Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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Use of highly-branched polyesters in cosmetic and dermatological formulations
Description
The present invention relates to compositions which comprise highly-branched
polyesters, and to the use of these highly-branched polyesters in cosmetics
and
dermatology.
Thickeners are used to a great degree in the field of pharmacy and cosmetics
for
increasing the viscosity of preparations.
The thickeners are chosen according to whether the preparation is aqueous,
oily or
surface-active. An overview on this topic is given in Hugo Janistyn, Handbuch
der
Kosmetika and Riechstoffe [Handbook of cosmetics and fragrances], Huthig
Verlag
Heidelberg, volume 1, 3rd edition, 1978, p. 979.
Examples of thickeners that are often used for aqueous solutions are fatty
acid
polyethylene glycol monoesters, fatty acid polyethylene glycol diesters, fatty
acid
alkanolamides, oxyethylated fatty alcohols, ethoxylated glycerol fatty acid
esters,
cellulose ethers, sodium alginate, polyacrylic acids, and neutral salts.
Polymers comprising carboxyl groups are also known as thickeners. These
include
homopolymers and copolymers of monoethylenically unsaturated carboxylic acids,
such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride and
itaconic acid.
These polymers are often crosslinked at least to a small extent. Such polymers
are
described, for example, in US 2,798,053, US 3,915,921, US 3,940,351 , US
4,062,817,
US 4,066,583, US 4,267,103, US 5,349,030 and US 5,373,044.
Frequent disadvantages of these polymers when used as thickeners are their pH
dependency and hydrolytic instability. Furthermore, large amounts of the
polymers are
often required for achieving the desired thickening effect, and the stability
of the
preparations in the presence of electrolytes is low.
Naturally occurring materials such as casein, alginates, methylcellulose,
hydroxyethylcellulose, hydroxypropylcellulose and carbomethoxycelIulose are
also
used as thickeners. These have, inter alia, the disadvantage of sensitivity to
microbiological factors and the addition of biocides is consequently required.
Typical thickeners of oily preparations, also called oil thickeners below, are
metal
soaps, amorphous silicon dioxide, hydroxystearin, compounds of quaternary
ammonium bases with bentonites, waxes and paraffins.
Surfactant solutions are thickened, for example, by fatty acid alkylolamides,
amine
oxides, cellulose derivates, polysaccharides and the aforementioned polymers
comprising carboxyl groups.
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2
High-functionality highly-branched polyesters and processes for their
preparation are
described, for example, in DE 101 63 163, DE 102 19 508, DE 102 40 817,
DE 103 48 463, DE 10 2004 026904 and DE 10 2005 060783.
WO 2006/018063 describes compositions for hair cosmetics which comprise
hydrophobically functionalized dendritic macromolecules. The dendritic
macromolecules are composed either of polyester units (obtainable under the
trade
name Boltorn) or of polyamide units (obtainable under the trade name Hybrane).
DE 10 2005 063 096 describes cosmetic compositions which comprise 0.05 to 20%
by
weight of at least one hyperbranched polyester and/or polyester amide. The
compositions reportedly have hair cleansing and/or hair care properties. The
polyesters
and/or polyester amides are not substituted.
WO 2004/078809 discloses highly-branched polymers and cosmetic compositions
comprising these.
It was an object of the present invention to find rheology-modifying, in
particular
thickening, in particular oil-thickening, polymers which are highly suitable
for cosmetic
applications and have good application properties especially in the field of
skin
cosmetics. Besides the good thickening effect for a small use of material,
these also
include clarity in the case of gel applications, (co-)emulsifying and
stabilizing effect for
oil-insoluble and/or difficult-to-stabilize components, good incorporability
into cosmetic
preparations. For gels in particular, the highest possible transparency
(clarity) of the
preparations is desired. In order to ensure the broadest possible
formulatability, it is
desired that the thickeners are low-color and low-odor, ideally colorless and
odorless.
Moreover, for use in (skin) cosmetic and/or dermatological applications, it is
necessary
that no allergenic reactions are triggered.
The object is achieved by the substituted highly-branched polyesters described
below.
Within the context of this invention, highly-branched polyesters are
understood as
meaning uncrosslinked macromolecules with hydroxyl groups and carboxyl groups
which are both structurally and also molecularly nonuniform. They can firstly
be
composed starting from a central molecule analogously to dendrimers, but with
PF 62797
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3
nonuniform chain length of the branches. They may secondly also be linear in
composition, with functional side groups, or else, as a combination of the two
extremes,
have linear and branched molecular moieties. For the definition of dendrimeric
and
hyperbranched polymers, see also P.J. Flory, J. Am. Chem. Soc. 1952, 74, 2718
and
H. Frey et al., Chem. Eur. J. 2000, 6, No. 14, 2499.
In connection with the present invention, "highly-branched" is understood as
meaning
that the degree of branching (DB), i.e. the average number of dendritic
linkages plus
the average number of end groups per molecule, divided by the sum of the
average
number of dendritic linkages, the average number of linear linkages and the
average
number of end groups, multiplied by 100, is 10 to 99.9%, preferably 20 to 99%,
particularly preferably 20-95%.
Besides the expression highly-branched, the expression hyperbranched is also
known
from the literature. Within the context of the present invention, the two
expressions
should be understood synonymously.
In connection with the present invention, "dendrimeric" is understood as
meaning that
the degree of branching is 99.9 - 100%. For the definition of the degree of
branching,
see H. Frey et al., Acta Polym. 1997, 48, 30.
Within the context of this document, uncrosslinked means that a degree of
branching of
less than 15% by weight, preferably of less than 10% by weight, determined via
the
insoluble fraction of the polymer, is present.
The insoluble fraction of the polymer was determined by extraction for 4 hours
with the
same solvent as is used for the gel permeation chromatography, i.e.
tetrahydrofuran,
dimethylacetamide or hexafluoroisopropanol, depending on in which solvent the
polymer is more soluble, in a Soxhlet apparatus and, after drying the residue
to
constant weight, weighing the remaining residue.
The highly-branched polyesters are prepared as described below.
At least one aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic
acid (A2) or
derivatives thereof and, if appropriate, a dihydric, aliphatic,
cycloaliphatic, araliphatic or
aromatic alcohol (B2), which has 2 OH groups, are reacted with
at least one x-hydric aliphatic, cycloaliphatic, araliphatic or aromatic
alcohol (Cr), which
has more than two OH groups and x is greater than 2, preferably between 3 and
8,
PF 62797
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particularly preferably between 3 and 6, very particularly preferably from 3
to 4 and in
particular 3,
if appropriate in the presence of further functionalized building blocks E,
where the ratio of the reactive groups in the reaction mixture is chosen so
that a molar
ratio of OH groups to carboxyl groups or derivatives thereof of from 5:1 to
1:5,
preferably from 4:1 to 1:4, particularly preferably from 3:1 to 1:3 and very
particularly
preferably from 2:1 to 1:2 is established.
