Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
7Z~
This invention relates to hair-conditioning shampoos
and body-washing preparations.
After washing with shampoos,shower and bath prepara-
tions based on synthetic anionic surfactants, the hair often
is in a cosmetically unsatisfactory state. When wet, it is
difficult to comb and feels dull. After drying, the washed
hair tends to develope a static charge, resulting in the well-
known "flying away" of freshly washed hair. In addition,
freshly washed hair often appears lustreless. For these reasons,
it is known that conditioning preparations may be applied to
hair after washing or shampooing. The preparations in question
are mostly rinses or cream-like lotions containing cation-active
surfactants. It is also known that certain substances may be
added to ordinary shampoos to obtain a certain conditioning
effect when the hair is washed. Substances of the type in ques-
tion include, for example, water soluble proteins or protein
degradation products, polycationic polymers, for example amino
polycarbamide resins of the type described in DE-OS No. 21 50 899,
polycationic cellulose derivatives of the type described in
US-PS No. 3,816,616 or polycationic guar derivatives of the type
described in US-PS No. 4,292,212. Many other water soluble
polymers containing cationic or quaternary ammonium groups have
been proposed for this purpose.
One disadvantage common to all known hair-conditioning
additives lies in their at least partly reduced effect when used
in anion-active hair washing preparations. Products having a
particularly strong effect often show excessive adsorption to
the hair and, as a result, reduce the elasticity, body and set
of the dried hair.
.., .~ ~
~ -2-
7~l~
Accordingly, the object of the present invention is
to provide a shampoo formulation based on the well-known,
heavily foaming anionic washing-active substances which, through
the presence of suitable hair-reviving additives, enables -the
hair to be readily combed when wet and also leaves the dry hair
with satisfactory cosmetic properties, including in particular
elasticity, body, sheen and set.
It has now been found that the hair-care properties
of a shampoo based on anionic washing-active substances may be
improved particularly effectively by adding to the shampoo a
combination of a polycationic guar derivative, a hardenable
cationic polycondensation product, a hydrophilic fatty acid
ester and a water soluble polyvinyl pyrrolidone. Accordingly,
the present invention relates to a hair conditioning shampoo
comprising in an aqueous medium 5% to 50% by weight of a water
soluble, anionic, alkali metal, magnesium ammonium or C2-C3
alkanol ammoni.um detergent salt, said detergent being selected
from the group consisting of C8-C18 alkyl sulfates, C8-C18 alkyl
polyglycol ether sulfates having 1 to 6 glycol ether groups in
the molecule, C10-Cl8 alkane sulfonates, C10-Cl8 olef.ln sul-
fonates, C8-C18 fatty acid alkylolamide polyglycol ether sul-
fates, C8-C18 fatty acid monoglyceride sulfates, C8-C18 alkyl-
sulfosuccinates, C6-C10 dialkylsulfosuccinates, C8-C18 alkyl
polyglycol ether carboxylates having 2 to 6 polyglycol ether
groups in the molecule, C8-C18 acyl sarcosinates, C8-C18 acyl
taurides and C8-C18 acyl isethionates and 1.7% to 14% by weight
of a mixture of conditioning agents consisting of (a) 0.1% to
4% by weight of 3(trime-thylamino)-2-hydroxypropyl guar chloride,
(b) 0.5% -to 5% by weight of a readily water soluble, hardenable
polycondensation product formed by reacting a water soluble
, 3
`~i -3-
~Z~7~1 3
polyamine containing reactive amino groups and having from 4
to 6 carbon atoms with an e-ther of poly C2-C3 alkylene glycol
having terminal halohydrin or hydroxyl groups followed by
reaction with either epichlorohydrin or additional reaction
product of said polyamine and said ether, (c) 1% to 4% by
weight of an esterification product formed by reacting from
1 to 2 moles of C8-C18 fatty acid with the adduct obtained by
reacting 4 to 20 moles of ethylene oxide with 1 mole of glycerol
and (d) 0.1% to 1% by weight of a polyvinyl pyrrolidone having
an average molecular weight of 10,000 to 70,000, the weight
ratio of ~a):(b3:(c):(d) being 1:0.5-4 : 0.5-4 : 0.15-0.5 and
the weight ratio of said anionic detergent to said conditioning
mixture being from 10:1 to 1:1.
