Note: Descriptions are shown in the official language in which they were submitted.
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Hair styling composition
The present invention relates to hair setting compositions comprising special
polyurethanes, and to the use of said polyurethanes for the preparation of
hair
setting compositions.
For shaping and stabilizing diverse hair styles, products are used which are
known
as hair setting compositions. Hair setting compositions are mostly in the form
of
setting mousses or hairsprays. Setting mousses and hairsprays differ little in
their
composition, but do differ in their application. Setting mousses are applied
to damp
hair as aids for modelling the hair style. In contrast to this, the hairsprays
are
sprayed onto dry ready-styled hair for fixing the hair style. Besides
hairsprays and
setting mousses, hair setting gels are also supplied.
In the case of hairsprays and setting mousses, the compositions for fixing or
shaping the hair style are usually in the form of preparations which can be
sprayed
from aerosol containers, squeezy bottles or by pump, spray or foaming devices
which consist of an alcoholic or aqueous-alcoholic solution of film-forming
natural
or synthetic polymers. These polymers can be selected from the group of
nonionic,
cationic, amphoteric or anionic polymers. In the case of hair setting gels,
the
preparations described above are adjusted to an acceptable viscosity using
conventional thickeners.
During the formulation of cosmetic products, it is to be taken into
consideration, as
in the case of technical applications such as, for example, with paints, that,
on
account of the environmental regulations for controlling the emission of
volatile
organic compounds (VOCs) into the atmosphere, the proportion of propellants
has
to be reduced. Within the context of the present patent application, VOCs are
understood as meaning organic, i.e. carbon-containing substances, which
readily
evaporate (are volatile) and/or are even in the form of a gas at low
temperatures
(e.g. room temperature (23 C)). According to the invention, the VOCs include
in
particular organic substances with boiling points in the range from -90 to
300 C,
in particular volatile hydrocarbons (e.g. propane, butane, isobutane, pentane,
etc.),
volatile ethers, such as dimethyl ether, volatile alcohols, such as methanol,
ethanol,
isopropanol and n-propanol and volatile amines. In particular, the proportion
of
VOCs through amines and organic solvents such as alcohols should be reduced in
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the cosmetic formulations, for example by replacing alcohols with water.
The film-forming polymers used in the prior art are preferably anionic or
amphoteric polymers based on acrylates. The use of conventional acrylates in
low-
VOC hair setting formulations leads to problems with the stability of low-VOC
compositions, such as sedimentation, separation etc. as is known to the person
skilled in the art.
Furthermore, the conventional film-forming polymers exhibit low moisture
and/or
water resistance when the hair is in contact with rain or perspiration, and/or
upon
contact with moisture or under the influence of high atmospheric humidity,
e.g.
while bathing.
The use of polyurethanes in hair setting compositions is known. EP 1049446 A
describes the use of certain polyurethanes in a hair care aerosol composition,
where the valve, the opening and also the initial throughput of the aerosol
composition are defined. Similarly, EP 1049443 A describes the use of certain
polyurethanes in hair care aerosol formulations, where the formulations
consist of
0.1 to 20% of polycondensate or polyurethanes and/or polyurea, 7.5 to 70% of
organic solvent, 15 to 85% of propellant and 0.01 to 20% of at least one
polyol. In
the patents cited above, it was found that the sprayability of the hair
aerosol is
improved compared to the prior art.
EP 1652509 A describes a gel which comprises at least one polyurethane with a
molecular weight between 400 000 and 5 000 000 g/mol and at least one
thickener.
In order to improve the water resistance, the applicant proposes the use of a
polyurethane with a higher molecular weight compared with the polymers of the
prior art. The advantages, described in the invention, of using a polyurethane
with
a high molecular weight were to be expected. However, the use of such a
polymer
in hairsprays and setting mousses is limited by the high molecular weight. The
person skilled in the art is aware that the use of a film former with an
excessively
high molecular weight impairs the sprayability of the formulation.
Polyurethanes for hair setting compositions are also described in the
following
patents: EP 0751162, EP 0637600, FR 2743297, WO 9403510 and EP 0619111.
WO 94/03510, EP 0619111 and EP 637600 describe polyurethanes of at least one
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diol containing acid or salt groups, in particular dimethylolpropanoic acid or
N-
methyldiethanolamine. EP 0751162 and FR 2743297 describe sequential
polyurethane and/or polyurea polycondensates which consist of at least one
polysiloxane block (FR 2743297) or of at least one polyurethane and/or
polyurea
block containing polysiloxane graft branches (EP 0751162), where the
polyurethane block consists of at least one diol containing acid or salt
groups, in
particular dimethylolpropanoic acid.
EP 1457196 A describes a hair care composition for aerosol which consists of
water, at least one organic solvent, at least one polyurethane and at least
one
propellant of dimethyl ether (DME) and at least one C3-4 hydrocarbon. The
preferred polyurethanes consist of a divalent C2-C10 radical containing a
carboxylic acid or sulfonic acid group, preferably dimethylolpropanoic acid.
Luviset
PUR (INCI name: Polyurethane-1) and Luviset Si PUR A (INCI name:
Polyurethane-6 = copolymer of dimethylolpropanoic acid, isophorone
diisocyanate,
neopentyl glycol, polyesterdiol and silicone diamine) are used for improving
the
sensory properties of hair setting sprays.
Similarly to EP 1457196, EP 789550 describes a composition comprising 10 to
60% by weight of DME, 39.9 to 89.9% of water, 0.1 to 15% by weight of
polyurethanes and 0 to 5% by weight of alcohol having 1 to 4 hydrocarbon
atoms.
The polyurethanes used have a similar structure to that in EP 1457196 A.
DE 19541326 A describes water-soluble or water-dispersible polyurethanes of..
a) a water-soluble or -dispersible urethane prepolymer with terminal
isocyanate groups and
b) at least one primary or secondary amine which has at least one ionogenic
or ionic group, and the salts thereof.
The urethane prepolymer is a water-soluble or water-dispersible polyurethane
with
terminal isocyanate groups which has ionogenic or ionic groups bonded to the
polymer chain. The ionogenic or ionic groups can comprise carboxylic acid
groups
and/or sulfonic acid groups and/or nitrogen-containing groups, in particular
dimethylolpropanoic acid. This results in a comparatively high hydrophilicity
of the
urethane prepolymer.
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The primary or secondary amines react with the terminal isocyanate groups of
the
urethane prepolymer and are bonded to the polyurethane via a urea group. The
amines are particularly preferably taurine, N-(1,1-dimethyl-2-hydroxyethyl)-3-
amino-2-hydroxypropane sulfonic acid or 4-aminobenzene sulfonic acid. The use
of said polyurethanes as aids in cosmetics, in particular as hair setting
compositions, is mentioned. Compared to other polyurethane polymers of the
prior
art, the polyurethanes are easier to wash out in experiments on artificial
model
heads.
However, the patents cited above do not mention important properties of the
film
former such as the resistance to moisture or water. The polyurethanes of the
prior
art are hydrophilic especially through use of 2-2-hydroxymethyl-substituted
carboxylic acids, preferably dimethylolpropanoic acid. By neutralizing the
carboxyl
groups on the main chain with amines or alkalis, the incorporation of the
polyurethane into a formulation with a low VOC becomes possible. The more
carboxylate groups present, the more hydrophilic the polymer and thus the
better it
dissolves in a solvent system which comprises a high proportion of water.
Formulations with a low content of VOC are possible with the polyurethanes
described above, but at the expense of important properties such as, in
particular,
curl hold at high humidity. This is because the large number of acid groups in
the
polymer chain accelerates the collapse of the hair style.
Furthermore, in the currently known aqueous systems based on polyurethane,
besides solvents, volatile amines are often also present which are used as
neutralizers. From toxicological points of view, these amines may be critical
for
such an application close to the body.
A further disadvantage of the systems according to the prior art is the large
amount of the corresponding film former which has to be added to achieve the
desired effects. This restricts the freedom when creating the formulation and
can,
moreover, lead to increased costs.
The object of the present invention is therefore to provide a low-VOC hair
setting
composition which has a very high moisture resistance even at a low use
concentration of the polyurethanes and leads to very good curl hold.
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The present invention thus provides in particular low-VOC hair setting
formulations
which have excellent curl hold even at high humidity and at low use
concentrations
of the polyurethane, compared to the hair setting formulations from the prior
art.
It has surprisingly been found that special polyurethanes, in particular
aqueous
polyurethane dispersions comprising them, which are prepared from water-
insoluble, non-water-dispersible, isocyanate-functional prepolymers are
particularly
well suited for achieving the object.
The present invention thus provides a hair setting composition comprising at
least
one polyurethane obtainable by reacting one or more water-insoluble, non-water-
dispersible, isocyanate-functional polyurethane prepolymers A) with one or
more
amino-functional compounds B).
Within the context of the invention, the term "water-insoluble, non-water-
dispersible polyurethane prepolymer" means in particular that the solubility
in
water of the prepolymer used according to the invention at 23 C is less than
10 g/litre, more preferably less than 5 g/litre, and the prepolymer does not
produce
a sedimentation-stable dispersion in water, in particular deionized water, at
23 . In
other words, the prepolymer settles out upon any attempt to disperse it in
water.
Preferably, the polyurethane prepolymer A) used according to the invention has
terminal isocyanate groups, i.e. the isocyanate groups are at the chain ends
of the
prepolymer. All of the chain ends of a prepolymer particularly preferably have
isocyanate groups.
Furthermore, the polyurethane prepolymer A) used according to the invention
preferably has essentially neither ionic nor ionogenic groups, i.e. the
content of
ionic and ionogenic groups is expediently below 15 milliequivalents per 100 g
of
polyurethane prepolymer A), preferably below 5 milliequivalents, particularly
preferably below 1 milliequivalent and very particularly preferably below
0.1 milliequivalent per 100 g of polyurethane prepolymer A).
The amino-functional compounds B) are preferably selected from primary and/or
secondary amines and/or diamines. In particular, the amino-functional
compounds
B) include at least one diamine. The amino-functional compounds B) are
preferably selected from amino-functional compounds B2), which have ionic or
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ionogenic groups, and amino-functional compounds B1), which have no ionic or
ionogenic group.
