CA2246293A1 - 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

W~ 97/30689 PCT~lJS97~l~2991 PERSONAL TREATMENT COMPOSITIONS AND/OR COSMETIC COMPOSITIONS
CONTAINING ENDURING PERFUME

TECHNICAL FIELD
The present invention relates to personal cleansing and/or cosmetic compositionscont~ining 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 cle~n~ing and cosmetic products provides olfactory aestheticbenefit and/or serves as a signal of cle~nlinPss. These are especially i,l~po~ functions of these personal care products. Personal care products generally include "rinse-ofr' products, such as soaps, liquid soaps, shampoos, hair conditioners, etc., which are applied to, e.g., skin or hair and then rinsed off from the skin or hair, and "leave-on" products, such as skin moisturizers, sun screen products, deodorants, hair sprays, mousse, etc., which are applied and are normally allowed to remain on, e.g., skin or hair.
Continuous 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~ing process.
a substantial amount of perfume in the personal cleanser compositions is lost with the rinse water and in the subsequent drying. On the other hand, some products, especially leave-on and cosmetic products can leave a considerable amount of material, including perfume material, on the body. It is extremely important that any m:~teri~l left on the body provide the maximum effect with tne miniml-m amount of material, and that the material be as safe and non-irrit~ting as possible.
People skilled in the perfume art, usually by experience, have some knowledge ofsome particular perfume ingredients that are "substantive" and/or non-irritating.
Subst~ntive perfume ingredients are those odorous compounds that effectively deposit on skin or hair in the cleaning process and are detectable on the subsequently dried skin or ~ hair by people with normal olfactory acuity. The knowledge of what perfume ingredients are substantive is spotty and incomplete.
The object of this invention is to provide personal cleansing compositions W O 97/30689 PC~US97/02991 containing enduring perfumes 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 and/or wasted in the cleaning and drying steps. It is also an object to provide perfumes that are non-irritating insofar as that is possible.
S SUMMARY OF THE ~NVENTION
The present invention relates to personal tre~tmçnt compositions compri.cin~
perfumes that provide a long lasting aesthetic benefit with a minimum amount of material ("enduring perfume") and which are relatively non-irritating. The present invention, in one aspect, especially relates to cleansing compositions that are normally rinsed, 10 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 comprising at least about 70% of perfume ingredients selected from the group con~i.cting of: ingredients having a boiling point of at least about 250~C
and a ClogP of at least about 3; cisjasmone; dimethyl benzyl carbinyl acetate;
ethyl vanillin; geranyl acetate; alpha-ionone; beta-ionone; gamma-ionone;
koavone; lauric aldehyde; methyl dihydrojasmonate; methyl nonyl ~cet~l~lehyde;
gamrna-nonalactone; phenoxy ethyl iso-butyrate; phenyl ethyl dimethyl carbinol;
phenyl ethyl dimethyl carbinyl acetate; alpha-methyl-4-(2-methylpropyl)-benzenepropanal; 6-acetyl- 1,1,3 ,4,4,6-hexamethyl tetrahydronaphthalene;
undecylenic aldehyde; vanillin; 2,5,5-trimethyl-2-pentyl-cyclopentanone; 2-tert-butylcyclohexanol; verdox; para-tert-butylcyclohexyl acetate; and mixtures thereof, the level of ingredients having a boiling point of at least about 250~C and a ClogP of at least about 3 being less than about 70%, and preferably less than about 65%, more preferably less than about 60%, so that the composition with only those ingredients is not an enduring perfume;
(B) from about 0.01% to about 95%, preferably from about 5% to about 85%, more preferably from about 3% to about 30%, and even more preferably from about 5%
to about 22%, of a s~ ct~nt system; and (C) the balance comprising carrier, normally liquid, including water, C I -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 11, preferably from about 4.5 to about 10.5, more preferably from about 5 to about 10.
Some of these cle~n.cin~ compositions are meant to be used and then rinsed off.
The enduring perfilme compositions are desirable for such personal cleansing CA 02246293 l998-08-l3 W O 97130689 P~T~U~97J~2991 compositions that are intended to be rinsed off, since the enduring perfume compositions deposit extremely efficiently. In another aspect, enduring perfume compositions are used in other personal treatment compositions, including cosmetics, skin treatment compositions, and/or cleansing compositions that are meant to be left on the skin~ or S simply wiped off, thereby leaving a substantial amount of material on the skin. The enduring perfume compositions are extremely desirable for such personal treatment compositions since they require minim~l material to provide long lasting effects even when the skin is in contact with the water, as when swlmming~ Personal tre~tmPntcompositions such as deodorants, perfumes, colognes, suntan lotions, skin softening 10 lotions, etc., which are meant to leave relative}y large amounts of m~tçr~1 on the skin, are especially improved by use of these enduring perfume compositions, since they minimi7~.
the amount of material in contact with the skin.
DETAILED DESCRIPTION OF THE ~NVENTION
The present invention relates to personal treatment compositions, including personal 15 cleansing compositions comprising, by weight of the personal cleansing 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 comprising at least about 70% of perfume ingredients selected from the group consisting of:
ingredients having a boiling point of at least about 250~C and a ClogP of at least about 3; cis-3asmone; dimethyl benzyl c~lJi~lyl acetate; ethyl vanillin; geranylacetate; alpha-ionone; beta-ionone; gamma-ionone; koavone; lauric aldehyde;
methyl dihydrojasmonate; methyl nonyl acetaldehyde; gamma-nonalactone;
phenoxy ethyl iso-butyrate; phenyl ethyl dimethyl carbinol; phenyl ethyl dimethyl carbinyl acetate; alpha-methyl-4-(2-m~lhyl~,.. ,l,yl)-benzen~ o~ al; 6-acetyl-1,1,3,4,4,6-hPx~m~thyl tetrahy~lr~ll~hthalene; undecylenic aldehyde; vanillin;

2,5,5-trimethyl-2-pentyl-cyclopentanone; 2-tert-butylcyclohexanol; verdox; para-tert-butylcyclohexyl ~et~t~; and mixtures thereof, the level of ingredients having a boiling point of at least about 250~C and a ClogP of at least about 3 being less than about 70%, preferably less than about 65%, and more preferably less than about 60%, so that the composition with only those ingredients is not an en~ ring perfume;
(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 lic~uid 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 11, preferably from about 4.5 to about 10.5, more preferably from about 5 to about 10, said enduring perfume composition preferably having at least about 70%, more preferably at least about 75%, even more preferably at least about 80%, and yet more preferably more than about 85%, of enduring perfume ingredients.
The present invention also relates in one aspect to personal tre~tm~nt compositions, e.g., those selected from the group con~icfing of: deodorants; antipc~s~ ; skin lotions;
suntan lotions; perfumes, and colognes, all of which are normally applied to one, or more, parts of the body ar d incompletely removed, said personal treatment compositions co~t~inin~ an effective amount of said enduring perfume compositions.
A. Endurin~ Perfume Composition Personal treatment, e.g., cleansing and/or cosmetic compositions in the art commonly contain perfumes to provide a good odor to the body. These conventionalperfume compositions are normally selected mainly for their odor quality, with some consideration of substantivity.
Enduring perfume ingredients, as disclosed herein, can be form~ ted into personal cle~nging and/or cosmetic compositions, including li~uid personal cleansing compositions, and are slLlbst~nti~lly deposited and remain on the body throughout any rinse and/or drying steps. These endl-ring perfume ingredients minimi7e the material wasted, while still providing the good aesthetics that the consumers value.
These enduring perfume ingredients are selected from the group consisting of: cis-jasmone; dimethyl benzyl carbinyl acetate; ethyl vanillin; geranyl acetate; alpha-ionone;
beta-ionone; gamma-ionone; koavone; lauric aldehyde; methyl dihydrojasmonate; methyl nonyl acetaldehyde; gamma-nonalactone; phenoxy ethyl iso-butyrate; phenyl ethyl dimethyl carbinol; phenyl ethyl dimethyl carbinyl acetate; alpha-methyl-4-(2-methylpropyl)-ben7~nr~. u~ al (Suzaral T); 6-acetyl- 1,1 ,3,4,4,6-hexarnethyl tetrahydron~phth~lene ~Tonalid); undecylenic aldehyde; vanillin; 2,5,5-trimethyl-2-pentyl-cyclopentanone (veloutone3; 2-tert-butylcyclohexanol (verdol); verdox; para-tert-butylcyclohexyl acetate (vertenex); and mixtures thereof. Enduring perfume compositions can be forn~ te~l using these enduring perfume ingredients, preferably at a level of at least about 5%, more preferably at least about 10%, and even more preferably at least about 20%, by weight of the enduring perfume composition, the total level of enduring W 097130689 PCT~U~97)D299 perfume ingredients, as disclosed herein, being at least about 70%, all by weight of said enduring perfume composition.
Other enduring perfume ingredients that can be used with the above named en~ n~ perfume ingredients can be characterized by boiling point (B.P.) and 5 octanol/water partitioning coefficient (P). The octanol/water partitioning coefficient of a perfume ingredient is the ratio between its equilibrium concentrations in octanol and in water. These other enduring perfume ingredients of this invention have a B.P., measured - at the normal, standard pressure, of about 250~C or higher, preferably more than about 260~C; and an octanol/water partitioning coefficent P of about 1,000 or higher. Since the 10 partitioning coefficients of these other enduring perfume ingredients of this invention have high values, they are more conveniently given ;n the form of their logarithm to the base 10, logP. Thus these other enduring 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.
15The boiling points of many perfume ingredients are given in, e.g., "Perfume and Flavor Chemicals (Aroma Chemicals)," Steffen Arctander, published by the author, 1969, incorporated herein by reference.
The logP of many perfume ingredients has been reported; for example, the Pomona92 ~t~h~e, available from Daylight Chemical Information Systems, Inc.
20 (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 experimental logP
values when they are available in the Pomona92 database. The "calculated logP" (ClogP) is dc~ cd by the fragment approach of Hansch and Leo (cf., A. Leo, in 25 Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. ~mmt?n~, J. B. Taylor and C. A. P~m~den, Eds., p. 295, Pergarnon Press, 1990, incorporated herein by reference).
The fragment approach is based on the chemical ~Ll~u;Lu~e of each perfume ingredient, and takes into account the nurnbers and types of atoms, the atom comlectivity, and chemical bonding. The ClogP values, which are the most reliable and widely used ~ctim~tes for this 30 physicochemical ~lopclLy, are preferably used instead of the cx~cl;mental logP values in the selection of these other entl~-rin~ perfume ingredients which are useful in the present invention.
Thus, when a perfume composition which is composed of the above named ingredients and, optionally, a level, less than about 70%, of ingredients having a B.P. of 35 about 250~C or higher and a ClogP of about 3 or higher, is used in a liquid personal cleansing composition, the perfume is very effectively deposited on skin or hair, and W O 97/30689 PCTrUS97/02991 remains substantive 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, usefulin li~uid personal cleansing compositions of the present invention. The enduring perfume compositions of the present invention contain at least about 3 different enduring perfurne ingredients, more preferably at least about 4 different enduring perfume ingredients, and even more preferably at least about 5 different enduring perfume ingredients.
Furthermore, the en~lllrinE perfume compositions of the present invention contain at least 10 about 60 wt.% of enduring perfume ingredients, preferably at least about 70 wt.~/o of enduring perfume ingredients, more ~lere-ably at least about 80 wt.% of enduring perfume ingredients, and even more preferably at least about 85 wt.% of enduring perfurne ingredients, the level of ingredients having a B.P. of at least about 250~C and a ClogP of more than about 3 being at a level of less than about 70%, preferably less than about 65%, 15 and more preferably less than about 60%, so that the composition with only those ingredients is not an enduring perfume. Personal cle~n~ing 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 about 4%, and even more preferably from about 0.01% to about 1 %, of an enduring perfume composition. Hair care and topical skin 20 care compositions that are not norrn~lly 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% 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 25 cologne, etc.
In the perfume art, some materials having no odor or very faint odor are used asdiluents or e~ten-lPrs Non-limiting exarnples of these materials are dipropylene glycol, diethyl phth~l,qte, triethyl citrate, isopropyl myristate, and benzyl benzoate. These materials are used for, e.g., solubilizing or diluting some solid or viscous perfume 30 ingredients to, e.g., improve h~ntlling and/or form~ ting, or stabilizing volatile ingredients, e.g., by reducing their vapor pressure. These materials are not counted in the definition/formulation of the enduring perfume compositions of the present invention.
Non-enduring perfume ingre~ient~, which are preferably minimi7~ofl in personal tre~tm~nt e.g., liquid personal cle~n~ing compositions of the present invention, are those 35 named above and 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~~ and a ClogP of less than -WC) 97/30689 PCT~17S97/02991 about 3Ø Table 2 gives some non-limitin~ examples of non-enduring perfilme ingredients. In some particular fabric softener compositions, some non-enduring perfilme ingredients can be used in small amounts, e.g., to improve product odor. However, to minimi7~? waste, the enduring perfilrne compositions of the present invention contain less 5 ~an about 30 wt.% of non-enduring perfume ingredients, preferably less than about 25 wt.% of non-enduring perfume ingredients, more preferably less than about 20 wt.% of non-en~llrin~ perfilme ingredients, and even more preferably less than about 15 wt.% of non-enduring perfilme ingredients.
Table I
Examples of Other Endurin~ Perfume In~redients Approximate Perfume In~redients B.P. ~~C) (a) ClogP
BP > 250~C and ClogP > 3.0 Allyl cyclohexanepropionate 267 3.935 Ambrettolide 300 6.261 Ambrox DL ~Dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan) 250 5.400 Amyl benz~,~.le 262 3.417 Amyl cinnzlrnS-t~ 310 3.771 Amyl cinnamic aldehyde 285 4.324 Amyl cinnamic aldehyde dimethyl acetal 300 4.033 iso-Amyl salicylate 277 4.601 Aurantiol 450 4.216 BeuGopl~,lone 306 3.120 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~-linPn~ 275 7.346 Cedrol 291 4.530 Cedryl acetate 303 5.436 Cedryl formate +250 5.070 Cinnamyl cinn~nn~t~ 370 5.480 Cyclohexyl salicylate 304 5.265 Cyclamen aldehyde 270 3.680 Dihydro isojasmonate +300 3.009 Diphenyl methane 262 4.059 Diphenyl oxide 252 4.240 Dodecalactone 258 4.359 iso E super +250 3.455 Ethylene brassylate 332 4.554 Ethyl methyl phenyl glycidate 260 3.165 Ethyl undecylenate 264 4.888 W O 97/30689 PCT~US97/02991 Exaltolide 280 5.346 Gala~olide +250 5.482 Geranyl anthranilate 31 4.216 Geranyl phenyl acetate +250 5.233 S HexRrlP~nolide 294 6.805 Hexenyl salicylate 271 4.716 Hexyl cinnamic aldehyde 305 5.473 Hexyl salicylate 290 5.260 alpha-lrone 250 3.820 Lilial (p-t-bucinal) 258 3.858 Linalyl benzoate 263 5.233 2-Methoxy n~phth~lene 274 3.235 gamma-n-Methyl ionone 252 4.309 Musk indanone +250 5.458 Musk ketone MP - 137~C 3.014 Musk tibetine MP = 136~C 3.831 Myristicin 276 3.200 OY ~hex;l~ec~nolide- 10 +300 4.336 Oy~he~ec~nolide-11 MP = 35~C 4.336 Patchouli alcohol 285 4.530 Phantolide 288 5.977 Phenyl ethyl benzoate 300 4.058 Phenylethylphenylacetate 325 3.767 Phenyl heptanol 261 3.478 Phenyl hexanol 258 3.299 alpha-Santalol 301 3.800 Thibetolide 280 6.246 delta-Un~ec~l~ctone 290 3.830 gamma-Un~1~c~ tt~tle 297 4.140 Undecavertol (4-methyl-3-decen-5-ol) 250 3.690 Vetiveryl acetate 285 4.882 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.

Table 2 Examples of Non-Endurin~ Perfume In~redients Approximate Perfume In~redients B.P. (~C~ C1O~P
BP < 250~C and ClogP < 3.0 Ben7~1rlehyde 179 1.480 Benzyl acetate 215 1.960 laevo-Carvone 231 2.083 Geraniol 230 2.649 WO 97/306g9 PCT)IIS97JD2991 _ g _ Hydroxycitronellal 241 1.541 Linalool 198 2.429 Nerol 227 2.649 Phenyl ethyl alcohol 220 1.183 alpha-Terpineol 219 2.569 BP > 250~C and ClogP < 3.~
Couma~in 291 l .412 Eugenol 253 2.307 iso-Eugenol 266 2.547 Indole 254 decompos 2.142 Methyl cinn~m~t~ 263 2.620 Methyl-N-methyl anthranilate 256 2.791 beta-Methyl naphthyl ketone 300 '.275 BP c 250~C and ClogP > 3.0 iso-Bornyl acetate 227 3.485 Carvacrol 238 3.401 alpha-Citronellol 225 3.193 para-Cymene 179 4.068 Dihydro myrcenol 208 3.030 d-Limonene 177 4.232 2~ Linalyl acetate 220 3.500 B. Personal Cleansin~ Compositions Which Are Nonnallv Rinsed Off I. Surfactant SYstem Some l~left;llcd surf~rt~nt~ for use in the surfactant systems herein~ as well as other cleansing product ingredients, are disclosed in the following references:
-Pat. No. Issue Date Inventor(s) 4,061,602 12/1977 Oberstar et al.
4,234,464 11/1980 Mor~h~ er 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 Llenado 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 Medcalfet al.

