Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
' 0050/50663 CA 02382970 2002-02-21
' ~ , 'r.
Cosmetic based on oligomers and polymers containing urethane
and/or urea functional group
The present invention relates to oligomers and polymers
containing urethane and/or urea groups, to the use of these
oligomers in pharmaceutical and cosmetic preparations, and to
cosmetic compositions comprising these oligomers and polymers.
In cosmetics, polymers with film-forming properties are used for
setting, shaping and improving the structure of the hair. These
hair-treatment compositions generally contain a solution of the
film former in an alcohol or in a mixture of alcohol and water.
Hair-setting compositions are generally sprayed onto the hair in
the form of aqueous-alcoholic solutions. Following the
evaporation of the solvent, the individual hairs are held in the
desired shape at their points of mutual contact by the polymer
which is left behind. The polymers should on the one hand be
sufficiently hydrophilic that they can be washed out of the hair,
yet on the other hand should be hydrophobic so that, even under
conditions of high atmospheric humidity, the hair treated with
the polymers retains its shape and the individual hairs do not
stick to one another. In order to obtain a highly efficient
hair-setting effect, moreover, it is also desirable to employ
polymers which have a relatively high molecular weight and a
relatively high glass transition temperature (at least 10~C).
A further demand which is currently being placed on
hair-treatment compositions is that they impart flexibility, a
natural appearance and shine to the hair, for example even when
the hair is naturally particularly strong and/or dark.
When formulating hair-setting compositions, a further
consideration is that because of the environmental regulations
governing the emission of volatile organic compounds (VOCs) into
the atmosphere, it is necessary to reduce the content of alcohol
and of propellant.
DE-A-42 25 045 and WO 94/03515 describe the use of water-soluble
or water-dispersible, anionic polyurethanes as hair-setting
agents. These polyurethanes are composed of
a) at least one compound which contains two or more active
hydrogen atoms per molecule,
0050/50663 CA 02382970 2002-02-21
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b) at least one diol containing an acid or salt group and
c) at least one diisocyanate.
The acid groups present in these polyurethanes can be converted
into the corresponding salts by neutralization with at least one
base. For this purpose, low molecular weight amines, such as
2-amino-2-methylpropanol, diethylaminopropylamine and
triisopropanolamine, are used.
EP-A-619 111 describes the use of polyurethanes based on organic
diisocyanates, diols and 2,2-hydroxymethyl-substituted
carboxylates in hair-setting compositions. At least~some of the
carboxylic acid groups are neutralized with an organic or
inorganic base, chosen from sodium hydroxide, potassium
hydroxide, 2-amino-2-methylpropanol, histidine,
tris(hydroxymethyl)aminomethane and triethanolamine.
DE-A-195 41 658 describes water-soluble and water-dispersible
graft polymers of a polyurethane prepolymer with terminal
isocyanate groups and a protein containing free amino groups.
EP-A-636 361 describes a cosmetic composition which comprises, in
a cosmetically compatible carrier, at least one pseudolatex based
on a polycondensate which contains at least one polysiloxane unit
and at least one polyurethane and/or polyurea unit having anionic
or cationic groups. The neutralizing agents used here are mineral
bases, low molecular weight amines and aminoalcohols, mineral
acids and low molecular weight carboxylic acids. WO 97/25021 has
a similar disclosure content. The wash-off of these film formers
is unsatisfactory. In addition, because of a high siloxane
content, they do not have the setting action required for a hair
polymer either.
DE-A-195 41 329 and WO 97/17052 describe hair-treatment
compositions comprising a hair-setting polymer which is
dispersible or soluble in water or in a water/alcohol mixture,
and additionally a water-soluble or -dispersible
siloxane-containing salt. Hairspray formulations based on these
siloxane-containing salts, a non-siloxane-containing hair-setting
polymer and a silicone oil lead to films which are readily
removed from the surface of the hair, e.g. by mechanical stress.
The setting action of these formulations is therefore in need of
improvement.
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DE-A-195 41 326 and WO 97/17386 describe water-soluble or
water-dispersible polyurethanes having terminal acid groups,
their preparation and their use. In this case, a polyurethane
prepolymer which is dispersible or soluble in water and has
terminal isocyanate groups is reacted with an aminosulfonic acid
or aminocarboxylic acid, in particular taurine, aspartic acid and
glutamic acid.
None of the abovementioned documents describes polyurethanes
based on diisocyanates and oligomers containing groups which are
reactive toward isocyanate groups, these oligomers in turn
comprising, in incorporated form, urethane and/or urea groups.
The use of such oligomers in polymer-bound and non-polymer-bound
form in cosmetic products is not described either.
Cosmetic and pharmaceutical compositions for the treatment of
skin and hair are subject to special requirements with regard to
their rheological properties. Thus, for example, it is a current
demand that skincare products have a high proportion of care
substances. These are often compounds such as natural oils and
fats, essential oils etc., which, because of their flow
properties, can only be incorporated into the desired application
form, for example stick form, using additives. Haircare products,
e.g. shampoos, are also subject to specific requirements with
regard to their viscosity. Such products generally have a higher
viscosity or a more solid consistency than .is achieved with the
active substances and care substances used alone. Additives for
adjusting the viscosity or the consistency should preferably be
used in as small amounts as possible.
WO-A 98/17705 describes a resin composition which comprises
ester-terminated polyamides and the use thereof for the
formulation of transparent gels of liquid hydrocarbons of low
polarity.
WO-A 97/36572 describes a base composition for the preparation of
cosmetic compositions which comprise at least one liquid silicone
and at least one gel-forming agent. The liquid silicone is used
here in amounts of from 0.5 to 95% by weight, based on the total
weight of the composition, the formulations illustrated by
working examples comprise at least 27% by weight. The gel formers
used are polymers which obligatorily comprise, in incorporated
form, siloxane groups and polar groups suitable for forming
hydrogen bridge bonds. The latter are chosen from ester groups,
urethane groups, urea groups, thiourea groups and amide groups.
The polymers used as gel formers are not suitable as thickeners
for oils which are not based on silicone. The thickening of oil
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mixtures of silicone oils and further oils different therefrom is
not described in this specification either.
It is an object of the present invention to provide novel
cosmetic compositions, in particular for the treatment of skin
and hair. The cosmetic composition should preferably have good
rheological properties. Cosmetic compositions in the form of
hair-treatment compositions should form tack-free films with good
flexible properties. These compositions should preferably impart
smoothness and suppleness to the hair.
Surprisingly, we have found that this object is achieved by
cosmetic compositions which comprise at least one oligomer which
comprises at least one diisocyanate and at least one compound
having at least two groups which are reactive toward isocyanate
groups, where the oligomer comprises, per molecule, at least two
urethane and/or urea groups and additionally at least two further
functional groups having active hydrogen atoms.
The present invention therefore provides a cosmetic composition,
comprising:
at least one oligomer or polymer of
A) at least one diisocyanate,
B) at least one compound having at least two groups which
are reactive toward isocyanate groups, which is chosen
from
B1) aliphatic and cycloaliphatic polyols, polyamines
and/or aminoalcohols,
B2) polyetherols and/or diaminopolyethers,
B3) polysiloxanes having at least two active hydrogen
atoms per molecule,
B4) polyester polyols,
and mixtures thereof, and
C) optionally at least one dicarboxylic acid and/or
hydroxycarboxylic acid,
where the oligomer comprises, per molecule, at least two
urethane and/or urea groups and additionally at least two
further functional groups chosen from hydroxyl, primary
and/or secondary amino groups.
0050/50663 CA 02382970 2002-02-21
According to a first preferred embodiment, the cosmetic
compositions according to the invention comprise at least one
oligomer as described above.
5 The cosmetic compositions according to the invention preferably
comprise the oligomers in the form of a separate component and/or
incorporated into a polymer. Preferred polymers which comprise
the oligomers in incorporated form are polyurethanes. Within the
scope of the present invention, the expression "polyurethanes"
also includes polymers which have urea groups instead of or in
addition to urethane groups.
The oligomer preferably has 2 to 50, in particular 3 to 45,
urethane and/or urea groups per molecule.
Preference is given to oligomers of components A) and B) which
have a molecular weight in the range from about 500 to 10 000,
preferably 600 to 8 000, in particular 700 to 7 000.
Also preferred are oligomers of components A), B) and C) which
have a molecular weight in the range from about 500 to 20 000,
preferably 600 to 15 000, in particular 700 to 10 000.
Oligomers which contain hydroxyl groups preferably have an
alcohol number (OH number) of from about 5 to 150 mg of KOH/g,
particularly preferably 10 to 150 mg of KOH/g, in particular 20
to 100 mg of KOH/g. Oligomers which contain amino groups
preferably have an amine number of from about 5 to 150 mg of
KOH/g, particularly preferably 10 to 150 mg of KOH/g, especially
preferably 20 to 100 mg of KOH/g. For oligomers which have both
hydroxyl and amino groups, the sum of alcohol and amine number is
preferably in the range from about 5 to 150, particularly
preferably 10 to 150, in particular 20 to 100.
Preferably, the oligomers do not have free isocyanate groups.
The cosmetic compositions based on said oligomers according to
the invention generally advantageously have good application
properties even without the addition of components which contain
silicone groups. Thus, for example, hair-treatment compositions
in which the oligomer and/or the other components of the
formulation are silicone-free nevertheless generally impart good
flexibility to the hair. In a preferred embodiment, the cosmetic
compositions according to the invention comprise at least one
oligomer which does not include silicone groups. In a further
preferred embodiment, the cosmetic compositions according to the
invention comprise an oligomer which contains silicone groups,
0050/50663
CA 02382970 2002-02-21
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the other components of the composition being silicone-free. Tn
particular, both the oligomer and the other components of the
cosmetic composition are silicone-free. A further suitable
embodiment relates to cosmetic compositions in which the oligomer
and/or at least one other component contain silicone groups.
According to a second preferred embodiment, the cosmetic
compositions according to the invention comprise at least one
polymer of
A) at least one diisocyanate,
B) at least one compound having at least two groups which are
reactive toward isocyanate groups, which is chosen from
B1) aliphatic and cycloaliphatic polyols, polyamines and/or
aminoalcohols,
B2) polyetherols and/or diaminopolyethers,
B3) polysiloxanes with at least two active hydrogen atoms per
molecule,
B4) polyester polyols,
and mixtures thereof, and
C) optionally at least one dicarboxylic acid and/or
hydroxycarboxylic acid.
The polymer preferably has 2 to 80, in particular 4 to 50,
urethane and/or urea groups per molecule.
Preference is given to polymers of components A) and B) which
have a molecular weight in the range from about 700 to 40 000,
preferably 1 000 to 20 000, in particular 1 500 to 15 000.
Preference is also given to polymers of components A), B) and C)
which have a molecular weight in the range from about 700 to
80 000, preferably 1 000 to 40 000, in particular 1 500 to
20 000.
Polymers containing hydroxyl groups preferably have an alcohol
number (OH number) of about 5 to 150 mg of KOH/g. Polymers which
contain amine groups preferably have an amine number of about 5
to 150 mg of KOH/g. For polymers which have both hydroxyl and
amino groups, the sum of alcohol and amine number is preferably
in the range from about 5 to 150.
0050/50663
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The polymers are preferably compatible toward hydrophobic
(nonpolar) compounds, i.e. are miscible in a wide concentration
range with them to form homogeneous mixtures. The polymers are
particularly soluble in liquid hydrophobic compounds. Such
polymers are referred to below as "oil-soluble".
As well as having the urethane and/or urea groups, the polymers
also preferably have further groups which are able to form
hydrogen bridging bonds. These are preferably amide groups.
Preference is given to polymers where the component B) includes
at least one polyester polyol B4). In particular, component B) is
chosen from polyester polyols B4) which include at least one
ester of a di- or polyhydric alcohol with at least one cyclic or
acyclic dicarboxylic acid, obtained by dimerization of
unsaturated C6-C3o-carboxylic acids.
The diisocyanates A) are preferably, chosen from aliphatic,
cycloaliphatic and/or aromatic diisocyanates, such as
tetramethylene diisocyanate, hexamethylene diisocyanate,
methylenediphenyl diisocyanate, 2,4- and 2,6-toluylene
diisocyanate and isomeric mixtures thereof, o-, m- and p-xylylene
diisocyanate, 1,5-naphthylene diisocyanate, 1,4-cyclohexylene
diisocyanate, dicyclohexylmethane diisocyanate and mixtures
thereof, in particular isophorone diisocyanate, hexamethylene
diisocyanate and/or dicyclohexylmethane diisocyanate. Particular
preference is given to using hexamethylene diisocyanate. If
desired, up to 3 mol$ of said compounds can be replaced by
triisocyanates.
The groups of component B) which are reactive toward isocyanate
groups are preferably hydroxyl groups, primary and/or secondary
amino groups.
Preferred polyol components B1) are diols whose molecular weight
is in a range from about 62 to 500 g/mol. These include, for
example, diols having 2 to 18 carbon atoms, preferably 2 to 10
carbon atoms, such as 1,2-ethanediol, 1,3-propanediol,
1,4-butanediol, 1,6-hexanediol, 1,5-pentanediol, 1,10-decanediol,
2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, di-,
tri-, tetra-, penta- and hexaethylene glycol, neopentyl glycol,
cyclohexanedimethylol, glycerol monostearate and mixtures
thereof.
Preferred components Bl) are also triols and polyhydric polyols
having 3 to 100, preferably 3 to 70, carbon atoms. Preferred
triols are, for example, glycerol and trimethanolpropane.
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0050/50663
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Preferred triols B1) are also the triesters of hydroxycarboxylic
acids with trihydric alcohols. These are preferably triglycerides
of hydroxycarboxylic acids, such as, for example, lactic acid,
hydroxystearic acid and ricinoleic acid. Also suitable are
naturally occurring mixtures which contain hydroxycarboxylic acid
triglycerides, in particular castor oil. Preferred polyhydric
polyols B1) are, for example, erythritol, pentaerythritol and
sorbitol.
