CA2816039A1

CA2816039A1 - Polyurethane thickener

Info

Publication number: CA2816039A1
Application number: CA2816039A
Authority: CA
Inventors: Holger Tuerk; Volker Wendel
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2010-10-22
Filing date: 2011-10-20
Publication date: 2012-04-26
Also published as: AU2011317583A1; CN103328527B; KR20130124307A; ES2545814T3; BR112013009597A2; JP2017031426A; BR112013009597B1; MX2013004524A; WO2012052508A3; CN103328527A; JP2013543033A; RU2013123092A; EP2630176A2; KR101834593B1; WO2012052508A2; JP6215432B2; EP2630176B1

Abstract

The present invention relates to a method for producing polyurethanes which contain at least three hydrophilic segments, at least four hydrophobic segments, optionally allophanate segments and/or isocyanurate segments and which are produced in the presence of alkaline earth metal carboxylates. The present invention further relates to the thus obtained polyurethanes per se, to their use as thickener for aqueous preparations and to preparations containing such polyurethanes.

Description

Polyurethane thickener Description The present invention relates to a process for preparing polyurethanes which comprise at least three hydrophilic sections, at least four hydrophobic sections, optionally allophanate segments and/or isocyanurate segments and which are prepared in the presence of alkali(ne earth) metal carboxylates.
Furthermore, the present invention relates to the polyurethanes per se, obtainable in this way, to the use thereof as thickeners for aqueous preparations, and to preparations comprising polyurethanes of this type.
Polyurethanes have been used for a long time in numerous fields of application for highly diverse purposes. Depending on the choice of starting materials and the stoichiometric ratio of the starting materials, polyurethanes are obtained with very different physicochemical properties.
Thickeners are used widely for increasing the viscosity of aqueous preparations, for example in the fields of cosmetics, human and animal nutrition, pharmacy and for detergents, paints and coatings. Inter alia, polyurethanes are also known as thickeners.
For example, polyurethane solutions or dispersions in water-dilutable aqueous or predominantly aqueous phase are referred to by the person skilled in the art as HEUR
thickeners ("hydrophobically modified ethylene oxide urethane copolymer"), and have already been used for a relatively long time in highly diverse fields of application, for example for thickening water-based emulsion paints.
The action principle of the thickening effect of the HEUR thickeners in the afore-mentioned example is assumed to be that the polyethylene glycol segments ensure the water compatibility and the hydrophobic segments construct a viscosity-imparting three-dimensional molecular association via an association with one another and also with dispersed binder particles of the emulsion paint to be thickened therein.
Thickeners are also used in the field of cosmetic preparations. Thickeners for cosmetic preparations are expected to have an adequate thickening effect even in preparations with a high content of salt. Furthermore, such thickeners should produce cosmetic preparations with a good texture and pleasant feel on the skin. Compatibility with numerous other auxiliaries, in particular with salts and surfactants, and also incorporability of the thickener itself and also of the other auxiliaries should be provided.

Moreover, the thickened preparations must have constant rheology and physical and chemical quality even upon long-term storage, and in the case of changes in temperature and pH. Finally, it should also be possible to produce these thickeners in a cost-effective manner and without a notable impact on the environment.
US 4079028 and US 4155892 disclose, inter alia, linear polyurethane thickeners. The preparation of the polyurethanes specified therein is catalyzed by the catalyst dibutyltin dilaurate (DBTL) customary in polyurethane chemistry. ' EP 1584331 and EP 1013264 describe polyurethane thickeners for cosmetic preparations. These are prepared in a single-step process by reaction without a diluent from polyol, polyisocyanate and fatty alcohol, which may be ethoxylated if desired, and without use of a catalyst.

3 describes polyurethane thickeners for various applications in aqueous media. These thickeners are prepared from hydrophilic polyols having at least two hydroxy groups, one or more hydrophobic compounds, e.g. long-chain alcohols, and at least difunctional isocyanates. Here, an excess of NCO groups is used.
The catalyst used is 1,8-diazabicyclo45-4-0]undec-7-ene (DABCO).
WO 02/88212 describes polyurethanes of ethoxylated long-chain alcohols and cyclic diisocyanate oligomers, for example isocyanurates, as starting materials. The polyurethanes described are prepared without using a catalyst.
EP 725097 describes polyurethane thickeners, during the preparation of which polyethers, produced by alkoxylation of alcohols or alkylphenols, are reacted with polyisocyanates with catalysis by DBTL, diazabicyclooctane or tin dioctoate, the ratio of NCO to OH equivalents being in the range from 0.9:1 to 1.2:1. These thickeners are proposed for use in the field of low shear forces, e.g. for the flow of water-based emulsion paints.
EP 1241198, EP 1241199, and EP 1241200 describe the preparation of polyurethane thickeners with DBTL catalysis and use of polyetherpolyols and urethane-group-containing polyetherpolyols with functionalities > 2 (for example ethoxylated sugars, glycerol, etc.).
EP 761780 and EP 1111014 describe polyurethane thickeners composed of polyethylene glycol, diisocyanate and branched, preferably long-chain-branched alkyl groups as hydrophobic component. The preparation takes place in the melt without using a catalyst.

WO 2009/135856 and WO 2009/135857 describe water-dispersible polyurethanes with an essentially linear backbone composed of alternating hydrophilic and hydrophobic sections and uses thereof. The polyurethane formation is catalyzed by titanium or zinc compounds.
It was an object of the present invention to provide novel thickeners for water-comprising preparations, in particular cosmetic preparation. The novel thickeners should have the best thickening effect possible. Moreover, the thickening effect of the novel thickeners should at least not be diminished by the presence of salts in the aqueous preparations.
A further aim was to provide polyurethane thickeners with the properties described, which are in addition tin-free, since this is desired for cosmetic applications.
The aforementioned objects are achieved by a process for preparing polyurethanes comprising l) at least two hydrophilic sections S, II) at least one hydrophilic section P different from S, IV) at least two hydrophobic sections D different from T, where a) to each section T is directly attached a section S, b) to each section S on at least one side is attached at least one section D, c) to each section P are attached at least two sections D, wherein the preparation takes place in the presence of at least one carboxylic acid salt of a metal selected from the group consisting of alkali metals, alkaline earth metals and mixtures thereof.
The polyurethanes obtainable by the process according to the invention are mixtures which comprise at least some of the described polyurethane structures. The polyurethanes obtainable by the process according to the invention are preferably dispersible in water. According to the invention, this comprises that they can also be emulsified in water or are completely or partially soluble in water.
The polyurethanes obtainable by the process according to the invention (also referred to hereinbelow as "polyurethanes according to the invention") are preferably at least partially branched. "At least partially branched" means that at least some of the polymer molecules are not linear, but have branching points.
Such branches may be present both in the hydrophobic sections and also the hydrophilic sections.