The 3-(trimethylamino)-2-hydroxy propyl guar chloride
is a cationic guar derivative known from United States Patent
Serial No. 3,589,978. The products described therein contain
as their basic uni L
: -3a-
2~3
two mannose units at-tached by a glucosidic bond and one galactose
unit attached to one of the hydroxyl groups of -the mannose unlts.
On average, each of the hexose rings carries three free hydroxyl
groups. These free hydroxyl groups are reacted with reactive
quaternary ammonium compounds to give the cationic polymers~
The cationic polymer used in the shampoo according to the
invention is commercially available under the name "Cosmedia(R)-
Guar C 261".
The readily wa-ter-soluble, hardenable polycondensation
products of water-soluble polyamines con-taining reac-tive amino
groups and polyalkylene oxide radicals and epichlorohydrin or
compounds containing more than one epoxide and/or halohydrin
group in the molecule are known from DE-PS No. 2,363,871. As
set forth in said paten-t, to prepare the hardenable polyconden-
sation products to be employed in the invented compositions, it
is necessary to proceed from polyamines with a content of poly-
alkylene oxide radicals, which are obtained via known procedure
by reacting polyamines, especially polyalkylene polyamines with
mono- and/or polyfunctional derivatives of polyalkylene oxides.
These mono- and/or polyfunctional derivatives oE polyalkylene
oxides ean contain, as reaetable groups, chlorohydrin radicals,
glycidyl radiealsl halogen or other xadicals capable of anion
formation sueh as, for example, sulfurie aeid radieals, alkyl-
sulfonie acid radicals and so forth. The polyalXylene oxide
groups present in the polyalkylene oxide derivatives can have
varying molecule sizes, in whieh case the starting material is
generally so chosen -tha-t approximately from 3 to 70 alkylene
oxide radicals are available. As an alkylene oxide, ethylene
oxide is the first to come under consideration; but o-ther cyclic
oxides, such as, for example, propylene oxide, as well as
- 4 -
t~2~
corresponding mixtures, are also usable. ~'he polyalkylene oxide
chains can also be interrupted, for example, via the inser-tion
of a dicarboxylic acid or diisocyanate radical.
Compounds usable as a second reaction component
include those containing in the molecule more than one epoxide
and/or halogen hydrin group, such as epichlorohydrin, dichloro-
hydrins or bifunctional reaction products of these compounds
with glycols, diglycols, polyalkylene oxides, glycerin, dicar-
boxylic acids, polycarboxylic acids, multivalent phenols, etc.
The preparation of certain hardenable polycondensa-
tion products to be employed in the inventive compositions can
be effected via an especially simple procedure by reacting a
polyalkylene glycol, e.g., a polyoxyethylene glycol having a
molecular weight of 1000 or 600, with epichlorohydrin to form
a bis chlorohydrin ether and by then further reacting this
product with sufficient polyamine, e.g., dipropylene triamine,
diethylene triamine or triethylene tetraamine, to produce in
the reaction mixture a ratio of available chlorine atoms -to
available amino hydrocarbon atoms in the range of from 4:5 to
7:5. In this production process, the intermediately formed
polyglycol polyamine is not isolated, but is immediately reacted
with additional polyglycol bis chlorohydrin ether to form the
desired polycondensation product. The reaction of the poly-
amines, which contain polyalkylene oxide radicals, with those
compounds containing in the molecule more than one epoxide
and/or halogen hydrin group, can be carried out in -the presence
of organic solvents or, preferably, of water. To speed up the
reaction, appropriate acid-binding substances, such as caustic
alkali, sodium carbonate, magnesium carbonate or triethanolamine
can also be included.
- 4a -
.
. ~ ,.
` ~z^~
The reaction is carried out a-t -temperatures between
50 and 100C for a period oE time sufficiently long to produce
a clear increase in the viscosity of the reaction product. The
reaction is terminated as soon as the desired degree of poly-
condensation-at which point the reaction product is still readily
soluble-has been achieved, if necessary by means of adjusting
the pH to <6. OE the cationic polycondensation products
described in German DE-OS No. 2,363,871, the polycondensate
produced as product F of the above-mentioned patent is particu-
larly suitable for use in the production of the hair-conditioning
shampoos according to the invention.
