CA2211004A1 - Personal treatment compositions and/or cosmetic compositions containing enduring perfume - Google Patents

Abstract

Personal treatment compositions including leave-on hair care compositions and leave-on skin care compositions, comprising from about 0.001 % to about 50 %, preferably from about 0.005 % to about 6 %, enduring perfume, are disclosed. The enduring perfume provides a lasting olfactory sensation thus minimizing the need to use large amounts.

Description

PERSONAL TREATMENI COMPOSITIONS AND/OR COSMETIC
COMPOSITIONS CONI AINING ENDURING PERF UME

TECHNICAL Fl!ELD
sThe present invention relates to personal cle~ncing and/or cosmetic compositions co.l~ -g enduring perfumes which are less likely to irritate skin and which provide efficient and long lasting perfume benefit, even after rinsing BACKGROUND OF THE INVENTION
Perfume in personal r~le~ncing and cosmetic products provides olfactory 0 aesthetic benefit and/or serves as a signal of cle~nliness These are especially important functions of these pc..,ol-al care products. Personal care products generally include "rinse-of~' products, such as soaps, liquid soaps, sharnpoos, hair conditioners, etc., which are applied to, e.g., skin or hair and l:hen rinsed off from the skin or hair, and "leave-on" products, such as skin moisturizers, sun screen products, deodorants, 15 hair sprays, mousse, etc., which are applied and are normally allowed to remain on, e.g., skin or hair.
~ ontinuous efforts are made to find improvements in both perfume delivery effectiveness and longevity on the body (e.g., skin and hair). During a Cle~n.cing process, a subst~nti~l amount of l)~.rullle in the personal cl~nc~r compositions is lost 20 with the rinse water and in the s~lhsequP,nt drying. On the other hand, some products, especially leave-on and cosmptic products can leave a considerable amount of material, inr.l~lfling ~ -c material, on the body. It is e,~L-c.-.cly important that any material le~ on the body provide the .. ~x;.,.. effect with the tninim~m amount of material, and that the material be as safe and non-i..i~alillg as possible.
2s People skilled in the pc,~---c art, usually by cAI,c~.e.lce, have some knowledge of some particular perfume i~ ;e~ that are "subst~ntive" and/or non-irritating.
Sul~sl~n~ e perfume ing~,die.lLs are those odorous compounds that effectively deposit on skin or hair in the cl~ni~g process and are detectable on the subsequently dried skin or hair by people with normal olfacto~y acuity. The knowledge of whatperfume ingredients are s~lbst~ntive is spotty and incol,lplete.
The object of this invention is to provide pcl~ollal c1e~n.ci~g compositions col~ g enduring perfilmes which are effectively retained and remain on the skin or hair for a long lasting aesthetic benefit with minimum amount of material, and not lost W O96/12467 PCT~US95/11864 and/or wasted in the cleaning and drying steps. It is also an object to provide 35 perfumes that are non-irritating insofar as that is possible.

S17M~L9RY OF T~ INVENTION
The present invention relates to personal tre~tment compositions comprising perfumes that provide a long lasting aesthetic benefit with a minimllm amount of40 material ("enduring perfume") and which are relatively non-irritating. The present invention, in one aspect, especially relates to cle~n.~ing compositions that are normally rinsed, preferably comprising, by weight of the composition:
(A) from about 0.001% to about 10%, preferably from about 0.005% to about 6%, more preferably from about 0.01% to about 4%, by weight of an enduring perfume composition;
(B) from about 0.01% to about 95%, preferably from about 5% to about 85%, more preferably from about 3% to about 30%, even more preferably from about 5% to about 22%, of a surfactant system; and (C) the balance comprising carrier, normally liquid, incllltling water, C 1 -C4monohydric alcohols, C2-C6 polyhydric alcohols, propylene carbonate, liquid polyalkylene glycols, and the like, and mixtures thereof, wherein the pH is from about 4 to about l l, preferably from about 4.5 to about 10.5, more preferably from about 5 to about 10.
Some of these cle~n~ing compositions are meant to be used and then rinsed 5s off. The enduring perfume compositions are desirable for such personal cleansing compositions that are intçn-~ed to be rinsed off, since the enduring perfume compositions deposit extremely Pffiri~ntly. In another aspect, enduring perfume compositions are used in other personal tre~tm~nt compositions, in~hltling cosmetics, skin treatment compositions, and/or cleansing compositions that are meant to be left 60 on the skin, or simply wiped off, thereby leaving a substantial amount of material on the skin. The enduring perfume compositions are extremely desirable for such personal trç~tment compositions since they require minim~l material to provide long lasting effects even when the skin is in contact with the water, as when ~wi.. ;.. g Personal tre~tmPnt compositions such as deodorants, perfumes, colognes, suntan 6s lotions, skin softening lotions, etc., which are meant to leave relatively large amounts of material on the skin, are especially improved by use of these enduring perfume compositions, since they ...i..;...;~e the amount of material in contact with the skin.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to personal tre~tment compositions, inchltling 70 personal cle~n.cing compositions comprising, by weight of the personal cleansing W O 96/12467 PCT~US95/1186 composition: -(A) from about 0.001% to about 10%, preferably from about 0.005% to about 6%, more preferably from about 0.01% to about 4%, even more preferably from about 0.01 to about 1% by weight of an enduring perfume composition;
75 (B) from about 0.01% to about 95%, preferably from about 5% to about 85%,more preferably from about 3% to about 30%, even more preferably from about ~% to about 22%, of a surfactant system; and (C) the balance comprising liquid carrier, normally comprising material selected from the group consisting of: water; C1-C4 monohydric alcohols; C2-C6 polyhydric alcohols; propylene carbonate; liquid polyalkylene glycols; and the like; and mixtures thereof, wherein the pH is from about 4 to about l l, preferably from about 4.5 to about 10.5, more preferably from about S to about lO, said enduring perfume composition preferably having at least about 70%, more preferably at least about 75%, even more 85 preferably at least about 80%, and yet more preferably more than about 85%, of components with a ClogP 23.0 and a boiling point of >'750~C.
The present invention also relates in one aspect to personal treatment compositions, e.g., those selected from the group con.cisting of: deodorants;
antipe~yh~nls, skin lotions; suntan lotions; perfumes, and colognes, all of which are so normally applied to one, or more, parts of the body and incompletely removed, said personal L.~;alnle.,l compositions co~ g an effective amount of said enduring perfume compositions.
A. Enduring Perfume Composition Personal tre~tm~nt, e.g., cle~n.cin~ and/or cosmetic compositions in the art ss commonly contain perfumes to provide a good odor to the body. These conventional perfume compositions are normally s~lected mainly for their odor quality, with some consideration of substantivity.
Enduring perfume ingredients, as disclosed herein, can be form.~l~ted into personal cle~n.cing and/or cosmetic compositions, inclu~ling liquid personal cleansing oo compositions, and are subst~nti~lly deposited and remain on the body throughout any rinse and/or drying steps. These enduring perfume ingredients .nil.i.~.;-,e the material wasted, while still providing the good aesthetics that the consumers value.
An enduring perfume ingredient is characterized by its boiling point (B.P.) and its octanoVwater partitioning coefficient (P). The octanol/water partitioning 05 coefficient of a perfume ingredient is the ratio between its equilibrium concentrations in octanol and in water. The perfume ingredients of this invention have a B.P., measured at the normal, standard pressure, of about 250~C or higher, preferably more CA 022ll004 l997-07-2l W O96/12467 PCT~US95/1186 than about 260~C; and an octanol/water partitioning coefficent P of about 1,000 or higher. Since the partitioning coefficients of the perfume ingredients of this invention 0 have high values, they are more conveniently given in the form of their logarithm to the base 10, logP. Thus the perfume ingredients of this invention have logP of about 3 or higher, preferably more than about 3.1, and even more preferably more than about 3.2.
The boiling points of many perfume ingredients are given in, e.g., "Perfume and Flavor Chemicals (Aroma Chemicals)," Steffen Arctander, published by the author, 1969, incol~ol~led herein by reference.
The logP of many perfume ingredients has been reported; for example, the Pomona92 ~l~t~b~e~ available from Daylight Chemical Information Systems, Inc.
(Daylight CIS), Irvine, California, contains many, along with citations to the original literature. However, the logP values are most conveniently calculated by the "CLOGP" program, also available from Daylight CIS. This program also lists ~,e,imental logP values when they are available in the Pomona92 database. The "calc.ll~ted logP" (ClogP) is determined by the fragment approach of Hansch and Leo (cf., A. Leo, in Colllplehensi~re Medicinal Chemistry, Vol. 4, C. Hansch, P. G.
125 S~mm~n~, J. B. Taylor and C. A. P~m~d~n, Eds., p. 295, Pergamon Press, 1990, incorporated herein by rer~lt;l~ce). The fragment approach is based on the chemical structure of each perfume ingredient, and takes into account the numbers and types of atoms, the atom connectivity, and chemical bonding. The ClogP values, which are the most reliable and widely used estim~tes for this physicochemical property, are 130 plefel~bly used instead of the expelilllellLal logP values in the selection of perfume ingredients which are useful in the present invention.
Thus, when a perfume composition which is composed of ingredients having a B.P. of about 250~C or higher and a ClogP of about 3 or higher, is used in a liquid personal c1e~n~ing composition, the perfume is very effectively deposited on skin or hair, and remains s~lan~ e after the rinsing and drying steps. Also, surprisingly, these same perfume compositions are very mild to skin and are relatively non-irritating, even on leave-on products.
Table 1 gives some non-limiting examples of enduring perfume ingredients, useful in liquid personal çle~n~ing compositions of the present invention. The 140 enduring perfume compositions of the present invention contain at least about 3 di~ere.ll enduring perfume ingredients, more preferably at least about 4 di~elellL
enduring perfume ingredients, and even more preferably at least about 5 di~lt;nLenduring perfume ingredients. Furthermore, the enduring perfume compositions of the present invention contain at least about 60 wt.% of enduring perfume ingredients, W O96/12467 . PCTrUS95/1186 145 preferably at least about 70 wt.% of enduring perfume ingredients, more preferably at least about 80 wt.% of enduring perfume ingredients, and even more preferably atleast about 85 wt.% of enduring perfume ingredients. Personal cleansing compositions of the present invention contain from about 0.001% to about 10%, preferably from about 0.005% to about 6%, more preferably from about 0.01% to 150 about 4%, and even more preferably from about 3.01% to about 1%, of an enduring perfume composition. Hair care and topical sl;in care compositions that are not normally rinsed off can contain from 0.001% to about 50%, preferably from about 0.001% to about 15%, more preferably from about 0.005% to about 6%, most preferably from about 0.01% to about 4%, and yet more preferably from about 0.01%
155 to about 1%, of said enduring perfume compositions. The high levels are associated mainly with body perfumes, such as fine fragrances, eau de toilette, eau de cologne, etc.
In the perfume art, some materials having no odor or very faint odor are used as dil-lents or extenders. Non-limiting examples of these materials are dipropylene 160 glycol, diethyl phth~l~te, triethyl citrate, isopropyl myristate, and benzyl benzoate.
These materials are used for, e.g., solubilizing or diluting some solid or viscous perfume ingredients to, e.g., improve h~nriling and/or form~ ting or stabilizingvolatile ingredients, e.g., by redllçing their vapor pressure. These materials are not counted in the definition/formulation of the enduring perfume compositions of the 165 present invention.
Non-enduring perfume ingredients, which are preferably .1.;.~;...i7ed in personal Lre~ , e.g., liquid personal clç~n.~ing compositions of the present invention, are those having a B.P. of less than about 250~C, or having a ClogP of less than about 3.0, or having both a B.P. of less than about 250~C and a ClogP of less than about 170 3Ø Table 2 gives some non-limiting examples of non-enduring perfume ingredients.
In some particular fabric softPner compositions, some non-enduring perfume ingredients can be used in small amounts, e.g., to improve product odor. However, to ,~ ln;~e waste, the enduring perfume compositions of the present invention contain less than about 30 wt.% of non-enduring perfume ingredients, preferably less 175 than about 25 wt.% of non-enduring perfume ingredients, more preferably less than about 20 wt.% of non-enduring perfume ingredients, and even more preferably lessthan about 15 wt.% of non-enduring perfume ingredients.

W O 96/12467 PCT~US95/1186 Table 1 180Examples of Endurin~ Perfume In~redients Approximate PerfumeIn~redients B.P. (~C) (a) ClogP
BP > 250~C and ClogP > 3.0 Allyl cycloh~-Y~nf propionate 267 3.935 Ambrettolide 300 6.261 Amyl benzoate 262 3.417 Amyl c;~ 310 3.771 190 Amyl cinn~mi~. aldehyde 285 4.324 Amyl cinn~mic aldehyde dimethyl acetal 300 4.033 iso-Amyl salicylate 277 4.601 ~ ~nti~l 450 4.216 Rf~n7l)ph~nonf; 306 3.120 195 Benzyl salicylate 300 4.383 para-tert-Butyl cyclohexyl acetate +250 4.019 iso-Butyl quinoline 252 4.193 beta-Caryophyllene 256 6.333 C~r1inP~nf~ 275 7.346 200 Cedrol 291 4.530 Cedryl acetate 303 5.436 Cedryl formate +250 5.070 Cinnamyl c;i .~ 370 5.480 Cyclohexyl salicylate 304 5.265 205 Cyclarnen aldehyde 270 3.680 Dihydro i~oj~ e +300 3.009 Diphenyl m~oth~nP 262 4.059 Diphenyl oxide 252 4.240 Doflfr~l~rtonf 258 4.359 210 iso E super +250 3.455 Ethylene bl~s~ylate 332 4.554 Ethyl methyl phenyl glycidate 260 3.165 Ethyl undecylenate 264 4.888 Fy~lto~ f 280 5.346 215 G~l~ynlide +250 5.482 Geranyl anthranilate 312 4.216 Geranyl phenyl acetate +250 5.233 ~PY~f~noli~l~f 294 6.805 Hexenyl salicylate 271 4.716 220 Hexyl cinn~mic aldehyde 305 5.473 Hexyl salicylate 290 5.260 alpha-Lrone 250 3.820 Lilial (p-t-bucinal) 258 3.858 Linalyl b~ e 263 5.233 225 2-Methoxy n~phth~l~,nf 274 3.235 Methyl ~Lhy~ u~lle +300 4.843 gamma-n-Me~yl ionone 252 4.309 Musk ;~ nf +250 5.458 Muskketone MP= 137~C 3.014 W O 96/12467 PCTrUS95/11861 230 Musktibetine MP = 136~C 3.831 My-risticin 276 3.200 Oy~hPy~dpc~n~ lir~P-10 +300 4.336 OY~hPy~dpr~n~ ç-l l MP = 35~C 4.336 Patchouli alcohol 285 4.530 235 Ph~ntoli~P 288 5.977 Phenyl ethyl be~ 300 4.058 Phenylethylphenylacetate 325 3.767 Phenyl hept~nol 261 3.478 Phenyl hexanol 258 3.299 240 alpha-Santalol 301 3.800 Thihetoli~le 280 6.246 delta-UndPr~l~ctone 290 3.830 gamma-Unr~P~ rtonP 297 4.140 Vetiveryl acetate 285 4.882 245 Yara-yara 274 3.235 Ylangene 250 6.268 (a) M.P. is melting point; these ingredients have a B.P. higher than 250~C.

250 Table 2 Examples of Non-Enduring Perfume In,eredients A,~ UAil-Lltt;
Perfume Ingl~liellL~ B.P. (~C) ClogP

BP < 250~C and ClogP < 3.0 Rçn7~1~1çhyde 179 1.480 Benzyl acetate 215 1.960 260 laevo-Carvone 231 2.083 Geraniol 230 2.649 II~d~uAy~ lullellal 241 1.541 cis-J~cmonP 248 2.712 Linalool 198 2.429 265 Nerol 227 2.649 Phenyl ethyl alcohol 220 1.183 alpha-Terpineol 219 2.569 BP>2500CandClogP<3.0 Coumarin 291 1.412 Eugenol 253 2.307 iso-Eugenol 266 2.547 ~ Indole 254 decom~,os 2.142 275 Methyl . ;~ e 263 2.620 Methyl diLy~oj~--.-u. ~ +300 2.275 Methyl-N-methylant ranilate 256 2.791 beta-Methyl naphthyl ketone 300 2.275 delta-Nf n~l~r~t~np 280 2.760 - -W O96/12467 PCTrUS95/1186 280 Vanillin 285 1.580 BP < 250OC and ClogP >3.0 iso-Bornyl acetat~ 2;~7 3.485 285 Carvacrol 238 3.4(~1 alpha-Citronellol 225 3.193 para-Cymene 179 4.068 Dihydro myrcenol 208 3.030 Geranyl acetate 245 3.715 290 d-T imnn~on~ 177 4.232 Linalyl acetate 220 3.500 Vertenex 232 4.060 B. Personal ClealL~,in~ Cc,~ siLions Which Are Normally Rinsed Off 295 I. Surfactant System Some p-efelled surf~t~nt~ for use in the surfactant systems herein, as well as other cleansing product ingredients, are disclosed in the following references:
Pat. No. IssueDate Inventor(s) 4,061,602 12/1977 Oberstar et al.
300 4,234,464 11/1980 Morshauser 4,472,297 9/1984 Bolich et al.
4,491,539 1/1985 Hoskins et al.
4,540,507 9/1985 Grollier 4,565,647 1/1986 T.lçn~Q
30s 4,673,525 6/1987 Small et al.
4,704,224 11/1987 Saud 4,788,006 11/1988 Bolich, Jr., et al.
4,812,253 3/1989 Small et al.
4,820,447 4/1989 Medcalf et al.
310 4,906,459 3/1990 Cobb et al.
4,923,635 5/1990 Simion et al.
4,954,282 9/1990 Rys et al.
All of said patents are incorporated herein by reference.
Numerous examples of other surf~ct~ntc are disclosed in the patents 315 incorporated herein by reference. They include anionic surf~ct~nt~, nonionicsurf~ct~nt~, cationic surf~ct~nte, amphoteric surf~ct lnt~, zwitterionic surfactants, and mixtures thereof. They include alkyl slllf~tçc, alkylpolyethyleneglycol s~llf~tes7 alkyl sulfonates, alkyl glyceryl ether sulfonates, anionic acyl sarcosinates, methyl acyl laurates, N-acyl gl~lt~m~tes acyl isethionates, alkyl sulfosuccinates, alkyl phosphate 320 esters, ethoxylated alkyl phosphate esters, trideceth slllf~tes" protein cond~n~tes, mixtures of ethoxylated alkyl sulfates and alkyl amine oxides, betaines, sultaines, and mixtures thereof. Tnchlded in the alkylpolyethyleneglycol sulfate surf~ct~nts are the alkyl ether sulfates with 1 to 12 ethoxy groups, especially ammonium and sodium lauryl ether s -lf~tes 325 The hydrophobic, e.g., alkyl, chains for the surf~ct~nts are normally Cg-C22, preferably C10-C18 1. Anionic Detergent Surfactants a. Soap Some pl~relled compositions of the present invention contain soaps derived 330 from essenti~lly saturated hydrocarbon chainlengths of from about 8 to about 22 carbon atoms. It is p-erelled that the soap be the sodium and/or potassium salts, but other soluble soaps can be used.
b. Synthetic Anionic Deter~ent Surf~ct~nt.~
Anionic nonsoap synthetic detergent surfactants can be exemplified by the alkali335 metal salts of organic sulfuric reaction products having in their molecular structure an alkyl radical co.~ g from 8 to 22 carbon atoms and a sulfonic acid or sulfuric acid ester radical (in~.hlde~ in the term alkyl is the alkyl portion of higher acyl radicals).
c. Sulfate Surf~ct~ntc The compositions hereof can comprise alkyl sulfate, alkyl ether sulfate, fatty 340 acid monoglyceride sulfate, or ",ix~u, es thereof, as a surfactant component.
Typically, such sulfate surf~ct~nt~, when present, are at a level of from about 1% to about 30%, preferably from about 10% to about 25%, more preferably from about 12% to about 22%, most preferably from about 15% to about 22%, by weight of the composition. These materials have the respective formulae (I) ROSO3M and (II) 345 RO(C2H4O)XSO3M, wherein R is alkyl or alkenyl of from about 8 to about 30 carbon atoms, x is 1 to 10, and M is H or a soluble salt-forming cation such as ammonium, alkanolammonium (such as triethanolammonium), monovalent metal cations, such as sodium and/or pot~i--m, polyvalent metal cations, such as magnesium and calcium, and/or mixtures of such cations. The cation M, of the 350 anionic surfactant should be chosen such that the anionic surfactant component is water soluble. Solubility will depend upon the particular anionic surf~ct~nts and/or cations chosen. As an aid to determining approp~iate mixtures of anionic surf~ct~nt~, the anionic surf~ct~nt.~ should be chosen such that the Kraffl temperature of the surf~c.t~nts chosen is about 15~C or less, preferably about 10~C or less, more 355 preferably about 0~C or less. It is also p~ere"ed that the anionic surfactant be soluble in the composition hereof.
Preferably, R has from about 10 to about 18 carbon atoms in both the alkyl and W O96/12467 PCT~US9S/1186 -la alkyl ether sulf~tee. The alkyl ether sulfates are typically made as condene~tion products of ethylene oxide and monohydric alcohols having from about 8 to about 24 360 carbon atoms. The alcohols can be derived from fats, e.g., coconut oil, palm kernel oil, or tallow, or can be synthetic. Such alcohols are preferably reacted with about 1 to about 10, more preferably from about 1 to about 4, most preferably from about 2 to about 3.5, molar proportions of ethylene oxide and the reeulting mixture of molecular species having, for example, an average of 3 moles of ethylene oxide per 365 mole of alcohol, is s--lf~ted and neutralized.
Specific examples of alkyl ether sulfates which can be used in the present invention are sodium and ammonium salts of coconut alkyl triethylene glycol ether sulfate; tallow alkyl triethylene glycol ether sulfate, and tallow alkyl hexaoxyethylene sulfate. Highly pr~r~.,ed alkyl ether sulfates are those comprising a mixture of370 individual compounds, said mixture having an average alkyl chain length of from about 12 to about 16 carbon atoms and an average degree of ethoxylation of from about 1 to about 4 moles of ethylene oxide.
d. Sulfonate Deter~ent Surf~ct~nts A suitable class of optional anionic detersive surf~ct~nt.c are aliphatic sulfonates 375 such as leplese.-Led by the water-soluble salts of the organic, sulfuric acid reaction products ofthe general formula a):
Rl-S03-M (I) wherein R1 is chosen from the group consisting of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about 24, preferably 380 about 12 to about 18, carbon atoms; and M is a cation, as previously described~
subject to the same limitations ~ dillg polyvalent metal cations as previously rli.ecueeed Important examples are the salts of an organic sulfuric acid reaction product of a hydrocarbon of the methane series, inc.l~ ing iso-, neo-, and n-paraffins, having about 8 to about 24 carbon atoms, preferably about 12 about 18 carbon atoms 38~ and a sulrollating agent, e.g., S03, H2S04, oleurn, obtained according to known sulfonation methods, inclu~in~ bleaching and hydrolysis. Prere~ed are alkali metal and ammonium sulfonated C12-Clg paraffins (e.g., normal and secondary paraffins).
Additional examples of synthetic anionic sulfonate detersive surf~rt~nte which can be added to the compositions of the present invention are the reaction products of 390 fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil, and fatty acid monoglyceride sulfonates as described in the patents incorporated herein by reference.