In a particularly preferred embodiment of the invention, the amino-functional
compounds B) include at least one amino-functional compound B2) which has
ionic and/or ionogenic (ion-forming) groups. The ionic and/or ionogenic group
used
is particularly preferably the sulfonate or the sulfonic acid group, yet more
preferably the sodium sulfonate group.
In a further preferred embodiment of the invention, the amino-functional
compounds B) include both amino-functional compounds B2) which have ionic
and/or ionogenic group, and also amino-functional compounds 131) which have no
ionic or ionogenic group.
Accordingly, polyurethanes within the context of the invention are polymeric
compounds which have at least two, preferably at least three, repeat units
containing urethane groups:
0
-N1O-
H
According to the invention, also included are those polyurethanes which, as a
result of the preparation, also have repeat units containing urea groups:
0
-N1N-
H H
as are formed in particular in the reaction of the isocyanate-terminated
prepolymers A) with the amino-functional compounds B).
The hair setting compositions according to the invention are in particular
water-
containing, i.e. aqueous, compositions in which the polyurethane is present in
dispersed form, i.e. in essentially non-dissolved form. Besides other liquid
media
which may be present if desired, such as, for example, solvents, water
generally
forms the main constituent (> 50% by weight) of the dispersion media, based on
the total amount of the liquid dispersion media in the cosmetic compositions
according to the invention, in some cases also the only liquid dispersion
medium.
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The hair setting compositions according to the invention preferably have a
content
of volatile organic compounds (VOCs) of less than 80% by weight, more
preferably
of less than 55% by weight, even more preferably of less than 40% by weight,
based on the hair setting composition.
The aqueous polyurethane dispersions used for the preparation of the hair
setting
compositions according to the invention preferably have a content of volatile
organic compounds (VOCs) of less than 10% by weight, more preferably of less
than 3% by weight, even more preferably of less than 1 % by weight, based on
the
aqueous polyurethane dispersion.
The content of volatile organic compounds (VOCs) is determined within the
context of the present invention in particular by gas chromatographic
analysis.
The non-water-soluble and non-water-dispersible, isocyanate-functional
polyurethane polymers used according to the invention have essentially neither
ionic nor ionogenic groups. The insolubility in water and/or lack of
dispersibility in
water refers to deionized water without the addition of surfactants. Within
the
context of the present invention this means that the proportion of ionic
and/or
ionogenic (ion-forming) groups, such as, in particular, anionic groups, such
as
carboxylate or sulfonate, or of cationic groups is less than 15
milliequivalents per
100 g of polyurethane prepolymer A), preferably less than 5 milliequivalents,
particularly preferably less than 1 milliequivalent and very particularly
preferably
less than 0.1 milliequivalent per 100 g of polyurethane prepolymer A).
In the case of acidic ionic and/or ionogenic groups, the acid number of the
prepolymer is expediently below 30 mg of KOH/g of prepolymer, preferably below
10 mg of KOH/g of prepolymer. The acid number indicates the mass of potassium
hydroxide in mg which is required to neutralize 1 g of the sample under
investigation (measurement in accordance with DIN EN ISO 211). The neutralized
acids, i.e. the corresponding salts, naturally have no acid number or a
reduced
acid number. According to the invention, the acid number of the corresponding
free acid is decisive here.
The prepolymers A) used for the preparation of the polyurethanes are
preferably
obtainable by reacting one or more polyols selected from the group which
consists
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of polyether polyols, polycarbonate polyols, polyether polycarbonate polyols
and/or
polyester polyols, and polyisocyanates, as is explained in more detail below.
The polyurethanes present in the hair setting compositions according to the
invention accordingly comprise, via the prepolymer A), preferably at least one
sequence selected from the group which consists of: polyether, polycarbonate,
polyether-polycarbonate and polyester sequences. According to the invention,
this
means in particular that the polyurethanes contain repeat units containing
ether
groups and/or carbonate groups or ester groups. The polyurethanes can contain,
for example, exclusively polyether sequences or exclusively polycarbonate
sequences or exclusively polyester sequences. However, they can also have both
polyether and polycarbonate sequences, as are formed, for example, during the
preparation of polycarbonate polyols using polyetherdiols, as is described in
more
detail below. In addition, they can have polyether-polycarbonate sequences
which
arise from the use of polyether-polycarbonate polyols, as described in more
detail
below.
Particularly preferred polyurethanes are obtained using polymeric polyether
polyols and/or polymeric polycarbonate polyols and/or polyether-polycarbonate
polyols or polyester polyols, each of which have number-average molecular
weights of preferably about 400 to about 6000 g/mol (here and in the case of
the
molecular weight data below, determined by gel permeation chromatography
relative to polystyrene standard in tetrahydofuran at 23 C). Their use during
the
preparation of the polyurethanes or polyurethane prepolymers leads, as a
result of
the reaction with polyisocyanates, to the formation of corresponding polyether
and/or polycarbonate and/or polyether-polycarbonate sequences or polyester
sequences in the polyurethanes with a corresponding molecular weight of these
sequences. According to the invention, particular preference is given to
polyurethanes which are obtained from polymeric polyetherdiols and/or
polymeric
polycarbonatediols and/or polyether-polycarbonate polyols or polyester polyols
with a linear structure.
The polyurethanes according to the invention are preferably essentially linear
molecules, but may also be branched, which is less preferred.
The number-average molecular weight of the polyurethanes preferably used
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according to the invention is, for example, from about 1000 to 200 000,
preferably
from 5000 to 150 000. Molecular weights above 200 000 can be disadvantageous
under certain circumstances since the hair setting compositions are sometimes
difficult to wash out.
The polyurethanes present in the hair setting compositions according to the
invention are added to the specified compositions in particular in the form of
aqueous dispersions.
Preferred polyurethanes or polyurethane dispersions to be used according to
the
invention are obtainable by preparing
A) isocyanate-functional prepolymers of
Al) organic polyisocyanates,
A2) polymeric polyols, preferably with number-average molecular weights
of from 400 to 8000 g/mol (here and in the case of the molecular
weight data below, determined by gel permeation chromatography
relative to polystyrene standard in tetrahydrofuran at 23 C), more
preferably 400 to 6000 g/mol and particularly preferably from 600 to
3000 g/mol, and OH functionalities of preferably 1.5 to 6, more
preferably 1.8 to 3, particularly preferably from 1.9 to 2.1,
A3) optionally hydroxy-functional compounds with molecular weights of
preferably 62 to 399 g/mol, and
A4) optionally nonionic hydrophilizing agents,
and
B) then reacting some or all of their free NCO groups
with one or more amino-functional compounds B), such as primary and/or
secondary amines and/or diamines.
The polyurethanes used according to the invention are preferably dispersed in
water before, during or after step B).
The reaction with a diamine or two or more diamines in step B) particularly
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preferably takes place with chain extension. In this connection,
monofunctional
amines can additionally be added as chain terminators to control the molecular
weight.
As component B), in particular amines can be used which have no ionic or
ionogenic, such as anionically hydrophilizing groups (component B1 below)) and
it
is possible to use amines which have ionic or ionogenic, such as, in
particular,
anionically hydrophilizing groups (component B2 below)).
Preferably, in step B) of the reaction of the prepolymer, a mixture of
component
131) and component B2) is reacted. By using component 131) it is possible to
build
up a high molar mass without the viscosity of the previously prepared
isocyanate-
functional prepolymer increasing to a degree which would be an obstacle to
processing. By using the combination of components 131) and B2) it is possible
to
achieve an optimum balance between hydrophilicity and chain length and thus
good substantivity without "build-up" effects arising.
The polyurethanes used according to the invention preferably have anionic
groups,
preferably sulfonate groups. These anionic groups are introduced into the
polyurethanes used according to the invention via the amine component B2)
reacted in step B). The polyurethanes used according to the invention
optionally
additionally have nonionic components for hydrophilization. Exclusively
sulfonate
groups are particularly preferably present in the polyurethanes used according
to
the invention for the hydrophilization; these are introduced into the
polyurethane
via corresponding diamines as component B2).
In order to achieve a good sedimentation stability, the number-average
particle
size of the special polyurethane dispersions is preferably less than 750 nm,
particularly preferably less than 500 nm, determined by means of laser
correlation
spectroscopy following dilution with deionized water (instrument: Malvern
Zetasizer
1000, Malver Inst. Limited).
The solids content of the polyurethane dispersions which is preferably used
for
preparing the hair setting composition of the invention is generally 10 to 70%
by
weight, preferably 30 to 65% by weight, particularly preferably 40 to 60% by
weight.
The solids contents are ascertained by heating a weighed sample at 125 C to
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constant weight. At constant weight, the solid-body content is calculated by
reweighing the sample.
Preferably, these polyurethane dispersions have less than 5% by weight,
particularly preferably less than 0.2% by weight, based on the mass of the
dispersions, of unbonded organic amines. The content in the hair setting
compositions is correspondingly yet lower.
Suitable polyisocyanates of component Al) are in particular the aliphatic,
aromatic
or cycloaliphatic polyisocyanates with an NCO functionality of greater than or
equal to 2 known per se to the person skilled in the art.
Examples of such suitable polyisocyanates are 1,4-butylene diisocyanate, 1,6-
hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4-
and/or
2,4,4-trim ethylhexamethylene diisocyanate, the isomeric bis(4,4'-
isocyanatocyclohexyl)methanes or mixtures thereof of any desired isomer
content,
1,4-cyclohexylene diisocyanate, 4-isocyanatomethyl-l,8-octane diisocyanate
(nonane triisocyanate), 1,4-phenylene diisocyanate, 2,4- and/or 2,6-tolylene
diisocyanate, 1,5-naphthylene diisocyanate, 2,2'- and/or 2,4'- and/or 4,4'-
diphenylmethane diisocyanate, 1,3- and/or 1,4-bis(2-isocyanatoprop-2-
yl)benzene
(TMXDI), 1,3-bis(isocyanatomethyl)benzene (XDI), and alkyl 2,6-
diisocyanatohexanoates (lysine diisocyanates) with C1-C8-alkyl groups.