PRODUCT F
Placed into a heatable and coolable agitator vessel,
equipped with a reflux cooler and a thermometer, are 180 kg. of
liquid polyglycol 600. At a temperature of approximately 30C
and with agitation, 2.7 kg. of tin tetrachloride are slowly
added to the same. After raising the heat to 68-78, 56 kg.
of epichlorohydrin are added with steady s-tirring and possible
cooling so quickly that the temperature of the mixture remains
between 68 and 70. Agitation is continued for an hour at
temperatures of approximately 70. The total quantity of the
obtained crude polyglycol-bis-chlorohdyrin ether amounts to
239 kg.
80 kg. of the obtained crude chlorohydrin ether are
placed in a second agitator vessel with a capacity of approxi-
mately 600 liters, capable of heating and cooling and equipped
with a thermometer and reflux cooler, and combined in the
presence of agi-tation wi-th 13.2 kg. of dipropylene triamine,
50 kg. of water and 28 kg. of caustic soda solution. The vessel
is then heated for 45 Minutes to the boiling point, with reflux
- 4b -
72~
cooling. The quantity of crude chlorohydrin ether of the poly-
glycol 600 remaining in the first vessel is then added with -the
application oE agitation and kept at boiling for an additional
20-30 minutes after the addition of a further 30 kg. of water.
the pH of the viscous reaction product is reduced during this
time to about 7.2. Vigorous cooling is then applied. The pH
is adjusted during cooling to 5.5-6 via the addition of approxi-
mately 38 kg. of 10% aqueous hydrochloric acid solution. The
yield is about 400 kg. of a slightly yellowish, slightly opaque
and highly viscous liquid. One product of this type is commer-
cially available for example under the name of Polyquart H(R).
The esterification produc-ts of ethylene oxide adducts
of glycerol and 4 to 20 moles of ethylene oxide with 1 to 2
moles of a C8-C18 fatty acid are known from DE-AS No. 20 24 051.
Of the esterification products mentioned therein, a partial
ester obtained by the addition of 7.4 moles of ethylene oxide
with 1 mole of glycerol, followed by the esterification of 1
mole of the resulting adduct with 1 mole of C8-C18 coconut oil
fatty acid, is particularly suitable for use in the hair-
conditioning shampoos according to the invention. A product
having this composition i5 commercially available for example
under the name of Ce-tiol HE(R).
Polyvinyl pyrrolidones having an average molecular
weight in the range of 10,000 to 70,000 are commercially avail-
able for example under the names Kollidon(R) and Luviskol(R).
Polyvinyl pyrrolidones having an average molecular weight
- 4c -
"Y~ .tl
~2~
of approximately 40.000, corresponding -to a K-value of approx-
imately 30, are particularly suitable for the production of the
hair-conditioning shampoos according to the invention.
The concentration of the above mentioned mixture of
essential conditioning agents in the final shampoo may range
from 1.7 ~ 14~ by weight, and a range from 2 - 8~ by weight is
preferred.
The ratio of the various essential conditioning agents
mentioned above may vary. Generally, the ratio will be about
l part of the guar derivative to 0,5 - 4 parts of Polyquart(R)H
to 0,5 - 4 parts of Cetiol~)HE to 0,15 - 0,5 parts of PVP.
The hair-conditioning shampoos according to the in-
vention preferably contain as water so],uble anionic washing-
active substances alkalimetal, magnesium, ammonium and/or C2-C3
alkanolammonium salts of alkyl sulfuric acid semi-esters con-
taining from 8 to 18 and preferably from 12 to 16 carbon atoms
in the alkyl radical or of alkyl polyglycol ether sulfuric acid
semi esterscontaining from 8 to 18 and preferably from 12 to 16
carbon atoms in the alkyl radical and from l to 6 glycol ether
groups in the molecule. Other suitable anionic washing-active
substances are primary and secondary linear alkane sulfonates
containing from 10 to 18 carbon atoms, alkene sulfonates and
hydroxy alkane sulfonates of the type obtained in the sulfonation
of olefins containing from 10 to 18 carbon atoms, C8 - Cl8
fatty acid alkylol amide polyglycol ether sulfates, C8 - Cl8
fatty acid monoglyceride sulfates, sulfosuccinic acid monoalkyl
esters containing from 8 to 18 carbon atoms in the alkyl group
or dialkyl esters con-taining from 6 -to 10 carbon atoms in the
alkyl groups, alkyl polyglycol ether carboxylates containing
from 8 to 18 carbon atoms in the alkyl group and 2 to 6 polygly-
~,~ -5-
'7Z~
col ether groups in the molecule and acyl sarcosines, acyl
taurides and acyl isethionates containg from 8 -to 18 carbon
atoms in the acyl group.
