Note: Descriptions are shown in the official language in which they were submitted.
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HAIR CAR~ PR~PARATION8
This invention relates to hair-treatment preparations
containing zwitterionic polymers.
After washing, dyeing, or permanent waving, hair often
shows unsatisfactory wet and dry combability, in addition
to which the curl retention capacity of dry hair is inade-
quate. To remedy this drawback, either appropriate com-
ponents have to be added to the hair treatment prepara-
tions, or the hair has to be subsequently subjected to a
separate treatment with these substances which, for this
purpose, are normally formulated as a rinse.
Polymeric compounds are frequently used as active sub-
stances of the type in question to improve the properties
of hair.
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Although cationic polymers, such as for example the
cellulose derivatives known from US Patents 3,816,616 and
3,472,840, are capable of distinctly improving wet comb-
ability, they effect only unsati~factory hair-~etting and
style-holding effects.
The use of zwitterionic polymers containing anionic
groups, mostly carboxyl groups, and quaternary ammonium
groups in the molecule in hair-treatment preparations is
also known. For example, DE-OS 21 50 557 describes the use
of polymers of zwitterionic monomers in hair-setting prep-
arations. The use of copolymers of dimethylaminoethyl
methacrylate, acrylic acid and methyl methacrylate in hair-
setting lotions and shampoos is also known from DE-OS 28 17
369.
These known zwitterionic polymers in hair-treatment
and hair-setting preparations have the disadvantage, par-
ticularly in formulations with anionic surfactants, that
their hair-conditioning and hair-setting properties are
gradually lost in the event of prolonged storage. Accord-
ingly, it was proposed in DE-OS 37 08 451 to use zwitter-
ionic polymers consisting of 30 to 70% monomers containing
quaternary ammonium groups, 10 to 30% monomeric olefinical-
ly unsaturated carboxylic acids, 10 to 30% monomeric ole-
finically unsaturated carboxylic acid esters and 0 to 40%
monomers containing tertiary amino groups. These polymers
are highly compatible with anionic and cationic surfactants
and have good hair-conditioning and style-holding proper-
ties.
Although, therefore, suitable polymers are available
for obtaining the desired effect~ on the hair, these poly-
mers are made up of at least 3 or 4 monomers. According-
ly, there is ~till a need for polymers which, for compar-
able properties, are less complex in structure, i.e. can be
synthesized from a smaller number of different monomers.
It has now surprisingly been found that certain zwit-
terionic polymers of monomers containing quaternary ammon-
ium groups and monomeric carboxylic acids have wet-comba-
2066226
bility-improving, hair-conditioning and style-holding
properties which, hitherto, have only been achieved with
polymers of a larger number of different monomers. In
addition, it is possible with these polymers to formulate
hair-treatment preparations based on anionic and/or ampho-
teric surfactants which, on the basis of their effect on
the wet combability of hair, correspond in their perform-
ance level to known cationic rinses.
Accordingly, the present in~ention relates to water-
based hair-treatment preparations containing zwitterionic
polymers, characterized in that the zwitterionic polymers
are essentially made up of
A) monomers containing quaternary ammonium groups corre-
sponding to general formula (I)
R1-CH=CR2-Co-Z-(CDH2n)-N(+)R3R4RS A( ) (I)
in which R1 and R2 independently of one another rep-
resent hydrogen or a methyl group and R3, R4 and R5
independently of one another represent Cl_4 alkyl
groups, Z is an NH group or an oxygen atom, n is an
integer of 2 to 5 and A( ) is the anion of an organic
or inorganic acid
and
B) monomeric carboxylic acids corresponding to general
formula (II)
R6-CH=CR7-CooH (II)
in which R6 and R7 independently of one another are
hydrogen or methyl groups.