W O 97130689 PCT~USg7/02991 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 surfactants are disclosed in the patents incorporatedherein by reference. They include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof. They include alkyl sulfates, alkylpolyethyleneglycol ~ f~tes, alkyl sulfonates, alkyl glyceryl ether sulfonates, anionic acyl sarcosinates, methyl acyl laurates, N-acyl glut~m~tes, acyl isethionates, alkyl sulfosuccinates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, trideceth s~lf~tes, protein condensates, mixtures of ethoxylated alkyl sulfates and alkyl amine oxides, bet~in~e~ sultaines, and mixtures thereof. Included in the alkylpolyethyleneglycol sulfate surfactants are the alkyl ether sulfates with 1 to 12 ethoxy groups, especially ammonium and sodium lauryl ether slllf~tes The hydrophobic, e.g., alkyl, chains for the surfactants are norrnally Cg-~22, preferably C~ 10-C 18-1. Anionic Detergent Surfactants a. Soap Some ,ule~led compositions of the present invention contain soaps derived from e~st?nti~lly saLul~led hydrocarbon chainlengths of from about 8 to about 22 carbon atoms.
It is preferred that the soap be the sodium and/or potassium salts, but other soluble soaps can be used.
b. SYnthetic Anionic Deter~ent Surfactants Anionic nonsoap synthetic detergent s--rf~-t~rlte can be exçmplified by the alkali metal salts of organic sulfuric reaction products having in their molecular structure an alkyl radical cont~inin~ from 8 to 22 carbon atoms and a sulfonic acid or sulfuric acid ester radical (included in the term allcyl is the alkyl portion of higher acyl radicals).
c. Sulfate Surf~ct,~nte The compositions hereof can comprise alkyl sulfate, alkyl ether sulfate, fatty acid monoglyceride sulfate, or mixtures thereof, as a ~llrf~rt~nt component. Typically, such sulfate surfactants, 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) 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-forrning cation such as ammonium, aLkanolammonium (such as WO 97/30689 PCT~US~7JO299 triethanolammonium), monovalent metal cations, such as sodium and/or potassium, polyvalent metal cations, such as m~gnesium and calcium, and/or mixtures of suchcations. The cation M, of the anionic surfactant should be chosen such that the anionic surfactant component is water soluble. Solubility will depend upon the particular anionic - 5 surfactants and/or cations chosen. As an aid to ~letermining ap~ropl;ate mixtures of anionic surf~(~t~nte~ the anionic surfactants should be chosen such that the Krafft te~ Jeld~ul~ of the surfactants chosen is about 15~C or less, preferably about 10~C or less, more preferably about 0~C or less. It is also preferred 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 alkyl ether sulfates. The alkyl ether sulfates are typically made as cont1~ne~tion products of ethylene oxide and monohydric alcohols having from about 8 to about 24 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 resulting mixture of molecular species having, for example, an average of 3 moles of ethylene oxide per mole of alcohol, is slllf~t~?~l and ne~ltr~li7.e-1 Specific examples of alkyl ether sulfates which can be used in the present invention are sodium and arnmoniurn salts of coconut alkyl triethylene glycol ether sulfate, tallow alkyl triethylene glycol ether sulfate, and tallow alkyl hexaoxyethylene sulfate. Highly plef~lled alkyl ether sulfates are those comprising a mixture of 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 Delt;l,~e,ll Surf~-~t~llte A suitable class of optional anionic detersive s-lrf~t~nte are aliphatic sulfonates such as ~ s~ ed by the water-soluble salts of the organic, sulfurlc acid reaction products of the general forrnula (I):
Rl-SO3-M (I) wherein R1 is chosen from the group con~i~ting of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about 24, preferably about 12 to about 18, carbon atoms; and M is a cation, as previously describedL, subject to the same limitations regarding polyvalent metal cations as previously discussed. Important examples are the salts of an organic sulfuric acid reaction product of a hydrocarbon of the methane series, including iso-, neo-, and n-p~d~ s, having about 8 to about 24 carbon CA 02246293 l998-08-l3 W 097/30689 PCT~US97/02991 atoms~ preferably about 12 about 18 carbon atoms and a sulfonating agent, e.g., SO3.
H2SO4, oleum. obtained according to known sulfonation methods, including bleaching and hydrolysis. Preferred are alkali metal and ammonium sulfonated C12-C1g paraffins (e.g., normal and secondary paraffins).
Additional examples of synthetic anionic sulfonate detersive surfactants which can be added to the compositions of the present invention are the reaction products of fatty acids esterified with isethionic acid and neutrali~ed with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid arnides of methyl tauride in which the fatty acids, for example, are derived from 10 coconut oil, and fatty acid monoglyceride sulfonates as described in the patents incorporated herein by reference.
Still other synthetic anionic detersive surfactants are in the class cle~ign~te~l as succinates. This class includes such surface active agents as disodium N-octadecylsulfos~ cin~te; tetrasodium N-( 1 ,2-dicarboxyethyl~-N-octadecylsulfosuccinate;
15 diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid;
dioctyl esters of sodium sulfosuccinic acid.
Other suitable anionic detersive surfactants include olefin sulfonates having about 12 to about 24 carbon atoms. The term "olefin sulfonates" is used herein to meancompounds which can be produced by the sulfonation of alpha-olefins by means of 20 uncomplexed sulfur trioxide, followed by neutral1zation of the acid reaction mixture in conditions such that any sulfones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-~lkSlnesl-lfonates. The sulfur trioxide can be liquid or gaseous, and is usually, but not nPcess~nly, diluted by inert diluents, for example, by liquid SO2, chlorinated hydrocarbons, etc., when used in the liquid form, or by air, 25 nitrogen, gaseous S02, etc., when used in the gaseous forrn.
The alpha-olefins from which the olefin sulfonates are derived are mono-olefins having about 12 to about 24 carbon atoms, preferably about 14 to about 16 carbon atoms.
Preferably, they are straight chain olefins.
In addition to the true alkene sulfonates and a proportion of hydroxy-30 ~lk~n~slllfonates, the olefin sulfonates can contain minor arnounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportion of re~t~nt~, the nature of the starting olefins and inlpuliLies in the olefin stock and side reactions during the sulfonation process.
Another class of anionic detersive sllrf~t~nt~ are the beta-alkyloxy alkane 35 sulfonates. These compounds have the following formula (IT):
Rl C(OR2)(~)cH2sO3M (II) WO ~7~30689 ~CT)US97/l~2991 where E~1 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 ~preferred) to about 3 carbon atoms, and M
~ is a water-soluble cation as hereinbefore described.
e. N-AcYlamino Acid Surfactants - 5 Yet other anionic detergent surfactant type is the N-acylamino acid surfactant type, which includes N-acyl hydrocarbyl acids and salts thereof, such as those represented by Fonnula III, as follows:
Rl - C (O)- N (R2) - (R3)n COOM (I~I) wherein: Rl is a C7-C23 alkyl or alkenyl radical, preferably Cg-C17; R2 is -H, Cl-C4 alkyl, phenyl, or -CH2COOM, preferably Cl-C4 alkyl, more preferably Cl-C2 alkyl; R3 is -CR42- or Cl-C2 alkoxy, wherein each R4 independently is -H or Cl-C6 alkyl oralkylester, and n is from I to 4, preferably 1 or 2, and M is -H or a cation as previously defin~l, preferably an alkali metal such as sodiurn or potassium.
A wide variety of N-acyl acid surfactants and their synthesis are described in Anionic Sl-rf~ct~nt~, Part Il, Surfactant Science Series, Vol. VII, edited by Warner M.
Linfield, Marcel Dekker, Inc. (New York and ~asel), 1976; pp 581-~17.
Especially preferred are compounds of Forrnula 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 potassiurn salt forms.
P,erelled anionic detersive surfactants for use in the present compositions include the sodium, ammonium, potassium or triethanolamine alkyl sulfates, especially those obtained by slllf~ing the higher alcohols (Cg-C 1 g carbon atoms), sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassiurn 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 12 carbon atoms, sodium alkyl glyceryl ether sulfonates; the reaction product of fatty acids having from 10 to 22 carbon atoms esterified with isethionic acid and neutralized with sodium hydroxide; water-soluble salts of condensation products of fatty acids with sarcosine; and others known in the art.
Some ~i..,.plcc of good lather-.?nh~n~ing, mild anionic detergent surfactants are e.g., sodium or potassium lauroyl sarcosinate, alkyl glyceryl ether sulfonate, sulfonated fatty esters, and sulfonated fatty acids.

W O 97/3068g PCTrUS97/02991 Other synthetic detergent surfactants which can be used include amphoteric~
zwitterionic, nonionic and, in certain instances, cationic surf~ç~nt~, e.g., at a level of from about I % to about 10%, preferably from about 2% to about 6% by weight of the product.
2. AmPhoteric Deter~ent Surfact~ntc Examples of amphoteric surfactants 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 qu~tem~ry amines in which at least one hydrophobic, e.g., aliphatic, radical which can be either straight or branched chain and which typically contains from about 8 to about 18 carbon atoms and in which at least one radical contains 10 an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples of compounds falling within this definition are sodium 3-dodecylaminopropionate, sodium 3-dodecylaminopropane sulfonate, N-alkyltaurines, such as the one prepared by reacting dodecylamine with sodium isethionate according to the te~hing of U.S. Pat. No. 2,658,072, N-higher alkyl aspartic acids, such as those produced 15 according to the te~ehin~ of U.S. Pat. No. 2,438,091, and the products sold under the trade name "Miranol" and described in U.S. Pat. No. 2,528,378.
The amphoteric surfactants hereof also include the imidazolinium amphoteric (zwitterionic) surf~ t~nt~ such as those depicted by Forrnula (IV):
RlCoN(R4) - (CH2)n - N+(R3)(R2)-CH2Z ~IV) 20 wherein Rl is Cg-C22 alkyl or alkenyl, preferably C12-C~6, R2 is hydrogen or CH2C02M, R3 is CH2CH20H or CH2CH20CH2CH COOM, R4 is hydrogen, CH2CH20H, or CH2CH20CH2CH2COOM, Z is C02M or CH2C02M, n is 2 or 3, preferably 2, M is hydrogen or a cation, such as alkali metal, ~lk~line earth metal, ammonium, or alkanol ~mmonium.
Suitable materials of this type are marketed under the tr~ ?n~me Miranol~) and are understood to comprise a complex mixture of species, and can exist in protonated and non-protonated species depending upon pH with respect to species that can have ahydrogen at R2. The imidazolinum amphoteric surfactant hereof can be derived via an imi-l~701iniurn inte~ne~i~te. However, it will be recognized by those in the art that it 30 needn't necPs~s~rily be derived via an imidazolinium.
Preferred amphoteric surfactants of Formula IV are monocarboxylates and dicarboxylates. Examples of these materials include cocoarnphocarboxy-propionate, cocoarnphocarboxypropionic acid, cocoamphocarboxyglycinate (alternately referred to as cocoarnphodiacetate), and cocoarnphoacetate.
Specific comrnercial products providing the imidazolinium derivative component of the present compositions include those sold under the trade names Miranol C2M CONC.

W O 97/30689 PCTnUS97)~2991 N.P., Miranol C2M CONC. O.P., Miranol C2M SF, Miranol CM Special (Miranol, Inc.);
Alkateric(~) 2CIP (Alkaril Chemicals); Amphoterge(g) W-2 (Lonza, Inc.); Monateric(!~
CDX-38, Monateric CSH-32 (Mona Industries~; Rewoteric~ AM-2C (Rewo Chemical Group); and Scheroteric(~) MS-2 (Scher Chemicals).
S Amphoteric sllrf~ct~nt~ also include arninoalkanoates ofthe formula (V):
R-NlI(CH2)nCOOM; (V) and imino~ lk~noates of the formula (VI):
R-N[(CH2)mcOOM]2 (VI) and mixtures thereof; wherein n and m are numbers from 1 to 4, 1~ is Cg-C22 alkyl or alkenyl, and M is hydrogen, alkali metal, ~Ik~lint? earth metal, ammonium or alkanolammonium.
Examples of such amphoteric surfactants include n-alkylaminopropionates and n-alkyliminodipropionates. Such materials are sold under the tr~clen~me 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 salts thereof.
Other zwitterionic sllrf~ct~nt~, in addition to the imi~ oliniums, can be exemplified by those which can be broadly described as derivatives of aliphatic ql-~t~rn~ry ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. A general formula (VIr) for thesecompounds is:
R2 - Y(+) (R3)x CH2 - R4 - Z(~) (VII) wherein R2 contains an alkyl, alkenyl, or hydroxy 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, Y is selected from the group con~ictin~ of nitro~en, 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 atoms and Z is a radical selected from the group con~i.ctin~ of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
Examples include: 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane- I -carboxylate; 5-[S-3-hydl~xyl lopyl-S-h~x~iecylsulfonio]-3-hydroxy~,~ .,Lal1e-l-sulfate; 3-~P,P-P-diethyl-P-3 ,6,9-tri-oxatetradexocylphosphonio] -2 -hy ~ Oxy~l o~ e- 1 -phosphate; 3 -[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropylammonio~-propanel-phosphonate; 3-(N,N-dimethyl-N-hP~ cylammonio)propane-l-sulfonate; 3-(N,N-dimethyl-N-h~ lecylamrnonio)-2-hydroxypropane- 1 -sulfonate; 4-[N,N-di(2-hydroxyethyl)-N-(2-hydroxydodecyl)ammonio]-butane- I -carboxylate; 3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane- 1 -phosphate; 3-(P,P-dimethyl-P-dodecylphosphonio)-propane- 1 -phosphonate; and 5-[N,N-di~3-hydroxypropyl)-N-hexadecylamrnonio3-2-hydroxy-pentane- 1 -sulfate.
S Zwitterionic detergent surfactants cont:~ining an amido linkage in the hydrophobic chain are especially desirable and include those represented by the Formula (VIII):
RsC(O)N(R4)(CH2)mN+(R2)(R3)YR1 (VIII) wherein: R1 is a member selected from the group consisting of: COOM and CH(OH)-CH2SO3M; R2 is C1-C3 alkyl or hydroxy (Cl-C3) alkyl, R3 is Cl-C3 alkyl or hydroxy 10 (Cl-C3) alkyl; R4 is a member selected from the group consisting of hydrogen and Cl-C3 alkyl; Rs is Cg-C2~ alkyl or alkenyl; Y is C 1 -C3 alkyl;
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 ~Ik~line earth cation metal, ammonium, or alkanolarnide.
The term "alkyl" or "hydroxyalkyl" means straight or branch ch~in~rl saturated, 15 aliphatic hydrocarbon radicals and substituted hydrocarbon radicals such as, for example, methyl, ethyl, propyl, isopropyl, hydroxypropyl, hydroxyethyl, and the like Examples of zwitterionics useful herein include the higher alkyl betaines such as coco dimethyl carboxymethyl betaine, }auryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha-carboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis(2-20 hydroxyethyl)carboxy methyl betaine, stearyl bis-(2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl bis-(2-hydroxypropyl) alpha-carboxyethyl betaine, etc. The sulfobetaines can be represented by coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl bis-(2-hydroxyethyl) sulfopropyl betaine, amido betaines amidosulfobetaines, and the like.
25 3. Cationic D~Le~ t Surfactants Many cationic surf~ct~nt~ are known to the art. By way of example, the followingcan be mentioned:
stearyldimethylbenzyl ammonium chloride;
dodecyltrimethylammonium chloride;
nonylbenzylethyldimethyl ammonium nitrate;
tetradecylpyridinium bromide;
laurylpyridinium chloride;
cetylpyridinium chloride;
laurylpyridinium chloride;
laurylisoquinolium bromide;
ditallow(hydrogenated)dimethyl ammonium chloride;

W O 9~130689 PCTnUS97/02991 dilauryldimethyl ammonium chloride; and stearalkonium chloride.
4. Nonionic Deter~ent Surf~t~nt.c Nonionic surfactants are typically compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound.
which can be aliphatic or alkyl aromatic in nature, but can include other surfactants that do not possess a charge group. Examples of ~!lcft~ d classes of nonionic surfactants are:
a. A11CY1 phenol ethoxylates. The polyethylene oxide condensates of alkyl phenols, e.g., the con-len~t;on products of alkyl phenols having an alkyl 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.
b. PolYethYlene ~Ivcol/poly~ropvlene ~lycol block copolYmers. Those derived fromthe con(1en~tion of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene (li~mine products which can be varied in composition depending upon the balance between the hydrophobic and hydrophilic elements which is desired. For example, compounds cont~ining from about 40% to about 80% polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted 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, are s~ti~f~tc-ry.
c. Fatty alcohol and fattY acid ethoxylates. The co~d~onc~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 conclen~t~ having from 10 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms. Other ethylene oxide conc~n~tion products are ethoxylated fatty acid esters of polyhydric alcohols (e.g., Tween 20-polyoxyethylene (20) sorbitan monolaurate).
d. Lon~ chain tertiary amine oxides. Long chain tertiary amine oxides colTesponding to the following general formula:
RlR2R3N--> O

, W 097/30689 PCTrUS97/02991 wherein R1 contains 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 I to 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 representation 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, dimethyldecylarnine oxide, dimethyltetradecylamine oxide, 3,6,9-trioxaheptadecyldiethylamine oxide, di(2-hydroxyethyl)-tetradecylamine oxide, 2-dodecoxyethyldimethylamine oxide, 3-dodecoxy-2-hydroxypropyldi(3-hydroxypropyl) amine oxide, dimethylhexadecylamine oxide.
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, from 0 to about 10 ethylene oxide 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 repres~ont~tion of a semipolar bond. Examples of suitable phosphine oxides are: dodecyldimethylphosphine oxide, tetradecylmethylethylphosphine oxide, 3,6,9-trioxaoctadecyldimethylphosphine oxide, cetyldimethylphosphine oxide, 3-dodecoxy-2-hydroxypropyldi(2-hydroxyethyl) phosphine oxide stearyldimethylphosphine oxide, cetylelhyl~lvpylphosphine oxide, oleyldiethylphosphine oxide, dodecyldiethylphosphine oxide, tetradecyldiethylphosphine oxide, dodecyldil.lo~yll)hosphine oxide, dodecyldi(hydroxymethyl)phosphine oxide, dodecyldi(2-hydroxyethyl3phosphine oxide, tetra-decylmethyl-2-hydroxypropylphosphine oxide, oleyldimethylphosphine oxide, 2-hydroxydodecyldimethylphosphine oxide.
f. Long chain dialkyl sulfoxides. Long chain dialkyl sulfoxides cont~ining one short chain alkyl or hydroxy alkyl radical of 1 to about 3 carbon atoms (usuallymethyl) and one long hydlophobic chain which contain alkyl, alkenyl, hydroxy alkyl, or keto alkyl radicals cont~inin~ from about 8 to about 20 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety.
Examples include: octadecyl methyl sulfoxide, 2-ketotridecyl methyl sulfoxide, W 097t30689 PCT~US97J~2991 3,6,9-trioxaoctadecyl 2-hydroxyethyl sulfoxide, dodecyl methyl sulfoxide, oleyl 3-hydroxypropyl sulfoxide, tetradecyl methyl sulfoxide, 3 methoxytridecyl - methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.
g. Alkvl polysaccharide (APS) surfactants such as the alkyl polyglycosides. Suchsurfactants are APS surfactants having a hydrophobic group with 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 (i.e., the hydrophobic moiety) can be s~tllr~te~l or Imsaturated, branched or unbranched, and unsubstituted or substituted (e.g., with hydroxy or cyclic rings).
h. PolvethYlene ~lycol (PEG) ~21Yceryl fatty esters~ such as those of the formula R(O)OCH2CH(OH)CH2(OCH2CH2)nOH wherein n is from about 5 to 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 surfactants are described in McCutcheon's, D~Ltl~enls And Emulsifiers, 1994 Annual, published by MC Publishing Company, which is incorporated here by reference, and in U.S. Patent No. 5,151,209, to McCall 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, I 992, all of which are incorporated by reference herein. For the purposes of the sl~rfa~t~nts described herein, it should be understood that the terms "alkyl" or "alkenyl" include mixtures of radicals which can contain one or more int~rm.o~ te linkages such as ether or polyether linkages or non-functional substi~lent~ such as hydroxyl or halogen radicals wherein the radical remains of hydrophobic ch~r~ t~r.
5. The Surfactant Svstems The present invention, especially in the aspect relating to personal cl~n.~in~
compositions that are normally rinsed, like sharnpoos and personal skin cleansers, 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 fronn about 5% to about 22% of a surfactant system. This surfactant system comprises anionic, nonionic, cationic, and/or zwitterionic type surfact~tnt.~ as described hereinbefore. For non-shampoo surfactant systems the surfactant system typically comprises at least one surfactant selected from the group con~i~ting of soap, acylglt~t~m~te~, alkyl sarcosinates,alkylpolyethyleneglycol sulfates, alkylglyceryl ether sulfonates, and/or acyl isethionates.

W O 97/30689 PCTrUS97/02991 a. Shampoo Surfactant SYstems The shampoo compositions of the present invention typically contain a detersive surfactant system to provide cleaning performance to the composition. The total detersive surfactant component will generally be present at a level from about 1% to about 30%, by 5 weight of the composition, preferably from about 12% to about 25%, more preferably from about 1~% to about 22%.
The shampoo compositions of the present invention optionally comprise from 0% toabout 20% of surfactants that build suds. When used, such optional suds buildingsurfactants 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 about 5%, although higher or lower levels can be used. Suitable surfactants for building suds include arnide foam boosters, e.g., fatty acid (e.g., C1o-C22) mono- and di- (Cl-Cs, especially Cl-C3) alkanol amides at a level of from about 0.1% to about 6%, preferably from about 0.5% to about 4%.
1~ b. Soap Surfactant Svstems Compositions of the present invention can comprise at least about 2% by weight of the surfactant system, ~lefc.dbly at least about 10%, more preferably at least about 25%, and even more preferably at least about 50% soap.
Preferably the alkali metal soap is Clo-C22, preferably C12-Clg, more preferablyC12-C14 (cocoate, laurate, PKO~ sodium, potassium, ammonium, triethanolammonium,and/or magnesium soap. Preferably these soaps have saturated alkyl chains.
These soaps are preferably prepared by the in situ saponification of the correspondirlg fatty acids, but they can also be introduced as preformed soaps.
The addition of Clo-C22 soap also decreases any "slippery feel" caused by any synthetic surfactant that is present.
A soap based liquid composition comprises:
(A) from about 5% to about 20% by weight of potassiurn Cg-C22 fat~y 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 consisting of: glycerin, glycerol, propylene glycol, polypropylene glycol, 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 of from 45 microns to about 120 microns; and CA 02246293 l998-08-l3 W 097/30689 PCTAUSg7J02991 -21-(E~ from about 0.~ to about 5~/0 glycol ester selected from the group consisting of glycol monoesters and diesters of fatty acids with a chainlength from about 10 to about 22, and mixtures thereof, typically formulated as a liquid which additionally comprises from about 35% to about 5 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 1:1 to about 15:1 and more preferably from about 3:1 to about 12:1; wherein said 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 (B) 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 below about ~.
The compositions can contain fatty acids derived from c~eellti~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 l~rop~,l lion of longer chain 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 con~i~fing of: glycerin, glycerol, propylene glycol, polypropylene glycol, polyethylene glycol, ethyl hexanediol, hexylene glycol, aliphatic alcohol; and mixtures thereof; and plcr~ldbly contains 10-30% of said polyol, preferably glycerol.
The petrolatum (emollient) useful in the above soap based liquid composition canbe any grade of white or yellow petrolatum recognized in the art as suitable for human application. The preferred type is USP Class III with a melting point between about 122~F and about 135~F (about 50~-57~C). Such a m~tf~ri~l iS col",~ .;ially available as Penreco Snow White Pet USP. The petrolatum of the present invention includes hydrocarbon mixtures formnl~te~ with mineral oils in combination with ~ Lrll~ waxes of various melting points.
Alternatively, the above soap based liquid composition can contain from about 0.5% to about 15% of a lipophilic emollient selected from the group con.ci~ting of: esters of fatty acids; glycerin mono-, di-, and tri-esters; epiderrnal 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 zlltern~t;vely e~lessed as a particle size distribution with 10% to 80% of the particles being about ~ 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 about 35~/0 to about 70%, preferably from about 40% to about 65%.
Liquid soap cleansers normally have a viscosity of from about I to about 150?000cps, preferably from about 500 cps to about 120,000 cps, more preferably from about 1,000 cps to about 45,000 cps, at about 26.7~C (about 80~F3, Brookfield RVTDCP with a Spindle CP-41 at 1 RPM for about 3 min~lteS.
The liquid soap is called 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. Q~tional In~redients 1. Optional Suspendin~e Agent The present compositions, and çspeci~lly shampoo compositions, can include a crystalline suspending agent. Other suspending agents useful for suspending emulsified oils (or other m~t~ri~l~) and for thickening the compositions can optionally be used.
The crystalline suspending agent will be used at an effective level for suspending emulsified 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 ~r~ d. In general, the compositions hereof will comprise from about 0.5% to about 10%, by weight, of a crystalline suspending agent or combination thereof. The crystalline suspending agent is preferably present in the sharnpoo 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 solubilized in a premix solution and then be recry~t~lli7~d 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 m~tf?ri~l.c and long chain arnine oxides, as well as ~ LLulc:s of such materials. Included are ethylene glycol long chain esters, alkanol amides of long chain fatty acids, long chain esters of long chain fatty acids, glyceryl long chain esters, long chain esters of long chain alkanol~mi~les, and long chain alkyl dimethyl arnine oxides, and mixtures thereof.