W O 96/12467 PCTrUS9~/1186 395 Still other synthetic anionic detersive surf~ct~nts are in the class design~ted as succin~tes. This class includes such surface active agents as disodium N-octadecylsulfosuccinate; tetrasodium N-(1,2-dicarboxyethyl)-N-octadecylsulfos~lcçin~te; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of sodium sulfosuccinic acid.
400 Other suitable anionic detersive surf~ct~nt~ include olefin sulfonates having about 12 to about 24 carbon atoms. The term "olefin sulfonates" is used herein to mean compounds which can be produced by the sulfonation of alpha-olefins by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sulfones which have been formed in the reaction 405 are hydrolyzed to give the corresponding hydroxy-alkanesulfonates. The sulfur trioxide can be liquid or gaseous, and is usually, but not necessarily, diluted by inert uent~ for example, by liquid S02, chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gaseous SO2, etc., when used in the gaseous form.
The ~upha-ûlefins froln wnich the o;efin suifonates are derived are mono-oiefins410 having about 12 to about 24 carbon atoms, preferably about 14 to about 16 carbon atoms. P. efel ~bly, they are straight chain olefins.
In addition to the true alkene sulfonates and a proportion of hydroxy-alkanesulfonates, the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportion of 415 re~ct~nt~, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process.
Another class of anionic detersive surf~ct~nte are the beta-alkyloxy alkane sulfonates. These compounds have the following formula (II):
Rl C(OR2)(EI)cH2sO3M (II) 420 where R1 is a straight chain alkyl group having from about 6 to about 20 carbon atoms, R2 is a lower alkyl group having from about 1 (plel~l-ed) to about 3 carbon atoms, and M is a water-soluble cation as hereinbef.ore described.
e. N-Acylamino Acid Surfactants Yet other anionic detergent surfactant type is the N-acylamino acid surfactant 42s type, which incll~des N-acyl hydrocarbyl acids and salts thereof, such as those ~c;plesell~ed by Formula m, as follows:
R1 C (O)- N (R2) - (R3)n COOM (m) wherein: R1 is a C7-C23 alkyl or alkenyl radical, preferably Cg-C17; R2 is -H, C1-C4 alkyl, phenyl, or -CH2COOM, preferably C1-C4 alkyl, more preferably C1-C2 alkyl;430 R3 is -CR42- or C1-C2 alkoxy, wherein each R4 independently is -H or C1-C6 alkyl W O96/12467 PCTrU$95/11864 or alkylester, and n is from 1 to 4, preferably 1 or 2; and M is -H or a cation as previously defined, preferably an alkali metal such as sodium or pot~ .m A wide variety of N-acyl acid surfAct~nt~ and their synthesis are described in Anionic Surf~ct~nt.~, Part II, Surfactant Science Series, Vol. VII, edited by Warner M.
435 Linfield, Marcel Dekker, Inc. (New York and Basel), 1976; pp 581-617.
Especially ple~,,ed are compounds of Formula III wherein R2 is methyl and R3 is -CH2-, and n is 1, which are known as the N-acyl sarcosinates, and acids thereof. Specific examples include lauroyl sarcosinate, myristoyl sarcosinate, cocoyl sarcosinate, and oleoyl sarcosinate, preferably in their sodium and potassium salt 440 forms.
Preferred anionic detersive surf~ct~nt~ for use in the present compositions include the sodium, ammonium, potassium or triethanolamine alkyl slllf~te~, especially those obtained by sl~lf~ting the higher alcohols (Cg-C1g carbon atoms), sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium 44s salts of sulfuric acid esters of the reaction product of 1 mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and 1 to 12 moles of ethylene oxide; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate with 1 to 10 units of ethylene oxide per molecule and in which the alkyl radicals contain from 8 to 12carbon atoms, sodium alkyl glyceryl ether sulfonates; the reaction product of fatty 4so acids having from 10 to 22 carbon atoms esterified with isethionic acid andneutralized with sodium hydroxide; water-soluble salts of condrn~tion products of fatty acids with sarcosine; and others known in the art.
Some examples of good lather-çnh~nring, mild anionic detergent surf~ct~n are e.g., sodium or potassium lauroyl sarcosinate, alkyl glyceryl ether sulfonate, 455 sulfonated fatty esters, and sulfonated fatty acids.
Other synthetic detergent surf~ct~nt~ which can be used include amphoteric, zwitterionic, nonionic and, in certain in.~t~nces, cationic surf~ct~nts, e.g., at a level of from about 1% to about 10%, preferably from about 2% to about 6% by weight of the product.
460 2. AmphotericDeter~ent Surfactants Examples of amphoteric surf~ct~nt.~ which can be used in the compositions of the present invention are those which are broadly described as derivatives of aliphatic secondary, tertiary, and/or quaternary amines in which at least one hydrophobic, e.g., aliphatic, radical which can be either straight or branched chain and which typically 465 contains from about 8 to about 18 carbon atoms and in which at least one radical contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate,phosphate, or phosphonate. Examples of compounds falling within this definition are W O 96/12467 PCT~US9~/11864 sodium 3-dodecylaminopropionate, sodium 3-dodecylaminopropane sulfonate, N-alkyltaurines, such as the one prepared by reacting dodecylamine with sodium 470 isethionate according to the te~ching of U.S. Pat. No. 2,658,072, N-higher alkyl aspartic acids, such as those produced according- to the te~ching of U.S. Pat. No.

2,438,091, and the products sold under the trade name "Miranol" and described inU.S. Pat. No. 2,528,378.
The amphoteric surf~t~nt~ hereof also include the imidazolinium amphoteric 475 (zwitterionic) surf~ct~nt.c such as those depicted by Formula (IV):
RlCoN~R4) - (CH2)n - N+(R3)(R2)-CH2Z (IV) wherein R1 is Cg-C22 alkyl or alkenyl, preferably C12-C16, R2 is hydrogen or CH2CO2M, R3 is CH2CH2OH or CH2CH2OCH2CH COOM, R4 is hydrogen, CH2CH2OH, or CH2CH2OCH2CH2COOM, Z is CO2M or CH2CO2M, n is 2 or 3, 48~ preferably 2, M is hydrogen or a cation, such as alkali metal, alkaline earth metal, ammonium, or alkanol ammonium.
Suitable materials of this type are marketed under the tradename Miranol(~) and are understood to comprise a complex mixture of species, and can exist in protonated and non-l)ro~ol1ated species depending upon pH with respect to species that can have 485 a hydrogen at R2. The imid~7Olinum amphoteric surfactant hereof can be derived via an imi~7Qlinium interme~ te. However, it will be recognized by those in the art that it needn't necessarily be derived via an imid~7Olinium.
Preferred amphoteric surf~ct~nt.~ of Formula IV are monocarboxylates and dicarboxylates. F.Y~mrles of these materials include cocoamphocarboxy-propionate, 490 cocoamphocarbo~ pionic acid, cocoamphocarboxyglycinate (alternately referred to as cocoampho~ cet~te), and cocoampho~cet~te.
Specific commercial products providing the imi~7Olinium derivative component of the present compositions include those sold under the trade names Miranol C2M CONC. N.P., Miranol C2M CONC. O.P., Miranol C2M SF, Miranol 495 CM Special (Miranol, Inc.); Alkateric(~) 2CIP (Alkaril Chemicals); Amphoterge(~ W-2 (Lonza, Inc.); Monateric~) CDX-38, Monateric CSH-32 (Mona Industries~;
Rewoteric(~) AM-2C (Rewo Chemical Group); and Scheroteric~) MS-2 (Scher Chemicals).
Amphoteric surf~ct~nt~ also include aminoalkanoates ofthe formula (V):
O soo R-NH(CH2)nCOOM; (V) and imino(li~lk~no~tes of the formula (VI):
R-N[(cH2)mcOoM]2 (VI) and mixtures thereof; wherein n and m are numbers from 1 to 4, R is Cg-C22 alkyl or alkenyl, and M is hydrogen, alkali metal, alkaline earth metal, ammonium or w o 96/12467 pcTrus95lll864 505 alkanolammonium.
Examples of such amphoteric surfactants include n-alkylaminopropionates and n-alkyliminodipropionates. Such materials are sold under the tradename Deriphat(~) by Henkel and Mirataine~) by Miranol, Inc. Specific examples include N-lauryl-beta-amino propionic acid or salts thereof, and N-lauryl-beta-imino-dipropionic acid or Sl0 salts thereof.
Other zwitterionic surf~ct~nt~7 in addition to the imi~701inillm.c, can be exemplified by those which can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight chain or branched and wherein one of the aliphatic 515 substit.-çnts contains from about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
A general formula (VII) for these compounds is:
R2 y(+) (R3)X CH2 - R4 - Z(~) (VII) wherein R2 contains an alkyl, alkenyl, or hydroxy alkyl radical of from about 8 to 520 about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety; Y is selected from the group consisting of nitrogen, phosphorus, and sulfur atoms; R3 is an alkyl or monohydroxyalkyl group co..~ 1 to about 3 carbon atoms; x is 1 when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorus atom; R4 is an alkylene or hydroxyalkylene of from 1 to about 4 carbon 525 atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
Examples include: 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carboxylate; 5-[S-3-hydroxypropyl-S-hPY~decylsulfonio]-3-hydroxypentane-1-sulfate;

3 -rP,P-P-diethyl-P-3,6,9-tri-oxatetradexocylphosphonio]-2-hydroxypropane- 1-530 phosphate; 3-[N,N-dil)lol)yl-N-3-dodecoxy-2-hydroxypropylammonio]-propanel-phosphonate; 3-(N,N-dimethyl-N-hexadecylammonio)propane- l -sulfonate; 3-(N,N-dimethyl-N-h~ decylammonio)-2-hydroxypropane-1-sulfonate; 4-rN,N-di(2-hydroxyethyl)-N-(2-hydroxydodecyl)ammonio]-butane- 1 -carboxylate; 3-rS-ethyl-S-(3 -dodecoxy-2-hydroxypropyl)sulfonio]-propane- 1 -phosphate; 3 -(P,P-dimethyl-P-535 dodecylphosphonio)-propane-1-phosphonate; and 5-rN,N-di(3-hydroxy~lol~yl)-N-h-oY~decylamrnonio]-2-hydroxy-pentane- 1 -sulfate.
Zwitterionic detergent surf~ct~ntc co.ll~ an amido linkage in the hydrophobic chain are especially desirable and include those r~l~sell~ed by the Forrnula (VIII):
540 R5c(o)N~p~4)(c H2)m N +(R2) ~ 3)~1Rl (~III) wherein: R1 is a member selected from the group consisting of: COOM and CH(OH)-W O 96/12467 PCT~US95/1186~

CH2S03M; R2 is C1-C3 alkyl or hydroxy (Cl-C3) alkyl; R3 is C1-C3 alkyl or hydroxy (C1-C3) alkyl; R4 is a member selected from the group consisting of hydrogen and C 1-C3 alkyl; Rs is Cg-C20 alkyl or alkenyl; Y is C 1-C3 alkyl;
S45 m is an integer from 2 to 7; n is the integer 1 or 0; M is hydrogen or a cation, such as an alkali metal or alkaline earth cation metal, ammonium, or alkanolamide.
The term "alkyl" or "hydroxyalkyl" means straight or branch ch~ine~, saturated, aliphatic hydrocarbon radicals and substituted hydrocarbon radicals such as, forexample, methyl, ethyl, propyl, isopropyl, hydroxypropyl, hydroxyethyl, and the like.
550 Examples of zwitterionics useful herein include the higher alkyl betaines such as coco dimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha-carboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis(2-hydroxyethyl)carboxy methyl betaine, stearyl bis-(2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl bis-(2-555 hydroxypropyl) alpha-carboxyethyl betaine, etc. The sulfobetaines can be leprese,l~ed by coco dimethyl sulroplu~yl betaine, stearyl dimethyl sulfopropyl betaine, lauryl bis-(2-hydroxyethyl) sulropropyl betaine, amido betaines amidosulfobetaines, and the like.
3. Cationic Deter~ent Surfactants Many cationic surf~ct~nts are known to the art. By way of example, the 560 following can be mentioned:
stearyldimethylbenzyl ammonium chloride;
dodecyltrimethylammonium chloride;
nonylbenzylethyldimethyl ammonium nitrate;
tetradecylpyridinium bromide;
565 laurylpyridinium chloride;
cetylpyridinium chloride;
laurylpyridinium chloride;
laurylisoquinolium bromide;
ditallow(hydrogenated)dimethyl ammonium chloride;
570 dilauryldimethyl ammonium chloride; and stearalkonium chloride.

4. Nonionic Deter~ent Surf~ct~nt~s Nonionic surf~ct~nt~ are typically compounds produced by the condçn.c~tion of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, S75 which can be aliphatic or alkyl aromatic in nature, but can include other surf~ct~nts that do not possess a charge group. Examples of preferred classes of nonionic surf~-t~nt~ are:

WO 96/12467 PCT/US95/1186'1 a. Alkyl phenol ethoxylates. The polyethylene oxide condenc~tes of alkyl phenols, e.g., the condçn.c~tion products of alkyl phenols having an alkyl 580 group cont~ining from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 10 to 60 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be derived from polymerized propylene, diisobutylene, octane, or nonane, for example.
585 b. Polyethylene ~IycoUpolypropylene ~Iycol block copolymers. Those derived from the condçn.c~tion of ethylene oxide with the product res~-lting from the reaction of propylene oxide and ethylene di~mine products which can be varied in composition depending upon the balance between the hydrophobic and hydrophilic elements which is desired. For example, compounds 590 co~ g from about 40% to about 80% polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resnlting from the reaction of ethylene oxide groups with a hydrophobic base con.ctituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of 2,500 to 3,000, s95 are s~ticf~ctory.
c. Fatty alcohol and fatty acid ethoxylates. The condenc~tion product of aliphatic alcohols having from 8 to 18 carbon atoms, in either straight chain or branched chain configuration with ethylene oxide, e.g., a coconut alcohol ethylene oxide cond~n.c~te having from 10 to 30 moles of ethylene oxide per 600 mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms. Other ethylene oxide condenc~tion products are ethoxylated fatty acid esters of polyhydric alcohols (e.g., Tween 20-polyoxyethylene (20) sorbitan monolaurate).
d. Long chain tertialy amine oxides. Long chain tertiary amine oxides 605 corresponding to the following general formula:
RlR2R3N~> O
wherein Rl conlains an alkyl, alkenyl or monohydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties, and from 0 to 1 glyceryl moiety, and R2 and R3 contain from 1 to 610 about 3 carbon atoms and from 0 to about 1 hydroxy group, e.g., methyl, ethyl, propyl, hydroxy ethyl, or hydroxy propyl radicals. The arrow in the formula is a conventional ~plese.lLaLion of a semipolar bond. Examples of amine oxides suitable for use in this invention include dimethyldodecylamine oxide, oleyldi(2-hydroxy ethyl) amine oxide, dimethyloctylamine oxide, WO 96/12467 PCT/US95/1186~

615 dimethyldecylamine oxide, dimethyltetradecylamine oxide, 3,6,9-trioxaheptadecyldiethylamine oxide, di(2-hydroxyethyl)-tetradecylamine oxide, 2-dodecoxyethyldimethylamine oxide, 3-dodecoxy-2-hydroxy~ropyldi(3-hyd-oxy~lol)yl) amine oxide, dimethylheY~decylamine oxide.
620 e. Long chain tertiary phosphine oxides. Long chain tertiary phosphine oxides corresponding to the following general formula:
RR'R"P--> O
wherein R contains an alkyl, alkenyl or monohydroxyalkyl radical ranging from 8 to 18 carbon atoms in chain length, iFrom 0 to about 10 ethylene oxide 625 moieties and from 0 to 1 glyceryl moiety and R' and R" are each alkyl or monohydroxyalkyl groups cont~ining from 1 to 3 carbon atoms. The arrow in the formula is a conventional representation of a semipolar bond.
Examples of suitable phosphine oxides are: dodecyldimethylphosphine oxide, tetradecylmethylethylphosphine oxide, 3,6,9-630 trioxaoctadecyldimethylphosphine oxide, cetyldimethylphosphine oxide, 3-dodecoxy-2-l,ydl ~xy~l opyldi(2-hydroxyethyl) phosphine oxide stearyldimethylphosphine oxide, cetylethylpropylphosphine oxide, oleyldiethylphosphine oxide, dodecyldiethylphosphine oxide, tetradecyldiethylphosphine oxide, dodecyldipropylphosphine oxide, 635 dodecyldi(hydroxymethyl)phosphine oxide, dodecyldi(2-hydroxyethyl)phosphine oxide, tetra-decylmethyl-2-hydroxy~ropylphosphine oxide, oleyldimethylphosphine oxide, 2-hydroxydodecyldimethylphosphine oxide.
~ Lon~ chain dialkyl sulfoxides. Long chain dialkyl sulfoxides co.,L~ g one 640 short chain alkyl or hydroxy alkyl radical of 1 to about 3 carbon atoms (usually methyl) and one long hydrophobic chain which contain alkyl, alkenyl, hydroxy alkyl, or keto alkyl radicals co.-l~;l-il-g from about 8 to about 20 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to 1 glycelyl moiety. Examples include: octadecyl methyl sulfoxide, 645 2-ketotridecyl methyl sulfoxide, 3,6,9-trioxaoctadecyl 2-hydroxyethyl sulfoxide, dodecyl methyl sulfoxide, oleyl 3-hydroxy~ropyl sulfoxide, tetradecyl methyl sulfoxide, 3 methoxytridecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3- hydroxy-4-dodecoxybutyl methyl sulfoxide.
650 g. Alkyl polysaccharide (APS) surf~ct~nts such as the alkyl polyglycosides.
Such surf~ct~nte are APS surf~ct~nt~ having a hydrophobic group with W O 96/12467 PCTrUS9~/11864 about 6 to about 30 carbon atoms and polysaccharide (e.g., polyglycoside) as the hydrophilic group. Optionally, there can be a polyalkylene-oxide group joining the hydrophobic and hydrophilic moieties. The alkyl group 655 (i.e., the hydrophobic moiety) can be saturated or unsaturated, branched or unbranched, and unsubstituted or substituted (e.g., with hydroxy or cyclic rings).
h. Polyethylene ~Iycol (PEG) glyceryl fatty esters, such as those of the formulaR(O)OCH2CH(OH)CH2(0CH2CH2)nOH wherein n is from about 5 to 660 about 200, preferably from about 20 to about 100, and R is an aliphatic hydrocarbyl having from about 8 to about 20 carbon atoms.
Many additional nonsoap surf~ct~nts are described in McCutcheon's, Detergents And Fmllleifiers, 1994 Annual, published by MC Publishing Company, which is incorporated here by reference, and in U.S. Patent No. 5,151,209, to McCall 665 et al., issued September 29, 1992; U.S. Patent No. 5,151,210, to Steuri et al., issued September 29, 1992; and U.S. Patent No. 5,120,532, to Wells et al., issued June 9, 1992, all of which are incorporated by reference herein. For the purposes of thesurf~r.t~nte described herein, it should be understood that the terms "alkyl" or"alkenyl" include mixtures of radicals which can contain one or more interme~ te670 linkages such as ether or polyether linkages or non-functional substituents such as hydroxyl or halogen radicals wherein the radical remains of hydrophobic character.

5. The Surfactant Systems The present invention, especially in the aspect relating to personal cle~n.eing compositions that are normally rinsed, like shampoos and personal skin cleansers, 675 comprises from about 0.01% to about 95%, preferably from about 5% to about 85%, more preferably from about 3% to about 30%, even more preferably from about 5%
to about 22% of a surfactant system. This surfactant system comprises anionic, nonionic, cationic, and/or zwitterionic type surf~ct~nt.e as described hereinbefore. For non-shampoo surfactant systems the surfactant system typically comprises at least one 680 surfactant selected from the group consisting of soap, acylf~lut~m~tes, alkyl ~ sarcosinates, alkylpolyethyleneglycol sl.lf~tes, alkylglyceryl ether sulfonates, and/or acyl isethionates. t a. Shampoo Surfactant Systems The shampoo compositions of the present invention typically contain a 685 detersive surfactant system to provide cle~ning performance to the composition. The total detersive surfactant component will generally be present at a level from about 1% to about 30%, by weight of the composition, preferably from about 12% to about 25%, more preferably from about 15% to about 22%.