Suitable starting monomers are, for example, dimethyl-
aminoethyl acrylamide, dimethylaminoethyl methacrylamide,
dimethylaminopropyl acrylamide, dimethylaminopropyl meth-
acrylamide, and diethylaminoethyl acrylamide in cases where
Z i8 an NH group or dimethylaminoethyl acrylate, dimethyl-
aminoethyl methacrylate, and diethylaminoethyl acrylate in
cases where Z is an oxygen atom.
35¦ The monomers mentioned are prepared by known methods
of the type described, for example, in US Patent 3,878,247,
DE-PS 28 19 735, DE-PS 28 36 520, DE-PS 34 02 59g or CH-
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PS 464 891.
The monomers containing a tertiary amino group are
then quaternized in known manner, methyl chloride, dimethyl
sulfate or diethyl sulfate being particularly suitable al-
kylating reagents. The quaternization reaction may takeplace in aqueous solution or in a solvent. Suitable pro-
cesses are described, for example, in DE-OS 33 30 326, DE-
oS 25 37 378, or DE-OS 32 44 274.
It is of advantage to use monomers corresponding to
formula (I) which are derivatives of acrylamide or meth-
acrylamide. Other preferred monomers are those which
contain halide, methoxysulfate, or ethoxysulfate ions as
counterions. Monomers of formula (I), in which R3, R4 and
R5 are methyl groups, are also preferred.
Acrylamidopropyl trimethyl ammonium chloride is a
particularly preferred monomer of formula (I).
Suitable monomeric carboxylic acids corresponding to
formula (II) are acrylic acid, methacrylic acid, crotonic
acid and 2-methyl crotonic acid. Acrylic acid or meth-
acrylic acid are preferred, acrylic acid being particularlypreferred.
The zwitterionic polymers according to the invention
are prepared from monomers corresponding to formulae (I)
and (II) by polymerization processes known per se. The
polymerization may be carried out either in aqueous solu-
tion or in aqueous/alcoholic solution. The alcohols used
are Cl_~ alcohols, preferably isopropanol, which simultan-
eously act as polymerization regulators. However, other
components may be added to the monomer solution as regula-
tors, including for example formic acid or mercaptans, suchas thioethanol and thioglycolic acid. The polymerization
i8 $nitiated by radical-forming ccmpounds. Redox systems
and/or thermally decomposing radical formers of the azo
compound type, such as for example azoisobutyronitrile,
azo-bis-(cyanopentanoic acid) or azo-bis-(amidinopropane)-
dihydrochloride, may be used for this purpose. Suitable
redox systems are, for example, combinations of hydrogen
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peroxide, potassium or ammonium peroxodisulfate and ter-
tiary butyl hydroperoxide with sodium ~ulfite, sodium di-
thionite or hydroxylamine hydrochloride as reducing com-
ponent.
The polymerization may be carried out isothermally or
under adiabatic conditions, the reaction temperature being
variable over the range from 20 to 200 C, depending on
the concentrations used, through the heat of polymerization
released. The reaction may have to be carried out under
the excess pressure spontaneously established. The reac-
tion temperature is preferably in the range from 20 to 100
o C.
The pH value during the copolymerization may vary over
a wide range. Polymerization is advantageously carried out
at low pH values, although it may also be carried out at pH
values above the neutral point. On completion of polymer-
ization, the reaction mixture is adjusted to a pH value of
5 to 10 and preferably 6 to 8 with an aqueous base, for ex-
ample sodium hydroxide, potassium hydroxide or ammonia.
Further particulars of the polymerization process can be
found in the Examples.
Polymers in which the monomers of formula (I) were
present in an excess over the monomers of formula (II) have
proved to be particularly effective. In a preferred em-
bodiment of the invention, therefore, the polymers used
consist of monomers corresponding to formula (I) and mon-
omers corresponding to formula (II) in a molar ratio of
60:40 to 95:5 and, more particularly, 75:25 to 95:5.