The dicarboxylic acids (A2) include, for example, aliphatic dicarboxylic
acids, such as
oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic
acid, suberic
acid, azelaic acid, sebacic acid, undecane-a,co-dicarboxylic acid, dodecane-
(X,c)-
dicarboxylic acid, cis- and trans-cyclohexane-1,2-dicarboxylic acid, cis- and
trans-
cyclohexane-1,3-dicarboxylic acid, cis- and trans-cyclohexane-1,4-dicarboxylic
acid,
cis- and trans-cyclopentane-1,2-dicarboxylic acid, cis- and trans-cyclopentane-
1,3-
dicarboxylic acid. Furthermore, it is also possible to use aromatic
dicarboxylic acids,
such as, for example, phthalic acid, isophthalic or terephthalic acid.
Unsaturated
dicarboxylic acids, such as maleic acid or fumaric acid, can also be used.
The specified dicarboxylic acids may also be substituted by one or more
radicals,
selected from
C1-C10-alkyl groups, for example methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl,
sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-
dimethylpropyl,
isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, 2-
ethylhexyl,
trimethylpentyl, n-nonyl or n-decyl,
C3-C12-cycloalkyl groups, for example cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl,
cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and
cyclododecyl;
preference is given to cyclopentyl, cyclohexyl and cycloheptyl;
alkylene groups such as methylene or ethylidene or
C6-C14-aryl groups, such as, for example, phenyl, 1-naphthyl, 2-naphthyl, 1-
anthryl,
2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-
phenanthryl and 9-
phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly
preferably
phenyl.
Examples of representatives of substituted dicarboxylic acids that may be
mentioned
are: 2-methylmalonic acid, 2-ethylmalonic acid, 2-phenylmalonic acid, 2-
methylsuccinic
PF 62797
CA 02781185 2012_0517
acid, 2-ethylsuccinic acid, 2-phenylsuccinic acid, itaconic acid, 3,3-
dimethyiglutaric
acid.
Furthermore, mixtures of two or more of the aforementioned dicarboxylic acids
can be
5 used.
The dicarboxylic acids can be used either as they are or in the form of
derivatives.
Derivatives are preferably understood as meaning
- the relevant anhydrides in monomeric or else polymeric form,
mono- or dialkyl esters, preferably mono- or di-C1-C4-alkyl ester,
particularly
preferably mono- or dimethyl esters or the corresponding mono- or diethyl
esters,
- also mono- and divinyl esters, and
- mixed esters, preferably mixed esters with different C,-C4-alkyl components,
particularly preferably mixed methylethyl esters.
Within the context of this document, C,-C4-alkyl is methyl, ethyl, isopropyl,
n-propyl,
n-butyl, isobutyl, sec-butyl and tert-butyl, preferably methyl, ethyl and n-
butyl,
particularly preferably methyl and ethyl and very particularly preferably
methyl.
Within the context of the present invention, it is also possible to use a
mixture of a
dicarboxylic acid and one or more of its derivatives. Within the context of
the present
invention, it is likewise possible to use a mixture of two or more different
derivatives of
one or more dicarboxylic acids.
Particular preference is given to using malonic acid, succinic acid, glutaric
acid, adipic
acid, 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid (hexahydrophthalic
acids), phthalic
acid, isophthalic acid, terephthalic acid or mono- or dialkyl esters thereof.
Diols (B2) that can be used according to the present invention are, for
example,
ethylene glycol, propan-1,2-diol, propane- 1,3-diol, butane- 1,2-diol, butane-
1,3-diol,
butane-l,4-diol, butane-2,3-diol, pentane-1,2-diol, pentan-1,3-diol, pentane-
1,4-diol,
pentane-1,5-diol, pentane-2,3-diol, pentane-2,4-diol, hexane-1,2-diol, hexane-
1,3-diol,
hexane-1,4-diol, hexane-1,5-diol, hexane-1,6-diol, hexane-2,5-diol, heptane-
1,2-diol,
1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,2-
decanediol, 1,10-
decanediol, 1,2-dodecanediol, 1, 1 2-dodecanediol, 1,5-hexadiene-3,4-diol, 1,2-
and 1,3-
cyclopentanediols, 1,2-, 1,3- and 1,4-cyclohexanediols, 1,1-, 1,2-, 1,3- and
1,4-bis-
(hydroxym ethyl)cyclohexanes, 1,1-, 1,2-, 1,3- and 1,4-
bis(hydroxyethyl)cyclohexanes,
neopentyl glycol, (2)-methyl-2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2-
ethyl-1,3-
hexanediol, 2,5-dimethyl-2,5-hexanediol, 2,2,4-trimethyl-1,3-pentanediol,
pinacol,
diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene
glycol,
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polyethylene glycols HO(CH2CH2O),-H or polypropylene glycols
HO(CH[CH3]CH2O)n-H, where n is an integer and n is >_ 4, polyethylene-
polypropylene
glycols, where the order of the ethylene oxide or propylene oxide units may be
blockwise or random, polytetramethylene glycols, preferably up to a molecular
weight
up to 5000 g/mol, poly-1,3-propanediols, preferably with a molecular weight up
to
5000 g/mol, polycaprolactones or mixtures of two or more representatives of
the above
compounds. Here, one or both hydroxyl groups in the aforementioned diols can
be
substituted by SH groups. Preferably used diols are ethylene glycol, 1,2-
propanediol,
1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-
octanediol, 1,2-,
1,3- and 1,4-cyclohexanediol, 1,3- and 1,4-bis(hydroxymethyl)cyclohexane, and
also
diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene
glycol.
The dihydric alcohols B2 can optionally also comprise further functionalities,
such as,
for example, carbonyl, carboxyl, alkoxycarbonyl or sulfonyl, such as, for
example,
dimethylolpropionic acid or dimethylolbutyric acid, and also C,-C4-alkyl
esters thereof,
although the alcohols B2 preferably have no further functionalities.
At least trifunctional alcohols (Cr) comprise glycerol, trimethylolmethane,
trimethylolethane, trimethylolpropane, 1,2,4-butantriol,
tris(hydroxymethyl)amine,
tris(hydroxyethyl)amine, tris(hydroxypropyl)amine, pentaerythritol,
diglycerol, triglycerol
or higher condensation products of glycerol, di(trimethylolpropane),
di(pentaerythritol),
trishydroxymethyl isocyanurate, tris(hydroxyethyl) isocyanurate (THEIC),
tris(hydroxypropyl) isocyanurate, inositols or sugars, such as, for example,
glucose,
fructose or sucrose, sugar alcohols, such as, for example, sorbitol, mannitol,
threitol,
erythritol, adonitol (ribitol), arabitol (Iyxitol), xylitol, dulcitol
(galactitol), maltitol, isomalt,
tri- or higher-functional polyetherols based on tri- or higher-functional
alcohols and
ethylene oxide, propylene oxide and/or butylene oxide.