In general, the concentration of anionic surfactants
in the shampoo may range from about 5 to about 50% by weight;
a preferred range is about 8 to about 30% by weight.
A preferred anionic surfactant comprises a mixture of
sodium lauryl polyglycol ether sulfate and fatty alcohol sulfate
in a ratio of about 2:1 to 1:1 by weight. The fatty alcohol
sulfate preferably contains an alcohol moiety with about 10
14 C-atoms, preferably 1~ - 14 C-atoms. The ratio of the total
amount of anionic surfactants present to the mixture of essen-
tial conditioning agents may vary from about 10 : 1 to 1 : 1,
preferably from 2,5 : 1 to 1,5 : 1.
In addition, the hair-conditioning shampoos according
to the invention may contain standard additives and set-up
agents, such as for example thickeners of the C8 - C18 fatty
acid alkylolamide type, opacifiers, for example of the ethylene
glycol distearate type, pH-stabilisers, such as alkali or ammon-
ium phosphates or citrates, preservatives, such as formaldehydeor p-hydroxybenzoic acid esters, dyes, fragrances and known
hair-cosmetic active substances, such as anti-dandruff agents
or sebostatics.
The hair-conditioning shampoos having the composition
according to the invention are distinguished by an unexpectedly
marked improvement in the hair-conditioning properties of hair
washed with them. For example, the so-called wet combability
of the hair conditioning shampoos according -to the invention is
considerably improved in relation to shampoos containing only
one of the conditioning components, e.g. Cosmedia Guar(R) C 261.
~2~72~3
This is the more surprising as the other essential ingredien-ts
have little or no influence on wet-combability themselves.
Similar surprising synergistic effects can be observed if the
parameters sheen, feel, and antistatic properties, the so-called
"conditioning effect", are investigated.
Also the feel (elasticity) and sheen of the dry hair
are improved by the shampoosaccording to the invention to a
greater extent than wi-th conventional shampoos containing for
example only one of the components required in accordance with
the invention. Finally, the tendency of the hair to develop
an electrostatic charge after drying is considerably reduced
by using the conditioning shampoo according to the invention.
The hair tends less to "fly away", can be combed more easily
and retains its shape for longer periods.
The hair-cosmetic effects obtained with a hair con-
ditioning shampoo according to the invention are shown in the
following examples by comparison with conventional shampoos.
EX~IPLES
Shampoo formulations according to the invention (Nos.
1 to 3) are compara-tively tested with analogous shampoo formu-
lations containing none (No. 10) or only part (Nos. 4 to 9) of
the necessary components of the shampoos according to the in-
vention.
The performance-tested shampoo formulations are set
out in Table 1.
EXAMPLE 1
Determination of wet-combability (laboratory test)
Wet-combability was determined by measuring the resis-
-tance to combing, i.e., the force required to draw a comb through
a tuft of hair. A modified tensile testing machine (type 1402
~ j,~ . ~g
~ Z -7-
as manufactured by the Zwick Company of Einsingen ~ber Ulm/
Danube) was used. The test arrangement is described in
"Riechstoffe, Aromen, Kosmetika, No. 12/1977", page 325,
columns 2 and 3.
Standardized strands oE hair which had been pre-
damaged by bleaching and permanent-waving under defined con-
ditions were used. They were washed with the shampoos set ou-t
in Table 1 in hand-warm water and rinsed with clear water.
