according to Claim 10 wherein said alkyl-amonium is selected from the group consisting of trimethylammonium, triethylammonium, dibutylammonium, butyldimethylammonium, and iso-propyldimethylammonium and mixtures thereof and wherein said sub-stituted alkylammonium is a hydroxyalkylammonium.

12. A detergent composition according to Claim 11 wherein at least one of X1 and X2 is a totally hydroxyalkylated alkylene diamine and wherein R is a condensation product of a hydrophobic group with from about 1 to about 10 moles of ethylene oxide.

13. A detergent composition according to Claim 12 wherein at least one of X1 and X2 is a hydroxyalkylated alkylene diamine wherein the said alkylene contains from 2 to about 6 carbon atoms, said alkylene diamine having been oxyalkylated with an alkylene oxide containing at least 2 carbon atoms or a mixture of alkylene oxides containing from 2 or more carbon atoms.

14. A detergent composition according to Claim 13 wherein at least one of X1 and X2 is N,N,N',N'-tetrakis(2-hydroxypropyl)-ethylene-diamine.

15. A detergent composition according to Claim 14 in a form selected from the group consisting of soaps, creams, solutions, mouthwashes, dentifrices or shampoos.

16. A detergent composition according to Claim 8 comprising a mixture of the diamine monoalkyl phosphate salts wherein R is selected from the group consisting of C12 to C14 alkyl or alkenyl and C16 to C18 alkyl or alkenyl and wherein said salts are present in a ratio of from about 60:40 to about 40:60.

17. A detergent composition according to Claim 8 comprising a mixture of the diamine monoalkyl phosphate salts wherein R is selected from the group consisting of the condensation product of a C12 to C14 alkyl or alkenyl with from about 1 to about 10 moles of ethylene oxide and the condensation product of a C16 to C18 alkyl or alkenyl with from about 1 to about 10 moles of ethylene oxide and wherein said salts are present in a ratio of from about 60:40 to about 40:60, respectively.

18. A detergent composition having low irritation effect comprising:
(a) one or more of a surfactant compound having the formula:

wherein R is alkyl or alkenyl having an average of from about 10 to 18 carbon atoms or R is the condensation product of an alkyl or alkenyl having an average of from about 10 to 18 carbon atoms with from about 1 to 10 moles of ethylene oxide, and wherein X1 and X2 are independently selected from the group consisting of hydrogen, alkali metal, ammonium, substituted ammonium and alkylene diamine, provided that at least one of X1 and X2 is a totally hydroxyalkylated alkylene diamine; and (b) one or more of a surfactant compound having the formula:

wherein R is a hydrophobic group or the condensation product of a hydrophobic group with ethylene oxide and wherein X3 is selected from the group consisting of hydrogen, alkali metal, ammonium, substituted ammonium and alkylene diamine; wherein the ratio of (a) to (b) is from about 99:1 to about 70:30.

19. A detergent composition according to Claim 18 wherein said substituted ammonium is selected from the group consisting of alkoxylated ammonium, alkylammonium, alkoxylated aliphatic amines, polyethoxylated amines and wherein at least one of X1 and X2 is N,N,N',N'-tetrakis(2-hydroxypropyl)-ethylene-diamine.

20. A detergent composition according to Claim 18 in a form selected from the group consisting of soaps, creams, solutions, mouthwashes, dentifrices or shampoos.