In one embodiment of the invention, at least some of the terminal hydrophobic sections T are branched.
In one embodiment of the invention, at least some of the hydrophobic sections D are branched.
One advantage of the polyurethanes obtainable according to the invention is that by using alkali(ne earth) metal carboxylates it is possible to generate branches of the polyisocyanates in the form of isocyanurate or allophanate structures in-situ and it is therefore not necessary to rely on polyisocyanates with already prepared isocyanurate or allophanate structures as starting compounds. Firstly, the starting materials are more favorable in terms of cost as a result and secondly the desired amount of such branching points can be adjusted to the desired degree via the amount of catalyst.
Furthermore, the process according to the invention leads less quickly to crosslinked structures than the use of preprepared isocyanurate or allophanate structures.
The backbone of the polyurethanes according to the invention is composed of alternating hydrophobic and hydrophilic sections, where the hydrophobic and hydrophilic sections alternate in the sequence, but may be different in terms of their size, length and nature. In the polyurethanes according to the invention, a hydrophobic section is preferably attached on both sides to a hydrophilic section. These hydrophobic sections may independently of one another be identical or different. Each section may be short-chain or an oligonner radical or a polymer radical. In the present case, "attached to a section" is understood as meaning that the connection takes place directly, i.e. that the two sections in question are directly adjacent in the polymer molecule.
Hydrophilic sections Hydrophilic is the term used here to refer to those sections which exhibit marked interaction with water. In general, hydrophilic sections consist of radicals of substances which are themselves hydrophilic.
Typical hydrophilic groups known to the person skilled in the art are, for example, nonionic polyether radicals. Polyether radicals may be homo-alkylene oxide radicals or mixtures of different alkylene oxide radicals. These different alkylene oxide radicals may be present in the polyether radicals in random distribution or be present in block form. Preferred polyether radicals are homo-ethylene oxide radicals.
Hereinbelow, ethylene oxide is also referred to as EO, and propylene oxide is also referred to as PO.
According to another embodiment, the polyether radicals comprise mixtures of EO
radicals and PO radicals. These may be present in the polyether radicals in random distribution or be present in block form. In one preferred embodiment, the EO
and PO
radicals are present in block form.
A particularly preferred embodiment includes polyether radicals which have at least 5 50% by weight of ethylene oxide radicals, for example polyether radicals which have more than 50% by weight of ethylene oxide radicals, and propylene oxide radicals as further alkylene oxide radicals. The polyether radicals very particularly preferably consist of ethylene oxide radicals.
The hydrophilicity of a substance can be determined, for example, by means of an opacity measurement of an aqueous solution.
Preferred hydrophilic sections are water-soluble. For the purposes of this invention, a substance is referred to as being soluble in a liquid phase if at least 1 g, preferably at least 10 g, of the substance dissolved at 20 C and a pressure of 1 bar to give a solution that looks clear to the human eye, i.e. without visible clouding in 1 liter of the liquid phase. Water-soluble substances are therefore substances which are soluble in an amount of at least 1 g, preferably at least 10 g, at 20 C and a pressure of 1 bar to give a solution that looks clear to the human eye, i.e. without visible clouding, in 1 liter of water, preferably demineralized water.
Hydrophobic sections By means of the process according to the invention, polyurethane molecules are obtained which comprise at least two terminal hydrophobic sections T and at least two hydrophobic sections D.
However, depending on how the reaction is carried out, polyurethane molecules are also obtained which comprise two hydrophobic sections T and only one hydrophobic section D.
In general, the hydrophobic sections consist of radicals of substances which are immiscible with water or only poorly miscible with water and are preferably lipophilic at the same time, i.e. are readily soluble in nonpolar solvents such= as, for example, fats and oils.
Typical hydrophobic sections T are, for example, hydrocarbon radicals, in particular long-chain hydrocarbon radicals.
In one embodiment of the invention, the hydrocarbon radicals are unbranched.
In another embodiment of the invention, the hydrocarbon radicals are branched.

In a further embodiment of the invention, the polyurethanes according to the invention comprise both branched and unbranched hydrocarbon radicals.
Long-chain aliphatic alcohols, aromatic alcohols and aliphatic diisocyanates are examples of hydrophobic substances, the radicals of which may be present in the hydrophobic sections of the polyurethanes according to the invention.
The polyurethanes prepared by the process according to the invention comprise at least two terminal hydrophobic sections (T) which, independently of one another, may be identical or different.
In one preferred embodiment, at least some of the polyurethanes according to the invention comprise more than two terminal hydrophobic sections (T).
The terminal hydrophobic sections T can be branched or unbranched. Preferably, at least one of the two terminal hydrophobic sections T is branched.
Preferably, the terminal hydrophobic sections T comprise at least one alkyl radical.
Preferably, this alkyl radical comprises 4 to 30 carbon atoms, particularly 8 to 30 and very particularly preferably 12 to 30 carbon atoms.
Preferably, the chain length of the main chain of the alkyl radicals which are present in the sections T is in the range from 4 to 30 carbon atoms. These are for example alkyl radicals of linear or branched alkanes such as, for example, butane, isobutane, pentane, isopentane, neopentane, hexane, heptane, octane, 2-ethylhexane, nonane, decane, undecane, dodecane, tridecane, isotridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, icosane, henicosane, docosane, tricosane, isotricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, 2-octyldodecane, 2-dodecylhexadecane, 2-tetradecyloctadecane, or monomethyl-branched isooctadecane.
The hydrophobic sections T can likewise also comprise radicals of cycloalkanes and -alkenes, as described for example in EP 761780 A2, p. 4, 11. 56-58, radicals of alkenes as described for example in EP 761780 A2, p. 4, II. 51-52, or alkylaryl radicals as described for example in EP 761780 A2, p. 4, II. 53-55.
The sections T particularly preferably comprise the above-described alkyl radicals with 8 to 30 carbon atoms, very particularly preferably with 12 to 30 carbon atoms.
The sections T consist of or preferably comprise the above-described aliphatic radicals, but may also comprise the above-described aromatic radicals or consist of them.

Preferably, at least one section T is a branched alkyl radical.
In one preferred embodiment, the side chains of the branched alkyl radicals have a chain length of at most 6, preferably of at most 4, carbon atoms.
In one embodiment, the branches are considerably shorter than the main chain.
In one embodiment, each branch of the sections T of the polyurethanes according to the invention has a chain length which corresponds at most to half of the chain length of the main chain of this section T. In one preferred embodiment, the branched alkyl radicals are iso- and/or neo-alkyl radicals. In one preferred embodiment, radicals of isoalkanes are used as branched alkyl radicals. Particular preference is given to a C13-alkyl radical, in particular an iso-C13-alkyl radical.
In another embodiment, the sections T comprise branched alkyl radicals, the side chains of which have a chain length of at least 4, preferably of at least 6, carbon atoms.
The sections T can be introduced into the polyurethanes according to the invention in various ways.
In one preferred embodiment, the sections T are introduced into the polyurethanes simultaneously and together with the hydrophilic sections S through the use of alkoxylated alcohols.
Suitable alcohols are, for example, the alkoxylated - linear alcohols from natural sources or from the Ziegler build-up reaction of ethylene in the presence of aluminum alkyl catalysts. Examples of suitable alcohols are Cs-Cm-alcohols, in particular C12-C30-alcohols. Particularly preferred alcohols which may be mentioned here are: n-dodecanol, n-tetradecanol, n- hexadecanol, n-octadecanol, n-eicosanol, n-docosanol, n-tetracosanol, n-hexacosanol, n-octacosanol and/or n-triacontanol, and also mixtures of the aforementioned alcohols, for example NAFOL
grades such as NAFOL 22+ (Sasol).
- oxo alcohols such as, for example, isoheptanol, isooctanol, isononanol, isodecanol, isoundecanol, isotridecanol (for example Exxal grades 7, 8, 9, 10, 11, 13).
- alcohols which are branched in the 2 position; these are the Guerbet alcohols known to the person skilled in the art which are accessible by dimerization of primary alcohols via the so-called Guerbet reaction. Particularly preferred alcohols which may be mentioned here are: Isofol012 (Sasol), Rilanit G16 (Cognis).

- alcohols which are obtained by the Friedel-Crafts alkylation with oligomerized olefins and which then comprise an aromatic ring as well as a saturated hydrocarbon radical.
Particularly preferred alcohols which may be mentioned here are:
isooctylphenol and isononylphenol.
- alcohols of the general formula (4) in EP 761780 A2, p. 4 R¨C¨R OH
\ 5 or alcohols of the general formula (5) in EP 761780 A2, p. 4 R¨C¨OH
'8R
where - R4, R6, R7 and R8, independently of one another, have the meaning described in EP 761780 A2, p. 4, lines 45 to 58; preferably, R4, R6, R7 and R8, independently of one another, are alkyl radicals having at least 4 carbon atoms and the total number of the carbon atoms in the alcohols is at most 30, - R6 is an alkylene radical such as, for example, ¨CH2-, -CH2-CH2-, -CH2-CH(CH3)-.
By way of example, mention may be made here of 2-decy1-1-tetradecanol as suitable alcohol.
In one embodiment, mixtures of ethoxylated C16-C18-fatty alcohols are used in order to introduce sections T into the polyurethanes.
In a further embodiment, ethoxylated iso-C13-oxo alcohols or mixtures thereof are used in order to introduce sections T into the polyurethanes.
In a further embodiment, mixtures comprising ethoxylated Ci6-C18-fatty alcohols and ethoxylated iso-C13-oxo alcohols are used in order to introduce sections T
into the polyurethanes.
In a further embodiment, the above-described alcohols of the general formula (4) or (5) in EP 761780 A2, p. 4, are used in their ethoxylated form in order to introduce sections T into the polyurethanes.