The shampoo compositions of the present invention optionally comprise from 690 0% to about 20% of surfact~nt.c that build suds. When used, such optional suds building surfactants are typically present at levels of from about 0.05% to about 20%, more typically from about 0.1% to about 10%, preferably from about 0.5% to about5%, although higher or lower levels can be used. Suitable surf~ct~nt.~ for building suds include amide foam boosters, e.g., fatty acid (e.g., Clo-C22) mono- and di- (Cl-695 Cs, especially C1-C3) alkanol amides at a level of from about 0.1% to about 6%, preferably from about 0.5% to about 4%.
b. Soap Surfactant Systems Compositions of the present invention can comprise at least about 2% by weight of the surfactant system, preferably at least about 10%, more preferably at 700 least about 25%, and even more preferably at least about 50% soap.
Preferably the alkali metal soap is C1o-C22, preferably C12-CIg, more preferably C12-C14 (cocoate, laurate, PKO) sodium,~ pot~sillm, ammonium, ~riethanoiammonium, and/or magnesium soap. Preferably these soaps have saturatedalkyl chains.
70s These soaps are preferably prepared by the in situ saponification of the corresponding fatty acids, but they can also be introduced as preformed soaps.
The addition of C1o-C22 soap also decreases any "slippery feel" caused by any synthetic surfactant that is present.
A soap based liquid composition comprises:
710 (A) from about 5% to about 20% by weight of potassium Cg-C22 fatty acid soap;
(B) from about 0.1 to about 7% Cg-C22 free fatty acid;
(C) from about 8% to about 35% of a polyol selected from the group con.~i~ting of: glycerin, glycerol, propylene glycol, polypropylene glycol, 715 polyethylene glycol, ethyl hexanediol, hexylene glycol, and other aliphatic alcohols; and mixtures thereof;
(D) from about 0.5% to about 15% petrolatum preferably having an average particle size offrom 45 microns to about 120 microns; and (E) from about 0.5 to about 5% glycol ester selected from the group 720 consisting of glycol monoesters and diesters of fatty acids with a chainlength from about 10 to about 22, and mixtures thereof, typically form~ ted as a liquid which additionally comprises from about 35% to about 70% water, wherein the ratio of said soap plus any synthetic surfactant, which is optionally added, to said free fatty acids plus glycol ester is preferably from about 72s 1:1 to about 15:1 and more preferably from about 3:1 to about 12:1; wherein said W O 96/12467 PCT~US95/1186 liquid has a viscosity of from about 500 cps to about 60,000 cps at about 26.7~C; and wherein the fatty acid of (A) and (13) have an Iodine Value of from zero to about 15.
The fatty acid matter of the above soap based liquid composition typically has an IV of from zero to about 15, preferably below about 10, more preferably below730 about 3.
The compositions can contain fatty acids derived from essçnti~lly saturated hydrocarbon chainlengths of from about 8 to about 22 carbon atoms. These fatty acids can be highly purified individual chainlengths and~or crude mixtures such as those derived from fats and oils. In general, the higher the proportion of longer chain 735 length fatty acids, the poorer the lather, but the greater the pearlescent appearance and mildness of the product.
The above soap based liquid composition can contain from about 8% to about 35% of a polyol selected from the group consisting of: glycerin, glycerol, propylene glycol, polypropylene glycol, polyethylene glycol, ethyl hexanediol, hexylene glycol, 740 aliphatic alcohol; and mixtures thereof; and preferably contains 10-30% of said polyol, preferably glycerol.
The petrolatum (emollient) useful in the above soap based liquid composition can be any grade of white or yellow petrolatum recognized in the art as suitable for human application. The pl~relled type is USP Class III with a melting point between 745 about 122~F and about 135~F (about 50~-57~C). Such a material is commercially available as Penreco Snow White Pet USP. The petrolatum of the present inventionin~ des hydrocarbon mixtures form~ ted with mineral oils in combination with paraffin waxes of various melting points.
Alternatively, the above soap based liquid composition can contain from about 750 0.5% to about 15% of a lipophilic emollient selected from the group consisting of:
esters of fatty acids; glycerin mono-, di-, and tri-esters; epidermal and sebaceous hydrocarbons such as cholesterol, cholesterol esters, squalene, squalane; silicone oils and gums; mineral oil; lanolin and lanolin derivatives; and mixtures thereof.
The petrolatum and/or emollient particle size is alternatively expressed as a 755 particle size distribution with 10% to 80% of the particles being about 5 microns to about 120 microns within the product, preferably 20% to 80% being from about 10 to about 110 microns, more preferably 25% to 80% from about 30 to about 110 microns, more preferably from about 60 to about 100 microns.
The level of water in the above soap based liquid composition is typically from 760 about 35% to about 70%, preferably from about 40% to about 65%.
Liquid soap sle~n~ers normally have a viscosity of from about 1 to about 150,000 cps, preferably from about 500 cps to about 120,000 cps, more preferably W O 96/12467 PCTrUS9~/1186 from about 1,000 cps to about 45,000 cps, at about 26.7~C (about 80~F), Brookfield RVTDCP with a Spindle CP-41 at 1 RPM for about 3 min~ltes.
765 The liquid soap is catled a dispersoid because at least some of the fatty matter, at the levels used herein, is insoluble. The above soap based liquid composition is phase stable, even after storage.
II. Optional In~redients 1. Optional Suspendin~ Agent 770 The present compositions, and especially shampoo compositions, can include a crystalline suspending agent. Other suspending agents useful for suspending emulsified oils (or other materials) and for thickening the compositions can optionally be used.
The crystalline suspending agent will be used at an effective level for 775 suspending çmlllcified oils or other materials. The suspension should, in general, be stable for at least one month at ambient temperature. Longer term shelf stability such as at least three months, preferably six months, most preferably at least about twenty-four months, is plere..ed. In general, the compositions hereof will comprise from about 0.~% to about 10%, by weight, of a crystalline suspending agent or 780 combination thereof. The crystalline suspending agent is preferably present in the shampoo compositions hereof at a level of about 0.5% to about 5%, more preferably about 1% to about 4%, most preferably about 1% to about 3%.
Preferred crystalline suspending agents are acyl derivatives and amine oxides, especially acyl derivatives, especially those which can be soiubilized in a premix 785 solution and then be recryst~ ed upon cooling. These materials will comprise long chain (e.g., Cg-C22 preferably C14-C22, more preferably C16-C22) aliphatic groups, i.e., long chain acyl derivative materials and long chain amine oxides, as well as mixtures of such materials. Tn~.hlded are ethylene glycol long chain esters, alkanol amides of long chain fatty acids, long chain esters of long chain fatty acids, glyceryl 790 long chain esters, long chain esters of long chain alkanolamides, and long chain alkyl dimethyl amine oxides, and mixtures thereof.
Suitable suspending agents for use herein include ethylene glycol esters of fatty acids preferably having from about 14 to about 22 carbon atoms, more preferably 16-22 carbon atoms. More ~.ere..ed are the ethylene glycol stearates, both mono and795 distearate, but particularly the distearate co~ il-g less than about 7% of the mono stearate. Other suspending agents include alkanol amides of fatty acids, preferably having from about 16 to about 22 carbon atoms, more preferably about 16 to 18 carbon atoms. Plefe~.~d alkanol amides are stearic monoethanolamide, stearic diethanolamide, stearic monoisop. opanolamide and stearic monoethanolamide W O96/12467 PCT~US95/11864 800 stearate. Other long chain acyl derivatives include long chain esters of long chain fatty acids (e.g., stearyl stearate, cetyl palmit~te); glyceryl esters (e.g., glyceryl distearate) and long chain esters of long chain alkanol amides (e.g., stearamidediethanolamide distearate, stearamide monoethanolamide stearate). Ethylene glycol esters of long chain carboxylic acids, long chain amine oxides, and alkanol amides of 80s long chain carboxylic acids, in addition to the preferred materials listed above, can be used as suspending agents.
Suspending agents also include long chain amine oxides such as alkyl (C16-C22) dimethyl amine oxides, e.g., stearyl dimethyl amine oxide. If the compositions contain an amine oxide or a long chain acyl derivative which is a surfactant, the 810 suspending function could also be provided by such amine oxide or acyl derivative, provided at least a portion of them are present in crystalline form, and additional suspending agent may not be needed.
Other long chain acyl derivatives that can Ibe used include N,N-dihydrocarbyl (C12-C22, preferably C16-Clg) amido benzoic acid and soluble salts thereof(e.g., Na 815 and K salts), particularly N,N-di(C16-Clg, and hydrogenated tallow) amido benzoic acid species of this family, which are commercially available from Stepan Company (Northfield, Illinois, USA).
The crystalline suspending agent serves to assist in suspending particulate ~ matter or emulsions of insoluble fluids, i.e., oils, in the shampoo compositions hereof, 820 and can give pearlescence to the product.
The crystalline suspending agent can be incorporated into the shampoos hereof by solubilizing it into a solution CO..I~ g water and the anionic sulfate surfactant at a temperature above the melting point of the suspending agent. The suspending agent is then recly~ e~, typically by cooling the solution to a temperature sufficient to 825 induce cryst~lli7~tion.
2. Optional Suspending A~ent Thickeners and Viscosity Modifiers Optional thickeners are categorized as cationic, nonionic, or anionic and are selected to provide the desired viscosities. Suitable thickeners are listed in the Glossary and Chapters 3, 4, 12 and 13 of the Handbook of Water-Soluble Gums and 830 Resins~ Robert L. Davidson, McGraw-Hill Book Co., New York, N.Y., 1980, incorporated by I t;rel ence herein.
Anionic thickeners include cros~linked polymers. These crosslinked polymers typically contain one or more monomers derived firom acrylic acid, substituted acrylic acids, and salts and esters of these acrylic acids and the substituted acrylic acids, 835 wherein the cro~.~linkin~ agent contains two or more carbon-carbon double bonds and is derived from a polyhydric alcohol. The p~ ed polymers for use herein are of two general types. The first type of polymer is a crosslinked homopolymer of an acrylic acid monomer or derivative thereof (e.g., wherein the acrylic acid has sub~titl1Pnts on the two and three carbon positions independently selected from the 840 group consisting of Cl 4 alkyl, -CN, -COOH, and mixtures thereof). The second type of polymer is a cro.cslin~ed copolymer having a first monomer selected from the group consisting of an acrylic acid monomer or derivative thereof (as just described in the previous sentPnce), a short chain alcohol (i.e. a C1 4) acrylate ester monomer or derivative thereof (e.g., wherein the acrylic acid portion of the ester has substituents 845 on the two and three carbon positions independently selected from the group consisting of Cl 4 alkyl, -CN, -COOH, and mixtures thereof~, and lllixlult;s thereof;
and a second monomer which is a long chain alcohol (i.e. Cg 40) acrylate ester monomer or derivative thereof (e.g., wherein the acrylic acid portion of the ester has substituents on the two and three carbon pOSitiOî1S independently selected from the 850 group consisting of Cl 4 alkyl, -CN, -COOH, and mixtures thereof). Combinations of these two types of polymers are also useful herein.
In the first type of cros.clinked homopolyrners the monomers are preferably selected from the group consisting of acrylic acid, meth~crylic acid, ethacrylic acid, and mixtures thereof, with acrylic acid being mos~ plefelled. In the second type of 855 cro~linkP,d copolymers the acrylic acid monomer or derivative thereof is preferably selected from the group consi~h~g of acrylic acid, meth~crylic acid, ethacrylic acid, and mixtures thereof, with acrylic acid, meth~crylic acid, and mixtures thereof being most plerelled. The short chain alcohol acrylate ester monomer or derivative thereof is preferably selected from the group consisting of C 1-4 alcohol acrylate esters, Cl 4 860 alcohol meth~c.rylate esters, Cl 4 alcohol ethacrylate esters, and mixtures thereof, with the Cl 4 alcohol acrylate esters, C1 4 alcohol methacrylate esters, and mixtures thereof, being most p-~relled. The long chain alcohol acrylate ester monomer is selected from Cg 40 alkyl acrylate esters, with C10 30 alkyl acrylate esters being pl ~r~ d.
865 The crosslinking agent in both of these types of polymers is a polyalkenyl polyether of a polyhydric alcohol cot~ more than one alkenyl ether group per molecule, wherein the parent polyhydric alcohol contains at least 3 carbon atoms and at least 3 hydloxyl groups. Plefelled crosslinkers are those selected from the group consisting of allyl ethers of sucrose and allyl ethers of pentaerythritol, and mixtures 870 thereof. These polymers useful in the present invention are more fully described in U.S. Patent No. 5,087,445, to Haffey et al., issued February 11, 1992; U.S. Patent No. 4,509,949, to Huang et al., issued April 5, 19~5; U.S. Patent No. 2,798,053, to Brown, issued July 2, 1957; which are incorporated by reference herein. See also, W O 96/12467 PCT~US95/1186 CTFA International Cosmetic Ingredient Dictionary, fourth edition, 1991, pp. 12 and 875 80; which are also incorporated herein by reference.
Other examples of anionic commercially a~ailable homopolymers useful herein include the carbomers, which are homopolymers of acrylic acid crosslinked with allyl ethers of sucrose or pentaerytritol. The carbomers are available as the Carbopol~
900 series from B.F. Goodrich. Examples of commercially available copolymers of 880 the second type useful herein include copolymers of C10 30 alkyl acrylates with one or more monomers of acrylic acid, methacrylic acid, or one of their short chain (i.e.
Cl 4 alcohol) esters, wherein the crosslinking agent is ar~ allyl ether of sucrose or pentaerytritol. These copolymers are known as acrylates/C10-30 alkyl acrylate crosspolymers and are commerically available as Carbopol~ 1342, Pemulen TR-1, 885 and Pemulen TR-2, from B.F. Goodrich. Other optional copolymers of acrylic acid crosslinked with polyallyl sucrose are provided by B.F. Goodrich Company as, forexample, Carbopol 934, 940, 941, and 956.
A carboxyvinyl polymer is an interpolymer of a monomeric mixture comprising a monomeric olefinically unsaturated carboxylic acid, and from about 0.01% to about 890 10% by weight of the total monomers of a polyether of a polyhydric alcohol, which polyhydric alcohol contains at least four carbon atoms to which are ~tt~ched at least three hydroxyl groups, the polyether cont~ining more than one alkenyl group per molecule. Other monoolefinic monomeric materials can be present in the monomericmixture if desired, even in predo,.lil,ant proportion. Carboxyvinyl polymers are895 subst~nti~lly insoluble in liquid, volatile organic hydrocarbons and are dimensionally stable on exposure to air.
Preferred polyhydric alcohols used to produce carboxyvinyl polymers include polyols selected from the class consisting of oligosaccharides, reduced derivatives thereof in which the carbonyl group is converted to an alcohol group, and soo pentaerythritol; more p~efe~ed are oligosaccharides, most p,~erelled is sucrose. It is prert;,lc:d that the hydroxyl groups ofthe polyol which are modified be etherified with allyl groups, the polyol having at least two allyl ether groups per polyol molecule.
When the polyol is sucrose, it is p,er~l~ed that the sucrose have at least about five allyl ether groups per sucrose molecule. It is preferred that the polyether of the 905 polyol comprise from about 0.01% to about 4% of the total monomers, more plt;r~.~bly from about 0.02% to about 2.5%.
Pl~,fell~d monomeric olefinically unsaturated carboxylic acids for use in producing carboxyvinyl polymers used herein include monomeric, polymerizable, alpha-beta monoolefinically unsaturated lower aliphatic carboxylic acids; more 910 prer~llt;d are monomeric monoolefinic acrylic acids ofthe structure:

W O96/12467 PCTrUS95/11864 CH2 = C(R) - COOH
where R is a substituent selected from the group consisting of hydrogen and lower alkyl groups; most plere.~ed is acrylic acid.
Preferred carboxyvinyl polymers used in formulations of the present invention 915 have a molecular weight of at least about 750,000; more yrere~led are carboxyvinyl polymers having a molecular weight of at least about 1,250,000; most pler~led are carboxyvinyl polymers having a molecular weight of at least about 3,000,000.
The anionic cellulosic thickeners can also include carboxymethyl cellulose and the like.
920 Nonionic cellulosic thickeners include, but are not limited to: 1. hydroxyethyl cellulose; 2. hydl oxylll~lllyl cellulose; 3. hydroxypropyl cellulose; and/or 4.hydroxybutyl methyl cellulose.
A suitable thickener is hydroxy ethyl cellulose, e.g., Natrosol(E~) 250 KR sold by The Aqualon Company.
925 Other thickeners useful herein include acrylated steareth-20 methylacrylate copolymer sold as Acrysolg) ICS-l by l~ohm and Haas Company; the carboxylic poly-mers disclosed in U.S. Pat. 5,318,774, Alban and Deckner, issued Jun. 7, 1994 (said patent being incorporated herein by reference); inorganic salts, i.e., chloride, sulf~t~s7 etc., at a level offrom about 0.1% to about 5%, preferably from about 0.5%
930 to about 3%; and fatty acids and fatty alcohols at a level of from about 1% to about 15%, preferably from about 2% to about 10%.
The liquid personal cle~ncin~ products can be thickened by using polymeric additives that hydrate, swell or molecularly associate to provide body (e.g., hydroxypropyl guar gum).
935 Liquid personal cle~n.cing products, e.g., the liquid soap described hereinbefore, can be made with from about 0.1% to about 5%, preferably from about 0.3% to about 3%, of a cationic polymer, having a molecular weight of from about 1,000 to about 5,000,000, especially those selected from the group consisting of:
(I) cationic polysaccharides;
940 (II) cationic copolymers of saccharides and synthetic cationic monomers, and (III) synthetic polymers selected from the group consisting of:
(A) cationic polyalkylene imines;
(B) cationic ethoxy polyalkylene imines; and (C) cationic poly[N-[-3-(dimethylammonio)propyl]-N'-[3-945 (ethyleneo~y~Lylene dimethylammonio)propyl]urea dichloride].
Detailed lists of suitable cationic polymers are set out in Small et al. and Medcalf et al., incorporated herein by reference.

-2~-Other materials can also be used as optiorlal suspension agents include those that can impart a gel-like viscosity to the composition, such as water soluble or 950 colloidally water soluble polymers like cellulose ethers (e.g., hydroxyethyl cellulose), guar gum, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl guar gum, starch and starch derivatives, and other thickeners, viscosity modifiers, gelling agents, etc.
Mixtures ofthese materials can also be used.
Another type of suspending agent that can be used is xanthan gum. Xanthan 955 gum is biosynthetic gum material that is commercially available. It is a heteropolysaccharide with a molecular weight of greater than 1 million. It is believed to contain D-glucose, D-mannose and D-glucuronate in the molar ratio of about 2.8:2.0:2Ø The polysaccharide is partially acetylated with about 4.7% acetyl. This information and other is found in Whistler, Roy L. Editor Industrial Gums -960 Polysaccharides and Their Derivatives New York: Ac~demic Press, 1973. Kelco, a Division of Merclc & Co., Inc., offers xanthan gum as Keltrol~. The gum, when used as a silicone hair conditioning component suspending agent, will typically be present in pourable, liquid formulations at a level of from about 0.02% to about 3%, preferably from about 0.03% to about 1.2%, in the compositions of the present s6s invention.
In general, the level of optional suspending agent and other viscosity modifiersshould preferably be as low as possible to achieve the benefit for which the material is added. Optional suspending agent thickeners, and viscosity modifiers, etc., whenused are in general used at a level of from about 0.01% to about 10%, most 970 commonly from about 0.02% to about 5.0%, preferably from about 0.1% to about2%, and more preferably from about 0.2% to about 1.0% by weight of the total composition.
3. Water The shampoo compositions of the present invention typically comprise from 975 about 40% to about 89%, preferably from about 50% to about 85%, more preferably from about 60% to about 80%, by weight, of water.
The pH of the shampoo compositions hereof is not generally critical and can be in the range of from 2 to about 10, preferably from about 3 to about 9, more preferably from about 4 to about 8, most preferably from about 5.5 to about 7.5.980 4. Insoluble~ F.tn~ ified FluidHairConditioningA~ent The present compositions will optionally comprise from about 0.05% to about 10%, preferably from about 0.1% to about 8%, more preferably from about 0.2% to about 5%, by weight, of a dispersed phase, i.e., an emulsion, of a water-insoluble, nonvolatile, fluid hair conditioning agent. This component will be suspended in the CA 022ll004 l997-07-2l W O 96/12467 PCT~US95/I186 98s form of droplets, which form a separate, discontinuous phase from the aqueous, continuous phase of the compositions. Number average droplet size is not critical to the invention, but is typically up to about 30 microns, preferably up to about 25 microns, and will typically be at least about 0.1 microns, more typically at least about 1 microns. Suitable fluid hair conditioning agents of this type include nonvolatile sso silicone hair conditioning agents and organic fluids, e.g., oils. This type of conditioning agent is a pl e~el ~ ed ingredient. It has also been found that the surfactant system of the present invention can improve deposition for this type of conditioning agent when suspended by a crystalline suspending agent, as well as for the anti-dandruff agents.
995 By "nonvolatile" what is meant is that the liquid exhibits very low or no significant vapor pressure at ambient conditions (e.g., 25~C), as is understood in the art, in general, less than 0.2 mm Hg (preferably less than 0.1 mm) at 25~C. The nonw ?atile oil preferably has a boiling point at ambient pressure of about 250~C or higi' more preferably about 275~C or higher, most preferably about 300~C or 1000 hig~. Mixtures of ~ ~ conditioning agents can be used. Individual components of the ~ ditioning agent .vhich are miscible may fall outside the boiling point limits, as long the overall conditioning agent is nonvolatile as defined above.
By "water insoluble" what is meant is that the material is not soluble in water (distilled or equivalent) at a concentration of 0.1%, at 25~C.
1005 5. Silicone Hair Conditionin~ Agent The non-volatile, water insoluble silicone hair conditioning agent component of the present invention is nonvolatile and insoluble in the composition. It will be inlel,lli~ed in the shampoo composition so as to be in the form of an emulsion, i.e., a separate, discontin.lol-s phase of dispersed, insoluble droplets. These droplets are 010 suspended with a suspending agent, numerous, non-exclusive suitable examples of which are described below. This dispersed silicone conditioning component will comprise a silicone fluid hair conditioning agent such as a silicone fluid and can also comprise other ingredients, such as a silicone resin to enh~nce silicone fluid deposition efficiency or enhance glossiness of the hair (especially when high refractive 015 index (e.g., above about 1.46) silicone conditioning agents are used (e.g., highly phenylated silicones).
The silicone hair conditioning agent phase can comprise volatile silicone colllpollents. Typically, if volatile silicones are present, it will be incidental to their use as a solvent or carrier for commercially available forms of nonvolatile silicone 1020 materials ingredients, such as silicone gums and resins.
The silicone hair conditioning agent component for use herein will preferably W O96/12467 PCT~US95/11864 have a viscosity of from about 20 to about 2,000,000 centistokes at 2~~C, more preferably from about 1,000 to about 1,800,000, even more preferably from about 50,000 to about 1,500,000, most preferably from about 100,000 to about 1,500,000.
1025 The viscosity can be measured by means of a glass capillary viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July 20, 1 970.
The silicone hair conditioning agent component will generally be used in the shampoo compositions hereof at levels of from about .05% to about 10% by weight of the composition, preferably from about 0.1% to about 8%, more preferably from1030 about 0.2% to about 5%, most preferably from about 0.5% to about 4%. The minimllm level that is used in a particular composition should be effective to provide a conditioning benefit. The maximum level that can be used is not limited by theory, but rather by practicality. It is generally unnecess~ry and expensive to use levels in excess of about 8%, although higher levels can be used if desired.
1035 One type of silicone fluid that can be used herein is a silicone oil. The term "silicone oil" shall mean flowable silicone materials having a viscosity of less than about 1,000,000 centi~tokes at 25~C. Generally, the viscosity of the fluid will be between about 5 and about 1,000,000 centistokes at 25~C, preferably between about 10 and about 100,000. Suitable silicone oils include polyalkyl siloxanes, polyaryl 040 siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, and mixtures thereof. Other insoluble, nonvolatile silicone fluids having hair conditioning properties can also be used.
More particularly silicone oils hereof include polyalkyl or polyaryl siloxanes with the following structure (IX):
1045 R - Si (R)2- O-[- Si ~R)2- ~ -]x- Si (R)2- R (IX) wherein R is aliphatic, preferably alkyl or alkenyl, or aryl, R can be substituted or unsubstitute~, and x is an integer from 1 to about 8,000. Suitable unsubstituted R
groups'include alkoxy, aryloxy, alkaryl, arylalkyl, arylalkenyl, ~lk~mino, and ether-substitllte~, hydroxyl-substit~lte~, and halogen-substituted aliphatic and aryl groups.
1050 Suitable R groups also include cationic amines and quaternary amrnonium groups.
The aliphatic and/or aryl groups substituted on the siloxane chain can have any structure as long as the res~.lting silicones remain fluid at room temperature, are hydrophobic, are neither irritating, toxic nor otherwise harmful when applied to the hair, are compatible with the other components of the composition, are chemically 1055 stable under normal use and storage conditions, are insoluble in the composition, and are capable of being deposited on and, of conditioning, the hair.
The two R groups on the silicon atom of each monomeric silicone unit can repft;sel,l the same group or dif~lenl groups. Preferably, the two R groups represent WO 96/12467 PCT/US9S/1186'1 the same group.
060 Preferred alkyl and alkenyl substituents are C1-Cs alkyls and alkenyls, more preferably from Cl-C4, most preferably from Cl-C2. The aliphatic portions of other alkyl-, alkenyl-, or alkynyl-co..~ g groups (suclh as alkoxy, alkaryl, and alk~mino) J can be straight or branched chains and preferably have from one to five carbon atoms, more preferably from one to four carbon atoms, even more preferably from one to 1065 three carbon atoms, most preferably from one to two carbon atoms. As di~cussed above, the R substit~1ente hereof can also contain amino functionalities, e.g., ~Ik~mino groups, which can be primary, secondary or tertiary amines or quaternary ammonium.
These include mono-, di- and tri-alkylamino and alkoxyamino groups wherein the aliphatic portion chain length is preferably as described above. The R substituents can 1070 also be substituted with other groups, such as halogens (e.g., chloride, fluoride, and bromide), halogenated aliphatic or aryl groups, and hydroxy (e.g., hydroxy substituted aliphatic groups). Suitable halogenated R groups could include, for example, tri-hzloger.zted (preferâbly fluûrû) alkyl grOUpS such as -R1-C~)3, wnerein Rl is C1-C3 alkyl. Examples of such polysiloxanes include polymethyl-3,3,3 075 trifluol ~ pl opylsiloxane.
The nonvolatile polyalkylsiloxane fluids that can be used include, for example, polydimethylsiloxanes. These siloxanes are available, for example, from the General Electric Company in their Viscasil R and SF 96 series, and from Dow Corning in their Dow Corning 200 series.
1080 Other suitable R groups include methyl, methoxy, ethoxy, propoxy, and aryloxy. The three R groups on the end caps of the silicone can also represent the same or difrerellL groups.
Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl. The pl~rt;,led silicones are polydimethyl siloxane, polydiethylsiloxane, 1085 and polymethylphenyl~ilox~ne. Polydimethylsiloxane is especially pre~lled.
The polyalkylaryl siloxane fluids that can be used, also in~ de, for example, polymethylphenylsiloxanes. These siloxanes are available, for example, from the General Electric Company as SF 1075 methyl phenyl fluid or from Dow Corning as 556 Cosmetic Grade Fluid.
1090 The polyether siloxane copolymers that can be used include, for example, a polypropylene oxide modified polydimethylsiloxane (e.g., Dow Corning DC-1248) although ethylene oxide or mixtures of ethylene oxide and propylene oxide can also be used. The ethylene oxide and polypropylene oxide level must be sufflciently low to prevent solubility in water and the composition hereo~
095 Alkylamino substituted silicones that can be used herein include those of the W O96/12467 PCTrUS9~11186 formula:
HO--[si(CH3)2~]x--[si(oH)L(cH2)3NH(cH2)2NH2]o]y_H
in which x and y are integers which depend on the molecular weight, the average molecular weight being approximately between 5,000 and 10,000. This polymer is 1100 also known as "amodimethicone".
Cationic silicone fiuids which can be used in the present compositions include those that correspond to the formula:
(Rl)aG3 a-Si-(-OSiG2)n-(-OSiGb(Rl)2 b)m~~~SiG3 a(Rl)a in which G is chosen from the group consisting of hydrogen, phenyl, OH, C 1-Cg alkyl 1105 and preferably methyl; a denotes 0 or an integer from 1 to 3, and preferably equals 0;
b denotes 0 or 1 and preferably equals 1; the sum n~m is a number from 1 to 2,000 and preferably from 50 to 150, n being able to denote a number from 0 to 1,999 and preferably from 49 to 149 and m being able to denote an integer from 1 to 2,000 and preferably from 1 to 10;
1110 R1 is a monovalent radical of formula CqH2qL in which q is an integer from 2 to 8 and L is chosen from the groups:
-N(R2)CH2-CH2-N(R2)2 -N(R.2)2 N~R2)3 A-1115 N~R2)CH2-CH2-N~(R2)3 A
in which each R2 is chosen from the group consisting of hydrogen, phenyl, benzyl, a saturated hydrocarbon radical, preferably an alkyl radical co.,~ g from 1 to 20 carbon atoms, and A- denotes a halide ion.
An especially p,~rel,ed cationic silicone corresponding to the formula 1120 imme~ ely above is the polymer known as "trimethylsilylamodimethicone," of formula (X):
(cH3)3-sio-[si(cH3)2o]n-[si(cH3)[(cH2)3NH(cH2)2NH2]o]m-si(cH3)3 (X) Other cationic silicone pol,vmers which can be used in the present compositions correspond to the formula (Xl):
1125 (R3)3-sio-[si(cH3)[E~4cH2cHoHcH2N+(R3)3Q-]o]r-[si(cH3)2o]s-si(R3)3 (XI) in which each R3 denotes a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, and more especially an alkyl or alkenyl radical such as methyl;
Q~ is a halide ion, preferably chloride;
r denotes an average shti~tis~l value from about 2 to about 20, preferably from about 1130 2 to about 8;
s denotes an average statistical value from about 20 to about 200, and preferably from about 20 to about 50.

