Note: Descriptions are shown in the official language in which they were submitted.
Express Mall No. N~
~;~ AttorneyL~ Docket: IR 474lA/~01-~
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2~35~ ~ol~ ~ 5S
HAIR CONDITIONING SHAMPOO CONTAINING
LONG CHAIN A~COHO~ COMPONENT
This invention relates to fiber conditioning
compositions. More particularly, it relates to hair condition-
ing compositions, especially shampoos, which are useful toclean human hair while simultaneously conditioning it, so tha-t
it will be more easily manageable (combable and of relatively
low static charge) after shampooing than if it had been
washed with a conventional shampoo.
Hair conditioning shampoos are well known in the
cosmetic art and are described in various patents and patent
applications. Cationic surfactants, such as quaternary
ammonium salts, have been employed in hair rinses and in
shampoos as conditioning agents, as have been various silicones
and other water insoluble conditioning agents, including
waxes, greases and oils. Shampoos have been made in solid,
gel, creme, and liquid forms, and in liquid form they have
been produced as solutions, emulsions, and suspensions or
dispersions. When shampoos are in emulsion or suspension
(or dispersion) form sometimes they tend to separate on
storage, which separation should be prevented in products
intended for commercial applications. The present invention
2~3~3
provides a fiber conditioning composition, preferably a condition-
ing shampoo, which includes a water insoluble conditioning agent
and a long chain saturated primary alcohol or derivative, of a
chain length in a certain range, which, it has been found,
stabilizes the emulsion or suspension, makes it desirably pearles-
cent, and also improves the hair conditioning effect thereof.
In accordance with the present invention a pearlescent
fiber conditioning composition, preferably a shampoo, in stable
emulsion or suspension form, comprises a surface active agent
(surfactant), a water insoluble fiber conditioning agent, a
long chain saturated primary alcohol of an average of 25 to 45
carbon atoms, or a derivative thereof, in sufficient proportion
to stabilize the emulsion or suspension and to make it pearles-
cent, and an a~ueous medium, which may include adjuvants and
other components of such fiber conditioning compositions. The
presence of the long chain alcohol or derivative thereof also
often improves conditioning of the treated fiber.
A search of the prior art resulted in the finding
of the following U.S. patents:
3,969,500; 4,707,293; 4,824,602;
4,470,982; 4,726,944; 4,850,732;
4,701,322; 4,728,457; 4,885,130 and
4,704,272; 4,803,237; 4,859,500
Also of interest is the Petrolite Corporation brochure entitled
25 UnilinTM Alcohols, copyrighted in 1985 and identified as SP-1040.
In another application which is being filed on the same
day as the present.application and is entitled Impro~ed Hair
2 ~ 3
Conditioning Shampoo (Hartnett et al.), there are described shampoos
like those of the present invention in which the anionic detergent
component is of a eertain type, which includes a shorter chain alkyl
group, preferably an octyl or deeyl group, as the lipophile there-
of. Such application represents an improvement of the presentinvention and necessarily discloses much of what is described herein.
Although the art found describes pearlescent shampoos and
the incorporation of various conditioning agents into shampoos, and
establishes that the long chain alcohols that are components of
the invented compositions are known materials, applicants are
unaware c)f any teaching in any of the referenees or in any combina-
tion thereof that would lead one to the present invention or that
would lead one to expect to obtain the advantages thereof.
In a broader aspect of this invention the fiber condi-
tioning composition thereof may be in liquid, creme, gel or paste
form and needs only to eomprise water insoluble fiber conditioning
agent and long chain saturated primary alcohol in an aqueous medium,
preferably with eationic fiber conditioning agent (which is also a
surfaetant but here will be considered as in the class of condition-
ing agents) also being present. In some such forms stabilization,which is effectable by the long chain saturated primary alcohol
(for ease of expression "or derivati~e" will often be omitted
henceforth), may be unnecessary, but other advantages of sueh
compounds are a]so obtainable, ineluding pearlescing effeet and
improvement in c:onditioning. In the hair conditioning shampoo
there will also be present a water soluble synthetic organic
detergent, preferably an anionie detergent, more preferably
a higher alkyl sulfate and/or higher alkyl ethoxy sul~ate.
2~ ~3~3
Such compositions may be in various non-liquid forms but prefer-
ably are in emulsified or suspended (or dispersed) form in an
aqueous medium, and preferably are liquids.
Of the water insoluble Eiber conditioning agents those
which are more preferred include: organosilicon compounds,e.g.,non-vola
tile silicones (especially aminosilicones), which include dimethicones;
polyethylenes; paraffins; petrolatums; microcrystalline waxes;
C18 36(mixed) fatty acids and corresponding triglycerides; stearyl
stearate; and quaternary ammonium and amine salts (which are classi-
fied herein with conditioning agents rather than with surfactants,although they act as both). The organosilicon compounds and silicones
that may be employed include any of those which are conditioning
agents for fibrous materials, various of which have been described
in the previously mentioned patents and applications. However, it
has been found that aminosilicones are usually more effective
conditioning agents in the compositions of this invention than are
conventional silicones, and of the aminosilicones the present types
are better yet. Thus, it is much preferred to utilize an amino-
silicone of the formula
Rl CH3 CH3 R5
R2 _ Si - O - (Sl - )X - (Si - O)y ~ S~ ~ R6
R3 CH3 R4 R7
i Rl R2 R3 R5 R6 and R7 are alkyls of 1 to 6
carbon atoms, and most preferably of 1 carbon atom each, R4
is _R8 - NH - CH2CH2 - NH2, R is alkylene of 3 to 6 carbon
atoms, and most preferably is an isobutyl group, x is an
average number :in the range of 100 to 10,000, and y is an
average number :in the range of 1 to 10, more preferably less
than 5, and most preferably 1, which is of an amine equivalent
-- 4 --
2~ ~3~3
in the range of 4,000 to 60,000. Preferably, x is in the
range of 200 or 300 to 10,000, more preferably 500 to
10,000, and most preferably 750 to 800 or 850, e.g., about
800, and y is in the range of 0 to 8, more preferably being
less than 3 and most preferably being about l. The amine
equivalent of such aminosilicone is preferably in the range
of 5,000 to 50,000, more preferably 10,000 to 40,000. For
the specific preferred aminosilicone utilized in the experi-
ments reported in this specification the molar percentage of
amine is about 0.125, the degree of polymerization is about
800, x is 797, y is one, and the molecular weight Inay be ~bout
60,000 daltons. Because molecular weights of high polymers
sometimes vary, depending on the measurement technique
utilized, it is suggested that primary reference should be
to the formula for identification of the aminosilicones
described, rather than placing primary reliance on the
molecular weights given. The described preferred aminosilicone
is available from Dow Corning Corporation, and it is identified
in the working examples herein as Dow Corning Aminosilicone
A (applicants' identification).