In this connection, particular preference is given to glycerol, diglycerol,
triglycerol,
trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, pentaerythritol,
tris(hydroxyethyl) isocyanurate, and polyetherols thereof based on ethylene
oxide
and/or propylene oxide.
The process according to the invention can be carried out without a diluent or
in the
presence of a solvent. Suitable solvents are, for example, hydrocarbons, such
as
paraffins or aromatics. Particularly suitable paraffins are n-heptane and
cyclohexane.
Particularly suitable aromatics are toluene, ortho-xylene, meta-xylene, para-
xylene,
xylene as isomer mixture, ethylbenzene, chlorobenzene and ortho- and meta-
dichlorobenzene. Also suitable as solvents in the absence of acidic catalysts
are very
particularly ethers, such as, for example, dioxane or tetrahydrofuran and
ketones, such
as, for example, methyl ethyl ketone and methyl isobutyl ketone.
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According to the invention, the amount of added solvent is at least 0.1 % by
weight,
based on the mass of the starting materials to be reacted that are used,
preferably at
least 1 % by weight and particularly preferably at least 10% by weight. It is
also possible
to use excesses of solvent, based on the mass of starting materials to be
reacted that
are used, for example 1.01 to 10-fold. Solvent amounts of more than 100-fold,
based
on the mass of starting materials to be reacted that are used, are not
advantageous
because at significantly lower concentrations of the reactants, the reaction
rate
diminishes significantly, which leads to uneconomical long reaction times.
In one preferred embodiment, the reaction is carried out free from solvents.
To carry out the process according to the invention it is possible to work in
the
presence of a water-withdrawing agent as additive, which is added at the start
of the
reaction. For example, molecular sieves, in particular molecular sieve 4A,
MgSO4 and
Na2SO4, are suitable. During the reaction it is also possible to add further
water-
withdrawing agent or to replace water-withdrawing agent with fresh water-
withdrawing
agent. During the reaction, it is also possible to distil off formed water
and/or alcohol
and, for example, to use a water separator, in which the water is removed with
the help
of an entrainer.
Furthermore, the removal can take place by stripping, for example take place
by
passing a gas that is inert under the reaction conditions through the reaction
mixture, if
appropriate in addition to a distillation. Suitable inert gases are preferably
nitrogen,
noble gases, carbon dioxide or combustion gases.
The process according to the invention can be carried out in the absence of
catalysts.
However, preference is given to working in the presence of at least one
catalyst. These
are preferably acidic inorganic, organometallic or organic catalysts or
mixtures of two or
more acidic inorganic, organometallic or organic catalysts.
Within the context of the present invention, examples of acidic inorganic
catalysts are
sulfuric acid, sulfates and hydrogensulfates, such as sodium hydrogensulfate,
phosphoric acid, phosphonic acid, hypophosphorous acid, aluminum sulfate
hydrate,
alaun, acidic silica gel (pH s 6, in particulars 5) and acidic aluminum oxide.
It is also
possible to use, for example, aluminum compounds of the general formula
AI(OR')3
and titanates of the general formula Ti(OR')4 as acidic inorganic catalysts,
where the
radicals R' may be in each case identical or different and are selected
independently of
one another from
C,-C20-alkyl radicals, for example methyl, ethyl, n-propyl, isopropyl, n-
butyl, isobutyl,
sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-
dimethylpropyl,
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CA 02781185 2012-051 7
8
isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl,
2-ethylhexyl, n-nonyl, n-decyl, n-dodecyl, n-hexadecyl or n-octadecyl.
C3-C12-cycloalkyl radicals, for example cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl,
cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and
cyclododecyl;
preference is given to cyclopentyl, cyclohexyl and cycloheptyl.
Preferably, the radicals R1 in AI(OR')3 and Ti(OR')4 are in each case
identical and
selected from n-butyl, isopropyl or 2-ethylhexyl.
Preferred acidic organometallic catalysts are selected, for example, from
dialkyltin
oxides R'2SnO or dialkyltin esters R'2Sn(OR2)2, where R' is defined as above
and may
be identical or different.
R2 can have the same meanings as R' and additionally be C6-C12-aryl, for
example
phenyl, o-, m- or p-tolyl, xylyl or naphthyl. R2 may in each case be identical
or different.
Examples of organotin catalysts are tin(II) n-octanoate, tin(II) 2-
ethylhexanoate, tin(II)
laurate, dibutyltin oxide, diphenyltin oxide, dibutyltin dichloride,
dibutyltin diacetate,
dibutyltin dilaurate, dibutyltin dimaleate or dioctyltin diacetate.
Particularly preferred representatives of acidic organometallic catalysts are
dibutyltin
oxide, diphenyltin oxide and dibutyltin dilaurate.
Preferred acidic organic catalysts are acidic organic compounds with, for
example,
phosphate groups, sulfonic acid groups, sulfate groups or phosphonic acid
groups.
Particular preference is given to sulfonic acids, such as, for example, para-
toluenesulfonic acid. It is also possible to use acidic ion exchangers as
acidic organic
catalysts, for example sulfonic-acid-group-containing polystyrene resins
crosslinked
with about 2 mol% of divinylbenzene.
It is also possible to use combinations of two or more of the aforementioned
catalysts.
It is also possible to use those organic or organometallic or else inorganic
catalysts
which are present in the form of discrete molecules in immobilized form, for
example on
silica gel or on zeolites.
If the desire is to use acidic inorganic, organometallic or organic catalysts,
then
according to the invention 0.1 to 10% by weight, preferably 0.2 to 2% by
weight, of
catalyst are used.
Enzymes or decomposition products of enzymes likewise belong to the organic
catalysts within the context of the present invention. Particular preference
is given to
PF 62797
CA 02781185 2012_0517
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effective amounts of a lipase obtainable, for example, from Candida
cylindracea,
Candida lipolytica, Candida rugosa, Candida antarctica, Candida utilis,
Chromobacterium viscosum, Geotrichum viscosum, Geotrichum candidum, Mucor
javanicus, Mucor mihei, pig pancreas, Pseudomonas spp., Pseudomonas
fluoprescens, Pseudomonas cepacia, Rhizopus arrhizus, Rhizopus delemar,
Rhizopus
niveus, Rhizopus oryzae, Aspergillus niger, Penicillium roquefortii,
Penicillium
camembertii or esterase from Bacillus spp. Bacillus thermoglucosidasius.
The process according to the invention is preferably carried out under an
inert gas
atmosphere, i.e. a gas that is inert under the reaction conditions, for
example under
carbon dioxide, combustion gases, nitrogen or noble gas, among which in
particular
argon should be mentioned.
The process according to the invention is carried out at temperatures of from
60 to
250 C. Preference is given to working at temperatures of from 80 to 200 C,
particularly
preferably at 100 to 180 C.