In order to minimize error, the resistance to combing
was determined 15 times with each of the shampoos to be tested
and the average values calculated. The average combing resis-
tance values are quoted in percent of the blank value. The
blank value was determined after shampooing with an aqueous
solution containing 10% by weight of sodium lauryl ether di-
ethenoxy sulfate and rinsing with clear water.
p ~ -7a-
'7~
* *
* ~C *
`CrD 1-- Ct tu iD 3 _ ** ~ tn r ~7 r
~r~ 8 ~- ic * Y ~ N ~, N
O 1~'C O G ~ X * * --~Dt rrDt ~ G~ ~
c O 1-- ~ ~r ~q t~ * O rt ~ Y O
:: D rt ri) ~ ~_ ~ Y iD ~h rt Y
`.1 r O ~ ol~O _ N rD
C ~_r ~D G ct o r O
GO 'C ~ ~u ~ . . ~ ( D ~:
D~ r) rt 3 ~
0 o ~0 0
rD'1 r 1 0 0 0 O ~ Y~) ___ ____
D) O ~n o~ t~) ~ ~ a~ ul o o o U~ ~n ~3
3 0 0 Ul l O O O O 1-- W 1~) _ _ ___ N W
O r ~t oP O i~ ~ r ~ O o O O O t'
r~ rD r~ ~ O O O O ~ ~ O . _ _ ~:~
r -` d t~ ~ r~ _ _ _l ~_.
rD D ~ D O O O I Y I I w ~ U
a~ a ~ r ~ r-- -- . O Ul ~n
rt rD ~ o D O O O I I ~ I w r~ u~ ul
O , ~P . ~ rD __.__._ __ _
O - r? vl ~ O O O ) I I)_ ~ ~ ~n r~
D~ o\ ~ ~ rD
O ~; ~ ~ O O o . I I I . __ _
,~ O;o ~ ~ r~ (n O ' Ul U~
'C ~ Cr) O O O O N I ~-- _ ._ _ D
O -- _________ _ . _ _._.____ __
~C .~ r~ o O ~ ~ I w ~ ~ ~D
rt __._ _ ___ ._._~_. a~ o O ~__~ __
~ . ....r~ ~:> c) ;~ l l l l ~ ~ ~n Y
3 o~ ~ ~ r~ . o
~..
r
~æ~
E~AMPLE 2
Testing of hair-cosmetic properties (salon test)
The testing and assessment of the hair-cosmetic
properties were carried out on 10 test subjects differing from
one another in the quality of their hair using the so-called
half-side test. The test was carried out by a trained hair-
dresser. The half-side test is used for the comparative test-
ing of two hair treatment preparations or one hair treatment
preparation and one standard on test subjects. In the present
tests, hair shampoo No. 1 according to the invention was used
as the standard. The comparison marks given in Table 2 are
a measure of the extent to which hair shampoos Nos. 4 to 10
differ from the assessment of shampoo No. 1.
Procedure and evalution
The hair of the test subjects was wetted and parted
in the middle. The standard shampoo was applied to the left-
hand half or the heads of 5 of the test subjects and the com-
parison shampoo to the right-hand half in equal quantities of
5 g in each case (pre-wash). In the case of the other 5 test
subjects, the other half of their heads was treated with the
same product. Both sides were shampooed in the same way and
rinsed with water. For the main wash, the shampoos were applied
once again to the same half of the head in quantities of 2.5 g,
rubbed in to form a lather and thoroughly rinsed out with clear
water.
During and after washing, the criteria set out in
Table 2 below were separately assessed by the hairdresser for
each of the two sides. Assessment was carried out by the
awarding of marks (1 - excellent, 2 - good, 3 - moderate,
4 - poor~. From the marks awarded for the 10 test subjectsr
7~
the average values were calculated for the same product. The
average values for the standard product were subtracted from
the average vaiues for the comparison product. The pair
difference thus obtained in the average values of the assess-
ments of 10 test subjects is shown in Table 2 below.
Result: The comparison shampoos were all judged to be poorer
in their hair-cosmetic properties than the standard
shampoo (shampoo No. 1 according to the invention).
T A B L E 2
Comparison with shampoo No. 1
(pair difference)
Salon tests 1 4 5 6 7 8 9 10
Wet hair
Combability + 0 -1.2 -0.6 -0.4 -1.0 -0.4 -0.6 -1.2
Feel + 0 -0.9 -0.8 ~0.3 -0.8 -0.5 -0.8 -0.8
_
Dry hair
Antistatic + 0 -0.5 -0.3 -0.5 -0.6 -0.1 -0.3 -0.6
Feel + 0 -0.5 -0.4 -0.6 -0.3 -0.5 -0.3 -0.6
(elasticity)
S!leen + 0 -0.5 -0.3 -0.2 -0.5 -0.4 _ 0.5
.~, .
: --
, ,~ .
--10--
