Hair styling conditioners

The present invention relates to rinse off hair conditioner compositions comprising from about 0.2% to about 20% of certain hair styling polymers, from about 0.2% to about 20% of certain non-aqueous solvents for said hair styling polymers, and from about 0.05% to about 25% of a hair conditioning agent, in an aqueous base, wherein the polymer and solvent are present in the composition as a dispersed fluid phase.

TECHNICAL FIELD 
The present invention relates to rinse off hair conditioner compositions 
which provide not only hair conditioning benefits, but also hair styling 
benefits. These are achieved by incorporating certain hair styling 
polymers and solvents for said polymers in a conditioner base. 
BACKGROUND OF THE INVENTION 
In washing, drying and styling one's hair several end results are desired. 
Firstly, and most obviously, one desires that the hair be thoroughly 
cleaned. Most desirable is a hair care process which maintains the look 
and feel of clean hair between hair washings. Also in the cleaning and 
styling process, one desires hair conditioning providing ease of combing, 
relief from static electricity, manageability, and soft hair feel. 
Generally, these benefits are provided by a separate hair conditioning 
product. 
Finally, one desires a hair care process or product that provides hair 
styling benefits, especially hair style achievement and hold. The desire 
to have hair retain a particular shape is widely held. Such style 
retention is generally accomplished by either of two routes: permanent 
chemical alteration or temporary alteration of hair style/shape. A 
temporary alteration is one which can be removed by water or by 
shampooing. Temporary style alteration has generally been accomplished by 
means of the application of a third separate composition or compositions 
to dampened hair after shampooing and/or conditioning. The materials used 
to provide setting benefits have generally been resins or gums and have 
been applied in the form of mousses, gels, lotions, or sprays. This 
approach presents several significant drawbacks to the user. It requires a 
separate step following shampooing and conditioning to apply the styling 
composition. In addition, since the style hold is provided by resin 
materials which set-up on the hair, the hair tends to feel sticky or stiff 
after application and it is difficult to restyle the hair without further 
application of the styling composition. 
It has now been discovered that two separate hair care benefits, i.e., 
conditioning and styling benefits, can be provided by a single hair care 
product. The present invention relates to rinse off hair conditioner 
compositions which comprise conditioners and certain hair styling agents. 
Rinsing with these products after shampooing provides hair conditioning 
and styling benefits. 
It has also been discovered that the aforementioned products provide some 
degree of restyling benefit to the hair. 
It is an object of the present invention to formulate hair care 
compositions which provide effective hair conditioning and styling 
properties. 
It is also an object of the present invention to formulate hair care 
compositions which provide conditioning and styling benefits from a single 
composition. 
It is a further object of the present invention to formulate hair care 
compositions which provide good style retention benefits without leaving 
hair with a stiff or sticky/tacky feel. 
It is a further object of the present invention to provide an improved 
method for conditioning and styling hair. 
These and other objects will become readily apparent from the detailed 
description which follows. 
SUMMARY OF THE INVENTION 
The present invention relates to rinse off hair conditioner compositions 
comprising: 
a. from about 0.05% to about 25% of a hair conditioning agent; 
b. from about 0.2% to about 20% of a hair styling polymer comprising: 
A. from 0% to about 50% of a polymerizable hydrophilic monomer (M.sub.A), 
or mixtures thereof; and 
B. from about 50% to about 100% of a polymerizable hydrophobic monomer 
(M.sub.B), or mixtures thereof; 
said polymer having a molecular weight of from about 5,000 to about 
1,000,000, a Tg of greater than about -20.degree. C., and a solubility 
parameter, .delta., of from about 8.5 to about 12.0; 
c. from about 0.2% to about 20% of a non-aqueous solvent which will 
solubilize said polymer, said solvent having a boiling point of less than 
or equal to about 300.degree. C., and a solubility in water at 25.degree. 
C. of greater than 0.2%; and 
d. the balance, an aqueous carrier; 
wherein the polymer and solvent are present in the hair conditioner as a 
dispersed fluid phase; and wherein the ratio of polymer to solvent is from 
about 10:90 to about 80:20.

DETAILED DESCRIPTION OF THE INVENTION 
The essential, as well as the optional, components of the present invention 
are described below. 
Styling Agents 
The conditioner compositions of the present invention contain, as an 
essential component, certain hair styling polymers. It is this component 
that provides hair styling benefits to the user. 
A wide variety of hair setting polymers are generally known for use as 
styling agents. Many polymers said to be useful in hair styling products 
are multi-component polymers which combine three, four and even more 
different monomers into the polymer chains. Frequently, one of the monomer 
components is vinyl pyrrolidone. Examples of such complex polymer systems 
are found in U.S. Pat. No. 3,222,329 to Grosser et al., issued Dec. 7, 
1965; U.S. Pat. No. 3,577,517 to Kubot et al., issued May 4, 1971; U.S. 
Pat. No. 4,012,501 to Farber, issued Mar. 15, 1977; U.S. Pat. No. 
4,272,511 to Papantoniou and Mondet, issued Jun. 9, 1981; and U.S. Pat. 
No. 4,196,190, to Gehman et al., issued Apr. 1, 1980. 
Other polymers said to be useful for hair styling compositions have been 
disclosed, such as block polymers. Examples of such block polymer systems 
are found in U.S. Pat. No. 3,907,984 to Calvert et al., issued Sep. 23, 
1975; U.S. Pat. No. 4,030,512 to Papantoniou et al., issued Jun. 21, 1977; 
and U.S. Pat. No. 4,283,384 to Jacquet et al., issued Aug. 11, 1981. 
It has now been found that styling polymers having water-solubilities 
within a certain range provide optimum hair styling benefits when 
delivered from a hair conditioner. The styling polymers of the present 
invention are of relatively low water-solubility. More specifically, these 
polymers have a solubility parameter, .delta., of between about 8.5 and 
about 12.0 (units equal (cal/cm.sup.3).sup.1/2), preferably from about 9.5 
to about 11.5, most preferably from about 11 to about 11.5. 
The solubility parameter is defined in the Polymer Handbook 3rd Ed. (John 
Wiley and Sons, New York), J. Brandrup and E. H. Immergut, Chapter VII, 
pp. 519-559, as the square root of the cohesive energy density and 
describes the attractive strength between molecules of the material. 
Solubility parameters may be determined by direct measurement, 
correlations with other physical properties, or indirect calculation. The 
solubility parameters of the present polymers were determined by indirect 
calculations of group contributions as described in section 2.3 on p. 
524-526 of the cited reference. 
It has been found that styling polymers having water solubilities within 
this range can be dispersed with the polymer solvent, as described infra, 
in conditioner compositions as a dispersed fluid phase. Formulation in 
this way has been shown to provide maximum deposition of styling polymer 
out of the conditioner composition and onto hair. Styling polymers having 
solubility parameters at the upper end of this range would be soluble by 
themselves in the present conditioner compositions. It has now been found 
that when these polymers are combined with the polymer solvents of the 
present invention (as defined infra) and then dispersed in the conditioner 
composition, they remain in the composition as a dispersed fluid phase. 
Polymers having solubility parameters greater than about 12.0 will be 
soluble in the conditioner composition (even when they are premixed with 
the present polymer solvents) preventing optimum deposition of polymer on 
hair. Styling polymers having solubility parameters lower than about 8.5 
are difficult to remove from hair and tend to build up on hair with 
repeated application. 
The present styling polymers must comprise at least one polymerizable 
hydrophobic monomer. The polymer may be a homopolymer or a copolymer of 
hydrophobic monomers. Alternatively, the present styling polymers may be a 
copolymer of a hydrophilic monomer and a hydrophobic monomer, or mixtures 
thereof. Hence, the present hair styling polymers comprise from 0% to 
about 50% of a polymerizable hydrophilic monomer (M.sub.A) or mixtures 
thereof, and from about 50% to about 100% of a polymerizable hydrophobic 
monomer (M.sub.B), or mixtures thereof. Of course, if the styling polymer 
comprises both M.sub.A monomer and M.sub.B monomer, then the monomers must 
be copolymerizable with each other. 