CA 02246293 l998-08-l3 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 preferred are the ethylene glycol stearates, both mono and distearate, but particularly the distearate cont~ining less than about 7% of the mono stearate. Other 5 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. Preferred alkanol amides are stearic monoethanolarnide, stearic diethanolamide, stearic monoisopl~opdnolamide and stearic monoethanolamide stearate. Other long chain acyl derivatives include long chain esters of long chain fatty acids (e.g., stearyl stearate, cetyl 10 p~lmit~te), glyceryl esters (e.g., glyceryl distearate) and long chain esters of long chain alkanol arnides (e.g., stearamide diethanolarnide distearate, stearamide monoethanolamide stearate). Ethylene glycol esters of long chain carboxylic acids, long chain amine oxides, and alkanol amides of long chain carboxylic acids, in addition to the preferred materials listed above, can be used as suspending agents.
Suspending agents also include long chain a}nine oxides such as allcyl (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 suspending function could also be provided by such amine oxide or acyl derivative, provided at least a portion of them are present in crystalline forrn, and additional suspending agent may not be 20 needed.
Other long chain acyl derivatives that can be used include N,N-dihydrocarbyl (C 12-C22, preferably C16-CIg) arnido benzoic acid and soluble salts thereof (e.g., Na and K
salts), particularly N,N-di(C 16-c l 8, and hydrogenated tallow) arnido benzoic acid species of this family, which are co~ lcl.;ially available from Stepan Company (Northfield, 25 ~llinois, US~).
The crystalline suspending agent serves to assist in suspending particulate matter or emulsions of insoluble fluids, i.e., oils, in the shampoo compositions hereof, and can give pearlescence to the product.
The crystalline suspending agent can be incorporated into the sharnpoos hereof by 30 solubilizing it into a solution co~ g water and the anionic sulfate surfactant at a Lt~ dLul~ above the melting point of the suspending agent. The suspending agent is then recryst~lli7~1 typically by cooling tne solution to a t~nl~ldLul~ sufficient to induce cry~t~lli7~tinn.
2. Optional Suspendin~e 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 W O 97/30689 PCT~US97/02991 Chapters 3, 4, 12 and 13 of the Handbook of Water-Soluble Gums and Resins. Robert L.
Davidson, McGraw-Hill Book Co., New York, N.Y., 1980, incorporated by reference herein.
Anionic thickeners include cro~inkç~l polymers. These crosslinked polymers typically contain one or more monomers derived from acrylic acid, substituted acrylic acids, and salts and esters of these acrylic acids and the substituted acrylic acids, wherein the cro~1inking agent contains two or more carbon-carbon double bonds and is derived from a polyhydric alcohol. The preferred polymers for use herein are of two general types. The first type of polymer is a crosslinked homopolymer of an acrylic acid10 monomer or derivative thereof (e.g., wherein the acrylic acid has substit~1~nt~ on the two and three carbon positions indep~n~len~ly se1ected from the group consisting of C 1-4 alkyl, -CN, -COOH, and mixtures thereof). The second type of polymer is a cro~link~d copolymer having a first monomer selected from the group consisting of an acrylic acid monomer or derivative thereof (as just described in the previous sentence), a short chain 1~ alcohol (i.e. a C 1-4) acrylate ester monomer or derivative thereof (e.g., wherein the acrylic acid portion of the ester has substituents on the t~vo and three carbon positions indepen-lt?nt1y selected from the group con~i~tin~ of Cl 4 alkyl, -CN, -COOH, and mixtures thereof), and ~ Lules 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 20 acid portion of the ester has substituents on the t~vo and three carbon positions independently selected from the 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 crosslinked homopolymers the monomers are preferably selected from the group con~i~ting of acrylic acid, methacrylic acid, ethacrylic acid, and L~ S
25 thereof, with acrylic acid being most preferred. In the second type of cros~1ink~1 copolymers the acrylic acid monomer or derivative thereof is preferably selected from the group con~i~tin~ of acrylic acid, methacrylic acid, ethacrylic acid, and mixtures thereof, with acrylic acid, methacrylic acid, and mixtures thereof being most pl.felled. The short chain alcohol acrylate ester monomer or derivative thereof is preferably selected from the 30 group con~i~ting of Cl 4 alcohol acrylate esters, Cl 4 alcohol methacrylate esters, Cl 4 alcohol ethacrylate esters, and mixtures thereof, with the C 1-4 alcohol acrylate esters, C 1-4 alcohol methacrylate esters, and nlix~ s thereof, being most prer~ d. The long chain alcohol acrylate ester monomer is selected from Cg 40 alkyl acrylate esters. with C10 30 alkyl acrylate esters being preferred.
The cros~1inking agent in both of these types of polymers is a polyalkenyl polyether of a polyhydric alcohol cont~ining more than one alkenyl ether group per molecule, W O 97t30689 PCT~US97~02991 wherein the parent polyhydric alcohol contains at least 3 carbon atoms and at least 3 hydroxyl groups. Preferred crosslinkers are those selected from the group consisting of - allyl ethers of sucrose and allyl ethers of pentaerythritol, and mixtures thereof. These polymers useful in the present invention are more fully described in U.S. Patent No.
~ 5 5,û87,445, to Haffey et al., issued February 1 1, 1992; U.S. Patent No. 4,509,949, to Huang et al., issued April S, 1985; U.S. Patent No. 2,798,053, to Brown, issued July 2, 1957;
which are incorporated by reference herein. See also, CT~A Tnt~ tional Cosmetic Ingredient Dictionary, fourth edition, 1991, pp. 12 and 80; which are also incorporated herein by reference.
Other examples of anionic commercially available homopolymers useful herein include the carbomers, which are homopolymers of acrylic acid croselink~-l with allyl ethers of sucrose or pentaerytritol. The carbomers are available as the Carbopol~ 900 series from B.F. Goodrich. Exarnples of commercially available copolymers of the second type useful herein include copolymers of C10 30 alkyl acrylates with one or morelS monomers of acrylic acid, methacrylic acid, or one of their short chain (i.e. C 1-4 alcohol) esters, wherein the crosslink;ng agent is an allyl ether of sucrose or pentaerytritol. These copolymers are known as acrylates/C10-30 alkyl acrylate crosspolymers and are comrnerically available as Carbopol~) 1342, Pemulen TR-1, 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, for example, ~arbopol 934, 940, 941, and 956.
A carboxyvinyl polymer is an interpolymer of a monomeric mixture comprising a monomeric olefinically ulls~ ed carboxylic acid, and from about 0.01% to about 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 attached at least three hydroxyl groups, the polyether cont~inin~ more than one alkenyl group per molecule. Othermonoolefinic monomeric materials can be present in the monomeric llli~lulc if desired, even in predolllina lt proportion. Carboxyvinyl polymers are substantially 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 coneietin~ of oligosaccharides, reduced derivatives thereof in which the carbonyl group is converted to an alcohol group, and pentaerythritol; more ed are oligosaccharides, most ~rel~cd is sucrose. It is ple~lled that the hydroxyl groups of the 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 preferred that the sucrose have at least about five allyl ether groups per sucrose molecule.

W O 97/30689 PCTrUS97/02991 It is preferred that the polyether of the polyol comprise from about 0.01% to about 4% of the total monomers~ more preferably from about 0.02% to about 2.5%.
Preferred monomeric olefinically unsaturated carboxylic acids for use in producing carboxyvinyl polymers used herein include monomeric, polymerizable, alpha-beta 5 monoolefinically unsaturated lower aliphatic carboxylic acids, more preferred are monomeric monoolefinic acrylic acids of the structure:
CH2 = C(R) - COOH
where R is a substituent selected from the group conxi~ting of hydrogen and lower alkyl groups; most preferred is acrylic acid.
Preferred carboxyvinyl polymers used in formulations of the present invention have a molecular weight of at least about 750,000; more ~l~relled are carboxyvinyl polymers having a molecular weight of at least about 1,250,000; most ~lc:r~ d 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 1 5 like.
Nonionic cellulosic thickeners include, but are not limited to: 1. hydroxyethyl cellulose; 2. hydroxymethyl cellulose; 3. hydroxypropyl cellulose; andlor 4. hydroxybutyl methyl cellulose.
A suitable thickener is hydroxy ethyl cellulose, e.g., Natrosol(~) 250 KR sold by The Aqualon Colllpdlly.
Other thickeners useful herein include acrylated steareth-20 methylacrylate copolymer sold as Acrysol~) ICS-l by Rohm and Haas Company; the carboxylic polymers 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, s~-lf~t~c, etc., at a level of from about 0.1% to about 5%, preferably from about 0.5% 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 cleansing products can be thickened by using polymeric additives that hydrate, swell or molecularly associate to provide body (e.g., hydroxypropyl guar gum).
Liquid personal cleansing 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;
(II) cationic copolymers of saccharides and synthetic cationic monomers, and CA 02246293 l998-08-l3 WO 97J30689 PCTnUS97JO2991 (III3 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-(ethyleneoxyethylene 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.
Other m~t.oris~l~ can also be used as optional suspension agents include those that can impart a gel-like viscosity to the composition, such as water soluble or colloidally water soluble polymers like cellulose etners (e.g., hydroxyethyl cellulose), guar gum, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl guar gurn, starch and starch derivatives, and other thickeners, viscosity modifiers, gelling agents, etc. Mixtures of these materials can also be used.
Another type of suspending agent that can be used is x~nth~n gum. Xanthan gum isbiosynthetic gum material that is cornmercially 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, ~oy L. Editor Industrial Gums - Polysaccharides and Their Derivatives New York: Academic Press, 1973. Kelco, a Division of Merck & Co., ~nc., offers ~a~ a~
as Keltrol(g. 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 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., when used are in general used at a level of from about 0.01% to about 10%, most commonly from about 0.02% to about 5.0%, preferably from about 0.1% to about 2%, 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 about 40% to about 89%, preferably from about 50% to about 85%, more preferably from about 60% to about 80%, by weight, of water.

CA 02246293 l998-08-l3 W O 97/30689 -28- PCTrUS97/02991 The p~ 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.
4. Insoluble. E~mulsified~ Fluid Hair Conditionin~ A~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 forrn of droplets, which forrn 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 rnicrons. Suitable fluid hairconditioning agents of this type include nonvolatile silicone hair conditioning agents and organic fluids, e.g., oils. This type of conditioning agent is a ~rer~.led 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.
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 mrn Hg (preferably less than 0.1 rnm) at 25~C. The nonvolatile oil preferably has a boiling point at ambient ~ 3~ of about 250~C or higher, more preferably about 275~C or higher, most preferably about 300~C or higher. Mixtures of the conditioning agents can be used. Individual components of the conditioning agent which are miscible may fall outside the boiling point limits, as long as 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.
5. Silicone Hair Conditionin~ A~ent The non-volatile, water insoluble silicone hair conditioning agent component of the present invention is nonvolatile and insoluble in the composition. It will be intermixed in the shampoo composition so as to be in the forrn of an emulsion, i.e., a separate, discontinuous phase of dispersed, insoluble droplets. These droplets are suspended with a suspending agent, nurnerous, 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~n~e silicone fluid deposition efficiency or enhance glossiness of W O 9713~689 PCTAUS97J~2991 the hair (especially when high refractive index (e.g., above about ~.46~ silicone conditioning agents are used (e.g., highly phenylated silicones).
- The silicone hair conditioning agent phase can comprise volatile silicone components. Typically, if volatile silicones are present, it will be incidental to their use as ~ 5 a solvent or carrier for comrnercially available forms of nonvolatile silicone materials ingredients, such as silicone gums and resins.
The silicone hair conditioning agent component for use herein will preferably have a viscosity of from about 20 to about 2,000,000 centistokes at 25~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. The viscosity can be measured by means of a glass capillary viscometer as set forth in ~ow Corning Corporate Test Method CTM0004, July 20, 1970.
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 from 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 maximurn level that can be used is not limited by theory, but rather by practicality. It is generally l-nneceS~zlry and expensive to use levels in excess of about 8%, although higher levels can be used if desired.
One type of silicone fluid that can be used herein is a silicone oil. The terrn "silicone oil" shall mean flowable silicone materials having a viscosity of less than about 1,000,000 centistokes at 25~C. Generally, the viscosity of the fluid will be between about 5 and about 1,000,000 centi~tckes at 25~C, preferably between about 10 and about100,000. Suitable silicone oils include polyalkyl siloxanes, polyaryl siloxanes~polyalkylaryl siloxanes, polyether siloxane copolymers, and lllixLul~s thereof. Other insoluble, nonvolatile silicone ~uids having hair conditioning ~lop~,.lies can also be used.
More particularly silicone oils hereof include polyalkyl or polyaryl siloxanes with the following structure (IX):
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 ~ub~LiLuLt:d or tm~lbstitl~te~l~ 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-substituted.
hydroxyl-substituted, and halogen-substituted aliphatic and aryl groups. Suitable R
groups also include cationic arnines and qll~tern~ry arnmonium groups.

W O 97/30689 PCTrUS97tO2991 -3~-The aliphatic and/or aryl groups substituted on the siloxane chain can have any structure as long as the resulting 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 stable under 5 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 represent the same group or different groups. Preferably, the two R groups represent the same group.
Preferred alkyl and alkenyl substituents are C 1 -C5 alkyls and alkenyls, more preferably from C1-C4, most preferably from C1-C2. The aliphatic portions of other alkyl-, alkenyl-, or alkynyl-containing groups (such as alkoxy, alkaryl, and :~lk~mino) 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 three carbon atoms, most preferably from one to two carbon atoms. As discussed above, the R
substituents hereof can also contain amino functionalities, e.g., ~lk~mino groups. which can be primary, secondary or tertiary amines or quaternary ammonium. These include mono-, di- and tri-alkylamino and alkoxyalnino groups wherein the aliphatic portion chain length is preferably as described above. The R substituents can 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 exarnple, tri-halogenated (preferably fluoro) alkyl groups such as -R1-C(F)3, wherein Rl is Cl-C3 alkyl. Examples of such polysiloxanes include polymethyl-3,3,3 trifluolu~iul)ylsiloxane.
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.
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 sarne or dir~r~
groups.
Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl. The prefe~red silicones are polydimethyl siloxane, polydiethylsiloxane, andpolymethylphenylsiloxane. Polydimethylsiloxane is especially pr~,rt;~ d.
The polyalkylaryl siloxane fluids that can be used, also include, for example, polymethylphenylsiloxanes. These siloxanes are available, for example, from the General -CA 02246293 l998-08-l3 W 097)30689 PCTnUS97J~2991 Electric ~ompany as S~ 1075 methyl phenyl fluid or from Dow Corning as 556 Cosmetic Grade Fluid.
The polyether siloxane copolymers that can be used include, for example, a polypropylene oxide modified polydimethylsiloxane (e.g., Dow Corning DC- 1248) ~ 5 although ethylene oxide or mixtures of ethylene oxide and propylene oxide can also be used. The ethylene oxide and polypropylene oxide level must be sufficiently low to prevent solubility in water and the composition hereof.
Alkylamino substituted silicones that can be used herein include those of the formula:
H~[si(CH332~]x--[si(oH)[(cH2)3NH(cH2)2NH2]o]~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 also known as "arnodimethicone".
Cationic silicone fluids 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-o-siG3-a(R )a in which G is chosen from the group consisting of hydrogen, phenyl, OH, C 1 -C8 alkyl 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 surn 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;
R1 is a monovalent radical of formula CqH29L 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(R2)2 -N+R2)3 A--N+R2)CH2-CH2-N+(R2)3 A-in which each R2 is chosen from the group consisting of hydrogen, phenyl, benzyl, a 30 saturated hydrocarbon radical, preferably an alkyl radical cont~ining from 1 to 20 carbon atoms, and A- denotes a halide ion.
An especially ple~llcd cationic silicone corresponding to the formula immedi~tely 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) W 097/30689 -32- PCT~US97/02991 Other cationic silicone polymers which can be used in the present compositions correspond to the formula (XI):
~ R3)3-sio-[Si(CH3)[R4CH2cHoHcH2N+(R3)3Q-]o],~[si~cH3)2o]s-si(R3)3 (XI) in which each R3 denotes a monovalent hydrocarbon radical having ~rom l to 18 carbon 5 atoms, and more especially an alkyl or alkenyl radical such as methyl;
Q~ is a halide ion? preferably chloride;
r denotes an average statistical value from about 2 to about 20, preferably from about 2 to about 8;
s denotes an average statistical value from about 20 to about 200, and preferably from 10 about 20 to about 50.
These compounds are described in greater detail in U.S. Pat. No. 4,185,017, incorporated herein by reference.
A polymer of this class which is especially ~l~r~ .d is that sold by Union Carbide under the name "UCAR 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 1,000,000 centi.ctok~s Silicone gums are described by Petrarch and others including U.S.
Pat. No. 4,152,416, Spitzer et al., issued May 1, 1979, and Noll, Walter, Chemistry and Technology of Silicones, New York: ~r~demic Press 1968. Also describing siliconegums are General Electric Silicone Rubber Product ~ata Sheets SE 30, SE 33, SE 54 and SE 76. All of these described references are incorporated herein by reference. The "silicone gurns" will typically have a mass molecular weight in excess of about 200,000, generally between about 200,000 and about 1,000,000. Specific examples include polydimethylsiloxane, (polydimethylsiloxane) (methylvinylsiloxane) copolymer, poly(dimethylsiloxane) (diphenyl siloxane)(methylvinylsiloxane) copolymer and mixtures thereof.
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.
Anotner categol~ of nonvolatile, insoluble silicone fluid conditioning agents are high refractive index silicones, having a refractive index of at least about 1.46, preferably at least about 1.48, more preferably at least about 1.52, most preferably at least about 1.55.
Although not int~nfled to .n~cl~e~rily be limiting, the refractive index of the polysiloxane wo g7J30689 PCT/US97Jn2991 fluid will generally be less than about 1.70, typically less than about 1.60. Polysiloxane "fluid" includes oiis as well as gums.
The high refractive index polysiloxane fluid suitable for purposes hereof includes those represented by general Formula (IX) above, as well as cyclic polysiloxanes such as 5 those represented by the formula below:

L~SiR203n~

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 of aryl-cont~inin~ R substituents to increase the refractive index to the diesired level, which is 10 described above. In addition, R and n must be selected so that the material is nonvolatile, as defined above.
Aryl-cont~ining sub~titll~nt~ contain alicyclic and heterocyclic five and six membered aryl rings, and substituents co..~ g fused five or six membered rings. The aryl rings themselves can be substituted or lln~l1hstituted. Substituents include aliphatic substituents, and can also include alkoxy ~ub~ e.~l!i, acyl substituents, ketones, halogens ~e.g., Cl and Br), ~min~, etc. Exemplary aryl-col-t~inirlg groups include substituted and ull~ub~iLuled arenes, such as phenyl, and phenyl derivatives such as phenyls with C 1 -C5 alkyl or alkenyl substihl~nt~, 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 sllk~LiL~ t~; derived from furan, imidazole, pyrrole, pyridine, etc.
Fused aryl ring ~ub~ Pnt~ include, for example, napth~len~o7 coumarin, and purine.
In general, the high lcirl~ e index polysiloxane fluids hereof will have a degree of aryl-cont~ining substihlent~ of at least about 15%, preferably at least about 20%, more preferably at least about 25%, even more preferably at least about 35%, most preferably at least about 50%. Typically, although it is not int~onlled to neces~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 sllbstin~tion. In general, the polysiloxane fluids hereof will have d surface tension of at least about 24 dynes/cm2, typically at least about 27 dynes/cm2.
Surface tension, for purposes hereof, is measured by a de Nouy ring tensiometer according to Dow Corning Col~o~d~e Test Method CTM 0461, Nov. 23, 1971. Changes in surface W O 97/30689 PCT~US97/02991 tension can be measured according to the above test method or according to ASTM
Method D 1331.
The preferred high refractive index polysiloxane fluids hereof will have a combination of phenyl or phenyl derivative substituents (preferably phenyl)~ with alkyl substituents, preferably C 1 -~4 alkyl (most preferably methyl), hydroxy~ C 1 -C4 alkylamino (especially -R1NHR2N~2 where each R1 and R2 independently is a C1-C3 alkyl), alkenyl, and/or aL~oxy.
High refractive index polysiloxane are available commercially from Dow 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 preferred 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 enhance spreading and thereby enhance glossiness (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 morepreferably at least about 20%, most preferably at least about 25%. P~dl~cti~ns in surface tension of the polysiloxane fluid/spreading agent ~ ure can provide improved shine enhancement of the hair.
Also, the spreading agent will preferably reduce the surface tension by at least about 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 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 ~om about 15 to about 30, more typically from about 18 to about 28, and most generally from about 20 to about 25 dynes/cm2.
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~nt~ are used, particularly high polysiloxane: spreading agent ratios can be effective due to the efficiency of these surf~et~nt~. Thus is co~Le~pl~te~l that ratios significantly above about 1000:1 can be used.