The pressure conditions of the process according to the invention are
generally not
critical. It is possible to work at significantly reduced pressure, for
example at 10 to
500 mbar. The process according to the invention can also be carried out at
pressures
above 500 mbar. For reasons of simplicity, preference is given to the reaction
at
atmospheric pressure; however, it is also possible to carry it out at slightly
increased
pressure, for example up to 1200 mbar. It is also possible to work under
significantly
increased pressure, for example at pressures up to 10 bar. Preference is given
to the
reaction at reduced or atmospheric pressure, particularly preferably at
atmospheric
pressure.
The reaction time of the process according to the invention is usually 10
minutes to
48 hours, preferably 30 minutes to 24 hours and particularly preferably 1 to
12 hours.
When the reaction is complete, the high-functionality highly- and
hyperbranched
polyesters can be isolated easily, for example by filtering off the catalyst
and, if
appropriate, stripping off the solvent, in which case the stripping off of the
solvent is
usually carried out at reduced pressure. Further highly suitable processing
methods are
precipitation of the polymer after adding water and subsequent washing and
drying.
d) If required, the reaction mixture can be subjected to a decoloring, for
example
through treatment with activated carbon or metal oxides, such as, for example,
aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, boron oxide
or
mixtures thereof, in amounts of, for example, 0.1 - 50% by weight, preferably
0.5
to 25% by weight, particularly preferably 1 - 10% by weight, at temperatures
of,
PF 62797
CA 02781185 2012_0517
for example, 10 to 200 C, preferably 20 to 180 C and particularly preferably
30 to
160 C.
This can take place by adding the pulverant or granular decolorizer to the
reaction
5 mixture and subsequent filtration or by passing the reaction mixture over a
bed of the
decolorizer in the form of any desired suitable moldings.
The decoloring of the reaction mixture can take place at any desired point in
the work-
up process, for example at the stage of the crude reaction mixture or
following optional
10 prewashing, neutralization, washing or solvent removal.
The reaction mixture can furthermore be subjected to a prewashing e) and/or a
neutralization f) and/or an afterwashing g), preferably merely to a
neutralization f). If
appropriate, the order of the neutralization f) and prewashing e) can also be
swapped.
Comprised products of value can be at least partially recovered from the
aqueous
phase of the washing and/or neutralization by acidification and extraction
with a solvent
and be reused.
Prior to the pre- or afterwashing, the reaction mixture is treated in a
washing apparatus
with a washing liquid, for example water or a 5-30% strength by weight,
preferably 5-
20, particularly preferably 5-15, % strength by weight sodium chloride
solution,
potassium chloride solution, ammonium chloride solution, sodium sulfate
solution or
ammonium sulfate solution, preferably water or sodium chloride solution.
The quantitative ratio of reaction mixture: washing liquid is generally 1:0.1 -
1,
preferably 1 : 0.2 - 0.8, particularly preferably 1 : 0.3 - 0.7.
The washing or neutralization can be carried out, for example, in a stirred
container or
in other conventional apparatuses, e.g. in a column or mixer-settler
apparatus.
In terms of processing, all extraction and washing methods and apparatuses
known per
se can be used for a washing or neutralization in the process according to the
invention, e.g. those described in Ullmann's Encyclopedia of Industrial
Chemistry, 6th
ed, 1999 Electronic Release, chapter: Liquid - Liquid Extraction - Apparatus.
For
example, these may be single-stage or multistage, preferably single-stage,
extractions,
and also those in the cocurrent or countercurrent mode, preferably
countercurrent
mode.
Preference is given to using sieve tray columns or columns with arranged
and/or
dumped packings, stirred containers or mixer-settler apparatuses, and also
pulsed
columns or those with rotating internals.
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The prewashing is preferably used when metal salts, preferably organotin
compounds,
are (co)used as catalyst.
An afterwashing may be advantageous for removing traces of base or salt from
the
neutralized reaction mixture.
For the neutralization f), the optionally prewashed reaction mixture, which
may still
comprise small amounts of catalyst and/or carboxylic acid, can be neutralized
with a
5-25, preferably 5-20, particularly preferably 5-15, % strength by weight
aqueous
solution of a base, such as, for example, alkali metal or alkaline earth metal
oxides,
hydroxides, carbonates or hydrogencarbonates, preferably sodium hydroxide
solution,
potassium hydroxide solution, sodium hydrogen carbonate, sodium carbonate,
potassium hydrogen carbonate, calcium hydroxide, milk of lime, ammonia,
ammoniacal
water or potassium carbonate, to which, if appropriate, 5 - 15% by weight of
sodium
chloride, potassium chloride, ammonium chloride or ammonium sulfate can be
added,
particularly preferably with sodium hydroxide solution or sodium hydroxide
solution/sodium chloride solution. The degree of neutralization is preferably
5 to
60 mol%, preferably 10 to 40 mol%, particularly preferably 20 to 30 mol%,
based on
the monomers comprising acid groups.
The base is added in a manner such that the temperature in the apparatus does
not
increase above 60 C, is preferably between 20 and 35 C and the pH is 4 - 13.
The
heat of neutralization is preferably dissipated by means of cooling the
container with
the help of internal cooling coils or via jacketed cooling.
The quantitative ratio of reaction mixture: neutralization liquid is generally
1 : 0.1 - 1,
preferably 1 : 0.2 - 0.8, particularly preferably 1 : 0.3 - 0.7.
As regards the apparatus, that stated above is applicable.
h) If a solvent is present in the reaction mixture, then this can be
substantially
removed by distillation. Preferably, any solvent present is removed from the
reaction mixture after washing and/or neutralization, but, if desired, this
can also
take place before the washing and/or neutralization.
For this, the reaction mixture can be used with an amount of storage
stabilizer such
that, following removal of the solvent, 100 - 500, preferably 200 - 500 and
particularly
preferably 200 - 400 ppm thereof are present in the target ester (residue).
The distillative removal of the majority of optionally used solvent or low-
boiling by-
products takes place, for example, in a stirred tank with jacketed heating
and/or internal
PF 62797
CA 02781185 2012_0517
12
heating coils under reduced pressure, for example at 20 - 700 mbar, preferably
30 to
500 and particularly preferably 50 - 150 mbar and a temperature of 40 -120 C.
The distillation can of course also take place in a falling-film evaporator or
thin-film
evaporator. For this, the reaction mixture is conveyed through the apparatus,
preferably
circulated several times, under reduced pressure, for example at 20 - 700
mbar,
preferably 30 to 500 and particularly preferably 50 - 150 mbar and a
temperature of
40 - 80 C.
A gas that is inert under the reaction conditions can advantageously be
introduced into
the distillation apparatus, for example 0.1 - 1, preferably 0.2 - 0.8 and
particularly
preferably 0.3 - 0.7 m3 of oxygen-containing gas per m3 of reaction mixture
and hour.