The zwitterionic polymers mentioned are preferably
present in the preparations according to the invention in
guantities of 0.1 to 10% by weight, based on the prepara-
tion as a whole. The polymers are very effective in im-
proving wet combability, even in low concentrations. ~y
contrast, their hair-conditioning and hair-setting effects
in most cases are cnly observed with concentrations above
about 1 % by weight. Accordingly, it is particularly pre-
*erred to use the polymers in quantities of about 1 to 5%
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by weight.
The zwitterionic polymers according to the invention
are preferably used in water-based preparations containing
surface-active compounds. Preferred surface-active com-
pounds are anior.ic, zwitterionic, amphoteric and/or non-
ionic surfactants.
Suitable anionic surfactants for the hair-treatment
preparations according to the invention are any anionic
surface-active compounds suitable for use on the human
body. They are characterized by a water-solubilizing an-
ionic group such as, for example, a carboxylate, sulfate,
sulfonate, or phosphate group and a lipophilic alkyl group
containing about 10 to 22 carbon atoms. In addition, gly-
col ether or polyglycol ether groups, ester, ether, and
amide groups and also hydroxyl groups may be present in the
molecule. Examples of suitable anionic surfactants are the
sodium, potassium, and ammonium salts and the mono-, di-
and tri-alkanolammonium salts - containing 2 or 3 carbon
atoms in the alkanol group - of:
20 - linear fatty acids containing 10 to 22 carbon atoms
(soaps);
- ether carboxylic acids corresponding to the formula
R-O-(CH2CH20)~-CH2-COOH, in which R is a linear C10_22
alkyl group and x = 0 or 1 to 10;
25 - acyl sarcosides containing 10 to 18 carbon atoms in
the acyl group;
- acyl taurides containing 10 to 18 carbon atomQ in the
acyl group;
- acyl isethionates containing 10 to 18 carbon atoms in
the acyl group;
- sulfosuccinic acid mono- and di-alkyl esters contain-
ing 8 to 18 carbon atoms in the alkyl group and sulfo-
succinic acid monoalkyl polyethoxyl esters containing
8 to 18 carbon atoms in the alkyl group and 1 to 6
ethoxyl groups;
- linear alkanesulfonates containing 12 to 18 carbon
atoms;
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- linear ~-olefin sulfonates containing 12 to 18 carbon
atoms;
- ~-sulfofatty acid methyl esters o~ fatty acids con-
taining 12 to 18 carbon atoms,;
- alkylsulfates and alkyl polyglycol ether sulfates cor-
responding to the formula R-O(CH2-CH20)~-OSO3H, in
which R is a preferably linear alkyl group containing
10 to 18 carbon atoms and x = O or 1 to 12;
- mixtures of surface-active hydroxysulfonates according
to DE-OS 37 25 030;
- sulfated hydroxyalkyl polyethylene and/or hydroxyal-
kylene propylene glycol ethers according to DE-OS 37
23 254;
- esters of tartaric acid and citric acid with alcohols
which are adducts of about 2 to 15 molecules of ethyl-
ene oxide and/or propylene oxide with fatty alcohols
containing 8 to 22 carbon atoms.
Preferred anionic surfactants are alkyl sulfates and
alkyl polyglycol ether sulfates containing 10 to 18 carbon
atoms in the alkyl group and up to 12 glycol ether groups
in the molecule.
Zwitterionic surfactants are surface-active compounds
which contain at least one quaternary ammonium group and at
least one -COO(~) or -S03(-) group in the molecule. Particu-
larly suitable zwitterionic surfactants are the so-called
betaines, such as N-alkyl-N,N-dimethyl ammonium glycinates,
for example coconut oil alkyl N,N-dimethyl ammonium glycin-
ate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates,
for example coconut oil acylaminopropyl-N,N-dimethyl am-
monium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxy-
ethyl imidazolines containing 8 to 18 carbon atoms in the
alkyl or acyl group, and also coconut oil acylaminoethyl
hydroxyethyl carboxymethyl glycinate.