WO 9~130689 PC~TJ'lJ~97Jn2991 Incorporated herein by reference is Silicon Compounds distributed by Petrarch Systems, Inc., 1984. This reference provides an extensive (though not exclusive) listing of suitable silicone fluids.
An optional ingredient that can be included in the silicone conditioning agent is - 5 silicone resin. Silicone resins are highly crosslinked polymeric siloxane systems. The cro~linking is introduced through the incorporation of trifunctional and tetrafunctional silanes with monof~nctional or difunctional, or both, silanes during m~nllf~çture of the silicone resin. As is well understood in the art, the degree of crosslillkin~ 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 cro~linking) such that they dry down to a rigid, or hard, filmL are considered to be silicone resins. The ratio of oxygen atoms to silicon atoms is indicative of the level of cro~linkin~ in a particular silicone m;~tt~ri?l. 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~nllf~rture of silicone resins include monomethyl-, dimethyl-, trimethyl-, monophenyl-, diphenyl-, methylphenyl-, monovinyl-, and methylvinyl-chlorosilanes, and tetrachlorosilane, with the methyl-substituted silanes being most comrnonly l1tili7P(l Preferred resins are offered by General Electric as GE SS4230 and SS4267. Commercially available silicone resins will 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 into the present compositions in such dissolved form, as will be readily apparent to those skilled in the art.
Background ms~t~riz~l on silicones including sections discussing silicone fluids, gums, and resins, ~ well ~ manufacture of silicones, can be found in Encyclopedia of Polymer Science and Fnginl~rin~, Volume 15, Second Edition, pp. 204-308, John Wiley & Sons, Inc., 1989, incorporated herein by reference.
Silicone mztttori~l~ and silicone resins in particular, can conveniently be identified according to a shorthand nom~nrlat~re system well known to those skilled in the art as "MDTQ" nomenclature. Under this system, the silicone is described according to the presence of various siloxane monomer units which make up the silicone. Briefly, the symbol M denotes the monofunctional unit (CH3)3SiOo 5; D denotes the difunctional unit (CH3)2SiO; T denotes the trifunctional unit (CH3)SiO1 5; and Q denotes the quadri- or tetra-functional unit SiO2. Primes of the unit symbols, e.g., M', D', T', and Q' denote c-lkstit~nt~ other than methyl, and must be specifically defined for each occurrence.

CA 02246293 l998-08-l3 Typical alternate substituents include groups such as vinyl, phenyls, amines, hydroxyls, etc~ The molar ratios of the various units, either in terrns 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 combination with molecular weight complete the 5 description of the silicone material under the MDTQ system. Higher relative molar amounts of T, Q, T' and/or Q' to D, D', M and/or M' in a silicone resin is indicative of higher levels of cro.s~linking As ~ c~l~se-l before, however, the overall level of cro~clink;ng can also be indicated by the oxygen to silicon ratio.
The silicone resins for use herein which are p~ Gd are MQ, MT~ MTQ, M~T and 10 MDTQ resins. Thus, the preferred silicone substituent is methyl. Especially preferred 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 ofthe resin is from about 1000 to about 10,000.
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 to about 400:1, preferably this ratio is from about 9:1 to about 200:1, more preferably from about 19:1 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 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.

6. Qr~anic HairConditionin~ 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 conditioning agents.
The organic hair conditioning materials hereof include fluids selected from the group con~i~tin~ 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 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 compatible functionalities, such as amides and alkoxy moieties (e.g., ethoxy or ether link~gç~, etc.).

WO 9713068~ PCTJUS97JD:2991 Hydrocarbon fluids include oils such as cyclic hydrocarbons, straight chain aliphatic hydrocarbons (saturated or unsaturated), and branched chain aliphatic hydrocarbons (saturated or unsaturated), and mixtures thereof. Straight chain hydrocarbon oils will preferably contain f~om about 12 to about l9 carbon atoms, although it is not necessarily meant to limit the hydrocarbons to this range. Branched chain hydrocarbon oils can and typically can contain higher numbers of carbon atoms. Also encompassed 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 substantially higher 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 tetr~c~n~, saturated and unsaturated pent~ec~ne, ~7dLu~d~ed and unsaturated hex~ cs~nP, 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~n~s, such as the permethyl-substituted isomers, e.g., the permethyl-substituted isomers of h~x~ec~ne and eiocosane, such as 2,2,4,4,6,6,8,8-dimethyl-10-methyl-~nd~c~ne and 2,2,4,4,6,6-dimethyl-8-methylnonane, sold by Perrnethyl Corporation. Polymeric organic m~teri~l~ are also useful conditioning agents. A preferred organic poiymer is polybutene, such as the copolymer of isobutylene and butene. A commercially available material of this type if L-14 polybutene from Amoco Chemical Co. (Chicago, Illinois, U.S.A.). Other polymeric conditioners can include polyisoprene, polybutadiene, and other hydrocarbon 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' and R is at least 10, preferably at least 20.
~atty esters include, for ex~mple7 alkyl and alkenyl esters of fatty acids having aliphatic chains with 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. Exarnples include isopropyl isostearate, hexyl laurate, isohexyl laurate, isohexyl palmitate, isopropyl palmitate, decyl oleate, isodecyl oleate, hexadecyl stearate, decyl stearate, isopropyl CA 02246293 l998-08-l3 W O 97/30689 PCTrUS97/02991 isostearate, dihexyldecyl adipate, lauryl lactate, myristyl lactate, cetyl lactate, oleyl stearate, oleyl oleate, oleyl myristate, lauryl acetate, cetyl propionate, and oleyl adipate.
The mono-carboxylic acid ester however need not necessarily contain at least onechain with at least 10 carbon atoms, so long as the total number of aliphatic chain carbon S atoms is at least 10. Examples include diisopropyl adipate, diisohexyl adipate, and diisopropyl sebacate.
Di- and tri-alkyl and alkenyl esters of carboxylic acids can also be used. Theseinclude, for example, esters of C4-Cg dicarboxylic acids such as C l -C22 esters(preferably C1-C6) of succinic acid, glutaric acid, adipic acid, hexanoic acid, heptanoic 10 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 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 15 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 monostearate, 1,3-butylene glycol monostearate, 1,3-butylene glycol distearate, polyoxyethylene polyol fatty acid ester, sorbitan fatty acid esters, and polyoxyethylene so~ fatty acid esters are satisfactory 20 polyhydric alcohol esters for use herein.
Glycerides include mono-, di-, and tri-glycerides. More specifically, included are the mono-, di-, and tri-esters of glycerol and long chain carboxylic acids, such as C I -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 25 liver oil, almond oil, avocado oil, palm oil, sesame oil, lanolin and soybean oil. Synthetic oils include triolein and tristearin glyceryl ~ r~t~. Preferred glycerides are di-, and tri-glycerides. Especially pl~fe.led are triglycerides.

7. Other Optional In~redients. Primarilv for Sharnpoo Compositions A variety of other optional ingredients are described below. The description below 30 is exemplary in nature.
Such optional ingredients include, for example, anti-dandruff actives such as zinc pyrithione, octopirox, selenium disulfide, sulfur, coal tar, and the like, preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea; cationic conditioning agents, including both cationic conditioning surfactants and cationic 35 con-iitiQning polymers; quaternary polymeric foam boosters, such as Polyqu~t~..fium 10, preferably from about 0.01% to about 0.2%, by weight of the composition; fatty alcohols;

Wb 97t30689 PCT/US971029gl block polymers of ethylene oxide and propylene oxide such as Pluronic F88 offered by BASF Wyandotte; sodium chloride, sodiurn sulfate, arnmonium 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 5 dyes. These opt;onal ingredients are typically used at levels of from about 0.01% to about 10% of the composition. The shampoo 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 ~lti~

8. Other Optional In~redients PrimarilY for Non-Sharn~oo Compositions Another component use~ul in the present invention is a nonionic, i.e., polyglycerol ester (PGE).
Groups of substances which are particularly suitable for use as nonionic surfactants 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 15 acid arnides; ethylene oxidefpropylene oxide block polymers; glycerol esters and polyglycerol esters; sorbitol and sorbitan esters; polyglycol esters of glycerol; ethoxylated lanolin derivatives; and alkanolarnides and sucrose esters.
A preferred liquid cleansing composition also contains from about 0.5% to about 10% of an emollient selected from the group con~i~tinF of esters of fatty acids; glycerin 20 mono-, di-, and tri-esters; epidermal and sebaceous hydrocarbons such as cholesterol, cholesterol esters, squalene, squalane; lanolin and derivatives, mineral oil, silicone oils and gums, and mixtures thereo~ and the like.
Other ingredients of the present invention are selected for the various applications.
E.g., alcohols, hydrotropes, colorants, and fillers such as talc, clay, calcium carbonate and 25 dextrin can also be used. Cetearyl alcohol is a mixture of cetyl and stearyl alcohols.
P~ Li~es, e.g., trisodiurn etidronate and sodiurn ethylene~ m;nPt~tr~ret~te (EDTA), generally at a level of less than 1% of the composition, can be incorporated in the cle~n~in~ products to prevent color and odor degradation. Antibacterials can also be incorporated, usually at levels up to 1.5%. Salts, both organic and inorganic, can b 30 incorporated into the compositions of the present invention. Examples include sodium chloride, sodiurn isethionate, sodium sulfate, and their equivalents.
The cleansing bath/shower compositions can contain a varie~y of non.o~enti~l optional ingredients suitable for rçn/1~ring such compositions more desirable. Such conventional optional ingredients are well known to those skilled in the art, e.g..
35 preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea; other thickeners and viscosity modifiers such as Cg-C1g ethanolamide (e.g., coconut W O 97/30689 PCT~US97/02991 ethanolamide) pH adjusting agents such as citric acid, succinic acid, phosphoric acid, sodium hydroxide, etc., suspending agents such as m~gnPsium/aluminum silicate;
perfumes; dyes, and sequestering agents such as disodium ethylenerii~mine tetraacetate.
III. Method Of Use For Shampoo Compositions S 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 general, including 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 includes working the composition through the hair such that most or all of the hair is contacted with the composition. After 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 skinand/or the body, and to provide olfactory aesthetic benefit. An effective amount 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 includes dispensing of the composition onto the hand, onto the body, or onto a washing implement, e.g., wash cloth, sponge, etc., and typically includes working the composition with the hands to develop lather. The lather can stand on the body for a length of time or can be rinsed immPrii~tt?ly 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 form~ ted into a wide variety of product types which are not normally removed by rinsing, including hair conditioner, hair spray, hair gel, hair tonic, mousse, hair curler, hair str~i~htPner, deodorant, antipe.~pi~ t, skin lotion, skin moisturizer, skin softening lotion, suntan lotion, sun screen lotion, sunless tanning composition, sl~in blP~hin~ composition, perfume, cologne, topical ph~rm~celltical skin care composition, e.g., anti-acnecomposition, non-steroidal anti-fl~mm~tf~ry composition, steroidal anti-fl~mm~tory composition, antipruritic composition, anesthetic composition, antimicrobial composition, and the like. The additional components required to formulate such products vary with W O 97/30689 PCTAU$97~2991 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 components.
I. Hair Care ComPOsitiOns The hair care compositions of the present invention can comprise a carrier, or a5 mixture 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 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 not darnage or negatively affect the aesthetics of hair or cause irritation to the underlying skin.
~arriers suitable for use with hair care compositions of the present invention include, for example, those used in the forrnulation of hair sprays, mousses, tonics, gels, conditioners, and rinses. The choice of a~p~ iate carrier will also depend on the particular copolymer to be used, and whether the product forrnulated is meant to be left on the surface to which it is applied (e.g., hair spray, mousse, tonic, or gel) or rinsed off after 15 use (e.g., conditioner, rinse).
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 C I -C6 alcohols, and mixtures thereof being ~refclled; and water, methanol, ethanol, iso~ pal1ol, propylene carbonate, and 20 mixtures thereof being more ~lc~.led. The carriers can also contain a wide variety of additional m~t~ including, but not limited to, acetone, hydrocarbons (such as isobutane, hexane, decene), halogen~ted hydrocarbons (such as Freons), esters (such as ethyl acetate, dibutyl phth~l~te), and volatile silicon derivatives (especially siloxanes such as phenyl pentamethyl disiloxane, methoxypropyl heptamethyl cyclotetrasiloxane, 25 chlolvpr~pyl pentamethyl disiloxane, 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 cornposition is a hair spray, tonic, gel, or mousse the ~ cd solvents include water, ethanol, volatile silicone derivatives, and mixtures thereof. The 30 solvents used in such mixtures can be miscible or immiscible with each other. Mousses and aerosol hair sprays can also utilize any of the conventional propellants to deliver the m~teri~l 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 trichlorofluoromethane, dichlorodifluoromethane, difluoroethane, dimethylether, propane, 35 n-butane or isobutane. A tonic or hair spray product having a low viscosity can also utilize an emulsifying agent. Ex~llples of suitable emulsifying agents include nonionic, CA 02246293 l998-08-l3 9 PCT~US97/02991 cationic, anionic surfactants, or mixtures thereof. Fluorosurfactants are especially preferred, 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 solvents, such as alcohols, and relatively high levels of water (e.g., in excess of about 10%, by weight S 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 compositions.
Suitable spray containers are well known in the art and include conventional, non-10 aerosol pump sprays i.e., "~tomi7ers," aerosol containers or cans having propellant, asdescribed above, and also pump aerosol containers ~ltili7.ing coll,plessed air as the propellent. Pump aerosol containers are disclosed, for example, in U.S. 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 ~efebvre, filed February 21, 1992, "Consumer Product Package Incorporating A Spray Device Utilizing Large Diameter Bubbles." Pump aerosols hair sprays using co~ essed air are also currently marketed by The Procter & Gamble Co",pal1y under their tr~len~tne Vidal Sassoon Airspray(~) hair sprays.
Where the hair care compositions are conditioners and rinses the carrier can include 20 a wide variety of conditioning materials. Various additional colll~70llell1~, 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. issued June 7, 1983; which are incorporated by reference herein. Some of these additional components are described below.
25 II. Topical SkinCare Coml~ositions The topical cosmetic and pharmaceutical compositions of the present invention can comprise a carrier. The carrier should be "cosmetically and/or ph~ reutically acceptable", which means that the carrier is suitable for topical application to the skin, has good aesthetic ~ c;,~ies, is compatible with the copolymers of the present invention and 30 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, including, but not limited to, oil-in-water, water-in-oil, water-in-oil-in-water, and oil-in-water-in-silicone emulsions, are usefill 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 35 delivered in the form of sprays using either mechanical pump co~ cl.7 or pressur-7Pd aerosol containers using conventional propellants. These carriers can also be delivered in CA 02246293 l998-08-l3 W 097/30689 PCTnU~97J0299 -43-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 5 single phase solvents (e.g., where the viscosity of the solvent has been increased to form a solid or semi-solid by the addition of ~plopliate 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. 172-139(December 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 slcin care compositions can comprise from about 50% to about99% by weight of the compositions of the present invention, preferably from about 75% to about 99%, and most preferably from about 85% to about 95%.
Preferred cosmetically and/or ph~ ceutically acceptable topical catriers includehydro-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, iso~,lo~anol, or mixtures thereof, and from about 1% to about 99% of water. More~re~lled is a carrier comprising from about 5% to about 60% of ethanol, isopropanol, or mixtures thereof, and from about 40% to about 95% of water. Especially plef~l~cd is a carrier comprising from about 20% to about 50% of ethanol, is()~ o~ ol, or mixtures thereof, and from about 50% to about 80% of water. When the carrier is an oil-in-water emulsion, the carrier can include any of the common excipient ingredients for ~l~p~illg 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 ~ t and/or Deodorant Compositions 1. Carriers.
Carriers for ~ er~,~irants 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 Residue A~ c~ Sticks); U.S. Pat. 5,019,375, Tanner, Nunn, Jr., and Luebbe, issued May 28, 1991, especially at Col. 3, line 16 through Col. 3,1ine 35 and Col. 4, line 64 through -WO 97/30689 PCTrUS97/02991 Col. 7. line 10 (Low Residue Antip~l 7~ildnt 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 (An~ ir~ t Creams), U.S. Pat. 5,156,834, Beckmeyer, Davis, and Kelm, issued Oct. 20 1992, especially at Col. 4, line 8 through Col. 5, line 64 (Anitperspirant Compositions); U.S. Pat. 5,200,174, Gardlik and Hofrichter, issued Aug. 6 1993~ especially at Col. 5, line 16 through Col. 7, line 34 and Col. 10, line 24 through Col.
12, line 44 (Gel Stick Antip~ t Composition Contzlining 2-Oxazolidinone Derivative and Process for Making Them); U.S. Pat. 5,284,649, Juneja, issued Feb. 8, 1994, especially at Col. 3, line 55 through Col. 5, line 42 ~Deodorant Gel Sticks Cont~inin~
10 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 Alr~ irant Composition), all of said patents being incorporated herein by reference. These patents also disclose many of the other ingredients that are useful in antipel ,pi,~ulL and deodorant products.
Some anli~cl~l irant gel stick compositions of the present invention include theingredients discussed below. Although the term "stick" as utili:zed herein includes semi-solid forms (i.e., preferably having a viscosity of at least about l,000,000 centipoise at 25~C), solid forms (i.e., preferably having an average penetration value within a given production batch from about 3 to about 25 mm over a period of 5 seconds as measured 20 ~tili7in~ American Society for Testing Materials (ASTM) Method D-5, with a penetration cone (Model H1312; sold by Humbolt ~nufs~ctllring Company) weighing 2.0 g (making the total mass 50 g and a Sommer & Runge Model PNR10 Penetrometer) are ~?refelled.
2. Gellin~ A~ent:
The "gelling agent" as used herein is a mixture of a primary gellant and a secondary 25 gellant; both ~ cll~sed hereinafter. The primary gellant is selected from the group con~i~tin~ of 12-hydroxystearic acid, esters of 12-hydroxystearic acid, amides of 12-hydroxystearic acid and ~ Lul~S thereof. The secondary gellant is selected from the group consisting of n-acyl arnino 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 30 12%; more preferably, from about 5% to about 10%. The primary gell~nt-secondary gellant ratio is typically between about 1:2 and about 20:1; preferably, from about l:l to about 10:1; more preferably, from about 2:1 to about 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 35 (discussed hereinafter) in the composition is relatively low; e.g., below about 25%.