Preferred aminoalcohols B1) are, for example, 2-aminoethanol,
2-(N-methylamino)ethanol, 3-aminopropanol, 4-aminobutanol,
1-ethylaminobutan-2-ol, 2-amino-2-methyl-1-propanol,
4-methyl-4-aminopentan-2-of etc.
Preferred polyamines B1) are, for example, diamines, such as
ethylenediamine, propylenediamine, 1,4-diaminobutane,
1,5-diaminopentane and 1,6-diaminohexane. Preferred triamines B1)
are, for example, diethylenetriamine,
N,N'-diethyldiethylenetriamine etc. Preferred higher-valency
polyamines are, for example, triethylenetetramine etc.
The compounds given as component B1) can be used individually or
in mixtures. Particular preference is given to using
1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol,
diethylene glycol, cyclohexanedimethylol and mixtures thereof.
Component B2) is preferably a polyetherol having a number-average
molecular weight in the range from about 300 to 5 000, preferably
about 400 to 4 000, in particular 500 to 1500. Preferred
polyetherols are polyalkylene glycols, e.g. polyethylene glycols,
polypropylene glycols, polytetrahydrofurans, copolymers of
ethylene oxide, propylene oxide and/or butylene oxide, which
contain, in copolymerized form, the alkylene oxide units in
random distribution or in the form of blocks, etc.
Polytetrahydrofurans and mixtures which contain these are
preferably used as component B2).
Suitable polytetrahydrofurans B2) can be prepared by cationic
polymerization of tetrahydrofuran in the presence of acidic
catalysts, such as, for example, sulfuric acid or fluorosulfuric
acid. Such preparation processes are known to the person skilled
in the art.
The polysiloxanes B3) are preferably a compound of the formula II
0050/50663 CA 02382970 2002-02-21
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R4 R4
E1-(CH2)i ~ i- ~ i-(CH2)1-E2 (II)
R5 R5
k
in which
R4 and R5 independently of one another are C1- to C4-alkyl, benzyl
or phenyl,
E1 and E2 independently of one another are OH or NHR6, where R6 is
hydrogen, C1- to C6-alkyl or C5- to C8-cycloalkyl,
i and 1 independently of one another are 2 to 8,
k is 3 to 50,
and mixtures thereof.
Suitable alkyl radicals are, for example, methyl, ethyl,
n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl etc.
Suitable cycloalkyl radicals are, for example, cyclopentyl,
cyclohexyl, cycloheptyl, cyclooctyl etc.
Preferably, R4 and R5 are both methyl.
These polysiloxanes B3) preferably have a number-average
molecular weight in the range from about 300 to 5 000, preferably
400 to 3 000.
The polysiloxanes B3) are also preferably a compound of the
formula III
CH3 CH3 CH3 CH3
CH3 ~ i-0 ~ i- ~ i- ~ i- CH3 ( III )
CH3 CH3 L Z CH3
s t
in which
the order of the siloxane units is arbitrary,
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0050/50663
s is a value from 5 to 200, preferably 10 to 100,
t is a value from 1 to 20, preferably 2 to 10,
5 Z is a radical of the formula -(CHZ)u-NHZ, in which a is an
integer from 1 to 10, preferably 2 to 6, or
Z is a radical of the formula -(CH2)X-NH-(CH2)y-NH2, in which
x and y independently of one another are 0 to 10, preferably
10 1 to 6, where the sum x + y is 1 to 10, preferably 2 to 6.
These include, for example, the MAN and MAR grades from Huls, and
the Finish grades from blacker, e.g. Finish WT 1270.
Suitable compounds B3) are also the polydimethylsiloxanes
described in EP-A-227 816, to which reference is hereby made.
Suitable polyester polyols B4) are linear and branched polymers
having terminal OH groups, e.g. those having at least two OH
groups. Polyester polyols can be prepared, for example, by
esterification of aliphatic, cycloaliphatic and aromatic di-,
tri- and/or polycarboxylic acids, and of hydroxycarboxylic acids
with di-, tri- and/or polyols. Preferred polyesterols B4) are
polyesterdiols.
The polyesterols B4) preferably have a number-average molecular
weight in the range from about 400 to 5 000, preferably 500 to
4 000, in particular 600 to 3 000.
Component B4) is preferably chosen from esters of di- or
polyhydric alcohols with at least one carboxylic acid, the
carboxylic acid being chosen from
- cyclic or acyclic dicarboxylic acids, obtained by
dimerization of unsaturated C6- to C3o-carboxylic acids,
- aliphatic, cycloaliphatic and/or aromatic Ca- to
C3o-dicarboxylic acids,
- aliphatic, cycloaliphatic and aromatic Cs- to
C3o-hydroxycarboxylic acids,
and mixtures thereof.
The dimerization of mono- or polyunsaturated carboxylic acids
gives mixtures of acyclic and cyclic dicarboxylic acids, which
are referred to as dimeric acids or dimer fatty acids. For the
preparation of component B4), preference is given to using dimer
fatty acid mixtures which contain dimer fatty acids having 8 to
0050/50663 CA 02382970 2002-02-21
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54 carbon atoms. Preference is given to dimer fatty acids having,
on average, 36 carbon atoms, which are obtained, for example, in
the dimerization of unsaturated C18-fatty acids. Dimer fatty acids
are commercially available and, depending on the production,
contain proportions of branched mono fatty acids and trimer fatty
acids. If desired, these can be separated off by distillation
prior to the use of the dimer acids for the preparation of
component B4). To prepare component B4), the dimer fatty acids
are esterified with diols, triols and/or polyols. Preferably, for
the preparation of component B4), dimer fatty acids are
esterified with aliphatic and/or cycloaliphatic diols, triols
and/or polyols, as are described above as component B1). If
desired, the alcohols can be used alone or in mixtures.
Preferred components B4) are also polyesterdiols, in particular
those based on aromatic dicarboxylic acids, such as terephthalic
acid, isophthalic acid, phthalic acid, Na or K sulfoisophthalic
acid etc., aliphatic dicarboxylic acids, such as adipic acid or
succinic acid etc., and cycloaliphatic dicarboxylic acids, such
as 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid. Suitable diol
components of these polyesterdiols B4) are, in particular,
aliphatic diols, such as ethylene glycol, propylene glycol,
1,6-hexanediol, neopentyl glycol, diethylene glycol, polyethylene
glycols, polypropylene glycols, 1,4-dimethylolcyclohexane.
Preference is given to polyesterdiols B4) based on aromatic and
aliphatic dicarboxylic acids and aliphatic diols, in particular
those in which the aromatic dicarboxylic acid constitutes 10 to
95 mold, in particular 40 to 90 mold of the total dicarboxylic
acid content (remainder aliphatic dicarboxylic acids).
Particularly preferred polyesterdiols B4) are the reaction
products of phthalic acid/diethylene glycol, isophthalic
acid/1,4-butanediol, isophthalic acid/adipic acid/1,6-hexanediol,
5-NaS03-isophthalic acid/phthalic acid/adipic acid/1,6-hexanediol,
adipic acid/ethylene glycol, isophthalic acid/adipic
acid/neopentyl glycol, isophthalic acid/adipic acid/neopentyl
glycol/diethylene glycol/dimethylolcyclohexane and
5-NaS03-isophthalic acid/isophthalic acid/adipic acid/neopentyl
glycol/diethylene glycol/dimethylolcyclohexane, isopthalic
acid/adipic adid, neopentyl glycol/dimethylolcyclohexane.
Preferred components B4) are also polyesterdiols based on linear
or branched C$- to C3o-di- or polycarboxylic acids. If desired,
these can have one or more additional functional groups, such as,
for example, hydroxyl groups. Suitable di- and polycarboxylic
acids are, for example, azela.ic acid, dodecanedioic acid, suberic
' 0050/50663
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acid, pimelic acid, sebacic acid, tetradecanedioic acid, citric
acid, ricinoleic acid, hydroxystearic acid and mixtures thereof.
Preferred diols for the preparation of this component B4) are,
for example, 1,6-hexanediol, neopentyl glycol,
1,4-dimethylolcyclohexane, diethylene glycol, glycerol
monostearate and mixtures thereof.
In a preferred embodiment, the cosmetic compositions according to
the invention comprise at least one oligomer from component A)
and B) which has at least two terminal groups having active
hydrogen atoms, which are chosen from hydroxyl, primary and/or
secondary amino groups.
The cosmetic compositions according to the invention preferably
comprise at least one oligomer which contains, in incorporated
form, at least one component B4) which is chosen from esters of
di- or polyhydric alcohols with at least one carboxylic acid,
where the carboxylic acid is chosen from
- cyclic and acyclic dicarboxylic acids, obtained by
dimerization of unsaturated C6- to C3o-carboxylic acids,
- aliphatic, cycloaliphatic and aromatic Ce- to C3o-dicarboxylic
acids,
- Cg- to C3o-hydroxycarboxylic acids
and mixtures thereof.
In a preferred embodiment, the cosmetic compositions according to
the invention comprise at least one oligomer from the components
A) and B4).
According to a further preferred embodiment, the cosmetic
compositions according to the invention comprise at least one
polymer of components A) and B), where component B) includes at
least one compound of component B4). Particular preference is
given to cosmetic compositions which comprise at least one
polymer of components A) and B4).
In a further preferred embodiment, the cosmetic compositions
according to the invention comprise at least one oligomer from
component A), B) and C). The carboxylic acid C) is preferably
chosen from the abovementioned cyclic and acyclic dicarboxylic
acids, obtained by dimerization of unsaturated C6- to
C3o-carboxylic acids, aliphatic, cycloaliphatic and aromatic C$-
to C3a-dicarboxylic acids, CB- to C3o-hydroxycarboxylic acids and
mixtures thereof. Component C) is particularly preferably chosen
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0050/50663
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from sebacic acid, azelaic acid, C36-dimer fatty acid, ricinoleic
acid, hydroxystearic acid and mixtures thereof.
The oligomers based on at least one carboxylic acid C) have
5 carboxylic ester and/or carboxamide groups, depending on the
functional groups of component B).
The cosmetic compositions preferably comprise at least one
oligomer from components A), B1) and C).
Preference is given to oligomers of components A), B1) and C),
which are obtainable by reacting at least one compound of the
formula I
HO-R1-A1-CO-NH-R2-NH-CO-A1-R1-OH (I)
in which
R1 is Cz- to C12-alkylene, C5- to C$-cycloalkylene or arylene,
where alkylene radicals may be interrupted by one or two CS-
to Ce-cycloalkylene or arylene radicals,
RZ is a radical derived from an aliphatic, cycloaliphatic or
aromatic diisocyanate following removal of the isocyanate
groups,
A1 is O or NR3, where R3 is hydrogen, C1- to C6-alkyl or C5- to
C8-cycloalkyl,
with at least one carboxylic acid C), which is chosen from cyclic
or acyclic dicarboxylic acids, obtained by dimerization of
unsaturated C6- to C3o-carboxylic acids, aliphatic, cycloaliphatic
and aromatic Cg- to C3o-dicarboxylic acids, Cg- to
C3o-hydroxycarboxylic acids, and mixtures thereof. In the formula
I, R1 may also be a radical derived from glycerol monostearate by
removal of the OH groups.
The cosmetic compositions preferably comprise at least one
polymer of components A), B1) and C).
Preference is given to polymers of components A), B1) and C)
which are obtainable by reacting at least one compound of the
formula I.P
H-Y-R1-Y-(- C ( O ) -NH-R2-NH-C ( O ) -X-R1-X-~- H ( I . P )
in which
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14
R1 is C2- bis C12-alkylene, C5- to Cg-cycloalkylene or arylene,
where alkylene radicals may be interrupted by one or two C5-
to C8-cycloalkylene or arylene radicals,
R2 is a radical derived from an aliphatic, cycloaliphatic or
aromatic diisocyanate following removal of the isocyanate
groups,
X in each repeat unit is O once and A1 once,
Y is O once and A1 once,
A1 is O or NR3, where R3 is hydrogen, C1- to C6-alkyl or C5- to
Ce-cycloalkyl, and
n is an integer from 1 to 20, and preferably 1 to 5,
with at least one carboxylic C) which is chosen from cyclic or
acyclic dicarboxylic acids, obtained by dimerization of
unsaturated C6- to C3o-carboxylic acids, aliphatic, cycloaliphatic
and aromatic C8- to C3o-dicarboxylic acids, CB- to
C3o-hydroxycarboxylic acids, and mixtures thereof. In the formula
I.P, R1 may also be a radical derived from glycerol monostearate
by removal of the OH groups.
For the preparation of these oligomers of the formula I or
polymers of the formula I.P, preference is given to reacting at
least one diisocyanate A) of the formula OCN-R2-NCO with at least
one compound B1) of the formula HO-R1-A1-H. Here, the radicals R1,
R2 and A1 are as defined above.
For the preparation of the compounds of the formulae I and I.P,
preference is given to using diisocyanates A) which are chosen
from aliphatic diisocyanates, such as tetramethylene
diisocyanate, hexamethylene diisocyanate and mixtures comprising
these.
For the preparation of the compounds of the formulae I and I.P,
preference is given to using diols and aminoalcohols of the
formula HO-R1-A1-H, which are chosen from the diols and
aminoalcohols given above as component B1). Particular preference
is given to aliphatic diols and aminoalcohols, such as
1,4-butanediol, 1,6-hexanediol, 4-aminobutanol, 6-aminohexanol
and mixtures thereof.
The molar ratio of diisocyanate to compound of the formula
HO-R1-A1-H is preferably in a range from 1:1.1 to 1:2.5,
preferably about 1:2.