Amphoteric surfactants are understood to be surface-
active compounds which, in addition to a C8_18 alkyl or acyl
group, contain at least one free amino group and at least
one -COOB- or -S03B- group in the molecule and which are
20~6226
capable of forming inner salts. Examples of suitable am-
photeric surfactants are N-alkyl glycines, N-alkylamino-
propionic acids, N-alkylaminobutyric acids, N-alkyliminodi-
propionic acids, N-hydroxyethyl-N-alkylamidopropyl gly-
cines, N-alkyl taurines, N-alkyl sarcosines, 2-alkylamino-
propionic acids, and alkylaminoacetic acids containing
about 8 to 18 carbon atoms in the alkyl group.
Nonionic surfactants are, above all, the adducts of 2
to 20 moles of ethylene oxide with preferably linear alco-
hols containing 12 to 18 carbon atoms, with alkylphenolscontaining 8 to 15 carbon atoms in the alkyl group, with
fatty acids containing 12 to 18 carbon atoms, with fatty
acid partial glycerides, with fatty acid sorbitan partial
esters, with fatty alkanolamides, and with methyl glucoside
fatty acid esters. Other suitable nonionic surfactants are
alkyl(oligo)glycosides, alkylamine oxide surfactants, and
fatty acid alkanolamides.
Cationic surfactants may also be present in the prep-
arations according to the invention providing they are com-
patible with the other components, for example anionic sur-
factants. Such cationic surfactants are known, for exam-
ple, from DE-OS 34 42 175.
The preparations according to the invention preferably
contain surface-active compounds in quantities of 0.1 to
40 % by weight, based on the preparation as a whole.
By virtue of their favorable hair-conditioning and
hair-setting properties and their compatibility with the
sub6tances typically used in hair-treatment preparations,
the zwitterionic polymers according to the invention are
suitable as setting and hair-conditioning components in any
standard water-based hair-washing and hair-care prepara-
tions, æuch as for example shampoos, after-rinses, hair
setting lotions, hair setting gels, and water-based color-
ing, permanent-wave, and permanent-wave fixing prepara-
tions.
Accordingly, the water-based hair-washing and hair-
care preparations according to the invention may contain
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any standard auxiliaries and additives for the particular
application envisaged in addition to the compulsory zwit-
terionic polymers.
For hair rinses, such auxiliaries and additives are,
for example, cationic surfactants, more particularly sur-
face-active quaternary ammonium salts, fatty alcohols con-
taining 12 to 22 carbon atoms, fatty acid partial glycer-
ides, cosmetic oil and fatty components, and water-soluble
polymers having a thickening effect. For hair setting lo-
tions and hair setting gels, the auxiliaries and additives
in question are, for example, cationic surfactants, cation-
ic, nonionic, or anionic polymers, and lower alcohols.
Hair-dyeing preparations contain substantive dyes or oxida-
tion dye precursors, anionic or nonionic surfactants, am-
monia or alkanolamines, and, optionally, antioxidants.
Permanent-wave fixing preparations contain an oxidizing
agent, for example H202, H202 adducts, or potassium bromate,
and also anionic or nonionic surfactants.
The preparations according to the invention preferably
have a pH value of 4 to 10 and, more preferably, 5 to 9.
The following Examples are intended to illustrate the
invention without limiting it in any way.
~pl-~
1. Preparation of a polymer of acrylamidopropyl tri--thyl
~-monium ohlorid- an~ aoryl~c aoid in a ~ol~r ratio of
3s1 ~polyn r Pl).