It is of course possible to additionally also introduce other sections T into the polyurethanes.
The hydrophobic sections T can of course also be introduced into the polyurethanes through any desired mixtures of the above-described ethoxylated alcohols.
By means of the process according to the invention, as is customary in the case of polymerization reactions, mixtures of different polymers are of course obtained, in the present case thus mixtures of different polyurethanes.
The term "polyurethane" used here can refer either to any individual polyurethane molecule or to the totality of the polyurethane molecules obtainable by the process according to the invention.
The polyurethanes obtainable by the preparation process according to the invention are preferably mixtures which comprise the described polyurethane structures.
Accordingly, the preparation of mixtures of polyurethanes, the terminal hydrophobic sections T of which are branched and/or unbranched alkyl radicals is also in accordance with the invention. The preparation of mixtures which comprise polyurethanes which comprise both branched and unbranched terminal, hydrophobic sections T is also in accordance with the invention.
Preferably, at least some of the polyurethane molecules obtainable by the process according to the invention comprise allophanate segments. The invention thus also provides a process according to the invention where at least some of the resulting polyurethanes comprise allophanate segments.
Preferably, at least some of the polyurethane molecules obtainable by the process according to the invention comprise isocyanurate segments.
The invention thus also provides a process according to the invention where at least some of the polyurethanes comprise isocyanurate segments.
Hydrophilic sections S
In the polyurethanes obtainable by the process according to the invention, to the terminal hydrophobic sections T are attached hydrophilic sections S.
In the polyurethanes, the sections S, independently of one another, may be identical or different, linear or branched.
In one embodiment, the hydrophilic sections S are of different lengths and linear.

The sections S preferably comprise radicals of alkylene oxides. Preferably, the number is in the range from 2 to 150 alkylene oxide radicals, particularly preferably in the range from 5 to 100 alkylene oxide radicals and very particularly preferably in the range from 10 to 100 alkylene oxide radicals.

The hydrophilic sections S comprise or consist preferably of ethylene oxide radicals. In one preferred embodiment, the hydrophilic sections S comprise ethylene oxide radicals (EO units), the number of which is in the range from 2 to 150 EO units, particularly preferably in the range from 5 to 100 EO units and very particularly preferably in the 10 range from 10 to 100 EO units.
In one preferred embodiment, the sections S consist of 5 to 30, preferably 10 to 25 EO
units.
In another embodiment, the sections S consist of 30 to 100, preferably 40 to units.
The number of EO units per molecule of ethoxylated alcohol is also referred to as degree of ethoxylation.
The ethoxylated alcohols preferably used in the process according to the invention have a degree of ethoxylation which is in the range from 2 to 150 ethylene oxide radicals, preferably in the range from 5 to 100 ethylene oxide radicals and further preferably in the range from 10 to 100 ethylene oxide radicals.
In a particularly preferred embodiment, the ethoxylated alcohols used have a degree of ethoxylation in the range from 10 to 25 ethylene oxide radicals.
In one embodiment, a branched, nonionic compound of the structural formula RO(CH2CH20)xH, where R is a C13-alkyl radical, preferably an iso-C13-alkyl radical, and where x = 3, 5, 6, 6.5, 7, 8, 10, 12, 15 or 20, preferably x = 10, is used as at least one of the alcohols used. Commercially, such an ethoxylated, alkyl-branched alcohol is available, for example, as LutensoloT010.
In one embodiment, at least one of the alcohols used is an alcohol of the general formula (4) in EP 761780 A2, p.4 R ¨C¨R OH
\ 5 or an alcohol of the general formula (5) in EP 761780 A2, p.4 R¨C¨OH
\ 8 where - R4, R6, R7 and R8, independently of one another, have the meaning described in EP 761780 A2, p.4, lines 45 to 58; preferably, R4, R6, R7 and R8, independently of one another, are alkyl radicals having at least 4 carbon atoms and the total number of the carbon atoms in the alcohols is at most 30, - R6 is an alkylene radical, such as, for example, ¨CH2-, -CH2-CH2-, -CH2-CH(CH3)-.
By way of example, mention may be made here of 2-decy1-1-tetradecanol as a suitable alcohol.
In one embodiment of the invention, mixtures of ethoxylated linear and ethoxylated branched long-chain alcohols, in particular mixtures of the aforementioned types, are used.
In one embodiment of the invention, the hydrophilic sections S comprise mixtures of EO and PO units.
The sections S can likewise comprise longer-chain alkylene oxide radicals, with the proviso that the sections S must be hydrophilic overall. The hydrophilicity can be controlled for example via the fraction of EO units in the sections S.
Hydrophobic sections D
To each hydrophilic section S is attached at least one hydrophobic section D.
Here, a section S may also be present in the interior of the molecule of the polyurethanes according to the invention. In this case, this section S is connected not like an edge-position section S to a section D and a section T, but on at least two sides to sections D. Preferably, a section S is connected in the interior of the molecule on both sides to one section D in each case.
For all edge-position sections S, it is the case that they are directly connected to an end-position section T. Should a section S be branched to a low extent, then it could be directly connected at two or more positions to hydrophobic sections D.
Preferably, to each hydrophilic section S is connected a hydrophobic section D on at least one side.

In a particularly preferred embodiment, all sections S are unbranched and edge-positioned and connected to a section T on one side and to a section D on the other side.
By means of the process according to the invention, polyurethane molecules are obtained which comprise at least two hydrophobic sections D. In addition, however, depending on how the process according to the invention is carried out, polyurethane molecules are also obtained which comprise only one hydrophobic section D.
In the polyurethane molecules with at least two hydrophobic sections D, these may be identical or, independently of one another, different.
The sections D can be branched with short-chain hydrophobic branches or be unbranched. Preferably, at least some of the sections D are branched.
Preferably, the sections D comprise at least one hydrophobic chain of carbon atoms, the length of which is in the range from 2 to 20 carbon atoms, preferably 3 to 16 carbon atoms and in particular in the range from 4 to 12 carbon atoms.
Preferably, the sections D comprise diisocyanate radicals. The sections D
particularly preferably comprise radicals of aliphatic diisocyanates. Thus, for example, a hydrophobic section D can consist of one or more aliphatic diisocyanate radicals.
Preferably, a section D consists of one to ten aliphatic diisocyanate radicals, particularly preferably of one to five aliphatic diisocyanate radicals; very particularly preferably, it comprises one, two or three aliphatic diisocyanate radicals.
The hydrophobic sections D can comprise aliphatic diisocyanate radicals with long, mid-length or short aliphatic units.
In one of the preferred embodiments, the sections D of the polyurethanes prepared by the process according to the invention are cycloaliphatic or aliphatic diisocyanate radicals.
Aliphatic diisocyanate radicals are particularly preferred as sections D.
Aliphatic diisocyanates which may be mentioned by way of example are: 1,4-butylene diisocyanate, 1,12-dodecamethylene diisocyanate, 1,10-decamethylene diisocyanate, 2¨butyl-2¨ethylpentamethylene diisocyanate, 2,4,4- or 2,2,4-trinnethylhexamethylene diisocyanate and in particular hexamethylene diisocyanate (HDI).
By way of example, cycloaliphatic diisocyanates which may be mentioned are:
isophorone diisocyanate (IPDI), 2¨isocyanatopropylcyclohexyl isocyanate, 4-methylcyclohexane 1,3¨diisocyanate (H¨TDI) and 1,3-bis(isocyanatomethyl)cyclohexane.

. .