Besides the aforementioned polyisocyanates, it is also possible to use
modified
diisocyanates which have a functionality of >_ 2 with uretdione, isocyanurate,
urethane, allophanate, biuret, iminooxadiazinedione or oxadiazinetrione
structure,
and also mixtures of these proportionately.
They are preferably polyisocyanates or polyisocyanate mixtures of the type
specified above with exclusively aliphatically or cycloaliphatically bonded
isocyanate groups or mixtures of these and an average NCO functionality of the
mixture of from 2 to 4, preferably 2 to 2.6 and particularly preferably 2 to
2.4, very
particularly preferably 2.
Hexamethylene diisocyanate, isophorone diisocyanate or the isomeric bis(4,4'-
isocyanatocyclohexyl)methanes, and mixtures of the aforementioned
diisocyanates are particularly preferably used in Al).
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In A2), polymeric polyols with a number-average molecular weight Mn of
preferably
400 to 8000 g/mol, more preferably from 400 to 6000 g/mol and particularly
preferably from 600 to 3000 g/mol are used. These preferably have an OH
functionality of from 1.5 to 6, particularly preferably from 1.8 to 3, very
particularly
preferably from 1.9 to 2.1.
The expression "polymeric" polyols means here in particular that the specified
polyols have at least two, more preferably at least three, repeat units joined
together.
Such polymeric polyols are the polyester polyols, polyacrylate polyols,
polyurethane polyols, polycarbonate polyols, polyether polyols, polyester
polyacrylate polyols, polyurethane polyacrylate polyols, polyurethane
polyester
polyols, polyurethane polyether polyols, polyurethane polycarbonate polyols
and
polyester polycarbonate polyols known per se in polyurethane coating
technology.
These can be used in A2) individually or in any desired mixtures with one
another.
The preferably used polyester polyols are the polycondensates known per se of
di-
and optionally tri- and tetraols and di- and optionally tri- and
tetracarboxylic acids
or hydroxycarboxylic acids or lactones. Instead of the free polycarboxylic
acids, it
is also possible to use the corresponding polycarboxylic acid anhydrides or
corresponding polycarboxylic acid esters of lower alcohols for the preparation
of
the polyesters.
Examples of suitable diols are ethylene glycol, butylene glycol, diethylene
glycol,
triethylene glycol, polyalkylene glycols, such as polyethylene glycol, also
1,2-
propanediol, 1,3-propanediol, butanediol(1,3), butanediol(1,4),
hexanediol(1,6) and
isomers, neopentyl glycol or hydroxypivalic neopentyl glycol ester, where
hexanediol(1,6) and isomers, butanediol(1,4), neopentyl glycol and
hydroxypivalic
neopentyl glycol ester are preferred. In addition, polyols such as trimethylol
propane, glycerol, erythritol, pentaerythritol, trimethylol benzene or
trishydroxyethyl
isocyanurate can also be used.
Dicarboxylic acids which can be used are phthalic acid, isophthalic acid,
terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid,
cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid,
glutaric acid,
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tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic
acid,
suberic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid and/or 2,2-
dimethylsuccinic acid. The corresponding anhydrides may also be used as acid
source.
If the average functionality of the polyol to be esterified is > than 2,
monocarboxylic
acids, such as benzoic acid and hexanecarboxylic acid, can additionally also
be
co-used.
Preferred acids are aliphatic or aromatic acids of the type specified above.
Particular preference is given to adipic acid, isophthalic acid and phthalic
acid.
Hydroxycarboxylic acids which can be co-used as reactants in the preparation
of a
polyester polyol with terminal hydroxyl groups are, for example,
hydroxycaproic
acid, hydroxybutyric acid, hydroxydecanoic acid, hydroxystearic acid and the
like.
Suitable lactones are caprolactone, butyrolactone and homologs. Preference is
given to caprolactone.
According to the invention, particularly preferred components A2) for the
preparation of the polyurethanes are polyester polyols with a number-average
molecular weight of from 600 to 3000 g/mol, in particular aliphatic polyester
polyols
based on aliphatic carboxylic acids and aliphatic polyols, in particular based
on
adipic acid and aliphatic alcohols, such as hexanediol and/or neopentyl
glycol.
Polycarbonates having hydroxyl groups, preferably polycarbonatediols, with
number-average molecular weights M, of from preferably 400 to 8000 g/mol,
preferably 600 to 3000 g/mol can likewise be used as component A2). These are
obtainable by reacting carbonic acid derivatives, such as diphenyl carbonate,
dimethyl carbonate or phosgene, with polyols, preferably diols.
Examples of such diols are ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and
1,4-
butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-
bishydroxymethylcyclohexane, 2-methyl-1,3-propanediol, 2,2,4-
trimethylpentanediol-1, 3, dipropylene glycol, polypropylene glycols,
dibutylene
glycol, polybutylene glycols, bisphenol A and lactone-modified diols of the
type
specified above.
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Preferably, the diol component comprises 40 to 100% by weight of hexanediol,
preference being given to 1,6-hexanediol and/or hexanediol derivatives. Such
hexanediol derivatives are based on hexanediol and, besides terminal OH
groups,
have ester or ether groups. Such derivatives are obtainable by reacting
hexanediol
with excess caprolactone or by etherifying hexanediol with itself to give the
di- or
trihexylene glycol.
Instead of or in addition to the pure polycarbonatediols, it is also possible
to use
polyether-polycarbonatediols in A2).
Polycarbonates having hydroxyl groups preferably have a linear structure.
Polyether polyols can likewise be used as component A2).
For example, the polytetramethylene glycol polyethers known per se in
polyurethane chemistry, as are obtainable through polymerization of
tetrahydrofuran by means of cationic ring opening, are particularly suitable.
Likewise suitable polyether polyols are the addition products, known per se,
of
styrene oxide, ethylene oxide, propylene oxide, butylene oxide and/or
epichlorohydrin onto di- or polyfunctional starter molecules. Thus, in
particular
polyalkylene glycols, such as polyethylene glycols, polypropylene glycols
and/or
polybutylene glycols, can be used, in particular those with the preferred
molecular
weights specified above.
Suitable starter molecules which can be used are all compounds known according
to the prior art, such as, for example, water, butyl diglycol, glycerol,
diethylene
glycol, trimethyloIpropane, propylene glycol, sorbitol, ethylenediamine,
triethanolamine, 1,4-butanediol.
Particularly preferred components in A2) are polytetramethylene glycol
polyethers
and polycarbonate polyols and mixtures thereof and particularly preferably
polytetramethylene glycol polyethers.
In preferred embodiments of the invention, component A2) is accordingly:
- mixtures comprising at least one polyether polyol and at least one
polycarbonate polyol,
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- mixtures comprising more than one polyether polyol, or a mixture of two or
more polyether polyols with different molecular weights, which are in
particular poly(tetramethylene glycol) polyether polyols (such as HO-(CH2-
CH2-CH2-CH2-O)X-H),
- mixtures comprising more than one polyether polyol and at least one
polycarbonate polyol, and also
- particularly preferably polyester polyols with a number-average molecular
weight of from 600 to 3000 g/mol, in particular aliphatic polyester polyols
based on aliphatic carboxylic acids and aliphatic polyols, in particular based
on adipic acid and aliphatic alcohols, such as hexanediol and/or neopentyl
glycol,
where component A), according to the definition, has essentially neither ionic
nor
ionogenic groups.
As component A3), polyols, in particular nonpolymeric polyols, of the
specified
preferred molecular weight range from 62 to 399 mol/g with up to 20 carbon
atoms,
such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-
propanediol, 1,3-
propanediol, 1,4-butanediol, 1,3-butylene glycol, cyclohexanediol, 1,4-
cyclohexanedimethanol, 1,6-hexanediol, neopentyl glycol, hydroquinone
dihydroxyethyl ether, bisphenol A (2,2-bis(4-hydroxyphenyl)propane),
hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane),
trimethylolpropane, trimethylolethane, glycerol, pentaerythritol, and any
mixtures
thereof can be used as desired.
Also suitable are ester diols of the specified molecular weight range, such as
a-hydroxybutyl E-hydroxycaproic acid ester, w-hydroxyhexyl y-hydroxybutyric
acid
ester, adipic acid (R-hydroxyethyl) ester or terephthalic acid bis(R-
hydroxyethyl)
ester.
In addition, as component A3), it is also possible to use monofunctional
isocyanate-reactive hydroxyl-group-containing compounds. Examples of such
monofunctional compounds are ethanol, n-butanol, ethylene glycol monobutyl
ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether,
propylene glycol monomethyl ether, dipropylene glycol monomethyl ether,
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tripropylene glycol monomethyl ether, dipropylene glycol monopropyl ether,
propylene glycol monobutyl ether, dipropylene glycol monobutyl ether,
tripropylene
glycol monobutyl ether, 2-ethylhexanol, 1-octanol, 1-dodecanol, 1-hexadecanol.
In one preferred embodiment of the invention, the polyurethane used according
to
the invention comprises less than about 10% by weight of component A3),
preferably less than 5% by weight of component A3), in each case based on the
total mass of the polyurethane, yet more preferably component A3) is not used
for
the preparation of the polyurethane.
To prepare the polyurethanes used according to the invention, one or more in
particular isocyanate-reactive nonionic hydrophilizing agents are optionally
used
as component A4). The hydrophilizing agents used as component A4) are in
particular different from components A2) and A3).
Suitable nonionically hydrophilizing compounds as component A4) are, for
example, polyoxyalkylene ethers which have isocyanate-reactive groups, such as
hydroxy, amino or thiol groups. Preference is given to monohydroxy-functional
polyalkylene oxide polyether alcohols having, on statistical average, 5 to 70,
preferably 7 to 55, ethylene oxide units per molecule, as are accessible in a
manner known per se by alkoxylation of suitable starter molecules (e.g. in
Ullmanns Encyclopadie der technischen Chemie [Ullmanns encyclopaedia of
industrial chemistry], 4th edition, Volume 19, Verlag Chemie, Weinheim pp. 31-
38).
These are either pure polyethylene oxide ethers or mixed polyalkylene oxide
ethers, where they contain at least 30 mol%, preferably at least 40 mol%,
ethylene
oxide units, based on all of the alkylene oxide units present.