The residual solvent content in the residue after distillation is generally
below 5% by
weight, preferably 0.5 - 5% and particularly preferably 1 to 3% by weight.
The removed solvent is condensed and preferably reused.
If required, solvent stripping i) can be carried out in addition to or instead
of the
distillation.
For this, the product, which may still comprise small solvent amounts or low-
boiling
impurities, is heated to 50 -150 C, preferably 80 -150 C and the remaining
solvent
amounts are removed using a suitable gas in a suitable apparatus. For
assistance, if
appropriate, a vacuum may also be applied.
Suitable apparatuses are, for example, columns of design known per se which
have
the customary internals, e.g. trays, dumped packings or ordered packings,
preferably
dumped packings. Suitable column internals are in principle all customary
internals, for
example trays, arranged packings and/or dumped packings. Of the trays,
preference is
given to bubble-cap trays, sieve dumped trays, valve trays, Thormann trays
and/or
dual-flow trays, and of the packings, preference is given to those with rings,
coils,
saddles, Raschig rings, Intos rings or Pall rings, barrel saddles or Interloxs
saddles,
Top-Pak etc., or meshes.
Also conceivable here is a falling-film evaporator, thin-film evaporator or
wiped-film
evaporator, such as, for example, a Luwa, Rotafilm or Sambay evaporator, which
may
be equipped with a demister, for example, as a splash guard.
Suitable gases are gases that are inert under the stripping conditions, in
particular
those which have been conditioned to a temperature of 50 to 100 C.
PF 62797
CA 02781185 2012_0517
13
The amount of stripping gas is, for example, 5 - 20, particularly preferably
10 - 20 and
very particularly preferably 10 to 15 m3 of stripping gas per m3 of reaction
mixture and
hour.
If necessary, at any desired stage of the work-up process, preferably after
washing/neutralization and, if appropriate, after solvent removal, the
esterification
mixture can be subjected to a filtration j) in order to remove precipitated
traces of salts
and also any decolorizer present.
It is preferred to omit a prewash or afterwash e) or g); just a filtration
step j) may be
sensible. It is likewise preferred to dispense with a neutralization f).
The order of steps e)/g), and also h) and j), is arbitrary.
The present invention further provides the high-functionality, highly- or
hyperbranched
polyesters obtainable by the process according to the invention. They are
characterized by particularly low fractions of discolorations and
resinifications.
The polyesters according to the invention have a molecular weight M, of at
least 500,
preferably at least 600 and particularly preferably 750 g/mol. The upper limit
of the
molecular weight Mn is preferably 100 000 g/mol, particularly preferably it is
not more
than 80 000 and very particularly preferably it is not more than 30 000 g/mol.
The data relating to the polydispersity and also to the number-average and
weight-
average molecular weight Mn and MH, refer here to measurements made by gel
permeation chromatography using polymethyl methacrylate as standard and
tetrahydrofuran, dimethylacetamide or hexafluoroisopropanol as eluent. The
method is
described in Analytiker Taschenbuch vol. 4, pages 433 to 442 , Berlin 1984.
The polydispersity of the polyesters is 1.2 to 50, preferably 1.4 to 40,
particularly
preferably 1.5 to 30 and very particularly preferably up to 10.
The solubility of the polyesters is usually very good; i.e. clear solutions at
25 C can be
prepared with a content up to 50% by weight, in some cases even up to 80% by
weight, of the polyesters according to the invention in tetrahydrofuran (THF),
ethyl
acetate, n-butyl acetate, ethanol and numerous other solvents, without gel
particles
being detectable by the naked eye. This demonstrates the low degree of
crosslinking of
the polyesters according to the invention.
The high-functionality highly- and hyperbranched polyesters are carboxy-
terminated,
carboxy- and hydroxy-terminated and preferably hydroxy-terminated.
PF 62797
CA 02781185 2012_0517
14
In one preferred embodiment, the highly-branched polyesters are completely or
partly
substituted by linear or branched Ca- to C40-alkyl and/or -alkenyl radicals.
Within the
context of the present invention, alkenyl radicals may be monounsaturated or
polyunsaturated.
Within the scope of the present invention, substitution means that the highly-
branched
polyesters are reacted with compounds A during and/or after the polymerization
reaction. Compounds A are notable for the fact that they comprise a linear or
branched
Ca- to Cao-alkyl and/or alkenyl radical and a reactive group. A reactive group
of
compound A is able to react with the highly-branched polyester. Preferably,
compounds A comprise precisely one linear or branched C4- to C4o-alkyl and/or
alkenyl
radical and precisely one reactive group.
Highly-branched polyesters which have been reacted with compounds A are
referred to
as substituted highly-branched polyesters.
The substitution can take place completely or partially. This means in the
case of
complete substitution that the reactive groups of the highly-branched
polyester have
reacted completely with compounds A. In the case of partial substitution, not
all of the
reactive groups of the highly-branched polyester have reacted with compounds
A.
Preferably, the highly-branched polyesters are substituted by octyl (capryl),
nonyl,
decyl (caprinyl), undecyl, dodecyl (laurinyl), tetradecyl, hexadecyl
(palmityl),
heptadecyl, octadecyl (stearyl) radicals and/or the corresponding mono- or
polyunsaturated equivalents, such as, for example, by dodecenyl, hexadienyl
(sorbinyl), octadecenyl (oleyl), linolyl or linolenyl radicals.
In this connection, equivalent is to be understood as meaning a hydrocarbon
radical
which differs from the corresponding linear or branched alkyl radical only by
virtue of
the fact that it has at least one double bond.
The substituted highly-branched polyesters are preferably obtained by reacting
the
resulting high-functionality highly- or hyperbranched polyesters with a
suitable
functionalization reagent which can react with the OH and/or ester groups of
the
polyester.
PF 62797
CA 02781185 2012_0517
High-functionality highly-branched polyesters comprising hydroxyl groups can
be
modified, for example, by adding acid derivative groups, such as esters,
anhydrides or
amides or molecules comprising isocyanate groups. For example, polyesters
comprising acid groups can be obtained through reaction with compounds
comprising
5 anhydride groups.
Here, the molar ratio of the reactive groups of the substitution compound to
the reactive
groups of the highly-branched polyester is from 1:10 to 1:1, preferably from
1:5 to
1:1.1, especially preferably from 1:2 to 1:1.2. A particularly preferred range
is 1:1.7 to
10 1:1.4.
In one preferred embodiment of the present invention, the substitution takes
place with
a carboxylic acid derivative of the formula R-CO-Y and/or an isocyanate of the
formula
R-NCO, where the radicals have the meaning below.
15 R is linear or branched C4- to Cao-alkyl.
Y is OR, OC(O)R2 or NR32. Here, R' is hydrogen or linear or branched Cl- to C6-
alkyl,
R2 is linear or branched C4- to Cao-alkyl, where R and R2 may be identical or
different.