CA 02246293 l998-08-l3 This gelling agent offers significant benefits when used in an antiperspirant gel sticL~. The gelling agent of the present invention exhibits unexpected benefits, e.g..
decreased residue upon application to the skin, increased hardness and better aesthetics~
relative to a similar composition having either of the two gellants alone. In fact, these 5 gellants in combination are more effective than either alone so that the overall level of gelling agent within the composition can be reduced while m~int~inin~ such desirable stick characteristics.
Moreover, when these gellants are used together as the gelling agent of the p~esent invention, degradation of the gelling agent by the acidic ~~ active during 10 m~nnf~eturing is unexpectedly significantly reduced; i.e., as colllpaled to each gellant alone. To further reduce degredation, a heated solution of the gelling agent and the liquid base material preferably remains in solution such that the antip~_.sl)il~lL active can be substantially uniformely mixed therein at a temperature less than about 120~C; more preferably, less than about 105~C; more ple~lably, less than about 95~C; and most 15 preferably, less than about 80~C (hereinafter, the "mixing ~lllpera~lre~). This reduced mixing L~ ;c,dlule is made possible partly because the primary gellant, once molten, is an unexpectedly good co-solvent for the secondary gellant, thereby facilitating their dissolution at a lower temperature. Additional methods of rec~ring the mixing t~ cldl~re or otherwise enabling a reduction of the interaction of the acidic a~ltip~ h~
20 active with other components, e.g., the gelling agent, is discussed hereinafter. Since lower mixing temperatures can be l~tili7ed the gelling agent is more compatible with additional gel stick components which have lower boiling points, such as perfumes.
a. Primarv Gellant The primary gellant of the gelling agent of the present invention is selected from 25 the group conci~tin~ of 12-hydroxystearic acid, esters of 12-hydroxystearic acid, amides of 12-hydro~y~Le~ic acid and mixtures thereof. The primary gellant is preferably selected from the group conci~fin~ of 12-hydroxystearic acid, 12-hydroxy~ ~ic acid methyl ester, 12-hydroxystearic acid ethyl ester, 12-hydroxystearic acid stearyl ester, 12-hydroxystearic acid benzyl ester, 12-hydroxystearic acid amide, isopropyl amide of 12-hydroxystearic 30 acid, butyl arnide of 12-hydl~y~Le~ic acid, benzyl amide of 12-hydroxystearic acid, phenyl amide of 12-hydroxystearic acid, t-butyl arnide of 12-hydroxystearic acid, cyclohexyl arnide of 12-hydroxystearic acid, 1~ m~ntyl arnide of 12-hydroxystearic acid, 2-~ m~ntyl arnide of 12-hydroxystearic acid, diisopropyl arnide of 12-hydroxystearic acid, and mixtures thereof; even more preferably, 12-hydroxystearic acid, isopropyl amide 35 of 12-hydroxystearic acid, and mixtures thereof.

_ CA 02246293 l998-08-l3 W O 97/30689 PCT~US97/02~91 b. Secondarv Gellant With regard to the secondary gellant of the gelling agent of the present invention.
N-ac~l amino acid derivatives include N-acyl amino acid amides and N-acyl amino acid esters prepared from glutamic acid, Iysine, glutamine, aspartic acid and mixtures thereof.
Preferably the N-acyl amino acid derivatives are selected from the group 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 arnide, N-lauroyl-glutamic acid didecyl amide, N-lauroyl-glutamic acid didodecyl amide, N-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-glutamic acid didodecyl amide, N-stearoyl-glutamic acid ditetradecyl amide, N-stearoyl-glutamic acid dihexadecyl amide, N-stearoyl-glutamic acid distearyl amide and mixtures thereof; more preferred, is n-lauroyl-glutamic acid dibutyl arnide, n-stearyl-glutamic acid dihexyl amide, and mixtures thereof.
3. Liquid Base Materials The liquid base matrix of antiperspirant stick compositions of the present invention is formed by combining the gelling agent with a liquid base material. As used herein, the term "liquid" refers to materials wh;ch are liquids at ambient conditions and the term "liquid base material" includes all liquids within the composition. It is important that the liquid base m~tPn~l be of a type, and used at a level sufficient to solubilize the gelling agent when heated, to perrnit substantially uniform mixing of the antip~l~yh~-t active into the heated solution at the mixing l~nl~,.dlure, and form a stick when cooled to ambient l~ -dlule. The liquid base material should be compatible with the gelling agent so that the mixture of the two remains homogeneous and does not phase separate during m~n~.f~turing and so that the fini~he-l product remains homogeneous and does not ph~e separate at ambient conditions over the normal shelf-life which may be upwards of one year. Furthermore, the liquid base m~teri~le are typically selected to provide aesthetic benefits, such as emolliency, low tack or minimi7~d visible residue, without significant i~lt~.r~ ,nce with the effectiveness of the antip~ 3h~lt active component. Lastly, the particular liquid base material should be safe for application to human skin.
The liquid base materials include emollients which have a solubility parameter from about S to about 11. 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 WO 971311689 PCT~lJS97/02991 parameter in the range of from about 5 to about 11, such that the average solubility parameter of the mixture is from about 6 to about 10. Solubility parameters are common to the art of antipel~pildl1t stick forrnulation and the means to determine them are disclosed by C.D. V~llgh~n, "Solubility Effects in Product, Package, Penetration and Preservation"
~ 5 103 Cosmetics and Toiletries 47-69, October, 1988; and C.D. V~llgh~n, " Using Solubility Parameters in Cosmetics Formulation", 36 J 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 includes a volatile, non-polar, oil and a non-volatile, relatively polar co-solvent; each ~liccll~secl more fully hereinafter. The term "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 atrnosphere and/or to m~tt~ri~l~ 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 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 aesthetic properties 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 prleferably from about 40% to about 60%.
Non-polar, volatile oils particularly useful in the present invention are selected from the group con~i~tin~ 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 usefill in the present invention may be either saturated or unsaturated, have an aliphatic character and be straight or branched ch~ine~l or contain alicyclic or aromatic rings. F.~mples of ~ler~ d non-polar, volatile hydrocarbons include isodecane (such as Perrnethyl-99A(~) which is available from Presperse Inc.) and the C7-Cg through C12-CIs iso~ dfrlns ~such as the Isopar(E~ Series available from Exxon Chemicals).
Non-polar, volatile silicone oils are highly pl~r~ d as the non-polar, volatile oil in the liquid base material, since they endow the anLipel~ildllL stick composition with highlv desirable aesthetics. Non-polar, volatile liquid silicone oils are disclosed in U.S. Pat.

W O 97/30689 PCT~US97/02991 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). Particularly preferred volatile silicone oils are cyclic and linear volatile silicones like those disclosed hereinbefore.
b. Relativelv Polar. Non-volatile Co-solvent 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-polar, volatile oil when subjected to reduced processing temperatures. The non-volati~e co-solvent is "relatively polar" as compared to the non-polar, volatile oil discussed 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 enables the inclusion of greater amounts of the non-polar, volatile oil. This is advantageous because, as discussed 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 minimum because it tends to adversely affect product cosmetics. Thus, the relatively polar, non-volatile co-solvent is preferably included at levels from about 5% to about 60%;
more preferably from about 5% to about 25%; and most preferably from about 7% to about 20%.
Relatively polar, non-volatile 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 isslled to 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 con~iqting of silicone oils; hydrocarbon oils; fatty alcohols; fatty acids; esters of mono and dibasic carboxylic acids with mono and polyhydric alcohols;
polyoxyethylenes; polyoxypropylenes; mixtures of polyoxyethylene and polyoxypropylene 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 ch~inP~l or contain alicyclic or aromatic rings.
More preferably, the relatively polar, non-volatile liquid co-solvent are selected 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 carboxylic acids and alcohols having from about 14-3(~ carbon atoms; esters of dibasic carboxylic acids and alcohols having from about 10-30 carbon atoms; esters of polyhydric alcohols and W ~ 971~0689 PCT~S97J~2991 carboxylic acids having from about 5-26 carbon aloms; ethoxylated, 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.
More preferred are propoxylated ethers of C14-Cl g fatty alcohols having a degree of propoxylation below about 50, esters of C2-C8 alcohols and C12-C26 carboxylic acids (e.g. ethyl myristate, isopropyl p~lmit~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 sebacate, diisopropyl iq~ip~te, 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 thereof.
Even more pre~erred are branched-chain aliphatic fatty alcohols having from about 12-26 carbon atoms. Even more preferred is isocetyl alcohol, octyldecanol, octyldodecanol and undecylperlt~tlec~ncl; and most pler~fed is octyldodecanol. Such preferred aliphatic fatty alcohols are particularly useful in combination with the volatile liquid silicone oils discussed herein to adjust the average solubility of the liquid base m~teri~l, c. Non-polar. Non-volatile Emollients In addition to the li~uids discussed above, the liquid base material can optionally include non-volatile, non-polar emollients which tend to improve product cosmetics.
~ypical non-volatile, non-polar emollients are disclosed, for example, in Cosmetics, Science, and Technology, Vol. 1, 27-104 edited by Balsam and S~ rin, 1972; U.S. Pat.
4,202,879 issued to Shelton on May 13, 1980; and U.S. Pat. 4,~16,261 issued to Luebbe et al. on March 28, 1989.get good dissolution. The non-volatile silicone oils useful in the present invention are e~eent~ y non-volatile polysiloxanes, paraffinic hydrocarbon oils, and mi~ s thereof. The polysiloxanes useful in the present invention selected from the group conci.ctin~ of polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxarles, poly-ethersiloxane copolymers, and mixtures thereof. Fx~mrles of these include polydimethyl siloxanes having viscosities of from about 5 to about 100,000 centistokes at 25~C.
Among the ~l~r~.. ed non-volatile silicone emollients usefill in the present compositions are the polydimethyl siloxanes having viscosities from about 2 to about 400 ~ centistokes at 25~C. Such polyalkylsiloxanes include the Viscasil~ series (sold by General Electric Company) and the Dow Corning 200 series (sold by Dow Corning Corp.3.
~ Polyalkylarylsiloxanes include polymethylphenyl siloxanes having viscosities of from about 15 to about 65 centistokes at 25~C. These are available, for example, as SF 1075 methyl-phenyl fluid (sold by Ge~eral Electric Cc~lllpal~y) and 556 Cosmetic Grade ~luid -W O 97/30689 PCTrUS97/0299 (sold by Dow Corning Corp.). Useful poly-ethersiloxane copolymers include. 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 surfactant (sold by General Electric Company). Polysiloxane ethylene glycol ether copolymers are plefe.l~d copolymers for use in the present compositions.
Non-volatile pa.drr~llic hydrocarbon oils usefi~l in the present invention include mineral 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. Pre~erred mineral oils have the following 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.
Preferred branched chain hydrocar~on oils have the following prope.lies:
(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 1 1 0~C and about 200~C.
Particularly ~lc:r~led branched-chain hydrocarbons include Permethyl 103A, whichcontains an average of about 24 carbon atoms; Permethyl 104A, which contains an average of about 68 carbon atoms; Permethyl 1 02A, 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 atoms and may be purchased from Ethyl Corp.
Additional components useful in formnl~ing these topical compositions are fi~rther 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 t:x~lplcs include the following:
1. Deodorant Active In~redients ~uitable types of deodorant actives include antimicrobial ingredients such as bactericides and fungicides. Exemplary deodorant actives include ~U~tçrn~ry ammonium compounds such as cetyl-trimethylammonium bromide, cetyl pyri~linil-m chloride, benzethonium chloride, diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, sodium N-lauryl sarcosine, sodium N-palmethyl sarcosine, lauroyl sarcosine, N-myristoyl glycine, potassium N-lauryl sarcosine, stearyl, trimethyl ammonium chloride, sodium alnminllm chlorohydroxy lactate, tricetylmethyl ammonium chloride, 2,4,4'-WO 97/30689 PCTJtJ~971t32991 trichlorio-'~'-hydroxy diphenyl ether, diaminoalkyl amides such as L-lysine hexadecyl amide. heavy metal salts of citrate, salicylate, and piroctose, especially zinc salts, and acids thereof, heavy metal salts of pyrithione, especially zinc pyrithione and zinc phenolsulfate. Still other antimicrobial ingredients 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 and tetraalkylammoniurn carbonates and bicarbonates, especially the sodium and potassium salts.
Mixtures of deodorant actives are also contemplated and intenfled to be 10 encompassed herein.
2. A~ILi~ ,irant Actives The compositions of the present invention can also contain an astringent ~,lip~ hallt 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 antiperspirant gel stick 15 composition. This active can be incorporated either in solubilized or particulate form.
These weight p~.ce,llages are calculated on an anhydrous metal salt basis (exclusive of, e.g., glycine, the salts of glycine, or other complexing agents). Such materials include, for example, many aluminum or zirconiurn astringent salts or complexes and are well known in the antipcl ,~ha~lt art.
The antipc.. ,l~h~ active is preferably in particulate forrn wherein the surface area of the active is relatively low. The surface area of the antipe"~ilal~L active can be reduced by increasing the size and density of the active particles. Consequently, the particulate antipt;,,~i.dnt active preferably has a density which is preferably greater than about 0.7 glcm3 and an average particle size (as measured by a Coulter Multisizer 11 m~nl~f~tured by Coulter Corporation, Haleah, Florida) greater than about 1 0 microns; more preferably, greater than about 30 microns; and most preferably, greater than about 40 microns. Such preferred materials can be purchased from Westwood Chemical Co~ ly, Middletown, N.Y. under the trade name Westchlor(13) ZR.
Suitable allLipe~ t active is disclosed, for example in U.S. Patent 4,147,766 which issued on April 3, 1979 to Ko7ic~h~
Any alllminl-m astringent allLip~ i,dnt salt or aluminum and/or zirconiurn astringent complex can be employed herein. Salts useful as astringent antiperspirant salts or as components of astringent complexes include al~ ll.., halides, ~Illminl~m hydroxy-h~lidec, zirconyl oxyh~lid~s, zirconyl hydroxy-halides, and mixtures of these 35 materials.

W O 97/30689 PCTrUS97/02991 Alllminum salts of this type include aluminum chloride and the all-minum hydroxyhalides having the general forrnula A12(OH)xQy.XH2O where Q is chlorine, bromine or iodine; where x is from about 2 to about 5, and x+y = about 6, and x and y do not need to be integers; and where X is from about 1 to about 6. Aluminunn 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 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 zirconyl salts and zirconyl hydroxy salts. These compounds may be represented by the following general empirical formula:
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 the group con~i~tin~: of halides, nitrate, s~llf~m?~te, sulfate, and mixtures thereof. Although only zirconium compounds are exemplified in this specification, it will be understood that other Group IVB metal compounds, including hafnium, can be used in the present invention.
As with the basic al~lminl-m compounds, it will be understood that the above formula is greatly simplified and is intended to lc~res~llt and include compounds having coordinated and/or bound water in various quantities, as well as polymers, mixtures and complexes of the above. As will be seen from the above formula, thezirconium hydroxy salts actually represent a range of compounds having various arnounts of the hydroxy group, varying from about 1.1 to only slightly greater than zero groups per molecule.
Several types of antiperspirant complexes lltili7in~ the above an~
salts are known in the art. For exarnple, U.S. Patent 3,792,068 issued to Luedders et al.
on February 12, 1974 discloses complexes of al-lminum, 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 comple~es are chemically analyzable for the presence of alllminllm, zirconium and chlorine. ZAG
complexes useful herein are identified by the specification of both the molar ratio of allmlinllm to zirconium (hereinafter "Al:Zr" ratio) and the molar ratio of total metal to chlorine (hereinafter "Metal:Cl" ratio). ZAG complexes useful herein have an Al:Zr ratio of from about 1.67 to about 12.5 and a Metal:Cl ratio of from about 0.73 to about 1 .93.

, CA 02246293 l998-08-l3 W O 97130689 PCTnUS97J02991 Preferred 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 consisting 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 nH2O, where Q is chloride, bromide 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 of from about 0.16 to about 1.2;
(3) p parts neutral amino acid selected from the group con~i~ting of glycine, dl-tryptophane, dl-b-phenyl~l~nint?, dl-valine, dl-methionine and b-alanine, and where p has a value of from about 0.06 to about 0.53, (B) co-drying the resultant mixture to a frîable solid; and (C) reducing the resultant dried inorganic-organic anlipc~ dnt complex to particulate form.
A preferred al~lminllm compound for ~l~al~lion of such ZAG type complexes is alllmim~m chlorhydroxide of the empirical formula A12(OH)sCl.2H2O. Preferred zirconium compounds for ~l~paldlion of such ZAG-type complexes are zirconyl hydroxychloride having the empirical formula ZrO(OH)Cl.3H20 and the zirconyl hydroxyhalides of the empirical formula ZrO(OH)2 aC12.nH2O wherein a is from about 1.5 to about 1.87, and n is from about 1 to about 7. The p~c~ ,d amino acid for prep~illg such ZAG-type complexes is glycine of the formula CH2(NH2)COOH. Salts of such amino acids can also be employed in the alllipelapila~ll complexes. See U.S.
Patent 4,017,599 issued to Rubino on April 12, 1977.
A wide variety of other types of ~llip~ ll complex~s are also known in the art. For example, U.S. Patent 3,903,258 issued to Siegal on September 2, 1975 discloses a zirconium ~ltlminnm complex p~ ,d by reacting zirconyl chloride with~lllminllm hydroxide and aillminnm chlorhydroxide. U.S. Patent 3,979,510 issued to Rubino on September 7, 1976 discloses an ~llipel~ t complex formed from certain alllminnm compounds, certain zirconium compounds, and certain complex zllllminllm buffers. U.S. Patent 3,981,896 issued to Pauling on September 21, 1976 discloses an antipe.s~ila,ll complex prepared from an alllminllm polyol compound, a zirconiumcompound and an organic buffer. U.S. Patent 3,970,748 issued to Mecca on July 20, 1976 discloses an aluminllm chlorhydroxy glycinate complex of the approximate general formula [A12(OH)4Cl]~H2CNH2COOH].
Of all the above types of antipc.~ ll actives, pfefell~:d compounds include the 5/6 basic alllminllm salts of the empirical formula A12(OH)sCl.2H2O; mixtures of W O 97/30689 PCT~US97/02991 AIC13.6H20 and A12(OH)sCl. 2H~O with al--min--m chloride to alllminllrn hydroxychloride weight ratios of up to about 0.5; ZAG type complexes wherein thezirconium sale is ZrO(OH)CI.3H2O, the alllminllm salt is A12(OH)sCI. 2H2O or theaforementioned mixtures of AIC13.6H2O and A12(OH)s Cl.2H2O wherein the total metal to chloride molar ratio in the complex is less than about 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 a is from about 1.5 to about 1.87 and n is from about 1 to about 7, the aluminum salt is A12(OH)sCI.2H2O, and the amino acid is glycine.
Solubilized antiperspirant actives which can be utilized in the present invention are also well known in the art. These materials utilize monohydric or polyhydricalcohols or water to solublize the anLip~ hdllt active before it is incorporated into the product. The levels of these polar solvents are typically less than about 25%, and preferably less than about 15% of the composition. Examples of such actives 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, Smith and Ward, filed June 23, 1989; and European Patent Application 0295070 which 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 arnount of a ph~rrn~reutical active. 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 benefitlrisk ratio), within the scope of sound medical judgement. A safe and effective amount of the ph~rrn~( eutical active will vary with the specific active, the ability of the composition to penetrate the active through the skin, the arnount 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~tm~nt the nature of concurrent therapy, and like factors.
The ph~rm~ceutical actives which can be used in the compositions of the 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 pharmaceutical actives can also be used.
Nonlimiting examples of pharmaceutical actives useful in the compositions of thepresent invention include anti-acne drugs. Anti-acne drugs ~l~fell~d for use in the present invention include the keratolytics such as salicylic acid, sulfur, lactic acid, glycolic, -WO 9713068g P~Tl~J597J(~2g9 pyruvic acid, urea, resorcinol, and N-acetylcysteine; retinoids such as retinoic acid and i~s derivatives (e.g., cis and trans); antibiotics and antimicrobials such as benzoyl peroxide, octopirox, erythromycin, zinc~ tetracyclin, triclosan~ azelaic acid and its derivatives, phenoxy ethanol and phenoxy proponol, ethylacetate, clindamycin and meclocycline;
S sebostats such as flavinoids; alpha and beta hydroxy acids, and bile salts such as scymnol sulfate and its derivatives, deoxycholate, and cholate. Preferred for use herein is salicylic acid.
Useful ph~rmaceutical actives in the compositions of the present invention include non-steroidal anti-infl~mm~tory drugs (NSAIDS). The NSAIDS can be selected from the 10 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. Pa~ent 4,985,459 to Sunshine et al., issued January 15, 1991, incorporated by reference herein. Most ~lcfelled are the propionic NSAIDS including but not limited to aspirin, acetaminophen, ibuprofen, naproxen, benoxaprofen, flurbiprofen, 15 fenoprofen, fenbufen, ketoprofen, indoprofen, pirprofen, carprofen, oxapro7in, pranoprofen, miroprofen, tioxaprofen, suprofen, alminoprofen, tiaprofenic acid, fluprofen and bucloxic acid. Also useful are the steroidal anti-infl~mm~tory drugs including hydrocortisone and the like.
Useful ph~ reutical actives in the compositions of the present invention include20 antipruritic drugs. A~ ic drugs ~l~rtll~d for inclusion in compositions of the present invention include ph~ reutically-acceptable salts of meth~iii7ine and trimep~ e. Useful ph~ eutical actives in the compositions of the present invention include include anesthetic drugs. Anesthetic drugs p-er~ d for inclusion in compositions of the present invention include ph~ reutically-acceptable salts of lidocaine, 25 bupivacaine, chlorprocaine, dibucaine, etidocaine, mepivacaine, tetr~c~in~7 dyclonine, hexylcaine, procaine, cocaine, ketamine, pramoxine and phenol. Useful ph~ f eutical actives in the compositions of the present invention include antimicrobial drugs~antibacterial, antifungal, a.,liplo~ozoal and antiviral drugs). Antimicrobial drugs preferred for inclusion in compositions of the present invention include pharmaceutically-30 acceptable salts of b-lactam drugs, ~uinolone drugs, ciprofloxacin, norfloxacin, tetracycline, erythromycin, ~mik~cin, triclosan, doxycycline, capreomycin, chlorhexidine, chlortetracycline, oxytetracycline, clin-1~mycin, ethambutol, metronidazole, pentamidine, gentamicin, kanamycin, lineomycin, methacycline, meth~on~nninP, minocycline, neomycin.
netilmicin, paromomycin, streptomycin, tobramycin, miconazole and ~m~nf~tlin~.
35 Antimicrobial drugs prefelTed for inclusion in compositions of the present invention include tetracycline hydrochloride, erythromycin estolate, t:,~lh,~ ycin stearate (salt).