So-called H12-MDI or diisocyanates termed "saturated MDI", such as, for example, 4,4'-methylenebis(cyclohexyl isocyanate) (alternatively also called dicyclohexylmethane 4,4'-diisocyanate) or 2,4'¨methylenebis(cyclohexyl) diisocyanate can also be present as radicals in sections D of the polyurethanes PU according to the invention.
It is of course possible, in the process according to the invention, to use mixtures of the abovementioned diisocyanates in order to prepare mixtures of different polyurethanes.
In one preferred embodiment, some of the polyurethanes obtainable by the process according to the invention comprise hydrophobic sections D with allophanate structures. Allophanate structures are formed as a result of the addition of an isocyanate group onto a urethane unit.
In one preferred embodiment, some of the polyurethanes prepared by the process according to the invention comprise hydrophobic sections D with isocyanurate structures. Isocyanurate structures are formed by the addition of 3 isocyanate groups (trinnerization).
In a further preferred embodiment, some of the polyurethanes prepared by the process according to the invention comprise both hydrophobic sections D with allophanate structures and also hydrophobic sections D with isocyanurate structures.
In a further embodiment, some of the polyurethanes prepared by the process according to the invention comprise hydrophobic sections D with biuret structures.
Biuret structures are formed as a result of the addition of an isocyanate group onto a urea unit. Urea units in turn are formed as a result of the addition of primary amines onto isocyanate groups.
Hydrophilic sections P
As a result of the process according to the invention, polyurethane molecules are obtained which comprise at least one hydrophilic section P different from the hydrophilic sections S. In this case, to P are attached at least two hydrophobic sections D. The sections P of the polyurethanes according to the invention can, independently of one another, be identical or different.
Depending on how the process according to the invention is carried out, however, polyurethane molecules are also additionally obtained which comprise no hydrophilic section P.
If more than one section P is present in a polyurethane according to the invention, then there is in each case at least one hydrophobic section D between the hydrophilic sections P. If more than one section P is present in a polyurethane according to the invention, then these may be identical or different.
In one embodiment, the polyurethanes according to the invention can comprise a sequence of sections in the order hydrophobic section D, then hydrophilic section S, then hydrophobic section D again between two hydrophilic sections P. Thus, if in a polyurethane according to the invention, more than one section P is present, then in such a case, the sections in the interior of the molecule can have a sequence of P-D-P
or of P-D-S-D-P. Should more than two sections P be present, then both sequences in one molecule are possible.
Preferably, only one or two sections P are present in a molecule of the polyurethanes obtainable according to the invention.
The hydrophilic sections P are preferably introduced into the polyurethanes through the use of hydrophilic polyols. Per molecule, these comprise at least two OH
groups and at least two functional groups which are selected from the functions -0- (ether groups) and -000- (ester groups), where the molecular weight of these hydrophilic compounds is at least 300 and preferably at least 1200.
One embodiment of the invention is a process according to the invention, wherein the at least one hydrophilic section P has a number-average molecular weight of from 1500 to 20 000 g/mol, preferably from 4000 to 12 000 g/mol.
Suitable hydrophilic polyols are, for example, the polymerization products of ethylene oxide, the copolymerization or graft polymerization products thereof, and the polyethers obtained by condensation of polyhydric alcohols or mixture thereof and the polyethers obtained by ethoxylation of polyhydric alcohols, amides, polyamides and amino alcohols. Examples thereof are, for example, polyethylene glycols, addition products of ethylene oxide onto trimethylolpropane, EO-PO block copolymers, OH-terminated polyesters, such as, for example, those of the multifunctional polycaprolactone type.
Preferred hydrophilic polyols are polyetherpolyols. These are those hydrophilic polyols which comprise at least two OH groups and at least two -0- functions (ether groups) per molecule. These polyetherpolyols are generally so hydrophilic that they are water-soluble at room temperature (20 C).
Of suitability for preparing the polyurethanes by the process according to the invention are preferably those polyetherpolyols which comprise predominantly polyethylene glycol. It is particularly preferred if these polyethylene glycols have an average amount of EO units in the range from 30 to 450 per molecule.

Preference is given to polyols of the general formula HO-(CH2-CH2-0)n-H, where n can assume the values 30 to 450. These are polyethylene glycols, which are condensation products of ethylene oxide with ethylene glycol or water.
Preferably, the molecular weight of these polyethylene glycols is adjusted to values in 5 the range from 1500 to 20 000 g/mol.
However, it is also possible to use EO-PO block copolymers in order to incorporate the sections P into the polyurethanes obtainable according to the invention. For example, it is possible to use EO-PO block copolymers of the general formula 10 H0-(E0)nr(PO)n-(E0)0-H, where m and o, independently of one another, are integers in the range from 10 to 100, preferably from 20 to 80, n is an integer in the range from 5 to 50, preferably from 20 to 40, and where m, n and o are selected such that HO-(E0),(PO)n-(E0)0-H is water-soluble.

15 According to the invention, the essentially linear polyether radicals which form the sections P preferably have a number-average molecular weight Mn of at least 1500 g/mol and at most 20 000 g/mol.
In a preferred embodiment, the essentially linear polyether radicals have number-average molecular weights in the range from 1500 g/mol to 15 000 g/mol.
In a further preferred embodiment, the essentially linear polyether radicals have number-average molecular weights in the range from 4000 g/mol to 12 000 g/mol.
In a particularly preferred embodiment, the essentially linear polyether radicals have number-average molecular weights in the range from 6000 g/mol to 10 000 g/mol.
In a particularly preferred embodiment, the linear polyether radicals have a number-average molecular weight Mn of about 10 000 g/mol.
In a further particularly preferred embodiment, the linear polyether radicals have a number-average molecular weight Mn of about 6000 g/mol.
All of the hydrophilic sections of the polyurethanes obtainable by the process according to the invention, i.e. the sections S and P, may be polyether radicals.
In one preferred embodiment, the hydrophilic sections of the polyurethanes according to the invention consist of - polyalkylene oxide units (sections P) and - polyethylene oxide units (sections S).

In one particularly preferred embodiment of the polyurethanes obtainable by the process according to the invention, all of the sections P and S consist of EO
units.
As a result of the process according to the invention, polyurethane molecules are obtained which comprise at least three hydrophilic sections. In one of the preferred embodiments, these are two sections S and at least one section P.
Additionally, however, depending on the reaction procedure, polyurethane molecules with only two hydrophilic sections S and without hydrophilic section P are also obtained.
As a result of the process according to the invention, polyurethanes are therefore also preferably obtained, according to the invention, which comprise l) at least two hydrophilic sections S, 11) no hydrophilic section P, 111) at least two terminal hydrophobic sections T, IV) at least one hydrophobic section D different from T, where a) to each section T is directly attached a section S, b) to each section S is attached a section D.
The polyurethanes prepared by means of the process according to the invention which additionally comprise allophanate structures preferably comprise at least three sections S and at least one section P.
Depending on the reaction procedure, however, polyurethanes are also additionally obtained which comprise allophanate structures and at least three sections S, but no section P.
Polyurethanes prepared by the process according to the invention which additionally comprise isocyanurate structures preferably comprise at least three sections S
and at least one section P.
Depending on the reaction procedure, however, polyurethanes are also additionally obtained which comprise isocyanurate structures and at least three sections S, but no section P.
At least some of the polyurethanes prepared by the process according to the invention are linear and have the following sequence of sections: T-S-D-P-D-S-T or T-S-D-P-D-P-D-S-T. Depending on the reaction procedure, however, polyurethanes are also additionally obtained which have the sequence T-S-D-S-T.