Particularly preferred nonionic compounds are monofunctional mixed
polyalkylene
oxide polyethers which have 40 to 100 mol% ethylene oxide units and 0 to
60 mol% propylene oxide units.
Suitable starter molecules for such nonionic hydrophilizing agents are in
particular
saturated monoalcohols, such as methanol, ethanol, n-propanol, isopropanol, n-
butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols
and
nonanols, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-
octadecanol,
cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexane,
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3-ethyl-3-hydroxymethyl oxetane or tetra hyd rofu rfu ryl alcohol, diethylene
glycol
monoalkyl ethers, such as, for example, diethylene glycol monobutyl ether,
unsaturated alcohols, such as ally) alcohol, 1,1-dimethylallyl alcohol or
oleyl
alcohol, aromatic alcohols, such as phenol, the isomeric cresols or methoxyphe-
nols, araliphatic alcohols, such as benzyl alcohol, anisyl alcohol or cinnamyl
alcohol, secondary monoamines, such as dimethylamine, diethylamine,
dipropylamine, diisopropylamine, dibutylamine, bis(2-ethylhexyl)amine, N-
methyl-
and N-ethylcyclohexylamine or dicyclohexylamine, and also heterocyclic
secondary amines, such as morpholine, pyrrolidine, piperidine or 1 H-pyrazole.
Preferred starter molecules are saturated monoalcohols of the type specified
above. Particular preference is given to using diethylene glycol monobutyl
ether or
n-butanol as starter molecules.
Alkylene oxides suitable for the alkoxylation reaction are in particular
ethylene
oxide and propylene oxide, which can be used in the alkoxylation reaction in
any
desired order or else in a mixture.
Component B) is preferably selected from primary or secondary amine and/or
diamines. It includes in particular diamines.
As component B) it is possible to use in particular amines which have no ionic
or
ionogenic, such as anionically hydrophilizing groups (component 131) below),
and it
is possible to use amines which have ionic or ionogenic, such as, in
particular,
anionically hydrophilizing groups (component B2) below). Preferably, in step
B) of
the reaction of the prepolymer, a mixture of component 131) and of component
B2)
is reacted.
For example, organic di- or polyamines, such as, for example, 1,2-
ethylenediamine,
1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, isophorone-
diamine, isomer mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 2-
methylpentamethylenediamine, diethylenetriamine, 4,4-diaminodicyclohexyl-
methane, hydrazine hydrate, and/or dimethylethylenediamine, can be used as
component B1).
Moreover, compounds which, besides a primary amino group, also have
secondary amino groups or, besides an amino group (primary or secondary), also
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have OH groups, can also be used as component B1). Examples thereof are
primary/secondary amines, such as diethanolamine, 3-amino-1-methylamino-
propane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-
amino-1-methylaminobutane, alkanolamines, such as N-aminoethylethanolamine,
ethanolamine, 3-aminopropanol, neopentanolamine.
In addition, monofunctional isocyanate-reactive amine compounds can also be
used as component B1), such as, for example, methylamine, ethylamine,
propylamine, butylamine, octylamine, laurylamine, stearylamine,
isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine,
dibutylamine, N-methylaminopropylamine, diethyl(methyl)aminopropylamine,
morpholine, piperidine, and suitable substituted derivatives thereof,
amidoamines
of diprimary amines and monocarboxylic acids, monoketime of diprimary amines,
primary/tertiary amines, such as N,N-dimethylaminopropylamine.
As component B1), preference is given to using 1,2-ethylenediamine, bis(4-
aminocyclohexyl)methane, 1,4-diaminobutane, isophoronediamine, ethanolamine,
diethanolamine and diethylenetriamine.
Component B) particularly preferably includes at least one component B2).
Suitable anionically hydrophilizing compounds as component B2) preferably
contain a sulfonic acid or sulfonate group, particularly preferably a sodium
sulfonate group. Suitable anionically hydrophilizing compounds as component
B2)
are, in particular, the alkali metal salts of mono- and diaminosulfonic acids.
Examples of such anionic hydrophilizing agents are salts of 2-(2-
aminoethylamino)ethanesulfonic acid, ethylenediamine-propyl- or -butylsulfonic
acid, 1,2- or 1,3-propylenediamine-f3-ethylsulfonic acid or taurine.
Furthermore, the
salt of cyclohexylaminopropanesulfonic acid (CAPS) from WO-A 01/88006 can be
used as anionic hydrophilizing agent.
Particularly preferred anionic hydrophilizing agents B2) are those which
contain
sulfonate groups as ionic groups and two amino groups, such as the salts of 2-
(2-
aminoethylamino)ethylsulfonic acid and 1,3-propylenediamine-o-ethylsulfonic
acid.
The polyurethanes used according to the invention particularly preferably
comprising at least one sulfonate group.
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Optionally, the anionic group in component B2) may also be a carboxylate or
carboxylic acid group. Component B2) is then preferably selected from
diaminocarboxylic acids. However, this embodiment is less preferred since
carboxylic-acid-based components B2) have to be used in higher concentrations.
For the hydrophilization, it is also possible to use mixtures of anionic
hydrophilizing
agents B2) and nonionic hydrophilizing agents A4).
In a preferred embodiment for the preparation of the special polyurethane
dispersions, components Al) to A4) and 131) to B2) are used in the following
amounts, the individual amounts always adding up to 100% by weight:
5 to 40% by weight of component Al),
55 to 90% by weight of A2),
0.5 to 20% by weight sum of components A3) and/or B1),
0.1 to 25% by weight sum of components A4) and/or B2), where, based on the
total amounts of components Al) to A4) and B1) to B2), particularly preferably
0.1
to 5% by weight of anionic or potentially anionic hydrophilizing agents B2)
are
used.
In a particularly preferred embodiment for the preparation of the special
polyurethane dispersions, components Al) to A4) and B1) to B2) are used in the
following amounts, the individual amounts always adding up to 100% by weight:
5 to 35% by weight of component Al),
60 to 90% by weight of A2),
0.5 to 15% by weight sum of components A3) and/or B1),
0.1 to 15% by weight sum of components A4) and/or B2), where, based on the
total amounts of components Al) to A4) and 131) to B2), particularly
preferably 0.2
to 4% by weight of anionic or potentially anionic hydrophilizing agents B2)
are
used.
In a very particularly preferred embodiment for the preparation of the special
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polyurethane dispersions, components Al) to A4) and B1) to B2) are used in the
following amounts, the individual amounts always adding up to 100% by weight:
to 30% by weight of component Al),
65 to 85% by weight of A2),
5 0.5 to 14% by weight sum of components A3 and/or B1),
0.1 to 13.5% by weight sum of components A4) and/or B2), where, based on the
total amounts of components Al) to A4) and 131) to B2), particularly
preferably 0.5
to 3.0% by weight of anionic or potentially anionic hydrophilizing agents from
B2)
are used.
10 The preparation of the polyurethane dispersions can be carried out in one
or more
stage(s) in homogeneous phase or, in the case of multistage reaction,
sometimes
in disperse phase. Following complete or partial polyaddition from Al) to A4),
a
dispersion, emulsification or dissolution step preferably takes place.
Afterwards, a
further polyaddition or modification optionally takes place in the disperse
phase.
In this connection, all of the methods known from the prior art, such as, for
example, prepolymer mixing process, acetone process or melt dispersion
process,
can be used. Preference is given to using the acetone process.
For the preparation in accordance with the acetone process, constituents A2)
to
A4) and the polyisocyanate component Al) for the preparation of an isocyanate-
functional polyurethane prepolymer are usually initially introduced in their
entirety
or in part and optionally diluted with a solvent which is miscible with water
but inert
towards isocyanate groups, and heated to temperatures in the range from 50 to
120 C. To increase the rate of the isocyanate addition reaction, the catalysts
known in polyurethane chemistry can be used.
Suitable solvents are the customary aliphatic, keto-functional solvents such
as
acetone, 2-butanone, which can be added not only at the start of the
preparation,
but optionally in parts also later on. Preference is given to acetone and 2-
butanone,
and particular preference is given to acetone. The addition of other solvents
without isocyanate-reactive groups is also possible, but not preferred.
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Any constituents of Al) to A4) not added at the start of the reaction are then
metered in.
During the preparation of the polyurethane prepolymer from Al) to A4), the
quantitative ratio of isocyanate groups to isocyanate-reactive groups is
generally
1.05 to 3.5, preferably 1.1 to 3.0, particularly preferably 1.1 to 2.5.
The reaction of components Al) to A4) to give the prepolymer takes place
partially
or completely, but preferably completely. Polyurethane prepolymers which
contain
free isocyanate groups are thus obtained without a diluent or in solution.
In the neutralization step for the partial or complete conversion of
potentially
anionic groups to anionic groups, bases such as tertiary amines, e.g.
trialkylamines having 1 to 12, preferably 1 to 6, carbon atoms, particularly
preferably 2 to 3 carbon atoms in each alkyl radical or very particularly
preferably
alkali metal bases such as the corresponding hydroxides are used.
The use of organic amines is not preferred.
Neutralizing agents which can be used are preferably inorganic bases, such as
aqueous ammonia solution or sodium hydroxide or potassium hydroxide.
Preference is given to sodium hydroxide and potassium hydroxide.
The quantitative amount of the bases is 50 and 125 mol%, preferably between 70
and 100 mol% of the quantitative amount of the acid groups to be neutralized.
The
neutralization can also take place at the same time as the dispersion by the
dispersion water already comprising the neutralizing agent.
Afterwards, in a further process step, in cases where it has still not
happened or
has only happened partially, the resulting prepolymer is dissolved with the
help of
aliphatic ketones such as acetone or 2-butanone.
The reaction of components Al) to A4) to give the prepolymer takes place
partially
or completely, but preferably completely. In this way, polyurethane
prepolymers
which contain free isocyanate groups are obtained without a diluent or in
solution.
During the chain extension in stage B), NH2- and/or NH-functional components
are
reacted with the remaining isocyanate groups of the prepolymer. Preferably,
the
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chain extension/termination is carried out prior to the dispersion in water.