R3 is hydrogen or linear or branched Cl- to C4-alkyl, where the two radicals
R3 may be
identical or different from one another.
Preferred compounds are linear C4-C40-alkyl isocyanates, particular preference
being
given to octyl (capryl) isocyanate, nonyl isocyanate, decyl (caprinyl)
isocyanate,
undecyl isocyanate, dodecyl (laurinyl) isocyanate, tetradecyl isocyanate,
hexadecyl
(palmityl) isocyanate, heptadecyl isocyanate, octadecyl (stearyl) isocyanate.
Further preferred compounds are linear C4-Cao-alkenyl isocyanates with one or
more
double bonds, particular preference being given to dodecenyl, hexadienyl
(sorbinyl),
octadecenyl (oleyl), linolyl or linolenyl isocyanate.
A very particularly preferred compound is stearyl isocyanate.
The substitution can take place, for example, in a subsequent process step
(step c)).
However, the substitution can also take place as early as during the
preparation of the
highly-branched polyesters.
Preferably, the substitution takes place in a subsequent process step.
If the substitution takes place in a subsequent process step, then preferably
the highly-
branched polyester is initially introduced and one or more compounds A are
added.
PF 62797
CA 02781185 2012_0517
16
The substitution usually takes place at a temperature from 0 to 300 C,
preferably 0 to
250 C, particularly preferably at 60 to 200 C and very particularly preferably
at 60 to
160 C without a diluent or in solution. Here, in general it is possible to use
all solvents
which are inert towards the particular starting materials. Preference is given
to using
organic solvents, such as, for example, decane, dodecane, benzene, toluene,
chlorobenzene, xylene, dimethylformamide, dimethylacetamide or solvent
naphtha.
In one preferred embodiment, the substitution reaction is carried out without
a diluent.
In order to increase the rate of the reaction, low molecular weight compounds
that are
released during the reaction can be removed from the reaction equilibrium, for
example
by distillation, if necessary under reduced pressure.
To complete the reaction, it may be necessary to raise the temperature of the
reaction
container following the addition of compound A or, if two or more different
compounds
A are used, following the addition of compounds A. The increase is usually 10
to 50 C,
it is preferably 20 to 40 C.
The substitution of the high-functionality polyesters in most cases takes
place in a
pressure range from 0.1 mbar to 20 bar, preferably at 1 mbar to 5 bar, in
reactors or
reactor cascades which are operated in batch operation, semicontinuously or
continuously.
The invention provides a cosmetic composition comprising at least one
substituted
highly-branched polyester.
The cosmetic composition preferably comprises at least one cosmetically
suitable
carrier.
The use of a substituted highly-branched polyester in cosmetic and/or
dermatological
formulations is in accordance with the invention.
Preference is given to the use in skin cosmetic formulations.
Preference is given to using a substituted highly-branched polyester as
thickener. In
this connection, in particular the use as oil thickener is preferred.
PF 62797
CA 02781185 2012_0517
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Skin cosmetic preparations
Skin cosmetic compositions according to the invention, in particular those for
skincare,
may be present and used in various forms. Thus, for example, they may be an
emulsion of the oil-in-water (O/W) type or a multiple emulsion, for example of
the
water-in-oil-in-water (W/O/W) type. Emulsifier-free formulations such as
hydrodispersions, hydrogels or a Pickering emulsion are also advantageous
embodiments.
The consistency of the formulations can range from pasty formulations via
flowable
formulations to low viscosity, sprayable products. Accordingly, creams,
lotions or
sprays can be formulated. For use, the cosmetic compositions according to the
invention are applied in an adequate amount to the skin in the manner
customary for
cosmetics and dermatological compositions.
The salt content in the surface of the skin is sufficient to lower the
viscosity of the
preparations according to the invention in such a way as to facilitate simple
spreading
and working-in of the preparations.
The skin cosmetic preparations according to the invention are present in
particular as
W/O or O/W skin creams, day and night creams, eye creams, face creams,
antiwrinkle
creams, mimic creams, moisturizing creams, bleaching creams, vitamin creams,
skin
lotions, care lotions and moisturizing lotions.
Further advantageous skin cosmetic preparations are face toners, face masks,
deodorants and other cosmetic lotions and preparations for decorative
cosmetics, for
example concealing sticks, stage make-up, mascara, eyeshadows, lipsticks, kohl
pencils, eyeliners, make-ups, foundations, blushers, powders and eyebrow
pencils.
Moreover, the compositions according to the invention can be used in nose
strips for
pore cleansing, in antiacne compositions, repellants, shaving compositions,
hair
removal compositions, intimate care compositions, foot care compositions, and
in baby
care. Besides the W/W emulsion polymer and suitable carriers, the skin
cosmetic
preparations according to the invention also comprise further active
ingredients and/or
auxiliaries customary in cosmetics, as described above and below.
These include preferably emulsifiers, preservatives, perfume oils, cosmetic
active
ingredients, such as phytantriol, vitamin A, E and C, retinol, bisabolol,
panthenol,
natural and synthetic photoprotective agents, bleaches, colorants, tinting
agents,
tanning agents, collagen, protein hydrolyzates, stablizers, pH regulators,
dyes, salts,
PF 62797
CA 02781185 2012_0517
18
thickeners, gel formers, consistency regulators, silicones, humectants,
conditioners,
refatting agents and further customary additives.
Further polymers may also be added to the compositions if specific properties
are to be
set. To establish certain properties, such as, for example, improving the feel
to the
touch, the spreading behavior, the water resistance and/or the binding of
active
ingredients and auxiliaries such as pigments, the compositions can
additionally also
comprise conditioning substances based on silicone compounds. Suitable
silicone
compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes,
polyarylalkylsiloxanes, polyether siloxanes or silicone resins.
Further possible ingredients of the compositions according to the invention
are
described below under the respective keyword.
Oils, fats and waxes
The skin and hair cosmetic compositions preferably also comprise oils, fats or
waxes.
Constituents of the oil phase and/or fatty phase of the cosmetic compositions
are
advantageously selected from the group of lecithins and fatty acid
triglycerides, namely
the triglycerol esters of saturated and/or unsaturated, branched and/or
unbranched
alkanecarboxylic acids of chain length from 8 to 24, in particular 12 to 18,
carbon
atoms. The fatty acid triglycerides can, for example, be advantageously
selected from
the group of synthetic, semisynthetic and natural oils, such as, for example,
olive oil,
sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil,
coconut oil,
castor oil, wheatgerm oil, grapeseed oil, thistle oil, evening primrose oil,
macadamia
nut oil and the like. Further polar oil components can be selected from the
group of
esters of saturated and/or unsaturated, branched and/or unbranched
alkanecarboxylic
acids of chain length from 3 to 30 carbon atoms and saturated and/or
unsaturated,
branched and/or unbranched alcohols of chain length from 3 to 30 carbon atoms,
and
also from the group of esters of aromatic carboxylic acids and saturated
and/or
unsaturated, branched and/or unbranched alcohols of chain length from 3 to 30
carbon
atoms. Such ester oils can then advantageously be selected from the group
consisting
of isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl
oleate, n-butyl
stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl
stearate, isononyl
isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl
stearate, 2-
octyldodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl
erucate,
dicaprylyl carbonate (Cetiol CC) and cocoglycerides (Myritol 331), butylene
glycol
dicaprylate/dicaprate and dibutyl adipate, and also synthetic, semisynthetic
and natural
mixtures of such esters, such as, for example, jojoba oil.