Preferred hydrophilic monomers of the present styling polymers include 
acrylic acid, methacrylic acid, N,N-dimethylacrylamide, dimethylaminoethyl 
methacrylate, methacrylamide, N-t-butyl acrylamide, maleic acid, maleic 
anhydride and its half esters, crotonic acid, itaconic acid, acrylamide, 
acrylate alcohols, hydroxyethyl methacrylate, vinyl pyrrolidone, vinyl 
ethers (such as methyl vinyl ether), maleimides, vinyl pyridine, vinyl 
imidazole, other polar vinyl heterocyclics, styrene sulfonate, allyl 
alcohol, vinyl alcohol (produced by the hydrolysis of vinyl acetate after 
polymerization), vinyl caprolactam, and mixtures thereof. 
Preferred hydrophobic monomers include acrylic or methacrylic acid esters 
of C.sub.1 -C.sub.18 alcohols, such as methanol, ethanol, 1-propanol, 
2-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol, 
3-pentanol, 2-methyl-1-butanol, 1-methyl-1-butanol, 3-methyl-1-butanol, 
1-methyl-1-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, t-butanol, 
cyclohexanol, neodecanol, 2-ethyl-1-butanol, 3-heptanol, benzyl alcohol, 
2-octanol, 6-methyl-1-heptanol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 
3,5,5-trimethyl-1-hexanol, 1-decanol, and the like, the alcohols having 
from about 1-18 carbon atoms with the average number of carbon atoms being 
from about 4-12; styrene; polystyrene macromer; vinyl acetate; vinyl 
chloride; vinylidene chloride; vinyl propionate; alpha-methylstyrene; 
t-butylstyrene; butadiene; cyclohexadiene; ethylene; propylene; vinyl 
toluene; methoxy ethyl methacrylate; and mixtures thereof. 
Optimum performance of the present hair styling polymers in terms of style 
hold has been found when the weight average molecular weight of the 
styling polymer is between about 5,000 and about 1,000,000, preferably 
between about 10,000 and about 200,000 and the glass transition 
temperature, Tg, (i.e., the temperature at which the polymer changes from 
a brittle vitreous state to a plastic state) of the styling polymer is 
greater than about -20.degree. C., preferably between about 0.degree. C. 
and about 80.degree. C., and most preferably between about 20.degree. C. 
and about 60.degree. C. 
Specific styling polymers of the present invention which provide the 
desired deposition/styling benefits out of a conditioner system are as 
follows: vinyl pyrrolidone/vinyl acetate copolymers (at ratios of up to 
about 30%, by weight, vinyl pyrrolidone); vinyl acetate homopolymer; 
t-butyl acrylate homopolymer; t-butyl styrene/ethyl hexyl methacrylate 
copolymer (50/50, by weight); dimethyl acrylamide/t-butyl acrylate/ethyl 
hexyl methacrylate copolymer (10/45/45); ethylene/vinyl acetate copolymer 
(12.5/87.5); allyl alcohol/styrene copolymer (19/81); vinyl chloride/vinyl 
acetate copolymer (83/17 and lower); vinyl pyrrolidone/vinyl acetate/butyl 
acrylate copolymer (10/78/12 and 10/70/20); vinyl pyrrolidone/vinyl 
acetate/butyl acrylate/styrene sulfonate copolymer (10/70/15/5); vinyl 
pyrrolidone/vinyl propionate copolymer (5/95); vinyl caprolactam/vinyl 
acetate copolymer (5/95); and styling resins sold under the trade names 
Ultrahold 8 by Ciba Geigy (ethyl acrylate/acrylic acid/N-t-butyl 
acrylamide copolymer), Resyn 28-1310.RTM. by National Starch and Luviset 
CA 66.RTM. by BASF (vinyl acetate/crotonic acid copolymer 90/10); Luviset 
CAP.RTM. by BASF (vinyl acetate/vinyl propionate/crotonic acid 50/40/10); 
and Resyn 28-2930.RTM. by National Starch (vinyl acetate/vinyl 
neodecanoate/crotonic acid copolymer). The most preferred copolymers for 
use in the present invention are copolymers of vinyl pyrrolidone and vinyl 
acetate containing at most 30% vinyl pyrrolidone. 
The polymer styling agent is present in the compositions of the present 
invention at a level of from about 0.2% to about 20%, preferably at a 
level of from about 2% to about 6%. At levels below about 0.2% styling 
polymer, the present hair style hold benefits cannot be achieved; at 
levels above about 20% styling polymer, interference with conditioning 
benefits may occur. 
The styling polymers of the present invention formulated in the present 
conditioner compositions provide hair styling benefits. Such benefits 
include ease of style achievement and style maintenance. The present 
compositions also provide some degree of restyling benefits. That is, 
after the hair is rinsed with the present compositions and styled, the 
hair "remembers" the style after being subjected to a force, such as 
combing, brushing or simply flattening of the hair. 
Polymer Solvent 
A second essential component of the present conditioner compositions is a 
non-aqueous solvent or diluent for the styling polymer. The solvent is 
necessary for dilution of the polymer so that it can be dispersed in the 
conditioner composition. The present solvents provide optimum deposition 
of polymer onto hair. The solvent also aids in delivering style 
achievement by making polymer deposited on the hair more tacky through the 
hair drying and styling process. Hence, the polymer remains adhered to the 
hair and it enables easy manipulation of the hair into the desired style. 
The particular polymer chosen for use in the present conditioner 
compositions must be soluble in the particular solvent utilized. This 
enables the dispersion of the polymer/solvent mixture as a dispersed fluid 
phase in the conditioner composition and maintenance of that dispersed 
second phase. Hence, the polymer solvents of the present invention have a 
solubility in water at 25.degree. C. of greater than 0.2%, preferably 
greater than about 0.5%, and as high as 100% soluble in water, but 
preferably less than 10% soluble in water. Some solvents which are 
completely water soluble will not remain as a dispersed fluid phase with 
the polymer in the conditioner composition. They will instead enter the 
aqueous conditioner base phase and destroy the dispersed phase of polymer 
and solvent in the conditioner. Many of the solvent materials of the 
present invention, if dispersed in the conditioner base alone, would be 
soluble. However, it has been found that when the solvents of the present 
invention are premixed with certain polymers of the present invention, 
prior to dispersion in the conditioner composition, they will remain in 
the polymer phase, i.e., unsolubilized in the conditioner base. 
The polymer solvent must also be volatile. Upon deposition of the 
polymer/solvent mixture on the hair, the solvent is volatilized leaving 
only the styling polymer on the hair, thus providing the maximum styling 
benefits. Generally, the polymer solvents of the present invention have a 
boiling point of less than or equal to about 300.degree. C. 
Additionally, the polymer solvent must not interact with the polymer 
styling agent in such a way that would substantially reduce the ability of 
the polymer to provide styling benefits to hair under ordinary use 
situations. The solvents must, of course, be of sufficiently high purity 
and sufficiently low toxicity to render them suitable for administration 
to human hair. 
The present more hydrophilic solvents are desirable for use in hair care 
compositions because they are safe to use, tend to have more aesthetically 
pleasing physical attributes, and because they tend to be less costly than 
other polymer solvents. 
Specific polymer solvent materials that have been found to be useful in the 
present invention include isopropanol, butyl alcohol, amyl alcohol, phenyl 
ethanol, benzyl alcohol, ethyl butyrate, isopropyl butyrate, phenyl ethyl 
dimethyl carbinol, and mixtures thereof. Preferred solvents for use herein 
are benzyl alcohol, ethyl butyrate, phenyl ethanol, phenyl ethyl dimethyl 
carbinol, and mixtures thereof. 
The amount of solvent to be used in the present conditioner compositions is 
an amount sufficient to solubilize the polymer and disperse it as a 
separate fluid phase in the conditioner composition. Generally, from about 
0.2% to about 20%, preferably from about 2% to about 6%, polymer solvent 
is used. At levels below about 0.2% solvent, the polymer cannot be 
sufficiently diluted; at levels above about 20% solvent, conditioner 
benefits may be negatively affected. The ratio of polymer to solvent in 
the present compositions is from about 10:90 to about 80:20, preferably 
from about 40:60 to about 60:40. 