The polyalkylenes that may be employed as water
insoluble conditioning agents in the present compositions
are preferably those of a molecular weight in the range of
1,000 to 5,000, more preferably l,000 to 4,000 and still
more preferably 2,000 to 2,50Q, e.g., about 2,000. Oxidized
2 ~ 3 ~ 3
versions of these polyalkylene polymers may also be used, which
create larger hydrocarbons with terminal carboxyl groups.
Although the alkylenes of these polymers will usually be ethylene,
it is within the invention to employ polymers of hydrocarbons
of 1 to 5 carbon atoms each, preferably 2 to 3 carbon atoms, in
which the molecular weight range may be from 1,000 to 10,000, or
even more, under some conditions. Usually however, the polymers
will be of ethylene and/or propylene, and almost always of
ethylene (polyethylene).
Paraffins that may be utilized will normally be of chain
lengths of 20 to 50 carbon atoms, preferably 20 to 40 carbon atoms,
and isoparaffins can be of chain lengths in the range of 12 to 16
carbon atoms, preferably 13 to 14 carbon atoms. The petrolatums
are petroleum jellies or mineral jellies which melt in the range
of 38 to 60C. and the microcrystalline waxes are of an average
molecular weight in the range of about 500 to 800 (which is about
twice that of the paraffins). C18_36 ~atty acids and correspond-
ing triglycerides are higher fatty acids and triglycerides which
are available from Croda Chemical Corporation(under the tradename
Syncrowax HGL-C, for example, for the triglycerides). Stearyl
stearate, which is representative of useful esters of both higher
fatty alcohols and higher fatty acids, is available from Inolex
Corporation, as ~exol SS.
The cationic conditioning agents (which may be considered
to be secondary conditioning agents in the in~ented conditioning
compositions) are preferably quaternary ammonium salts, although
other cationic compounds of fiber conditioning properties may also
-- 6 --
2~3~3
be employed, at least in part. Thus, known amines, amine salts,
imidazolinium salts and betaines, and such cationic materials as
are described in U.S. patent 4,000,077 may be substituted for at
least some of the quaternary ammonium salt, as may be complexes
of cationic and anionic surfactants, such as have been described
in U.S. patents 4,896,422 and 4,888,119 and in U.S. patent
application S.N. 06/916,069.
The preferred quaternary ammonium salts are of the
formula R9,R10,Rll,R12 N X , wherein at least one of the R
groups is lower alkyl and at least one is higher alkyl, with
the others being higher and/or lower alkyl. Preferably R9 is
lower alkyl, such as of 1 to 4 carbon atoms, R10 and Rll are
higher alkyls of 10 to 40 carbon atoms, R12 is such a higher
alkyl or lower alkyl, and X is a salt-forming anion, such as
halide, lower alkosulfate or lower carboxylic acid radical,
e.g., chloride, bromide, methosulfate, ethosulfate, citrate or
acetate. The lower alkyl will preferably be o~ 1 to 3 carbon
atoms, more preferably being of 1 or 2 carbon atoms, and most
preferably, in most cases, will be methyl, and the higher
alkyl will preferably be of 10 to 22 carbon atoms, more
preferably 12 to 18 or 20 carbon atoms, most preferably of
14 to 18 carbon atoms, e.g., 16 or 18 carbon atoms. The anion
is preferably a halogen, such as chlorine, bromine or iodine,
with chloride and bromine being preferred and with chlorine
being more preferred.
The number of lower alkyls on the quaternary
nitrogen will preferably be 1 or 2 and the number of higher
alkyls will usually be 2 or 3. Thus, such compounds have
2 or 3 long chain alkyls and 2 or 1 short chain alkyl(s)
of 12 to 20 and 1 or 2 carbon atOTnS~ respectively. It has
been found to be desirable to have at least 30 carbon atoms
in the quaternary ammonium salt and preferably at least 34.
The most preferred higher alkyls are cetyl and stearyl and
the most preferred lower alkyl is methyl. The more prefer-
red quaternary ammonium halides include tricetyl methyl
ammonium chloride and distearyl dimethyl ammonium chloride,
but other such quaternary ammonium salts, are also operative,
including dicetyl dimethyl ammonium chloride and tristearyl
methyl ammonium chloride, corresponding bromides, amines,
amine salts, betaines and complexes of the previously mention-
ed U.S. patents, which are hereby incorporated by reference.
Such alternative cationic surfactants and complexes ~ay be
employed as at least part of the cationic surfactant content
of the invented compositions.
The long chain primary alcohol of the compositions
of this invention is preferably a saturated compound, with
the hydroxy group being terminally located. Such alcohol
will normally be of a distribution of homologous alcohols
and typically all are of even numbers of carbon atoms,
averaging 24 to 45 carbon atoms (on a weight basis),
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c~93~3
preferably 28 to 42 carbon atoms, more preferably about 30 to40 carbon atoms and most preferably 30 to 40 carbon atoms.
When the average number of carbon atoms in the chain is
less than 24 the desired effectiveness of such alcohols in
S the present formulations is decreased, with the stabilization,
fiber conditioning and pearlescinq actions being diminished,
and when such chain length is more than 45 carbon atoms,
e.g., of an average of about 50 carbon atoms, such alcohols
are not satisfactorily dispersible in the described composi-
tions. In addition to the mentioned long chain alcohols,related compounds such as corresponding alkoxylated alcohols,
corresponding fatty acids and long chain saturated primary
alcohol esters, may be substituted, at least in part. Of
such "derivatives" the alkoxylated alcohols are preferred,
and the most preferred of these are the ethoxylated alcohols,
which will normally contain up to about 20 ethoxy groups per
mole, e.g., about 10 to 20. However, the alcohols, which are
the preferred embodiments of the invention, normally will
be employed alone or in mixture with related compounds from
the "derivatives" group, with the alcohol being the major
proportion of the total "alcohol plus derivatives" content.