In one preferred embodiment of the invention, at least some of the polyurethanes prepared by the process according to the invention comprise allophanate and/or isocyanurate structures and have the following sequence of sections:
T¨S¨D¨P¨D¨S¨T
For example, polyurethanes prepared by the process according to the invention which additionally comprise allophanate structures have the following structure:

0 z N 0 x N
-y N
OCH2.+1 0 _z For example, polyurethanes prepared by the process according to the invention which additionally comprise isocyanurate structures have the following structure:
H -Nyo _z CnH2re 1 0 z OC,,H2n,õ
¨ Y

_ z OCArn-1 For each section P, it is the case that its molecular weight is greater than that of each section S present in the same molecule.
The ratio of the molecular weights Mn of each hydrophilic section S of the polyurethanes according to the invention to the molecular weight of each hydrophilic section P is in the range from 1:1.4 to 1:140, preferably in the range from 1:1.7 to 1:120.
In one preferred embodiment, the ratio is 1:x, where x is equal to or greater than 2, preferably equal to or greater than 2.3 and particularly preferably x is equal to or greater than 2.8. The ratio is particularly preferably in the range from 1:2.8 to 1:115, very particularly preferably in the range from 1:3 to 1:95 and especially preferably in the range from 1:3.4 to 1:80.
As a result of the process according to the invention, mixtures of different polyurethanes are generally obtained. Such a mixture can comprise e.g.
polyurethanes which have the same sequence of the sections T, S, D and/or P, but differ from one another structurally in at least one of the sections. One example of this which may be mentioned is a different section structure or a different section chain length. Thus, the sections T in a mixture of the polyurethanes prepared by the process according to the invention can be different. For example, a mixture according to the invention can comprise polyurethanes, the sections T of which are all branched, and/or those, the sections T of which are all linear, and/or those polyurethanes which comprise both at least one linear section T and also at least one branched section T.
In one embodiment, the sum of the molecular weights of all sections T plus the molecular weights of sections D should be kept less than or equal to the sum of the molecular weights of all of the sections P.
Catalyst To prepare the polyurethanes by the process according to the invention, the catalyst used is carboxylic acid salts of alkali metals, carboxylic acid salts of alkaline earth metals or mixtures thereof.
The carboxylic acids, the alkali(ne earth) metal salts of which are used as catalysts in the process according to the invention, are preferably monocarboxylic acids of the general formula R-COOH, where R can be any desired organic, for example an aliphatic, an aromatic or a heterocyclic radical.
Preferably, R is an aliphatic radical, thus for example an alkyl radical, an alkenyl radical or an alkynyl radical. R can also comprise heteroatonns; for example, the carboxylic acid may be a hydroxycarboxylic acid.
In one embodiment of the invention, R is a hydrocarbon radical having 1 to 20, preferably having 1 to 12, carbon atoms. R may be linear or branched, saturated or unsaturated.
In one embodiment of the invention, the carboxylic acid is acetic acid.
In a further embodiment of the invention, the carboxylic acid is octanoic acid.
In a further embodiment of the invention, the carboxylic acid is 2-ethylhexanoic acid.
In a further embodiment of the invention, the carboxylic acid is neodecanoic acid.
In a further embodiment of the invention, the carboxylic acid is n-decanoic acid.
In a further embodiment of the invention, the carboxylic acid is stearic acid.

In a further embodiment of the invention, the carboxylic acid is ricinoleic acid ((9Z,12R)-12-hydroxy-9-octadecenoic acid).
In a further embodiment of the invention, the carboxylic acid is a hydroxycarboxylic acid, such as, for example, citric acid or lactic acid, in particular lactic acid.
If at least one carboxylic acid salt of an alkali metal is selected as catalyst, then the alkali metal is preferably selected from sodium and potassium, particularly preferably potassium. =
If at least one carboxylic acid salt of an alkaline earth metal is selected as catalyst, then the alkaline earth metal is preferably selected from calcium and magnesium, particularly preferably calcium.
In one preferred embodiment of the invention, the catalyst used for the preparation of the polyurethanes by the process according to the invention is potassium acetate.
In one preferred embodiment of the invention, the catalyst used for the preparation of the polyurethanes by the process according to the invention is potassium lactate.
It is of course also possible to use mixtures of two or more carboxylic acid salts of alkali(ne earth) metals as catalysts for preparing polyurethanes PU according to the invention.
In one preferred embodiment, one catalyst is used.
In addition to these catalysts, further catalysts known to the person skilled in the art in the field of polyurethane preparation can be used.
Such catalysts usually used in polyurethane chemistry are organic amines, in particular tertiary aliphatic, cycloaliphatic or aromatic amines, and Lewis-acidic organic metal compounds.
Suitable Lewis-acidic organic metal compounds are e.g. metal complexes such as acetylacetonates of iron, titanium, zinc, aluminum, cobalt, manganese, nickel and zirconium, such as e.g. zirconium 2,2,6,6-tetramethy1-3,5-heptanedionate.
Further suitable metal compounds are described by Blank et al. in Progress in Organic Coatings, 1999, 35, 19 ff.
Bismuth, cobalt or zinc catalysts and also cesium or titanium salts can also be used as catalysts.

In one embodiment of the invention, the amount of such further catalysts which are not carboxylic acid salts of alkali metals, carboxylic acid salts of alkaline earth metals or mixtures thereof, is at most 10% by weight, preferably at most 5% by weight, particularly preferably at most 1% by weight and in particular at most 0.1% by weight, 5 of the total amount of catalyst.
One embodiment of the invention is the process according to the invention wherein the preparation takes place in the presence of less than 10 ppm of tin.
10 A further embodiment of the invention is the process according to the invention wherein the preparation takes place in the presence of less than 10 ppm of zinc.
In a further embodiment of the invention, apart from the at least one carboxylic acid salt of at least one metal selected from alkali metals, alkaline earth metals and mixtures 15 thereof, no further catalysts are used for preparing the polyurethanes.
The catalyst or the mixture of catalysts is preferably used in an amount in the range from 50 ppm to 5000 ppm, based on the total weight of all reacting compounds.
Preferably, the catalyst is used in an amount in the range from 50 to 2500 ppm, 20 particularly preferably in an amount in the range from 100 to 1000 ppm, based on the total weight of all reacting compounds.
The catalyst can be added to the reaction mixture in solid or liquid form, depending on the nature of the catalyst. Suitable solvents are non-aqueous solvents such as, for example, aromatic or aliphatic hydrocarbons, inter alia toluene, xylene, ethyl acetate, hexane and cyclohexane, and also carboxylic acid esters, such as, for example, ethyl acetate. Furthermore suitable solvents are acetone, THF, DMSO, DMF, DMAc and N-methylpyrrolidone and N-ethylpyrrolidone.
The catalyst/catalyst mixture is preferably used in dissolved form, particularly preferably dissolved in the polyetherpolyols with which the hydrophilic sections P are introduced into the polyurethanes.
The catalyst may already be present, at least partially, in the polyetherpolyols used for the process according to the invention if, during the preparation thereof, carboxylic acid salts of alkali(ne earth) metals have been used or have been formed.
In one embodiment of the invention, the polyetherdiols used in the process according to the invention thus comprise at least some of the catalyst, if appropriate the total required amount of catalyst.

In one embodiment of the invention, the polyetherdiols used in the process according to the invention prior to the start of the process already comprise at least some of the required catalyst and the remainder is added to carry out the process.
In the process according to the invention for preparing the polyurethanes, preference is given to using the following starting materials:
A) Compounds which introduce the hydrophilic sections P into the polyurethanes:
preferably polyols of the general formula HO-(CH2-CH2-0)n-H, where n preferably assumes the values 30 to 450; these are polyethylene glycols which are condensation products of ethylene oxide with ethylene glycol or water.
Preferred polyethylene glycols have a number-average molecular weight in the range from 6000 to 12 000 g/mol and particularly preferred ones have a number-average molecular weight of from 6000 to 10 000 g/mol.
B) Compounds which introduce the terminal hydrophobic sections T and the hydrophilic sections S adjacent in each case to the sections T: preferably ethoxylated C16-C18-fatty alcohols, ethoxylated iso-C13-oxo alcohols, ethoxylated branched alcohols as in Production Examples 1 to 24 of EP 761780 A2 and mixtures thereof.
C) Compounds which introduce the hydrophobic sections D: aliphatic diisocyanates, in particular hexamethylene diisocyanate (HD!).
The process according to the invention for the preparation of the polyurethanes comprises, in one embodiment, the following steps:
l) preparation of a mixture comprising a. at least one polyetherdiol with a molecular weight in the range from 6000 to 12 000 g/mol, b. at least one alkyl-branched C8-C30-, preferably C12-C3o-alkanol which has been ethoxylated with 10 to 100 mol, preferably with 10 to 40 mol, further preferably with 10 to 25 mol, of ethylene oxide per mol of alkanol, c. at least one carboxylic acid salt of at least one alkali metal or alkaline earth metal, preferably a potassium carboxylate, II) optionally heating the mixture from step l) to 60 to 120 C, preferably to 80 to 100 C;