European Patent Publications 0320218, published Jun. 14, 1989, and 0323715, 
published Jul. 12, 1989, disclose certain hair styling polymers and 
solvents therefor, useful in hair care compositions, including shampoos 
and rinse-off hair conditioners. EPO Patent Publication 0323715 teaches 
polymer and solvent systems having very low water solubilities (polymer is 
less than 0.1% soluble in water, diluent is less than 0.2% soluble in 
water) which are dispersed as a separate fluid phase in hair care 
compositions. 
Conditioning Agent 
The conditioner compositions of the present invention comprise, in addition 
to the styling polymer and solvent therefor, a conditioning agent. The 
conditioning agent is present in the compositions of the present invention 
at a level of from about 0.05% to about 25%, preferably from about 2% to 
about 10%. These conditioning agents may comprise conditioning agents 
typically used in hair conditioner compositions. Such agents generally 
comprise a lipid material and a cationic surfactant. These agents together 
provide not only hair conditioning benefits, such as anti-static, soft 
hair feel, and ease of combing, but also provide a gel-network thickened 
vehicle for the styling polymer and solvent of the present compositions. 
Gel-type vehicles are generally described in the following documents, all 
incorporated by reference herein: Barry, "The Self Bodying Action of the 
Mixed Emulsifier Sodium Dodecyl Sulfate/Cetyl Alcohol", 28 J. of Colloid 
and Interface Science 82-91 (1968); Barry, et al., "The Self-Bodying 
Action of Alkyltrimethylammonium Bromides/Cetostearyl Alcohol Mixed 
Emulsifiers; Influence of Quaternary Chain Length", 35 J. of Colloid and 
Interface Science 689-708 (1971); and Barry, et al., "Rheology of Systems 
Containing Cetomacrogol 1000--Cetostearyl Alcohol, I. Self Bodying 
Action", 38 J. of Colloid and Interface Science 616-625 (1972). 
The conditioning agents may comprise one or more lipid materials which are 
essentially water-insoluble, and contain hydrophobic and hydrophilic 
moieties. Lipid materials include naturally or synthetically-derived 
acids, acid derivatives, alcohols, esters, ethers, ketones, and amides 
with carbon chains of from about 12 to about 22, preferably from about 16 
to about 18, carbon atoms in length. Fatty alcohols and fatty esters are 
preferred; fatty alcohols are particularly preferred. 
Lipid materials among those useful herein are disclosed in Bailey's 
Industrial Oil and Fat Products, (3rd edition, D. Swern, ed., 1979), 
incorporated by reference herein. Fatty alcohols included among those 
useful herein are disclosed in the following documents, all incorporated 
by reference herein: U.S. Pat. No. 3,155,591, Hilfer, issued Nov. 3, 1964; 
U.S. Pat. No. 4,165,369, Watanabe, et al., issued Aug. 21, 1979; U.S. Pat. 
No. 4,269,824, Villamarin, et al., issued May 26, 1981; British 
Specification 1,532,585, published Nov. 15, 1978; and Fukushima, et al., 
"The Effect of Cetostearyl Alcohol in Cosmetic Emulsions", 98 Cosmetics & 
Toiletries 89-112 (1983). Fatty esters included among those useful herein 
are disclosed in U.S. Pat. No. 3,341,465, Kaufman, et al., issued Sep. 12, 
1976 (incorporated by reference herein). 
Preferred esters for use herein include cetyl palmitate and 
glycerylmonostearate. Cetyl alcohol and stearyl alcohol are preferred 
alcohols. A particularly preferred lipid material is comprised of a 
mixture of cetyl alcohol and stearyl alcohol containing from about 55% to 
about 65% (by weight of mixture) of cetyl alcohol. 
Cationic surfactants useful in the present conditioner compositions, 
contain amino or quaternary ammonium hydrophilic moieties which are 
positively charged when dissolved in the aqueous composition of the 
present invention. Cationic surfactants among those useful herein are 
disclosed in the following documents, all incorporated by reference 
herein: McCutcheon's, Emulsifiers & Detergents, (1989, published by the M. 
C. Publishing Company) Schwartz, et al., Surface Active Agents, Their 
Chemistry and Technology, New York: Interscience Publishers, 1949; U.S. 
Pat. No. 3,155,591, Hilfer, issued Nov. 3, 1964; U.S. Pat. No. 3,929,678, 
Laughlin, et al., issued Dec. 30, 1975; U.S. Pat. No. 3,959,461, Bailey, 
et al., issued May 25, 1976; and U.S. Pat. No. 4,387,090, Bolich, Jr., 
issued Jun. 7, 1983. If included in the compositions of the present 
invention, the cationic surfactant is present at from about 0.05% to about 
5%. 
Among the quaternary ammonium-containing cationic surfactant materials 
useful herein are those of the general formula: 
##STR1## 
wherein R.sub.1 -R.sub.4 are independently an aliphatic group of from 
about 1 to about 22 carbon atoms, or an aromatic, alkoxy, polyoxyalkylene, 
alkylamido, hydroxyalkyl, aryl or alkylaryl group having from about 12 to 
about 22 carbon atoms; and X is an anion selected from halogen, acetate, 
phosphate, nitrate and alkylsulfate radicals. The aliphatic groups may 
contain, in addition to carbon and hydrogen atoms, ether linkages, and 
other groups such as amino groups. 
Other quaternary ammonium salts useful herein have the formula: 
##STR2## 
wherein R.sub.1 is an aliphatic group having from about 16 to about 22 
carbon atoms, R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 are selected 
from hydrogen and alkyl having from about 1 to about 4 carbon atoms, and X 
is an ion selected from halogen, acetate, phosphate, nitrate and alkyl 
sulfate radicals. Such quaternary ammonium salts include tallow propane 
diammonium dichloride. 
Preferred quaternary ammonium salts include dialkyldimethylammonium 
chlorides, wherein the alkyl groups have from about 12 to about 22 carbon 
atoms and are derived from long-chain fatty acids, such as hydrogenated 
tallow fatty acid (tallow fatty acids yield quaternary compounds wherein 
R.sub.1 and R.sub.2 have predominately from 16 to 18 carbon atoms). 
Examples of quaternary ammonium salts useful in the present invention 
include ditallowdimethyl ammonium chloride, ditallowdimethyl ammonium 
methyl sulfate, dihexadecyl dimethyl ammonium chloride, di(hydrogenated 
tallow) dimethyl ammonium chloride, dioctadecyl dimethyl ammonium 
chloride, dieicosyl dimethyl ammonium chloride, didocosyl dimethyl 
ammonium chloride, di(hydrogenated tallow) dimethyl ammonium acetate, 
dihexadecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium 
acetate, ditallow dipropyl ammonium phosphate, ditallow dimethyl ammonium 
nitrate, di(coconutalkyl) dimethyl ammonium chloride, and stearyl dimethyl 
benzyl ammonium chloride. Ditallow dimethyl ammonium chloride, dicetyl 
dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride and 
cetyl trimethyl ammonium chloride are preferred quaternary ammonium salts 
useful herein. Di-(hydrogenated tallow) dimethyl ammonium chloride is a 
particularly preferred quaternary ammonium salt. 
Salts of primary, secondary and tertiary fatty amines are also preferred 
cationic surfactant materials. The alkyl groups of such amines preferably 
have from about 12 to about 22 carbon atoms, and may be substituted or 
unsubstituted. Secondary and tertiary amines are preferred, tertiary 
amines are particularly preferred. Such amines, useful herein, include 
stearamido propyl dimethyl amine, diethyl amino ethyl stearamide, dimethyl 
stearamine, dimethyl soyamine, soyamine, myristyl amine, tridecyl amine, 
ethyl stearylamine, N-tallowpropane diamine, ethoxylated (5 moles E.O.) 
stearylamine, dihydroxy ethyl stearylamine, and arachidylbehenylamine. 