The oligomers of component A) and B) present in the cosmetic
compositions according to the invention are prepared by reacting
at least one diisocyanate A) with the groups of component B)
CA 02382970 2002-02-21
005050663
which are reactive toward isocyanate groups. If, for the
reaction, hydroxyl-containing components B) are used, then the
reaction is generally carried out at an elevated temperature in
the range from about 40 to 150°C, preferably about 70 to 120°C.
5 The reaction can be carried out without solvent in the melt or in
a suitable solvent or solvent mixture. The suitable solvents are
aprotically polar solvents, e.g. tetrahydrofuran, ethyl acetate,
N-methylpyrrolidone, dimethylformamide and, preferably, ketones,
such as acetone and methyl ethyl ketone. Oligomers which do not
10 contain hydroxyl-containing components in incorporated form are
prepared by reacting the amine-containing components B) with the
diisocyanates A) at a temperature in the range from about 0 to
60°C, preferably 10 to 50°C. As well as the abovementioned
solvents, the preparation of oligomers which do not contain
15 hydroxyl-containing components in incorporated form can also be
carried out in water, C1- to C4-alcohols, such as methanol,
n-propanol, isopropanol, n-butanol and, preferably, in ethanol
and ethanol/water mixtures. The reaction is preferably carried
out under an inert gas atmosphere, such as, for example, under
nitrogen. Furthermore, the reaction is preferably carried out at
ambient pressure or under elevated pressure. The components are
preferably used in amounts such that the ratio of NCO equivalent
of the compounds of component A) to equivalent of active hydrogen
atom of component B) is in a range from about 0.3:1 to 1.1:1,
preferably 0.4:1 to 0.9:1.
The preparation of oligomers of components A), B) and C) is
preferably carried out by reacting at least one reaction product
from components A) and B) with at least one carboxylic acid C).
The preparation is preferably carried out without the addition of
a solvent. The reaction temperature is preferably in the range
from about 100 to 250°C, in particular 150 to 220°C. The water
of
reaction formed during the reaction is removed by customary
methods known to the person skilled in the art, such as, for
example, by distillation. The reaction can be carried out at
atmospheric pressure or, preferably, at reduced pressure. The
polycondensation reaction can be accelerated using catalysts in
the amounts customary for this purpose. Suitable catalysts are,
for example, sulfuric acid, phosphoric acid, alkyl- and
arylsulfonic acids, acidic ion exchangers, tetrabutyl titanate
etc.
Oligomers of components A), B) and C) can also be prepared by
reacting at least one reaction product of components A) and B)
with a derivative of an acid C). Suitable derivatives are, for
' CA 02382970 2002-02-21
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16
example, the acid halides, anhydrides and esters with C1- to
C4-alkanols.
In the preparation of oligomers of components A), B) and C), the
molar ratio of reaction product from A) and B) to dicarboxylic
acid or hydroxycarboxylic acid C) is preferably chosen such that
the resulting oligomers essentially have no free carboxylic acid
groups:
The polymers present in the cosmetic compositions according to
the invention are generally prepared as described above for the
oligomers. The reaction of components A) and B) is preferably
carried out without a diluent or in the melt. The temperature is
preferably in the range from about 60 to 170~C. If desired, a
temperature gradient can be used where, for example, the starting
materials are firstly reacted for about 1 to 8 hours at a
temperature in the range from about 60 to 100~C and then for about
1 to 6 hours at a temperature in the range from about 100 to
170°C. The reaction is preferably carried out under an inert gas
atmosphere. The resulting polymers preferably have no free
isocyanate groups. Any isocyanate groups still present can be
deactivated by final reaction with at least one compound having
groups which are reactive toward isocyanate groups. For this
purpose, preference is given to using natural or synthetic fatty
alcohols, fatty amines or hydroxycarboxylic acids different from
C). Preference is also given to castor oil.
For the preparation of oil-soluble polymers, it is possible,
preferably, to proceed according to two alternative synthesis
routes Syn 1 and Syn 2:
Syn 1:
- reaction of at least one dicarboxylic acid, preferably a
dimer fatty acid, with at least one diol to give a
polyesterdiol and
- reaction of the polyesterdiol with at least one diisocyanate
to give an oil-soluble polymer.
Syn 2:
- reaction of at least one diisocyanate with at least one diol
to give a urethane-containing diol or a polyurethanediol and
' CA 02382970 2002-02-21
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17
- reaction of the polyurethanediol with at least one
dicarboxylic acid, preferably a dimer fatty acid, to give an
oil-soluble polymer.
Particular preference is given to synthesis route Syn 2. The
reactions are preferably carried out in the melt or in an oil as
solvent. Preference is given to the preparation in a cosmetically
compatible oil as is also used for the formulation of cosmetic
compositions which comprise the oil-soluble polymers according to
the invention.
The cosmetic compositions preferably comprise at least one
oligomer of components A) and B1). In the preparation of these
oligomers, the ratio of NCO equivalent of the compounds of
component A) to equivalent of active hydrogen atom of compounds
of component B1) is in a range from about 0.3:1 to 0.9:1. The
oligomers of components A) and B1) preferably have a molecular
weight in the range from about 500 to 5 000, particularly
preferably 600 to 3 000, in particular 700 to 2 000.
The cosmetic compositions preferably comprise at least one
oligomer of components A) and BZ). In the preparation of these
oligomers, the ratio of NCO equivalent of the compounds of
component A) to equivalent of active hydrogen atom of components
B2) is in a range from about 0.5:1 to 1:1, preferably 0.5:1 to
0.95:1, particularly preferably 0.5:1 to 0.8:1. The oligomers of
components A) and B2) preferably have a molecular weight in a
range from about 500 to 5 000, particularly preferably 600 to
3 000. Polymers of components A) and B2) preferably have a
molecular weight in the range up to about 15 000, particularly
preferably about 6 000.
The cosmetic compositions preferably comprise at least one
oligomer of components A) and B3). In the preparation of these
oligomers, the ratio of NCO equivalent of the compounds of
component A) to equivalent of active hydrogen atom of components
B3) is in a range from about 0.5:1 to 0.9:1. These polysiloxanes
preferably have a number-average molecular weight in a range from
about 300 to 5 000, preferably 400 to 3 000.
The cosmetic compositions preferably comprise at least one
oligomer of components A) and B4). In the preparation of these
oligomers, the ratio of NCO equivalent of compounds of component
A) to equivalent of active hydrogen atom of components B4) is in
a range from about 0.4:1 to 1:1, preferably 0.4:1 to 0.95:1,
particularly preferably 0.4:1 to 0.9:1. The molecular weight of
the oligomers of components A) and B4) is preferably in a range
CA 02382970 2002-02-21
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18
from about 500 to 7 000, particularly preferably 600 to 6 000, in
particular 700 to 5 000. Polymers of components A) and B4)
preferably have a molecular weight in the range up to about
20 000, particularly preferably about 12 000, in particular about
10 000.
The cosmetic compositions preferably comprise at least one
oligomer of components A), B), particularly preferably B1), and
C). These reaction products preferably have a molecular weight in
the range from about 500 to 20 000, preferably 600 to 15 000, in
particular 700 to 10 000.
The invention further provides an oligomer which comprises, in
incorporated form, at least one diisocyanate A) and at least one
component B4), as described above.
The invention further provides an oligomer which comprises, in
incorporated form, at least one diisocyanate A), at least one
component B) and at least one dicarboxylic acid and/or
hydroxycarboxylic acid C), as described above.
In a preferred embodiment, the cosmetic compositions according to
the invention comprise at least one oligomer, as described above,
in the form of a separate component.
In a preferred embodiment, the cosmetic compositions according to
the invention which comprise the oligomers or the polymers as a
separate component are in the form of a hair-treatment
composition. These include, for example, hairsprays, setting
foams, hair mousse, hair gel and shampoos. Suitable components
for formulating hair-treatment compositions are described in
detail below for hair-treatment compositions based on polymers
which comprise the oligomers in copolymerized form. Reference is
made to the entire contents of the ingredients and formulations
cited therein. The hair-treatment compositions preferably
comprise the oligomers in an amount in the range from about 0.01
to 20~ by weight, preferably 0.1 to 15~ by weight, based on the
total amount of the composition. Generally, hair cosmetics based
on the oligomers described above have better film properties,
such as, for example, reduced tackiness, compared with
corresponding products without these additives. Better
flexibility is generally achieved with the compositions according
to the invention than with conventional compositions. The hair
treated with the compositions according to the invention thus
generally has goad suppleness and/or combability.
' CA 02382970 2002-02-21
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1g
To formulate hair-setting compositions, preference is given to
using oligomers of components A) and B1).
In a further preferred embodiment, the cosmetic compositions
according to the invention are in the form of an oil-containing
or fat-containing cosmetic preparation. These include, for
example, creams, mascara, eye makeup, face makeup, cosmetic oils,
baby oil, bath oil, make-up remover, skin moisturizers,
sunscreens, lipcare compositions, anhydrous hand cleansers,
medicinal ointments etc.
The oil-containing or fat-containing cosmetic compositions
according to the invention have, for example, an oil or fat
component chosen from: hydrocarbons of low polarity, such as
mineral oils; linear saturated hydrocarbons, such as tetradecane,
hexadecane, octadecane etc.; cyclic hydrocarbons, such as
decahydronaphthalene; branched hydrocarbons; esters, preferably
esters of fatty acids, such as, for example, the esters of CZ- to
C24-monoalcohols with C1- to C22-monocarboxylic acids, such as
isopropyl isostearate, n-propyl myristate, isopropyl myristate,
n-propyl palmitate, isopropyl palmitate, hexacosanyl palmitate,
octacosanyl palmitate, triacontanyl palmitate, dotriacontanyl
palmitate, tetratriacontanyl palmitate, hexacosanyl stearate,
octacosanyl stearate, triacontanyl stearate, dotriacontanyl
stearate, tetratriacontanyl stearate; salicylates, such as C1- to
Clo-salicylates, e.g. octyl salicylate; benzoate esters, such as
C1o- to C15-alkyl benzoates, benzyl benzoate; other cosmetic
esters, such as fatty acid triglycerides, propylene glycol
monolaurate, polyethylene glycol monolaurate, castor oil, C1o- to
C15-alkyl lactates, etc. The oil-containing or fat-containing
cosmetic compositions according to the invention generally
comprise these components in an amount of at least 0.1,
preferably at least 0.2, especially at least 0.5% by weight.
Suitable amounts, for example, are about 0.1 to 99.9% by weight,
preferably 1 to 99.9% by weight, particularly preferably 10 to
90% by weight, especially 20 to 80% by weight, based on the total
weight of the composition.
The oil-containing or fat-containing cosmetic compositions
according to the invention generally comprise the oligomers and
polymers described above or the reaction products thereof in an
amount of from about 0.1 to 50% by weight, preferably 0.2 to 40%
by weight, particularly preferably 0.2 to 30% by weight, in
particular 0.5 to 10% by weight, based on the total amount of the
composition.
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Furthermore, the oil-containing or fat-containing cosmetic
compositions can comprise auxiliaries and/or additives, such as
emulsifiers, superfatting agents, stabilizers, waxes, bodying
agents, thickeners, silicone compounds, biogenic active
5 ingredients, film formers, preservatives, hydrotropic agents,
solubilizers, UV adsorbers, dyes and fragrances etc.
For the preparation of the oil- or fat-containing cosmetic
compositions according to the invention, preference is given to
10 using an oligomer which comprises, in incorporated form, at least
one diisocyanate A) and at least one component B), which is
chosen from components B2) to B4). For the preparation of the
oil- or fat-containing compositions, preference is also given to
using an oligomer of components A), B), preferably B1), and C).
The rheological properties and the consistency of the novel oil-
and fat-containing cosmetic products based on oligomers described
above can generally be adjusted within a wide range. Depending on
the basic consistency of the cosmetic composition, it is possible
to vary the properties, generally depending on the feed amount of
the oligomer, from a low-viscosity to a solid consistency.
Skin-cosmetic products can thus advantageously be formulated
which have a high proportion of low-viscosity oil- or
fat-containing components.
The oligomers described are advantageously suitable for
formulating gels. The term °gel~~ generally means a formulation
which has a higher viscosity than a liquid and is
self-supporting, i.e. retains a shape given to it without a
shape-stabilizing coating. To formulate gels, all of the oil
components given above which are liquid at ambient temperature
are generally suitable. Advantageously, gels based on the
oligomers described above are generally transparent. They can be
formulated with customary additives to give cosmetic compositions
according to the invention, such as, for example, lipcare
compositions, deodorants, antiperspirants, make-up, etc.
Advantageously, the oligomers described can also be used for the
preparation of gel-based non-cosmetic products. These include,
for example, automotive waxes and polishes, candles, furniture
polishes, leathercare compositions, metal cleaners, household
cleaners, etc.
The oligomers described are also advantageously suitable for the
preparation of customary O/W and W/0 formulations, such as, for
example, creams, in which case they may generally be used either
in the oil phase or in the water phase.
' CA 02382970 2002-02-21
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21
The invention further provides for the use of oligomers and
reaction products thereof, as described above, as components of
pharmaceutical and cosmetic preparations, preferably in cosmetic
preparations for the treatment of skin or of hair, for modifying
rheological properties of compositions based on compounds of low
polarity, and as intermediates for the preparation of
water-soluble or water-dispersible polyurethanes.
The invention further provides for the use of oligomers and
reaction products thereof, as described above, as or in coatings
and as or in treatment compositions for nonabsorbent surfaces,
preferably metals, plastics, synthetic textile fibers and glass,
and for absorbent surfaces, preferably wood, paper, cotton and
leather.