PF 62797 CA 027811852012-05-17
19
In addition, one or more oil components can be advantageously selected from
the
group of branched and unbranched hydrocarbons and hydrocarbon waxes, the
silicone
oils, the dialkyl ethers, the group of saturated or unsaturated, branched or
unbranched
alcohols.
Any desired mixtures of such oil and wax components are also to be used
advantageously within the context of the present invention. It may in some
instances
also be advantageous to use waxes, for example cetyl palmitate, as the sole
lipid
component of the oil phase.
According to the invention, the oil component is advantageously selected from
the
group consisting of 2-ethylhexyl isostearate, octyldodecanol, isotridecyl
isononanoate,
isoeicosane, 2-ethylhexyl cocoate, C12-15-alkyl benzoate, caprylic-capric
triglyceride,
dicaprylyl ether.
Mixtures of C12-C15-alkyl benzoate and 2-ethylhexyl isostearate, mixtures of
C12-
C15-alkyl benzoate and isotridecyl isononanoate, and also mixtures of C12-C15-
alkyl
benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate are
advantageous
according to the invention.
According to the invention, as oils with a polarity of from 5 to 50 mN/m,
particular
preference is given to using fatty acid triglycerides, in particular soybean
oil and/or
almond oil.
Of the hydrocarbons, paraffin oil, squalane, squalene and in particular
polyisobutenes,
which may also be hydrogenated, are to be used advantageously within the
context of
the present invention.
In addition, the oil phase can be advantageously selected from the group of
Guerbet
alcohols. Guerbet alcohols are produced by the reaction equation
R
R-CH2-CH2-OH R-CH-CH2-OH
catalyst
by oxidation of an alcohol to give an aldehyde, by aldol condensation of the
aldehyde,
elimination of water from the aldol and hydrogenation of the allylaldehyde.
Guerbet
alcohols are liquid even at low temperatures and cause virtually no skin
irritations. They
can be used advantageously as fatting, superfatting and also refatting
constituents in
cosmetic compositions.
PF 62797
CA 02781185 2012-051 7
The use of Guerbet alcohols in cosmetics is known per se. Such species are
then
characterized in most cases by the structure
H
Rl- --CH2-OH
I
R2
Here, R, and R2 are generally unbranched alkyl radicals.
5 According to the invention, the Guerbet alcohol or alcohols are
advantageously
selected from the group where
R, = propyl, butyl, pentyl, hexyl, heptyl or octyl and
R2 = hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl or
tetradecyl.
10 Guerbet alcohols preferred according to the invention are 2-butyloctanol
(commercially
available, for example, as Isofol 12 (Condea)) and 2-hexyldecanol
(commercially
available, for example, as Isofol 16 (Condea)).
Mixtures of Guerbet alcohols according to the invention are also to be used
advantageously according to the invention, such as, for example, mixtures of 2-
butyl-
15 octanol and 2-hexyldecanol (commercially available, for example, as Isofol
14
(Condea)).
Any desired mixtures of such oil and wax components are also to be used
advantageously within the context of the present invention. Among the
polyolefins,
polydecenes are the preferred substances.
20 The oil component can advantageously also have a content of cyclic or
linear silicone
oils or consist entirely of such oils, although it is preferred to use an
additional content
of other oil phase components besides the silicone oil or the silicone oils.
Low molecular weight silicones or silicone oils are generally defined by the
following
general formula
RI
R2-O-Si-O-R3
R4
Higher molecular weight silicones or silicone oils are generally defined by
the following
general formula
PF 62797
CA 02781185 2012_0517
21
R1 R2
O--Si--O-Si
R3 R4
M
where the silicon atoms can be substituted by identical or different alkyl
radicals and/or
aryl radicals, which are shown here in general terms by the radicals R, to R4.
However,
the number of different radicals is not necessarily limited to 4. m can here
assume
values from 2 to 200 000.
Cyclic silicones to be used advantageously according to the invention are
generally
defined by the following general formula
R, R2
O-Si-O-Si
I I e
R3 R4
n
where the silicon atoms can be substituted by identical or different alkyl
radicals and/or
aryl radicals, which are represented here in general terms by the radicals R,
to R4.
However, the number of different radicals is not necessarily limited to 4. n
can here
assume values from 3/2 to 20. Fractional values for n take into consideration
that odd
numbers of siloxyl groups may be present in the cycle.
Phenyltrimethicone is advantageously selected as silicone oil. Other silicone
oils, for
example dimethicone, hexamethylcyclotrisiloxane, phenyldimethicone,
cyclomethicone
(e.g. decamethylcyclopentasiloxane), hexamethylcyclotrisiloxane,
polydimethylsiloxane, poly(methylphenylsiloxane), cetyldimethicone,
behenoxydimethicone are also to be used advantageously within the context of
the
present invention. Also advantageous are mixtures of cyclomethicone and
isotridecyl
isononanoate, and also those of cyclomethicone and 2-ethylhexyl isostearate.
However, it is also advantageous to select silicone oils of similar
constitution to the
compounds referred to above, the organic side chains of which are derivatized,
for
example polyethoxylated and/or polypropoxylated. These include, for example,
polysiloxanepolyalkyl-polyether copolymers, such as, for example, cetyl-
dimethicone
copolyol.
PF 62797
CA 02781185 2012_0517
22
Cyclomethicone (octamethylcyclotetrasiloxane) is advantageously used as
silicone oil
to be used according to the invention.
Fat and/or wax components to be used advantageously can be selected from the
group
of vegetable waxes, animal waxes, mineral waxes and petrochemical waxes. For
example, candelilla wax, carnauba wax, Japan wax, esparto grass wax, cork wax,
guaruma wax, rice germ oil wax, sugar cane wax, berry wax, ouricury wax,
montan
wax, jojoba wax, shea butter, beeswax, shellac wax, spermaceti, lanolin (wool
wax),
uropygial grease, ceresin, ozokerite (earth wax), paraffin waxes and micro
waxes.