201.17 kg of water, 89.59 kg of a 60% by weiqht aque-
ous solution of acrylamidopropyl trimethyl ammonium chlor-
ide and 6.25 kg of acrylic acid were introduced into a re-
actor equipped with an impeller stirrer, a heating and
cooling system, a reflux condenser, and a temperature mea-
surinq instrument. A pH value of 3.4 was spontaneously es-
tablished. The solution was purged with nitrogen and then
heated to 60 C. Solutions of 0.06 kg of azo-bis-(amidin-
opropane)-dihydrochloride in 1.00 kg of water, 0.024 kg of
potassium peroxodisulfate in 1,000 kg of water, and 0.012
kg of sodium disulfite in 1,000 kg of water were then suc-
206622~
cessively added to the mixture with stirring. Only slight
heating occurred. The reaction mixture was heated to 80 -
85 C and kept at that temperature for 4 hours. The pol-
ymerization was then terminated. The viscous solution was
S cooled to 30-40 C and neutralized with 5,000 kg of 45%
aqueous sodium hydroxide.
The clear colorless polymer solution had the following
characteristic data: pH value 6.9, dry matter 20%, product
viscosity 13,800 mPa s, intrinsic viscosity 220 ml/g (in
10% NaCl solution).
2. Applioation~ Ex~ples
2.1. Hair rinse No. 1
Components % by weight
Fatty alcohol (C12_l4) poly(3EO)glYcol ether
lS sulfate, Na salt, 28% aqueous solution S.o
Coconut oil acyl(C 2_l8)aminopropyl di-
methyl glycine, 30~ aqueous solution 1.0
Polymer Pl (20% active substance in water) 2.5
Water ad 100
The rinse is in the form of a cloudy solution. The
wet combability of hair treated with this rinse was very
good. No adverse effect on the hair or static charging of
the hair was observed.
2.2 Hair rinse No. 2
Components % by weight
Fatty alcohol (C~ ) poly(3 EO)
glycol ether sulfate, Na salt,
28% aqueous solution 5.0
DehytonO AB 30l 1.0
Polymer Pl (20% active substance in water) 2.5
Water ad 100
Fatty amine derivative of betaine structure, approx.
30% active substance in water, CTFA name: coco-betaine
(HENKEL)
The rinse is in the form of a cloudy solution. The
wet combability of hair treated with this rinse was very
2~66226
good.
2.3 Hair rinse No. 3
Components % by weight
Sulfosuccinic acid semiester based on a
Cl2-l~ alkyl poly(3 EO)glycol ether, di-
sodium salt (40% active substance in water,
CTFA name: disodium laurethsulfosuccinate 0.9
Texapon~ K14 S spez.2 1.2
Dehyton~ AB 30 1.0
Polymer P1 (20% active substance in water) 2.5
Water ad lO0
2 Sodium lauryl myristyl ether sulfate, about 30% active
substance in water (HENKEL)
The wet combability of hair treated with this rinse
was good to very good.
2.4 Hair rinse No. 4
Components % by weight
Sulfosuccinic acid semiester based on a
Cl~ alkyl poly(3 EO)glycol ether, di-
so~lum salt (40% active substance in water),
CTFA name: disodium laurethsulfosuccinate l.0
DehytonD AB 30 7.5
Polymer P1 (20S active substance in water) 2.5
Water ad 100
The rinse is present in the form of an almost clear
solution. The wet combability of hair treated with this
rinse was very good.
2.S Hair rinse No. 5
Components % by weight
C16_l8 fatty alcohol 3.0
Coconut oil acyl(C 2_18)aminopropyl di-
methyl glycine, 30~ agueous solution 8.0
Fatty alcohol (C12_1~) poly(3 EO)glycol
ether sulfate, Na salt, 28% agueous
3S solution S.0
Polymer P1 (20% active substance in water) 2.5
Water ad lO0
11
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To prepare this hair rinse, the mixture of surfactants
and polymer was introduced into the molten fat phase and
emulsified therein. The wet combability of hair treated
with this rinse was excellent.
2.6 Hair shampoo No. 1
Components % by weight
Fatty alcohol (C12_14) poly(3 EO)glycol
ether sulfate, Na salt, 28% aqueous solution 50.0
Coconut oil acyl(Cl2_1B)aminopropyl di-
methyl glycine, 30% aqueous solution 10.0
Polymer Pl (20% active substance in water) 5.0
Water ad 100
The wet combability of hair shampooed with this prepa-
ration was excellent.