Examples of commercial materials which may be employed in
the present compositions are those manufactured by Petrolite
Corporation and sold through their Petrolite Specialty
2 13 ~ 3
Polymers Group under the name Uni]inTM Alcohols, as described
in the technical bulletin previously referred to in this
specification. Such alcohols may be 75 to 90~, e.g., 80
to 85%, of the commercial product, with the balance of such
products being substantially all saturated hydrocarbons
of corresponding chain lengths. In such products the distri-
bution curve for the alcohol is substantially bell-shaped,
with no chain length of alcohol being more than 10% of the
total content thereof, and with the corresponding hydrocarbon
content being of a substantially flat distribution curve,
with about 1 or 2% of each of the hydrocarbons being present.
Such distribution curves, as bar graphs, are given in the
Petrolite bulletin previously mentioned. The alcohols (and
corresponding hydrocarbons) present will normally be of chain
15 lengths such that at least 80% are in the range of 18 or 20
to 54 carbon atoms, with at least 80% being in the range of
about 18 or 20 to 44 carbon atoms for an alcohol averaging
about 30 carbon atoms and with at least 80% being in the
range of about 28 or 30 to 54 carbon atoms when the alcohol
averages about 40 carbon atoms. Examples of the long chain
primary alcohols are Unilin-425 alcohol, which averages 30
carbon atoms in its chain, Unilin-550 alcohol, which averages
40 carbon atoms in its chain, and Unilin-350, which averages
about 26 carbon atoms in its chain. A derivative, Unithox-550,
is an ethoxylated such alcohol of an average of 40 carbon atoms
in the alkyl chain, ethoxylated with up to 20 ethoxy groups, e.g., 13.
The water soluble synthetic organic anionic detergent,
which is present in the shampoo embodiments of this invention,
-- 10 --
2~ 1~3~3
and may also be present in some conditioning embodiments, too,
is normally a lipophile sulfate OI sulfonate, although other
hydrophile groups than sulfate and sulfonate may also be employed,
such as phosphate and phosphonate. The salt forming cation of
such compounds is normally alkali metal, ammonium or alkanolaminel
with sodium and ammonium salts being preferred. It is also prefer-
red for the anionic detergent to be a lipophile sulfate or a
mixture of sulfates. The anionic detergent lipophile will be an
alkyl group, preferably a higher fatty alkyl of 12 to 18 carbon
atoms, although the increasingly broader ranges of 10, 8 and 6, or up to
18 or 20 carbon atoms, are also contemplated. Such detergents
appear to be most compatible with the described shampoos and yield
good cleaning and conditioning, while not interfering with pearlesc-
ing and conditioning effects of the composition. Particularly
desirable detergents are ammonium lauryl sulfate and sodium lauryl
ethoxyether sulfate having 1 to 6 ethoxy groups per mole, prefer~
ably 2 or 3.
Although the preferred anionic detergents are those
described above, other such anionic detergents may be substituted,
ate least in minor proportion, for them, and such other anionic
detergents are described in McCutcheon's Deter~ents and Emulsifiers,
North American Edition, published in 1984. ~dditionally, it may
be desirable to employ amphoteric, ampholytic and z~itterionic
detergents in such compositions and sometimes, relatively small
proportions of nonionic detergents, and such are also described
in such publication, which is hereby incorporated herein by
reference. Also, see the description of suitable detergents in
S.N. 07/432,952, previously referred to herein and incorporated
by reference. Sometimes relatively small proportions of such
3 ~ ~
surfactants, which term is used here in a broad sense and includes
various emulsifiers and dispersing agents, too, may be employed in
non-shampoo hair conditioners and fiber conditioning compositions.
For the preferred detergent combinations referred to
above, those of higher fatty alkyl sulfate and higher fatty alkyl
ethoxylate sulfate, the preferred proportions are in the ranges of
2:1 - 8:1 of alkyl sulfate to alkyl ethoxy sulfate and it is prefer-
red that the alkyl sulfate be an ammonium salt and the alkyl alkoxy
sulfate be a sodium salt. However, either such detergent may be
employed alone and in in some preferred formulations the ethoxylated
detergent has been omitted.
The various required components of the present compositions
are dissolved and/or emulsified and/or suspended in an aqueous medium.
Such medium may include various non-interfering normal fiber condi-
tioning composition and shampoo composition constituents known inthe art, but a few of these will be specifically mentioned herein
because they are especially desirable components of the present
composition and contribute in a significant manner to its desirable
properties. Higher fatty alkanolamides have long be~n known as
foaming agents and foam stabilizers. Such compounds will usually
be of 12 to 16 carbon atoms in the acyl group, which is reacted
with a lower (l to 3 carbon atoms) mono- or dialkanolamine. In the
present formulations the best alkanolamide is considered to be
lauric monoethanolamide but cocodiethanolamide is of about equivalent
effect. However, other known foam stabilizers and foaming agents
may also be employed too,in whole or in part, such as the betaines
and related materials. Various gums and other thickening materials ar~
also useful in shampoo compositions but it has been found that the best
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2~ ~3~
of these in the present compositions are hydroxyethyl celluloses.
Such are available from Aqualon Corporation under the trademark
Natrosol, such as Natrosol 250 HHR and Natrosol 330 CS, which
preferably are employed in mixture, with the content of the former
being from 2 to 5 times that of the latter. Although the hydroxy-
ethyl celluloses are preferred, other such synthetic gums and
thickeners, e.g., methyl cellulose, hydroxypropyl-methyl cellulose,
PolyquaternumTM-10, modified starches, and natural gums and thick-
eners, e.g., guar gum, may be substituted, at least in part, depend-
ing on the product. Another important constituent of the presentcomposition is mineral oil, when polyethylene is employed as a hair
conditioning agent. The mineral oil is employed to solubilize and
to help disperse the polyethylene, which, if not satisfactorily
dispersed in the composition, will be of little hair conditioning
effect and tends to settle out.