Suitable amine salts include the halogen, acetate, phosphate, nitrate, 
citrate, lactate and alkyl sulfate salts. Such salts include stearylamine 
hydrochloride, soyamine chloride, stearylamine formate, N-tallowpropane 
diamine dichloride and stearamidopropyl dimethylamine citrate. Cationic 
amine surfactants included among those useful in the present invention are 
disclosed in U.S. Pat. No. 4,275,055, Nachtigal, et al., issued Jun. 23, 
1981, incorporated by reference herein. 
If included in the compositions of the present invention, the lipid 
material is present at from about 0.1% to about 10.0% of the composition; 
the cationic surfactant material is present at from about 0.05% to about 
5.0% of the composition. 
Alternative hair conditioning agents that can be used in addition to or 
instead of the cationic surfactants described above are protein 
derivatives, such as hydrolyzed animal proteins. For example, Crotein SPA 
(Croda) or Lexeine X250 (Inolex) or Polypeptide LSN (Stephan) can be 
utilized in the present conditioner compositions. Such agents are 
generally present at a level of from about 0.05% to about 5.0%. 
Other hair conditioning agents which can be used in addition to or instead 
of the above-described cationic surfactant plus lipid material are 
siloxane or siloxane-containing materials which are present at a level of 
from about 0.01% to about 10% of the conditioner composition, preferably 
from about 0.1% to about 5%, most preferably from about 0.2% to about 3%. 
Siloxanes (see, for example, U.S. Pat. No. 3,208,911, Oppliger, issued Sep. 
28, 1965) and siloxane-containing polymers have been taught for use in 
hair conditioning compositions. U.S. Pat. No. 4,601,902, Fridd et al., 
issued Jul. 22, 1986, describes hair conditioning or shampoo/conditioner 
compositions which include a polydiorganosiloxane having quaternary 
ammonium substituted groups attached to the silicon, and a 
polydiorgano-siloxane having silicon-bonded substituents which are 
amino-substituted hydrocarbon groups. U.S. Pat. No. 4,654,161, Kollmeier 
et al., issued Mar. 31, 1987, describes a group of organopoly-siloxanes 
containing betaine substituents. When used in hair care compositions, 
these compounds are said to provide good conditioning, compatibility with 
anionic components, hair substantivity, and low skin irritation. U.S. Pat. 
No. 4,563,347, Starch, issued Jan. 7, 1986, relates to hair conditioning 
compositions which include siloxane components containing substituents to 
provide attachment to hair. Japanese Published Application 56-129,300, 
Lion Corporation, published Oct. 9, 1981, relates to shampoo conditioner 
compositions which include an organopolysiloxaner-oxyalkylene copolymer 
together with an acrylic resin. U.S. Pat. No. 4,479,893, Hirota et al., 
issued Oct. 30, 1984, describes shampoo conditioner compositions 
containing a phosphate ester surfactant and a silicon derivative (e.g., 
polyether- or alcohol-modified siloxanes). Polyether-modified 
polysiloxanes are also disclosed for use in shampoos in U.S. Pat. No. 
3,957,970, Korkis, issued May 18, 1976. U.S. Pat. No. 4,185,087, Morlino, 
issued Jan. 22, 1980, describes quaternary nitrogen derivatives of 
trialkylamino hydroxy organosilicon compounds which are said to have 
superior hair conditioning properties. 
Siloxane-derived materials have also been used in hair styling 
compositions. Japanese Published Application 56-092,811, Lion Corporation, 
published Dec. 27, 1979, describes hair setting compositions which 
comprise an amphoteric acrylic resin, a polyoxyalkylene-denatured 
organopolysiloxane, and polyethylene glycol. U.S. Pat. No. 4,744,978, 
Homan et al., issued May 17, 1988, describes hair styling compositions 
(such as hair sprays) which include the combination of a carboxyfunctional 
polydimethyl-siloxane and a cationic organic polymer containing amine or 
ammonium groups. Hair styling compositions which include 
poly-diorganosiloxanes and a cationic organic polymer are taught in U.S. 
Pat. No. 4,733,677, Gee et al., issued Mar. 29, 1988, and U.S. Pat. No. 
4,724,851, Cornwall et al., issued Feb. 16, 1988. Finally, European Patent 
Application 117,360, Cantrell et al., published Sep. 5, 1984, discloses 
compositions, containing a siloxane polymer having at least one 
nitrogen-hydrogen bond, a surfactant, and a solubilized titanate, 
zirconate or germanate, which act as both a conditioner and a hair styling 
aid. 
Nonvolatile silicone fluids are useful as the conditioning agent component 
in the compositions of the present invention. Examples of such materials 
include polydimethylsiloxane gums and fluids, aminosilicones and 
phenylsilicones. More specifically, materials such as polyalKyl or 
polyaryl siloxanes with the following structure: 
##STR3## 
wherein R is alkyl or aryl, and x is an integer from about 7 to about 
8,000 may be used. A represents groups which block the ends of the 
silicone chains. 
The alkyl or aryl groups substituted on the siloxane chain (R) or at the 
ends of the siloxane chains (A) may 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 normal use and storage conditions, and are capable 
of being deposited on and of conditioning hair. 
Suitable A groups include methyl, methoxy, ethoxy, propoxy, and aryloxy. 
The two R groups on the silicone atom may represent the same group or 
different groups. Preferably, the two R groups represent the same group. 
Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyl and 
phenylmethyl. The preferred silicones are polydimethyl siloxane, 
polydiethylsiloxane, and polymethylphenylsiloxane. Polydimethylsiloxane is 
especially preferred. 
Suitable methods for preparing these silicone materials are disclosed in 
U.S. Pat. Nos. 2,826,551 and 3,964,500 and references cited therein. 
Silicones useful in the present invention are also commercially available. 
Suitable examples include Viscasil, a trademark of the General Electric 
Company and silicones offered by Dow Corning Corporation and by SWS 
Silicones, a division of Stauffer Chemical Company. 
Other useful silicone conditioning materials include materials of the 
formula: 
##STR4## 
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 "amodimethicone". 
Other silicone cationic polymer conditioning agents which can be used in 
the present compositions correspond to the formula: 
EQU (R.sub.1).sub.a G.sub.3-a --Si--(--OSiG.sub.2).sub.n --(OSiG.sub.b 
(R.sub.1).sub.2-b).sub.m --O--SiG.sub.3-a (R.sub.1).sub.a 
in which G is chosen from the group consisting of hydrogen, phenyl, OH, 
C.sub.1 -C.sub.8 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 sum n+m is a number from 1 to 
2,000 and preferably from 50 to 150, n being able to denote a number from 
0 to 1,999 and preferably from 49 to 149 and m being able to denote an 
integer from 1 to 2,000 and preferably from 1 to 10; 
R.sub.1 is a monovalent radical of formula C.sub.q H.sub.2q L in which q is 
an integer from 2 to 8 and L is chosen from the groups 
##STR5## 
in which R.sub.2 is chosen from the group consisting of hydrogen, phenyl, 
benzyl, a saturated hydrocarbon radical, preferably an alkyl radical 
containing from 1 to 20 carbon atoms, and A.sup.- denotes a halide ion. 
These compounds are described in greater detail in European Patent 
Application EP 95,238. An especially preferred polymer corresponding to 
this formula is the polymer known as "trimethylsilylamodimethicone" of 
formula: 
##STR6## 
Other silicone cationic polymer conditioning agents which can be used in 
the present compositions correspond to the formula: 
##STR7## 
in which R.sub.3 denotes a monovalent hydrocarbon radical having from 1 to 
18 carbon atoms, and more especially an alkyl or alkenyl radical such as 
methyl; R.sub.4 denotes a hydrocarbon radical such as, preferably a 
C.sub.1 -C.sub.18 alkylene radical or a C.sub.1 -C.sub.18, and preferably 
C.sub.1 -C.sub.8, alkyleneoxy radical; 
Q.sup.- is a halide ion, preferably chloride; 
r denotes an average statistical value from 2 to 20, preferably from 2 to 
8; 
s denotes an average statistical value from 20 to 200, and preferably from 
20 to 50. 
These compounds are described in greater detail in U.S. Pat. No. 4,185,017. 