Said oligomers are particularly suitable as thickeners for
liquids of low polarity, preferably oils. Preference is given to
using oligomers as thickeners for oils which have a proportion,
based on the total weight, of urethane and/or urea groups of at
most 5% by weight. These components preferably have high
compatibility with non-silicone-containing oils. They are
generally soluble in silicone oils, non-silicone-containing oils
or mixtures thereof. Advantageously, the resulting solutions are
generally clear. Advantageously, clear cosmetic formulations can,
for example, be colored more easily than ones which are already
colored. The above-described oligomers and reaction products
thereof are preferably suitable for use in personal care
products, such as, for example, cosmetic compositions, e.g. eye
make-up, face make-up, baby oil, bath oil, make-up remover, skin
moisturizers, sunscreens, lipcare compositions, anhydrous hand
cleansers, cosmetic gels, ointments, waxes, medicinal ointments,
perfumes and suppositories. They are also advantageously suitable
for formulating hair cosmetic products, such as hairsprays,
setting foams, hair mousse, hair gel and shampoos. They are
furthermore preferably suitable for use in decorative cosmetics,
in particular mascara and eyeshadows. In addition, the oligomers
described above and the reaction products thereof can
advantageously be used in household products, such as automotive
waxes and polishes, candles, furniture polishes, metal cleaners
and metal polishes, household cleaners, color removers and
carrier materials for insecticides. They are further suitable for
use in technical or industrial products, such as, for example, in
fuels, greases, soldering pastes, rust inhibitors and inkjet
printer cartridges.
' CA 02382970 2002-02-21
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22
The abovedescribed oil-soluble polymers are suitable, in
particular, for formulating cosmetic compositions based on
hydrophobic compounds.
5 The invention therefore further provides a cosmetic composition,
comprising:
i) at least one oil-soluble polyurethane which comprises, in
incorporated form,
A) at least one diisocyanate,
B) at least one compound having at least two groups which
are reactive toward isocyanate groups, which is chosen
from
B1) aliphatic and cycloaliphatic polyols, polyamines
and/or amino alcohols,
B2) polyetherols and/or diaminopolyethers,
B3) polysiloxanes having at least two active hydrogen
atoms per molecule,
B4) polyester polyols,
and mixtures thereof, and
C) optionally at least one dicarboxylic acid and/or
hydroxycarboxylic acid,
35
ii) at least one cosmetically compatible hydrophobic compound,
iii)optionally at least one cosmetic active substance different
from ii) and
iv) optionally at least one additive.
With regard to the oil-soluble polyurethanes used as component
i), reference is made to the above statements regarding the
polymers.
Component A) is preferably chosen from aliphatic diisocyanates,
such as tetramethylene diisocyanate, hexamethylene diisocyanate
etc. Particular preference is given to using hexamethylene
diisocyanate.
Component B) preferably includes at least one polyester polyol
B4). Component B) is preferably chosen from polyester polyols B4)
which include at least one ester of a di- or polyhydric alcohol
0050/50663 CA 02382970 2002-02-21
23
with at least one cyclic or acyclic dicarboxylic acid, obtained
by dimerization of unsaturated C6- to C3o-carboxylic acids.
The hydrophobic compounds of component ii) are chosen from
essentially water-insoluble (hydrophobic) cosmetically acceptable
oil or fatty components. These include, preferably,
water-insoluble liquids. "Water-insoluble" is understood as
meaning a solubility in water of generally at most 1 g/1 at 20~C.
The hydrophobic compounds of component ii) are preferably chosen
from
I) oils, preferably mineral oils, fully synthetic oils, oils of
vegetable and animal origin and essential oils, fats,
saturated acyclic and cyclic hydrocarbons, esters of
monocarboxylic acids with mono-, di- or trihydric alcohols,
silicone oils and mixtures thereof,
II) synthetic polyethylene waxes different from I),
III)vaseline,
and mixtures thereof.
With regard to the oil and/or fatty component I, reference is
made to that stated above.
The compounds of component II are preferably chosen from
polyethylene waxes and wax mixtures with a proportion of
incorporated ethylene units or a polyethylene proportion of at
least 60% by weight, based on the total weight of the compounds
of component II. Examples of suitable polyethylene waxes are
homopolymeric polyethylene waxes, micronized polyethylene waxes,
copolymeric polyethylene waxes, oxidized polyethylene waxes,
mixtures of polyethylene waxes with further waxes, such as, for
example, polyether waxes, montanic acid waxes, montanic ester
waxes etc. The copolymeric polyethylene waxes preferably have
acrylic acid or vinyl acetate as comonomers. Suitable
commercially available polyethylene waxes are the Luwax~ grades
from BASF Aktiengesellschaft. Particular preference is given to
using pulverulent and granular homopolymeric polyethylene waxes
(e. g. Luwax~A and AH grades), copolymeric granular polyethylene
waxes (Luwax~EAS and EVA grades) and mixtures thereof.
Suitable as components (III) are natural, synthetic and slack wax
vaselines. These also include products with the CTFA name
"Petrolatum", and the products which are primarily referred to in
the USA as "petroleum jelly". Preference is given to using
CA 02382970 2002-02-21
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15
24
vaseline which is able to form the most uniformly coherent and
resistant layer as possible. These include., preferably, grades
with a low solids content and/or high viscosity. Preference is
given to using the grades listed in DAB 10 (German pharmacopeia
5 10).
Preference is given to cosmetic compositions where the
hydrophobic compound includes at least one component II) and/or
III).
Suitable cosmetic active substances iii) are those mentioned
above. These include, preferably, vitamins, dyes, pigments, W
absorbers, care components, plant extracts, natural oils, such as
olive oil, palm oil, almond oil or mixtures thereof, etc.
Suitable additives iv) are those mentioned above. These include,
in particular, emulsifiers, superfatting agents, stabilizers,
waxes, bodying agents, thickeners, silicone compounds, biogenic
active ingredients, film formers, preservatives, hydrotropic
agents, solubilizers, UV absorbers, dyes and fragrances,
bactericides, perfumes, hand modifiers, etc.
The invention further provides for the use of the oil-soluble
polyurethanes, as defined above, as or in cosmetic oil, pomade,
ointment and wax bases, and for the formulation of O/W and W/O
emulsions as component of pharmaceutical and cosmetic
preparations, preferably in cosmetic preparations for the
treatment of the skin or of the hair, for modifying the
rheological properties of compositions based on compounds of low
polarity, as or in coatings and as or in treatment compositions
for nonabsorbent surfaces, preferably metals, plastics, synthetic
textile fibers and glass, and for absorbent surfaces, preferably
wood, paper, cotton and leather, and as thickeners for liquids of
low polarity.
In contrast to the polymers described, the above-described
oligomers always necessarily have at least two functional groups
chosen from hydroxyl and primary and secondary amino groups. They
are suitable, in an advantageous manner, for constructing
segmented polyurethanes which have these oligomers in
incorporated form as repeat unit.
The invention thus further provides segmented polyurethanes which
comprise, in incorporated form, at least one oligomer, as
described above, at least one low molecular weight chain
extender, at least one compound having at least one ionogenic
~~50/50663 CA 02382970 2002-02-21
and/or ionic (hydrophilic or dispersion-active) group and at
least one diisocyanate.
The polyurethanes based on the oligomers described above are
5 water-soluble or water-dispersible.
The oligomers described above are particularly suitable as
components for the preparation of water-soluble or
water-dispersible polyurethanes. The invention further provides
10 water-soluble or water-dispersible polyurethanes of:
a) at least one oligomer, as described above,
b) at least one compound having a molecular weight in the range
from 56 to 600, which contains two active hydrogen atoms per
15 molecule,
c) at least one compound which has two active hydrogen atoms and
at least one ionogenic and/or ionic group per molecule,
d) optionally at least one polymer having at least two active
hydrogen atoms per molecule,
20 e) at least one diisocyanate.
The polyurethanes according to the invention comprise at least
one of the oligomers described above as component a) in
incorporated (copolymerized) form.
30
Component b) is preferably a diol, diamine, amino alcohol, or a
mixture thereof. The molecular weight of these compounds is
preferably in a range from about 56 to 500. If desired, up to
3 mol% of said compounds can be replaced by triols or triamines.
Preference is given to using diols as component b). Diols which
can be used are, for example, ethylene glycol, propylene glycol,
butylene glycol, neopentyl glycol, cyclohexanedimethylol, di-,
tri-, tetra-, penta- or hexaethylene glycol and mixtures thereof.
Preference is given to using neopentyl glycol, glycerol
monostearate and/or cyclohexanedimethylol.
Suitable aminoalcohols b) are, for example, 2-aminoethanol,
2-(N-methylamino)ethanol, 3-aminopropanol, 4-aminobutanol,
1-ethylaminobutan-2-ol, 2-amino-2-methyl-1-propanol,
4-methyl-4-aminopentan-2-of etc.
Suitable diamines b) are, for example, ethylenediamine,
propylenediamine, 1,4-diaminobutane, 1,5-diaminopentane and
1,6-diaminohexane.
0050/50663 CA 02382970 2002-02-21
2G
Suitable diamines b) are also diamines of the formula
Ra-NH-(CH2)2-3-NH2, where Ra is C8- to CZZ-alkyl or Ce- to
C22-alkenyl, where the alkylene radical can have 1, 2 or 3
nonadjacent double bonds. The molecular weight of these diamines
b) is preferably in a range from about 160 to 400.
Other suitable diamines b), which are customarily used as chain
extenders, are, for example, hexamethylenediamine, piperazine,
1,2-diaminocyclohexane, 1,3-diaminocyclohexane,
I,4-diaminocyclohexane, neopentanediamine,
4,4'-diaminodicyclohexylmethane etc.
Suitable compounds c) have two active hydrogen atoms and at least
one ionogenic and/or ionic group per molecule, the groups being
anionogenic, anionic, cationogenic or cationic.
Preferred compounds c) having two active hydrogen atoms and at
least one anionogenic and/or anionic group per molecule are, for
example, compounds containing carboxylate and/or sulfonate
groups. Particularly preferred components c) are
2,2-hydroxymethylalkylcarboxylic acids, such as
dimethylolpropanoic acid, and mixtures which contain
2,2-hydroxymethylalkylcarboxylic acids, such as
dimethylolpropanoic acid.
Suitable diamines and/or diols c) having anionogenic or anionic
groups are compounds of the formula
O O
I~ I~
HO-R-O-C ( \ C-O-R-OH
HOOC / COON
and/or
O O
HO-R-O- II \ II-O-R-OH
S03Me
in which R is in each case a C2-C1s-alkylene group, and Me is Na
or K.
As component c) it is also possible to use compounds of the
formula
0050/50663 CA 02382970 2002-02-21
27
H2N(CH2)w-NH-(CH2)x-C00-M+
H2N(CH2)w-NH-(CH2)x-SOg-M+
in which w and x independently of one another are an integer from
1 to 8, in particular from 1 to 6, and M is Li, Na or K, and
compounds~of the formula
H2N(CH2CH20)y(CH2CH(CH3)O)z(CH2)w-NH-(CH2)x-S03-M+
in which w and x areas defined above, y and z independently of
one another are an integer from 0 to 50, where at least one of
the two variables y or z is > 0. The order of the alkylene oxide
units is arbitrary. The last-named compounds preferably have a
number-average molecular weight in the range from about 400 to
3 000. A suitable compound of this type is, for example Poly ESP
520 from Raschig.
The polyurethanes can also comprise, in incorporated form,
compounds c) which have two active hydrogen atoms and at least
one cationogenic and/or cationic group, preferably at least one
nitrogen-containing group, per molecule. The nitrogen-containing
group is preferably a tertiary amino group or a quaternary
ammonium group. Preference is given, for example, to compounds of
the formulae
R9 R9
HO- R~ - ~ - Rs - OH Rl~Ht~- R7 - ~ - Ra - NHR11
HO- R7 - N NH R1~HN- R7 - N NH
U V
n n
HO- R7 - N N- Rs - OH R1~HN- R7 - N N- Rs -NHRil
U U
R9 R12
X-
HO- R7 - ~ ~-R1 ~- OH HO- R~ N N- R8 - OH
~ 12X X ~ R13
~~O
(CH2)o
O-
7 ~+ s -
HO-R -N-R OH
R9
~05~/50663 CA 02382970 2002-02-21
2$
in which
- R~ and R8, which can be identical or different, are
C2-C8-alkylene,
- R9, R1z and R13, which can be identical or different, are
C1-C6-alkyl, phenyl or phenyl-C1-C4-alkyl,
R1~ and R11, which can be identical or different, are H or
C1-C6-alkyl,
o is 1, 2 or 3,
Xe is chloride, bromide, iodide, C1-C6-alkyl sulfate or
S042'/2
Particular preference is given to N-(C1-C6-alkyl)diethanolamines,
such as methyldiethanolamine and N-alkyl-dialkylenetriamines such
as N-methyl-dipropylenetriamine. These are preferably used in
combination with dimethylolpropanoic acid as component c).
Also suitable as component c) are mixtures comprising two or more
of the abovementioned compounds having anionic and/or anionogenic
groups, two or more of the abovementioned compounds having
cationic and/or cationogenic groups or mixtures which comprise at
least one of the abovementioned compounds having anionic or
anionogenic groups and at least one of the abovementioned
compounds having cationic or cationogenic groups. Preference is
given to using, for example, mixtures which comprise
dimethylolpropanoic acid and N-methyldiethanolamine. In a
preferred embodiment, the polyurethanes comprise predominantly or
exclusively anionogenic and/or anionic groups as ionogenic and/or
ionic groups. In a further preferred embodiment, the
polyurethanes comprise predominantly or exclusively cationogenic
and/or cationic groups as ionogenic and/or ionic groups. The
polyurethanes thus preferably comprise a component c) in
incorporated form which comprises predominantly, preferably in an
amount of at least 80% by weight, in particular in an amount of
at least 90% by weight, based on the total amount of component
c), either anionogenic (anionic) compounds or cationogenic
(cationic) compounds.
Component d) is preferably a polymer having a number-average
molecular weight, in the range from about 300 to 5 000, preferably
from about 400 to 4 000, in particular from 500 to 3 000.