Other components which may be employed in the present
compositions include: ethylene glycol monostearate, ethylene glycol
distearate and propylene glycol distearate, all of which have
pearlescing properties; viscosity control agents, such as propylene
glycol and sodium chloride; pH adjusting agents, such as citric
acid and citra~es; sequestrants, such as EDTA; antifreezes, such
as propylene glycol; solvents, such as ethanol and isopropanol;
preservatives and antioxidants, such as Germaben II (Sutton
Laboratories); anti-dandruff agents, such as zinc pyrithione or
Climbazole (see ~ ,867,971); colorants and perfumes.
Water, employed to make the aqueous medium, which may
be present not only in liquid preparations but also in gels, pastes
and cremes, is preferably deionized a n d irràdiated water of
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2 ~ 3
essentially 2ero hardness but it may also be tap water, although it
is preferred to keep the hardness below 50 p.p.m., as calcium
carbonate. However, other tap waters of hardnesses as high as 200
p.p.m. will sometimes also be useEul, but usually they will be avoided
The proportions of the various components present in the
invented liquid conditioning and shampoo compositions to obtain the
desdribed desirable properties will now be given.
The surfactant content range, for both conditioning
compositions, e.g., hair rinses, and shampoos, will be in the range
of 1 to 35%, preferably 2 to 35%, and more preferably 3, 5 or 8 to 25%,
such ranges being lower for the "conditioning compositions" and high-
er for the shampoos. Such ranges for the sha~poos are normally 5 to
35%, preferably 8 to 25 or 30% and more preferably 10 to 20%. For
alkyl sulfate - alkyl ethoxylate sulfate shampoos ranges are usually
5 to 25%, preferably 10 to 20% and more preferably 10 to 15% o~
the former and up to 15%, preferably 0 or 1 to 10% and more prefer-
ably 0 or 1 to 5% of the latter. When either such sulfated deter-
gent is employed alone the ranges for the alkyl sulfate apply.
The content of water insoluble conditioning agent(s)
(excluding the content of cationic surfactant) will be a conditioning
proportion or such a proportion which, in conjunction with the
cationic surfactant present, serves satisfactorily to condition
fibers or hair, which will normally be in the range of 0.3 to 10%
for both fiber conditioning and shampoo compositions, preferably 0.3
to 7%, and more preferably 0.3 to 5%. The cationic surfactant is
present in a fiber conditioning or conditioning supplementing pro-
portion, which will normally be from 0.1 to 5%, for both fiber
conditioning compositions and shampoos, preferably be.ing 0.1 to 3%
and more preferably 0.1 or 0.3 to 0.7% or 1~. The long chain
- 14 -
saturated primary alcohol and/or "derivat:Lves" thereof will normally
total 0.5 to 10~, preferably 0.5 to Sor 6~, more preferably 1 to 5~.
The content of aqueous medium (which may include various adjuvants)
will normally be in the range of 75 to 99%, with the water content
of such a shampoo being 60 to 90~, preferably 63 to 85%, and more
preferably 63 to 80~. However, the water and aqueous medium
contents may be varied, depending on the proportions of adjuvants
desirably present in the composition. Normally the ratio of contents
of long chain saturated primary alcohol and/or "derivatives" to
conditioning agent(s) will be in the range of 0.2 to 5, preferably
in the range of 0.3 to 3, with ratios of 0.5 to 2 and about 1 bein~
more and most preferred, respectively.
In various shampoo compositions within the invention
the proportions of components may be varied within the ranges
given, as will be indicated by the following ranges of proportions
of the components of some different types of preferred compositions.
For a shampoo comprising lipophile sulfates, qu~texnary
ammonium salt, aminosilicone and long chain saturated primary
alcohol, in water, there will usually be present 5 to 18% of
fatty alcohol sulfate, preferably as its ammonium salt, 0 or 1 to l
of fatty alcohol ether sulfate, preferably as its sodium salt
(and the range of ratios can be 1:10 to 10:1), 0.2 to 2% of
quaternary ammonium salt, 0.5 to 10% of the aminosilicone, 0.5 to
5 or 6% of the long chain saturated primary alcohol and/or its
"derivatives", 65 to 85~ of water and any balance of shampoo
adjuvant(s). Preferred ranges are 10 to 15% or 20%, 0 or 1 to 5%,
- 15 -
3 5 6~
0.1 to 0.7%, 0.8 to 4%, 1 to 5.0% and 63 to 80%, respectively.
Such compositions may also comprise 0.2 to 2% of hydroxyethyl
cellulose (or other suitable thickener), 2 to 5% o~ lauric mono-
ethanolamide or cocodiethanolamide, 0 or 0.5 to 2% of micro
crystalline wax and 0 or 0.5 to 1% of petrolatum.
For another such composition the first six of the
ranges will be the same as immediately previously mentioned
but there will also be present 0.3 to 2% of polyethylene and
0.3 to 2% of mineral oil, preferably 0.5 to 1.5% and 0.5 to 2%,
respectively. The hydroxyethyl cellulose and lauric mono-
ethanolamide components are in the same proportions as given
for the previous formulas but 0.1 to 2~, preferably 0.1 to 1%
of paraffin wax and 0.1 to 2%, preferably 0.1 to 0.5~ of iso-
paraffin are also present.
In an additional embodiment of the invention, wherein
the shampoo includes polyethylene as the basic hair conditioning
agent, together with quaternary ammonium halide, and with a high
molecular weight lipid solubilizing agent, such as mineral
oil, to solubilize the polyethylene, the proportions of
components are like those previous given for the anionic
detergents, the cationic conditioner, the long chain
saturated primary alcohol and/or "derivatives" thereof,
the water and any adjuvants present. Howevex, in such compo-
sition the aminosilicone can be omitted and the proportion
of alkoxylate detergent may be increased to 15~ wile proportions
- 16 -
2 ~ 3
of polyethylene and mineral oil will normally be 0.3 to 2%
for each, and preferably will be in the ranges of 0.5 to 1.5
and 0.5 to 2%, respectively. Other components which are also
desirably present include 0.2 to 2% of hydroxyethyl cellulose,
2 to 5% of lauric monoethanolamicle, 0.1 to 1% of paraffin
wax and 0.1 to 0.5% of isoparaffin.