CA 02246293 l998-08-l3 W O 97/3~689 PCT~US97/02991 amikacin sulfate, doxycycline hydrochloride, capreomycin sulfate. chlorhexidine gluconate, chlorhexidine hydrochloride, chlortetracycline hydrochloride, oxytetracycline hydrochloride~ clindamycin hydrochloride, ethambutol hydrochloride, metronid~olehydrochloride, pentarnidine hydrochloride, gentamicin sulfate, kanarnycin sulfate, lineomycin hydrochloride, methacycline hydrochloride, methen~mine hippurate, methenamine mandelate, minocycline hydrochloride, neomycin sulfate, netilmicin sulfate.
paromomycin sulfate, streptomycin sulfate, tobramycin sulfate, miconazole hydrochloride.
~m~nf~line hydrochloride, ~ nf~rline sulfate, triclosan, octopirox, parachlorometa xylenol, nystatin, tolnaftate and clotrimazole.
4. Sunscreenin~A~ents.
Also useful herein are sunscreening agents. A wide variety of sunscreening 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, 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 usefill in the compositions of the instant invention are those selected from the group consisting of 2-ethylhexyl p-methoxyci~n~ , 2-ethylhexyl N,N-dimethyl-p-aminobenzoate, p-aminobenzoic acid, 2-phenylbenzimidazole-5-sulfonic acid, octocrylene, oxybenzone, homomenthyl salicylate, octyl salicylate, 4,4'-methoxy-t-butyldibenzoylmethane, 4-isopropyl dibenzoylmethane, 3-benzylidene carnphor, 3-(4-methylbenzylidene) camphor~
titanium dioxide, zinc oxide, silica, iron oxide, and ~ Lu~S thereof.
Still other useful sunscreens are those disclosed in U.S. Patent No. 4,937,370, to Sabatelli, issued June 26, 1990, and U.S. Patent No. 4,999,186, to Sabatelli et al., issued March 12, 1991; these two references are incol~o.dl~d by reference herein in their entirety. The sunscreening agents disclosed therein have, in a single molecule, two distinct chromophore moieties which exhibit .lirrt;~ t ultra-violet radiation absorption spectra. One of the chromophore moieties absorbs predo...i.-~..lly in the UVB radiation range and the other absorbs strongly in the WA radiation range. These sunscreening 30 agents provide higher efficacy, broader UV absorption, lower skin penetration and longer lasting efficacy relative to conventional sunscreens. Especially preferred examples of these sunscreens include those selected from the group con~i~ting of 4-N,N-~2-ethylhexyl)methylarninobenzoic acid ester of 2,4-dihydroxybenzophenone, 4-N,N-(2-ethylhexyl)methylaminobenzoic acid ester with 4-hydroxydibenzoylmethane, 4-N,N- (2-ethylhexyl)methylarninobenzoic acid ester of 2-hydroxy-4-(2-CA 02246293 l998-08-l3 WO ~7130689 PCTnUS97J~2991 hydroxyethoxy)benzophenone, 4-N,N-('~-ethylhexyl)-methylarninobenzoic acid ester of 4-(2-hydroxyethoxy)dibenzoylmethane, and mixtures thereof.
~ Generally, the sunscreens can comprise from about 0.5% to about 20% of the compositions useful herein. Exact arnounts will vary depending upon the sunscreen 5 chosen 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 herein by reference in its entirety.
5. Sunless tannin~ a~ents. Also useful in the present ;nvention are sunless tanning 10 agents including dihydroxyacetone, glyceraldehyde, indoles and their derivatives, and the like. These sunless tanning agents can also be used in combination with the susscreen agents.
6. Conditionin~ Agents. Other useful actives include the conditioning agents disclosed hereinbefore, including hydrocarbons, silicone fluids, and cationic materials.
15 The hydrocarbons can be either straight or branched chain and can contain from about 10 to about 16, preferably from about 12 to about 16 carbon atoms. Examples of suitable hydrocarbons are decane, dodecane, tetr~lec~ne~ tri(ler~n~7 and ~ LuleS 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 20 cylic materials have viscosities of less than about 10 centistokes.
Cationic conditionin~ agents useful herein can include qll~t~m~ry arnmoniurn salts or the salts of fatty amines. Preferred ~3u~ laly 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 q~ .y ammoniurn 25 salts include ditallow dimethyl ammonium chloride, ditallow dimethyl arnmonium methyl sulfate, ~iihP~ P~cyl dimethyl ammoniurn chloride, and di(hydrogen~tP~l tallow) ammonium chloride. Other ~ y arnmonium salts useful herein are dicationics such as tallow propane diamrnonium dichloride. Quaternary imid~olinium salts are also useful herein. Examples of such materials are those imitl~olinium salts co..~ g C12 z alkyl groups such as 1-methyl-1-[(stearoylamide)ethyl]-2-heptadecyl-4, 5-dihydroimidazolinium chloride, 1 -methyl- 1 -[(palmitoylamide)ethylJ-2-octadecyl-4,5-dihydroimidazolinium chloride and 1 -methyl- 1 -[(tallowamide)-ethyl]-2-tallow-imidazolinium methyl sulfate. Also useful herein are salts of fatty axnines. Examples of such compounds include stearylamine hydrochloride, soyamine hydrochloride, and stearylarnine formate. Usefill conditioning agents are disclosed in U.S. Patent No.
4,387,090, to Bolich, issued June 7, 1983, which is incorporated by reference herein.

W O 97/30689 PCT~US97/02991 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 1% to about 10% and most preferably from about 2% to about 5%. These materials inciudeurea; guanidine, glycolic acid and glycolate salts (e.g. ammonium and quaternary alkyl ammonium), lactic acid and lactate salts (e.g. arnmonium and quaternary alkyl ammonium); aloe vera in any of its variety of forms (e.g., aloe vera gel); polyhydroxy alcohols such as sorbitol, glycerol, hl-x~netriol, propylene glycol, butylene glycol, hexylene glycol and the like; polyethylene glycols; sugars and starches; sugar and starch derivatives (e.g., alkoxylated glucose); hyaluronic acid; lact~mic~e monoethanolamine;
~- et~mide monoethanolamine; and mixtures thereof. Preferred humectants and moichlri7~rs are glycerol, butylene glycol, hexylene glycol, and mixtures thereof.
The compositions of the present invention, especially the conditioner compositions, can contain one or more surfactants as disclosed hereinbefore. These surfactants are useful adjuncts for the carriers of the present compositions. For conditioners, the ~l~fell~d level of surfactant is from about 0.2% to about 3%. Surfactants useful in compositions of the present invention include anionic, nonionic, cationic, zwitterionic and arnphoteric surfactants.
8. Carboxvlic Acid CopolvmerThickeners 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 about 0.05% to about 0.75% and most preferably from about 0.10% to about 0.50% of carboxylic acid polymer thickeners.
9. F,~ lsifiers The non-rinsed compositions herein can contain various em~ ifiers. These em~ ifiers are useful for emulsifying the various carrier components of the compositions herein, and are not re~uired for solubilizing or dispersing the copolymers of the present invention. Suitable emulsifiers can include any of a wide variety of nonionic, cationic, anionic? and zwitterionic emulsifiers disclosed in the prior patents and other references.
See McCutcheon's, Detergents and Fmlll~ifiers, North American Edition ~1986), published by Allured Publishing Corporation; U.S. 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 herein by reference in their entirety.

WO 97/30689 PCT/lJS97~D2991 Suitable emulsifier types include esters of glycerin, esters of propylene glycol, 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, ethoxylated alcohols, alkyl phosphates, polyoxyethylene fat~y ether phosphates, fatty acid amides, acyl lactylates, soaps and mixtures thereof.
Suitable ernul~ifiers can include, 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 em~ ifiers 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 5% of the compositions of the present invention.
1 0. Emollients The non-rinsed compositions useful in the methods of the present invention can also optionally comprise at least one emollient. Examples of suitable emollients include, 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. 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 total from about 1% to about 50%, preferably from about 1% to about 25%, and more preferably from about 1% to about 10% by weight of the compositions useful in the present invention.
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 p~I thi~k~ning agents (e.g.
polyacrylamide and C13 14 isoyara~ln and laureth-7, available as Sepigel from Seppic Colyo~dLion; polyquaternium and mineral oil, available as Salcare SC92, from Allied Colloids; cro~clinkec~ methyl quaternized dimethylaminomethacrylate and mineral oil, available as Salcare SC95 from Allied Colloids; resins; gums and thickeners such as x~nth~n gum, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose.
alkyl-modified hydroxyalkyl celluloses (e.g. Iong chain aLkyl modified hydroxyethyl celluloses such as cetyl hydroxyethylcellulose), and m~ siulll alllm;nllm silicate:
cationic polymers and thickeners (e.g., cationic guar gum derivatives such as guar WO 97/30689 PCTrUS97/02991 hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyltrimonium chloride, available as the Jaguar C series from Rhone-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 S Corporation as Ganex(~) V-220); suspending agents such as ethylene glycol distearate and the like; preservatives for m~int~ining the antimicrobial integrity of the compositions; skin penetration aids such as dimethylsulfoxide (DMSO), 1-dodecylazacycloheptan-2-one(available as Azone from the Upjohn Co.) and the like; antioxidants; chelatorg and sequestrants; and aesthetic components such as fragrances, colorings, essenti~l oils, skin sen~t~o~, astringents, skin soothing agents, skin healing agents and the like, nonlimiting examples of these ~e~thPtic components include panthenol and derivatives (e.g. éthyl panthenol), pantothenic acid and its derivatives, clove oil, menthol, camphor, eucalyptus oil, eugenol, menthyl lactate, witch hazel distillate, allantoin, bisabalol, dipotassium glycyrrhi7in~t,o and the like. Other useful actives include skin bleaching (or liphtening) agents including but not limited to hydro~uinone, ascorbic acid, kojic acid and sodiurn metabisulfite. Actives which are especially useful for hair care compositions include anti-- dandruff actives such as zinc pyrithione, octopirox, selenium ~i~Ulfi(lP7 sulfur, coal tar, and the like, and hair curling and/or str~ight~ning actives as are well known in the art.
Method of Usin~ Non-Rinsed Hair and Skin Care ComPositions The hair care and skin care compositions of the present invention are used in conventional ways to provide the desired benefit appf~pliate to the product such as hair styling, holding, cle~n~inP~, conditioning and the like for hair care compositions and benefits such as moi~tllri7~tiQn~ sun protection, anti-acne, anti-wrinkling, artificial t~nninp, analgesic, and other cosmetic and ph~ e~lfical benefits for skin care compositions.
Such methods of use depend upon the type of composition employed 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 prior to drying and styling of the hair.
After such compositions are applied to the hair, the hair is dried and styled in the usual ways of the user. Hair sprays are typically applied to dry hair after it has already been dried and styled. Cosmetic and ph~rrn~ce~ltical topical skin care compositions are applied to and rubbed into the skin.
3~ The following examples further illustrate ~lerell~ d embo-1im~ntc within the scope of the present invention. The exarnples are given solely for the purposes of illustration W 0 971306X9 PCTnUS97J~2991 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 ~lefelled 5 embodiments 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 approximations, unless otherwise stated.
Five different perfurne compositions are used in the following examples. Perfilme A and E-I are exarnples of end-lrin~ perfi~ne compositions of this in~,rention. Comparative Perfilmes B, C, and D are non-enduring perfilme compositions which are outside the scope of this invention.
Perfume A
A~ xill~ate Perfume In~redients B.P. (~C)Clo~P Wt.%
Tonalid ~ -- 20 Ethylene brassylate 332 4.554 20 Phantolide +300 5.482 20 Hexyl cinnamic aldehyde 305 5.473 20 Tetrahydro linalool 191 3.517 20 Total 100 Co~ dli~e Perfi~ne B

A~ xil~at~
Perfiune In~redients B.P. (~C)Clo~P Wt.%
Benzyl acetate 215 1.960 20 laevo-Carvone 231 2.083 20 Dihydro myrcenol 208 3.030 20 Hydroxycitronellal 241 1.541 20 Phenyl ethyl alcohol 220 1.183 20 Total 100 -WO 97/30689 CA 0 2 2 4 6 2 9 3 l 9 9 8 - O 8 - 13 PCT/US97/02991 Comparative Perfi~me B contains about 80% of non-enduring peri~ume ingredients having BP < 250~C and ClogP < 3Ø
Co~ al~Li~e Perfùme C

Approximate Perfume In~eredients B.P. f~C) ClogP Wt.%

Eugenol 253 2.307 20 iso-Eugenol 266 2.547 20 Fenchylalcohol 200 2.579 20 Methyl dihydrojasmonate ~300 2.420 20 Vanillin 285 1.580 20 Total 100 Comparative Perfume C contains about 60% of non-enduring perfume ingredients having ClogP < 3Ø

Coll.paldlive Perfurne D
Approximate Perfilme Ingredients B.P. (~C) Clo~P Wt.%
Iso-Bornyl acetate 227 3.485 20 para- Cymene 179 4.068 20 d-Limonene 177 4.232 20 garnma-n-Methyl ionone 252 4.309 20 Tetrahydromyrcenol 200 3.517 20 Total 100 Colll~dLive Perfiume D contains about 80% of non-enduring perfume ingredients having BP c 250~C and ClogP > 3Ø

P~.f~ ~ E Woody Floral - J~e~in Type Ingredients BP ClogP Wt.%

Geranyl acetate --- --- 8 beta-Ionone --- -- 5 Cis-Jasmone --- ---Methyl dihydro3asmonate --- --- 10 WO 97/30689 PCTrUS97JD2991 Suzaral T --- ~- 3 para-tert-Butyl cyclohexyl acetate ~ - 10 Arnyl cinnamic aldehyde 285 4.324 4 iso-Amyl salicylate 277 4.601 8 Benzophenone 306 3.120 2 Cedrol 291 4.530 3 Cedryl forrnate ~25û 5.070 Hexyl cinnamic aldehyde 305 5.473 10 Musk indanone +250 5.458 3 Patchouli alcohol 285 4.530 2 Phenyl hexanol 258 3 299 8 Ylangene 250 6.268 2 Benzyl Acetate 215 1.960 6 Linalool 198 2.429 7 Linalyl acetate 220 3.500 7 Total l O0 ~*) M.P. is melting point, this ingredient has a B.P. higher than 250~C.

Perfume F Fruity Floral Ingredients BP ClogP Wt.%
gamma-Nonalactone --- --- 3 Tonalid --- --- 10 Vertenex --- --- 5 Verdox ~~~ ~~~ 3 Allyl cyclohexane propionate 267 3.935 4 Amyl benzoate 262 3.417 2 Amyl cinnamic aldehyde dirnethyl acetal 300 4.033 5 Aurantiol 450 4.216 3 Dodec~ tone 258 4.359 3 Ethylene brassylate 332 4.554 S
Ethyl methyl phenyl glycidate 260 3.165 2 Galaxolide (50% in IPM) +250 5.482 12 Hexyl cinnamic aldehyde 305 5.473 10 S Hexyl salicylate 290 5.260 10 Lilial (p-t-bucinal) 258 3.858 10 Undecavertol 250 3.690 2 Allyl caproate 185 2.772 3 Fructone --- --- 8 Total 100 Perfume G Rose Floral Ingredients BP ClogP Wt.%

Dimethyl benzyl c~billyl acetate --- --- S
Phenyl ethyl dimethyl carbinol --- --- S
Phenyl ethyl dimethyl carbinyl acetate --- --- 5 iso-Amyl salicylate 277 4.601 10 Benzophenone 306 3.120 5 Cyclarnen aldehyde 270 3.680 5 Diphenyl oxide 252 4.240 10 Geranyl phenyl acetate ~250 5.233 Hexyl cinnamic aldehyde 305 5.473 10 gamma-n-Methyl ionone 252 4.309 5 Lilial (p-t-bucinal) 258 3.858 10 Phenyl hexanol 258 3.299 6 Phenyl heptanol 261 3.478 2 Phenyl ethyl alcohol 220 1.183 15 alpha-Terpineol 219 2.569 6 Total 100 W~ 9'J/30689 PCT/lJS97JD2991 Perfume H Woody Musk Ingredients BP ClogP Wt.%

S alpha-Ionone --- --- 2 gamma-Ionone --- --- 2 Koavone --- --- 8 Methyl dihydrojasmonate --- --- 6 Phenoxy ethyl iso-butyrate --- --- 8 Tonalid --- --- 8 Ambrettolide 300 6.261 5 Ambrox DL 250 5.400 2 Exaltolide 280 5.346 5 Galaxolide (50% in IPM)+250 5.482 10 Hex~ c~nolide 294 6.805 gamma-n-Methyl ionone 252 4.309 5 isoE super +250 3.455 8 Musk indanone +250 5.458 9 Musktibetine MP = 136~C(*) 3.831 s Pachouli alcohol 283 4.530 5 Vetiveryl acetate 285 4.882 5 Cetalox --~
Coumarin 291 1.412 5 Total 100 (*) M.P. is melting point; this ingredient has a B.P. higher than 250~C.