W O96/12467 PCT~US95/1186 These compounds are described in greater detail in U.S. Pat. No. 4,185,017, incorporated herein by reference.
1135 A polymer of this class which is especially prere"ed is that sold by Union Carbide under the name "~JCAR Silicone ALE 56".
Another silicone fluid that can be especially useful in the silicone conditioning agents is insoluble silicone gum. The term "silicone gum", as used herein, meanspolyorganosiloxane materials having a viscosity at 25~C of greater than or equal to 1140 1,000,000 centistokes. Silicone gums are described by Petrarch and others inclll-ling U.S. Pat. No. 4,152,416, Spitzer et al., issued May 1, 1979, and Noll, Walter, Chemistry and Technology of Silicones, New York: Ac~dçmic Press 1968. Also describing silicone gums are General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76. All of these described references are incorporated 45 herein by reference. The "silicone gums" will typically have a mass molecular weight in excess of about 200,000, generally between about 200,000 and about 1,000,000.Specific exal~ples include polydimethy;siioxane, (poiydimethyisiioxane) (methylvinylsiloxane) copolymer, poly(dimethylsiloxane) (diphenyl ~ siloxane)(methylvinylsiloxane) copolymer and mixtures thereof.
1150 Preferably the silicone hair conditioning agent comprises a mixture of a polydimethylsiloxane gum, having a viscosity greater than about 1,000,000 centistokes and polydimethylsiloxane oil having a viscosity of from about 10 centistokes to about 100,000 centistokes, wherein the ratio of gum to fluid is from about 30:70 to about 70:30, preferably from about 40:60 to about 60:40.
1155 Another category of nonvolatile, insoluble silicone fluid conditioning agents are high refractive index silicones, having a refract;ve index of at least about 1.46, preferably at least about 1.48, more pre~l~bly at least about 1.52, most preferably at least about 1.55. Although not j~tended to necessarily be limiting the refractive index of the polysiloxane fluid will generally be less than about 1.70, typically less 1160 than about 1.60. Polysiloxane "fluid" in~ des oils as well as gums.
The high refractive index polysiloxane fluid suitable for purposes hereof in~ludes those represented by general Formula (IX) above, as well as cyclic polysiloxanes such as those represented by the formula below:
L ~
[SiR20]

1165 wherein R is as defined above, n is from about 3 to about 7, preferably from 3 to 5.
The high refractive index polysiloxane fluids hereof contain a sufficient amount W O96/12467 PCTrUS95/1186 of aryl-cont~ining R substituçnts to increase the refractive index to the desired level, which is described above. In addition, R and n must be selected so that the material is nonvolatile, as defined above.
1170 Aryl-co.~ g substit-1çnt~ contain alicyclic and heterocyclic five and sixmembered aryl rings, and substituenti cont~ining fused five or six membered rings.
The aryl rings themselves can be substituted or unsubstituted. Substituents include aliphatic substit~lent.s7 and can also include alkoxy subctit~1çnt~t~ acyl substit~lents, ketones, halogens (e.g., Cl and Br), amines, etc. Exemplary aryl-cont~ining groups 1175 include substituted and unsubstituted arenes, such as phenyl, and phenyl derivatives such as phenyls with Cl-Cs alkyl or alkenyl substituents, e.g., allylphenyl, methyl phenyl and ethyl phenyl, vinyl phenyls such as styrenyl, and phenyl alkynes (e.g., phenyl C2-C4 alkynes). Heterocyclic aryl groups include substituents derived from furan, imi~ole, pyrrole, pyridine, etc. Fused aryl ring substit~lent.~ include, for 1180 example, napthalene, coumarin, and purine.
j In general, the high refractive index polysiloxane fluids hereof will have a degree of aryl-cor.~ ing substituen~ of at least about 15%, preferably at least about 20%, more ple~l~bly at least about 25%, even more preferably at least about 35%,most preferably at least about 50%. Typically, although it is not int~.n~ed to 1185 nec~ss~rily limit the invention, the degree of aryl substitution will be less than about 90%, more generally less than about 85%, preferably from about 55% to about 80%.These polysiloxane fluids are also characterized by relatively high surface tensions as a result of their aryl substitution. In general, the polysiloxane fluids hereof will have a surface tension of at least about 24 dynes/cm2, typically at least about 27 1190 dynes/cm2. Surface tension, for purposes hereof, is measured by a de Nouy ring tensiometer according to Dow Corning Corporate Test Method CTM 0461, Nov. 23, 1971. Changes in surface tension can be measured according to the above test method or accordillg to ASTM Method D 1331.
The p~er~.,ed high refractive index polysiloxane fluids hereof will have a 1195 combination of phenyl or phenyl derivative substit~lents (preferably phenyl), with alkyl substituent.~, pl~rt;l~ly Cl-C4 alkyl (most pre~erably methyl), hydroxy, Cl-C4 alkylamino (especially-R1NHR2NH2 where each Rl and R2 independently is a Cl-C3 alkyl), alkenyl, and/or alkoxy.
High refractive index polysiloxane are available commercially from Dow 1200 Corning Corporation (Midland, Michigan, U.S.A.) Huls America (Piscataway, New Jersey, U.S.A.), and General Electric Silicones (Waterford, New York, U.S.A.).
It is prere,l~d to utilize high refractive index silicones in solution with a spreading agent, such as a silicone resin or a surfactant, to reduce the surface tension by a sufficient amount to ~nh~nce spreading and thereby enhance glossiness 1205 (subsequent to drying) of hair treated with the composition. In general, a sufficient amount of the spreading agent to reduce the surface tension of the high refractive index polysiloxane fluid by at least about 5%, preferably at least about 10%, more preferably at least about 15%, even more pre~erably at least about 20%, most preferably at least about 25%. Reductions in surface tension of the polysiloxane1210 fluid/spreading agent mixture can provide improved shine enhancement of the hair.
Also, the spreading agent will preferably reduce the surface tension by at leastabout 2 dynes/cm2, preferably at least about 3 dynes/cm2, even more preferably at least about 4 dynes/cm2, most preferably at least about 5 dynes/cm2.
The surface tension of the mixture of the polysiloxane fluid and the spreading 215 agent, at the proportions present in the final product, is preferably 30 dynes/cm2 or less, more preferably about 28 dynes/cm2 or less most preferably about 25 dynes/cm2 or less. Typically the surface tension will be in the range of from about 15 to about 30, more typically from about 18 to about 28, and most generally from about 20 to about 25 dynes/cm2.
220 The weight ratio of the highly arylated polysiloxane fluid to the spreading agent will, in general, be between about 1000:1 and about 1:1, preferably between about 100:1 and about 2:1, more preferably between about 50:1 and about 2:1, most preferably from about 25:1 to about 2:1. When fluorinated surf~ct~nts are used, particularly high polysiloxane: spreading agent ratios can be effective due to the 1225 efficiency of these surf~ct~nt~. Thus is contemplated that ratios significantly above about 1000:1 canbeused.
Incorporated herein by lerelence is Silicon Compounds distributed by Petrarch Systems, Inc., 1984. This reference provides an extensive (though not exclusive)listing of suitable silicone fluids.
1230 An optional ingredient that can be included in the silicone conditioning agent is silicone resin. Silicone resins are highly crosslinked polymeric siloxane systems. The cro.~.~lin~ing is introduced through the incorporation of trifunctional and tetra-functional silanes with monofunctional or difunctional, or both, silanes during m~mlf~ctllre of the silicone resin. As is well understood in the art, the degree of 235 crosslinking that is required in order to result in a silicone resin will vary according to the specific silane units incorporated into the silicone resin. In general, silicone materials which have a sufficient level of trifunctional and tetrafunctional siloxane monomer units (and hence, a sufficient level of cros~linking) such that they dry down to a rigid, or hard, film are considered to be silicone resins. The ratio of oxygen 1240 atoms to silicon atoms is indicative of the level of cros~linking in a particular silicone WQ 96/12467 PCTrUS9~/11864 material. Silicone materials which have at least about 1.1 oxygen atoms per silicon atom will generally be silicone resins herein. Preferably, the ratio of oxygen:silicon atoms is at least about 1.2:1Ø Silanes used in the m~mlf~ctllre of silicone resins include monomethyl-, dimethyl-, trimethyl-, monophenyl-, diphenyl-, methylphenyl-, 1245 monovinyl-, and methylvinyl-chlorosilanes, and tetrachlorosilane, with the methyl-substituted silanes being most commonly ~Itili7~d P~Çel~ed resins are offered byGeneral Electric as GE SS4230 and SS4267. Commercially available silicone resinswill generally be supplied in a dissolved form in a low viscosity volatile or nonvolatile silicone fluid. The silicone resins for use herein should be supplied and incorporated 1250 into the present compositions in such dissolved form, as will be readily appare--l to those skilled in the art.
Background material on silicones inclu~ing sections discu~ing silicone fluids, gums, and resins, as well as m~nllf~ctllre of silicones, can be found in Encyclopedia of Polymer Science and Engineering, Volume 15, Second Edition, pp. 204-3087 John 1255 Wiley & Sons, Inc., 1989, incorporated herein by reference.
Silicone materials and silicone resins in particular, can conveniently be identified according to a shorthand nom~ncl~hlre system well known to those skilled in the art as "MDTQ" nom~ncl~tl-re. Under this system, the silicone is described according to the presence of various siloxane monomer units which make up the silicone. Briefly, 1260 the symbol M denotes the monofunctional unit (CH3)3SiOo 5; D denotes the difunctional unit (CH3)2SiO; T denotes the trifimctional unit (CH3)SiO1 5; and Qdenotes the quadri- or tetra-functional unit SiO2. Primes of the unit symbols, e.g., M', D', T', and Q' denote substituents other than methyl, and must be specifically defined for each occurrence. Typical alternate substihlen~s include groups such as 1265 vinyl, phenyls, amines, hydroxyls, etc. The molar ratios of the various units, either in terms of subscripts to the symbols indicating the total number of each type of unit in the silicone (or an average thereof) or as specifically indicated ratios in co---bination with molecular weight complete the description of the silicone material under the MDTQ system. Higher relative molar amounts of T, Q, T' and/or Q' to D, D', M
1270 and/or M' in a silicone resin is indicative of higher levels of cros~linking As di~c~ed before, however, the overall level of cro~linkin~ can also be indicated by the oxygen to silicon ratio.
The silicone resins for use herein which are p~ere~ed are MQ, MT, MTQ, MDT and MDTQ resins. Thus, the p~ere~.ed silicone substituent is methyl.
1275 Especially p-~;;re.. ed are MQ resins wherein the M:Q ratio is from about 0.5:1.0 to about 1.5:1.0 and the average molecular weight of the resin is from about 1000 to about 10,000.

WO 96/12467 PCT/US9~/1186 1 The weight ratio of the nonvolatile silicone fluid, having refractive index below about 1.46, to the silicone resin component, when used, is preferably from about 4:1 1280 to about 400:1, preferably this ratio is from about 9:1 to about 200:1, more preferably from about l9:1 to about 100:1, particularly when the silicone fluid component is a polydimethylsiloxane fluid or a mixture of polydimethylsiloxane fluid and polydimethylsiloxane gum as described above. Insofar as the silicone resin forms a part of the same phase in the compositions hereof as the silicone fluid, i.e., the 285 conditioning active, the sum of the fluid and resin should be included in determining the level of conditioning agent in the composition.
Silicones which can be utilized in the compositions of the present invention include those described in U.S. Pat. No. 5,154,849, Visscher et al., which is herein incorporated by reference.
1290 6. Organic Hair Conditionin~ A~ent The organic fluid hair conditioning agents hereof generally will have a viscosity of about 3 million cS or less, preferably about 2 million cS or less, more preferably about 1.5 million cS or less (as measured by a Bohlin VOR Rheometer, or equivalent). For purposes hereof, "organic" shall not include silicone hair 1295 conditioning agents.
The organic hair conditioning materials hereof include fluids selected from the group consisting of hydrocarbon fluids and fatty esters. The fatty esters hereof are characterized by having at least 10 carbon atoms, and include esters with hydrocarbyl chains derived from fatty acids or alcohols, e.g., mono-esters, polyhydric alcohol 1300 esters, and di- and tri-carboxylic acid esters. The hydrocarbyl radicals of the fatty esters hereof can also include or have covalently bonded thereto other conlpaLible functionalities, such as amides and alkoxy moieties (e.g., ethoxy or ether link~ges7 etc.).
Hydrocarbon fluids include oils such as cyclic hydrocarbons, straight chain 1305 aliphatic hydrocarbons ~saturated or unsaturated), and branched chain aliphatic hydrocarbons (saturated or unsalul ~ted), and mixtures thereof. Straight chain hydrocarbon oils will preferably contain from about 12 to about l9 carbon atoms,although it is not necess~rily meant to limit the hydrocarbons to this range. Branched chain hydrocarbon oils can and typically can contain higher numbers of carbon atoms.
310 Also encop~csed herein are polymeric hydrocarbons of alkenyl monomers, such as C2-C6 alkenyl monomers. These polymers can be straight or branched chain polymers. The straight chain polymers will typically be relatively short in length, having a total number of carbon atoms as described above for straight chain hydrocarbons in general. The branched chain polymers can have subst~nti~lly higher 1315 chain length. The number average molecular weight of such materials can vary widely, but will typically be up to about 500, preferably from about 200 to about 400, more preferably from about 300 to about 350. Specific examples of suitable materials include paraffin oil, mineral oil, saturated and unsaturated dodecane, saturated and unsaturated tridecane, saturated and unsaturated tetradecane, saturated and 1320 unsaturated pent~dec~nç7 saturated and unsaturated hexadecane, and mixtures thereof. Branched-chain isomers of these compounds, as well as of higher chain length hydrocarbons, can also be used. Exemplary branched-chain isomers are highly branched saturated or unsaturated ~lk~nec, such as the permethyl-substituted isomers, e.g., the permethyl-substituted isomers of hexadecane and eiocosane, such as 1325 2,2,4,4,6,6,8,8-dimethyl-10-methyll-ndec~ne and 2,2,4,4,6,6-dimethyl-8-methylnonane, sold by Permethyl Corporation. Polymeric organic materials are also useful conditioning agents. A plerelled organic polymer is polybutene, such as the copolymer of isobutylene and butene. A commercially available material of this type if L-14 polybute,ie l.o... ~IIOCO Che.ll;Cal CO. (Chicago, Illinois, U.S.A.). Oiher 1330 polymeric conditioners can include polyisoprene, polybutadiene, and otherhydrocarbon polymers of C4 to C12 straight and branched chain, mono- and di-unsaturated aliphatic monomers, and derivatives thereof.
Monocarboxylic acid esters hereof include esters of alcohols and/or acids of theformula R'COOR wherein alkyl or alkenyl radicals and the sum of carbon atoms in R' 1335 and R is at least 10, preferably at least 20.
Fatty esters include, for example, alkyl and alkenyl esters of fatty acids having aliphatic chains ~,vith from about 10 to about 22 carbon atoms, and alkyl and alkenyl fatty alcohol carboxylic acid esters having an alkyl and/or alkenyl alcohol-derived aliphatic chain with about 10 to about 22 carbon atoms, and combinations thereof.
1340 Examples include isopropyl isostearate, hexyl laurate, isohexyl laurate, isohexyl p~lmit~te, isopropyl p~lmit~te, decyl oleate, isodecyl oleate, hexadecyl stearate, decyl stearate, isopropyl isostearate, dihexyldecyl adipate, lauryl lactate, myristyl lactate, cetyl lactate, oleyl stearate, oleyl oleate, oleyl myristate, lauryl acetate, cetyl propionate, and oleyl adipate.
1345 The mono-carboxylic acid ester however need not necessarily contain at least one chain with at least 10 carbon atoms, so long as the total number of aliphatic chain carbon atoms is at least 10. Examples include diisopropyl adipate, diisohexyl adipate, and diisopropyl seb~c~te.
Di- and tri-alkyl and alkenyl esters of carboxylic acids can also be used. These1350 in~ rie, for example, esters of C4-Cg dicarboxylic acids such as C1-C22 esters (pr~;rel~bly C1-C6) of succinic acid, glutaric acid, adipic acid, hexanoic acid, W O96/12467 PCTrUS95/1186 heptanoic acid, and octanoic acid. Specific example include isocetyl stearyol stearate, diisopropyl adipate, and tristearyl citrate.
Polyhydric alcohol esters include alkylene glycol esters, for example ethylene 1355 glycol mono and di-fatty acid esters, diethylene glycol mono- and di-fatty acid esters, polyethylene glycol mono- and di-fatty acid esters, propylene glycol mono- and di-fatty acid esters, polypropylene glycol monooleate, polypropylene glycol 2000 monostearate, ethoxylated propylene glycol monostearate, glyceryl mono- and di-fatty acid esters, polyglycerol poly-fatty acid esters, ethoxylated glyceryl 360 monostearate, 1,3-butylene glycol monostearate, 1,3-butylene glycol distearate, polyoxyethylene polyol fatty acid ester, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters are sati~f~ctory polyhydric alcohol esters for use herein.
Glycerides include mono-, di-, and tri-glycelides. More specifically, included are the mono-, di-, and tri-esters of glycerol and long chain carboxylic acids, such as 365 C 1 -C22 carboxylic acids. A variety of these types of materials can be obtained from vegetable and animal fats and oils, such as castor oil, safflower oil, cottonseed oil, corn oil, olive oil, cod liver oil, almond oil, avocado oil, palm oil, sesame oil, lanolin and soybean oil. Synthetic oils include triolein and tristearin glyceryl dilaurate.
Preferred glycerides are di-, and tri-glycerides. Especially preferred are triglycerides.
370 7. Other Optional In~redients~ Primarily for Shampoo Compositions A variety of other optional ingredients are described below. The description below is exemplary in nature.
Such optional ingredients include, for example, anti-dandruff actives such as zinc pyrithione, octopirox, sel~ni~-m di~--lfit1~7 sulfur, coal tar, and the like, 375 preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imi~olidinyl urea; cationic conditioning agents, in~ ding both cationic conditioning surf~ct~nts and cationic conditioning polymers; quaternary polymeric foam boosters, such as Polyquaternium 10, preferably from about 0.01% to about 0.2%, by weight of the composition; fatty alcohols; block polymers of ethylene oxide and propylene oxide 1380 such as Pluronic F88 offered by BASF Wyandotte; sodium chloride, sodium sulfate;
ammonium xylene sulfonate; propylene glycol; polyvinyl alcohol; ethyl alcohol; pH
adjusting agents such as citric acid, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate, etc.; perfumes; and dyes. These optional ingredients are typically used at levels offrom about 0.01% to about 10% ofthe composition. The shampoo 1385 compositions herein can also contain a builder, but preferably less than about 1%, or none at all. This list of optional ingredients is not meant to be exclusive, and other optional components can be utili7ed.

8. Other Optional Ingredients Primarily for Non-Shampoo Compositions Another component useful in the present invention is a nonionic, i.e., 1390 polyglycerol ester (PGE).
Groups of substances which are particl~larly suitable for use as nonionic surfRct~nt~ are alkoxylated fatty alcohols or alkylphenols, preferably alkoxylated with ethylene oxide or mixtures of ethylene oxide or propylene oxide; polyglycol esters of fatty acids or fatty acid amides; ethylene oxide/propylene oxide block polymers;1395 glycerol esters and polyglycerol esters; sorbitol and sorbitan esters; polyglycol esters of glycerol; ethoxylated lanolin derivatives; and alkanolamides and sucrose esters.
A plefelled liquid cleansing composition also contains from about 0.5% to about 10% of an emollient selected from the group consisting of esters of fatty acids;
glycerin mono-, di-, and tri-esters; epidermal and sebaceous hydrocarbons such as 1400 cholesterol, cholesterol esters, squalene, squalane; lanolin and derivatives, mineral oil, silicone oils and gums, and mixtures thereof and the like.
Other ingredients of the present invention are selected for the various applications. E.g., alcohols, hydloLl(Jpes, colorants, and fillers such as talc, clay, calcium carbonate and dextrin can also be used. Cetearyl alcohol is a mixture of cetyl 1405 and stearyl alcohols. Preservatives, e.g., trisodium etidronate and sodium ethylenedi~minetetrRRcetRte (EDTA), generally at a level of less than 1% of the composition, can be incorporated in the cleansing products to prevent color and odor degradation. ~ntibRcterials can also be incorporated, usually at levels up to 1.5%.
Salts, both organic and inorganic, can be incorporated into the compositions of the 1410 present invention. Examples include sodium chloride, sodium isethionate, sodium sulfate, and their equivalents.
The cleansing bath/shower compositions can contain a variety of nonessçnti~l optional ingredients suitable for rendering such compositions more desirable. Such conventional optional ingredients are well known to those skilled in the art, e.g., 415 preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea; other thickeners and viscosity modifiers such as Cg-C 1 8 ethanolamide (e.g., coconut ethanolamide) pH adjusting agents such as citric acid, succinic acid, phosphoric acid, sodium hydroxide, etc.; suspending agents such as mR~nesil-m/al~lmimlm silicate; perfumes; dyes; and sequestering agents such as 1420 disodium ethylenerliRmine tetrRRcetRte.
III. Method Of Use For Shampoo Compositions The present compositions are used in a conventional manner for cleaning hair, controlling dry skin on the scalp, and to provide olfactory aesthetic benefit. The compositions hereof can also be effective for cleaning the skin (e.g., the body in .