In a further shampoo of the invention the proportions
of the anionic detergents, cationic surfactant, aminosilicone,
long chain saturated primary alcohol and or "derivatives",
other adjuvants and water are the same as in the first of
these types of formulas given except for the fact that the
long chain saturated primary alcohol present (which may
include a derivative thereof) preferably comprises ~.5 or 1 to 2 or 3%
of a chain length averaging about 30 carbon atoms and
to 2 or 3~ of a chain length averaging about 40 carbon atoms.
In a modification of that formula there is also present 0.5
to 2% of a polyethoxylated long chain saturated primary
alcohol (a "derivative") wherein the alcohol is of an average
of about 40 carbon atoms and is ethoxylated with 10 to 20
moles, e.g., 13 moles, of ethylene oxide per mole. Both
such formulas, which include no gum or gum~like material
(hydroxyethyl cellulosel may be supplemented with 2 to 5% of
lauric monoethanolamide, 0.5 to 2~ of C18_36 acid triglyceride
and 0.1 to 0.5% of citrate, preferably sodium citrate. A
further modification of the immediately preceding formula
2~3~3
includes the presences, as hair conditioning agents, of 0.1 to
1% of paraffin wax and 0.5 to 1.5~ of normally solid poly-
ethylene of a molecular weight in the range of 1,000 to
4,000, with 0.5 to 2% of mineral oil of a molecular weight
in the range of 300 to 800,present as a solvent medium for the
polyethylene.
Other preferred formula types comprise the same
proportions of anionic detergents, cationic surfactant,
aminosilicone, long chain saturated primary alcohol, water
and shampoo adjuvant(s),as in the immediately preceding formula,
but also include as a supplementing conditioning agent, 0.25
to 5% of C18 36(mixed) acid triglyceride- Such composition
may also include 2 to 5% of lauric monoethanolamide, 0~2 to
2% of hydroxyethyl cellulose, 0.5 to 2% of microcrystalline
wax and 0.5 to 1~ of petrolatum. Instead of the microcrystal-
line wax and petrolatum there may be substituted 0.5 to 1.5%
o~ the previously described polyethylene and 0.5 to 2% of the
described mineral oil.
For gels, pastes, thicker cremes and cake materials
within the invention the required, optional and adjuvant
components will normally be in the same ran~es of proportions
as in the aqueous compositions, with the proportion of water
often being decreased, sometimes to as low as 30 or 40%. Also,
the water may be replaced, upto 50% thereof in some instances,
but usually to no more than 20%, by another solvent, e.g.,
ethanol or isopropanol~
- 18 -
2~3~3
Although the fiber conditioning and hair conditioning
compositions o~ this invention may be in the various physical
forms mentioned, preferably they are in liquid form (of lotion
appearance) and the most preferred embodiment of the invention
is a liquid hair conditioning sharnpoo. Such compositions should
be stable chemically and physically to be acceptable in the
marketplace. They should not deteriorate to an unacceptable
extent on storage, and should not have components settle out or
phases separating during storage. The presence of the mentioned
long chain primary alcohols (of the Unilin or Unithox type[s])
stabilizes the invented compositions, in addition to giving them
an attractive pearlescent appearance and improving fiber condi~
tioning. Also, such shampoos are of desirable viscosities, so
as to be pourable, and yet will not be so thin that they run
uncontrollably. The desired viscosity range is 1,000 to
15,000 centipoises at room temperature (25C.), preferably 3,000
to 6,000 centipoises. The invented shampoos are non-settling
and non-separating, and do not chemically deteriorate on storage 9
as has been established by accelerated aging tests at elevated
temperatures. The shampoo viscosity may change slightly on
storage but such a change does not significantly affect the
shampoo's properties. Also, the desired use viscosity can be
obtained by manufacturing a shampoo at a certain viscosity
which allows for any expected viscosity change before use.
The improved hair conditioning obtained by use of the
invented compositions, compared to controls, from which the
-- 19 --
-" 2 ~ 3
mentioned conditioning agents have been omitte~ is very notice-
able to even the casual user of the invented shampoo or other
conditioning composition, and is measurable in standard tests
that are used to evaluate conditioning and its components,
including ease of wet combing, ease of dry combing, manage-
ability, static charge retention and flyaway. The casual
shampooer will note that the hair is easier to comb after shampoo-
ing, in both wet and dry states, compared to control hair washed
with a shampoo that is not under the invention (with condition-
ing components or some of them missing from it~. Scientifictests also prove that the force needed to move a comb through a
standard hair tress after treatment ~shampooing) of the hair
with an invented shampoo, and rinsing, is measurably less than
that when such a control is employed in the same manner. Such
results are confirmed by panel tests, in which several experienced
evaluators, using both the experimental and control products in
blind tests, evaluate them for such combing ease, ~anageability
and static characteristics and effects.
Uses of the invented compositions, including the shampoos,
are not required to be different from normal uses of hair condi-
tioning shampoos and other fiber conditioning compositions. Condi-
tioning compositions may be applied at room temperature or at
somewhat elevated temperatures in normal quantities and may be
left on the hair for different lengths of time, depending on the
extent of conditioning desired. Usually the conditioning ~gent
- 20 -
3 ~ 3
and the hair will be at a temperature in the range of 15 to 50C.,
preferably 20 to 40C., and the conditioning composition will be
in contact with the hair for from 30 seconds to ten minutes,
preferably one to five minutes. The amount of composition applied
will normally be in the range of 0.1 to 25 grams, often being 0.2
to 10 g. or 0.5 to 2 or 5 g., on the basis of the non-aqueous
and non-solvent components of the composition. On the basis of
the shampoo which may be employed such application rates may be
in the range of 0.5 to 50 grams, often 2 to 15 or 20 grams and
frequently five or ten grams per use. The applied conditioning
composition may be brushed and/or combed through the hair and
may be subsequently washed out, may be allowed to remain on the
hair or may be partially removed, as by towelling. When the
shampoo is employed to wash and condition the hair it will be
rinsed off with water after remaining on the hair as an aqueous
foam for a sufficient length of time, usually 1 to 5 minutesl 50 as
satisfactorily to condition the hair, and may then be wet combed,
driedl as by blow dryingl and dry combed or brushed to the
desired style.