Polymers d) which may be used are, for example, polyesterdiols,
polyetherols, polysiloxanes and mixtures thereof. Polyetherols
are preferably polyalkylene glycols, for example polyethylene
glycols, polypropylene glycols, polytetrahydrofurans etc.,
copolymers of ethylene oxide and propylene oxide or block
copolymers of ethylene oxide, propylene oxide and butylene oxide
050/50663 CA 02382970 2002-02-21
2g
which contain, in copolymexized form, the alkylene oxide units in
random distribution or in the form of blocks. a,w-Diamino-
polyethers which can be prepared by amination of polyalkylene
oxides with ammonia are also suitable. Preference is given to
using polyesterdiols or mixtures which contain them as component
d).
Suitable polytetrahydrofurans d) can be prepared by cationic
polymerization of tetrahydrofuran in the presence of acidic
catalysts, such as, for example, sulfuric acid or fluorosulfuric
acid. Such preparation processes are known to the person skilled
in the art.
Preferred polyesterdiols d) have a number-average molecular
weight in the range from about 400 to 5 000, preferably from 500
to 3 000, in particular, from 600 to 2 000.
Suitable polyesterdiols are all those which are normally employed
to prepare polyurethanes, especially those based on aromatic
dicarboxylic acids, such as terephthalic acid, isophthalic acid,
phthalic acid, Na- or K-sulfoisophthalic acid, etc., on aliphatic
dicarboxylic acids, such as adipic or succinic acid, etc., and on
cycloaliphatic dicarboxylic acids, such as 1,2-, 1,3- or
1,4-cyclohexanedicarboxylic acid. Particularly suitable diols are
aliphatic diols, such as ethylene glycol, propylene glycol,
1,6-hexanediol, neopentyl glycol, diethylene glycol, polyethylene
glycols, polypropylene glycols, 1,4-dimethylolcyclohexane.
Preference is given to polyesterdiols based on aromatic and
aliphatic dicarboxylic acids and aliphatic diols, especially
those in which the aromatic dicarboxylic acid accounts for from
10 to 95 mol%, in particular from 40 to 90 mol% of the overall
dicarboxylic acid content (the remainder being aliphatic
dicarboxylic acids).
Particularly preferred polyesterdiols are the reaction products
of phthalic acid/diethylene glycol, isophthalic
acid/1,4-butanediol, isophthalic acid/adipic acid/1,6-hexanediol,
5-NaS03-isophthalic acid/phthalic acid/adipic acid/1,6-hexanediol,
adipic acid/ethylene glycol, isophthalic acid/adipic
acid/neopentyl glycol, isophthalic acid/adipic acid/neopentyl
glycol/diethylene glycol/dimethylolcyclohexane, and
5-NaS03-isophthalic acid/isophthalic acid/adipic acid/neopentyl
glycol/diethylene glycol/dimethylolcyclohexane, isophthalic
acid/adipic acid, neopentylglycol/dimethylolcyclohexane.
0050/50663 CA 02382970 2002-02-21
Also preferred as component d) are the polyesterdiols already
given above as component B4) which are based on linear or
branched, C8- to C3o-di- or polycarboxylic acids and Ce- to
C3a-hydroxycarboxylic acids. Preferred carboxylic acids and
5 hydroxycarboxylic acids are, for example, azelaic acid,
dodecanedioic acid, subaric acid, pimelic acid, sebacic acid,
tetradecanedioic acid, citric acid, ricinoleic acid,
hydroxystearic acid and mixtures thereof. The diol component used
for the preparation of these polyesterdiols is preferably
10 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl
glycol, 1,4-dimethylolcyclohexane, diethylene glycol, glycerol
monostearate and mixtures thereof:
Also preferred as component d) are the abovementioned
15 polysiloxanes B3). Preferably, only one of the components a) or
d) comprises a polysiloxane. .
Component d) is also preferably a diaminopolyether siloxane of
the formula IV which is chosen from
- polysiloxanes having repeat units of the formula IV.I
H3 I H3
Si O-Si R13-NH-R14-(CH2CH20)~(CH2CH(CH3)0)W-R13-NH-R14
CH3 CH3 a
b
in which (IV.1)
a is an integer from 0 to 100,
b is an integer from 1 to 8,
R13 and R14 independently of one another are C1- to
Ce-alkylene,
the order of the alkylene oxide units is arbitrary and v and
w independently of one another are an integer from 0 to
200, where the sum v + w is > 0,
- polysiloxanes of the formula IV.2
CH3 CH3 CH3 CH3 CH
3
CH3 ~ i-0 ~ i- ~ i-0 ~ i.-0 ~ i.- CH3
CH3 CH3 c L (~ H2 ) f d L ~ 15 a CHg
Z1 NR16R17 ( IV.2 )
0050/50663 CA 02382970 2002-02-21
31
in which
R15 is a C1- to Ce-alkylene radical,
R16 and R17 independently of one another are hydrogen, C1- to
Ce-alkyl or C5- to C8-cycloalkyl,
the order of the siloxane units is arbitrary, c, d and a
independently of one another are 0 to 100, where the sum
c + d + a is at least 3,
f is an integer from 2 to 8,
Z1 is a radical of the formula V
-R18- ( CHzCH20 ) g ( CHyCH ( CH3 ) O ) h-R19 ( V )
in which
~5 the order of the alkylene oxide units is arbitrary and g
and h independently of one another are an integer
from 0 to 200, where the sum g + h is > 0,
R18 is a C1- to C8-alkylene radical, and
R19 is hydrogen or a C1- to C8-alkyl radical,
and mixtures thereof.
Preferably, in formula IV.1, R13 and R14 independently of one
another are a C2- to C4-alkylene radical. In particular, R13 and
R14 independently of one another are a C2- to C3-alkylene radical.
The molecular weight of the compound of the formula IV.1 is
preferably in a range from about 300 to 100 000.
In the formula IV.1, a is preferably an integer from 1 to 20,
such as, for example, from 2 to 10.
The total number of alkylene oxide units in the compound of the
formula IV.1, i.e. the sum v + w, is preferably in a range from
about 3 to 200, preferably from 5 to 180.
Preference is given to the end groups of the polysiloxanes having
repeat units of the formula IV.1 selected from (CH3)3Si0, H,
C1 C8-alkyl and mixtures thereof.
Suitable alkoxylated siloxaneamines of the formula IV.1 are
described, for example, in w0-A-97/32917, to the entire contents
of which reference is made here. Commercially available compounds
are, for example, the Silsoft0 products from Witco, e.g. SilsoftOO
A-843.
0050/50663 CA 02382970 2002-02-21
32
Preferably, in the formula IV.2, the radical R15 is a
C2-C4-alkylene radical.
Preferably, in the formula IV.2, R16 and R1~ independently of one
another are hydrogen or C1-C4-alkyl.
Preferably, the sum c + d + a is chosen such that the molecular
weight of the compound of the formula IV.2 is in a range from
about 300 to 100 000, preferably from 500 to 50 000.
Preferably, the total amount of alkylene oxide units in the
radical of the formula V, i.e. the sum g + h, is in a range from
about 3 to 200, preferably from 5 to 80.
Preferably, in the formula V, the radical Rlg is CZ-C4-alkyl.
Preferably, in the formula V,~the radical R19 is hydrogen or
C1-C4-alkyl.
A suitable compound of the formula IV.2 is, for example, SilsoftOO
A-858 from Witco.
Component e) is a customary aliphatic, cycloaliphatic and/or
aromatic diisocyanate, such as tetramethylene diisocyanate,
hexamethylene diisocyanate, methylenediphenyl diisocyanate, 2,4-
and 2,6-tolylene diisocyanate and isomer mixtures thereof, o-, m-
and p-xylylene diisocyanate, 1,5-naphthylene diisocyanate,
1,4-cyclohexylene diisocyanate, dicyclohexylmethane diisocyanate
and mixtures thereof, especially isophorone diisocyanate,
hexamethylene diisocyanate and/or dicyclohexylmethane
diisocyanate. If desired, up to 3 mold of said compounds can be
replaced by triisocyanates.
The polyurethanes according to the invention are prepared by
reacting at least one oligomer a) and the compounds of components
b) and c), and optionally d), with the diisocyanate component e).
Here, the ratio of NCO equivalent of component e) to equivalent
of active hydrogen atom of components a) to d) is generally in a
range from about 0.6:1 to 1.4:1, preferably 0.8:1 to 1.2:1, in
particular 0.9:1 to 1.1:1. The reaction can preferably be carried
out without solvents or in a suitable inert solvent or solvent
mixture. Suitable solvents are aprotically polar solvents, e.g.
tetrahydrofuran, ethyl acetate, N-methylpyrrolidone,
dimethylformamide and, preferably, ketones, such as acetone and
methyl ethyl ketone. The reaction is preferably carried out under
an inert gas atmosphere, such as, for example, under nitrogen. In
addition, the reaction is preferably carried out at ambient
0050/50663 CA 02382970 2002-02-21
33
pressure or under increased pressure. If components a.) to d)
contain hydroxyl-containing compounds, then the reaction
temperature is preferably in a range from about 50 to 150~C. The
reaction is then preferably carried out in a solvent or solvent
mixture which does not have active hydrogen atoms. Preference is
given to using ketones, such as acetone, methyl ethyl ketone and
mixtures thereof. If, as components a) to d), compounds which
have primary and/or secondary amino groups as the groups reactive
toward isocyanate groups are used exclusively or predominantly,
then the reaction temperature is preferably in a range from about
5 to 80~C, particularly preferably 5 to 40~C. The reaction can
then, if desired, be carried out in a solvent or solvent mixture
which may have active hydrogen atoms. In addition to those given
above, preference is then given to using alcohols, such as
methanol and ethanol, mixtures of alcohols and water, and
mixtures of alcohols and the abovementioned ketones. If the
resulting polyurethanes still have free isocyanate groups, then
these are then deactivated by adding amines, preferably
aminoalcohols. Suitable aminoalcohols are those given above,
preferably 2-amino-2-methyl-1-propanol.
The oligomers a) used for the preparation of the polyurethanes
according to the invention can, in accordance with a suitable
embodiment, as already described, be prepared separately and be
isolated and/or purified by customary methods prior to use in the
polyurethane preparation.
According to a preferred embodiment, the preparation of the
oligomers a) and the preparation of the polyurethanes according
to the invention is carried out without isolation of an
intermediate. The two reactions preferably take place one after
the other in the same reaction vessel.
The polyurethanes preferably comprise
- 0.3 to 50% by weight, preferably 0.5 to 40% by weight, of at
least one oligomer a),
- 0.5 to 25% by weight, preferably 1 to 20% by weight, of at
least one component b),
- 0.5 to 50% by weight, preferably 3 to 45% by weight, of at
least one component c),
- 0 to 25% by weight, preferably 0.01 to 15% by weight, of at
least one component d),
~~5~/50663 CA 02382970 2002-02-21
34
- 25 to 60% by weight, preferably 35 to 53% by weight, of at
least one component e)
in copolymerized form.
The polyurethanes which contain acid groups can be partially or
completely neutralized with a base. The polyurethanes which
contain amine groups can be partially or completely protonated or
quaternized.
The resulting salts of the polyurethanes generally have better
water solubility or dispersibility in water than the non-
neutralized polyurethanes. Bases which can be used to neutralize
the polyurethanes are alkali metal bases, such as sodium
hydroxide solution, potassium hydroxide solution, sodium
carbonate, sodium hydrogencarbonate, potassium carbonate or
potassium hydrogencarbonate, and alkaline earth metal bases, such
as calcium hydroxide, calcium oxide, magnesium hydroxide or
magnesium carbonate, and ammonia and amines. Suitable amines are,
for example, C1-C6-alkylamines, preferably n-propylamine and
n-butylamine, dialkylamines, preferably diethylpropylamine and
dipropylmethylamine, trialkylamines, preferably triethylamine and
triisopropylamine, C1-C6-alkyldiethanolamines, preferably methyl-
or ethyldiethanolamine and di-C1-C6-alkylethanolamines, and
glucamine and methylglucamine. 2-Amino-2-methyl-1-propanol,
diethylaminopropylamine and triisopropanolamine have proven
successful for the neutralization of polyurethanes which contain
acid groups, particularly for use in hair-treatment compositions.
Polyurethanes which contain acid groups can also be neutralized
using mixtures of two or more bases, e.g. mixtures of sodium
hydroxide solution and triisopropanolamine. Depending on the
intended use, the neutralization can be partial, e.g. up to 20 to
40%, or complete, i.e. up to 100%.
Because of their cationic groups, polyurethanes which contain
amine groups or protonated or quaternized amine groups are
generally readily soluble in water or water/alcohol mixtures or
are at least dispersible without the aid of emulsifiers. Charged
cationic groups can be produced from the tertiary amine nitrogens
present either by protonation, e.g. with carboxylic acids, such
as lactic acid, or mineral acids, such as phosphoric acid,
sulfuric acid and hydrochloric acid, or by quaternization, e.g.
with alkylating agents, such as C1- to C4-alkyl halides or
sulfates. Examples of such alkylating agents are ethyl chloride,
ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate
and diethyl sulfate.
0~5~/50663 CA 02382970 2002-02-21
Polyurethanes which have both cationogenic and also anionogenic
groups can be subjected successively to neutralization with at
least one acid, neutralization with at least one base and, if
desired, additionally to quaternization. The order of the
5 neutralization steps is generally arbitrary.
If, in the preparation of the polymeric salts, a water-miscible
organic solvent is used, then this can be removed immediately
afterwards by customary processes known to the person skilled in
10 the art, e.g. by distillation at reduced pressure. Prior to
removal of the solvent, water can additionally be added to the
polymeric salt. Replacement of the solvent by water gives a
solution or dispersion of the polymeric salt, from which, if
desired, the polymeric salt can be obtained in the usual manner,
15 e.g. by spray drying.