Perfume I Fruity Floral Powder Ingredients BP ClogP Wt.%

Ethyl Vanillin --- --- 2 Lauric Aldehyde --- ---Methyl dihydrojasmonate --- --- 3 W O 97/30689 PCT~US97/02991 Methyl nonyl acetaldehyde --- --- 1 Suzaral T --- --- 5 Tonalid --- --- 5 Veloutone --- --- 2 Verdol --- --- 3 Allyl cyclohexanepropionate 267 3.935 3 Arnyl cinnamic aldehyde dimethyl acetal 300 4.033 8 Cyclamen aldehyde 270 3.680 5 Cedryl acetate 303 5.436 2 Ethylene brassylate 332 4.554 8 Hexyl cinnamic aldehyde 305 5.473 11 Hexyl salicylate 290 5.260 5 Pachouli alcohol 283 4.530 5 Phenyl hexanol 258 3.299 10 Benzoin Claire 50% in DEP 344 2.380 3 Cinnamic alcohol 258 1.950 2 Citral 228 3.120 3 Geranyl nitrile 222 3.139 5 d-Limonene (Orange terpenes) 177 4.232 8 Total 100 The following perfumes c~).. l~;,.ing large amounts of other entll~nng ~lrulllc ingredients can also be used, with the addition of sufficient perfume ingredients selected from the group con~ ting of: cisjasmone; dimethyl benzyl carbinyl acetate; et~l vanillin; geranyl acetate; alpha-ionone; beta-ionone; gamma-ionone; koavone; lauric aldehyde; methyl dihydroj~mon~te; methyl nonyl ~cet~ ohyde; gamma-nonalactone;
phenoxy ethyl iso-butyrate; phenyl ethyl dimethyl carbinol; phenyl ethyl dimethyl carbinyl acetate; alpha-methyl-4-(2-methylpropyl)-benzent;~lopdllal; 6-acetyl-1,1,3,4,4,6-h.ox~n~thyl tetrahydlol~phth~lent; undecylenic aldehyde; vanillin; 2,5,5-trimethyl-2-pentyl-cyclopert~n~ ne; 2-tert-butylcyclohe~nol; verdox; para-tert-butylcyclohexyl acetate; and mi~llu.3 thereof, so that the level of ingredients having a boiling point of at least about 250~C and a ClogP of at least about 3 is less than about 70% of the composition.
-WO 97t30689 PCTJUS97~0299 Perfume J
Perfume In~redients Approximate B.P. ~~C) Clo~P Wt.%
I

Benzyl salicylate 300 4.383 20 Ethylene brassylate 332 4.554 20 Galaxolide - 50%~a) +300 5.482 20 Hexyl cinnamic aldehyde 305 5.473 20 Tetrahydro linalool 191 3.517 20 Total 100 (a) A 50% solution in benzyl bt?n70~te. Perfilme J contains about 80% of e~ nn~ perfume components having BP > 250~C and ClogP > 3Ø

Perîume K

Perfilme In~redients Approximate B.P. (~C) Clo~P Wt.%
Benzyl acetate 215 1.960 4 Benzyl salicylate 300 4.383 12 Coumarin 291 1.412 4 Ethylene brassylate 332 4.554 10 Galaxolide - 50%(a) ~300 5.482 10 Hexyl cinnarnic aldehyde 305 4.853 20 Lilial 258 3.858 15 Methyl dihydro isojasmonate +300 3.009 5 garnrna-n-Methyl ionone 252 4.309 10 Patchouli alcohol 283 4.530 4 Tetrahydro linalool 191 3.517 6 Total 100 (a) used as a 50% solution in isopropyl myristate which is not counted in the composition. Perfilrne K contains about 86% of enduring perfurne components having BP > 250~C and ClogP > 3Ø

Pel ~c L Fruity Floral Ingredients BP ClogP Wt.%

Allyl cyclohexane propionate 267 3.935 4 Amyl ben7n~te 262 3.417 2 WO 97/30689 PCTrUS97/02991 Amyl cinnamic aldehyde dimethyl acetal 300 4.033 S
Aurantiol 450 4.216 3 Dodecalactone 258 4.359 3 Ethylene brassylate 332 4.554 5 Ethyl methyl phenyl glycidate 260 3.165 2 Exaltolide 280 5.346 5 Galaxolide ~50% in IPM) +250 5.482 15 Elexyl cinnamic aldehyde 305 5.473 13 Hexyl salicylate 290 5.260 10 iso E super +250 3.455 8 Lilial (p-t-bucinal) 258 3.858 10 gamma-Un~lec~l~ctone 297 4.140 3.5 delta-Un-lee~ tone 290 3.830 0.5 lS Allyl caproate 185 2.772 3 Fructone - - 8 Total 100 Perfume M Floral Ingredients BP ClogP Wt.%
Benzyl salicylate 300 4.383 5 iso-Butyl quinoline 252 4.193 beta-Caryophyllene 256 6.333 Cyclohexyl salicylate 304 5.265 ~
Dihydro isojasmonate +300 3.009 9 Ethyl undecylenate 264 4.888 2 Galaxolide (50~/~ in IPM) +250 5.482 10 Hexyl cinnamic aldehyde 305 5.473 15 Hexenyl salicylate 271 4.716 1.9 alpha-Irone 250 3.820 0.1 Lilial (p-t-bucinal) 258 3.858 16 Methyl dihydrojasmonate +300 2.420 9 2-Methoxy nz~.phth~lene 274 3.235 2 Phenyl ethyl benzoate 300 4.058 2 Phenylethylphenylacetate 325 3.767 2 Tonalid 248 6.247 4 Citronellol 225 3.193 9 Phenyl ethyl alcohol 220 1.183 10 Total 100 WO 97J30689 PCT/~JS97J02991 Perfume N Rose Floral Ingredients BP ClogP Wt.%
S iso-Amyl salicylate 277 4.601 10 Benzophenone 306 3.120 5 Cyclamen aldehyde 270 3.680 Diphenyl oxide 252 4.240 19 Geranyl phenyl acetate +250 5.233 Hexyl cinnamic aldehyde 305 5.473 10 gamma-n-Methyl ionone 252 4.309 Lilial (p-t-bucinal) 258 3.858 10 Phenyl hexanol 258 3.299 8 Phenyl heptanol 261 3.478 2 Phenyl ethyl alcohol 220 1.183 15 alpha-Terpineol 219 2.569 10 Total 100 Perfume O Woody Musk Ingredients BP ClogP Wt.%
Arnbrettolide 300 6.261 5 para-tert-Butyl cyclohexyl acetate +250 4.019 10 Cedrol 291 4.530 10 Exaltolide 280 5.346 5 Galaxolide (50% in IPM) +250 5.482 15 Hex~lec~nolide 294 6.805 gamma-n-Methyl ionone 252 4.309 10 iso E super +250 3.455 8 Musk indanone +250 5.458 9 Musk tibetine MP = 136~C(*~ 3.831 5 Pachouli alcohol 283 4.530 5 Vetiveryl acetate 285 4.882 5 Methyl dihydrojasmonate +300 2.420 6 Cetalox Coumarin 291 1.412 5 Total 100 (*) M.P. is meltinp point; this ingredient has a B.P. higher than 250~C.

Perfume P Fruity Floral Powder Ingredients BP ClogP Wt.%
S Allyl cyclohexane propionate 267 3.935 3 Amyl cirmamic aldehyde dimethyl acetal 300 4.033 8 Aurantiol ~300 4.216 3 Cyclamen aldehyde 270 3.680 5 Cedryl acetate 303 5.436 2 Ethylene brassylate 332 4.554 8 Galaxolide (50% in~PM) +250 5.482 5 Hexyl cinnamic aldehyde 305 5.473 12 Hexyl salicylate 290 5.260 5 Lilial (p-t-bucinal) 258 3.858 5 Myristicin 276 3.200 2 Pachouli alcohol 283 4.530 5 Phenyl hexanol 258 3.299 10 Anisic Aldehyde 248 1.779 Benzoin Claire 50% in DEP 344 2.380 3 C;nn~mic alcohol 258 1.950 2 Citral 228 3.120 3 Decyl aldehyde 209 4.008 Ethyl Vanillin ~303 1.879 0.5 Geranyl nitrile 222 3.139 5 Methyl dihydrojasmonate ~300 2.420 3.5 d-Limonene (Orange terpenes) 177 4.232 8 Total 100 Perfume O Woody Powder Floral Ingredients BP ClogP Wt.%
Amyl ci~";.. "~l~ 310 3.771 5 Amyl cinnamic aldehyde 285 4.324 8 para-tert-Butyl cyclohexyl acetate +250 4.019 10 linene 275 7.346 Cedrol 291 4.530 5 Cinnamyl çinn~mZ~te 370 5.480 5 Diphenyl methane 262 4.059 3 Do~ec~l~ctone 258 4.359 3 Exaltolide 280 5.346 2 Geranyl a~ lilate 312 4.216 2 Lilial (p-t-bucinal) 258 3.858 3.5 gamma-Methyl ionone 252 4.309 5 , WO 97/306f~9 PCT~US97J02991 Musk indanone+250 5.458 5 Musk ketoneMP = 137~C(*) 3.014 0.5 Musk tibetineMP = 136~C(*) 3.831 3 beta-Naphthol methyl ether (yara-yara) 274 3.235 2 Pachoulialcohol 283 4.530 4 Phantolide 288 5.977 5 alpha-Santalol 301 3.800 3 Ethyl çinn~m~t~ 271 2.990 Hexyl cinnamic aldehyde 305 5.473 10 ~nisic Aldehyde 248 1.779 0.5 Linalyl acetate 220 3.500 2 Linalool 198 2.429 2 Methyl ~u~LlL~ ilate 237 2.024 0.5 Benzoin Claire 50% in DEP 344 2.380 4 Ethyl Vanillin ~303 1.879 Methyl cinn~m~t~ 263 2.620 Vanillin 285 1.275 3 Total 100 (*) M.P. is melting point; these ingredients have a B.P. higher than 250~C.

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 thematerials together at elevated tell,pc.dlu,e, e.g., about 72~C. The silicone resin, if any, and silicone fluid co~ nelll are first mixed together before being mixed with the other ingredients. The other ingredients are added and the compl~ete mixture is mixed thoroughly at the elevated leln~JcL~Llul~ and is then pumped through a high shear mill and then through a heat ex~h~n~er to cool it to ambient l~ p~LdluLe. The average particle size of the silicone is preferably from about 0.5 to about 20 microns. Also ~ltem~tely, a portion of the liquid co~ ollents or soluble components (including, for example, cationic polymer conditioning agent) can be added to the composition after cooling the mix of surfactants and solids, if no insoluble ingredients exist, all ingredients can be combined at ambient temperature.
Alternately, the silicone conditioning agent can be processed by:
(1) mixing with anionic surfactant and fatty alcohol, such as cetyl and stearyl alcohols at elevated te~ dllre, to form a premix co~ i"i..g dispersed silicone. The premix can then be added to and mixed with the rem~ining materials of the shampoo, pumped thorough a high shear mill, and cooled; or W O 97/30689 PCTrUS97/02991 (2) adding silicone, arnmonium laureth-3 sulfate and ammonium chloride to a high shear mixing vessel and mixing for about 30 minutes 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 emulsified.
The compositions of the Examples 1-10 provide excellent in-use hair cleaning, lather, mildness, conditioning (where app~icable), and especially long lasting perfume benefit even after the hair is dried with an electric hair dryer.

TABLE
l 0 Compositions In~redients 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 Sulfate 4.5 4.5 1.5 8.0 3.0 Sodium Lauryl Sarcosinate(6) -- -- 3.75 0.5 --Coconut Monoethanol Amide 2.5 l.0 -- -- l.0 Polyquaternium lO(l) 0.025 0.025 -- -- 0.05 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 --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 -- -- -- --Perfume E -- 0.65 -- -- --Perfume ~ - 0.40 -- --Perfume G -- -- ~~ 0-50 ~~
Perfume H -- -- -- -- 0.25 DMDM Hydantoin 0.20 0.20 0.30 0.30 0.30 PEG 600(4) 0.125 0.125 -- -- --, WO g7J30fif~9 PCT~JS97~0299 Sodium Sulfate 0.50 0.25 -- -- 1.0 Tricetylmethylammonium chloride(7) -- 0 15 0.55 -- --Color Solution (ppm) 10 10 20 20 20 S Sodium ChlorideAdd as needed to thicken to target viscosity Ammonium Xylene Sulfonate(3)Add as needed to thicken to target viscosity Water q.s. to 100%

TABLE
comPositions In~redients 6 7 8 9 10 (ppm or %, by weight, of composition) Sodium Laureth-3 Sulfate 13.5 13.5 16.0 8.0 16.0 Ammonium Lauryl Sulfate 4.5 -- -- 8.0 3.0 Cocoamidopropyl Betaine(5) -- 5.0 3.75 0.5 --Coconut Monoethanol Amide 2.5 1.0 -- -- 1.0 Polyquaternium 10(1~ 0.025 0.025 -- -- 0.05 Dimethicone Copolyol -- 1.5 1.0 -- --Propylene Glycol 1.0 -- -- -- --Glycerine 1.0 -- -- -- --Perfume E 0.65 -- -- -- --Perfume F -- 0.65 -- -- --Perfurne G -- -- 0.40 -- --Perfume H -- 0.50 Perfume I -- -- -- -- 0.25 DMDM EIydantoin 0.20 0.20 0.30 0.30 0.30 SodiumSulfate 0.50 0.25 -- -- 1.0 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 Water q.s. to 100%

Ucare(~) Polymer JR-30M, comrnercially available from Union Carbide Corporation.
2 A 40/60 blend of SE-76 silicone gum available from GE Sili cones and a silicone fluid having a viscosity of about 350 centistokes.
3 Comrnercially available as a 40% solution and used to thin product to target viscosity.
4 Commercially available as a 100% active fluid.
Available under the tr~lf?n~m~ Genagen(~) CAB from Hoechst Celanese as a 30% active solution.
6 Available under the traclerl~me Hamposyl(~) L-30 from ~mp~hire Chemical Corp. as a 30% active solution.
7 "TCMAC" available cornrnercially from Akzo-Chemie as Arquad~)-3 16 as a 90% suspension.

ComParative Examples 11 - 1 3 Sharnpoo Compositions of the Coml,d.dlive F~ntples 11-13 are made similarly to that of Example 1, except that the non-endl-ring perfurnes B. C, and D respectively, are 20 used instead of Perfurne A. Hair worked with shampoo composition of the Comperative Exarnples 11-13 has noticeably less perfume odor and less long lasting perfurne odor especially after the drying step with an electric hair dryer, than when the shampoo composition of Exarnple 1 is used.
25 EXAMPLES 14 to 21 (Foamin~ shower products) The following are personal cleansing compositions in the forrn of foarning shower products and which are r~.c:se~ e of the present invention:
Compositions Component 14 15 16 17 18 Arnphoteric(l) 7.5 3.0 5.0 5.0 2.5 Sodium N-lauryl-beta-amino propionate -- 5.0 3.0 -- 5.0 Sodium laureth3 sulfate 7.5 9.0 10.010.0 7.5 APG(2) 2.5 -- 2.0 2.0 ~oconut diethanolamide3.0 1.0 -- 2.0 1.0 WO 97/30689 PCTnJS97J(>2991 Cocoamidopropyldimethyl-carboxymethyl betaine -- 2.0 2.0 1.0 2.5 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 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 E 0.70 -- -- -- --Perfi me F -- 0.70 -- -- --Perfilme G -- -- 0.70 -- --Perfume H -- -- -- 0.70 --Perfilme I -- -- -- -- 0.70 Water to 100 Compositions In~redients 19 20 21 Amphoteric(l) 5.0 5.0 Sodium laureth-3 sulfate 10.0 10.0 APG(2) 2.5 2.5 Coconut diethanolamide 3.0 Coconut monoethanolarnide - 3.0 2.82 Cocoamidopropylclim~thyl-carboxymethyl betaine 2.5 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 Myristic acid 2.0 2.0 2.0 Maleated soybean oil - - 2.0 Soybean oil 5.0 5.0 8.0 Preservative 0.2 0.2 Pearlescer 2.0 1.0 Perfurne A 1.0 Perfume F - 1.0 W09713~689 PCTrUS97/02991 Perfume G - - 1.70 Na/Mg laureth-3-3.6 sulfate - - 12.0 Sodium lauryl amphoacetate - - 6.0 Decylglucoside - - 2.5 S Polyquaternium-10 (JR-30M) - - 0.40 Glycerine - 3.0 3.0 Titanium dioxide - - 0.10 Sodium benzoate - - 0.25 Glydant - - 0.13 Sodium EDTA - - 0.13 Mg sulfate heptahydrate - - 0.55 Water to 100 (1) Empigen~ CDR 60 - an aqueous mixture of about 26.5% cocoamphoacetate (the amphoteric of Formula I and/or IV in which Rl is coconut alkyl, R2 is H, and Z is C02Na) and about 1.5% cocoampho~ cet~te (the arnphoteric of Formula I and/or IV in which Rl is coconut alkyl, R2 is CH2CO2Na, and Z is C02Na).
(2) Alkylpolysaccharide of Formula VI in which R is Cg-Clo alkyl, t is 0, Z is a glycose residue, and x is about l.S.
(3) Maleated soybean oil m~rk~tf~d by Van Dyke.
(4) Merquat(~) 550 - copolymer of acrylarnide and dimethyldiallyl ammoniumchloride, mol. wt. 2.5 x 106 (8% solution).
(5) Polymer JR-400~) - hydroxyethylcellulose reacted with epichlorohydrin and qu~ nized with trimethylarnine, mol. wt. 4 x 106.
Compositions 14 to 18 are prepared by: forming a gel phase A of Merquat 550 and/or JR-400 in water; forming an a~ueous phase B contzlining the ~ i"i..g water-soluble, oil-insoluble ingredients; forming an oil phase C col.~ g the Ceraphyl GA, myristic acid, coconut diethanolamide, and p~?~rlescer; ~lrnixing phases A and B and heating to about 65-70~C; heating phase C to about 65-70~C and ~mixin~i with mix of 30 phases A and B; cooling to about 40-45~C; adding preservative, and cooling to ambient temperature and adding the perfume A. Compositions 19 to 21 are plepaled by: forming a surfactant phase A cont~inin~ a portion of the water, the anionic and amphotericsurfactants 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 35 glycerate and oil; ~fimixing B with A at about 40-50~C; adding the l~.OAi~ g water, preservative and perfume B; cooling to ambient ~ pe~ UIe; and ~mixing the Ceraphyl W O 97/30689 PcTnus97Jo2991 GA. The average particle size of the emulsion droplets is about 30 micron (Malvern Series 2600 laser diffraction).
The products provide excellent in-use and efficacy benefits including cleansing and lathering together with improved mildness and skin conditioning (hydration, suppleness, S etc.), and especially long lasting perfiume benefit.
Co~ a,dlive Examples 22-24 Foaming shower compositions of Co~ ~ali~e Examples 22-24 are made similar to that of Exarnple 19, except that the non-en~ ring Perfurnes B, C, and D, respectively, are used instead of Perfume A. The compositions of Comparative Examples 22-24 provide less 10 noticeable perfume odor benefit and the perfume odor is ~ignific~n11y less long lasting, as compared to the composition of Example 19.
EXAMPLES 25 to 34 ~Personal Cleansing Compositions Contzlining Soap) Compositions In~redients 25 26 27 28 29 1) Soap (K or Na) 15.00 11.00 11.00 8.00 1.00 30% Laurate 30% Myristate 25% p?.lmit~tf-15% Stearate 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 4) Sodium Laureth-3 Sulfate 0.66 0.66 0.66 0.66 0.66 5)Cocamidopropyl- 1.33 1.33 1.33 1.33 1.33 betaine 6) Glycerine 15.00 15.00 15.00 15.00 15.00 7) Propylene glycol 9.00 9.00 9.00 9.00 9.00 8) Polyquaternium 10 0.80 0.80 0.80 0.80 0.80 9)Ethyleneglycol 1.50 1.50 1.50 1.50 1.50 distearate (EDTA) 10) Propylparaben 0.10 0.10 0.10 O.lu 0.10 11) Methylparaben 0.20 0.20 0.20 0.20 0.20 12~ Perfume E 1.00 -- -- -- --13~ Perfume F -- 1.00 -- -- --CA 02246293 l998-08-l3 W O 97/30689 -78- PCTrUS97/02991 14) Perfùme G -- -- 1.00 -- --15) Perfume H -- -- -- 1.00 --16) Perfume I -- -- -- -- 1.00 17) KOH or NaOH If necessary, adjust premix to pH=7---------18) Water Balance to 100 Compositions In~redients 30 31 32 33 34 1 ) Soap (K or Na) 20.00 25.00 15.00 15.001 1.00 30% Laurate 30% Myristate 25% Palmitate 15% Stearate 2)Fattyacids 1.5 1.0 1.50 1.50 1.50 (above ratios) 3) Na Lauryl 6.00 -- 6.00 6.00 6.00 - Sarcosinate 4) Sodium Laureth-3 Sulfate 0.66 -- 0.66 0.66 0.66 5) Cocamidopropyl- -- -- 1.33 1.33 1.33 betaine 6) Glycerine -- 10.00 15.00 -- 15.00 7) Propylene glycol 9.00 9.00 9.00 15.00 --8) Polyqu~L~l~.lull~ 10 -- -- 0.80 0.80 0.80 9) Ethylene glycol -- -- 1.50 1.50 1.50 distearate (EDTA) 10) Propylparaben 0.10 0.10 0.10 0.10 0.10 ll)Methylparaben 0.20 0.20 0.20 0.20 0.20 12) Perfume E 1.10 -- -- -- --13) Perfurne F -- 1.10 -- -- --14) Perfi~rne G -- -- 1.10 -- --15) Perfume H -- -- -- 1 10 --16) Perfume I -- -- -- -- 1.10 17) KOH or NaOH If nececs~ry, adjust premix to pH=7---------18) Water Balance to 100 CA 02246293 l998-08-l3 WO 97/30689 P~TnU~97)~2991 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. ~dding the propylene glycol to the mixing vessel, continue heating and mixing;
5 3. In a separate mixing vessel, mixing the Polyquaternium 10 polymer into the glycerin ~polymer premix), until the polymer hydrates (approximately 10 minutes);
4. When the fatty acids are completely melted, reacting the fatty acid mixture to soap with KOH (45% solution) and the water;
5. After reaction is completed, adding the following ingredients one at a time, ensuring complete mixing between each and ., ~ a batch ~ e of about 150~F
to 160~F:
a) Polymer premix b) Ethylene glycol distearate c) Methyl and propylparaben d) Sodiurn lauroyl sarcosinate e) Cocamidopropyl betaine f) Sodiurn laureth-3 sulfate 6. Flash cooling the batch to about 90~F to 95~F then adding and thoroughly mixing in the following materials:
a) Phenoxyethanol b) Perfume (Per~ollal Cleansing Emulsion Compositions without Soap) 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 In~redients 35 36 37 38 34 Na Mg Laureth-3.6 sulfate 12.00 12.00 12.00 20.00 12.00 Lauroamphoacetate6.00 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 PEG-6 caprylic/ 4.00 4.00 4.00 4.00 4.00 capric glycerides W O 97/30689 PCT~US97/02991 Glycerine 3.00 3.00 3.00 3.00 3 00 Maleated soybean oil 2.00 2.00 2.00 2.00 2.00 Myristic acid 1.60 1.60 1.60 1.60 1.60 Citric acid 1.40 1.40 1.40 1.40 1.40 S 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 Titanium dioxide 0.10 0. l 0 0.10 0.10 0.10 Mg Sulfate hepta- 0.10 0.10 0.10 0.10 0.10 hydrate Perfurne ~ 1.00 -- -- -- --Perfume F -- 1.00 -- -- --Perfume G -- -- 1.00 -- --Perfurne H -- -- -- 1.00 --Perfume I -- -- -- -- 1.00 Water Balance to 100 Compositions In~redients 40 41 42 43 Na Mg Laureth-3.6 sulfate 12.00 15.00 -- --Lauroampho~cet~te -- 6.00 10.00 8.00 Decylglucoside 2.50 -- 2.50 2.50 Cocamide ME~ -- -- 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 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 Citric acid 1.40 1.40 1.40 1.40 Polyquaterniurn 10 0.40 0.40 0.40 0.40 Sodium benzoate 0.25 0.25 0.25 0.25 Glydant 0.14 0.14 0.14 0.14 WO 97/30689 PCTJIJS97JI>2991 Disodium EDTA 0.13 0.13 0.13 0.13 Titanium dioxide 0.10 0.10 0.10 0.10 Mg Sulfate hepta- 0.10 0.10 0.10 0.10 hydrate Perfume F 1.20 -- -- --Perfume G -- 1.20 -- --Perfurne H -- -- 1.20 --Perfume I i -- -- -- 1.20 Water R~l~nce to 100 Compositions 35 to 43 are prepared by: forming a gel phase A by dis~ersing 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 lauroamph~ et~te while mixin~. Then add sodiurn magnesium laureth-3.6 sulfate. Add sodium ben7Oate, 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 oil.
Add phase B to phase A and mix until çm~ ified, then start cooling.
Adjust pH if nPcess~ry with citric acid.
At about 45~-50~C add glycerine. At about 40~-45~C add DMDM Hydantoin, maleated soybean oil, magnesium sulfate heptahydrate, and perfume. Cool to ambient temperature.
l~XAMPLES 44 TO 54 The following exarnples are liquid hand washing compositions cont~ining enduringperfilrne compositions.
ComPositions In~redients 44 45 Sodiurn lauryl sulfate 6.00 3.80 Sodiurn laureth-3 sulfate 4.00 7.60 Cocarnidopropyl betaine 1.20 1.35 Lauramide DEA 2.86 2.50 Sodium sulfate 0.45 2.10 TetrasodiumEDTA 0.10 0.10 Glydant 0.20 0.20 Citric acid 0.20 0.25 CA 02246293 l998-08-l3 W O 97/30689 -82- PCTrUS97/02991 Ethylene glycol distearate 1.50 --Pearlescer o 43 Polymer Jaguar C- l 4S 0.25 --Perfume E 0.25 --Perfume F -- 0.30 Water -----Balance to 100----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 --Mono sodium lauryl -- -- -- 13.33 --phosphate Ammonium or sodium 6.00 ~.00 2.00 -- --laureth-3 sulfate - Cocoamphodiacetate 3.00 3.00 2.00 2.0 --Decylglucoside -- -- -- -- 3.0 Lauramine oxide -- -- -- -- 10.0 Glucose amide 2.71 2.70 -- -- 2.70 NaLauryl sarcosinate -- 1.50 -- 2.0 --Cocamidopropyl -- 3.75 2.00 2.0 --betaine Soybean oil -- -- 4.00 -- --Caprylic/capric -- -- 2.50 2.50 --glycerides Glycerine 5.00 -- -- -- --Dimethicone copolyol 2.00 -- -- -- --(Dow 193) Zinc stearate -- 0.80 -- -- --Cetylalcohol -- 1.00 1.00 1.50 1.50 Carbomer -- 0.40 -- 1.50 --EGDS -- 1.00 1.00 -- --Polyquaternium 10 l.00 -- 0.80 0.40 --Polyqu~ iu,ll 1 1 -- 0.~0 -- -- --Perfilrne G 0.90 -- - ~~ --WO 97130689 - 83 - PCTJlJS97JD2991 Perfume H -- o.go Peffiume I -- -- 0.90 -- --Perfume E -- -- -- 0 90 --Perfume F -- -- -- -- 0.80 S Sodium benzoate 0.25 0.25 0.25 0.25 0.25 Disodium EDTA0.13 0.13 0.13 0.13 0.13 DMDM Hydantoin0.14 0.14 0.14 0.14 0.14 Water Balance to 100 1 0 Compositions In~redients 51 52 53 54 Ammonium or sodium12.00 5.00 -- --laureth-3 sulfate Cocamidopropyl arnine -- 5.00 2.50 2.00 1 5 oxide Na Lauryl sarcosinate 3.00 -- -- --Sodium cocoyl -- 5.00 -- 10.00 isethionate Cocarnidopropyl -- -- -- 2.0 betaine Glycerine -- -- 10.00 --Propylene glycol -- -- -- 9.00 Sodium benzoate 0.25 0.25 0.25 0.25 Disodium EDTA 0.13 0.13 0.13 0.13 DMDM Hydantoin 0.14 0.14 0.14 0.14 Perfume G 0.90 -- -- --Perfume H -- 0.80 -- --Perfume I -- -- 0.80 --Perfilme E -- -- -- 0.80 Water -Balance to 100 Compositions 44 to 54 are ~r~ d by: forming a gel phase A comprising water and polymer ~e.g., Carbomer, Poly-lua~ ium 10, Polyquaternium 11). When phase A is completely dispersed, begin heating to about 70~C. Add all additional ingredients except 35 preservatives (DMDM Hydantoin, disodiurn EDTA, and sodium berl7o~te) and fragrance.