Suitable components B) for the chain extension are, in particular, organic di-
or
polyamines B1), such as, for example, ethylenediamine, 1,2- and 1,3-
diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, isophoronediamine,
isomer mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 2-
methylpentamethylenediamine, diethylenetriamine, diaminodicyclohexylmethane
and/or dimethylethylenediamine.
Moreover, it is also possible to use compounds 131) which, besides a primary
amino group, also have secondary amino groups or, besides an amino group
(primary or secondary), also have OH groups. Examples thereof are
primary/secondary amines, such as diethanolamine, 3-amino-1-methylamino-
propane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-
amino-1 -methylaminobutane, alkanolamines, such as N-aminoethylethanolamine,
ethanolamine, 3-aminopropanol, neopentanolamine be used for the chain
extension and/or termination.
For the chain termination, use is usually made of amines 131) having a group
which
is reactive towards isocyanates, such as methylamine, ethylamine, propylamine,
butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine,
dimethylamine, dethylamine, dipropylamine, dibutylamine, N-
methylaminopropylamine, diethyl(methyl)aminopropylamine, morpholine,
piperidine, and suitable substituted derivatives thereof, amidoamines of
diprimary
amines and monocarboxylic acids, monoketime of diprimary amines,
primary/tertiary amines, such as N,N-dimethylaminopropylamine.
If anionic hydrophilizing agents corresponding to the definition of B2) with
NH2 or
NH groups are used for the chain extension, the chain extension of the
prepolymers preferably takes place before the dispersion.
The degree of chain extension, i.e. the equivalent ratio of NCO-reactive
groups of
the compounds used for the chain extension and chain termination to free NCO
groups of the prepolymer is generally between 40 and 150%, preferably between
50 and 110%, particularly preferably between 60 and 100%.
The aminic components B1) and B2) can optionally be used in water- or solvent-
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diluted form in the process according to the invention individually or in
mixtures,
with any order of the addition being possible in principle.
If water or organic solvents are co-used as diluents, then the diluent content
in the
component used in B) for the chain extension is preferably 40 to 95% by
weight.
The dispersion preferably takes place after the chain extension. For this, the
dissolved and chain-extended polyurethane polymer is optionally either
introduced
into the dispersion water with strong shear, such as, for example, with
vigorous
stirring, or, conversely, the dispersion water is stirred into the chain-
extended
polyurethane polymer solutions. Preferably, the water is added to the
dissolved
chain-extended polyurethane polymer.
The solvent still present in the dispersions after the dispersion step is then
usually
removed by distillation. Removal during dispersion is likewise possible.
The residual content of organic solvents in the polyurethane dispersions
prepared
in this way is typically less than 10% by weight, preferably less than 3% by
weight,
based on the total dispersion.
The pH of the aqueous polyurethane dispersions used according to the invention
is typically less than 8.0, preferably less than 7.5 and is particularly
preferably
between 5.5 and 7.5.
The hair setting compositions within the context of the present invention can
advantageously be present in the form of a spray, a mousse, a gel, an
emulsion, a
solution or a cream, such as in the form of a setting mousse, setting fluid,
hairspray, styling gel, styling cream, aerosol mousse etc.
The hair setting composition according to the invention comprises preferably
0.1 to
20% by weight of the polyurethane described above and in particular 0.5 to 10%
by weight, in each case based on the total weight of the composition.
Besides the polyurethane described above, the composition according to the
invention can comprise further suitable film formers which can in particular
also
contribute to the setting and the styling of the hair.
The concentration of one or more further film formers can be from 0 to 20% by
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weight and in particular 0 to 10% by weight, in each case based on the total
weight
of the composition.
The film former or film formers are advantageously selected from the group of
water-soluble or water-dispersible polyurethanes different from the
polyurethanes
used according to the invention, the polyureas, silicone resins and/or
polyesters,
and also the nonionic, anionic, amphoteric and/or cationic polymers and their
mixtures.
Advantageous nonionic polymers which may be present in compositions according
to the invention alone or in a mixture, preferably also with anionic and/or
amphoteric and/or zwitterionic polymers, are selected from:
- polyalkyloxazolines,
- vinyl acetate homopolymers or copolymers. These include, for example,
copolymers of vinyl acetate and acrylic acid esters, copolymers of vinyl
acetate and ethylene, copolymers of vinyl acetate and maleic acid esters,
- acrylic acid ester copolymers, such as, for example, the copolymers of alkyl
acrylate and alkyl methacrylate, copolymers of alkyl acrylate and urethanes,
- copolymers of acrylonitrile and nonionic monomer selected from butadiene
and (meth)acrylate,
- styrene homopolymers and copolymers. These include, for example,
homopolystyrene, copolymers of styrene and alkyl (meth)acrylate,
copolymers of styrene, alkyl methacrylate and alkyl acrylate, copolymers of
styrene and butadiene, copolymers of styrene, butadiene and vinylpyridine,
- polyamides,
- vinyllactam homopolymers or copolymers, such as vinylpyrrolidone homo-
or copolymers; these include, for example, polyvinylpyrrolidone,
polyvinylcaprolactam, copolymers of N-vinylpyrrolidone and vinyl acetate
and/or vinyl propionate in various concentration ratios, polyvinylcaprolactam,
polyvinylamides and salts thereof, and also copolymers of vinylpyrrolidone
and dimethylaminoethyl methacrylate, terpolymers of vinylcaprolactam,
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vinylpyrrolidone and dimethylaminoethyl methacrylate,
- polysiloxanes,
- homopolymers of N-vinylformamide e.g. PVF from National Starch.
Particularly preferred nonionic polymers are acrylic acid ester copolymers,
homopolymers of vinylpyrrolidone and copolymers, polyvinylcaprolactam.
Very particularly preferred nonionic polymers are homopolymers of
vinylpyrrolidone, e.g. Luviskol K from BASF, copolymers of vinylpyrrolidone
and
vinyl acetate, e.g. Luviskol VA grades from BASF or PVPVA S630L from ISP,
terpolymers of vinylpyrrolidone, vinyl acetate and propionate, such as, for
example,
Luviskol VAP from BASF and polyvinylcaprolactams, e.g. Luviskol PLUS from
BASF.
Advantageous anionic polymers are homopolymers or copolymers with monomer
units containing acid groups which are optionally copolymerized with
comonomers
which contain no acid groups. Suitable monomers are unsaturated, free-
radically
polymerizable compounds which have at least one acid group, in particular
carboxylic acid, sulfonic acid or phosphonic acid.
Advantageous anionic polymers comprising carboxylic acid group are-
- Acrylic acid or methacrylic acid homopolymer or copolymer or the salts
thereof.
These include, for example, the copolymers of acrylic acid and acrylamides
and/or
sodium salts thereof, copolymers of acrylic acid and/or methacrylic acid and
an
unsaturated monomer selected from ethylenes, styrene, vinyl esters, acrylic
acid
esters, methacrylic acid esters, optionally ethoxylated compounds, copolymers
of
vinylpyrrolidones, acrylic acid and C1-C20 alkyl methacrylates, e.g.
Acrylidone
LM from ISP, copolymers of methacrylic acid, ethyl acrylates and tert-butyl
acrylates, e.g. Luvimer 100 P from BASF.
- Crotonic acid derivative homopolymer or copolymer or the salts thereof.
These
include, for example, vinyl acetate/crotonic acid, vinyl acetate/acrylate
and/or vinyl
acetate/vinyl neodecanoate/crotonic acid copolymers, sodium acrylate/vinyl
alcohol copolymers,
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- Unsaturated C4-C8 carboxylic acid derivatives or carboxylic acid anhydride
copolymer selected from copolymers of maleic acid or maleic anhydride or
fumaric
acid or fumaric anhydride or itaconic acid or itaconic anhydride and at least
one
monomer selected from vinyl esters, vinyl ethers, vinyl halogen derivatives,
phenyl
vinyl derivatives, acrylic acid, acrylic acid esters or copolymers of maleic
acid or
maleic anhydride or fumaric acid or fumaric anhydride or itaconic acid or
itaconic
anhydride and at least one monomer selected from allyl esters, methallyl
esters
and optionally acrylamides, methacrylamides, alpha-olefin, acrylic acid
esters,
methacrylic acid esters, vinylpyrrolidones. Further preferred polymers are
methyl
vinyl ether/maleic acid copolymers, which are formed by hydrolysis of vinyl
ether/maleic anhydride copolymers. These polymers can also be partially
esterified
(ethyl, isopropyl or butyl esters) or partially amidated.
- Water-soluble or -dispersible anionic polyurethanes, e.g. Luviset PUR from
BASF, which are different from the polyurethanes according to the invention,
where this list is of course not intended to be limiting.
Advantageous anionic polymers containing sulfonic acid group are salts of
polyvinylsulfonic acid, salts of polystyrene sulfonic acid, such as, for
example,
sodium polystyrene sulfonate or salts of polyacrylamide sulfonic acid.
Particularly advantageous anionic polymers are acrylic acid copolymers,
crotonic
acid derivative copolymer, copolymers of maleic acid or maleic anhydride or
fumaric acid or fumaric anhydride or itaconic acid or itaconic anhydride and
at
least one monomer selected from vinyl esters, vinyl ethers, vinyl halogen
derivatives, phenyl vinyl derivatives, acrylic acid, acrylic acid esters and
salts of
polystyrene sulfonic acid.
Very particularly advantageous anionic polymers are acrylate copolymers, e.g.
Luvimer from BASF, ethyl acrylate/N-tert-butylacrylamide/acrylic acid
copolymers
ULTRAHOLD STRONG from BASF, VA/crotonate/vinyl neodecanoate copolymer,
e.g. Resyn 28-2930 from National Starch, copolymers such as, for example,
copolymers of methyl vinyl ether and maleic anhydride partially esterified
e.g.
GANTREZ from ISP and sodium polystyrene sulfonates e.g. Flexan 130 from
National Starch.