III) if appropriate, reducing the water content of the mixture to a water content of at most 1000 ppm, preferably at most 300 ppm, based in each case on the total weight of the mixture;
IV) addition of at least one diisocyanate, preferably hexamethylene diisocyanate, to the mixture;
V) leaving the resulting reaction mixture to react until the isocyanate content is at most 0.1 /0 by weight, based on the total weight of the reaction mixture.
Reaction mixture is understood as meaning the totality of all substances which are present in the reaction space after the point at which the total amount of catalysts, isocyanates, substances reactive towards isocyanates and all further substances, such as for example solvents, have been completely supplied to the reaction space.
Solvents is understood as meaning phases that are liquid at 20 C and a pressure of 1 bar in which one or more of the starting materials for the polyurethanes, i.e. the substances which introduce the hydrophilic and/or hydrophobic sections into the polyurethanes or which act as catalyst, are soluble at 20 C and 1 bar.
In one embodiment of the invention the amount of solvents which are different from the substances which introduce the hydrophilic and hydrophobic sections into the polyurethanes or which act as catalyst is in the range from 0 to 10% by weight, further preferably from 0 to 5% by weight and in particular 0 to 1% by weight, based in each case on the weight of the reaction mixture.
In one embodiment of the invention, the process according to the invention is carried out essentially in the absence of solvents which are different from the substances which introduce the hydrophilic and/or hydrophobic sections into the polyurethanes or which act as catalyst.
In one embodiment of the invention, the amount of such substances which, following the complete addition of all substances during the reaction, are present in the reaction space and are neither catalysts, nor substances which are incorporated into the polyurethanes which form and consequently introduce the hydrophilic and hydrophobic sections into the polyurethanes, nor reaction products, is at most 10% by weight, preferably at most 5% by weight, further preferably at most 1% by weight and particularly preferably at most 0.1% by weight, of the total amount of all of the substances present in the reaction space during the reaction.
In simple terms, in one preferred embodiment, apart from the substances which introduce the hydrophilic and/or hydrophobic sections into the polyurethanes, the reaction products, if appropriate small amounts of water and the catalysts, the reaction mixture comprises no further substances.
The preferred process in which, apart from the starting materials for the polyurethane formation, no further solvents are used, leads to a more rapid reaction and solvents do not have to be separated off.
A further advantage of dispensing with solvents, in particular organic solvents which are different from the substances which introduce the hydrophilic and/or hydrophobic sections into the polyurethanes or which act as catalyst, is the better acceptance of the resulting polyurethanes as ingredients of cosmetic preparations.
If solvents are nevertheless used in the process according to the invention which are different from the substances which introduce the hydrophilic and/or hydrophobic sections into the polyurethanes or which act as catalyst, then these are removed as far as possible after the reaction. "After the reaction" means the point at which the content of isocyanate groups is at most still 0.1% by weight, based on the total weight of the reaction mixture.
Single-stage process In a preferred embodiment, the process is carried out as a single-stage process.
"Single-stage" means here that the substances with groups reactive towards isocyanate groups are essentially brought into contact together and simultaneously with the substances carrying isocyanate groups.
In one preferred embodiment of the invention, a mixture of the substances with groups reactive towards isocyanate groups is thus brought into contact with the substances carrying isocyanate groups.
In this case, it is possible for the entire amount of all of the substances with groups reactive towards isocyanate groups to be brought into contact with the substances carrying isocyanate groups right at the start of the reaction in the reaction space. Such a procedure is described, for example, in example 10 of EP 761780 A2 on p.14, lines 29 to 47 and the following examples 11 to 24.
One characteristic of the single-stage process is that all types of substances with groups reactive towards isocyanate groups are present alongside one another at every point in the reaction. However, it is not obligatory that the quantitative ratio of the different substances in the mixture is constant.

In the case of the single-stage reaction as opposed to the two-stage reaction, the polyol is not firstly brought into contact with an excess of polyisocyanate, giving prepolymers of the structure -D-P-D- and ¨D-P-D-P-D- with isocyanate chain ends, and these being reacted in the second step with the ethoxylated alcohol, then giving the structures T-S-D-P-D-S-T or T-S-D-P-D-P-D-S-T.
In the preferred single-stage reaction, from the start, as well as structures T-S-D-P-D-S-T and T-S-D-P-D-P-D-S-T, also structures T-S-D-S-T are formed.
However, for the single-stage process, it is not obligatory that the entire amounts of all of the substances with groups reactive towards isocyanate groups are already provided in the reaction space at the start of the reaction. It is also conceivable that, at the start of the reaction, only in each case some of each substance with groups reactive towards isocyanate groups are provided in the reaction space and the remainder of the substances in each case is added during the reaction.
In the two-stage process, in the first stage, the majority of the substances with two or more groups reactive towards isocyanate is brought into contact with the substances carrying isocyanate groups, and the substances with only one group reactive towards isocyanate groups react in the second stage with the remaining isocyanate groups and form the chain ends of the polyurethanes.
In the single-stage process, the amount of polymers with the structure T-S-D-S-T is larger than in the two-stage process, whereas in the two-stage process the amount of polymers with the structure T-S-D-P-D-S-T is greater.
In one preferred embodiment, the polyurethanes prepared by the process according to the invention are transferred to an aqueous phase, optionally after solvents have been separated off.
It is advantageous to stabilize the aqueous mixture obtained after transferring the reaction products to water.
Suitable free-radical scavengers are for example hydroxy-TEMPO, 2,6-di-tert-butyl-p-kresol (KerobitoTBK), hydroquinone monomethyl ether, tocopherol and mixtures of these compounds. These stabilizers are used in an amount in the range from 5-500 ppm, based on the weight of the aqueous mixture.
It is also advantageous to use preservatives. Of suitability are, for example, phenoxyethanol, methylisothiazolinone, ethylhexylglycerol, 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione, benzoic acid, parabens and mixtures of these substances. The preservatives are used in amounts in the range from 0.1 to 1% by weight, based on the aqueous mixture.
Preferably, substances with groups reactive towards isocyanate groups are used in the 5 process according to the invention that are essentially water-free in order to prevent a competing reaction of the isocyanate groups with water. The water can be separated off from these substances in the process according to the invention by azeotropic distillation, drying in vacuo or other methods known to the person skilled in the art. For example, the water is removed up to a water content of the substances of at most 500 10 ppm, preferably at most 300 ppm.
The preparation of the actual reaction can for example involve exposing the substances with groups reactive towards isocyanate groups to reduced pressure, preferably vacuum, and thus largely removing the water.
The water-comprising substances can also be mixed with a solvent such as xylene, toluene or acetone and the water can be removed together with the added solvent by azeotropic distillation.
In the process according to the invention, the ratio (mol to mol) of the polyetherdiols used to diisocyanates used can be in the range from 1:1.1 to 1:2. Preferably, the ratio is in the range from 1:1.1 to 1:1.9. The ratio is particularly preferably in the range from 1:1.1 to 1:1.8. The ratio is especially preferably in the range from 1:1.2 to 1:1.75. The ratio can of course also be 1:x where x is greater than or equal to 1.3, preferably x is greater than or equal to 1.5.
In one embodiment, this results in no, one or two sections P preferably being present in one molecule of the polyurethanes obtainable according to the invention.
In one embodiment of the process according to the invention, in addition to the stated ranges of the ratio of polyetherdiols to diisocyanates, the ratio of polyetherdiols to ethoxylated alcohols is additionally chosen such that the molar quantitative ratio of polyetherdiols used to ethoxylated alcohols used is in the range from 5:1 to 1:2.
Preferably, this ratio is in the range from 2:1 to 1:2, particularly preferably in the range from 1.5:1 to 1:2 and most preferably about 1:1.
For a particularly preferred process according to the invention, it is the case that a molar quantitative ratio of polyetherdiols to diisocyanates to ethoxylated alcohols of 1:1.2 to 1:75:1 to 2 and in particular 1:1.5:1 is used.