A polymer of this class which is especially preferred is that sold by UNION 
CARBIDE under the name "UCAR SILICONE ALE 56". 
Conditioning agent materials also useful in the compositions of the present 
invention are silicone polymer materials which provide both style 
retention and conditioning benefits to the hair. These materials comprise 
rigid silicone polymers. 
Some examples of such materials include, but are not limited to, filler 
reinforced polydimethyl siloxane gums including those having end groups 
such as hydroxyl; cross linked siloxanes, such as organic substituted 
silicone elastomers; organic substituted siloxane gums, including those 
having end groups such as hydroxyl; and resin reinforced siloxanes. 
The rigid silicone polymers useful in the present invention have complex 
viscosities of at least 2.times.10.sup.5 poise (P), preferably about 
1.times.10.sup.7 poise, where complex viscosity is measured by subjecting 
a sample to oscillatory shear at a fixed frequency of 0.1 rad/sec at 
25.degree. C. using a Rheometric Fluids Spectrometer.RTM. measuring films 
having a thickness of about 1 millimeter. The resulting viscous and 
elastic force responses are combined to determine the complex modulus 
which is divided by the imposed frequency to compute the complex 
viscosity. 
A preferred siloxane gum useful in the present invention is a 
diphenyl-dimethyl polysiloxane gum having a molecular weight of at least 
about 500,000, and must be diphenyl substituted to the extent of 3% or 
more, preferably at least about 5%. 
The siloxane gums may also be filler reinforced to provide additional 
rigidity. Silica is the preferred filler. Generally such reinforced gums 
comprise up to about 15-20% silica. 
Silicone resins also useful in formulating the rigid silicones in the 
present compositions are silicone polymers with a high degree of 
crosslinking introduced through the use of trifunctional and 
tetrafunctional silanes. Typical silanes used in the manufacture of resins 
are monomethyl, dimethyl, monophenyl, diphenyl, methylphenyl, monovinyl, 
and methylvinyl chlorosilanes, together with tetrachlorosilane. A 
preferred resin is one offered by General Electric as GE SR545. This resin 
is provided as a solution in toluene which is stripped prior to the 
resin's use. This resin is used in combination with the siloxane gum to 
provide extra rigidity. 
Other rigid silicone polymers of use herein are those siloxanes which have 
been sparingly crosslinked but are still soluble in solvents such as 
cyclomethicone. Precursors for the rigid material can be any high 
molecular weight polydimethyl siloxanes, polydimethyl siloxanes containing 
vinyl groups and other siloxanes. Methods of crosslinking include heat 
curing with organic peroxides such as dibenzoyl peroxide and di-t-butyl 
peroxide, heat vulcanization with sulfur, and high-energy radiation. 
Obviously, the silicone conditioning agent should be selected such that it 
does not interfere with the hair style holding performance of the styling 
polymers of the present invention. Preferably the silicone conditioning 
agent comprises a polydimethylsiloxane gum, having a viscosity greater 
than about 1,000,000 centipoise and a dimethicone fluid having a viscosity 
of from about 2 centipoise to about 100,000 centipoise, 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. 
Alternatively, the hair styling agent and hair conditioning agent of the 
present compositions can be provided by a single material. Examples of 
such materials are copolymers having siloxane macromers grafted thereto, 
which meet the functional limitations as defined supra. That is, the 
non-silicone backbone of such polymers should have a molecular weight of 
from about 5,000 to about 1,000,000, a Tg of greater than about 
-20.degree. C., and a solubility parameter of from about 8.5 to about 
12.0. 
Preferred polymers comprise a polymeric backbone and, grafted to the 
backbone, a polydimethylsiloxane macromer having a weight average 
molecular weight of from about 1,000 to about 50,000, preferably from 
about 5,000 to about 40,000, most preferably about 10,000. The polymer is 
such that when it is formulated into the finished hair care composition 
used to treat the hair, and then the hair dried, the polymer phase 
separates into a discontinuous phase which includes the 
polydimethylsiloxane macromer and a continuous phase which includes the 
backbone. It is believed that this phase separation property provides a 
specific orientation of the polymer on hair which results in the desired 
hair conditioning and setting benefits. 
In its broadest aspect, the copolymers comprise C monomers together with 
monomers selected from the group consisting of A monomers, B monomers, and 
mixtures thereof. These copolymers contain at least A or B monomers 
together with C monomers, and preferred copolymers contain A, B and C 
monomers. 
Examples of useful copolymers and how they are made are described in detail 
in U.S. Pat. No. 4,693,935, Mazurek, issued Sep. 15, 1987, and U.S. Pat. 
No. 4,728,571, Clemens et al., issued Mar. 1, 1988, both of which are 
incorporated herein by reference. These copolymers are comprised of 
monomers A, C and, optionally, B, which are defined as follows. A, is at 
least one free radically polymerizable vinyl monomer or monomers. B, when 
used, comprises at least one monomer copolymerizable with A. When used, B 
may be up to about 30%, preferably up to about 10%, more preferably 5%, of 
the total monomers in the copolymer. Monomer C comprises from about 0.01% 
to about 50.0% of the total monomers in the copolymer. 
Representative examples of A monomers are the same as the hydrophobic 
monomers described supra for the styling polymers of the present invention 
which do not comprise siloxane macromers. 
Representative examples of B monomers are the same as the hydrophilic 
monomers described supra for the styling polymers of the present invention 
which do not comprise siloxane macromers. 
The C monomer has the general formula: 
EQU X(Y).sub.n Si(R).sub.3--m Z.sub.m 
wherein X is a vinyl group copolymerizable with the A and B monomers; Y is 
a divalent linking group; R is a hydrogen, lower alkyl, aryl or alkoxy; Z 
is a monovalent siloxane polymeric moiety having a number average 
molecular weight of at least about 500, is essentially unreactive under 
copolymerization conditions and is pendant from the vinyl polymeric 
backbone, described above; n is 0 or 1; and m is an integer from 1 to 
3.degree. C. has a weight average molecular weight of from about 1,000 to 
about 50,000, preferably from about 5,000 to about 40,000, most preferably 
about 10,000. Preferably, the C monomer has a formula selected from the 
following group: 
##STR8## 
In those structures, m is 1, 2 or 3 (preferably m=1); p is 0 or 1; R" is 
alkyl or hydrogen; q is an integer from 2 to 6; s is an integer from 0 to 
2; X is 
##STR9## 
R.sup.1 is hydrogen or --COOH (preferably R.sup.1 is hydrogen); R.sup.2 is 
hydrogen, methyl or --CH.sub.2 COOH (preferably R.sup.2 is methyl); Z is 
##STR10## 
R.sup.4 is alkyl, alkoxy, alkylamino, aryl, or hydroxyl (preferably 
R.sup.4 is alkyl); and r is an integer from about 5 to about 700 
(preferably r is about 250). 
The preferred of these siloxane containing copolymers generally comprise 
from 50% to about 98% (preferably from about 85% to about 98%, more 
preferably from about 90% to about 97%) of monomer A, from 0% to about 30% 
(preferably from about 2% to about 8%) of monomer B, and from about 0.1% 
to about 50% (preferably from about 0.5% to about 20%, most preferably 
from about 2% to about 10%) of monomer C. The combination of the A and B 
monomers preferably comprises from about 50.0% to about 99.9% (more 
preferably about 80% to about 99%, most preferably from about 90% to about 
98%) of the polymer. 