The pH of the aqueous solutions or dispersions can be adjusted by
adding an acid or base. Suitable acids and bases are those given
above as additional neutralizing agents. The pH for anionic
20 polymeric salts is preferably in the alkaline range, in
particular > 7.5. Preferably, the pH for cationic polyurethanes
is in the acidic range, in particular from 5.5 to 6.5.
The polyurethanes according to the invention are soluble in water
25 or dispersible in water. They generally form clear and tack-free
films and can be washed out very readily with water.
Advantageously, the polyurethanes according to the invention also
give films having a very good elasticity. This elasticity is
generally higher than the elasticity which is usually obtained in
30 the case of polyurethanes known from the prior art.
Hair-treatment compositions based on these polymers impart very
good suppleness to the hair.
The polyurethanes or polyureas according to the invention are
35 generally soluble or dispersible in alcohols, alcohol/water
mixtures and/or in water without the aid of emulsifiers.
Preferred alcohols for the preparation of formulations of the
polyurethanes according to the invention are, in particular, C1-
to C4-alkanols, such as methanol, ethanol, n-propanol,
isopropanol, n-butanol and mixtures thereof.
The polyurethanes according to the invention can be used as
auxiliaries in cosmetics, preferably as or in coatings for
keratin-containing and keratin-analogous surfaces, such as hair,
skin and nails. They are particularly suitable for hair
cosmetics, preferably as setting polymers in hairsprays, setting
foams, hair mousse, hair gel and shampoos. They are also
CA 02382970 2002-02-21
0050/50663
36
preferably suitable for use in decorative cosmetics, in
particular in mascara, make-up and eyeshadows. They can also be
advantageously used as polymeric emulsifiers or co-emulsifiers
for the formulation of cosmetic or pharmaceutical preparations
for the skin. Because of their hydrophilic and hydrophobic
properties, they are suitable both for oil- and fat-containing
preparations, and for O/W and W/O emulsions. The polyurethanes
according to the invention can also be used as auxiliaries in
pharmacy, preferably as or in coatings or binders for solid
medicament forms. The polyurethanes mentioned above can also be
used in creams and as tablet coatings and tablet binders. They
are also suitable as binders and adhesives for cosmetic products.
The polyurethanes according to the invention are also preferably
suitable for use as or in coatings for the textile, paper,
printing, leather and adhesives industry.
The invention also provides a cosmetic or pharmaceutical
composition which comprises at least one polyurethane according
to the invention. The composition generally comprises the
polymeric salts in an amount in the range from about 0.2 to 30%
by weight, preferably from 0.5 to 20% by weight, based on the
total weight of the composition.
The cosmetic compositions according to the invention are suitable
in particular as coating compositions for keratin-containing and
keratin-analogous surfaces (hair, skin and nails). The compounds
used therein are water-soluble or water-dispersible. If the
compounds used in the compositions according to the invention are
water-dispersible, they can be used in the form of aqueous
microdispersions having particle diameters of customarily from 1
to 350 mm, preferably from 1 to 250 mm. The solid contents of the
preparations is usually in a range from about 0.5 to 20% by
weight, preferably from 1 to 12% by weight. These
microdispersions do not generally require emulsifiers or
surfactants for their stabilization.
Preferably, the compositions according to the invention can be in
the form of a hair-treatment composition, such as setting foam,
hair mousse, hair gel, shampoo and, in particular, in the form of
a hairspray. For use as hair-setting compositions, preference is
here given to compositions which comprise polyurethanes which
have at least one glass transition temperature Tg of >_ 10~C,
preferably >_ 20~C. The K value of these polymers (measured in
accordance with E. Fikentscher, Cellulose-Chemie 13 (1932), pp.
58-64) on a 1% strength by weight solution in
N-methylpyrrolidone, is preferably in a range from 23 to 90, in
particular from 25 to 60. If the polyurethanes according to the
~ CA 02382970 2002-02-21
0050/50663
37
invention have siloxane groups, then the siloxane content of
these polymers is generally from 0.05 to 20% by weight, based on
the total weight of the incorporated components.
The compositions are preferably hair-treatment compositions. They
are usually in the form of an aqueous dispersion or in the form
of an alcoholic or aqueous-alcoholic solution. Examples of
suitable alcohols are ethanol, propanol, isopropanol etc.
In addition, the hair-treatment compositions according to the
invention can generally comprise customary cosmetic auxiliaries,
for example softeners, such as glycerol and glycol; emollients;
perfumes; surfactants; W absorbers; dyes; antistats; combability
improvers; preservatives; and antifoams.
If the compositions according to the invention are formulated as
hairsprays, they comprise a sufficient amount of a propellant,
for example a low-boiling hydrocarbon or ether, such as propane,
butane, isobutane or dimethyl ether. Propellants which can be
used are also compressed gases, such as nitrogen, air or carbon
dioxide. The amount of propellant can be kept low so as not to
raise the VOC content unnecessarily. In general, the amount is
then no more than 55% by weight based on the total weight of the
composition. However, higher VOC contents of 85% by weight and
above are also possible if desired.
The polyurethanes described above can also be used in the
compositions in combination with other hair polymers. Such
polymers are, in particular:
- nonionic, water-soluble or water-dispersible polymers or
oligomers, such as polyvinylcaprolactam, e.g. Luviskol Plus
(BASF), or polyvinylpyrrolidone and its copolymers, in
particular with vinyl esters, such as vinyl acetate, e.g.
Luviskol VA 37 (BASF); polyamides, e.g. those based on
itaconic acid and aliphatic diamines, as described, for
example, in DE-A-43 33 238; polyvinyl alcohols and
derivatives thereof; polymers based on cellulose;
- amphoteric or zwitterionoic polymers such as the
octylacrylamide/methylmethacrylate/tert-butylaminoethyl
methacrylate/2-hydroxypropyl methacrylate copolymers
obtainable under the names Amphomer~ (National Starch), and
zwitterionic polymers as disclosed, for example in German
Patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369
and DE 37 08 451. Acrylamidopropyltrimethylammonium
chloride/acrylic acid and methacrylic acid copolymers and
~ CA 02382970 2002-02-21
0050/50663
38
alkali metal and ammonium salts thereof are preferred
zwitterionic polymers. Other suitable zwitterionic polymers
are methacroylethylbetaine/methacrylate copolymers, which are
available commercially under the name Amersette~ (AMERCHOL),
and copolymers of hydroxyethyl methacrylate, methyl
methacrylate, N,N-dimethylaminoethyl methacrylate and acrylic
acid (JordaponRp);
anionic polymers, such as vinyl acetate/crotonic acid
copolymers, as are commercially available, for example under
the names Resyn~ (NATIONAL STARCH), Luviset~ (BASF) and
Gafset~ (GAF), and vinylpyrrolidone/vinylacrylate copolymers,
obtainable for example under the tradename Luviflex~ (BASF).
A preferred polymer is the vinyl pyrrolidone/acrylate
terpolymer available under the name Luviflex~ VBM-35 (BASF).
Acrylic acid/ethyl acrylate/N-tert-butylacrylamide
terpolymers, which are marketed, for example under the name
Ultrahold0 strong (BASF), and Luvimer~ (BASF, terpolymer of
t-butyl acrylate, ethyl acrylate and methacrylic acid),
sodium sulfonate-containing polyamides or sodium
sulfonate-containing polyesters, or
- cationic (quaternized) polymers, e.g. cationic polyacrylate
copolymers based on N-vinyl lactams and derivatives thereof
(N-vinylpyrrolidone, N-vinylcaprolactam etc.) and customary
cationic hair-conditioning polymers, e.g. Luviquat0
(copolymer of vinylpyrrolidone and vinylimidazolium
methochloride), Luviquat ~ Hold (copolymer of quaternized
N-vinylimidazole, N-vinylpyrrolidone and N-vinylcaprolactam),
Merquat~ (polymer based on dimethyldiallylammonium chloride),
Gafquat~ (quaternary polymers formed by reacting
polyvinylpyrrolidone with quaternary ammonium compounds),
polymer ,1R (hydroxyethylcellulose with cationic groups),
polyquaternium grades (CTFA names) etc., chitosan and
chitosan derivatives;
- nonionic, siloxane-containing, water-soluble or -dispersible
polymers, e.g. polyether siloxanes, such as Tegopren~
(Goldschmidt) or Belsil~ (blacker).
The polymers according to the invention can be used as a mixture
with an amide-containing hair polymer. These include, for
example, the polyurethanes described in DE-A-42 25 045, the
above-described vinylpyrrolidone/acrylate terpolymers and acrylic
acid/ethyl acrylate/N-tert-butylacrylamide terpolymers (e. g.
UltraholdOOstrong from BASF AG), the above-described
amide-containing amphoteric polymers (e.g. AmphomerOO) and in
0050/50663 CA 02382970 2002-02-21
39
particular copolymers which have a proportion of amide-containing
monomers, such as N-vinyllactams, of at least 30% by weight (e. g.
Luviskol~plus and Luviskol ~VA37 from BASF AG).
The other hair polymers are preferably present in amounts up to
10% by weight, based on the total weight of the composition.
A preferred hair-treatment composition comprises:
a) from 0.5 to 20% by weight, preferably from 1 to 10% by
weight, of at least one water-soluble or -dispersible
polyurethane according to the invention,
b) from 50 to 99.5% by weight, preferably from 55 to 99% by
weight, of a solvent chosen from water and water-miscible
solvents, preferably Cz-C5-alcohols, in particular ethanol,
and mixtures thereof,
c) from 0 to 70% by weight, preferably from 0.1 to 50% by
weight, of a propellant, preferably chosen from dimethyl
ether and alkanes, such as, for example, propane/butane
mixtures,
d) from 0 to 10% by weight, preferably from 0.1 to 10% by
weight, of at least one water-soluble or -dispersible hair
polymer which is different from a),
e) from 0 to 0.5% by weight, preferably from 0.001 to 2% by
weight, of at least one water-soluble or water-dispersible
silicone compound,
f) from 0 to 1% by weight, preferably 0.0001 to 0.5% by weight,
of at least one compound chosen from esters and amides of
saturated and mono- or polyunsaturated C5- to C3o-carboxylic
acids, saturated and mono- or polyunsaturated CB- to
C3o-alcohols and mixtures thereof,
and customary additives.
The composition according to the invention can comprise, as
component d), at least one other water-soluble or -dispersible
hair polymer. The proportion of this component is then generally
from about 0.1 to 10% by weight, based on the total weight of the
composition. Preference is given in this connection to using
water-soluble or water-dispersible polyurethanes which do not
contain siloxane groups in copolymerized form.
~ CA 02382970 2002-02-21
0050/50663
The composition according to the invention can comprise, as
component e), at least one nonionic, siloxane-containing,
water-soluble or water-dispersible polymer, chosen in particular
from the above-described polyether siloxanes. The proportion of
5 this component is then generally from about 0.001 to 2% by
weight, based on the total weight of the composition.
The composition according to the invention can comprise, as
additional component, at least one water-insoluble silicone, in
10 particular a polydimethylsiloxane, e.g. the Abil~ grades from
Goldschmidt. The proportion of this component is then generally
from about 0.0001 to 0.2% by weight, preferably from 0.001 to
0.1% by weight, based on the total weight of the composition.
15 The composition according to the invention can additionally
comprise, where appropriate, an antifoam based, for example, on
silicone. The amount of the antifoam is then generally up to
about 0.001% by weight, based on the total amount of the
composition.
The composition according to the invention preferably comprises,
as component f), at least one ester of the formula R2~-CO-OR21, in
which R2~ is a straight-chain or branched C5- to C3o-, preferably
Cla- to C2o-alkyl or -alkenyl radical, where the alkenyl radical
can have 1, 2, 3 or 4 nonadjacent double bonds. R21 is preferably
a straight-chain or branched C1- to C3o-, in particular CS- to
C22-alkyl radical or a straight-chain or branched C6- to C3a-, in
particular C$- to C22-alkenyl radical, which can have 1, 2, 3 or 4
nonadjacent double bonds.
Preference is given to using the esters of caproic acid, caprylic
acid, 2-ethylhexanoic acid, capric acid, lauric acid,
isotridecanoic acid, myristic acid, palmitic acid, palmoleic
acid, stearic acid, isostearic acid, oleic acid, elaidic acid,
petroselic acid, linoleic acid, linolenic acid, elaeostearic
acid, arachidic acid, gadoleic acid, behenic acid and erucic
acid, and mixtures thereof, with lauryl alcohol, isotridecyl
alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol,
stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl
alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl
alcohol, elaeostearyl alcohol, arachidyl alcohol, gadoleyl
alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol,
and mixtures thereof. Preference is given to using esters which
have, in the fatty acid and fatty alcohol components together, at
least 24, preferably at least 30 carbon atoms and optionally a
0050/50663
CA 02382970 2002-02-21
41
double bond. Typical examples are oleyl erucate, erucyl oleate,
behenyl oleate and cetearyl oleate.
Also preferred as component f) are amides of the formula
Ra°-CO-NR22Rz3, where R2° can have the meanings given
above, and
R22 and R23 independently of one another are hydrogen, C1- to
C12-alkyl or C5- to Ce-cycloalkyl.
Also preferred as component f) are saturated, and mono- or
polyunsaturated alcohols. Suitable C8- to C3°-alkyl radicals are
those mentioned above. The alcohols can be used individually or
as mixtures. Such alcohols and alcohol mixtures are obtainable,
for example, by hydrogenation of fatty acids from natural fats
and oils or of synthetic fatty acids, e.g. from the catalytic
oxidation of paraffins. Suitable alcohols and alcohol mixtures
are also obtainable by hydroformylation of olefins with
simultaneous hydrogenation of the aldehydes, mixtures of
straight-chain and branched primary alcohols (oxo alcohols)
generally resulting. Suitable alcohols and alcohol mixtures are
also obtainable by partial oxidation of n-paraffins by known
processes, giving predominantly linear secondary alcohols. Also
suitable are the essentially primary, straight-chain and
even-numbered Ziegler alcohols.