Further advantageous fat and/or wax components are chemically modified waxes
and
synthetic waxes, such as, for example, Syncrowax HRC (glyceryl tribehenate),
and
Syncrowax AW 1 C (C18-36-fatty acid), and also montan ester waxes, sasol
waxes,
hydrogenated jojoba waxes, synthetic or modified beeswaxes (e.g. dimethicone
copolyol beeswax and/or C3o-5o-alkyl beeswax), cetyl ricinoleates, such as,
for example
Tegosoft CR, polyalkylene waxes, polyethylene glycol waxes, but also
chemically
modified fats, such as, for example, hydrogenated plant oils (for example
hydrogenated
castor oil and/or hydrogenated coconut fatty glycerides), triglycerides, such
as, for
example, hydrogenated soy glyceride, trihydroxystearin, fatty acids, fatty
acid esters
and glycol esters, such as, for example, C2o-ao-alkyl stearate, C2o-4o-alkyl
hydroxystearoylstearate and/or glycol montanate. Also certain organosilicon
compounds which have similar physical properties to the specified fat and/or
wax
components, such as, for example, stearoxytrimethylsilane, are furthermore
advantageous.
According to the invention, the fat and/or wax components can be used either
individually or as a mixture in the compositions.
Any desired mixtures of such oil and wax components are also to be used
advantageously within the context of the present invention.
The oil phase is advantageously selected from the group consisting of 2-
ethylhexyl
isostearate, octyldodecanol, isotridecyl isononanoate, butylene glycol
dicaprylate/dicaprate, 2-ethyihexyl cocoate, C12-15-alkyl benzoate, caprylic-
capric
triglyceride, dicaprylyl ether.
Mixtures of octyldodecanol, caprylic-capric triglyceride, dicaprylyl ether,
dicaprylyl
carbonate, cocoglycerides or mixtures of C12-15-alkyl benzoate and 2-
ethyihexyl
isostearate, mixtures of C12-15-alkyl benzoate and butylene glycol
dicaprylate/dicaprate,
and also mixtures of C12-15-alkyl benzoate, 2-ethyihexyl isostearate and
isotridecyl
isononanoate are particularly advantageous.
PF 62797
CA 02,8õ8520,2-051]
23
Of the hydrocarbons, paraffin oil, cycloparaffin, squalane, squalene,
hydrogenated
polyisobutene and polydecene are to be used advantageously within the context
of the
present invention.
The oil component can also be advantageously selected from the group of
phospholipids. The phospholipids are phosphoric acid esters of acylated
glycerols. Of
greatest importance among the phosphatidylcholines are, for example, the
lecithins,
which are characterized by the general structure
0
11
0 CH2-0-C-R" 11 1
R-C-O-CH O CH3
CH2-O-P-O-CH2-CH2--N CH3
0 CH3
where Rand R" are typically unbranched aliphatic radicals having 15 or 17
carbon
atoms and up to 4 cis double bonds.
According to the invention, as paraffin oil advantageous according to the
invention it is
possible to use Merkur Weissoel Pharma 40 from Merkur Vaseline, Shell Ondina
917,
Shell Ondina 927, Shell Oil 4222, Shell Ondina 933 from Shell & DEA Oil,
Pionier
6301 S, Pionier 2071 (Hansen & Rosenthal).
Suitable cosmetically compatible oil and fat components are described in Karl-
Heinz
Schrader, Grundlagen and Rezepturen der Kosmetika [Fundamentals and
formulations
of cosmetics], 2nd edition, Verlag Huthig, Heidelberg, pp. 319 - 355, to which
reference
is hereby made in its entirety.
Further embodiments of the present invention are given in the claims, the
description
and the examples. It goes without saying that the features of the subject
matter
according to the invention that have been specified above and are still to be
explained
below can be used not only in the combination stated in each case, but also in
other
combinations, without departing from the scope of the invention.
The present invention will be illustrated by the examples below.
Examples
Measurement methods
The IR measurements were carried out using a Nicolet 210 instrument.
w PF 62797 CA 027811852012-05-17
24
The acid number and the hydroxyl number were determined in accordance with DIN
53240, part 2.
The molecular weight was determined with the help of gel permeation
chromatography
using a refractometer as detector. The mobile phase used was
dimethylacetamide, and
the standard used for determining the molecular weight was polymethyl
methacrylate
(PMMA).
Feed materials
DBTL: Dibutyltin dilaurate, manufacturer: Sigma-Aldrich
Paraffin oil: Nujol, Fluka AG
Example 1: Preparation of a highly-branched polyester
233.2 g of adipic acid (1.6 mol) and 266.0 g (1.33 mol) of a triol based on
trimethylolpropane which has been etherified in a random manner with 1,2-
propylene
oxide units were initially introduced into a 1000 ml glass reactor fitted with
stirrer, reflux
condenser, gas inlet, attached thereto a vacuum system with interconnected
cold trap
and internal thermometer. After adding 200 ppm of DBTL, the mixture was heated
to
150 C. During this, the internal pressure was reduced to a final value of ca.
10 mbar in
such a way that the water that formed was removed in a controlled manner.
Stirring
was carried out for 5.5 hours at this temperature. The acid number was 68 mg
KOH/g.
97 g of the aforementioned triol (0.8 equivalents per acid group) were added
to the
reaction mixture. The reaction mixture was stirred for a further 5 hours at an
internal
pressure of ca. 10 mbar and then cooled to ambient temperature at this
pressure.
The end product was obtained as viscous, clear liquid which has the following
properties: acid number = 26 mg KOH/g; hydroxyl number = 204 mg KOH/g;
viscosity:
6800 mPas (75 C)
Examples 2 - 8: Modification of the highly-branched polyester with stearyl
isocyanate
Highly-branched polyester from example 1 was initially introduced into a 250
ml glass
reactor equipped with stirrer, reflux condenser, gas inlet, internal
thermometer and
dropping funnel, which comprised the required amount of stearyl isocyanate.
The
amounts of highly-branched polyester and stearyl isocyanate used are given in
the
table below.
The reactor was heated to 80 C and the isocyanate was added dropwise over the
course of 15 minutes. The reaction mixture was then stirred for a further 2
hours at
PF 62797
CA 02781185 2012_0517
120 C and the reaction progress was monitored via the disappearance of the
isocyanate groups with the help of IR spectroscopy (disappearance of the
isocyanate
band at 2270 cm-1).
Example 2 3 4 5 6 7 8
Highly-branched polyester 50 50 51.2 76.6 50 50 50
(example 1) [g]
Mol% NCO 40 50 60 70 80 90 100
Amount of stearyl isocyanate [g] 21.5 26.9 33.1 58 43.04 48.4 53.8
5
Example 9: Gel formation by adding the stearyl-modified highly-branched
polyester to
paraffin oil
Various amounts (0.5 to 20% by weight) of the polymers in examples 3 to 8 were
10 dissolved in paraffin oil. The concentration at which visible gel formation
occurred is
given in the table below:
Polymer from example ... 3 4 5 6 7 8
NCO/OH ratio [%] 50 60 70 80 90 100
Gel formation concentration (%) 10 10 7 6 4 4