WO 96/12467 PCT/US95/1186~1 1425 general, inclllrlin~ the underarm and crotch areas). An effective amount of the composition, typically from about 1 g to about 20 g of the composition, for cleaning hair or other region of the body, is applied to the hair or other region that has preferably been wetted, generally with water, and then rinsed off. Application to the hair typically inr.ludes working the composition through the hair such that most or all 430 of the hair is contacted with the composition. A~er the rinse step, the wet hair is normally dried, e.g., with an electric hair dryer.
IV. Method Of Use For Personal Cleansin~ Non-Shampoo Compositions The present compositions are used in a conventional manner for cleaning the skin and/or the body, and to provide olfactory aesthetic benefit. An effective amount 1435 of the composition, typically from about 1 g to about 15 g of the composition, is applied to the body that has preferably been wetted, generally with water.
Application to the body inr.l~-des dispensing of the composition onto the hand, onto the body, or onto a washing implement, e.g., wash cloth, sponge, etc., and typically incl~ldes working the composition with the hands to develop lather. The lather can 440 stand on the body for a length of time or can be rinsed immediately with water. Once the product is rinsed from the body the washing procedure can be repeated.
C. Hair Care And Topical Skin Care Compositions Which Are Not Normally Rinsed (Removed) The enduring perfumes of the present invention can be formul~ted into a wide variety of product types which are not normally removed by rinsing, in~lu(ling hair conditioner, hair spray, hair gel, hair tonic, mousse, hair curler, hair straightener, deodorant, antipe~ , skin lotion, skin moisturizer, skin softening lotion, suntan lotion, sun screen lotion, sunless tanning composition, skin bleaching composition, perfume, cologne, topical pharm~.eutical skin care composition, e.g., anti-acne 450 composition, non-steroidal anti-fl~mm~tory composition, steroidal anti-fl~mm~tory composition, antipruritic composition, ~nesthetic composition, antimicrobial composition, and the like. The additional components required to formulate such products vary with product type and can be routinely chosen by one skilled in the art.
The following is a description of some of these compositions and additional 1455 components.
I. Hair Care Compositions The hair care compositions of the present invention can comprise a carrier, or amixture of such carriers, which are suitable for application to the hair. The carriers are present at from about 0.5% to about 99.5%, preferably from about 5.0% to about 1460 99.5%, more preferably from about 10.0% to about 98.0%, of the composition. As used herein, the phrase "suitable for application to hair" means that the carrier does W O96/12467 PCT~US95/1186 not damage or negatively affect the aesthetics of hair or cause irritation to the underlying skin.
Carriers suitable for use with hair care compositions of the present invention 1465 inr.l~ldç, for example, those used in the formulation of hair sprays, mousses, tonics, gels, conditioners, and rinses. The choice of applop"ate carrier will also depend on the particular copolymer to be used, and whether the product formlll~ted is meant to be left on the surface to which it is applied (e.g., hair spray, mousse, tonic, or gel) or rinsed offafter use (e.g., conditioner, rinse).
1470 The carriers used herein can include a wide range of components conventionally used in hair care compositions. The carriers can contain a solvent to dissolve or disperse the particular copolymer being used, with water, the Cl-C6 alcohols, and mixtures thereof being prer~" ~d; and water, methanol, ethanol, isopropanol, propylene carbonate, and mixtures thereof being more plere~d. The 1475 carriers can also contain a wide variety of additional materials incl~l~in~ but not limited to, acetone, hydrocarbons (such as isobutane, hexane, decene), halogenated hydrocarbons (such as Freons), esters (such as ethyl acetate, dibutyl phth~l~te), and ~ volatile silicon derivatives (especially siloxanes such as phenyl pent~met~yl disiloxane, methoxypropyl heptamethyl cyclotetrasiloxane, chloropropyl pentamethyl disiloxane, 1480 hydroxypropyl pentamethyl disiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, cyclomethicone, and dimethicone having for example, a viscosity at 25~C of about 15 centipoise or less), and mixtures thereof. When the hair care composition is a hair spray, tonic, gel, or mousse the pl efel . ed solvents include water, ethanol, volatile silicone derivatives, and mixtures thereof. The solvents used in such 1485 mixtures can be miscible or ;.. ~ ble with each other. Mousses and aerosol hair sprays can also utilize any of the conventional propellants to deliver the material as a foam (in the case of a mousse) or as a fine, uniform spray (in the case of an aerosol hair spray). Examples of suitable propellants include materials such as trichlorofluorometh~ne, dichlorodifluorometh~ne, difluoroethane, dimethylether, 1490 propane, n-butane or isobutane. A tonic or hair spray product having a low viscosity can also utilize an emulsifying agent. Examples of suitable emulsifying agents include nonionic, cationic, anionic surf~ct~nt.c, or mixtures thereof. Fluorosurf~ct~nts are especially plefe"ed, particularly if the product is a hair spray composition and most especially if it is a spray composition having relatively low levels of volatile organic 1495 solvents, such as alcohols, and relatively high levels of water (e.g., in excess of about 10%, by weight water). If such an emulsifying agent is used, it is preferably present at a level of from about 0.01% to about 7.5% of the composition. The level of propellant can be adjusted as desired but is generally from about 3% to about 30% of mousse compositions and from about 15% to about 50% of the aerosol hair spray 1500 compositions.
Suitable spray containers are well known in the art and include conventional, non-aerosol pump sprays i.e., "atomizers," aerosol containers or cans having propellant, as described above, and also pump aerosol containers lltili~ing compressed air as the propellent. Pump aerosol containers are disclosed, for example, in U.S.
505 Patents 4,077,441, March 7, 1978, Olofsson and 4,850,577, July 25, 1989, TerStege, both incorporated by reference herein, and also in U.S. Serial No. 07/839,648, Gosselin, Lund, Sojka, and Lefebvre, filed February 21, 1992, "Consumer Product Package Incorporating A Spray Device Utilizing Large Diameter Bubbles." Pump aerosols hair sprays using co,l~pl essed air are also currently marketed by The Procter 1510 & Gamble Company under their tra~n~me Vidal Sassoon Airspray g) hair sprays.
Where the hair care compositions are conditioners and rinses the carrier can include a wide variety of conditioning materials. Various additional components useful in hair care compositions are described in U.S. Patent No. 5,106,609, to Bolich, Jr. et al., issued April 21, 1992; and U.S. Patent No. 4,387,090, to Bolich, Jr.
1515 issued June 7, 1983; which are incorporated by reference herein. Some of these additional components are described below.
II. Topical Skin Care Compositions The topical cosmetic and pharm~celltic~l compositions of the present invention can comprise a carrier. The carrier should be "cosmetically and/or pharm~ceutically 1520 acceptable", which means that the carrier is suitable for topical application to the skin, has good aesthetic prope,~ies, is co...palible with the copolymers of the present invention and any other components, and will not cause any untoward safety or toxicity concerns.
The carrier can be in a wide variety of forms. For example, emulsion carriers, 525 in~lllrling but not limited to, oil-in-water, water-in-oil, water-in-oil-in-water, and oil-in-water-in-silicone emulsions, are useful herein. These emulsions can cover a broad range of viscosities, e.g, from about 100 cps to about 200,000 cps. These emulsions can also be delivered in the form of sprays using either mechanical pump containers or pressurized aerosol containers using conventional propellants. These carriers can also 1530 be delivered in the form of a mousse. Other suitable topical carriers include anhydrous liquid solvents such as oils, alcohols, and silicones (e.g., mineral oil, ethanol, isopropanol, dimethicone, cyclomethicone, and the like); aqueous-based single phase liquid solvents (e.g., hydro-alcoholic solvent systems); and thickened versions of these anhydrous and aqueous-based single phase solvents (e.g., where the 5~5 viscosity of the solvent has been increased to form a solid or semi-solid by the W O96112467 PCTrUS9511186 addition of applc p~iate gums, resins, waxes, polymers, salts, and the like). Examples of topical carrier systems useful in the present invention are described in the following four references all of which are incorporated herein by reference in their entirety:
"Sun Products Formulary" Cosmetics & Toiletries, vol. 105, pp. 122-139 (December1540 1990); "Sun Products Formulary", Cosmetics & Toiletries, vol. 102, pp. 117-136 (March 1987); U.S. Patent No. 4,960,764 to Figueroa et al., issued October 2, 1990;
and U.S. Patent No. 4,254,105 to Fukuda et al., issued March 3, 1981.
The carriers of the skin care compositions can comprise from about 50% to about 99% by weight of the compositions of the present invention, preferably from 1545 about 75% to about 99%, and most preferably from about 85% to about 95%.
Preferred co.smetic~lly and/or pharm~ceutically acceptable topical carriers include hydro-alcoholic systems and oil-in-water emulsions. When the carrier is a hydro-alcoholic system, the carrier can comprise from about 1% to about 99% of ethanol, isopropanol, or mixtures thereof, and from about 1 % to about 99% of water.
i55û ~ore plele.,ed is a carrier comprising from a~out 5% to about 60% of ethanoi, isoplopanol, or mixtures thereof, and from about 40% to about 95% of water.
Especially plerel,~;d is a carrier comprising from about 20% to about 50% of ethanol, isopropanol, or mixtures thereof, and from about 50% to about 80% of water. Whenthe carrier is an oil-in-water emulsion, the carrier can include any of the common 1555 excipient ingredients for plepa,ing these emulsions. In fine fragrances, the carrier is typically ethanol at levels of from about 50% to about 85%, whereas in colognes, the carrier level is even higher, e.g., from about 80% to about 95%.
III. Antipe, ~pi, ~n~ and/or Deodorant Compositions 1. Carriers.
1560 Carriers for allLipel~ Ls and deodorants are well known in the art. Some particularly desirable ones are disclosed in U.S. Pat. 4,944,937, McCall, issued Jul.
31, 1990, especially at Col. 2, line 51 through Col. 7, line 11 (Cosmetic Sticks); U.S.
Pat. 4,985,238, Tanner, Nunn, Jr., and Luebbe, issued Jan. 15, 1991, especially at Col. 2, line 41 through Col. 3, line 32 and Col. 5, line45 through Col. 6, line 31 (Low 1565 Residue Alllipel~p;l~ Sticks); U.S. Pat. 5,019,375, Tanner, Nunn, Jr., and Luebbe, issued May 28, 1991, especially at Col. 3, line 16 lhrough Col. 3, line 35 and Col. 4, line 64 through Col. 7, line 10 (Low Residue Antipel~.ilalll Creams); U.S. Pat.
5,069,897, Orr, issued Dec. 3, 1991, especially at Col. 3, line 1 through Col. 4, line 49 and Col. 5, line 65 through Col. 6, line 64 (Antip~ uilanL Creams); U.S. Pat.570 5,156,834, Beckmeyer, Davis, and Kelm, issued Oct. 20 1992, especially at Col. 4, line 8 through Col. 5, line 64 (Anitpel~l)ilalll Compositions); U.S. Pat. 5,200,174, Gardlik and Hofrichter, issued Aug. 6 1993, especially at Col. 5, line 16 through Col.

W O96/12467 PCT~US95/1186 . -43-7, line 34 and Col. 10, line 24 through Col. 12, line 44 (Gel Stick Antipel~h~
Composition Cont~ining 2-Oxazolidinone Derivative and Process for Making Them);
1575 U.S. Pat. 5,284,64~, Juneja, issued Feb. 8, 1994, especially at Col. 3, line 55 through Col. 5, line 42 (Deodorant Gel Sticks Co~ g l-Hydroxy Pyridinethione Active);
and U.S. Pat. 5,298,326, Orr and Newcomer, issued Mar 29, 1994, especially at Col.

6, line 14 through Col. 8, line 21 (Liquid Antipel~pil~nl Composition), all of said patents being incorporated herein by reference. These patents also disclose many of 1580 the other ingredients that are useful in antipel~ and deodorant products.
Some antipels,uil~nl gel stick compositions ofthe present invention include the ingredients rli~c~lssed below. Although the term "stick" as utilized herein includçs semi-solid forms (i.e., preferably having a viscosity of at least about 1,000,000 centipoise at 25~C), solid forms (i.e., preferably having an average penetration value 1585 within a given production batch from about 3 to about 25 mm over a period of 5 seconds as measured utili7.ing American Society for Testing Materials (ASTM) Method D-5, with a penetration cone (Model H1312; sold by Humbolt Manufacturing Company) weighing 2.0 g (making the total mass 50 g and a Sommer & Runge Model PNR10 Penetrometer) are pl~;relled.
1590 2. Gelling A~ent:
The "gelling agent" as used herein is a mixture of a primary gellant and a secondary gellant; both rli~cllssed hereinafter. The primary gellant is selected from the group consisting of 12-hydroxystearic acid, esters of 12-hydroxystearic acid, amides of 12-hydroxystearic acid and mixtures thereof. The secondary gellant is selected 1595 from the group con~i~ting of n-acyl amino acid derivatives. The level of the gelling agent within the composition is typically from about 1% to about 15%; preferably, from about 3% to about 12%; more preferably, from about 5% to about 10%. The primary gellant:secondary gellant ratio is typically between about 1:2 and about 20:1;
preferably, from about 1:1 to about 10:1; more preferably, from about 2:1 to about 1600 7:1; and even more preferably, from about 3:1 to about 5:1. The primary gellant:secondary gellant ratio appears to be more critical when the level of polar, non-volatile liquid within the liquid base material (~i~cussed hereina~er) in the composition is relatively low; e.g., below about 25%.
This gelling agent offers significant benefits when used in an antipel~ nl gel 1605 stick. The gelling agent of the present invention exhibits unexpected benefits, e.g., decreased residue upon application to the skin, increased hardness and better ~esthetics, relative to a similar composition having either of the two gellants alone. In fact, these gellants in colllbil-aLion are more effective than either alone so that the overall level of gelling agent within the composition can be reduced while ~ g 1610 such desirable stick characteristics.
Moreover, when these gellants are used together as the gelling agent of the present invention, degradation of the gelling agent by the acidic antipe-~pil~ active during m~mlf~ctllring is unexpectedly significantly reduced; i.e., as compared to each gellant alone. To further reduce degredation, a heated solution of the gelling agent 1615 and the liquid base material preferably remains in solution such that the antipe.spi-~l-L
active can be substantially uniformely mixed therein at a temperature less than about 120~C; more preferably, less than about 105~C; more preferably, less than about 95~C;
and most preferably, less than about 80~C (hereinafter, the "mixing temperature").
This reduced mixing temperature is made possible partly because the primary gellant, 1620 once molten, is an unexpectedly good co-solvent for the secondary gellant, thereby f~.ilit~qting their dissolution at a lower temperature. Additional methods of re~lcing the mixing temperature or otherwise enabling a reduction of the interaction of the acidic antipe-~pi-~llL active with other components, e.g., the gelling agent, is discussed hereinafter. Since lower mixing temperatures can be ~Itili7e~1~ the gelling agent is more 1625 compatible with additional gel stick components which have lower boiling points, such as perfumes.
a. Primary Gellant The primary gellant of the gelling agent of the present invention is selected from the group consisting of 12-hydroxystearic acid, esters of 12-hydroxystearic acid, 1630 amides of 12-hydroxystearic acid and mixtures thereof. The primary gellant is preferably selected from the group consisting of 12-hydroxystearic acid, 12-hydl~xy~Learic acid methyl ester, 12-hydroxystearic acid ethyl ester, 12-hyd.oxy~earic acid stearyl ester, 12-hydroxystearic acid benzyl ester, 12-hydroxystearic acid amide, isopropyl amide of 12-hydroxystearic acid, butyl amide of 12-hydroxystearic acid, 1635 ben_yl amide of 12-hydroxystearic acid, phenyl amide of 12-hydroxystearic acid, t-butyl amide of 12-hydroxystearic acid, cyclohexyl amide of 12-hydroxystearic acid, 1-~rl~m~ntyl amide of 12-hydloxy~learic acid, 2-~m~ntyl amide of 12-hydroxystearicacid, diisop.ul~yl amide of 12-hydloxy~learic acid, and mixtures thereof; even more preferably, 12-hydroxystearic acid, isopropyl amide of 12-hydroxystearic acid, and 1640 mixtures thereof.
b. Secondary Gellant With regard to the secondary gellant of the gelling agent of the present invention, N-acyl amino acid derivatives include N-acyl amino acid amides and N-acyl amino acid esters prepared from glutamic acid, Iysine, gl~lt~mine, aspartic acid and 1645 mixtures thereof.
Preferably the N-acyl amino acid derivatives are selected from the group WO 96/12467 PCT/US95/1186~1 consisting of N-lauroyl-glutamic acid diethyl amide, N-lauroyl-glutamic acid dibutyl amide, N-lauroyl-glutamic acid dihexyl amide, N-lauroyl-glutamic acid dioctyl amide, N-lauroyl-glutamic acid didecyl amide, N-lauroyl-glutamic acid didodecyl amide, N-1650 lauroyl-glutamic acid ditetradecyl amide, N-lauroyl-glutamic acid dihexadecyl amide, N-lauroyl-glutamic acid distearyl amide, N-stearoyl-glutamic acid dibutyl amide, N-stearoyl-glutamic acid dihexyl amide, N-stearoyl-glutamic acid diheptyl amide, N-stearoyl-glutamic acid dioctyl amide, N-stearoyl-glutamic acid didecyl amide, N-stearoyl-glutarnic acid didodecyl amide, N-stearoyl-glutamic acid ditetradecyl amide, 1655 N-stearoyl-glutamic acid ~ihe~ecyl amide, N-stearoyl-glutamic acid distearyl amide and mixtures thereof; more pler~ d, is n-lauroyl-glutamic acid dibutyl amide, n-stearyl-glutamic acid dihexyl amide, and mixtures thereof.
3. Liquid Base Materials The liquid base matrix of antipel~,uh~-" stick compositions of the present 1660 invention is formed by combining the gelling agent with a liquid base material. As used herein, the term "liquid" refers to materials which are liquids at ambient conditions and the term "liquid base material" inçlu(les all liquids within the composition. It is important that the liquid base material be of a type, and used at a level sufficient to solubilize the gelling agent when heated, to permit s~1bst~nti~11y 1665 uniform mixing of the antipe-~,~)h~ active into the heated solution at the mixing temperature, and form a stick when cooled to ambient temperature. The liquid base material should be con",aLilJle with the gelling agent so that the mixture of the two remains homogeneous and does not phase separate during m~nllf~ct~lring and so that the fini.~hed product remains homogeneous and does not phase separate at ambient1670 conditions over the normal shelf-life which may be upwards of one year. Furthermore, the liquid base materials are typically selected to provide ~esthetic benefits, such as emolliency, low tack or ~ ;",i,ed visible residue, without significant interference with the effectiveness of the anli~e~ allL active component. Lastly, the particular liquid base material should be safe for application to human skin.
1675 The liquid base materials include emollients which have a solubility parameter from about 5 to about 1 1. It is preferable that, in aggregate, the average solubility parameter of the liquid base material be from about 6 to about 10. Hence, a mixture of emollients may be used as the liquid base material herein, each having a solubility parameter in the range of from about 5 to about 1 1, such that the average solubility 680 parameter of the mixture is from about 6 to about 10. Solubility parameters are common to the art of antipel~;lal.l stick formulation and the means to determinethem are disclosed by C.D. V~l~gh~n, "Solubility Effects in Product, Package, Penetration and Preservation" 103 Cosmetics and Toiletries 47-69, October, 1988;

W O 96/12467 PCT~US95/1186 and C.D. Va~lgh~n, " Using Solubility Parameters in Cosmetics Formulation", 36 J1685 Soc. Cosmetic Chemists 319-333, Sept/Oct, 1985.
The liquid base material of the present invention is preferably used at levels from about 10% to about 95%; and more preferably from about 45% to about 80%.
The liquid base material preferably inr1~des a volatile, non-polar, oil and a non-volatile, relatively polar co-solvent; each ~i~c-lssed more fully hereinafter. The term 1690 "non-volatile" as used herein refers to materials which exhibit a vapor pressure of no more than about 0.2mm Hg at 25~C at one atmosphere and/or to materials which have a boiling point at one atmosphere of at least about 300~C. The term "volatile" as used herein refers to all materials which are not "non-volatile" as previously defined herein.
The phrase "relatively polar" as used herein means more polar than another material in 1695 terms of solubulity parameter; i.e., the higher the solubility parameter the more polar the liquid. The term "non-polar" typically means that the emollient has a solubility parameter below about 6.5.
a. Non-polar~ Volatile Oil The non-polar, volatile oil tends to impart highly desirable aesth~tic properties 1700 to the gel stick. Consequently, the non-polar, volatile oils are preferably utilized at a fairly high level. Such non-polar, volatile oils are preferably used at levels from about 10% to about 70%; more preferably, from about 25% to about 60%; more preferably from about 40% to about 60%.
Non-polar, volatile oils particularly useful in the present invention are selected 1705 from the group consisting of silicone oils; hydrocarbons; and mixtures thereof. Such non-polar, volatile oils are disclosed, for example, in Cosmetics, Science, and Technology, Vol. 1, 27-104 edited by Balsam and Sagarin, 1972. The non-polar, volatile oils useful in the present invention may be either saturated or unsaturated, have an aliphatic character and be straight or branched chained or contain alicyclic or 1710 aromatic rings. Examples of pler~.led non-polar, volatile hydrocarbons include isodecane (such as Permethyl-99A(~ which is available from Presperse Inc.) and the C7-Cg through C12-C1s isoparaffins (such as the Isopar(~) Series available from Exxon Chemicals).
Non-polar, volatile silicone oils are highly pl~~re--~d as the non-polar, volatile 1715 oil in the liquid base material, since they endow the antipe~pi,~ stick composition with highly desirable aesthetics. Non-polar, volatile liquid silicone oils are disclosed in U.S. Pat. 4,781,917 issued to Luebbe et al. on Nov. 1, 1988. Additionally, a description of various volatile silicones materials is found in Todd et al., "Volatile Silicone Fluids for Cosmetics", Cosmetics and Toiletries, 91:27-32 (1976).
1720 Particularly prere~.ed volatile silicone oils are cyclic and linear volatile silicones like W O 96/12467 PCTrUS95/1186 those disclosed hereinbefore.
b. Relatively Polar Non-volatile Co-solven~
The relatively polar co-solvent aids in the utilization of reduced processing temperatures by solubulizing at least one of the gellants and being soluble in the non-1725 polar, volatile oil when subjected to reduced processing temperatures. The non-volatile co-solvent is "relatively polar" as compared to the non-polar, volatile oil tli~c~ ed above. Therefore, the non-volatile co-solvent is more polar (i.e., has a higher solubility parameter) than at least one of the non-polar, volatile oils.
In addition to enabling reduced processing temperatures, the co-solvent 1730 enables the inclusion of greater amounts of the non-polar, volatile oil. This is advantageous because, as di~c~.s~ed above, the non-polar, volatile oil provides significant cosmetic benefits. The quantity of relatively polar, non-volatile co-solvent, however, is preferably kept to a minim--m because it tends to adversely affect product cosmetics. Thus, the relatively polar, non-volatile co-solvent is preferably included at 1735 levels from about 5% to about 60%; more preferably from about 5% to about 25%;
and most preferably from about ?n~'~ to about 20%.
Relatively polar, non-vola~lle liquids potentially useful as the co-solvent in the present invention are disclosed, for example, in Cosmetics, Science, and Technology, Vol. 1, 27-104 edited by Balsam and Sagarin, 1972; U.S. Pat. 4,202,879 issued to1740 Shelton on May 13, 1980; and U.S. Pat. 4,816,261 issued to Luebbe et al. on March 28, 1989. Relatively polar, non-volatile co-solvents useful in the present invention are preferably selected from the group consisting of silicone oils; hydrocarbon oils; fatty alcohols; fatty acids; esters of mono and dibasic carboxylic acids with mono andpolyhydric alcohols; polyoxyethylenes; polyoxypropylenes; mixtures of 1745 polyoxyelhylene and polyoxy~ulopylene ethers of fatty alcohols; and mixtures thereof.
The relatively polar, non-volatile co-solvents useful in the present invention may be either saturated or unsaturated, have an aliphatic character and be straight or branched chained or contain alicyclic or aromatic rings.
More preferably, the relatively polar, non-volatile liquid co-solvent are selected 1750 from the group consisting of fatty alcohols having from about 12-26 carbon atoms;
fatty acids having from about 12-26 carbon atoms; esters of monobasic carboxylicacids and alcohols having from about 14-30 carbon atoms; esters of dibasic carboxylic acids and alcohols having from about 10-30 carbon atoms; esters of polyhydric alcohols and carboxylic acids having from about 5-26 carbon atoms; ethoxylated, 1755 propoxylated, and mixtures of ethoxylated and propoxylated ethers of fatty alcohols with from about 12-26 carbon atoms and a degree of ethoxylation and propoxylation of below about 50; and mixtures thereof.