Preferred alcohols f) are the Guerbet alcohols. Guerbet alcohols
which are preferably used as component f) are preferably obtained
by base-catalyzed self-condensation of linear and/or branched
alcohols having 6 to 22 and preferably 8 to 18 carbon atoms. A
review on this topic can be found in A. J. O'Lennick in Soap
Cosm. Chem. Spec. (April) 52 (1987). Typical examples are
condensation products of technical-grade fatty alcohol cuts
having 8 to 10 or 16 to 18 carbon atoms.
The compounds given above as component f) can be used
individually or as mixtures. The cosmetic compositions according
to the invention which comprise component f) generally have good
performance properties, such as, for example, good flexibility
and a pleasant feel, even without the use of silicone-containing
components.
In addition to the abovementioned components, the composition
according to the invention preferably comprises:
g) from 0 to 40% by weight, preferably from 0.1 to 35% by
weight, of at least one surfactant,
0050/50663
CA 02382970 2002-02-21
42
h) from 0 to 5% by weight, preferably from 0.05 to 4% by weight,
of at least one dye and/or UV absorber,
i) from 0 to 3% by weight, preferably from 0.05 to 2.5% by
weight, of at least one salt,
k) from 0 to 3% by weight, preferably from 0.05 to 2.5% by
weight, of at least one thickener,
and optionally other customary additives. These are then each
generally present in an amount of from about 0 to 0.2% by weight,
preferably from 0.001 to 0.2% by weight based on the total weight
of the composition.
The compositions according to the invention have the advantage
that on the one hand they impart the desired hold to hair and the
polymers can be washed out easily (are redispersible), and on the
other hand the hair remains elastic.
Advantageously, the polyurethanes according to the invention are
also suitable as components in hair-treatment compositions which
additionally comprise at least one other traditional hair
polymer. With these mixtures, too, better flexibilities are
generally achieved than for the corresponding polymers or
mixtures which do not contain the polyurethanes according to the
invention. The polyurethanes according to the invention are
therefore also suitable for improving the elasticity of
conventional hair-setting compositions. These then generally
impart very good flexibility and suppleness to the hair.
The invention is illustrated in more detail by reference to the
nonlimiting examples below.
I. Preparation of oligomers
Oligomer O1:
Preparation of a polyurethanediol from hexamethylene diisocyanate
and neopentyl glycol
In a four-necked flask, which was fitted with stirrer, dropping
funnel, thermometer, reflux condenser and equipment for working
under nitrogen, 624 g (6 mol) of neopentyl glycol and 0.3 g of
tetrabutyl orthotitanate were dissolved in 490 g of methyl ethyl
ketone with heating to a temperature of about 50~C and with
stirring. Then, with stirring, 840 g (5 mol) of hexamethylene
diisocyanate were added dropwise, and the reaction temperature
0050/50663
CA 02382970 2002-02-21
43
increased. The reaction mixture was then stirred for 2 hours
under reflux and then cooled to room temperature with stirring.
This gave a clear, high-viscosity 75% strength by weight solution
of a polyurethane diol having an OH number of abaut 75 and a
number-average molecular weight of about 1500 g/mol.
Oligomer 02:
Preparation of a polyurethane based on polytetrahydrofuran
A four-necked flask, which was fitted with stirrer, dropping
funnel, thermometer, reflux condenser and equipment for working
under nitrogen, was charged with 650 g (1 mol) of
polytetrahydrofuran (Mn = 650 g/mol) and 0.1 g of tetrabutyl
orthotitanate, and the mixture was heated to about 50°C with
stirring. Then, with stirring, 109.5 g (0.65 mol) of
hexamethylene diisocyanate were added dropwise, and the reaction
temperature increased. The reaction mixture was stirred for a
further 3 hours at 80°C. Cooling to room temperature gave a
wax-like product having an OH number of about 50 with a
number-average molecular weight of about 2250 g/mol.
Oligomer 02 can also be prepared analogously to the preparation
procedure for oligomer O1, i.e. in a solvent, such as methyl
ethyl ketone.
Oligomer 03:
Preparation of a polyurethane based on a polyesterdiol
The polycondensation of 3.5 mol of sebacic acid and 4.5 mol of
1,6-hexanediol gave a hydroxyl-containing polyesterdiol having a
number-average molecular weight of about 1150 g/mol. Analogously
to the preparation procedure for oligomer 02, 1 mol of the
polyesterdiol and 0.65 mol of hexamethylene diisocyanate were
reacted. This gave a hard wax-like product having an OH number of
about 30 and a number-average molecular weight of about
3700 g/mol.
Oligomer 04 was prepared analogously to oligomer 03. The starting
materials used and the amounts thereof are given in Table 1
below.
Oligomer 05:
Preparation of a polyurethane based on a polysiloxanediol
~ CA 02382970 2002-02-21
0050/50663
44
According to the general preparation procedure for oligomer O1,
1 mol of polysiloxanediol (Mn = 900 g/mol, Tegomer~ H-Si 2122
from Goldschmidt) and 0.65 mol of hexamethylene diisocyanate were
reacted in methyl ethyl ketone.
The preparation of oligomers of this type can also be carried out
according to the general procedure for oligomer 02, i.e. without
the addition of a solvent.
Oligomer 06:
Preparation of a polyurethane based on a polysiloxanediamine
Analogously to the preparation procedure for oligomer O1, 1 mol
of polysiloxanediamine (Mn = 900 g/mol, Tegomer~ A-Si 2122 from
Goldschmidt) and 0.65 mol of hexamethylene diisocyanate were
reacted in methyl ethyl ketone at a temperature of about 30~C and
without the addition of a catalyst.
Oligomer 07:
Preparation of a hydroxyl-containing reaction product of a
polyurethanediol with a dimer fatty acid
In a four-necked flask, which was fitted with stirrer, dropping
funnel, thermometer, reflux condenser and equipment for working
under nitrogen, in accordance with the general preparation
procedure for oligomer O1, a polyurethanediol was prepared from
2 mol of 1,6-hexanediol and 1 mol of hexamethylene diisocyanate.
The reflux condenser was then replaced by a descending condenser.
Under a nitrogen atmosphere, 0.65 mol of a dimer fatty acid were
added and the reaction mixture was heated, the methyl ethyl
ketone being distilled off firstly at a temperature of from 80 to
110~C. After a further temperature increase to 160~C, the reaction
mixture was stirred for a further 3 hours, and the reaction
temperature then increased by about 20~C per hour until it had
reached about 210~C. After a further 5 hours at about 210~C, the
acid number was less than 2. The mixture was left to cool to room
temperature, giving a yellow, almost clear wax having an OH
number of about 48 and a number-average molecular weight of about
2300 g/mol.
Oligomer 08:
Preparation of a hydroxyl-containing reaction product of a
polyurethane with sebacic acid
CA 02382970 2002-02-21
0050/50663
Analogously to the general preparation procedure for the reaction
product 07, a polyurethanediol was firstly prepared from 2 mol of
1,6-hexanediol and 1 mol of hexamethylene diisocyanate, and then
reacted with 0.65 mol of sebacic acid.
5
15
25
35
45
0050/50663
CA 02382970 2002-02-21
46
.,
w
x
H
1
r1 o
I H I I I I I I
1 n
a~ ~
~
....~
.I
b b b
.-. .r.1
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b ~ 1 I I I H W 1 1 .d U
U
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A 4-1 (t1 I I 1 M I 1 O I ~ N
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ri
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U r-, tc1.r1 1
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CT
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CT O 1f1
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v l0 I 1 I I I I I V
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~O
CA 02382970 2002-02-21
0050/50663
47
II. Preparation of polymers
II.1: Oil-soluble polymers P9 to P11
The polymers P9 to P11 were prepared analogously to the
preparation procedure for oligomer 03 from starting materials
according to Table 2.
II.2: Water-soluble polymers P12 and P13
20
30
40
The polymers P12 and P13 were prepared without a diluent
analogously to the preparation procedure for oligomer 02 from
starting materials according to Table 2.
CA 02382970 2002-02-21
0050/50663
48
o r-,
o r..., o m
1 1 I '-Io
a
I
w
tr, b
.r.,
-.
U
H O
1 I .-~1 I
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p ri r1~ O O O N
oz ~ a~w w w U '
x b s~ w w~
_ _ _ _ _ _
.-1 N M sr M
~O
0050/50663
CA 02382970 2002-02-21
49
Performance examples (oligomers O1 to 08 and oil-soluble polymers
P9 to P11):
To prepare formulations of the abovementioned oligomers and
polymers, these are mixed with a C12- to C15-alkyl benzoate
(Finsolv~ TN) in an amount according to Table 3 and the
properties of the resulting mixtures are assessed.
Table 3:
Example No. Oil component
20% by wt. 10% by wt. 5% by wt.
O1 insoluble insoluble insoluble
02 virtually clear virtually clear clear viscous
viscous oil viscous oil oil
03 solid, slightly solid, virtually just solid,
opaque wax clear wax virtually clear
wax
04 solid clear wax solid clear wax clear
high-viscosity
oil
05 virtually virtually clear, virtually
clear, viscous viscous oil, clear, viscous
oil, separates separates into oil, separates
into two phases two phases upon into two phases
upon standing standing upon standing
06 opaque viscous slightly opaque virtually
oil, separates viscous oil, clear, viscous
into two phases separates into oil, separates
upon standing two phases upon into two phases
standing upon standing
Q7 very solid, solid clear wax clear
clear wax high-viscosity
oil
p8 very solid, solid, slightly virtually clear
clear wax opaque wax high-viscosity
oil
p9 very solid, solid, clear wax just solid,
clear wax clear wax
P10 just solid, just solid, clearclear viscous
clear wax wax; becomes oilyoil
on shaking
P11 solid, just solid, clear viscous
virtually clear virtually clear oil
wax wax; becomes oily
upon shaking
- CA 02382970 2002-02-21
0050/50663
Formulation examples for use in skin cosmetics (oligomers O1 to
08 and oil-soluble polymers P9 to P11):
Table 4:
5
Substance Field of use
Oil base Ointment Wax base Stick base
base
Oligomer/polymer04, 07, 08, 04, 07, 04, 07, 04, 07,
from Ex. No./ P9, P10, P11/ 08, P9/ P9/ 08, P9/
10 bY ~ ] 5 5 10 3 0
Paraffin oil 10 - - -
[% by wt.]
15 Cosmetic oil:
FinsolvOO TN1) 60 Fins. &/or65 60
Miglyol2) _ _ _
Migl. 30
Castor oil _ _ 15 10
[% by wt.]
20 Paraf f in wax3 - 5 5 -
)
Vaseline 20 50 5 -
Beeswax4 ) 5 5 - -
Cetyl alcohol - 5 - -
1) C12-C15-alkyl benzoate
Z) neutral oil, triglyceride of saturated vegetable fatty acids
3) homopolymeric polyethylene wax (Luwax~ A, BASF),
copolymeric polyethylene wax, acrylic acid copolymer (Luwax~
EAS, BASF),
copolymeric polyethylene wax, vinyl acetate copolymer (Luwax~
EVA, BASF)
and mixtures thereof
4) e.g. Berry Wax and/or Ultrabee WD (both Kahl, Germany)
40
The formulations can comprise further components chosen from
color pigments, oil-soluble vitamins, oil-soluble UV absorbers,
perfume, essential oils, preservatives, etc.
X050/50663 CA 02382970 2002-02-21
51
Examples of emulsifier-free emulsions (oligomers and oil-soluble
polymers):
Oil phase: % by Chemical name/
wt. CTFA name:
Finsolv~ TN 18 C12-Cis-alkyl benzoate
Oligomer/polymer 04, 07, 2
08, P9, P10, P11
Nip Nip~, Nipa Laboratories0.1 methyl- and propyl-4-
Ltd. USA hydroxybenzoate (7:3)
Water phase: % by
wt.
Water 79.2
Carbopol 940 0.4 Polyacrylic acid
(Goodrich)
Mowiol 4/88 0.2 Polyvinyl alcohol (degree
of saponification 88%,
Hoesch)
Germall 115 0.1 Imidazolidinylurea
Preparation of the emulsifier-free emulsions
To prepare the emulsifier-free emulsions, the components for oil
and water phase are weighed separately and the oil phase is
homogenized at about 100~C and the water phase is homogenized at
about 60~C. The heated oil phase (20-80~C) is then slowly added,
with stirring, to the likewise optionally heated water phase
(0-80~C). The higher the temperatures of the water and oil phase,
the finer the resulting emulsions. Neutralization with
2-amino-2-methylpropanol (50% strength in water) to pH 7.5 to 8.5
gives stable emulsions.
Examples of creams (oligomers and oil-soluble polymers):
Oil phase: % by Chemical name/CTFA name:
wt.
Paraffin oil 4.5
Cremophor~ A6 (BASF AG) 2.5 Ceteareth-6 (stearyl
alcohol ethoxylate)
Cremophor~ A6 (BASF AG) 2.5 Ceteareth-25 (fatty alcohol
ethoxylate)
Cetyl alcohol 3.5
Glycerol monostearate s.e.2.5 Glyceryl stearate
Isopropyl palmitate 2.0
Luvitol ~ EHO (BASF AG) 6.2 Cetearyl octanoate
CA 02382970 2002-02-21
0050/50663
52
Oligomer/Polymer 04, 07, 1.1
08, P9, P10, P11
Nip NipO, Nipa Laboratories0.1 methyl- and propyl-4-
Ltd. USA hydroxybenzoate (7:3)
Water phase: % by
wt.
Water 75.0
Germall 115 0.1 Imidazolidinylurea
Oil phase: % by Chemical name/CTFA name:
wt.