To manufacture the present compositions, including
shampoos, no complex procedures have to be followed, but to
obtain best stability and pearlescence, and greatest condition-
ing activity, after storage of the invented compositions, it will
be desirable to form a dispersion of the w~ter soluble lipophile
sulfate and/or sulfonate detergent(s) and adjuvants in water
- 21 -
--~ 2~3~3
at an elevated temperature, such as 70 to 95C., dissolve
and/or disperse cationic conditioning agent, such as quaternary
ammonium salt, with any lipophilic materials, such as hydro-
carbons, including polyethylene, mineral oil, microcrystalline
wax, petrolatum, paraffin and isoparaffin, long chain alcohol,
triglyceride and stearyl stearate as a melt or liquid mix at
elevated temperature, and admix the two mixes at such elevated
temperature, after which the heated aminosilicone may be admixed
with the resulting mix (it may sometimes also be included with
the lipophiles), with the various mixings taking place with the
portions to be mixed at approximately the same temperatures.
It is sometimes desirable for the aminosilicone to be mixed in
after the main pre-mixing to promote better stability of the
product. When adjuvants are present those which are water
soluble and/or dispersible may be mixed in with the aqueous
phase materials and those which are not water soluble or
dispersible in the aqueous medium may be blended in with the
lipophilic materials, such as the hydrocarbons, or in some
instances may be added to the mixture of the hydrophilic and
lipophilic materials either before or after cooling to room
temperature. Normally perfume will be added to the other mixed
components after cooling to room temperature and the amino-
silicone will be added at elevated temperature and before such
cooling. The perfume is added to the cooled composition to
avoid losses thereof due to volatilizations of components and to
- 22 -
2 ~ 3
prevent any degradation due to heating it. When the procedure
described is not followed, as when the various components of the
compositions are blended indiscriminately, unstable products may
result, which can separate or settle out on storage, and such
unstable compositions tend to have poorer conditioning properties
than the stable conditioning compositions and shampoos that are
made according to the invented procedure.
The following examples illustrate but do not limit
the invention. Unless otherwise indicated all parts are by
weight and all temperatures are in degrees Centigrade in the
examples, other parts of the specification, and in the claims.
- 23 -
EXAMPLE 1
% (by weight)
Component lA lB lC
Ammonium lauryl sulfate 12.50 12.50 12.50
Sodium lauryl ether sulfate2.50 2.50 2.50
(2 EtO per mole)
Distearyl dimethyl ammonium chloride 0.50 0.50 0.50
Aminosilicone A (Dow-Corning~2.50 - 1.50
Long chain alcohol (Unilin 425, 2.50 2.50 2.50
Petrolite Corp.)
Polyethylene (M.W. = 2,000, - 0.75 0.75
Allied Corp.)
Microcrystalline Wax (M.P. = 82C.~1.00 - _
Paraffin wax (M.P. = 53~C., Boler - 0.35 0.35
Petroleum Corp.)
Isoparaffins (IsoparTM M, Exxon Corp.) -0.250.25
Petrolatum, white (Alba ProtopetT~) 0.75
Mineral oil (BritolTM 50, Boler - 1.00 1.00
Petroleum Corp.)
Hydroxyethyl cellulose 250 HHR 0.57 0.67 0.67
(Aqualon Corp.)
Hydroxyethyl cellulose 330 CS 0.18 d.23 0.23
(Aqualon Corp.)
Lauric monoethanolamide 3.50 3.50 3.50
Sodium chloride 0.20 0.20 0.20
Preservative (GermabenTM II)0.500.50 0.50
Perfume 0.80 0.80 0.80
Colorant 0.10 0.10 0.10
Deionized water 71.90 73.65 72.15
100.00 100.00 100.00
- 24 -
2~3~ ~
Compositions of Formulas lA, lB and lC are made by the
method described in the specification, with mixings of the hydro-
philic components, separate mixings of the lipophilic components
and admixings thereof, all conducted at elevated temperature,
e.g., 80C., followed by admixings of the aminosilicone components,
when present, and sodium chloride,to adjust the viscosity, and
final addition of perfume after c~ooling of the unperfumed shampoo
to about room temperature (25C.), which is when pearlescence occurs~
The products made are all attractively pearlescent
liquid shampoos of viscosities in the range of 3,000 to 6,000
centipoises at 25C. and of pH's in the range of 6 to 7, and are
all found to be stable by elevated temperature storage tests,
with no appreciable separation or settling out of components.
When tested for hair conditioning capabilities, according to the
tests described in the specification, they are found to be good
conditioning shampoos, all being better than controls that do not
contain the water insoluble conditioning agents present in the
given formulas. The conditioning obtained from each of the
described formulas is at least equivalent to the best of all the
commercial conditioning shampoos presently on the market and the
shampoo of Formula lC is even measurably and significantly better
in conditioning action than such commercial product.
When the anionic detergent component is removed from
the lC formula the hair conditioning (and fiber conditioning)
composition resulting is useful for the treatment of fibrous
- 25 -
2 ~ 3 ~ 3
materials and may be employed as a rinse for human hair. In both
such applications, even after rinsing off the product with water
the fibrous material treated will be of lower static charge,
will be soft and pliant to the touch, and will be glossy and
attractive in appearance. Also, when human hair is 50 treated
it will be less subject to objectionable "flayaway" and will be
more readily combable and manageable.
In other modifications of Formu~ lA, lB and lC,
which are also outside this invention, like the modification of
Formula lC mentioned above, when the long chain alcohol is omitted
from the formulas and is replaced by deioni~ed water the shampoo
tends to become unstable and to separate into different phases
and/or have components thereof settle out on elevated tempera-
ture storage. Also, hair conditioning is not as good and
pearlescence is either non-occurring or is diminished and less
attractive.
When Aminosilicone A is replaced by conventional non-
volatile silicones or other aminosilicones in Formulas l~ and lC
conditioning activity is noticeably diminished (but is still
present). Such activity for Formula lC may be increased further
by adding 1% of Aminosilicone A to the formula in replacemenk
of 1% of the deionized water, so as to increase the percentage
of Aminosilicone A to 2.50%, equal to that of Formula lA.
Similarly, when 2.50% of Aminosilicone A is added to the
formula of Example lB in place of a like percentage of water,
conditioning is also substantially improved.
2~3~3
EXAMPLE 2
% (by weight)
Component _ 2B 2C_
Ammonium lauryl sulfate 12.50 12.5012.50
Sodium lauryl diethoxy sulfate2.50 2.50 2.50
Distearyl dimethyl ammonium chloride0.50 0.50 0.50
Aminosilicone A (Dow-Corning)1.50 - 1.50
Long chain linear alcohol (Unilin 1.50 1.50 1.50
425, Petrolite Corp.)