Specific polymers which may be used in the present invention include the 
following (the weight percents below refer to the amount of reactants 
added in the polymerization reaction, not necessarily the amount in the 
finished polymer): 
polyvinyl pyrrolidone/vinyl acetate/polydimethylsiloxane (PDMS) macromer - 
10,000 molecular weight (5/90/5 w/w/w) (I) 
acrylic acid/n-butylmethacrylate/polydimethylsiloxane (PDMS) 
macromer-20,000 molecular weight (10/70/20 w/w/w) (II) 
N,N-dimethylacrylamide/isobutyl methacrylate/PDMS macromer-20,000 molecular 
weight (20/60/20 w/w/w) (III) 
t-butylacrylate/PDMS macromer-10,000 molecular weight (80/20 w/w) (IV) 
t-butylacrylate/N,N-dimethylacrylamide/PDMS macromer-10,000 molecular 
weight (70/10/20 w/w/w) (V) 
t-butylacrylate/acrylic acid/PDMS macromer-10,000 molecular weight (75/5/20 
w/w/w) (VI) 
polyvinyl pyrrolidone/vinyl acetate/polydimethylsiloxane-20,000 molecular 
weight (4/95/1 w/w/w) (VII) 
polyvinyl pyrrolidone/vinyl acetate/polydimethyl siloxane-20,000 molecular 
weight (2.5/95/2.5 w/w/w) (VIII) 
As with the non-siloxane containing styling polymers described supra, the 
present copolymers must be diluted with a polymer solvent of the present 
invention prior to combination with the remaining conditioner composition 
ingredients. This will enable the formation of a dispersed phase of 
polymer and solvent in the conditioner composition. 
When these siloxane containing copolymers are used in the conditioner 
compositions of the present invention to act as both a hair styling 
polymer and hair conditioning agent, they are generally present at a level 
of from about 0.2% to about 20%, preferably from about 2% to about 6%. 
Most preferably these materials which act as both the hair styling polymer 
and hair conditioning agent in the present compositions comprise a 
polyvinyl pyrrolidone/polydimethyl siloxane/vinyl acetate copolymer 
wherein the non-silicone backbone of the copolymer has a molecular weight 
of from about 10,000 to about 200,000, a T.sub.g of from about 20.degree. 
C. to about 60.degree. C., and a solubility parameter, .delta., of from 
about 11.0 to about 11.5. 
The present silicone conditioning agents can be used in conditioner vehicle 
systems thickened with materials other than the lipid material plus 
cationic surfactant gel-network vehicle systems described supra. 
Nonionic water-soluble cellulose ethers have been employed as thickeners in 
hair care compositions. Widely used, commercially-available nonionic 
cellulose ethers include methyl cellulose, hydroxy propyl methyl 
cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and ethyl 
hydroxyethyl cellulose. 
Better thickening efficiency is realized with higher molecular weight 
cellulose ethers. However, production of such materials is difficult and 
expensive. Though crosslinking of these polymers is an alternative means 
to achieve high viscosity solutions, good crosslinking techniques are not 
known. Of course, high concentrations of polymers will also provide high 
viscosity but such an approach is inefficient and impractical, 
particularly due to the high expense involved. Furthermore, use of highly 
crosslinked polymers or high levels of polymeric thickeners may result in 
a vehicle system that is too elastic for the present uses. 
Alternative water-soluble polymeric thickeners sometimes used to thicken 
conditioner compositions are natural polysaccharides such as guar gum, 
xanthan gum and locust bean gum. 
A number of references teach the use of nonionic cellulose ethers and 
water-soluble gums for thickening hair care compositions. See for example, 
U.S. Pat. No. 4,557,928, Glover, issued Dec. 10, 1985, teaching a hair 
conditioner comprising a suspension system which consists of one of glucan 
gum, guar gum, and hydroxyethylcellulose; and U.S. Pat. No. 4,581,230, 
Grollier et al., issued Apr. 8, 1986, which teaches cosmetic compositions 
for treating hair which comprise as thickening agents 
hydroxyethylcellulose, or water-soluble vegetable thickening agents, such 
as guar gum. Japanese Patent Publication 61-053211, published Mar. 7, 
1986, discloses a hair colorant containing an aromatic alcohol, xanthan 
gum, and hydroxyethylcellulose. 
Certain cellulose ethers have been disclosed in U.S. Pat. No. 4,228,277, 
Landoll, issued Oct. 14, 1980, which are relatively low molecular weight 
but which are capable of producing highly viscous aqueous solutions in 
practical concentrations. These materials are nonionic cellulose ethers 
having a sufficient degree of nonionic substitution selected from the 
group consisting of methyl, hydroxyethyl, and hydroxypropyl to cause them 
to be water-soluble and which are further substituted with a hydrocarbon 
radical having from about 10 to 24 carbon atoms in an amount between about 
0.2 weight percent and the amount which renders said cellulose ether less 
than 1%, by weight, soluble in water. The cellulose ether to be modified 
is preferably one of low to medium molecular weight; i.e., less than about 
800,000 and preferably between about 20,000 and 700,000 (about 75 to 2500 
D.P.). 
The Landoll patent teaches that any nonionic water-soluble cellulose ether 
can be employed as the cellulose ether substrate. Thus, e.g., hydroxyethyl 
cellulose, hydroxypropyl cellulose, methyl cellulose, hydroxypropyl methyl 
cellulose, ethyl hydroxyethyl cellulose, and methyl hydroxyethyl cellulose 
can all be modified. The amount of nonionic substituent such as methyl, 
hydroxyethyl or hydroxypropyl is taught not to be critical so long as 
there is an amount sufficient to assure that the ether is water-soluble. 
The preferred cellulose ether substrate is hydroxyethyl cellulose (HEC) of 
about 50,000 to 700,000 molecular weight. Hydroxyethyl cellulose of this 
molecular weight level is the most hydrophilic of the materials 
contemplated. It can thus be modified to a greater extent than can other 
water-soluble cellulose ether substrates before insolubility is achieved. 
Accordingly, control of the modification process and control of the 
properties of the modified product can be more precise with this 
substrate. Hydrophilicity of the most commonly used nonionic cellulose 
ethers varies in the general direction: 
hydroxyethyl.fwdarw.hydroxypropyl.fwdarw.hydroxypropyl 
methyl.fwdarw.methyl. 
The long chain alkyl modifier can be attached to the cellulose ether 
substrate via an ether, ester or urethane linkage. The ether linkage is 
preferred. 
Although the materials taught in Landoll are referred to as being "long 
chain alkyl group modified", it will be recognized that except in the case 
where modification is effected with an alkyl halide, the modifier is not a 
simple long chain alkyl group. The group is actually an alphahydroxyalkyl 
radical in the case of an epoxide, a urethane radical in the case of an 
isocyanate, or an acyl radical in the case of an acid or acyl chloride. 
Nonetheless, the terminology "long chain alkyl group is used since the 
size and effect of the hydrocarbon portion of the modifying molecule 
completely obscure any noticeable effect from the connecting group. 
Properties are not significantly different from those of the product 
modified with the simple long chain alkyl group. 
One commercially available material which meets these requirements is 
NATROSOL PLUS Grade 430, hydrophobically modified hydroxyethylcellulose 
available from Aqualon Company, Wilmington, Delaware. This material has a 
C.sub.16 a alkyl substitution of about 0.5% to about 0.9% by weight. The 
hydroxyethyl molar substitution for this material is from about 2.8 to 
about 3.2. The average molecular weight for the water-soluble cellulose 
prior to modification is approximately 300,000. 
The most preferred material of this type is sold under the trade name 
NATROSOL PLUS CS Grade D-67, by Aqualon Company, Wilmington, Del. This 
material has a C.sub.16 a alkyl substitution of from about 0.50% to about 
0.95%, by weight. The hydroxyethyl molar substitution for this material is 
from about 2.3 to about 3.3. The average molecular weight for the 
water-soluble cellulose prior to modification is approximately 700,000. 
These modified cellulose ethers have been disclosed for use in a variety of 
composition types. Landoll ('277) teaches the use of these materials in 
shampoo formulations. Hercules trade literature teaches the use of these 
materials in shampoos. U.S. Pat. No. 4,683,004, Goddard, issued Jul. 28, 
1987, discloses the use of these materials in mousse compositions for the 
hair. 
These materials can be used with certain secondary thickening materials to 
provide a rheology very much like the gel-network structure provided by 
lipid material plus cationic surfactant based conditioner compositions 
described supra. 
The first of these secondary thickening materials is a water-soluble 
polymeric material, having a molecular weight greater than about 20,000. 
By "water-soluble polymer" is meant that the material will form 
substantially a clear solution in water at a 1% concentration at 
75.degree. C. and the material will increase the viscosity of the water. 