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Advantageous amphoteric polymers can be selected from the polymers which
contain units A and B distributed randomly in the polymer chain, where A means
a
unit which is derived from a monomer with at least one basic nitrogen atom,
and B
is a unit which originates from an acidic monomer which has one or more
carboxy
groups or sulfonic acid groups, or A and B can be groups which are derived
from
zwitterionic carboxybetaine monomers or sulfobetaine monomers; A and B can
also be a cationic polymer chain which contains primary, secondary, tertiary
or
quaternary groups, in which at least one amino group carries a carboxy group
or
sulfonic acid group which is bonded via a hydrocarbon group, or B and C are
part
of a polymer chain with ethylene-a,(3-dicarboxylic acid unit in which the
carboxylic
acid groups have been reacted with a polyamine which contains one or more
primary or secondary amino groups.
Particularly advantageous amphoteric polymers are:
- Polymers which are formed during the copolymerization of a monomer
derived from a vinyl compound with carboxy group, such as, in particular,
acrylic acid, methacrylic acid, maleic acid, a-chloroacrylic acid, and a basic
monomer which is derived from a vinyl compound which is substituted and
contains at least one basic atom, such as, in particular, dialkylaminoalkyl
methacrylate and acrylate, dialkylaminoalkylmethacrylamide and
-acrylamide. Such compounds have been described in the American patent
No. 3 836 537.
- Polymers with units which are derived from: a) at least one monomer which
is selected from the acrylamides or methacrylamides which are substituted
on the nitrogen atom by an alkyl group, b) at least one acidic comonomer
which contains one or more reactive carboxy groups, and c) at least one
basic comonomer, such as esters of acrylic acid and methacrylic acid with
primary, secondary, tertiary and quaternary amino substituents and the
quartenization product of dimethylaminoethyl methacrylate with dimethyl
sulphate or diethyl sulphate.
N-substituted acrylamides or methacrylamides particularly preferred
according to the invention are compounds whose alkyl groups contain 2 to
12 carbon atoms, particularly N-ethylacrylamide, N-t-butylacrylamide, N-t-
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octylacrylamide, N-octylacrylamide, N-decylacrylamide, N-
dodecylacrylamide, and the corresponding methacrylamides.
The acidic comonomers are selected in particular from acrylic acid,
methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid and
the alkyl monoesters having 1 to 4 carbon atoms of maleic acid, maleic
anhydride, fumaric acid or fumaric anhydride.
Preferred basic comonomers are aminoethyl methacrylate, butylaminoethyl
methacrylate, N,N-di methylaminoethyl methacrylate, N-t-butylaminoethyl
methacrylate.
- Crosslinked and completely or partially acylated polyamino amides which
are derived from polyamino amides of the following general formula:
-[CO-R-CO-Z]-
in which R is a divalent group which is derived from a saturated dicarboxylic
acid, an aliphatic mono- or dicarboxylic acid with ethylenic double bond, an
ester of these acids with a lower alkanol having 1 to 6 carbon atoms or a
group which is formed upon the addition of one of these acids onto a bis-
primary or bis-secondary amine, and Z is a group which is derived from a
bis-primary, mono- or bis-secondary polyalkylenepolyamine, and preferably:
a) in quantitative fractions from 60 to 100 mol% the groups -NH-[(CH2)X
NH-]p- where x = 2 and p = 2 or 3 or x = 3 and p = 2, where this group is
derived from diethylenetriamine, triethylenetetramine or
dipropylenetriamine; b) in quantitative fractions of from 0 to 40 moI% the
group -NH-[(CH2)X NH-]p-, in which x = 2 and p = 1, which is derived from
ethylenediamine, or the group which originates from piperazine:
-N N-
c) in quantitative fractions of from 0 to 20 mol%, the group -H-(CH2)6-NH-,
which is derived from hexamethylenediamine, where these
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polyaminoamides are crosslinked by adding a bifunctional crosslinking
agent, which is selected from epihalohydrins, diepoxides, dianhydrides and
bis-unsaturated derivatives, in an amount of from 0.025 to 0.35 mol of
crosslinking agent per amino group of the polyaminoamide, and acylated
with acrylic acid, chloroacetic acid or an alkanesultone or salts thereof.
The saturated carboxylic acids are preferably selected from the acids
having 6 to 10 carbon atoms, such as adipic acid, 2,2,4-trimethyladipic acid
and 2,4,4,-trimethyladipic acid, terephthalic acid; acids with ethylenic
double
bond, such as, for example, acrylic acid, methacrylic acid and itaconic acid.
The alkanesultones used in the acylation are preferably propanesultone or
butanesultone, the salts of the acylating agents are preferably the sodium
salts or potassium salts.
- Polymers with zwitterionic units of the following formula: [R121
114
R11 C N-(CH2)z-C-O-
R13 R15
Y
in which R11 is a polymerizable unsaturated group, such as acrylate,
methacrylate, acrylamide or methacrylamide, y and z are integers from 1 to
3, R12 and R13 are a hydrogen atom, methyl, ethyl or propyl, R14 and R15 are
a hydrogen atom or an alkyl group which is selected such that the sum of
the carbon atoms R14 and R15 does not exceed 10.
Polymers which contain such units can also have units which originate from
non-zwitterionic monomers, such as dimethyl- and diethylaminoethyl
acrylate or dimethyl- and diethylaminoethyl methacrylate or alkyl acrylates
or alkyl methacrylates, acrylamides or methacrylamides or vinyl acetate.
- Polymers which are derived from chitosan and contain monomer units
which correspond to the following formulae:
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CH2OH
H O O-
H
OH H
H
H NHCOCH3
CH2OH
H 0 O-
H
OH x
H
H NH,
CH,OH
(OH 0 O-
H
H
H NH
C=O
R16-COOH
where the first unit is present in quantitative fractions of from 0 to 30%,
the
second unit is present in quantitative fractions of from 5 to 50% and the
third unit is present in quantitative fractions of from 30 to 90%, with the
proviso that, in the third unit, R16 is a group of the following formula:
R18 R19
R17- C -(O)Q- C
in which: if q = 0, the groups R17, R18 and R19, which are identical or
different, are in each case a hydrogen atom, methyl, hydroxy, acetoxy or
amino, a monoalkylamine radical or a dialkylamine radical which is
optionally interrupted by one or more nitrogen atoms and/or optionally one
or more of the groups amino, hydroxy, carboxy, alkylthio, sulfonic acid,
alkylthio, whose alkyl group carries an amino radical, where at least one of
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the groups R17, R18 and R19 is in this case a hydrogen atom; or if q = 1, the
groups R17, R18 and R19 are in each case a hydrogen atom, and also the
salts which form these compounds with bases or acids.
Polymers which correspond to the following general formula and which are
described, for example, in the French patent 1 400 366.-
R20
(CH-CH2) CH CH
COOH CO
N-R21
R24
N-R23
R22
in which R20 is a hydrogen atom, CH3O, CH3CH2O or phenyl, R21 is a
hydrogen atom or a lower alkyl group, such as methyl or ethyl, R22 is a
hydrogen atom or a lower C1_6-alkyl group, such as methyl or ethyl, R23 is a
lower C1_6-alkyl group, such as methyl or ethyl or a group of the formula:
-R24-N(R22)2, where R24 is a group -CH2-CH2, -CH2-CH2-CH2- or -CH2-
CH(CH3)- and where R22 has the meanings given above.
- Polymers which can be formed during the N-carboxyalkylation of chitosan,
such as N-carboxymethyl chitosan or N-carboxybutyl chitosan.
- Amphoteric polymers of the type -D-X-D-X, which are selected from:
a) polymers which are formed through the action of chloroacetic acid or
sodium chloroacetate on compounds with at least one unit of the following
formula: D-X-D-X,
in which D is the group
\
-N / N-
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and X is the symbols E or E', where E or E', which are identical or different,
are a
divalent group, which is a straight-chain or branched alkylene group having up
to 7
carbon atoms in the main chain, which is present in unsubstituted form or is
substituted by hydroxy groups and can contain one or more oxygen atoms,
nitrogen atoms or sulphur atoms and 1 to 3 aromatic and/or heterocyclic rings;
where the oxygen atoms, nitrogen atoms and sulphur atoms are present in the
form of the following groups: ether, thioether, sulfoxide, sulfone, sulfonium,
alkylamine, alkenylamine, hydroxy, benzylamine, amine oxide, quaternary
ammonium, amide, imide, alcohol, ester and/or urethane.
b) Polymers of the formula D-X-D-X, in which D is the group
-N N-
and X is the symbol E or E' and at least once E'; where E has the meanings
given
above and E' is a divalent group, which is a straight-chain or branched
alkylene
group having up to 7 carbon atoms in the main chain, which is present in
unsubstituted form or is substituted by one or more hydroxy groups and
contains
one or more nitrogen atoms, where the nitrogen atom is substituted by an alkyl
group, which is optionally interrupted by an oxygen atom and obligatorily
contains
one or more carboxy functions or one or more hydroxy functions and is
betainized
through reaction with chloroacetic acid or sodium chloroacetate.
- Alkyl(C,_5) vinyl ether/maleic anhydride copolymers which are partially
modified by semiamidation with an N,N-dialkylaminoalkylamine, such as
N,N-dimethylaminopropylamine or an N,N-dialkylaminoalcohol. These
polymers can also contain further comonomers, such as vinylcaprolactam.
Very particularly advantageous amphoteric polymers are, for example, the
copolymers octylacrylamide/acrylates/butylaminoethyl methacrylate copolymers
which are commercially available under the names AMPHOMER , AMPHOMER
LV 71 or BALANCE 47 from NATIONAL STARCH, and methyl
methacrylate/methyl dimethylcarboxymethylammonium ethyl methacrylate
copolymers.
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It is optionally advantageous to neutralize the anionic and amphoteric
polymers
using suitable bases in order to improve their solubility and/or
dispersibility in water.
The following bases can be used as neutralizing agents for polymers which
contain acid groups: hydroxides whose cation is an ammonium or an alkali
metal,
such as, for example, NaOH or KOH.
Other neutralizing agents are primary, secondary or tertiary amines, amino
alcohols or ammonia. Preference is given here to 2-amino-2-methyl-1,3-
propanediol (AMPD), 2-amino-2-ethyl-1,3-propanediol (AEPD), 2-amino-2-methyl-
1-propanol (AMP), 2-amino-1-butanol (AB), 2-amino-1,3-propanediol,
monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA),
monoisopropanolamine (MIPA), diisopropanolamine (DIPA), triisopropanolamine
(TIPA), dimethyllaurylamine (DML), dimethylmyristalamine (DMM) and
dimethylstearamine (DMS).