Long chain linear alcohol (Unilin 1.00 1.00 1.00
550, Petrolite Corp.)
Long chain linear alconol ethoxylate1.00 1.00 1.00
(UnithoxTM 550, Petrolite Corp.)
C triglyceride (Syncrowax 1.00 1.00 1.00
18-36 HGL-C, croda CorP~)
Paraffin wax (M.P. = 53C., - 0.35 0.35
Boler Petroleum Corp.)
Polyethylene 617-A (Allied Corp.) - 0.75 0.75
Mineral oil (Britol 50, Boler - 1.00 1.00
Petroleum Corp.)
Isoparaffin (Isopar M, Exxon Corp.) - 0.25 0.25
Lauric monoethanolamide 3.50 3.50 3.50
Preservative (Germaben II) 0.50 0.50 0.50
Sodium citrate 0.25 0.25 0.25
Perfume 0.80 0.80 0.80
Colorant 0.10 0.10 0.10
Deionized water 73.35 72.5071.00
100.00 100.00100.00
The shampoo compositions of this example are made
by the method described in Example 1 and elsewhere in the specifi-
cation, and it is found that all the shampoos made are
- 27 -
-
2~3~
attractively pearlescent and are stable under elevated
temperature storage conditions. Additionally, they are
excellent hair conditioning shampoos, equalling or exceeding
shampooing and hair conditioning properties of the best
commercial hair conditioning shampoo on the market, with
Formulas 2A and 2B equalling such conditioning power and
Formula 2C surpassing it. The three shampoos made are of
desired viscosity and pH, like those of the compositions of
Example 1.
- 28 -
2 ~ 3 ~ 3
EXAMPLE 3
%(by weight)
Component 3A 3B
Ammonium lauryl sulfate 12.50 12.50
Sodium lauryl ethoxylate sulfate (2 EtO) 2.50 2.50
Distearyl dimethyl ammonium chloride0.50 0.50
Aminosilicone A (Dow-Corning) 1.50 1.50
Long chain alcohol (Unilin 425) 1.00 1.00
Microcrystalline wax 1.00
10 Petrolatum, white 0-75
Syncrowax HGL-C (Croda Corp.) 0.75 0.75
Polyethylene 617-A (Allied Corporation) - 0.75
Mineral oil (Britol-50) - 1.00
Lauric monoethanolamide 3.50 3.50
Hydroxyethyl cellulos~ 0.75 0 D 7 5
Preservative (Germaben II) 0.50 0~50
Colorant 0.10 0.10
Perfume G.80 OD 80
Deionized water 73.85 73.85
100.00 100.00
Shampoo compositions of this example are made in the
same manner as described in Examples 1 and 2, and in the preceding
specification (and also in U.S. patent application S.~. 07/432,952).
The two shampoos made both utilize long chain saturated primary
alcohol of the IJnilin 425 type in conjunction with C18 36(mixed~
- 29 -
triglyceride, aminosilicone and polyethylene or with aminosilicone,
microcrystalline wax and petrolatum, as water insoluble condition-
ing agents. The shampoos made are attractively pearlescent
and are stable on elevated temperature storage. Additionally,
they are of improved hair conditioning properties, with the
3B formula being even better in hair conditioning than the
3A formula. When the amounts of the Aminosilicone A and
Unilin 425 are increased, to 2.50% and 2.00%, at the expense
of the deioni~ed water, conditionings are improved even
further, and stabilities and pearlescences are still excellent.
- 30 -
2 ~ 3 ~ 3
EXAMPLE 4
% (by weight)
Component _ 4B 4C 4D_
Ammonium lauryl sulfate 12.5012.5012.50 12.50
Sodium lauryl diethoxy sulfate2.50 2.50 2.50 2.50
Distearyl dimethyl ammonium chloride0.50 0.50 0.50 0.50
Aminosilicone A (Dow-Corning)1.501.501.50
g chain (C30 average) alcohol2.502.50 1.50 2.50
g in ( 40 average) alcohol 1.00
Unithox 550 lon~ chain (C40 average) ~ ~1.00
alcohol ethoxylate (13 EtO)
Microcrystalline wax 1.00 - - -
Petrolatum, white 0.75
Syncrowax HGL-C - - 1.00
Polyethylene 617-A (Allied Corp.) - 0.75 - 0.75
Paraffin wax (M.P. = 53C.) - 0 35 _ 0 35
Mineral oil (Britol 50) - 1.00 - 1.00
Isopar M - 0.25 - 0.25
Lauric monoethanolamide 3.503.503.50 3.50
Hydroxyethyl cellulose 250 HHR0.57 0.67 - 0.67
Hydroxyethyl cellulose 330 CS 0.18 0.23 _ 0.23
Preservative 0.500.500.50 0.50
NaCl 0.200.200.20 0.20
Sodium citrate - - 0.25
Colorant 0.100.100.10 0.10
Perfume 0.800.80Q.80 0.80
Deionized Water 72.907?.1573.15 73.65
100.00 100.00 100.00 100.00
- 31 -
2 ~ 3
The compositions of this example are made in the same
manner as described in Examples 1-3 and in U.S. patent application
S.N. 07/432,952. The products resulting, all of which contain a
long chain alcohol or derivative of type(s) described herein which
improve(s) conditioning and stability and make(s) the shampoo
pearlescent, are all attractive pearlescent liquids of pH'S
the range of 6 to 7 and viscosities in the range of 3,000 to 6,000
centipoises at 25~C. All are of improved stability, compared
to compositions which do not contain the long chain alcohol or
derivative thereof, and all are excellent cleaning agents and
conditioners for hair. It will be noted that all the compositions
contain the preferred long chain C30 average alcohol,with Fo~m~la
4C also including the corresponding C40 average a
ethoxylated such alcohol.
Formula 4C also contains no gums and relies for
conditioning primarily on AminoSiliCOne A, the long chain
alcohols, the "derivative" thereof, and long chain fatty
acid triglyceride (Syncrowax). Best conditioning and stabiliz-
ing effects are obtained with Formula 4C but all of the four
compositions are excellent conditioning shampoos, competitive
in desirable conditioning properties, stability and appearance
with the best commercial conditioning shampoos that are on
the market.