WO 96/12467 PCT/US9511186.1 More plef~--ed are propoxylated ethers of C14-Clg fatty alcohols having a degree of propoxylation below about 50, esters of C2-C8 alcohols and C12-C26 1760 carboxylic acids (e.g. ethyl myristate, isopropyl p~lnlit~te), esters of C12-C26 alcohols and benzoic acid (e.g. Finsolv TN(~) supplied by Finetex), diesters of C2-Cg alcohols and adipic, sebacic, and phthalic acids (e.g., diisopropyl seb~c~te, diisopropyl ~dirate, di-n-butyl phth~l~te), polyhydric alcohol esters of C6-C26 carboxylic acids (e.g., propylene glycol dicaprate/dicaprylate, propylene glycol isostearate); and mixtures 1765 thereof.
Even more p.~re--ed are branched-chain aliphatic fatty alcohols having from about 12-26 carbon atoms. Even more ple~ d is isocetyl alcohol, octyldecanol, octyldodecanol and undecylpent~dec~nnl; and most prere..ed is octyldodecanol. Such p. ere.. ed aliphatic fatty alcohols are particularly useful in combination with the volatile 1770 liquid silicone oils ~ c~esed herein to adjust the average solubility of the liquid base material.
c. Non-polar~ Non-volatile Emollients In addition to the liquids ~ cus~ed above, the liquid base material can optionally include non-volatile, non-polar emollients which tend to improve product 1775 cosmetics Typical non-volatile, non-polar emollients are disclosed, for example, in Cosmetics, Science, and Technology, Vol. 1, 27-104 edited by Balsam and Sagarin,1972; U.S. Pat. 4,202,879 issued to Shelton on May 13, 1980; and U.S. Pat.
4,816,261 issued to Luebbe et al. on March 28, 1989.get good dissolution. The non-volatile silicone oils useful in the present invention are ess~.nti~lly non-volatile 1780 polysiloxanes, pa arr~ic hydrocarbon oils, and mixtures thereof. The polysiloxanes useful in the present invention selected from the group consisting of polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, poly-ethersiloxane copolymers, and mixtures thereof. Examples of these include polydimethyl siloxanes having viscosities of from about 5 to about 100,000 centistokes at 25~C.
1785 Among the p-~rt;-.ed non-volatile silicone emollients useful in the present compositions are the pol~di.,.~lllyl siloxanes having viscosities from about 2 to about 400 centistokes at 25~C. Such polyalkylsiloxanes include the Viscasil~) series (sold by General Electric Co---pa--y) and the Dow Cor ~ing 200 series (sold by Dow Corning Corp.). Polyalkylarylsiloxanes include polymethylphenyl siloxanes having viscosities 1790 of from about 15 to about 65 centistokes at 25~C. These are available, for example, as SF 1075 methyl-phenyl fluid (sold by General Electric Company) and 556 Cosmetic Grade Fluid (sold by Dow Corning Corp.). Useful poly-ethersiloxane copolymers in~ de, for example, a polyoxyalkylene ether copolymer having a viscosity of about 1200 to 1500 centistokes at 25~C. Such a fluid is available as SF1066 organosilicone W O 96/12467 PCT~US95/11864 1795 surfactant (sold by General Electric Company). Polysiloxane ethylene glycol ether copolymers are pl ere- ~ ed copolymers for use in the present compositions.
Non-volatile paraffinic hydrocarbon oils useful in the present invention includemineral oils and certain branched-chain hydrocarbons. Examples of these fluids are disclosed in U.S. Pat. 5,019,375 issued to Tanner et al. on May 28, 1991. Preferred 1800 mineral oils have the foltowing properties:
(1) viscosity from about 5 centistokes to about 70 centistokes at 40~C;
(2) density between about 0.82 and 0.89 g/cm3 at 25~C;
(3) flash point between about 138~C and about 216~C; and (4) carbon chain length between about 14 and about 40 carbon atoms.
1805 Preferred branched chain hydrocarbon oils have the following properties:
(1) density between about 0.79 and about 0.89 g/cm3 at 20~C
(2) boiling point greater than about 250~C; and (3) flash point between about 110~C and about 200~C.
Particularly plere.,cd branched-chain hydrocarbons include Permethyl 103A, which1810 contains an average of about 24 carbon atoms; Permethyl 104A, which contains an average of about 6~ carbon atoms; Permethyl 102A, which contains an average of about 20 carbon atoms; all of which may be purchased from Permethyl Corporation;and Ethylflo 364 which contains a mixture of 30 carbon atoms and 40 carbon atomsand may be purchased from Ethyl Corp.
1815 Additional components useful in form~ ting these topical compositions are further described below.
IV. Additional Components A wide variety of additional components can be employed in the hair care and topical skin compositions herein. Non-limiting examples include the following:
1820 1. Deodorant Active In~redients Suitable types of deodorant actives include antimicrobial ingredients such as bactericides and fimgici~ec Exemplary deodorant actives include quaternary ammonium compounds such as cetyl-trimethylamnnonium bromide, cetyl pyridinium chloride, benzethonium chloride, diisobutyl phenoxy ethoxy ethyl dimethyl benzyl1825 ammonium chloride, sodium N-lauryl sarcosine, sodium N-palmethyl sarcosine, ~ Iauroyl sarcosine, N-myristoyl glycine, potassium N-lauryl sarcosine, stearyl, trimethyl ammonium chloride, sodium ~Illmimlm chlorohydroxy lactate, tricetylmethyl ammonium chloride, 2,4,4'-trichlorio-2'-hydroxy diphenyl ether, tli~mino~lkyl amides such as L-lysine hPx~decyl amide, heavy metal salts of citrate, salicylate, and 1830 piroctose, especially zinc salts, and acids thereof, heavy metal salts of pyrithione, especially zinc pyrithione and zinc phenolsulfate. Still other antimicrobial ingredients W O96112467 PCT~US95/1186 include farnesol.
Other deodorant actives include odor absorbing materials such as carbonate and bicarbonate salts, e.g. as the alkali metal carbonates and bicarbonates, ammonium 1835 and tetraalkylammonium carbonates and bicarbonates, especially the sodium and potassium salts.
Mixtures of deodorant actives are also contemplated and intended to be encompa~.ced herein.
2. Antipel ~y;, ~-ll Actives 1840 The compositions of the present invention can also contain an astringent antipel~pil~n~ active. These actives are typically used at levels from about 0.5% to about 60%, preferably from about 5% to about 35%, in, e.g., an antipel~ llL gel stick composition. This active can be incorporated either in solubilized or particulate form. These weight percentages are calculated on an anhydrous metal 845 salt basis (exclusive of, e.g., glycine, the salts of glycine, or other complexing ager.ts). Such nn. ter.clls inc!~:de, for exar"ple, mla,-,y alum.ir.;;.,. or zirconiu astringent salts or complexes and are well known in the antipe- ~ art.
The al~ipel~pilalll active is p~fel~bly in particulate form wherein the surface area of the active is relatively low. The surface area of the antipe~
1850 active can be reduced by increasing the size and density of the active particles.
Consequently, the particulate antipe~ lll active preferably has a density which is preferably greater than about 0.7 g/cm3 and an average particle size (as measured by a Coulter ~I~It~ 7er 1 1 mAn~foct--red by Coulter Corporation, Haleah, Florida) greater than about 10 microns; more p.t;re.~bly, greater than about 30 microns;
855 and most plt;rel~bly, greater than about 40 microns. Such pl~;~ed materials can be purchased from Westwood Chemical Company, Middletown, N.Y. under the trade name Westchlor(~) ZR. Suitable antipe-~ n~ active is disclosed, for example in U.S. Patent 4,147,766 which issued on April 3, 1979 to ~o7isç~P~
Any Olumim~m astringent antipe.~ a.lL salt or al-lmin-~m and/or zirconium 1860 astringent complex can be employed herein. Salts useful as a~L.ingen~
antipe.~yi~nl salts or as components of astringent complexes include oluminl~m halides, Al--min--m hydroxy-halides, zirconyl oxyhalides, zirconyl hydroxy-halides, and ~l~ixLules of these materials.
,~lumim~m salts of this type include ~ minllm chloride and the ~ min~m 1865 hydroxyhalides having the general formula A12(0H)xQy.XH20 where Q is chlorine, bromine or iodine; where x is from about 2 to about 5, and x+y = about6, and x and y do not need to be integers; and where X is from about 1 to about 6.
salts of this type can be prepared in the manner described more fully in U.S. Patent 3,887,692 issued to Gilman on June 3, 1975, and U.S. Patent 1870 3,904,741 issued to Jones and Rubino on September 9, 1975.
The zirconium compounds which are useful in the present invention include both the zirconium oxy salts and zirconium hydroxy salts, also referred to as the ~ co"yl salts and zirconyl hydroxy salts. These compounds may be represented by the following general empirical formula:
1875 ZrO(OH)2-nzBz wherein z may vary from about 0.9 to about 2 and need not be an integer, n is the valence of B, 2-nz is greater than or equal to 0, and B may be selected from thegroup consisting of halides, nitrate, sulf~m~t~, sulfate, and mixtures thereof.
Although only zirconium compounds are exemplified in this specification, it will be 1880 understood that other Group IVB metal compounds, inclll~ing h~fnillm, can be used in the present invention.
As with the basic ~ min~lm compounds, it will be understood that the above formula is greatly simplified and is intended to represent and include compounds having coordinated and/or bound water in various quantities, as well 1885 as polymers, mixtures and complexes of the above. As will be seen from the above formula, the ~i,coniu", hydroxy salts actually ,epl-esenl a range of compounds having various amounts of the hydroxy group, ~arying from about 1.1 to only ~ slightly greater than zero groups per molecule.
Several types of antipe,s~ nl complexes lltili7ing the above antipe, ~ n~
1890 salts are known in the art. For eY~mrle, U.S. Patent 3,792,068 issued to TlledC~ÇrS
et al. on February 12, 1974 discloses complexes of ~lllmin~lm, zirconium and amino acids, such as glycine. Complexes such as those disclosed in the Luedders et al. patent and other similar complexes are commonly known as ZAG. ZAG
complexes are chemically analyzable for the presence of ~lllmimlmi zirconium and1895 chlorine. ZAG complexes useful herein are identified by the specification of both the molar ratio of ~ min-lm to zirconium (hereinafter "Al:Zr" ratio) and the molar ratio of total metal to chlorine (he,t;inaner "Metal:CI" ratio). ZAG complexes useful herein have an Al:Zr ratio of from about 1.67 to about 12.5 and a Metal:CI
ratio offrom about 0.73 to about 1.93.
soo Pltrellt;d ZAG complexes are formed by (A) co-dissolving in water (1) one part A12(0H)6 mQm, wherein Q is an anion selected from the group co~ g of chloride, bromide and iodide, and m is a number from about 0.8 to about 2.0;
(2) x parts Zr~(~H)2-aQa nH2~, where Q is chloride, bromide W O96/12467 PCTrUS95/11864 or iodide; where a is from about 1 to about 2; where n is from about 1 to about 8;
and where x has a value offrom about 0 16 to about 1.2;
(3) p parts neutral amino acid selected from the group consisting of glycine, dl-tryptophane, dl-b-phenylalanine, dl-valine, dl-methionine o and b-alanine, and where p has a value of from about 0 06 to about 0.53;
(B) co-drying the result~nt mixture to a friable solid; and (C) recl~lçing the reslllt~nt dried inorganic-organic antipe complex to particulate form A prefel,~d ~ minllm compound for preparation of such ZAG type 1915 complexes is ~Inminllm chlorhydroxide of the empirical formula A12(OH)sC12H2O. Preferred zirconium compounds for plepa~alion of such ZAG-type complexes are zirconyl hydroxychloride having the empirical formula ZrO(OH)CI 3H2O and the zirconyl hydroxyhalides of the empirical formula ZrO(OH)2 aC12 nH20 wherein a is from about 1 5 to about 1 87, and n is from 1920 about 1 to about 7 The p,erel.ed amino acid for plepa~ing such ZAG-type complexes is glycine of the formula CH2(NH2)COOH. Salts of such amino acids can also be employed in the antipe-spi-~l complexes See U.S Patent 4,017,599 issued to Rubino on April 12, 1977.
A wide variety of other types of antipe-~,)i-anl complexes are also known 1925 in the art For example U S Patent 3,903 258 issued to Siegal on September 2, 1975 discloses a zirconium ~lllmimlm complex prepared by reacting zirconyl chloride with alllmin..m hydroxide and ~IIlmimlm chlorhydroxide U S Patent 3,979,510 issued to Rubino on September 7, 1976 discloses an antipe,~l,i.a.ll complex formed from certain ~ min~m compounds, certain zirconium 1930 compounds, and certain complex ~I~Imimlm buffers U S Patent 3,981,896 issued to Pauling on September 21, 1976 discloses an antipe.~pi,~"l complex prepared from an ~IIlminum polyol compound, a zirconium compound and an organic buffer U S. Patent 3,970,748 issued to Mecca on July :20, 1976 discloses an ~IIlminllm chlorhydroxy glycinate complex of the appl ox-"~ale general formula 1935 [A12(~ H)4CI][H2CN H2CO O ~-Of all the above types of antipe,~pi,a~l actives, pleielled compounds include the 5/6 basic al--min--m salts of the empirical formula A12(OH)sC1 2H2O;lwes of AIC13 6H20 and A12(OH)sCI. 2H20 with ~IIlmimlm chloride to ~IIlmimlm hydroxychloride weight ratios of up to about 0.5; ZAG type complexes 1940 wherein the zirconium salt is ZrO(OH)CI.3H20~ the ~l~lmin~m salt is A12(OH)sCI
2H20 or the aforementioned mixtures of AIC13 6H20 and A12(OH)s Cl.2H20 wherein the total metal to chloride molar ratio in the complex is less than about wo 96/12467 PCTIUS95/1186~

1.25 and the Al:Zr molar ratio is about 3.3, and the amino acid is glycine; and ZAG-type complexes wherein the zirconium salt is ZrO(OH)2 aCla.nH2O wherein ~ 1945 a is from about 1.5 to about 1.87 and n is from about 1 to about 7, the alumin-lm salt is A12(OH)sCI.2H2O, and the amino acid is glycine.
Solubilized antipe~li-allL actives which can be utilized in the present invention are also well known in the art. These materials utilize monohydric or polyhydric alcohols or water to solublize the antiperspirant active before it is1950 incorporated into the product. The levels of these polar solvents are typically less than a~ ~ut 25%, and preferably less than about 15% of the composition.
Examples of such act~ves are taught, for example, in U.S. Patent 4,137,306 issued to Rubino on January 30, 1979; U.S. Patent Application Serial No. 370,559, Smithand Ward, filed June 23, 1989; and European Patent Application 0295070 which 1955 published December 14, 1988, all of said patents and applications being incorporated herein by reference.
3. Pharmaceutical Actives The compositions of the present invention, especially the topical skin care compositions, can comprise a safe and effective amount of a pharm~ce~ltical active.
1960 The phrase "safe and effective amount", as used herein, means an amount of an active high enough to significantly or positively modify the condition to be treated, but low enough to avoid serious side effects (at a reasonable benefit/risk ratio), within the scope of sound medic~l judgement. A safe and effective amount of the pharm~celltical active will vary with the specific active, the ability of the composition 1965 to penel,~Le the active through the skin, the amount of composition to be applied, the particular condition being treated, the age and physical condition of the patient being treated, the severity of the condition, the duration of the tre~tmPnt, the nature of concurrent therapy, and like factors.
The pharm~cel-tic~l actives which can be used in the compositions of the 1970 present invention preferably comprise from about 0.1% to about 20% by weight of the compositions, more preferably from about 0.1% to about 10%, and most preferably from about 0.1% to about 5%. Mixtures of pharm~ce~ltical actives can also be used.
Nonlimi~ing examples of pharm~ce~ltical actives useful in the compositions of 1975 the present invention include anti-acne drugs. Anti-acne drugs pl~relled for use in the present invention include the keratolytics such as salicylic acid, sulfur, lactic acid, glycolic, pyruvic acid, urea, resorcinol, and N-acetylcysteine; retinoi~ls such as retinoic acid and its derivatives (e.g., cis and trans); antibiotics and antimicrobials such as benzoyl peroxide, octopirox, e~y~ lycin, zinc, tetracyclin, triclosan, azelaic W O96/12467 PCT~US9~/1186 1980 acid and its derivatives, phenoxy ethanol and phenoxy proponol, ethyl~cet~te, clindamycin and meclocycline; sebostats such as flavinoids; alpha and beta hydroxy acids; and bile salts such as scymnol sulfate and its derivatives, deoxycholate, and cholate. Plt;re~ed for use herein is salicylic acid.
Useful pharm~r,eutical actives in the compositions of the present invention 85 include non-steroidal anti-infl~mm~tory drugs (NSAIDS). The NSAIDS can be selected from the following categories: propionic acid derivatives; acetic acid derivatives; fenamic acid derivatives; biphenylcarboxylic acid derivatives; and oxicams. All of these NSAIDS are fully described in the U.S. Patent 4,985,459 toSunshine et al., issued January 15, 1991, incorporated by reference herein. Most1990 p~ ed are the propionic NSAIDS inclll~ing but not limited to aspirin, acet~min~-phen, ibuprofen, naproxen, benoxaprofen, flurbiprofen, fenoprofen, fenbufen, ketoprofen, indoprofen, pirprofen, carprofen, oxapl ozin, pranoprofen,miroprofen, tioxaprofen, suprofen, alminoprofen, tiaprofenic acid, fluprofen andbucloxic acid. Also useful are the steroidal anti-infiammatory drugs incl~ing 199S hydrocortisone and the like.
Useful pharm~r,eutical actives in the compositions of the present invention include antipruritic drugs. Antipruritic drugs pl~re-l~d for inclusion in compositions of the present invention include pharrn~ce~ltically-acceptable salts of methtlili7ine and trimeprazine. Useful pharrn~ce~ltical actives in the compositions of the present2000 invention include include ~nesthetic drugs. ~n~sthetic drugs p~erelled for inclusion in compositions of the present invention include pharmaceutically-acceptable salts of lidocaine, bupivacaine, chlorprocaine, dibucaine, etidocaine, mepivacaine, tetracaine, dyclonine, hexylcaine, procaine, cocaine, ket~mine, pramoxine and phenol. Usefulpharm~ceutic~l actives in the compositions of the present invention include 200s antimicrobial drugs (~ntib~cterial~ ~ntifilng~l, anliprotozoal and antiviral drugs).
Antimicrobial drugs plt;relled for inclusion in compositions of the present invention include pharm~ceutically-acceptable salts of b-lactam drugs, quinolone drugs, ciprofloxacin, norfloxacin, tetracycline, erythromycin, ~mik~cin, triclosan, doxycycline, capreomycin, chlorhexidine, chlortetracycline, oxytetracycline, 2010 clind~mycin, ethambutol, metronidazole, pelll~ll~idine, gell~ icin, k~namycill, lineolllycin, methacycline, methPn~minç, minocycline, neomycin, netilmicin, paromomycin, streptomycin, tobramycin, miconazole and ~m~nf~-line. Antimicrobialdrugs plerelled for inclusion in compositions of the present invention include tetracycline hydrochloride, elylllrolllycin estolate, erythromycin stearate (salt), 2015 ~mik~r.in sulfate, doxycycline hydrochloride, capreolllycin sulfate, chlorhexidine gluconate, chlorh~xidine hydrochloride, chlortetracycline hydrochloride, oxytetracycline hydrochloride, clin~l~mycin hydrochloride, ethambutol hydrochloride, metronidazole hydrochloride, pentamidine hydrochloride, gentamicin sulfate, ~ kanamycin sulfate, lineomycin hydrochloride, methacycline hydrochloride, 2020 methen~mine hippurate, methç~ e m~n~lel~te, minocycline hydrochloride, neomycin sulfate, netilmicin sulfate, paromomycin sulfate, streptomycin sulfate,tobramycin sulfate, miconazole hydrochloride, ~ml~nf~line hydrochloride, ~m~nf~ine sulfate, triclosan, octopirox, parachlorometa xylenol, nystatin, tolnaftate and clotrimazole.
2025 4. Sunscreening A~ents.
Also useful herein are sunscreening agents. A wide variety of sunscleenil~g agents are described in U.S. Patent No. 5,087,445, to Haffey et al., issued February 11, 1992; U.S. Patent No. 5,073,372, to Turner et al., issued December 17, 1991;U.S. Patent No. 5,073,371, to Turner et al. issued December 17, 1991; and Segarin, 2030 et al., at Chapter VIII, pages 189 et seq., of Cosmetics Science and Technology, all of which are incorporated herein by reference in their entirety. Preferred among those sunscreens which are useful in the compositions of the instant invention are those selected from the group consisting of 2-ethylhexyl p-methoxyci~ "-~le, 2-ethylhexyl N,N-dimethyl-p-aminobçn7O~tç7 p-aminobenzoic acid, 2-phenylbenzimidazole-5-2035 sulfonic acid, octocrylene, oxybenzone, homomenthyl salicylate, octyl salicylate, 4,4'-methoxy-t-butyldibenzoylmeth~n~, 4-isopropyl dibenzoylmeth~nP7 3-benzylidene camphor, 3-(4-methylbenzylidene) camphor, titanium dioxide, zinc oxide, silica, iron oxide, and mixtures thereof.
Still other useful suns~ireells are those disclosed in U.S. Patent No. 4,937,370, 2040 to S~b~tçlli issued June 26, 1990; and U.S. Patent No. 4,999,186, to S~hatelli et al., issued March 12, 1991; these two rerelel1ces are incorporated by reference herein in their entirety. The sunscreening agents disclosed therein have, in a single molecule, two distinct chromophore moieties which exhibit di~l ~;nl ultra-violet radiationabsorption spectra. One of the chromophore moieties absorbs predonul1alllly in the 2045 UVB radiation range and the other absorbs strongly in the WA radiation range.
These sunscreening agents provide higher efficacy, broader W absorption, lower skin penetration and longer lasting efficacy relative to conventional sunscreens.
Especially ple~lled examples of these sunscreens include those selected from thegroup cons,slii1g of 4-N,N-(2-ethylhexyl)methylaminobenzoic acid ester of 2,4-2050 dihydroxyl,enzophenone, 4-N,N-(2-ethylhexyl)methylaminobenzoic acid ester with 4-hydlo~ydllJell20ylmeth~ne, 4-N,N- (2-ethylhexyl)methylaminobenzoic acid ester of 2-hydl oAy-4-(2-hydroxyethoxy)benzophenone, 4-N,N-(2-ethylhexyl)-methylaminobenzoic acid ester of 4-(2-hydroxyethoxy)dibenzoylmeth~ne, and mixtures thereof.
205s Generally, the sunscreens can comprise from about 0.5% to about 20% of the compositions useful herein. Exact amounts will vary depending upon the sunscreenchosen and the desired Sun Protection Factor (SPF). SPF is a commonly used measure of photoprotection of a sunscreen against erythema. See Federal Register, Vol. 43, No. 166, pp. 38206-38269, August 25, 1978, which is incorporated herein2060 by reference in its entirety.
5. Sunless tanning agents. Also useful in the present invention are sunless tanning agents inclu~ing dihydroxyacetone, glyceraldehyde, indoles and their derivatives, and the like. These sunless tanning agents can also be used in combination with the sunscreen agents.
2065 6. Conditionin~ Agents. Other useful actives include the conditioning agents disclosed hereinbefore, incl~lding hydrocarbons, silicone fluids, and cationic materials.
The hydrocarbons can be either straight or branched chain and can contain from about 10 to about 16, preferah!y from. about 12 to about 16 .,arbor. atorrls. Exar"ples ûf suitable hydrocarbons are decane, dodecane, tetradecane, tridecane, and mixtures2070 thereof.
Silicone conditioning agents useful herein are the ones disclosed hereinbefore, especially those that have viscosities of less than about 5 centistokes at 25~C, while the cylic materials have viscosities of less than about 10 centistokes.
Cationic conditioning agents useful herein can include quaternary ammonium 207s salts or the salts of fatty amines. ~rere"ed quaternary ammonium salts are dialkyl dimethyl ammonium chlorides, wherein the alkyl groups have from 12 to 22 carbon atoms and are derived from long-chain fatty acids. Representative examples of quaternary ammonium salts include ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, ~iih~x~decyl dimethyl ammonium chloride, and 2080 di(hydrog~n~ted tallow) ammonium chloride. Other qauternary ammonium salts useful herein are dicationics such as tallow propane diammonium dichloride.
Quaternary imid~7Olinium salts are also useful herein. Examples of such materials are those imid~7.olinium salts co~ g C12 22 all~yl groups such as 1-methyl-1-[(stearoylamide)ethyl]-2-heptadecyl-4, 5-dihydroimid~7Qlinium chloride, 1-methyl-1-2085 [(palmitoylamide)ethyl]-2-octadecyl-4,5-dihydl~oill~ida_olinium chloride and l-methyl-l-[(tal-lowamide)-ethyl]-2-tallow-imidazolinium methyl sulfate. Also useful herein are salts of fatty amines. Examples of such compounds include stearylamine hydrochloride, soyamine hydrochloride, and stearylamine formate. Useful conditioning agents are disclosed in U.S. Patent No. 4,387,090, to Bolich, issued June 2090 7, 1983, which is incorporated by reference herein.

WO 96/12467 PCT/US9~/1186 7. Humectants and Moisturizers The compositions of the present invention can contain one or more humectant or moisturizing materials. A variety of these materials can be employed and each can be present at a level of from about 0.1% to about 20%, more preferably from about 2095 1% to about 10% and most preferably from about 2% to about S%. These materials include urea; ~l~ni~line; glycolic acid and glycolate salts (e.g. ammonium and quaternary alkyl ammonium); lactic acid and lactate salts (e.g. ammonium and quaternary alkyl ammonium); aloe vera in any of its variety of forms (e.g., aloe vera gel); polyhydroxy alcohols such as sorbitol, glycerol, hexanetriol, propylene glycol, 2100 butylene glycol, hexylene glycol and the like; polyethylene glycols; sugars and starches; sugar and starch derivatives (e.g., alkoxylated glucose); hyaluronic acid;
l~r,t~mide monoethanolamine; acet~mide monoethanolamine; and mixtures thereof.
Preferred hllmect~nt.c and moisturizers are glycerol, butylene glycol, hexylene glycol, and mixtures thereof.
2105 The compositions of the present invention, especially the conditionercompositions, can contain one or more surf~ct~ntc as disclosed hereinbefore. These surf~r,t~ntc are useful adjuncts for the carriers of the present compositions. For conditioners, the p-ere"~d level of surfactant is from about 0.2% to about 3%.
Surf~ct~nts useful in compositions of the present invention include anionic, nonionic, 2110 cationic, zwitterionic and amphoteric surf~ct~ntc 8. Carboxylic Acid Copolymer Thickeners Another component useful in the compositions herein is a carboxylic copolymer thickener as disclosed hereinbefore. The non-rinsed compositions of the present invention can comprise from about 0.025% to about 1%, more preferably from about2115 0.05% to about 0.75% and most prefelably from about 0.10% to about 0.50% of carboxylic acid polymer thickeners.

9. F,m~llSifiers The non-rinsed compositions herein can contain various rmlllcifiers. These çmlllcifiers are useful for emulsifying the various carrier components of the 2120 compositions herein, and are not required for solubilizing or dispersing the copolymers of the present invention. Suitable çm~lcifiers can include any of a wide variety of nonionic, cationic, anionic, and zwitterionic çmlll~ifiers disclosed in the prior patents and other references. See McCutcheon's, Detergents and Fm~llcifiers, North American Edition (1986), published by Allured Publishing Corporation; U.S
2125 Patent No. 5,011,681 to Ciotti et al., issued April 30, 1991; U.S. Patent No 4,421,769 to Dixon et al., issued December 20, 1983; and U.S. Patent No. 3,755,560 to Dickert et al., issued August 28, 1973; these four references are incorporated W O96112467 PCTrU$95/11861 herein by reference in their entirety.
Suitable emulsifier types include esters of glycerin, esters of propylene glycol, 2130 fatty acid esters of polyethylene glycol, fatty acid esters of polypropylene glycol, esters of sorbitol, esters of sorbitan anhydrides, carboxylic acid copolymers, esters and ethers of glucose, ethoxylated ethers, ethox~lated alcohols, alkyl phosphates, polyo~y~Ll,~lene fatty ether phosphates, fatty acid amides, acyl lactylates, soaps and mixtures thereof.
2135 Suitable çml-lcifiers can incl~1de~ but are not limited to, polyethylene glycol 20 sorbitan monolaurate (Polysorbate 20), polyethylene glycol 5 soya sterol, Steareth-20, Ceteareth-20, PPG-2 methyl glucose ether distearate, Ceteth-10, Polysorbate 80, cetyl phosphate, potassium cetyl phosphate, diethanolamine cetyl phosphate, Polysorbate 60, glyceryl stearate, PEG-100 stearate, and mixtures thereof. The 2140 emulsifiers can be used individually or as a mixture of two or more and can comprise from about 0.1% to about 10%, more preferably from about 1% to about 7%, and most preferably from about 1% to about ~% of the compositions of the present invention.