The neutralization can be partial or complete depending on the intended
application.
In some cases, it is also possible, but less preferred, to use cationic
polymers,
such as, for example, polymers which contain primary, secondary, tertiary
and/or
quaternary amino groups which are bonded as part of the polymer chain or
directly
to the polymer chain.
The cosmetic acceptable medium comprises in particular water and optionally a
cosmetically suitable solvent. The preferred solvents are aliphatic alcohols
having
C2-4 carbon atoms, such as ethanol, isopropanol, t-butanol, n-butanol; polyol,
such as propylene glycol, glycerol, ethylene glycol and polyol ethers;
acetone;
unbranched or branched hydrocarbons, such as pentane, hexane, isopentane and
cyclic hydrocarbons, such as cyclopentane and cyclohexane; and mixtures
thereof.
A very particularly preferred solvent is ethanol.
However, the content of such solvents, in accordance with the fact that
according
to the invention these are preferably low-VOC hair setting compositions, is
preferably less than 80% by weight, or preferably less than 55% by weight, yet
more preferably less than 40% by weight.
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The water fraction can be in particular in the range, for example, from 20 to
94%
by weight, preferably from 30 to 80% by weight, more preferably from more than
45 to 70% by weight, based on the total weight of the composition. The medium
is
advantageously an aqueous-alcoholic mixture. The quantitative fraction of the
alcohol in the mixture is in the range from 0 to 90% by weight, preferably 0
to 70%
by weight, more preferably 0 to 55% by weight, yet more preferably 0 to 40% by
weight, based on the total weight of the composition.
The hair setting compositions according to the invention can furthermore
advantageously comprise thickeners. Advantageous thickeners are..
- Crosslinked or uncrosslinked acrylic acid or methacrylic acid homopolymers
or copolymers. These include crosslinked homopolymers of methacrylic
acid or acrylic acid, copolymers of acrylic acid and/or methacrylic acid and
monomers which are derived from other acrylic or vinyl monomers, such as
C10-30 alkyl acrylates, C10-30-alkyl methacrylates and vinyl acetate.
- Thickening polymers of natural origin, for example based on cellulose, guar
gum, xanthan, scleroglucan, gellan gum, rhamsan and karaya gum,
alginates, maltodextrin, starch and its derivatives, carob seed flour,
hyaluronic acid.
Nonionic, anionic, cationic or amphoteric associative polymers, e.g. based
on polyethylene glycols and their derivatives, or polyurethanes.
Crosslinked or uncrosslinked homopolymers or copolymers based on
acrylamide or methacrylamide, such as homopolymers of 2-acrylamido-2-
methylpropanesulfonic acid, copolymers of acrylamide or methacrylamide
and methacryloyloxyethyltrimethylammonium chloride or copolymers of
acrylamide and 2-acrylamido-2-methylpropanesulfonic acid.
Particularly advantageous thickeners are thickening polymers of natural
origin,
crosslinked acrylic acid or methacrylic acid homopolymers or copolymers and
crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid.
Very particularly advantageous thickeners are xanthan gum, such as the
products
supplied under the names Keltrol and Kelza by CP Kelco or the products from
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RHODIA with the name Rhodopol, and guar gum, such as the products available
under the name Jaguar HP105 from RHODIA.
Very particularly advantageous thickeners are crosslinked homopolymers of
methacrylic acid or acrylic acid which are commercially available from
Lubrizol
under the names Carbopol 940, Carbopol 941, Carbopol 980, Carbopol 981,
Carbopol ETD 2001, Carbopol EDT 2050, Carbopol 2984, Carbopol 5984 and
Carbopol Ultrez 10, from 3V under the names Synthalen K, Synthalen L and
Synthalen MS, and from PROTEX under the names Modarez V 1250 PX,
Modarez V2000 PX, Viscaron Al 600 PE and Viscaron A700 PE.
Very particularly advantageous thickeners are crosslinked polymers of acrylic
acid
or methacrylic acid and a C10.30-alkyl acrylate or C10_30-alkyl methacrylate
and
copolymers of acrylic acid or methacrylic acid and vinylpyrrolidone. Such
copolymers are commercially available, for example, from Lubrizol under the
names Carbopol 1342, Carbopol 1382, Pemulen TR1 or Pemulen TR2 and
from ISP under the names Ultrathix P-100 (INCI: Acrylic AcidNP Crosspolymer).
Very particularly advantageous thickeners are crosslinked copolymers of 2-
acrylamido-2-methylpropanesulfonic acid. Such copolymers are available, for
example, from Clariant under the names Aristoflex AVC (INCI: Ammonium
AcryloyldimethyltaurateNP Copolymer).
If the thickeners are used, they are generally present in a concentration of
from 0%
to 2% by weight, preferably 0% to 1% by weight, based on the total weight of
the
composition.
The hair setting compositions according to the invention can moreover comprise
a
propellant gas. Here, it is advantageous to use the propellant gas in an
amount of
from 0 to 40% by weight and particularly preferably in a concentration of from
0 to
20% by weight, based on the total weight of the formulation.
The propellant gases preferred according to the invention are hydrocarbons
such
as propane, isobutane and n-butane, and mixtures thereof. However, compressed
air, carbon dioxide, nitrogen, nitrogen dioxide and dimethyl ether, and
mixtures of
all of these gases can also be used advantageously according to the invention.
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The person skilled in the art is of course aware that there are propellant
gases
which are nontoxic per se which would in principle be suitable for realizing
the
present invention in the form of aerosol preparations, but which nevertheless
have
to be dispensed with on account of an unacceptable impact on the environment
or
other accompanying circumstances, in particular fluorocarbons and
chlorofluorocarbons (CFCs), such as, for example, 1,2-difluoroethane
(propellant
152 A).
Furthermore, hair care active ingredients can be used in the hair setting
formulations according to the invention. Care substances which can preferably
be
used are cyclic polydimethylsiloxanes (cyclomethicones) in concentrations of
e.g.
0-1.0% by weight of the total formulation or silicone surfactants (polyether-
modified
siloxanes) of the type dimethicone copolyol or simethicone, e.g. in
concentrations
of 0-1.0% by weight of the total weight of the composition. Cyclomethicones
are
supplied, inter alia, under the trade names Abil K4 by Goldschmidt or e.g. DC
244,
DC 245 or DC 345 by Dow Corning. Dimethicone copolyols are supplied, for
example, under the trade name DC 193 by Dow Corning or Belsil DM 6031 by
Wacker.
Optionally, conventional additives may likewise be present in the hair setting
composition, for example in order to impart certain modifying properties to
the
composition; these are silicones or silicone derivatives, wetting agents,
humectants, softeners such as glycerol, glycol and phthalic esters and ethers,
fragrances and perfumes, UV absorbers, dyes, pigments, and other colorants,
anticorrosive agents, neutralizing agents, antioxidants, antiadhesives,
combining
agents and conditioners, antistatic agents, lustre agents, preservatives,
proteins
and derivatives thereof, amino acids, vitamins, emulsifiers, surface-active
agents,
viscosity modifiers, thickeners and rheology modifiers, gelling agents,
opacifiers,
stabilizers, surfactants, sequestrants, complexing agents, pearlizing agents,
aesthetic enhancers, fatty acids, fatty alcohols, triglycerides, botanic
extracts,
clarifying auxiliaries and film formers.
These additives are generally present in a concentration of from about 0.001%
to
15% by weight, preferably 0.01% to 10% by weight, based on the total weight of
the hair setting composition.
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The hair setting compositions according to the invention can advantageously be
in
the form of a pump spray or aerosol packaging. The hair setting compositions
according to the invention can advantageously be foamed using a propellant
gas.
Accordingly, pump spray, aerosol packagings and foam dispensers based on
pump spray or aerosol packaging which contain the hair setting composition
according to the invention are likewise a constituent of the invention.
A preferred embodiment of the hair setting compositions according to the
invention
is in the form of a spray, which additionally comprises one or more of the
following
constituents: cosmetically suitable solvents, such as aliphatic alcohols
having 2-4
carbon atoms, preferably ethanol, polyols, acetone, unbranched or branched
hydrocarbons, cyclic hydrocarbons and mixtures thereof, and also propellant
gases, such as hydrocarbons, compressed air, carbon dioxide, nitrogen,
nitrogen
dioxide, dimethyl ether, fluorocarbons and chlorofluorocarbons, preferably
dimethyl
ether and/or a propane/butane mixture.
The present invention is illustrated by reference to the examples below, which
are
not to be understood as being limiting. Unless stated otherwise, all
quantitative
data, fractions and percentages are based on the weight and the total amount
or
on the total weight of the compositions.
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Examples:
Unless designated otherwise, all of the percentages refer to the weight.
Unless noted differently, all of the analytical measurements refer to
measurements
at temperatures of 23 C.
The solids or solid-body contents are determined by heating a weighed sample
at
125 C to constant weight. At constant weight, the solid-body content is
calculated
by reweighing the sample.
Unless expressly mentioned otherwise, NCO contents were determined
volumetrically in accordance with DIN-EN ISO 11909.
The control on free NCO groups was carried out by means of IR spectroscopy
(band at 2260 cm-1).
The stated viscosities were determined by means of rotary viscometry in
accordance with DIN 53019 at 23 C using a rotary viscometer from Anton Paar
Germany GmbH, Ostfildern, Germany.
The average particle sizes (the number-average is stated) of the polyurethane
dispersions were determined following dilution with deionized water by means
of
laser correlation spectroscopy (instrument: Malvern Zetasizer 1000, Malvern
Inst.
Limited).