Examples of water-soluble polymers which are desirably used as the 
additional thickening component in the present vehicle systems, include 
hydroxyethylcellulose, hydroxypropyl cellulose, hydroxypropyl 
methylcellulose, polyethylene glycol, polyacrylamide, polyacrylic acid, 
polyvinyl alcohol, polyvinyl pyrrolidone K-120, dextrans, for example 
Dextran purified crude Grade 2P, available from D&O Chemicals, 
carboxymethylcellulose, plant exudates such as acacia, ghatti, and 
tragacanth, seaweed extracts such as sodium alginate, propylene glycol 
alginate, sodium carrageenan, and Ucare JR-polymer (a cationic modified 
hydroxyethyl cellulose available from Union Carbide). Preferred as the 
additional thickener for the present vehicle systems are natural 
polysaccharide materials. Examples of such materials are guar gum, locust 
bean gum, and xanthan gum. Also preferred as the additional thickener in 
the present compositions is hydroxyethylcellulose having a molecular 
weight of about 700,000. 
When such systems are used to thicken the present compositions, from about 
0.3% to about 5.0%, preferably from about 0.4% to about 3.0% of the 
hydrophobically modified hydroxyethyl cellulose is utilized with from 
about 0.3% to about 5.0%, preferably from about 0.4% to about 3.0% of the 
water-soluble polymeric material. 
An alternative secondary thickening material for the hydrophobically 
modified hydroxyethyl cellulose is a water-soluble surfactant having a 
molecular weight of less than about 20,000. By "water-soluble surfactant" 
is meant surfactant materials which form clear isotropic solutions when 
dissolved in water at 0.2 weight percent at ambient conditions. 
Essentially any water-soluble surfactant material which meets these 
requirements will work in the present invention. However, the following 
materials have been found to be particularly preferred: cetyl betaine, 
ammonium lauryl sulfate, ammonium laureth sulfate, cetyl trimethyl 
ammonium chloride, and mixtures thereof. 
When such systems are used to thicken the present compositions, from about 
0.1% to about 10.0%, preferably from about 0.2% to about 5.0% of the 
hydrophobically-modified hydroxyethyl cellulose is utilized with from 
about 0.02% to about 0.30%, preferably from about 0.05% to about 0.30%, 
most preferably from about 0.05% to about 0.20%, of the water-soluble 
surfactant. The water-soluble surfactant level is kept low because higher 
levels of water-soluble surfactants interfere with the 
hydrophobically-modified hydroxyethyl cellulose thickener and produce 
compositions with much less desirable rheologies. 
A final alternative secondary thickening material for the 
hydrophobically-modified hydroxyethyl cellulose is a water-insoluble 
surfactant having a molecular weight of less than about 20,000. By 
"water-insoluble surfactant" is meant surfactant materials which do not 
form clear isotropic solutions when dissolved in water at greater than 0.2 
weight percent at ambient conditions. 
Essentially any water-insoluble surfactant material which meets these 
requirements will work in the present invention. However, the following 
materials have been found to be particularly preferred: stearamide DEA, 
cocoamide MEA, dimethyl stearamine oxide, glyceryl monooleate, sucrose 
stearate, PEG-2 stearamine, Ceteth-2, a polyethylene glycol ether of cetyl 
alcohol of the formula CH.sub.3 --(CH.sub.2).sub.14 --CH.sub.2 
--(OCH.sub.2 CH.sub.2).sub.n --OH, where n has an average value of 2 
(commercially available under the trade name Brij 56 from ICI Americas), 
glycerol stearate citrate, dihydrogenated tallow dimethyl ammonium 
chloride, Poloxamer 181, a polyoxyethylene, polyoxypropylene block polymer 
of the formula 
##STR11## 
wherein on average x=3, y=30 and z=3 (commercially available from BASF 
Wyandotte under the trade name Pluronic L-61), hydrogenated tallow 
dimethyl betaine, and hydrogenated tallow amide DEA. 
When such systems are used to thicken the present compositions, from about 
0.1% to about 10.0%, preferably from about 0.2% to about 5.0% of the 
hydrophobically-modified hydroxyethyl cellulose is utilized with from 
about 0.02% to about 10.0%, preferably from about 0.05% to about 3.0%, 
most preferably from about 0.05% to about 2.0%, of the water-insoluble 
surfactant. 
The conditioner compositions of the present invention which are thickened 
with the hydrophobically-modified hydroxyethyl cellulose plus secondary 
thickening materials, as described above preferably also contain a 
material which provides additional rheological benefits to the cosmetic 
compositions formulated therewith. These materials are chelating agents. 
In general, such materials include monodentate and multidentate agents. 
Specific examples of useful chelating agents include 
ethylene-diaminetetraacetic acid (EDTA), and salts thereof, 
nitrilotriacetic acid (NTA) and salts thereof, hydroxyethyl ethylene 
diamine triacetic acid (HEEDTA) and salts thereof, diethylene triamine 
pentaacetic acid (DTPA) and salts thereof, diethanolglycine (DEG) and 
salts thereof, ethanol diglycine (EDG) and salts thereof, citric acid and 
salts thereof, phosphoric acid and salts. The most preferred of these is 
EDTA. The chelating agents tend to make the vehicle systems useful in the 
present invention smoother and less gelatinous in consistency. 
If a chelating agent is present as a rheological aid in the compositions of 
the present invention it is present at a level of from about 0.05% to 
about 1.0%, preferably from about 0.05% to about 0.3%, of the composition. 
An additional component which may be used in the conditioner compositions 
of the present invention which are thickener with the hydrophobically 
modified hydroxyethyl cellulose plus secondary thickening materials, as 
described above, is a material which acts as a distributing aid for the 
composition. Such a material helps to distribute the composition onto the 
hair avoiding localized deposition of the conditioning and styling 
components onto the hair. Without such a component in a composition, some 
components in the composition would not be deposited and spread out as 
evenly, and hence, would not be quite as effective. 
Distributing aid materials useful in the present invention are actually a 
subclass of the class of materials which can be used as the water-soluble 
polymer secondary thickener in the present invention. This subclass is 
defined as follows: water-soluble polymer materials having high molecular 
weight, i.e., greater than 1,000,000; and/or strong ionic character. By 
strong ionic character is meant that the material conducts electricity at 
greater than 30 millivolts. This can be measured by evaluating conductance 
of a 1% solution of polymer in DRO (double reverse osmosis) water 
preserved with 0.03% Kathon CG (a preservative available from Rohm & Haas) 
using a calibrated Corning 130 pH meter. The probes used were as follows: 
the reference electrode is an Orion Model 9001 single junction. The pH 
electrode is an Orion Model 9161, silver-silver chloride. The probes are 
set 3/8 of an inch apart. The pH meter is set to millivolt readings. The 
absolute measurement is recorded after 4 minutes immersion. 
Examples of water soluble polymer materials which meet these requirements 
and hence, can act as distributing aids in the present compositions 
include xanthan gum; Dextran purified crude Grade 2P available from D&O 
chemicals; carboxymethyl celluloses; for example, CMC's 4HIF, 4M6F, 7HF, 
7M8SF, 7LF, 9H4F, 9M8, 12M8P, 16M31, (all available from Aqualon); plant 
exudates such as acacia, ghatti and tragacanth; seaweed extracts such as 
sodium alginate, propylene glycol alginate, and sodium carrageenan; high 
molecular weight hydroxyethyl celluloses such as Natrosol 250H and 
Natrosol 250HHR (available from Aqualon); and pectin. 
Because the class of materials which may act as distributing aids in the 
present compositions is a subset of the optional water-soluble polymer 
secondary thickener, the materials in this subclass may be used to provide 
both benefits to the composition. For example, xanthan gum is a 
water-soluble natural polysaccharide material which additionally has a 
high molecular weight. Hence, this material could be used by itself to 
provide both additional thickening benefits and distributing benefits. 
However, it may be necessary to use such materials at slightly higher 
levels to provide both benefits. 