CA 02246293 l998-08-l3 W O 97/30689 PCTfUS97/02991 Cool to about 30~C and add fragrance and preservatives. Cool to ambient temperature while mixing.

Hair Spray Hair spray compositions are prepared from the following components lltili7ing conventional mixing techniques.

Comoositions In~redients 56 57 5~
Water QS 100 QS 100 QS 100 QS 100 Ethanol (SCA40) 79.0 79.0 79.0 90.0 Copolymer(1) 4.0 4.0 3.0 3.0 Perfume F 0.1 -- -- --Perfume G -- 0.2 -- --Perfume H -- -- 0.3 --Perfume I -- 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) 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) ofazoisobutyronitrile (AIBN) initator, in about 200 mL of acetone. The resulting solution is refluxed slowly for about 24 hours. The reaction is then qllt?n~hecl by the addition of about 5 mL of m~tll~n~ l and cooled to room temperature. The solvents are removed by rotary evaporation and the resl~lting polymer is dissolved in about 250 rnL of dry acetGl,iLl;le. Next, about 20.0 g (about 0.2018 mol) of 2-ethyl-2-ox~oline and about 0.44 g (about 0.0029 mol) of sodium iodide is added and the solution is heated to about 90~C
for about 20 hours. The resllltinE solution is filtered and the solvent is ev~ulak:d to yield about 45.0 g (about 86% yield) of the therrnoplastic elastomeric copolymer.
Ple~)~dLion 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, the W 0~7130689 PCT~US97JD2991 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.
S E~AMPLES 59-62 Rec~-lce~l Volatile Organic Content Hairspray Hair spray compositions are ~ p~ed from the following components ~It;1i7;n~
conventional mixing techniques.
In~redients 59 i 60 61 62 Water QS 100 QS 100 QS 100 QS 100 Ethanol 54 0 54.0 54.0 54 0 Copolymer of Example 58 4.0 3.0 4.0 3.0 Perfume E 0.05 Perfume F -- 0.2 Perfume G -- -- 0.1 --Perfume H -- -- -- 0.15 These products are ~el)~ed by first dissolving the polymer in the ethanol with stirring. The water and fragrance are then added with stirnng. The resulting hair spray 20 compositions can then be packaged in a nonaerosol spray pump. ~It~ tively, 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.

Mousse Mousse compositions are ~lep~ed from the following com~ol~ tili7ing conventional mixing techniques.

In~redients 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 OleylTaurate 1.67 1.67 1.67 DMDM Hydantoin 0.78 0.78 0.78 Disodium EDTA 0.20 0.20 0.20 Polyoxvalkylated isostearyl alcohol ( 1 ) 0.10 0.10 0.10 Perfilme E 0.10 -- --Perfume F -- 0.10 --Perfurne I -- -- 0.10 Propellant (2) 7.0 7.0 7.0 (2) Available as Aerosurf(~ 66-E 10.
~3) Available as a mixture of about 82.46% isobutane, about 16.57% propane, and about 0.001% butane.

These products are prepared by first dissolving the polymer in water with stirring. The rem~ining ingredients, except the propellant, are then added with stirring. The resulting mousse concentrate can then be combined with conventional propellants (e.g., Propellant 15 A46) and packaged in an aerosol spray. These mousses are usefill for application to the hair to provide a styling and holding benefit.

Hair Tonic Hair tonic compositions are prepared from the following components ~tili7ing conventional mixing techniques.
In~redients Ethanol QS 100 QS 100 QS 100 Copolymer of Example 58 0.75 1.00 1.25 Perfume G 0.10 Perfume H -- 0.20 0.30 These products are prepal~,d by dissolving the polymer in the ethanol with stirring and then adding the fragrance and any colors.
These hair tonics are useful for application to the hair to provide a styling and holding benefit.
E~AMPLE 69 Hair Conditioner A hair conditioner composition is plepal~ d from the following components utili7ing conventional mixing techniques.

WO 97t30689 PCTnUS97J02991 ln~redients Wei~ht %

Styling Agent Premix Copolymer of Example 58 1.00 <

Silicone Premix Silicone gum, GE SE76~1) 0.30 Octamethyl cyclotetrasiloxane 1.70 Main Mix Water QS l 00 Cetyl Alcohol 1.00 Quaternium l 8(2) 0.85 Stearyl Alcohol 0.70 Hydroxethyl cellulose 0.50 Ceteareth-20 0.35 Perfume E 0.20 Dimethicone copolyol 0.20 Citric Acid 0.13 Methylchloroisothiazolinone (and) methylisothi~olinone 0.04 Sodium Chloride 0.01 1 Commercially available from General Electric.
2 Dimethyl Di(Hydrogenated Tallow) Ammonium Chloride The product is pl~al- d 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 this temperature, the two premixes are add separately with moderate agitation and the resultant conditioner is allowed to cool to room temperature.
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.
.

W 097/30689 PCTrUS97/02991 In~redient Wei~ht %
Water QS 100 Salicylic Acid 2.0 Copolymer from Example 58 1 2.0 Ethanol (SDA40) 40.0 Perfume F o o5 The compositon display skin penetration of the salicylic acid as well as improved skin reel and residue characteristics and is useful for the treatment of acne.

10 Topical Analgesic Composition A topical analgesic composition is made by combining the following ingredients llti1i7ing conventional mixing techniques.
In~eredients Wei~ht %
Water, Purified QS100 Ibuprofen 2.0 Copolymer from Example 581 2.0 Ethanol (SDA 40) 20.0 Per~ume G 0 03 The compositions display skin penetration of the ibuprofen active as well as 20 improved skin feel and residue characteristics together with excellent moi~tllri7ing, emolliency, rub-in and absorption characteristics.
~XAMPL,E 72 Sunless Tanning Composition A composition for sunless tanning is made by combining the following ingredients1lti1i7ing conventional mixing techniques.
In~redients Wei~ht %
Phase A
Water qs 100 Copolymer from Example 58 2.00 Carbomer 934 (1) 0.20 Carbomer 980 (2) 0.15 Acrylic Acid Copolymer (3) 0.15 CA 02246293 l998-08-l3 W O g7~30689 PC~S97J~2991 Phase B
PPG-20 Methyl Glucose Ether Distearate 2.00 Tocopheryl Acetate 1.20 ,~ 5 Mineral Oil 2.00 Stearyl Alcohol 1.00 Shea Butter 1.00 Cetyl Alcohol 1.00 Ceteareth-20 2.50 Ceteth-2 1.00 Ceteth 10 1.00 Phase C
DEA-Cetyl Phosphate 0.75 Phase D
Dihydroxyacetone 3.00 Phase E
Butylene Glycol 2.00 DMDM Hydantoin (and) Iodopropynyl Butylcarbamate 0.25 Phase F
Perfume H 1.00 Cyclomethicone 2.00 (1) Available as Carbopol(g) 934 from B.F. Goodrich.
25 (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 s~;y~dl~ vessel the Phase B ingredients are combined and heated to about 85-90~C until melted. Next, the DEA-Cetyl Phosphate is added to the liquid Phase 30 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 resulting solution is mixed into the emulsion. In another vessel, the Phase E 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 ~ ingredients are added to the emulsion with mixin~, which is then 5 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 tan.

Sunsclt:ell Composition An oil-in-water emulsion is pl~a,ed by combining the following components ~lt~ in~conventionalmixing techniques.
In~redients Wei~ht %
Phase A
Water QS 100 Carbomer 954 (1) 0.24 Carbomer 1342 (2) 0.16 Copolymer from Exmaple VI (3) 1.75 Disodium EDTA 0.05 Phase B
Isoarachidyl Ne-~pe~ o~te (4) 2.00 PVP Eicosene Copolymer (5) 2.00 Octyl Methoxycinn~m~te 7.50 Octocrylene 4.00 Oxybenzone 1.00 Titanium Dioxide 2.00 Cetyl P~lmit~t~? 0 75 Stearoxytrimethylsilane (and) Stearyl Alcohol (6) 0.50 Glyceryl Tribeh~ tt? (7) o 75 Dimethicone 1.00 Tocopheryl Acetate 0.10 DEA-Cetyl Phosphate 0.20 Phase C
Water 2.00 Triethanolamine 99% 0.60 WO 97/30689 PCTnUS97102991 _ 91 _ Phase D
Water 2.00 t Perfume I 0 05 Butylene Glycol 2.00 DMDM Hydantoin (and) Iodopropynyl Butylcarbarnate (8) 0.25 dL P~nthenol 1 00 Phase E
Cyclomethicone 1.00 10 ( 1 ) Available as CarbopolR 954 from B.F. Goodrich.
(2) Available as CarbopolR 1342 from B.F. Goodrich.
(3) Alternatively, the sunscreen compositions are prepared using the copolymers of Examples VIII and IX.
(4) Available as Elefac I-205 from Bernel Chemical.
15 (5) Available as Ganex V-220 from GAF Corporation.
(6) Available as DC 580 Wax from Dow Corning.
(7) Available as Synchrowax 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 20 about 75-85~C. In a separate vessel the Phase B ingredients (except DEA-CetylPhosphate) are combined 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 em~ n. The Phase C ingredients are combined until dissolved and then added to the emulsion. The emulsion is then cooled to about 40-45~C
25 with continl1e~l mixing In another vessel, the Phase D 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 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 30 the harmful effects of ultraviolet radiation.

W O 97/30689 PCTrUS97/02991 Facial Moisturizer A leave-on facial emulsion composition con~ining a cationic hydrophobic surfactant is prepared by combining the following components l1tili7ing conventional mixing techniques.
In~redients Wei~ht %
Water QS 100 Copolymer from Example 58 1.00 Glycerin 3.00 Cetyl Palmitate 3.00 Cetyl Alcohol 1.26 Quaternium-22 1.00 Glyceryl Monohydroxy Stearate 0.74 Dimethicone 0.60 Stearic Acid 0.55 Octyldodecyl Myristate 0.20 Perfume L 0.06 Carbomer 1342 0.125 Tetrasodium EDTA 0.10 DMDM Hydantoin and Iodopropynyl Butyl Carbamate 0.10 Carbomer 951 0.075 This emulsion is useful for application to the skin as a moi~ ri7Pr.

The following compositions are representative of a.,lip~ irant compositions herein.
In~redients 75 76 77 7879 80 81 82 N-Lauroyl-L-glutamic acid-di-n-butyl amide(l) 4 5 1 3 2 2 2 30 12-hydroxystearic acid 2 5 5 6 7 3 6 12 CyclomethiconeD 5(2) - 40 49 3943 40 43 46 Polyphenylmethylsiloxane(3) - - - 3 - - 5 Light mineral oil(4) 23 Panalane-L-14E(5) - 15 10 11 35 Isopropyl Myristate - 15 15 16 - - 11 Isopropyl Alcohol - - - - 18 Captex 200(6) - - - - - 15 C 12-C 15 Alcohols Benzoate(7) - - - - - - 8 W Og7/3068g P~T~us97Jo29 PPG-3 Myristyl Ether - - - - - - - 26 Diisopropyl Sebacate(8) 43 - - - - - - -Alllminnm Zirconium Trichlorhydrex Gly(9~ 24.9 19.8 19.9 19.89 - 39.88 24.8 Alurninum Chlorohydrate(l0) - - - - 29.86 - - 9.85 Perfilme F 0.1 - 0.01 Perfi~ne G - 0.02 - 0.1 1 Perfume H - - - - 0.14 - 0.2 Perfume I - - - - - 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.
(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(~ DIS supplied by Scher Chemicals Inc.
(9) Supplied by Westwood Chemical Co.
(10) Westchlor~) DM200 supplied by Westwood ChPmic~l Co.

E~AMPLE 83 The following is another example of a deodorant composition.
An antipeL~hdllt stick composition of the present invention is p,e~ d as 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.
In~redients Wei~ht %
Cyclomethicone D-5 (1) 39.8 Light Mineral Oil (2) 11.5 Dimethicone (50 csk) (3) 1.5 Stearyl Alcohol 14.0 Hydrogenated Castor Oil (4) 4.5 Eicosanol 0.2 Talc 1.4 Fumed Silica (5) 1.0 Perfume E 0.1 Alllminllm Chlorohydrate (6) 26.0 100%

CA 02246293 l998-08-l3 W O 97/30689 PCT~US97/02991 (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 5 (4) Castor Wax MP 80, supplied by NL Industries (5) Cab-O-Sil HS-5, supplied by Cabot Corporation ~6) Reheis 501 macrospherical aluminum chlorohydrate, supplied by Reheis Chemical Company When the above compositions are prepared with Perfumes J-Q (as modified) 10 replacing Perfumes A and E-I, substantially identical results are obtained in that the compositions are perfumed with an enduring perfilme.

Claims (8)

WHAT IS CLAIMED IS:

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, said perfume composition comprising at least about 70% of enduring perfume ingredients selected from the group consisting of: ingredients having a boiling point of at least about 250°C and a ClogP of at least about 3; cis-jasmone;
dimethyl benzyl carbinyl acetate; ethyl vanillin; geranyl acetate; alpha-ionone,beta-ionone; gamma-ionone; koavone; lauric aldehyde; methyl dihydrojasmonate, methyl nonyl acetaldehyde; gamma-nonalactone; phenoxy ethyl iso-butyrate; phenyl ethyl dimethyl carbinol; phenyl ethyl dimethyl carbinyl acetate; alpha-methyl-4-(2-methylpropyl)-benzenepropanal; 6-acetyl-1,1,3,4,4,6-hexamethyl tetrahydronaphthalene; undecylenic aldehyde; vanillin; 2,5,5-trimethyl-2-pentyl-cyclopentanone; 2-tert-butylcyclohexanol; verdox; para-tert-butylcyclohexyl acetate;
and mixtures thereof, the level of ingredients having a boiling point of at least about 250°C and a ClogP of at least about 3 being less than about 70% so that the composition with only those ingredients is not an enduring perfume.

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 14 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%, of said enduring perfume ingredients and less than about 65% of components with ClogP ~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 about 5% of enduring perfume ingredients selected from the group consisting of: cis-jasmone; dimethyl benzyl carbinyl acetate, ethyl vanillin; geranyl acetate; alpha-ionone; beta-ionone; gamma-ionone; koavone; lauric aldehyde; methyl dihydrojasmonate; methyl nonyl acetaldehyde; gamma-nonalactone;phenoxy ethyl iso-butyrate; phenyl ethyl dimethyl carbinol; phenyl ethyl dimethyl carbinyl acetate; alpha-methyl-4-(2-methylpropyl)-benzenepropanal;
6-acetyl-1,1,3,4,4,6-hexamethyl tetrahydronaphthalene; undecylenic aldehyde; vanillin;
2,5,5-trimethyl-2-pentyl-cyclopentanone; 2-tert-butylcyclohexanol; verdox;
para-tert-butylcyclohexyl acetate; and mixtures thereof.

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