10. Emollients 2145 The non-rinsed compositions useful in the methods of the present invention can also optionally comprise at least one emollient. Examples of suitable emollientsinrlude, but are not limited to, volatile and non-volatile silicone oils, highly branched hydrocarbons, and non-polar carboxylic acid and alcohol esters, and mixtures thereof.
Emollients useful in the instant invention are further described in U.S. Patent No.
2150 4,919,934, to Deckner et al., issued April 24 1990, which is incorporated herein by reference in its entirety.
The emollients can typically comprise in totat from about 1% to about 50%, preferably from about 1% to about 25%, and more preferably from about 1% to about 10% by weight ofthe compositions useful in the present invention.
2155 11. Additional Optional Components A variety of additional components can be incorporated into the non-rinsed compositions herein. Non-limiting examples of these additional components include vitamins and derivatives thereof (e.g., ascorbic acid, vitamin E, tocopheryl acetate, retinoic acid, retinol, retinoids, and the like); low pH thickening agents (e.g.2160 polyacrylamide and C13 14 isoparaffin and laureth-7, available as Sepigel from Seppic Co")ol~lion; polyquaternium and mineral oil, available as Salcare SC92, from Atlied Colloids; crosslinked methyl quaternized dimethylaminometh~crylate and mineral oit, available as Salcare SC95 from Atlied Colloids; resins; gums and thickeners such as ~nth~n gum, carboxymethyl cetlulose, hydroxymethyl cellulose, 2165 hydroxyethyl cellulose, alkyl-modified hydroxyalkyl celluloses (e.g. Iong chain alkyl modified hydroxyethyl celluloses such as cetyl hydroxyethylcellulose), and magnesium ~ mimlm silicate; cationic polymers and thickeners (e.g., cationic guar gum derivatives such as guar hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyltrimonillm chloride, available as the Jaguar C series from Rhone-2170 Poulenc; polymers for aiding the film-forming properties and substantivity of the composition (such as a copolymer of eicosene and vinyl pyrrolidone, an example of which is available from GAF Chemical Corporation as Ganex~) V-220); suspending agents such as ethylene glycol distearate and the like; preservatives for ,.,~i"~ ;"g the antimicrobial integrity of the compositions; skin penetration aids such as 2175 dimethylsulfoxide (DMSO), 1-dodecylazacycloheptan-2-one (available as Azone from the Upjohn Co.) and the like; antioxidants; chelators and sequestrants; and aesthetic components such as fragrances, colorings, e.c.senti~l oils, skin sçn.~tes, astringents, skin soothing agents, skin healing agents and the like, nonlimiting examples of these aesthetic components include panthenol and derivatives (e.g. ethyl p~nthenol), 2180 pantothenic acid and its derivatives, clove oil, menthol, camphor, eucalyptus oil, eugenol, menthyl lactate, witch hazel di~till~te7 allantoin, bisabalol, dipotassium glyl;y~ ~ hi ~ e and the like. Other useful actives include skin bleaching (or lip;htpning) agents inclutling but not limited to hydroquinone, ascorbic acid, kojic acid and sodium metabisulfite. Actives which are especially useful for hair care 2185 compositions include anti-dandruff actives such as zinc pyrithione, octopirox, eleni..m ~ lfic~e, sulfur, coal tar, and the like, and. hair curling and/or str~ightening actives as are well known in the art.
Method of Using Non-Rinsed Hair and Skin Care Compositions The hair care and skin care compositions of the present invention are used in 2190 conventional ways to provide the desired benefit appropriate to the product such as hair styling, holding, cle~n~ing, conditioning and the like for hair care compositions and benefits such as moisturization, sun protection, anti-acne, anti-wrinkling, artificial t~ming, analgesic, and other cosmetic and pharm~celltical benefits for skin carecompositions. Such methods of use depend upon the type of composition employed 219~ but generally involve application of an effective amount of the product to the hair or skin, which can then be allowed to remain on the hair (as in the case of spray, mousse, or gel products), or allowed to remain on the skin (as in the case of the skin care compositions). By "effective amount" is meant an amount sufficient to provide the benefit desired. Preferably, mousse, and gel products are applied to wet or damp hair 2200 prior to drying and styling of the hair. A~er such compositions are applied to the hair, the hair is dried and styled in the usual ways of the user. Hair sprays are w 096/12467 PCT~US95/11861 typically applied to dry hair after it has already been dried and styled. Cosmetic and pharm~celltical topical skin care compositions are applied to and rubbed into the skin.
The following examples further illustrate ple~--ed embodiments within the 220s scope of the present invention. The examples are given solely for the purposes of illustration and are not to be construed as limitations of the present invention as many variations of the invention are possible without departing from its spirit and scope.
EXAMPLES
The following Examples further describe and demonstrate the pi ere. . ed 2210 embo-lim~nt~ within the scope of the present invention. The Examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention as many variations thereof are possible without departing from its spirit and scope. All percentages, ratios, and parts herein, in the Specification, Examples, and Claims, are by weight and are apploxin~ations~ unless otherwise stated.
2215 Five di~le.-l perfume compositions are used in the following examples.
Perfume A and B are examples of enduring perfume compositions of this invention.Co-..pa.ali~re Perfumes C, D, and F are non-enduring perfume compositions which are outside the scope of this invention.

2220 Perfume A

Appl o~ te PerfumeIngredients B.P. (~C) ClogP Wt.%
Benzyl salicylate 300 4.383 20 Ethylene brassylate 332 4.554 20 222s Galaxolide- 50%(a) +300 5.482 20 Hexyl ~inn~ c aldehyde 305 5.473 20 Tetrahydro linalool 191 3.517 20 Total 1 00 2230 (a) A 50% solution in benzyl benzoate. Perfume A contains about 80% of enduring perfume components having BP > 250~C and ClogP > 3Ø
Perfume B

Approxi--.ale PerfumeIngredients B.P. (~C) ClogP Wt.%
2235 Benzyl acetate 215 1.960 4 Benzyl salicylate 300 4.383 12 Coumarin 291 1.412 4 Ethylene brassylate 332 4.554 10 WO 96/12467 PCT~US95/11864 Galaxolide- 50%(a) +300 5 482 10 2240 Hexyl cinnamic aldehyde 305 4 853 20 Lilial 258 3 858 15 Methyl dihydro isojasmonate +300 3.009 5 gamma-n-Methyl ionone 252 4.309 10 Patchouli alcohol 283 4.530 4 2245 Tetrahydro linalool 191 3.517 6 Total 100 (a) used as a 50% solution in isopropyl myristate which is not counted in the composition Perfume B contains about 86% of enduring perfume components 2250 having BP > 250~C and ClogP ' 3 0.

Comparative Perfume C

Ap,ol oxi-l-ate Perfume Ingredients B.P (~C) ClogP Wt %
2255 Benzyl acetate 215 1.960 20 laevo-Carvone 231 2 083 20 Dihydromyrcenol 208 3 030 20 Hydroxy~iiL.onellal 241 1 541 20 Phenylethylalcohol 220 1 183 20 2260 Total 100 Comparative Perfume C contains about 80% of non-enduring perfume ingredients having BP < 250~C and ClogP < 3 0.

2265 Co-~ a-~ive Perfume D

Appl oximate Perfume In~redients B P (~C) Clo~P Wt.%
Eugenol 253 2.307 20 iso-Eugenol 266 2.547 20 2270 Fenchyl alcohol 200 2 579 20 Methyl dihydrojasmonate +300 2.319 20 Vanillin 285 1.580 20 Total 100 Co,l,pa,aLi~te Perfume D contains about 80% of non-enduring perfume 2275 ingredients having BP > 250~C and ClogP < 3.0 WO 96/12467 PCTIUS95/1186~1 Co~pa-~ re Perfume E

Approximate PerfumeIn~redientsB.P. (~C) Clo~P Wt.%
2280 Iso-Bornyl acetate 227 3.485 20 para- Cymene 179 4.068 20 d-Limonene 177 4.232 20 gamma-n-Methyl ionone 252 4.309 20 Tetrahydromyrcenol 200 3.517 20 2285 Total 100 Con,pa, ~live Perfume E contains about 80% of non-enduring perfume ingredients having BP < 250~C and ClogP > 3Ø

2290 EXAMPLES 1-10 (Shampoo Compositions) The following examples exemplify shampoo compositions of the present invention.
The compositions of the present invention, in general, can be made by mixing the materials together at elevated temperature, e.g., about 72~C. The silicone resin, if 2295 any, and silicone fluid component are first mixed together before being mixed with the other ingredients. The other ingredients are added and the complete mixture is mixed thoroughly at the elevated temperature and is then pumped through a high shear mill and then through a heat exchal1ger to cool it to ambient temperature. The average particle size of the silicone is plere~ably from about 0.5 to about 20 microns. Also 2300 alternately, a portion of the liquid components or soluble components (incl~l~ling, for example, cationic polymer conditioning agent) can be added to the composition after cooling the mix of surf~ct~nt~ and solids; if no insoluble ingredients exist, all ingredients can be combined at ambient temperature.
Alternately, the silicone conditioning agent can be processed by:
2305 (1) mixing with anionic surfactant and fatty alcohol, such as cetyl and stearyl alcohols at elevated temperature, to form a premix co~ -E dispersed silicone. The premix can then be added to and mixed with the ,~ g materials of the shampoo, pumped thorough a high shear mill, and cooled; or 2310 (2) adding silicone, ammonium laureth-3 sulfate and ammonium chloride to a high shear mixing vessel and mixing for about 30 mimltes or until the desired silicone particle size is achieved. Levels of the three ingredients and time of mixing will very depending of type of oil to be çmlll.cified.

. CA 02211004 1997-07-21 wo 96/12467 PCT/Us95/11864 The compositions of the Examples 1-10 provide excellent in-use hair cleaning, 2315 lather, mildness, conditioning (where applicable), and especially long lasting perfume benefit even after the hair is dried with an electric hair dryer.
TABLE
Compositions 2320 Ingredients 1 2 3 4 5 (ppm or %, by weight, of composition) Sodium Laureth-3 Sulfate 13.50 13.5 16.0 8.0 16.0 Ammonium Lauryl 2325 Sulfate 4.5 4.5 1.5 8.0 3.0 Sodium Lauryl Sarcosinate(6) -- -- 3.75 0.5 --Coconut Monoethanol Amide 2.5 1.0 -- -- 1.0 Polyquaternium 10(1) 0.025 0.025 -- -- 0.05 2330 Ethylene Glycol Distearate 1.5 1.5 2.0 3.0 2.5 Dimethicone(2) -- 0.5 1.0 2.5 --Cetyl Alcohol -- -- -- 0.4 --Stearyl Alcohol -- -- -- 0.2 --2335 Propylene Glycol 1.0 -- -- -- --Light Mineral Oil 0.5 -- 0.5 Isopropyl Isostearate -- 0.5 0.5 -- 1.5 Glycerine 1.0 -- -- -- --Perfume A 0.65 0.65 -- -- --2340 Perfume B -- -- 0.40 0.50 0.25 DMDM Hydal,loin 0.20 0.20 0.30 0.30 0.30 PEG600(4) 0.125 0.125 -- -- --Sodium Sulfate 0.50 0.25 -- -- 1.0 Tricetylmethylammonium 2345 chloride(7) -- 0.15 0.55 -- --Color Solution (ppm) 10 10 20 20 20 Sodium ChlorideAdd as needed to thicken to target viscosity Ammonium Xylene Sulfonate(3)Add as needed to thicken to target viscosity 2350 Water q.s. to 100%

W O96/12467 PCT~US9~/1186 -6~-TABLE
Compositions In~redients 6 7 8 9 10 2355 (ppm or %, by weight, of composition) Sodium Laureth-3 Sulfate 13.5 13.516.0 8.0 16.0 Ammonium Lauryl Sulfate 4.5 -- -- 8.0 3.0 2360 Cocoamidopropyl Betaine(5) -- 5.03.75 0.5 --Coconut Monoethanol Amide 2.5 1.0 -- -- 1.0 Polyquaternium 10(1) 0.025 0.025 -- -- 0.05 2365 Dimethicone Copolyol -- 1.5 1.0 -- --Propylene Glycol 1.0 -- -- -- --Glycerine 1.0 -- -- -- --Perfume B 0.65 0.650.40 0.50 0.25 DMDM Hydantoin 0.20 0.200.30 0.30 0.30 2370 Sodium Sulfate 0.50 0.25 -- -- 1.0 Color Solution (ppm) 10 10 20 20 20 Sodium Chloride Add as needed to thicken to target viscosity Ammonium Xylene Sulfonate(3) Add as needed to thicken to target viscosity 2375 Water q.s. to 100%

Ucare(~ Polymer JR-30M, commercially available from Union Carbide Corporation.
2 A 40/60 blend of SE-76 silicone gum available from GE Sili 2380 cones and a silicone fluid having a viscosity of about 350 centistokes.
3 Commercially available as a 40% solution and used to thin product to target viscosity.
4 Commercially available as a 100% active fluid.
2385 5 Available under the tr~dçn~me Genagen(~) CAB from Hoechst Celanese as a 30% active solution.
6 Available under the tradename Hamposyl(~) L-30 from Hampshire wo 96/12467 P c TruS95/ll864 Chemical Corp. as a 30% active solution.
7 "T C M A C" available commercially from Akzo-Chemie as Arquad(~-3 16 2390 as a 90% suspension.

Co--lpal~ e Examples 11-13 Shampoo Compositions of the Co---par~ /e Examples 11-13 are made similarly to that of Example 1, except that the non-enduring perfumes C, D, and E
respectively, are used instead of Perfume A. Hair worked with shampoo composition 239s of the Comperative Examples 11-13 has noticeably less perfume odor and less long lasting perfume odor especially after the drying step with an electric hair dryer, than when the shampoo composition of Example 1 is used.

EXAMPLES 14 to 21 (Foaming shower products) 2400 The following are personal cleansing compositions in the form of foaming shower products and which are representative of the present invention:
Compositions Component 14 15 16 1 7 18 A m photeric(l) 7.5 3.0 5.0 5.0 2.5 2405 Sodium N-lauryl-beta-amino propionate -- 5.0 3.0 -- 5.0 Sodium laureth-3 sulfate 7.5 9.0 10.0 10.0 7.5 A P G(2) 2.5 -- 2.0 2.0 Coconut diethanolamide 3.0 1.0 -- 2.0 1.0 2410 Cocoamidopropyldimethyl-carboxymethyl betaine -- 2.0 2.0 1.0 2.S
Ceraphyl GA(3) 5.0 4.0 6.0 6.0 5.0 Polymer 1(4) -- 0.1 0.2 -- 0.1 Polymer 2(5) 0.2 0.1 -- 0.2 0.1 2415 Myristic acid 4.0 2.0 1.5 1.0 2.0 Preservative 0.15 0.15 0.15 0.15 0.15 Pearlescer 0.5 -- -- 1.0 1.0 Perfume A 0.7 0.7 0.7 0.7 0.7 Water to 100 Compositions Ingredients 19 20 21 Amphoteric(1) 5.0 5.0 Sodiumlaureth-3 sulfate 10.0 10.0 WO 96tl2467 PCTrU$95/11864 2425 APG(2) 2.5 2.5 Coconut diethanolamide 3.0 Coconut monoethanolamide - 3.0 2.82 Cocoamidopropyldimethyl-carboxymethyl betaine 2.5 - -2430 Ceraphyl GA(3) 5.0 5.0 Polymer 1(4) 0.2 Polymer 2(5) - 0.2 PEG(6) caprylic/capric glyceride 2.0 1.0 4.0 2435 Myristic acid 2.0 2.0 2.0 M~le~ted soybean oil - - 2.0 Soybean oil 5.0 5.0 8.0 Preservative 0.2 0.2 Pearlescer 2.0 1.0 2440 Perfume B 1.0 1.0 1.70 NalMg laureth-3-3.6 sulfate - - 12.0 Sodium lauryl amphoacet~te - - 6.0 Decylglucoside - - 2.5 Polyquaternium-10 (JR-30M) - - 0.40 2445 Glycerine - 3.0 3.0 Titanium dioxide - - 0.10 Sodium benzoate - - 0.25 Glydant - - 0.13 SodiumEDTA - 0.13 2450 Mg sulfate heptahydrate - - 0.55 Water - to 100 (1) Empigent~) CDR 60 - an aqueous mixture of about 26.5%
cocoamphoacetate (the amphoteric of Formula I and/or IV in which R1 is coconut alkyl, R2 is H, and Z is CO2Na) and about 1.5%
2455 cocoamphocli~cet~te (the amphoteric of Formula I and/or IV in which R
is coconut alkyl, R2 is CH2CO2Na, and Z is CO2Na).
(2) Alkylpolysaccharide of Formula VI in which R is C8-Clo alkyl, t is 0, Z
is a glycose residue, and x is about 1.5.
(3) Maleated soybean oil marketed by Van Dyke.
2460 (4) Merquat(~) 550 - copolymer of acrylamide and dimethyldiallyl ammonil~mchloride, mol. wt. 2.5 x 106 (8% solution).

WO 96/12467 PCTrUS95/11864 (5) Polymer JR-400(~) - hydroxyethylcellulose reacted with epichlorohydrin and quaternized with trimethylamine, mol. wt. 4 x 106.
Compositions 14 to 18 are prepared by: forming a gel phase A of Merquat 2465 550 and/or JR-400 in water; forming an aqueous phase B co~ g the ~ ing water-soluble, oil-insoluble ingredients; forming an oil phase C cor.~ the Ceraphyl GA, myristic acid, coconut diethanolamide, and pearlescer; admixing phases A and B and heating to about 65-70~C; heating phase C to about 65-70~C and admixing with mix of phases A and B; cooling to about 40-45~C; adding preservative, 2470 and cooling to ambient temperature and adding the perfume A. Compositions 19 to 21 are prepared by: forming a surfactant phase A cont~ining a portion of the water, the anionic and amphoteric surf~ct~nts and the rem~ining water-soluble, oil-insoluble ingredients; forming an oil phase B cont~ining the myristic acid, coconut diethanolamide, PEG(6) caprylic/capryl glycerate and oil; admixing B with A at about 2475 40-50~C; adding the r.?m~ining water, preservative and perfume B; cooling to ambient temperature; and arlmixing the Ceraphyl GA. The average particle size of the emulsion droplets is about 30 micron (~Ialvern Series 2600 laser diffraction).
The products provide excellent in-use and efficacy benefits incl~ ing cleansing and lathering together with improved miltlne~s and skin conditioning (hydration,2480 suppleness, etc.), and especially long lasting perfume benefit.
Co"~)a,a~ive E~a.n~lcs 22-24 Foaming shower compositions of Compa~ e Examples 22-24 are made similar to that of Example 1 9, except that the non-enduring Perfumes C, D and E, respectively, are used instead of Perfume B. The compositions of Comparative Examples 22-24 2485 provide less noticeable perfume odor benefit and the perfume odor is significantly less long lasting, as compared to the composition of Example 1 9.
EXAMPLES 25 to 34 (;Personal Cleansing Compositions Co~t~ining Soap) Compositions Ingredients 25 26 27 28 29 2490 1) Soap ~K or Na)15.00 1 1.00 1 1.00 8.00 1.00 30% Laurate 30% Myristate 25% p~lmit~te 15% Stearate 2495 2) Fatty acids 4.50 1.50 1.50 0.50 0.50 (above ratios) 3) Na Lauryl 6.00 6.00 6.00 6.00 6.00 Sarcosinate W O96/12467 PCTrUS9S/1186 4) Sodium Laureth-3 2500 Sulfate 0.660.66 0.66 0.66 0.66 5) Cocamidopropyl- 1.33 1.331.33 1.33 1.33 betaine 6) Glycerine 15.0015.00 15.0015.0015.00 7) Propylene glycol9.00 9.009.00 9.00 9.00 2s0s 8) Polyquaternium 100.800.80 0.80 0.80 0.80 9) Ethylene glycol1.50 1.501.50 1.50 1.50 distearate (EDTA) 10) Propylparaben 0.10 0.100.10 0.10 0.10 1 1) Methylparaben0.20 0.200.20 0.20 0.20 2510 12) Perfume A 1.001.00 -- -- --13) Perfume B -- -- 1.001.00 1.00 14) KOH or NaOH If necessary, adjust premix to pH=7 1 5) Water Balance to 100 2515 Compositions In~redients 30 3 1 32 33 34 1) Soap (K orNa) 20.00 25.00 15.00 15.00 11.00 30% Laurate 30% Myristate 2520 25% Palmit~te 15% Stearate 2) Fatty acids 1.5 1.0 1.50 1.50 1.50 (above ratios) 3) Na Lauryl 6.00 -- 6.00 6.00 6.00 2525 Sarcosinate 4) Sodium Laureth-3 Sulfate 0.66 -- 0.66 0.66 0.66 5) Cocamidopropyl- -- -- 1.33 1.33 1.33 betaine 2530 6) Glycerine -- 10.00 15.00 -- 15.00 7) Propylene glycol 9.00 9.00 9.00 1 5.00 --8) Polyquaternium 10 -- -- 0.80 0.80 0.80 9) Ethylene glycol -- -- 1.50 1.50 1.50 distearate (EDTA) 2s3s 10) P~u~yl~)a~ben 0.10 0.10 0.10 0.10 0.10 W O96/12467 PCTrUS95/1186 11) Methylparaben 0.20 0.20 0.20 0.20 0.20 12)PerfumeB 1.10 1.10 1.10 1.10 1.10 13) KOH or NaOH ------- If necess~ry~ adjust premix to pH=7 14) Water R~ nce to 100 -Compositions 25 through 34 were prepared as follows:
1. Adding the fatty acids to the mixing vessel and begin heating to about 150~F to 160~F;
2. Adding the propylene glycol to the mixing vessel, continue heating and mixing;
2545 3. In a separate mixing vessel, mixing the Polyquaternium 10 polymer into the glycerin (polymer premix), until the polymer hydrates (app~ ,ately 10 min~lteS);
4. When the fatty acids are completely melted, reacting the fatty acid mixture to soap with KOH (45% solution) and the water;
2550 5. A~er reaction is completed, adding the following ingredients one at a time, ensuring complete mixing between each and m~int~ining a batch temperature of about 150~F to 160~F:
a) Polymer premix b) Ethylene glycol distearate 2555 C) Methyl and p~ Jylpal~ben d) Sodium lauroyl sarcosinate e) Cocamidopropyl betaine f) Sodium laureth-3 sulfate 6. Flash cooling the batch to about 90~F to 95~F then adding and thoroughly 2560 mixing in the following materials:
a) Phenoxyethanol b) Perfume (Personal Cle~n~ing Emulsion Compositions without Soap) 2565 The following oil-in-water emulsions contain no soap, have an average oil droplet size of about 30 microns, and have a pH from about 4.5 to about 7.5.