2.7 Hair shampoo No. 2
Components % by weight
Fatty alcohol (Cl2_14) poly(3 EO)glycol
ether sulfate, Na salt, 28% aqueous solution 45.0
Coconut oil acyl(C12_1~)aminopropyl di-
methyl glycine, 30% aqueous solution 15.0
Akypo~ RLM 100 NV3 5.0
Polymer Pl (20% active substance in water) 5.0
Water ad 100
3 Aqueous solution of Cl2_l~ alkyl-O-(CH2-CH2-O)l0-CH2-
CO~ONa, 22% active substance (CHEM-Y)
This sha~poo not only freed the hair from soil and
grease, it al50 had a distinct conditioning effect on wet
hair and left dry hair with body and volume.
To quantify the effect obtained by the polymer, a lS
cm long strand of hair (2 g) was wound onto a glass tube
having a external diameter of 1.7 cm, fixed and treated
with 0.2 g of the shampoo. The hair strand was then rinsed
with water and dried. A measure of the stability of the
curl obtained after withdrawal of the glass rod is the curl
retention value. The curl retention value is defined as
t(l-l~)/(l-lo)] * 100% where 1 is the length of the hair
12
2~66226
strand (15 cm~, lo i8 the length of the hair curl immediate-
ly after drying and 1~ is the length of the hair curl after
storage for 48 h under constant conditions (30C/40% rela-
tive air humidity) in a drying cabinet. The curls treated
with the shampoo according to the invention had a curl re-
tention value of 94.7% whereas curls treated with a similar
shampoo to which polymer P1 had not been added showed a
curl retention of only 87.1%.
2.8 Hair shampoo No. 3
Components % by weight
Texapon~ K14 S spez. 15.0
Sulfosuccinic acid semiester based on a Cl _lq
alkyl polyglycol (3 EO) ether, disodium sa~t
(40% active substance in water), CTFA name:
disodium laurethsulfosuccinate 12.0
Ethoxylated (g EO) palm kernel oil fatty
acid 1.0
Alkyl glucoside APG-600 4.0
Dehyton0 CBs 9-7
Polymer Pl (20% active substance in water) 5.0
Water ad 100
q Aqueous solution of RO(Z)~ with Z = glucose, x = 1.4
and R = n-alkyl(Cl2_l4), (50% active substance)
(HORIZON)5 s Aqueous solution of a fatty amine derivative of
betaine structure, CTFA name: coco-betaine (approx.
31% active substance, approx. 6.5% NaCl) (HENKEL)
The shampoo is clear and colorless. This shampoo had
an excellent conditioning effect on the hair.
2.9 Hair shampoo No. 4
Components % by weight
Sulfosuccinic acid semiester based on a Cl _lq
alkyl polyglycol (3 EO) ether, disodium sa~t
(40% active substance in water), CTFA name:
disodium laurethsulfosuccinate 12.0
Ethoxylated (9 EO) palm kernel oil fatty
acid 1.0
Dehyton0 CB 10.0
13
2~66226
Eucarol~ TA6 20.0
Polymer Pl (20% active substance in water) 1.2
Water ad 100
6 Aqueous solution of sodium laureth-7-tartrate, 25%
active substance (ROL)
This clear shampoo was distinguished in particular by
an excellent conditioning effect coupled with a good clean-
ing effect.
2.10 Hair shampoo No. 5
Components % by weight
Sulfosuccinic acid semiester based on a C~
alkyl polyglycol (3 EO) ether, disodium sa~t
(40% active substance in water), CTFA name:
disodium laurethsulfosuccinate 15.0
Dehyton~ C~ 12.0
Alkyl glucoside APG-600 4.0
Polymer Pl (20% active substance in water) 1.2
Water ad 100
This clear shampoo left the shampooed hair with very
good wet combability.