EXAMPLE 5
In preceding Examples 1-4 the preferred a~monium
lauryl sulfate and sodium lauryl ethoxy sulfate mixtures were
32 -
2~3~3
employed but similar results are obtainable when other higher
alkyl sulfates, such as the sodium and triethanolamine salts
of C14 18 alkyl sulfuric acids, are employed. Similarly, the
sodium lauryl ethoxy sulfate can be replaced by sodium C14 18
ethoxy sulfates wherein the ethoxy group is of 1 or 2 to 5 or 6
carbon atoms, preferably 3, and the sodium is replaced by
ammonium or triethanolamine. In like manner the distearyl
dimethyl ammonium chloride may be replaced by other quaternary
ammonium salts, such as tricetyl methyl ammonium bromide or
chloride, dilauryl diethyl ammonium chloride and sometimes even
by trimethyl stearyl ammonium chloride or the corresponding
tallowyl compound (in which the alkyl is that obtained from
beef tallow). Variations in the other water insoluble hair
conditioning agents may be made, utilizing other embodiments
of such materials within the description given in the specifi-
cation, including other ethoxylated long chain primary alcohols
of an average of 24 to 40 carbon atoms in the alcohol chain,
and corresponding esters and acids. Various adjuvants may be
substituted for those in the given formulas. For example, the
monoethanolamide may be replaced by lauric myristic mono or
diethanolamide or the corresponding coco alkanolamide, or by
corresponding isopropanolamides, EDTA may be included, and the
hydroxylated ethyl celluloses may be replaced by hydroxylated
propylmethyl celluloses, methyl cellulose or other suitable gums
or thickeners. In such cases the compositions made will be of
high quality and will be satisfactorily conditioning, stable
and attractively pearlescent shampoos of desired pH and viscosity.
2~33~3
Similarly, when the anionic detergent(s) is/are omitted from
the formula conditioning rinses and fiber conditioners are
obtainable which will be of similar properties and which
satisfactorily condition fibrous materials, such as hair,
in the manner described. Such compositions may be in liquid,
gel, paste or creme form.
EXAMPLE 6
% (by weight)
Component A
Part I
10 Irradiated deionized water 72.19 71.89
Hydroxyethyl cellulose (Natrosol 250 HHR) 0.20
Ammonium lauryl sulfate 15.00 15.00
Monobasic ammonium phosphate (buffer)0.10 0.10
Part II
15 Unilin 425 3.00 3.00
Cocodiethanolamide 4.00 5.00
Part III
Aminosilicone A 3. no 3.00
Part IV
20 Perfume (CP Paris K3-157 new revised 3~0.80 0.80
Sodium chloride 0.50
100 . 00100 . 00
- 34 -
3 ~ 3
In essentially the same manner previously described,
the components of each of Parts I and II were separately mixed
and were then admixed at 90~C., followed by sequential additions
thereto of Parts III and IV, with the addition of Part IV being
at room temperature. The shampoos made are both pearlescent and
attractive in appearance, and are of desired viscosity and
pH. Both condition hair washed with them as well as or
better than the most effective of the leading hair conditioning
shampoos on the U.S. market at present.
In the formula given the quantity of ~minosilicone A
is on the basis of pure aminosilicone, although it was
employed together with one part of a solvent for the silicone
per three parts of silicone, so as to reduce its viscosity (and
such was also employed in the other Examples,in which the
quantities are also on the basis of the pure ~minosilicone.
Also, the ammonium phosphate bufEer may be employed in a
proportion up to 0.20% in these formulas.
In a variation of the formula,instead of employing
Unilin 425, Unilin 550 or pure long chain linear saturated
alcohols of 30 or 36 carbon atoms to the molecule (or a mixture
thereof) may be substituted and the results are equivalent.
However, further improvements in conditionings may be obtained
by incorporation in the formulas of quaternary ammonium salt,
e.g., distearyl dimethyl ammonium chloride, and other condition-
ing agents, e.g., microcrystalline wax, petrolatum, polyethyleneand beeswax. Also, the aminosilicone may be replaced by non-amino-
- 35 -
2 ~ 3
silicones and dimethicones, such as the silicones of U.S. patent
No. 4,704,~72, and other non-volatile (pre~erred) water insoluble
silicones.
EXAMPLE 7
The compositions of the preceding examples may be
further modified, by changing the proportions of the various
components thereof +10%, +20% and +30~, while maintaining
them within the ranges recited elsewhere in the specification,
and the modified compositions resulting will be stable,
pearlescent shampoos and fiber conditioning products of
improved hair conditioning and fiber conditioning properties.
When such are employed to shampoo the hair or are used as
conditioning hair rinses, according to the processes described
in this specification, which include application to the
fibrous material or hair, often in the presence of additional
water, followed by rinsing, the hair is satisfactorily
cleaned and conditioned. It may be combed more readily when
wet or dry, will not accumulate objectionable static charges
and will be manageable and softer to the touch.
The compositions of this invention, as represented
by the formulas and descriptions given in the preceding
examples, are significant advances in the fiber conditioning
and hair conditioning arts. By utilizing the described long
chain primary alcohol, which is preferably completely saturated,
- 36 -
-
2~ ~ ~3~
or its "derivative(s)", in conjunction with the described
water insoluble conditioning agent(s) (and cationic surfactant~,
it has been possible to make ~rea~tly improved hair conditioning
compositions, such as shampoos, which are as good as or
better in conditioning properties than any such compositions
previously marketed. Such has been accomplished by utilizing
the mentioned long chain alcohols or their derivatives, such
as the Unilins and Unithoxes, which are available materials
but which were heretofore not known as components of hair
conditioning compositions or shampoos.
The various patents, patent applications and
publications previously referred to in this specification
are hereby incorporated herein by reference.
This application is a continuation-in-part of
U.S. patent applications S.N's. 07/432,644 and 07/432,952,
which are both continuations-in-part of S.N. 07/369,361.
The invention has been described with reference to
illustrations and examples thereof but is not intended to be
limited to these because it is evident that one of skill in
the art, with the present specification before him or her,
will be able to utilize substitutes and equivalents without
departing ~rom the invention.
37