Compositions Ingredients 35 36 37 38 34 Na Mg Laureth 2570 3.6sulfate 12.0012.00 12.00 20.00 12.00 Lauroamphn~cet~te6.00 6.00 6.00 6.00 6.00 Decylglucoside 2.50 2.50 2.50 2.50 2.50 Cocamide MEA 2.82 2.82 2.82 -- 2.82 Soybean oil 8.00 8.00 8.00 8.00 8.00 2575 PEG-6 caprylic/ 4.00 4.00 4.00 4.00 4.00 capric glycerides Glycerine 3.00 3.00 3.00 3.00 3.00 Maleated soybean oil2.00 2.00 2.00 2.00 2.00 Myristic acid 1.60 1.60 1.60 1.60 1.60 2580 Citric acid 1.40 1.40 1.40 1.40 1.40 Polyquaternium 10 0.40 0.40 0.40 0.40 --Sodium benzoate 0.25 0.25 0.25 0.25 0.25 Glydant 0.14 0.14 0.14 0.14 0.14 Disodium EDTA 0.13 0.13 0.13 0.13 0.13 2585 Titanium dioxide 0.10 0.10 0.10 0.10 0.10 ~Mg Sulfate hepta- 0.10 0.10 0.10 0.10 0.10 hydrate Perfume A 1.00 1.00 1.00 1.00 1.00 Water R,~l~nce to 100 Compositions Ingredients 40 41 42 43 Na Mg Laureth-3.6 sulfate 12.00 15.00 -- --2595 Lauroampho~cet~te -- 6.00 10.00 8.00 Decylglucoside 2.50 -- 2.50 2.50 Cocamide MEA -- -- 2.82 2.802 Soybean oil 8.00 8.00 8.00 8.00 PEG-6 caprylic/ 4.00 4.00 4.00 4.00 2600 capric glycerides Glycerine 3.00 3.00 3.00 3.00 Maleated 2.00 2.00 2.00 2.00 soybean oil Myristic acid 1.60 -- 1.60 1.60 2605 Citric acid 1.40 1.40 1.40 1.40 Polyquaternium 10 0.40 0.40 0.40 0.40 Sodium ben7O~te 0.25 0.25 0.25 0.25 Glydant 0.14 0.14 0.14 0.14 DisodiumEDTA 0.13 0.13 0.13 0.13 2610 Titanium dioxide 0.10 0.10 0.10 0.10 MgSulfatehepta- 0.10 0.10 0.10 0.10 hydrate Perfume B 1.20 1.20 1.20 1.20 Water Ral~nce to 100 Compositions 35 to 43 are prepared by: forming a gel phase A by dispersing Polyquaternium 10 in water at about 25~C with strong agitation. When phase A is thoroughly dispersed begin heating to about 45~-50~C and add decylglucoside and lauroamphoacet~te while mixing. Then add sodium magnesium laureth-3.6 sulfate.
2620 Add sodium benzoate, disodium EDTA, citric acid, and titanium dioxide while heating to about 60~-65~C and mix until homogeneous.
Prepare phase B by mixing per-6 carpylic/capric glycerides, cocamide MEA, and myristic acid together at about 60~-65~C. When solids have melted, add soybean oll.
2625 Add phase B to phase A and rnix until em~ll.cified, then start cooling. Adjust pH if necess~ry with citric acid.
At about 45~-50~C add glycerine. At about 40~-45~C add DMDM
Hydantoin, maleated soybean oil, m~gnesillm sulfate heptahydrate, and perfume.
Cool to ambient temperature.

The following examples are liquid hand washing compositions co..~ iog enduring perfume compositions.
Compositions Ingredients 44 45 2635 Sodium lauryl sulfate 6.00 3.80 Sodiumlaureth-3 sulfate 4.00 7.60 Cocamidopropyl betaine 1.20 1.35 Lauramide DEA 2.86 2.50 Sodium sulfate 0.45 2.10 2640 TetrasodiumEDTA 0.10 0.10 Glydant 0.20 0.20 Citric acid 0.20 0.25 Ethylene glycol distearate 1.50 --Pearlese;er -- û.43 2645 Polymer Jaguar C-14S û.25 --WO 96/12467 PCT~US95/11864 Perfume A 0.25 --Perfume B -- 0 30 Water -----Balance to 100----2650 Compositions In~redients 46 47 48 49 50 Myristic acid -- -- 7.51 1.50 --Tallow fatty acid -- -- 6.51 -- --Potassium hydroxide -- -- 2.90 3.36 --2655 Mono sodium lauryl -- -- -- 13.33 --phosphate Ammonium or sodium 6.00 6.00 2.00 -- --laureth-3 sulfate Cocoamphodi~cet~te 3.00 3.00 2.00 2.0 --2660 Decylglucoside -- -- -- -- 3.0 Lauramine oxide -- -- -- -- 10.0 Glucose amide 2.71 2.70 -- -- 2.70 Na Lauryl sarcosinate -- 1.50 -- 2.0 --Cocamidopropyl -- 3.75 2.00 2.0 --2665 betaine Soybean oil -- 4.00 -- --Caprylic/capric -- -- 2.50 2.50 --glycerides Glycerine 5.00 --2670 Dimethicone copolyol 2.00 -- -- --(Dow 193) Zinc stearate -- 0.80 -- -- --Cetyl alcohol -- 1.00 1.00 1.50 1.50 Carbomer -- 0.40 -- 1.50 --2675 EGDS -- 1.00 1.00 -- --Polyquaternium 10 1.00 -- 0.80 0.40 --Polyquaternium 11 -- 0.80 -- -- --Perfume A 0.90 0.90 0.90 0.90 0.80 Sodium benzoate 0.25 0.25 0.25 0.25 0.25 2680 DisodiumEDTA 0.13 0.13 0.13 0.13 0.13 DMDM Hydantoin 0.14 0.14 0.14 0.14 0.14 Water Balance to 100 W O 96/12467 PCT~US95/1186 Compositions ~ 2685 Ingredients 51 52 53 54 Ammonium or sodium 12.00 5.00 -- -laureth-3 sulfate Cocamidopropyl amine -- 5.00 2.50 2.00 oxide 2690 Na Lauryl sarcosinate 3.00 -- -- --Sodium cocoyl -- 5.00 -- 10.00 isethionate Cocamidopropyl -- -- -- 2.0 betaine 2695 Glycerine -- -- 10.00 --Propylene glycol -- -- -- 9.00 Sodium benzoate0.25 0.25 0.25 0.25 Disodium EDTA 0.13 0.13 0.13 0.13 DMDMHydantoin 0.14 0.14 0.14 0.14 2700 Perfume B 0.90 0.80 0.80 0.80 Water Balance to 100 Compositions 44 to 54 are plc;pa~ed by: forming a gel phase A comprising water and polymer (e.g., Carbomer, Polyquaternium 10, Polyquaternium 11). When 2705 phase A is completely dispersed, begin heating to about 70~C. Add all additional ingredients except preservatives (DMDM Hydantoin, disodium EDTA, and sodium benzoate) and fragrance. Cool to about 30~C and add fragrance, and preservatives.
Cool to ambient temperature while mixing.

2710 Hair Spray Hair spray compositions are prepared from the following components utili7ing conventional mixing techniques.

Compositions Ingredients Water QS 100 QS 100 QS 100 QS 100 Ethanol (SCA 40) 79.0 79.0 79.0 90.0 W O96/12467 PCTAUS9~/11864 Copolymer(1) 4.0 4.0 3 0 3 0 2720 Perfume B 0.1 0.2 0.3 0.4 (1) Poly(n-butyl-co-2-methoxyethylacrylate)-graft-poly(2-ethyl-2-oxazoline) thermoplastic elastomeric copolymer, prepared by the following method.
To a 500 mL round-bottomed flask is added about 20.8 g (about 0.1623 mol) 2725 of n-butyl acrylate, about 11.2 g (about 0.0861 mol) of 2-methoxyethyl acrylate, about 0.30 g (about 0.002 mol) p-vinylbenzyl chloride, and about 0.02 g (about 0.0012 mol) of azoisobutyronitrile (AIBN) initator, in about 200 mL of acetone. The resl.lting solution is refluxed slowly for about 24 hours. The reaction is then q~lenr.h~d by the addition of about 5 mL of methanol and cooled to room 2730 temperature. The solvents are removed by rotary evaporation and the resulting polymer is dissolved in about 250 mL of dry acetonitrile. Next, about 20.0 g (about 0.2018 mol) of 2-ethyl-2-oxazoline and about 0.44 g (about 0.0029 mol) of sodiumiodide is added and the solution is heated to about 90~C for about 20 hours. Thereslllting solution is filtered and the solvent is evaporated to yield about 45.0 g (about 2735 86% yield) of the thermoplastic elastomeric copolymer.
P,epal~lion of Compositions 55-58 These products are prepared by first dissolving the polymer in the ethanol with stirring. The water and fragrance are then added with stirring. The resulting hair spray compositions can then be packaged in a nonaerosol spray pump. Alternatively, 2740 the compositions can be combined with conventional propellants and packaged in an aerosol spray.
These hair sprays are useful for application to the hair to provide a styling and holding benefit.

2745 Red~lced Volatile Organic Content Hairspray Hair spray compositions are prepared from the following components lltili7ing conventional mixing techniques.
Ingredients 59 60 61 62 Water QS 100 QS 100 QS 100 QS 100 2750 Ethanol 54.0 54.0 54.0 54.0 Copolymer of Example 58 4.0 3.0 4.0 3.0 PerfumeB 0.05 0.2 0.1 0.15 These products are prepared by first dissolving the polymer in the ethanol with 2755 stirring. The water and fragrance are then added with stirring. The reslllting hair W O96/12467 PCTrUS95/1186 spray compositions can then be packaged in a nonaerosol spray pump. Alternatively, the compositions can be combined with conventional propellants and packaged in an aerosol spray.
These hair sprays are useful for application to the hair to provide a styling and holding 2760 benefit.
EX~MPLES 63-65 Mousse Mousse compositions are prepared from the following components ~Itili~ing conventional mixing techniques.
276s Ingredients Water QS 100 QS 100 QS 100 Copolymer of Example 58 3.00 2.50 3.50 Lauramide DEA 0.33 0.33 0.33 Sodium Methyl Oleyl Taurate 1.67 1.67 1.67 2770 DMDM Hydantoin 0.78 0.78 0.78 Disodium EDTA 0.20 0.20 0.20 Polyox,valkylated isostearyl alcohol (1) 0.10 0.10 0.10 Perfume B 0.10 0.10 0.10 Propellant (2) 7.0 7.0 7.0 (2) Available as Aerosurf~ 66-E10.
(3) Available as a mixture of about 82.46% isobutane, about 16.57% propane, and about 0.001% butane.

2780 These products are prepared by first dissolving the polymer in water with stirring.
The ~ ingredients, except the propellant, are then added with stirring. The r~s~llting mousse concen~ e can then be combined with conventional propellants (e.g., Propellant A46) and pa~ ged in an aerosol spray. These mousses are usefulfor application to the hair to provide a styling and holding benefit.

Hair Tonic Hair tonic compositions are prepared from the following components l1tili~ing conventional mixing techniques.

Ingredients Ethanol QS 100 QS 100 QS 100 Copolymer of Example 58 0.75 1.00 1.25 PerfumeA 0.10 -- --Perfume A -- 0.20 0.30 These products are prepared by dissolving the polymer in the ethanol with stirring and then adding the fragrance and any colors.
These hair tonics are useful for application ~o the hair to provide a styling and holding benefit.
2800 EX~MPLE 69 Hair Conditioner A hair conditioner composition is prepared ~om the following components lltili7ing conventional mixing techniques.
In~redients Wei~ht %

Styling Agent Premix Copolymer of Example 58 1.00 Silicone Premix Silicone gum, GE SE76(1) 0.30 2810 Oct~methyl cyclotetrasiloxane 1.70 r. ~ ;x Water QS100 Cetyl Alcohol 1.00 Quaternium 18(2) 0.85 2815 Stearyl Alcohol 0.70 Hydroxethyl cellulose 0.50 Ceteareth-20 0.35 Perfume A 0.20 Dimethicone copolyol ~ 0.20 2820 CitricAcid 0.13 W O 96/12467 PCT~US95/11864 Methylchloroisothiazolinone (and) methylisothiazolinone 0.04 Sodium Chloride 0.01 1 Commercially available from General Electric.
2825 2 Dimethyl Di(Hydrog~n~ted Tallow) Ammonium Chloride The product is prepared by co-mixing all the Main Mix ingredients, heating to about 60~C with mixing, and colloid milling while cooling to about 45~C. At thistemperature, the two premixes are add separately with moderate agitation and theres -lt~nt conditioner is allowed to cool to room temperature.
2830 This product is useful as a rinse offhair conditioner.

Anti-Acne Composition An anti-acne composition is made by combining the following components using conventional mixing technology.
2835 Ingredient Wei~ht %
Water QS100 Salicylic Acid 2.0 Copolymer from Example 58 1 2.0 Ethanol (SDA 40) 40.0 2840 Perfume B 0.05 The compositon display skin penetration of the salicylic acid as well as improved skin reel and residue characteristics and is useful for the tre~tment of acne.

Topical Analgesic Composition 2845 A topical ~n~lgç~ic composition is made by combinillg the following ingredients utili7:ing conventional mixing techniques.
Ingredients Weight %
Water, Purified QS100 Ibuprofen 2.0 2850 Copolymer from Example 58 1 2.0 Ethanol (SDA 40~ 20.0 Pt,ru.. ,c B 0.03 The compositions display skin penetration of the ibuprofen active as well as improved skin feel and residue characteristics together with excellent moisturizing, W O96/12467 PCTrU$95/1186 2855 emolliency, rub-in and absorption characteristics.

Sunless Tanning Composition A composition for sunless tanning is made by combining the following ingredients l1tili7ing conventional mixing techniques.
2860 Ingredients Weight %
Phase A
Water qs 100 Copolymer from Example 58 2.00 Carbomer 934 (1) 0.20 2865 Carbomer 980 (2) 0.15 Acrylic Acid Copolymer (3) 0.15 Phase B
PPG-20 Methyl Glucose Ether Distearate 2.00 2870 Tocopheryl Acetate 1.20 Mineral Oil 2.00 Stearyl Alcohol 1.00 Shea Butter 1.00 Cetyl Alcohol 1.00 2875 Ceteareth-20 2.50 Ceteth-2 1.00 Ceteth-10 1.00 Phase C
2880 DEA-Cetyl Phosphate 0.75 Phase D
Dihydroxyacetone 3.00 Phase E
Butylene Glycol 2.00 2885 DMDM Hydantoin (and) Iodopropynyl Butylcarbamate 0.25 Phase F
Perfume B 1.00 Cyclomethicone 2.00 2890 (i) Available as Carbopol~ 934 from B.F. Goodrich.
(2) Available as Carbopol(~) 980 from B.F. Goodrich.
(3) Available as Pemulen~ TRl from B.F. Goodrich.
In a suitable vessel the Phase A ingredients are dispersed in the water and heated to about 75-85~C. In a separate vessel the Phase B ingredients are combined 2895 and heated to about 85-90~C until melted. Next, the DEA-Cetyl Phosphate is added to the liquid Phase B and stirred until dissolved. This mixture is then added to Phase A to form the emulsion. The emulsion is cooled to about 40-45~C with continued mixing. Next, in a separate vessel, the dihydroxyacetone is dissolved in water and the res-llting solution is mi-xed into the emulsion. In another vessel, the Phase E
2900 ingredients are heated with mixing to about 40-45~C until a clear solution is formed and this solution is then added to the emulsion. Finally, the Phase F ingredients are added to the emulsion with mixing, which is then cooled to about 30-35~C, and then to room temperature.
This emulsion is useful for topical application to the skin to provide an artificial 2905 tan.

Sunscreen Composition An oil-in-water emulsion is prepaled by colllbinillg the following components utili7ing conventional mixing techniques.
2910 In~redients Wei~ht %
Phase A
Water QS100 Carbomer 954 (1.) 0.24 Ch,l,~ l 1342 (2) 0.16 291~ Copolymer ~om Exmaple VI (3) 1.75 Di~otlil.m EDTA 0.05 Phase B
Isoarachidyl Neopçnt~no~te (4) 2.00 PVP Eicosene Copolymer (5) 2.00 2920 Octyl Methoxyçi~ te 7.50 Octocrylene 4.00 Oxybenzone 1.00 Titanium Dioxide 2.00 Cetyl Palmit~te 0.75 2925 Stearo~y~lhllethylsilane (and) Stearyl Alcohol (6) 0.50 Glyceryl Tribehenate (7) 0.75 Dimethicone 1.00 Tocopheryl Acetate 0.10 2930 DEA-Cetyl Phosphate 0.20 Phase C
Water 2.00 Triethanolamine 99% 0.60 Phase D
2935 Water 2.00 Perfilme B 0.05 Butylene Glycol 2.00 DMDM Hydantoin (and) Iodopl ol)y"yl Butylcarbamate (8) 0.25 2940 dL P~nthP,nol 1.00 Phase E
Cyclomethicone 1.00 (1) Available as CarbopolR 954 from B.F. Goodrich.
(2) Available as CarbopolR 1342 from B.F. Goodrich.
2945 (3) Alternatively, the sunscreen compositions are prepared using the copolymers of Examples VIII and IX.
(4) Available as Elefac I-205 from Bernel Chemical.
(5) Available as Ganex V-220 from GAF Corporation.
(6) Available as DC 580 Wax from Dow Corning.
2950 (7) Available as Synchrow~x HRC from Croda.
(8) Available as Glydant Plus from Lonza.
In a suitable vessel the Phase A ingredients are dispersed in the water and heated to about 75-85~C. In a separate vessel the Phase B ingredients (except DEA-W O96/12467 PCTrUS95/11864 Cetyl Phosphate) are combined and heated to about 85-90~C until melted. Next, the 2955 DEA-Cetyl Phosphate is added to the liquid Phase B and stirred until dissolved. This mixture is then added to Phase A to form the emulsion. The Phase C ingredients are combined until dissolved and then added to the emulsion. The emulsion is then cooled to about 40-45~C with continued mixing. In another vessel, the Phase D
ingredients are heated with mixing to about 40-45~C until a clear solution is formed 2960 and this solution is then added to the emulsion. Finally, the emulsion is cooled to about 35~C and the Phase E ingredient is added and mixed.
This emulsion is useful for topical application to the skin to provide protection from the harmful effects of ultraviolet radiation.

2965 Facial Moisturizer A leave-on facial emulsion composition cont~ining a cationic hydrophobic surfactant is prepared by combining the following components l-tili7ing conventional mixing techniques.
Ingredients Weight %
2970 Water QS100 Copolymer from Example 58 1.00 Glycerin 3.00 Cetyl P~lmit~te 3.00 Cetyl Alcohol 1.26 2975 Quaternium-22 1.00 Glyceryl Monohydroxy Stearate 0.74 Dimethicone 0.60 Stearic Acid 0.55 Octyldodecyl Myristate 0.20 2980 Perfume B 0.06 Carbomer 1342 0.125 Tetrasodium EDTA 0.10 DMDM Hydantoin and Iodopropynyl Butyl C&.l,&,-lale 0.10 2985 Carbomer 951 0.075 This emulsion is useful for application to the skin as a moisturizer.

The following compositions are .eplesenla~ e of antipe-~ -l composions herein.

W O96/12467 PCT~US95/llX6 2990 Ingredients 75 76 77 78 79 80 81 82 N-Lauroyl-L-glutamic acid-di-n-butyl amide(1) 4 5 1 3 2 2 2 12-l.yd.oxy~Learic acid 2 5 5 6 7 3 6 12 Cyclomethicone D-5(2) - 40 49 39 43 40 43 46 2995 Polyphenylmethylsiloxane(3) - - - 3 - - 5 Light mineral oil(4) 23 Panalane-L-14E(5) - 15 10 11 - - - -IsopropylMyristate - 15 15 16 - - 11 Isopropyl Alcohol - - - - 18 3000 Captex 200(6) - - - - - 15 C12-C15 Alcohols Benzoate(7) - - - - - - 8 PPG-3 Myristyl Ether - - - - - - - 26 Diisopropyl Sebacate(8) 43 min~-m Zirconium 300s Trichlo~hydl~x Gly(9) 24.9 19.8 19.9 19.89 - 39.88 24.8 ~lllmimlm Chlorohydrate(10) - - - - 29.86 - - 9.85 Perfume A 0.1 - 0.01 0.14 0.2 PerfumeB - 0.02 - 0.11 - 0.12 - 0.15 Talc 3 - - 2 - - - 5 (1) GP-l supplied by Ajinomoto, Inc.
(2) Dow Corning 245 Fluid-cyclic polydimethylsiloxane (3) Dow Corning 556 Fluid (4) Benol White Mineral Oil supplied by Witco Chemical Corp.
3015 (5) Polyisobutene supplied by Amoco Chemical Company (6) Propylene glycol dicaprate/dicaprylate supplied by Capital City Products (7) Finsolv~ TN supplied by Finetex (8) Schercemol(E~) DIS supplied by Scher Chemic~l~ Inc.
(9) Supplied by Westwood Chemical Co.
3020 (10) Westchlor(~) DM200 supplied by Westwood Chemical Co.

The following is another example of a deodorant composition.
An antipe~ n~ stick composition of the present invention is prepared as 3025 follows. All of the ingredients described below are combined and heated to about 82~C with agitation. The batch is then cooled to about 52~C and poured into canisters.
Ingredients Weight %
Cyclometh;coneD-5 (1) 39.8 3030 Light Mineral Oil (2) 11.5 Dimethicone (50 csk) (3) 1.5 Stearyl Alcohol 14.0 Hydro~Pn~ted Castor Oil (4) 4.5 W O96/12467 PCT~US95111864 Eicosanol 0.2 3035 Talc 1.4 Fumed Silica (5) 1.0 Perfume A 0.1 .~ltlminllm Chlorohydrate (6) 26 0 100%
3040 (1) A 5 carbon cyclic polydimethylsiloxane supplied by G.E. Silicones (2) Benol White Mineral Oil, supplied by Witco Chemical Corporation (viscosity = 18-20 csk at 40~C; density = 0.839-0.855 g/cm3) (3) Supplied by Dow Corning (4) Castor Wax MP 80, supplied by NL Industries 3045 (5) Cab-O-Sil HS-5, supplied by Cabot Corporation (6) Reheis 501 macrospherical ~ minllm chlorohydrate, supplied by Reheis Chemical Company 30so

Claims (8)

1. Personal treatment composition selected from the group consisting of: leave-on hair care composition and leave-on skin care composition, all of which are normally applied to one, or more, parts of the body and incompletely removed, said personal treatment composition containing an effective amount of enduring perfume composition.

2. The composition of Claim 1 wherein the hair care composition is selected fromthe group consisting of hair conditioner, hair spray, hair gel, hair tonic, mousse, hair curler and hair straightener.

3. The composition of Claim 1 wherein the skin care composition is selected fromthe group consisting of deodorant, antiperspirant, skin lotion, skin moisturizer, skin softening lotion, suntan lotion, sun screen lotion, sunless tanning composition, skin bleaching composition, topical pharmaceutical skin care composition, perfume, and cologne.

4. The composition of Claim 3 wherein the topical pharmaceutical skin care composition is selected from the group consisting of anti-acne composition, non-steroidal anti-flammatory composition, steroidal anti-flammatory composition, antipruritic composition, anesthetic composition, and antimicrobial composition.

5. The composition of any of Claims 1-4 wherein the enduring perfume composition is at a level of from about 0.001% to about 50%, preferably from about 0.005% to about 6%, more preferably from about 0.01% to about 4%, by weight, and even more preferably from about 0.01% to about 1%, by weight.

6. The composition of any of Claims 1-5 wherein said enduring perfume composition has at least about 70%, preferably at least about 75%, more preferably at least about 80%, and even more preferably at least about 85%, components withClogP~3.0 and boiling point of ~250°C.

7. The composition of any of Claims 1-6 wherein said enduring perfume composition contains at least 70% of materials selected from the group consisting of:
Allyl cyclohexane propionate; Ambrettolide; Amyl benzoate; Amyl cinnamate; Amyl cinnamic aldehyde; Amyl cinnamic aldehyde dimethyl acetal; iso-Amyl salicylate;
Aurantiol; Benzophenone; Benzyl salicylate; para-tert-Butyl cyclohexyl acetate;
iso-Butyl quinoline; beta-Caryophyllene; Cadinene; Cedrol; Cedryl acetate; Cedryl formate; Cinnamyl cinnamate; Cyclohexyl salicylate; Cyclamen aldehyde; Dihydro isojasmonate; Diphenyl methane; Diphenyl oxide; Dodecalactone; iso E super;
Ethylene brassylate; Ethylmethyl phenyl glycidate, Ethyl undecylenate; Exaltolide;
Galaxolide; Geranyl anthranilate; Geranyl phenyl acetate, Hexadecanolide; Hexenyl salicylate; Hexyl cinnamic aldehyde, Hexyl salicylate; alpha-Irone; Lilial (p-t-bucinal); Linalyl benzoate; 2-Methoxy naphthalene; Methyl dihydrojasmone;
gamma-n-Methyl ionone; Musk indanone; Musk ketone; Musk tibetine; Myristicin;
Oxahexadecanolide-10; Oxahexadecanolide-11; Patchouli alcohol; Phantolide;
Phenyl ethyl benzoate; Phenylethylphenylacetate; Phenyl heptanol; Phenyl hexanol;
alpha-Santalol; Thibetolide; delta-Undecalactone; gamma-Undecalactone; Vetiverylacetate; yara-yara; Ylangene; and mixtures thereof.

8. The process of using the composition of any of Claims 1-7 comprising the step of applying an effective amount of said composition to at least one part of the human body.