Substances used and abbreviations:
Diaminosulfonate: NH2-CH2CH2-NH-CH2CH2-SO3Na (45% strength in
water)
Desmophen 2020/C2200: Polycarbonate polyol, OH number 56 mg of KOH/g,
number-average molecular weight 2000 g/mol (Bayer
MaterialScience AG, Leverkusen, Germany)
PoIyTHF 2000: Polytetramethylene glycol polyol, OH number 56 mg of
KOH/g, number-average molecular weight 2000 g/mol
(BASF AG, Ludwigshafen, Germany)
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PoIyTHF 1000: Polytetramethylene glycol polyol, OH number 112 mg of
KOH/g, number-average molecular weight 1000 g/mol
(BASF AG, Ludwigshafen, Germany)
Polyether LB 25: Monofunctional polyether based on ethylene
oxide/propylene oxide of number-average molecular
weight 2250 g/mol, OH number 25 mg of KOH/g (Bayer
MaterialScience AG, Leverkusen, Germany)
Example 1: Polyurethane dispersion 1
987.O g of PoIyTHF 2000 (component A2)), 375.4 g of PoIyTHF 1000
(component A2)), 761.3 g of Desmophen C2200 (component A2)) and 44.3 g of
Polyether LB 25 (component A4)) were heated to 70 C in a standard stirring
apparatus. A mixture of 237.0 g of hexamethylene diisocyanate (component Al))
and 313.2 g of isophorone diisocyanate (component Al)) was then added and the
mixture was stirred at 120 C until the theoretical NCO value was reached. The
finished prepolymer was dissolved with 4830 g of acetone and in so doing
cooled
to 50 C, and then a solution of 25.1 g of ethylenediamine (component B1)),
116.5 g of isophoronediamine (component B1)), 61.7 g of diaminosulfonate
(component B2)) and 1030 g of water was then metered in. The afterstirring
time
was 10 min. The mixture was then dispersed by adding 1250 g of water. The
solvent was removed by distillation in vacuo.
The resulting white dispersion had the following properties:
Solids content: 61%
Particle size (LCS): 312 nm
Viscosity (viscometer: 23 C): 241 mPas
pH (23 C): 6.02
pH (23 C): 7.15
Example 2: Polyurethane dispersion 2
450 g of PoIyTHF 1000 (component A2)) and 2100 g of PoIyTHF 2000
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(component A2)) were heated to 70 C. A mixture of 225.8 g of hexamethylene
diisocyanate (component Al)) and 298.4 g of isophorone diisocyanate (component
Al)) was then added and the mixture was stirred at 100-115 C until the actual
NCO value fell below the theoretical NCO value. The finished prepolymer was
dissolved with 5460 g of acetone at 50 C and then a solution of 29.5 g of
ethylenediamine (component B1)), 143.2 g of diaminosulfonate (component B2))
and 610 g of water was then metered in. The afterstirring time was 15 min. The
mixture was then dispersed by adding 1880 g of water. The solvent was removed
by distillation in vacuo and a storage-stable dispersion was obtained.
Solids content: 56%
Particle size (LCS): 276 nm
Viscosity: 1000 mPas
Example 3: Polyurethane dispersion 3
1649.0 g of a polyester of adipic acid, hexanediol and neopentyl glycol with
an
average molecular weight of 1700 g/mol (component A2)) were heated to 65 C.
291.7 g of hexamethylene diisocyanate (component Al)) were then added and the
mixture was stirred at 100-115 C until the actual NCO value fell below the
theoretical NCO value. The finished prepolymer was dissolved with 3450 g of
acetone at 50 C and then a solution of 16.8 g of ethylenediamine (component
B1)),
109.7 g of diaminosulfonate (component B2)) and 425 g of water was metered in.
The afterstirring time was 15 min. The mixture was then dispersed by adding
1880 g of water. The solvent was removed by distillation in vacuo and a
storage-
stable dispersion was obtained.
Solids content: 42%
Particle size (LCS): 168 nm
Viscosity: 425 mPas
pH: 7.07
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Example 4: Polyurethane dispersion 4
340 g of a polyester of adipic acid, hexanediol and neopentyl glycol with an
average molecular weight of 1700 g/mol (component A2)) were heated to 65 C.
60.1 g of hexamethylene diisocyanate (component Al)) were then added and the
mixture was stirred at 105 C until the actual NCO value fell below the
theoretical
NCO value. The finished prepolymer was dissolved with 711 g of acetone at 50 C
and then a solution of 2.1 g of ethylenediamine (component B1)), 32.4 g of
diaminosulfonate (component B2)) and 104.3 g of water was metered in. The
afterstirring time was 15 min. The mixture was then dispersed by adding 1880 g
of
water. The solvent was removed by distillation in vacuo, and a storage-stable
dispersion was obtained.
Solids content: 40%
Particle size (LCS): 198 nm
Viscosity: 700 mPas
pH: 6.31
Example 5: Polyurethane dispersion 5
450 g of PoIyTHF 1000 (component A2)) and 2100 g of PoIyTHF 2000
(component A2)) were heated to 70 C. A mixture of 225.8 g of hexamethylene
diisocyanate (component Al)) and 298.4 g of isophorone diisocyanate (component
Al)) was then added and the mixture was stirred at 100-115 C until the actual
NCO value fell below the theoretical NCO value. The finished prepolymer was
dissolved with 5460 g of acetone at 50 C and then a solution of 351 g of
diaminosulfonate (component B2)) and 610 g of water was metered in. The
afterstirring time was 15 min. The mixture was then dispersed by adding 1880 g
of
water. The solvent was removed by distillation in vacuo and a storage-stable
dispersion was obtained.
Solids content: 42%
Viscosity: 1370 mPas
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Application-related comparative experiments:
For the so-called "Curl Retention" experiments, commercial European mixed hair
from Kerling (useful length: 19 cm, Kerling colour number 6/0) are used. The
hair
is subjected to a standardized washing procedure prior to use. The hair
softened
for 15 min in water is shampooed for 2 minutes using 15% by weight sodium
dodecyl sulphate solution, thoroughly rinsed with warm water, blow-dried on a
cold
setting and conditioned at 22 C and 55% relative humidity. Hair tresses 0.5 cm
in
width are wound whilst damp onto spiral rollers, blow-dried on a hot setting
for
35 min, then sprayed with polymer dispersion and conditioned overnight.
For the application of the polymer dispersion, a spray head from Seaquist
Perfect
Dispensing GmbH is used: pump atomizer type PZ 1/150 HV (24/410). From a
distance of 30 cm, the compositions according to the invention are applied to
the
hair material by brisk actuation of the spray head.
The "Curl Retention" experiment is carried out in a special climatized chamber
with
a relative humidity of > 98%. The temperature of the chamber is 30 C. The
prepared tresses are hung simultaneously in the chamber. The length of the
curls
is read off on a scale at certain times. Each experiment is carried out on
three
tresses.
Experiment A B
Ethanol (% by wt.) 50 50
Polyurethane (% by wt. solid)') 4 2
Water (% by wt.) ad 100 ad 100
Spray bursts 12 4
Parts by weight are stated. ' ) : Based on solid in the aqueous polyurethane
dispersion.
Figure 1 shows the results achieved in experiment A.
Figure 2 shows the results achieved in experiment B.
In the figures:
0 means blank experiments, without polyurethane
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Polyurethanes of the prior art, comprising dimethylpropanoic acid:
(Polyurethanes comprising dimethylolpropanoic acid are usually prepared by
incorporating the dimethylolpropanoic acid into a prepolymer which is water-
soluble or water-dispersible, cf. WO 94/03510, EP 0619111 and EP 637600).
^ Polyurethane of the prior art, Luviset PUR from BASF, INCI name:
Polyurethane-1, polyurethane of a diisocyanate, dimethylolpropanoic acid,
polyesterdiol and aliphatic diol.
= Polyurethane of the prior art, DynamX POLYMER from National Starch, INCI
name: Polyurethane 14 (and) AMP-acrylates copolymer, polyurethane-14 consists
of isophorone diisocyanate, propyleneglycol, dimethylpropanoic acid, diol,
polyether.
A Polyurethane according to the invention as in example 4
The experiments clearly show that the best curl hold is achieved with the
polyurethane used according to the invention.
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Application-related examples:
(Parts by weight are stated).
"Pump-setting spray"
A B
Polyurethane according to the
2 10
invention (based on solid)
Ethanol 55 30
Perfume q.s. q.s.
Water ad 100 ad 100
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Aerosol hairsprays
C D E F G
Polyurethane according to the
10 2 5 8
invention (based on solid)
Octylacrylamide/acrylate/
butylaminoethyl methacrylate' 1.8
(based on solid)
Acrylate copolymer2 2
Aminomethylpropanol q.s q.s
Glycerol 0.5
Panthenol 0.5 0.5
PEG/PPG-18/18 dimethicone 0.5
PEG-12 dimethicone 0.05
Propylene glycol 0.5
Cyclomethicone 1.0 1.0
Benzophenone-3 0.1 0.1 0.1
Perfume q.s q.s q.s q.s q.s
Ethanol 14.5 20 60 30 20
Water ad 100 ad 100 ad 100 ad 100 ad 100
Propane/butane 3.5 bar (20 C) 20 10
Dimethyl ether 40 30 30 20
Fluorocarbon 152 A 20
1 Amphomer, National starch
2 Luvimer P-100, BASF
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Hair mousse
H I
Polyurethane according to the
2 4
invention (based on solid)
Glycerol 0.1
Panthenol 0.05 0.5
Polyquaternium-4 2
Cetyltrimethylammonium chloride 0.2 0.5
PEG-12 dimethicone 0.5
Cyclomethicone 0.5
Benzophenone-3 0,1
Perfume q.s. q.s.
Ethanol 15 10
Water ad 100 ad 100
Preservative q.s. q.s.
Dimethyl ether 10 7
Fluorocarbon 152 A 3
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Hair gel/cream
J K L
Polyurethane according to the
2 8
invention (based on solid)
Carbomer 0.8
Acrylic acidNP copolymer 0.5
Ammonium
0.8
acryloyldimethyltaurateNP copolymer
Glycerol 0.5
Panthenol 0.5 0.5
Propylene glycol 0.2
Cyclomethicone 0.2
Neutralizing agent q.s. q.s. q.s.
Perfume q.s. q.s. q.s.
Ethanol 20
Water ad 100 ad 100 ad 100
Preservative q.s. q.s. q.s.