The invention also provides the process according to the invention wherein in each case at least one alkoxylated C4-C30-alcohol, one polyetherdiol and one diisocyanate are used for preparing the polyurethanes.
Preference is given to such a process wherein at least one C4-C30-alcohol is a branched C12-C30-alkanol, at least one polyetherdiol has a molecular weight Mn in the range from 4000 to 12 000 g/niol and at least one diisocyanate is an aliphatic diisocyanate.
The invention also provides the use of the polyurethanes according to the invention for preparing aqueous preparations. Preference is given here to preparations which comprise at least 5% by weight, in particular at least 20% by weight, very particularly preferably at least 30% by weight and most preferably at least 70% by weight, of water.
Preference is given to preparations which comprise at most 95% by weight, particularly preferably at most 90% by weight and in particular at most 85% by weight, of water.
The preparations comprising water are, for example, solutions, emulsions, suspensions or dispersions.
In addition to the polyurethanes obtainable by the process according to the invention, it is possible to use further substances for preparing the preparations, such as e.g.
customary auxiliaries (for example dispersants and/or stabilizers), surfactants, preservatives, antifoams, fragrances, wetting agents, UV filters, pigments, emollients, active ingredients, further thickeners, dyes, softeners, humectants and/or other polymers.
The polyurethanes obtainable by the process according to the invention and mixtures thereof are preferably used for effectively and stably thickening preparations with a content of salts and pigments of more than 1% by weight, based on the preparation.
Here, "stably" means maintaining an increased viscosity compared with the unthickened state over a period of several weeks and/or when increasing the temperature of the preparation, for example to up to 50 C.
The polyurethanes obtainable by the process according to the invention exhibit their thickening effect even at elevated temperatures up to about 50 C.
Furthermore, the polyurethanes obtainable by the process according to the invention exhibit a thickening effect in a broad pH from 2 to 13.

=

The polyurethanes obtainable by the process according to the invention furthermore have an influence on the structure of the preparations in which they enlarge the finely divided nature of the particles dispersed therein, i.e. reduce the particle size.
The polyurethanes obtainable by the process according to the invention and mixtures thereof can also be used for preparing water-comprising preparations which comprise at least one salt or at least one surfactant or mixtures thereof.
In connection with the present invention, surfactants are also understood as meaning emulsifiers and also mixtures of surfactants and emulsifiers. In connection with the present invention, salt is understood as meaning salts and also salt-like structures also with a low pKa value and mixtures thereof.
The polyurethanes obtainable according to the invention are particularly preferably used in order to prepare preparations which comprise at least 0.05% by weight of salt and/or at least 0.5% by weight of surfactants, very particularly preferably comprising at least 0.1% (w/w) of salt and/or at least 1% by weight of surfactants.
In a further embodiment, the polyurethanes obtainable by the process according to the invention are used for preparing preparations which comprise at least 5% by weight, preferably at least 10% by weight, of salt.
In a further embodiment, the polyurethanes obtainable by the process according to the invention are used for preparing preparations which comprise up to 25% by weight of surfactants, preferably up to 20% by weight and particularly preferably 15% by weight or fewer surfactants.
In a further embodiment, the polyurethanes obtainable by the process according to the invention are used for preparing preparations which comprise at least 1% by weight of salt and up to 20% by weight of surfactants, preferably up to 15% by weight of surfactants.
The polyurethanes obtainable by the process according to the invention are preferably used for preparing preparations which are oil-in-water emulsions.
Typically, oil-in-water emulsions comprise oil in the range from more than 0 to 40% by weight. Preferably, according to the invention, oil-in-water emulsions are prepared which comprise an oil fraction in the range from 5 to 40% by weight, particularly in the range from 10 to 35% by weight and in particular from 15 to 30% by weight, of oil.
The polyurethanes obtainable by the process according to the invention are very particularly preferably used for preparing preparations which are oil-in-water emulsions and moreover comprise at least one salt.

The preparations according to the invention which comprise a polyurethane obtainable by the process according to the invention may be, for example, solutions, emulsions, suspensions or dispersions.
In one embodiment, a preparation according to the invention is a dispersion, preferably an aqueous dispersion of the polyurethanes obtainable by the process according to the invention, as can be obtained from the reaction products by work-up after the preparation process. For this, for example, water is added to the reaction mixture after the reaction to produce a dispersion. If desired, the addition of a preservative and/or stabilizer can also take place.
In one embodiment, a dispersion according to the invention comprises up to 50%
by weight of the polyurethanes obtainable according to the invention.
In another embodiment, a dispersion according to the invention comprises 25%
by weight solids fraction.
Very particular preference is given to aqueous dispersions comprising up to 25% by weight of the polyurethanes obtainable according to the invention, at least one of the above-described preservatives suitable for cosmetic applications and, if desired, at least one of the above-described stabilizers suitable for cosmetic applications.
In another embodiment, the polyurethane obtainable according to the invention is in the form of a powder. Such a powder can be obtained, for example, by spray-drying or freeze-drying the aqueous dispersion.
To prepare the preparations according to the invention, which may be, for example, solutions, emulsions, suspensions or dispersions, the polyurethanes according to the invention are preferably used in the form of aqueous dispersions or as a powder, as can be obtained, for example, from the preparation process by appropriate work-up.
Further ingredients may be present in the preparations according to the invention depending on the intended use.
The preparations comprising the polyurethanes according to the invention can comprise further thickeners. Such further thickeners are known to the person skilled in the art. Suitable thickeners are specified for example in "Kosmetik und Hygiene von Kopf bis Full [Cosmetics and Hygiene from Head to Toe]", Ed. W. Umbach, 3rd edition, Wiley-VCH, 2004, pp. 235-236. Suitable further thickeners for the preparations according to the invention are described for example also on page 37, line 12 to page 38, line 8 of WO 2006/106140. Reference is hereby made to the contents of the cited passages in their entirety.
In one embodiment of this invention, however, no further thickeners are used besides the polyurethanes according to the invention for preparing the preparations according to the invention.
Preference is given to polyurethanes according to the invention, the 10%
strength by weight aqueous dispersions thereof having, at a shear rate of 100 1/s, a dynamic viscosity (measured as described below) of at least 100 mPa*s, particularly preferably of at least 200 mPa*s and very particularly preferably of at least 300 mPa*s.
The aqueous dispersions of the polyurethanes obtainable by the process according to the invention can in this case either exhibit Newtonian or else non-Newtonian behavior.
Non-Newtonian 10% strength by weight aqueous dispersions which comprise the polyurethanes obtainable by the process according to the invention have, at a shear rate of 100 1/s, dynamic viscosities of at least 1000 mPa*s, particularly preferably of at least 3000 mPa*s.
The person skilled in the art is aware that, in water-comprising preparations, many thickeners lose their effectiveness, i.e. the viscosity of the preparation decreases, as soon as the preparations comprise salts or surfactants. By contrast, the polyurethanes according to the invention permit a stable viscosity of aqueous preparations even upon the addition of salts and/or surfactants.
Particular preference is given to polyurethanes according to the invention which, in the case of a salt concentration of at least 0.5% by weight following the addition, lead to a stabilization of the dynamic viscosity, measured as described below, of the aqueous preparations comprising them.
Particular preference is given to those polyurethanes which permit a stable dynamic viscosity even upon the addition of at least 0.5% by weight of salt and addition of at least 1% by weight of surfactant.
In a further embodiment, the presence of the polyurethanes according to the invention in salt-containing aqueous preparations leads to an increase in the viscosity compared to preparations which comprise only salt or only polyurethanes according to the invention.
The order in which polyurethane and salt are added is irrelevant in this case.