It is also possible to use two separate materials as the optional 
water-soluble polymer secondary thickener and the distributing aid of the 
present invention. This would be done when the water-soluble polymer 
secondary thickener was not a high molecular weight material or of strong 
ionic character. Locust bean gum is such a material. A distributing aid 
such as xanthan gum could be used with locust bean gum to provide the 
additional distributing benefits. 
If a distributing aid is present in the conditioning compositions of the 
present invention, it should be present at a level of from about 0.02% to 
about 2.5%, preferably from about 0.05% to about 1.0%, of the cosmetic 
composition. If the distributing aid is bifunctional, i.e., acting as both 
the optional secondary thickener and the distributing aid it should be 
present at a level of from about 0.2% to about 5.0% of the composition. 
The hair conditioner compositions herein can contain a variety of other 
optional components suitable for rendering such compositions more 
cosmetically or aesthetically acceptable or to provide them with 
additional usage benefits. Such conventional optional ingredients are 
well-known to those skilled in the art, e.g., pearlescent aids, such as 
TiOz coated mica, ethylene glycol distearate, and PEG 3 distearate; 
opacifiers; preservatives, such as benzyl alcohol, Glydant, Kathon, methyl 
paraben, propyl paraben and imidazolidinyl urea; fatty alcohols, such as 
cetearyl alcohol; sodium chloride; sodium sulfate; polyvinyl alcohol; 
ethyl alcohol; pH adjusting agents, such as citric acid, sodium citrate, 
succinic acid, phosphoric acid, monosodium phosphate, disodium phosphate, 
sodium hydroxide, and sodium carbonate; coloring agents, such as any of 
the FD&C or D&C dyes; perfumes; sequestering agents, such as disodium 
ethylenediamine tetra-acetate; and polymer plasticizing agents, such as 
glycerin and propylene glycol. The present compositions can also 
optionally comprise thickeners and viscosity modifiers, such as a 
diethanolamide of a long chain fatty acid (e.g., PEG 3 lauric 
diethanolamide), lauramide DEA, cocomonoethanol amide, dimethicone 
copolyols, guar gum, xanthan gum, methyl cellulose, hydroxyethyl 
cellulose, starches and starch derivatives. Such optional ingredients 
generally are used individually at levels of from about 0.01% to about 
10.0%, preferably from about 0.05% to about 5.0%, of the conditioner 
composition. 
As with all compositions, the present invention should not contain optional 
components which unduly interfere with the conditioning and hair style 
holding performance of the present conditioner compositions. 
Aqueous Carrier 
The balance of the present conditioner compositions comprises water or 
water combined with some other carrier substance which does not interfere 
with the conditioning and style hold benefits of the present compositions. 
Method of Making 
The hair conditioner compositions of the present invention can be made 
using conventional formulation and mixing techniques. The polymer must 
first be dissolved in the polymer solvent. The remaining ingredients are 
combined in a separate vessel and the polymer/solvent mixture is added. 
Methods of making various types of hair conditioner compositions are 
described in the following examples. 
Method of Use 
The hair conditioner compositions of the present invention are used in 
conventional ways to provide the hair conditioning and styling hold 
benefits of the present invention. Such method generally involves 
application of an effective amount of the conditioner product to wet 
shampooed hair, which is massaged through and then rinsed from the hair. 
By "effective amount" is meant an amount sufficient to provide the hair 
conditioning and style hold benefits desired considering the length and 
texture of the hair. After the hair is treated with the compositions of 
the present invention, the hair is dried and styled in the usual ways of 
the user. 
The following examples illustrate the present invention. It will be 
appreciated that other modifications of the present invention within the 
skill of those in the cosmetic composition formulation art can be 
undertaken without departing from the spirit and scope of this invention. 
All parts, percentages, and ratios herein are by weight unless otherwise 
specified. 
EXAMPLE I 
The following is a rinse-off hair conditioner composition representative of 
the present invention. 
______________________________________ 
Component Weight % 
______________________________________ 
Natrosol Plus CS Grade D-67.sup.1 
0.60 
Locust bean gum 0.50 
EDTA, disodium salt 0.15 
DTDMAC 0.65 
Glydant 0.40 
Styling Polymer/Solvent Premix 
Polyvinylpyrrolidone/Vinyl Acetate (5/95) 
3.00 
Benzyl Alcohol 3.00 
Silicone Conditioning Agent Premix 
Dimethicone Gum.sup.2 0.50 
Decamethyl cyclopenta siloxane 
2.83 
Water q.s. to 100% 
______________________________________ 
.sup.1 Hydrophobicallymodified hydroxyethyl cellulose commercially 
available from Aqualon Co. 
.sup.2 SE76 dimethicone gum available from GE Silicones 
This product is prepared by first dissolving the 
polyvinyl-pyrrolidone/vinyl acetate (5/95) copolymer in the benzyl 
alcohol. The dimethicone gum and decamethyl cyclopenta siloxane are also 
separately premixed. The remaining components are combined in a separate 
vessel with heating and stirring. The polymer/solvent mixture and silicone 
conditioning agent premix are then added to the remaining components 
either hot or after they have been cooled. 
This conditioner product provides hair conditioning and hair style holding 
benefits. 
EXAMPLE II 
The following is a rinse-off hair conditioner composition representative of 
the present invention. 
______________________________________ 
Component Weight % 
______________________________________ 
Styling Polymer/Solvent Premix 
Poly t-Butyl Acrylate (MW = 100,000) 
1.50 
Ethyl n-Butyrate 2.50 
Stearalkonium Chloride 3.80 
Cetyl Alcohol 1.35 
Stearyl Alcohol 1.35 
Ceteth-2 0.80 
Glyceryl Stearate 0.50 
Quaternized hydrolyzed protein 
0.50 
Citric Acid 0.11 
Sodium Chloride 0.10 
Kathon CG 0.03 
Water q.s. to 100% 
______________________________________ 
This product is prepared by first dissolving the poly-t-butyl acrylate in 
the ethyl n-butyrate. The remaining components are combined in a separate 
vessel with heating and stirring. The polymer/solvent mixture is then 
added to the remaining components either hot or after they have been 
cooled. 
This conditioner product provides hair conditioning and hair style holding 
benefits. 
EXAMPLE III 
The following is a rinse-off hair conditioner composition representative of 
the present invention. 
______________________________________ 
Component Weight % 
______________________________________ 
Styling Polymer/Solvent Premix 
Polyvinylpyrrolidone/vinyl acetate (30/70) 
4.0 
Isopropanol 5.0 
Silicone Conditioning Agent Premix 
Dimethicone Gum.sup.1 0.30 
Decamethyl cyclopenta siloxane 
1.70 
DTDMAC 0.85 
Hydroxyethyl cellulose 0.50 
Cetyl Alcohol 0.90 
Stearyl Alcohol 0.80 
Ceteareth-20 0.50 
Lexamine S13 0.15 
Glyceral Monostearate 0.50 
Citric Acid 0.11 
Kathon 0.03 
Water q.s. to 100% 
______________________________________ 
.sup.1 SE76 available from GE Silicones 
This product is prepared using the method described in Example I. 
This conditioner product provides hair conditioning and hair style holding 
benefits. 
EXAMPLE IV 
The following is a rinse-off hair conditioner composition representative of 
the present invention. 
______________________________________ 
Component Weight % 
______________________________________ 
N,N-dimethylacrylamide/isobutyl 
2.00 
methacrylate/ethyl hexyl methacrylate/ 
10K silicone macromer - copolymer 
(30/30/20/20) 
Diethyl Phthalate 6.00 
DTDMAC 0.90 
Cetyl Alcohol 1.10 
Stearyl Alcohol 0.70 
Ceteareth-20 0.60 
Glyceryl Monostearate 0.50 
Citric Acid 0.11 
Kathon 0.03 
Water q.s. to 100% 
______________________________________ 
This product is prepared by first dissolving the styling copolymer in the 
diethyl phthalate. The remaining components are combined in a separate 
vessel with heating and stirring to melt the solids. The polymer/solvent 
mixture is then added to the remaining components either hot or after they 
have cooled. 
This conditioner product provides hair conditioning as well as hair style 
hold benefits.