Paraffin oil 4.5
Cremophor~ A6 (BASF AG) 2.5 Ceteareth-6 (stearyl
alcohol ethoxylate)
Cremophor0 A6 (BASF AG) 2.5 Ceteareth-25 (fatty
alcohol ethoxylate)
Luwax~ A 3.6
Glycerol monostearate s.e. 2.5 Glyceryl stearate
Isopropyl palmitate 2.0
Luvitol0 EHO (BASF AG) 6.2 Cetearyl octanoate
Oligomer/Polymer 04, 07, 1.0
08, P9, P10, P11
Nip NipO, Nipa Laboratories0.1 Methyl- and Propyl-4-
Ltd. USA hydroxybenzoate (7:3)
Water phase: % by
wt.
p12 or P13 1.0
Water 74.0
Germall 115 0.1 Imidazolidinylurea
Preparation:
Weigh and homogenize separately, with stirring, the oil phases
and water phase at a temperature of about 80~C. Slowly stir in the
water phase into the oil phase. Cool slowly to room temperature
with stirring.
Examples for use in hair cosmetics (water-soluble polymers 12 and
13):
0050/50663 CA 02382970 2002-02-21
53
Gel with water-soluble polymers and polyvinyl alcohol
Composition % by wt.
a) Aqueous solution of Carbopol 940 (1% 100
strength)1~
b) Aqueous solution of Polymer 12 or 13 (10%50
strength)
c) Aqueous solution of Mowiol 4/88 (20% 49
strength)2>
d) AMP solution (10% strength)3~ 1
1? Carbopol 940: polyacrylic acid (Goodrich)
2) Mowiol 4/88: Polyvinyl alcohol (degree of saponification 88%,
Hoesch)
3) AMP: aminomethylpropanol
Preparation:
A mixture of b), c) and d) is brought to a temperature of about
40~C with stirring. An aqueous polyacrylic acid solution is then
added, and stirring is continued until the mixture produces a
slightly opaque homogeneous solution. The solution is cooled to a
temperature of about 25~C with stirring. The addition of
aminomethylpropanol gives a clear gel.
III. Polyurethane preparation
Preparation method A:
Example 3
In a stirred apparatus, which was fitted with stirrer, dropping
funnel, thermometer, reflux condenser and equipment for working
under nitrogen, 600 g (0.3 mol) of oligomer O1, 600 g (0.4 mol)
of a polyesterdiol (Mn = 1 500 g/mol, prepared from isophthalic
acid, adipic acid, neopentyl glycol and cyclohexanedimethylol),
124.8 g (1.2 mol) of neopentyl glycol, 375.2 g (2.8 mol) of
dimethylolpropanoic acid and 0.5 g of tetrabutyl orthotitanate
were dissolved in 760 g of methyl ethyl ketone with heating to a
temperature of about 80~C and with stirring. After everything had
dissolved, the reaction mixture was cooled to about 50~C. Then,
with stirring, 1111 g (5 mol) of isophorone diisocyanate were
added dropwise, and the reaction temperature increased. The
reaction mixture was then stirred under reflux until the
isocyanate group content of the mixture remained virtually
constant, and then cooled to room temperature with stirring.
0~5~/50663 CA 02382970 2002-02-21
54
Then,. to convert the free isocyanate groups, 276 g (3.1 mol) of
2-amino-2-methyl-1-propanol was added as an aqueous solution to
the mixture at a temperature of about 40~C in order to neutralize
the mixture to 100%. The flexibility properties of the resulting
polymers are given in Table 5. Distilling off the solvent under
reduced pressure at 40~C gives an aqueous (micro)dispersion.
Pulverulent products can be obtained by spraydrying.
The polymers C1, 2, 4-6 and 11 were prepared analogously to this
preparation procedure.
All carboxylic acid-containing polyurethanes were neutralized to
100% with 2-amino-2-methyl-1-propanol. The cationic polyurethanes
11 and 12 were neutralized with lactic acid, and polyurethane 13
was quaternized with dimethyl sulfate.
Preparation procedure B:
Example 7
In a stirred apparatus, which was equipped with stirrer, dropping
funnel, thermometer, reflux condenser and equipment for working
under nitrogen, 600 g (0.4 mol) of a polyesterdiol
(Mn = 1 000 g/mol, prepared from isophthalic acid, adipic acid,
neopentyl glycol and cyclohexanedi.methylol), 187.2 g (1.8 mol) of
neopentyl glycol and 0.5 g of tetrabutyl orthotitanate were
dissolved in 350 g of methyl ethyl ketone with heating to a
temperature of about 50~C and with stirring. Then, with stirring,
252 g (1.5 mol) of hexamethylene diisocyanate were added
dropwise, and the reaction temperature increased. The reaction
mixture was stirred under reflux for about 2 hours and then
cooled to room temperature. 124.8 g (1.2 mol) of neopentyl
glycol, 375.2 g (2.8 mol) of dimethylolpropanoic acid and 200 g
of methyl ethyl ketone were then added to the reaction mixture
and dissolved with heating to a temperature of about 80~C and with
stirring. After everything had dissolved, the reaction mixture
was cooled to about 50~C. Then, with stirring, a mixture of 222 g
(1 mol) of isophorone diisocyanate and 672 g (4 mol) of
hexamethylene diisocyanate were added dropwise, and the reaction
temperature increased. The reaction mixture was then stirred
under reflux until the isocyanate group content remained
virtually constant, and was then cooled to room temperature with
stirring. Then, to convert the free isocyanate groups, 276 g
(3.1 mol) of 2-amino-2-methyl-1-propanol were added as an aqueous
solution to the mixture at a temperature of about 40~C in order to
neutralize the mixture to 100%. Distilling of the solvent under
0050/50663 CA 02382970 2002-02-21
reduced pressure at 40~C gives an aqueous (micro)dispersion.
Pulverulent products can be obtained by spraydrying.
Polymers 8-10, 12 and 13 were prepared analogously to this
5 preparation procedure.
The performance properties were assessed by the awarding of
grades for flexibility by independent experts. The grading table
is given in Table 6.
15
25
35
45
0050/50663
CA 02382970 2002-02-21
56
I
.r.,
~I a~
M N N N N N
~ r.~ I 1 1 I I I
ya
(ra ,-1 cr M M M N N ~1 H H H H
O1
I
td
~I 'O
(d O
N O .1~
~1 +~ ~ FC~C ~ ~ ~ x a1 x CG
~
H r1
L1 O
flW. '
H a !l7t(1!f1M N N r1 r1 ~" r1 M
~
n
O
.
I 1 1 I 1 1 I I I -1 M
H
00 0000 O~00 0000 00 O O
. . . . .
~
A N N N N N N N N M M 1
n * * * *
N N N N N N GO N Ca OD N
N N N N
~r ~ ~r
., .~ .~
H O u1 ltd !f1 00 OD N
~
x I ( ( H M M r1 M ri N N
1 ,.i
00 ~
I~M M M t~ M
O.~',' I 0 0 0 0 0 1 I 1 I O
a
1
r1 1 .('.,
r~ ~d
O
O ~C r1
(~
W O' a 1 I I 1 1 I I I O I I
W
x
H
~
1
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p p.~ a I I 1 1 I I I I I I o
cd
1
N
_ _
O O
,1.~ .-. * * *
.-,
N r~ r~
O O O t~ d~ crd~ eh V
_
~
O W b o I o O o I o I o o I
O
v
5C O ~ o
W ~ U N M ~1'tlllGI~ 00 Cv r1 .-I
H
0050/50663
CA 02382970 2002-02-21
57
I
0
U
N
U
1 O
s~
d
,-I
W O
N U
N H
~r
O r1
.i
O N
M
'b
f'.1O r1
N
b
.
1 I 4..1~ r-a
O
~ cd rd C7
00 N 00 '~ ~ O
N H
e-Ir1ri ~ '~ r-1
<i
~d O N
r1
O
00 00 'N ~ p ri
. o
r1 ~i ~ ~ ~'
U U '~ O
~
N ~ II N
.
1-I ~ O
~ ~
N CL ~ b~
I t ~ O O' ~ H
t ~
n
o O
~
0
O '~ O ~ p ~
* O O O
v ~ U ~ v ~ rt
O ~ ' ~
+~ ''t ?, O U ~ O
I o U 'L1 ~ ~ O N W ?~
i-1 N S-r ov w-I r1s~O O W
rti 1.~ .i~ T7 O ~dCiUJ 1
.G u1 O N p U !3rnir1 r-I
* * U U t~ i~ 4) ?iO ..O'i
~ ~ N ~ ~
er fn r X r ,err.,' b~ G
?
O o ~ W .~ W x G ~ O ~
~
~ ?i I
G ~ ~ ~d'Jr~1 N
m ~ at s~~ ~ O I
~
O~
~~
O a~ x z A z H
1 1
O r1 5C
U 'd W O
s~ x r1
a~ a~ H
E
O r-1 r1 H C7P.IW A QI
N M _ _
~' * w w w x z A ~ H
0050/50663 CA 02382970 2002-02-21
58
Table 6: Flexibility
grade Flexibility
1 very flexible
2 flexible
3 moderately flexible
4 brittle
Application examples
Examples 14 to 25
Aerosol hairspray formulations with a VOC content of 97% by
weight:
Polyurethane as in Ex. 2-13 3.00% by weight
Ethanol 57.00% by weight
Dimethyl ether 34.96% by weight
Perfume, additives q.s.
(inc. erucic esters)
Examples 26 to 37
Compact aerosol hairspray formulations with a VOC content of 80%
by weight:
Polyurethane as in Ex. 2-13 5.00% byweight
Ethanol 40.00% byweight
Dimethyl ether 34.96% byweight
Water 15.00% byweight
Perfume, additives q.s.
Examples 38 to 49
Hairspray formulations with a VOC content of 55% by weight:
Polyurethane as in Ex. 2-13 3.00% byweight
Ethanol 20.00% byweight
Water 42.00% byweight
Dimethyl ether 34.96% byweight
Perfume, additives q.s.
Examples 50 to 61
Pump hairspray:
Polyurethane as in Ex. 2-13 5.00% by weight
Ethanol 54.96% by weight
Water 40.00% by weight
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CA 02382970 2002-02-21
59
Perfume, additives q.s.
Examples 62 to 73
Foam conditioner :[% by weight]
Polymer 2-13 (25% strength aqueous
solution) 20.00
Cremophor~ A25~? 0.20
Comperlan~ KD$) 0.10
Water 69.70
Propane/butane 9.96
Perfume, preservatives q.s.
7) CTFA Name: Ceteareth 25, BASF AG, reaction product of fatty
alcohol and ethylene oxide
$) CTFA Name: Cocamide DEA, Henkel, coconut fatty acid amide
To prepare the foam conditioner, the components are weighed in
and dissolved with stirring. They are then transferred to a
dispenser and the propellent is added.
Examples 74 to 85
Aerosol hairspray with a VOC content of 80% by weight based on
polyurethane oligomers
Polymer as in Ex. 2-13 5.00% by weight
Oligomer 2-8 0.10% by weight
Ethanol 40.00% by weight
Dimethyl ether 34.96% by weight
Water 14.90% by weight
Perfume, additives q.s.
Examples 86 to 88
Conditioner shampoo: [% by weight)
A) Texapon~ NSO 28% strength9) 50.00
Comperlan~ RD 1.00
Polymer 11-13 (25% strength aqueous
solution) 20.00
Perfume oil q.s.
B) Water 27.5
Sodium chloride 1.5
Preservative q.s.
9) Sodium lauryl sulfate, Henkel
0050/50663 CA 02382970 2002-02-21
To prepare the conditioner shampoos, components A) and B) are
weighed in separately and dissolved with mixing. Phase B) is then
slowly added to phase A).
5 Examples of applications in skin cosmetics
Examples 89 to 95
O/W creams
10
Oil phase: % by CTFA Name:
weight
Oligomer 2-8 1.1
Cremophor~ A6 (BASF AG) 3.5 Ceteareth-6
(stearyl alcohol
15 ethoxylate)
Cremophor~ A25 (BASF AG) 3.5 Ceteareth-25
(fatty alcohol ethoxylate)
Glycerol monostearate s.e. 2.5 Glyceryl stearate
Paraffin oil 7.5
20
Cetyl alcohol 3.5
Luvitol0 EHO (BASF AG) 3.2 Cetearyl octanoate
Nip-NipO, Nipa Laboratories0.1 Methyl and Propyl
Ltd., USA 4-hydroxybenzoate (7:3)
25
Water phase: % by
weight
Water 75.0
Germall II, Sutton 0.1 Diazolidinylurea
30Laboratories Inc., USA
To prepare the creams, the components for the oil and water phase
are weighed separately and homogenized at 80°C. The water phase is
then slowly added to the oil phase with stirring. The mixture is
35 then left to cool to room temperature with stirring.
Examples 96 to 107
O/W creams
40
Oil phase: % by CTFA Name:
weight
CremophorO A6 (BASF AG) 3.5 Ceteareth-6
(stearyl alcohol
ethoxylate)
45Cremophor~ A25 (BASF AG) 3.5 Ceteareth-25
(fatty alcohol ethoxylate)
Glycerol monostearate s.e. 2.5 Glyceryl stearate
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Paraffin oil 7.5
Cetyl alcohol 3.5
LuvitolRO EHO (BASF AG) 3.2 Cetearyl octanoate
Nip-NipRp, Nipa Laboratories0.1 Methyl and Propyl
Ltd., USA 4-hydroxybenzoate (7:3)
Water phase: % by
weight
Polymer 2-13 1.5
Water 74.6
Germall II, Sutton 0.1 Diazolidinylurea
Laboratories Inc., USA
To prepare the creams, the components for the oil and water phase
are weighed separately and homogenized at 80~C. The water phase is
then slowly added to the oil phase with stirring. The mixture is
then left to cool to room temperature with stirring.
25
35
45