Particular preference is given to polyurethanes according to the invention which lead to an increase in the dynamic viscosity of aqueous salt- and/or surfactant-containing preparations.
5 Polyurethanes according to the invention which, in the case of a salt concentration of the aqueous preparation of at least 0.5% by weight lead to an increase in the dynamic viscosity of the aqueous solution are especially preferred.
Polyurethanes according to the invention which, in the case of a salt concentration of 10 greater than or equal to 0.05% by weight lead to an increase in the dynamic viscosity of the aqueous preparation are especially preferred. Particular preference is given to those polyurethanes which lead to an increase in the dynamic viscosity compared to preparations which comprise less than 0.05% by weight, preferably less than or equal to 0.01% by weight, of salt, or less than 0.5% by weight, preferably less than or equal 15 to 0.1% by weight, of surfactant.
A further advantage of the polyurethanes obtainable by the process according to the invention is the micelle formation in water. The critical material concentration for micelle formation, also called critical micelle concentration (CMC) indicates the concentration 20 of a substance, in most cases of a substance which has hydrophobic and hydrophilic sections on the inside, at which micelles with an average particle size of less than or equal to 200 nm, in particular less than or equal to 100 nm (determinable by means of dynamic light scattering as described hereinbelow) are spontaneously formed.
The CMC of the polyurethanes according to the invention in water, determined as described 25 hereinbelow, is preferably less than or equal to 1 g/I, particularly preferably less than or equal to 0.5 g/I, especially preferably less than or equal to 0.25 g/I and very particularly preferably less than or equal to 0.1 g/I.
A further advantage of the process according to the invention, of the polyurethanes 30 obtainable thereby and of the preparations according to the invention is the use of alkali(ne earth) metal carboxylate catalysts and thus the simultaneous omission of cosmetically unacceptable catalysts during the preparation of the polyurethanes.
In the field of cosmetic preparations, the known processes with tin are no longer desired since tin may also be present in the products and preparations resulting therefrom.
The use of the alkali(ne earth) metal carboxylates as catalysts for the process according to the invention permits the in-situ production of allophanate and isocyanurate structures and thus the economically advantageous production of branched hydrophobic sections D of the polyurethanes. By virtue of partially branched sections D, polyurethane thickeners with higher efficiency can be obtained.

On account of their tolerance toward high salt contents and simultaneously high surfactant contents even at extreme pH values, the polyurethanes according to the invention can advantageously also be used as thickeners in homecare preparations, such as, for example, liquid cleaners.
In particular, the polyurethanes according to the invention are also suitable as rheology modifiers for preparations containing hydrogen peroxide.
Cosmetic preparations The polyurethanes obtainable according to the invention are preferably used in cosmetic preparations. The invention thus provides cosmetic preparations comprising the polyurethanes obtainable according to the invention.
One embodiment of the invention is water-comprising cosmetic preparations comprising polyurethanes obtainable according to the invention.
The preparations according to the invention can be in the form of aqueous or aqueous-alcoholic solutions, 0/VV (preferably) and W/O emulsions, hydrodispersion formulations, solids-stabilized formulations, stick formulations, PIT
formulations, in the form of creams, foams, sprays (pump spray or aerosol), gels, gel sprays, lotions, oils, oil gels or mousses and accordingly be formulated with customary further auxiliaries.
Preferably, the preparations according to the invention are in the form of a gel, foam, mousse, spray, ointment, cream, emulsion, suspension, lotion, milk or paste.
The invention preferably relates to cosmetic preparations which are selected from gels, gel creams, milks, hydroformulations, stick formulations, cosmetic oils and oil gels, mascara, self-tanning compositions, face care compositions, body care compositions, aftersun preparations. The term cosmetic preparations is also understood as meaning preparations for oral care.
Further cosmetic preparations according to the invention are skin cosmetic preparations, in particular those for caring for the skin. These are present in particular as W/O or preferably 0/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 preferred preparations according to the invention are face masks, cosmetic lotions and preparations for the use in decorative cosmetics, for example for concealing sticks, stage make-up, mascara and eyeshadows, lipsticks, kohl pencils, eyeliners, make-ups, foundations, blushers, powders and eyebrow pencils.
Further preparations according to the invention are antiacne compositions, repellents, shaving compositions, hair removal compositions, intimate care compositions, foot care compositions and baby care products.
Further preferred preparations according to the invention are washing, showering and bathing preparations. Within the context of this invention, washing, showering and bathing preparations are soaps of liquid to gel-like consistency, transparent soaps, luxury soaps, deodorant soaps, cream soaps, baby soaps, skin protection soaps, abrasive soaps and syndets, pasty soaps, soft soaps and washing pastes, liquid washing, showering and bathing preparations, such as washing lotions, shower baths and shower gels, foam baths, oil baths and scrub preparations, shaving foams, shaving lotions and shaving creams.
Cosmetic preparations which comprise specific polyurethanes are described for example in WO 2009/135857. The polyurethanes of the present invention obtainable according to the invention are generally also suitable for use in the preparations described in WO 2009/135857. Reference is hereby made expressly to the disclosure in WO 2009/135857.
Within the context of the present invention, the polyurethanes used in the preparations of WO 2009/135857 are replaced by the polyurethanes of this invention. The polyurethanes according to the invention are thus used in the preparations of WO 2009/135857 preferably in place of the polyurethanes used therein.
Suitable ingredients for the preparations according to the invention are described in WO 2009/135857, p. 24 to p. 35, to which reference is made in its entirety.
By way of example cosmetic UV photoprotective compositions comprising the polyurethanes obtained according to the invention are in accordance with the invention.
Within the context of this invention, cosmetic photoprotective compositions are understood as meaning cosmetic preparations which comprise at least one, preferably two or more, UV filter substances.
UV photoprotective compositions corresponding to the UV photoprotective composition preparations according to the invention are described in WO 2009/135857, p. 35 to p.
42, to which reference is made in its entirety.

The invention also relates to cosmetic preparations, preferably in liquid or pasty form, for use on the skin, on semi mucosa, on mucosa and in particular on keratin materials such as hair, eyelashes and eyebrows, in particular for the shaping, decoration, coloring, beautifying of the same, and also for caring for the skin and the skin appendages. In principle, the preparations according to the invention, upon suitable adjustment and coloring, can also be used as make-up, concealer, camouflage, eyeshadows, eyeliners, lip liners, blushers, lip blush, lip gloss, sun protection composition, sun block, temporary tattoo, colored effect sunscreen for surfers and the like.
A preferred embodiment of the present invention is thus cosmetic preparations for decorative cosmetics.
Preparations corresponding to the preparations according to the invention for decorative cosmetics are described in WO 2009/135857, p. 43 to p. 46, to which reference is made in its entirety.
The present invention provides aqueous preparations which, besides the polyurethanes obtainable according to the invention, further comprise at least one salt or surfactant or both.
A further embodiment of the invention is shampoos and cosmetic cleaning compositions comprising the polyurethanes obtainable according to the invention.
Preparations corresponding to the shampoos and cosmetic cleaning compositions according to the invention are described analogously in WO 2009/135857, p. 46 to p. 55, to which reference is made in its entirety.
A further embodiment of the invention is deodorants or antiperspirants, in particular deodorant lotions and deodorant or antiperspirant sticks, comprising the polyurethanes obtainable according to the invention and based on oil-in-water dispersion or emulsion for the application of active ingredients, in particular of water-soluble active ingredients, to the skin.
Preparations corresponding to the deodorants and antiperspirants according to the invention are described analogously in WO 2009/135857, p. 55 to p. 59, to which reference is made in its entirety.
A further embodiment of the invention is hair colorants comprising the polyurethanes obtainable according to the invention.

Preparations corresponding to the hair colorants comprising the polyurethanes obtainable according to the invention are described analogously in WO
2009/135857, p. 59 to p. 65, to which reference is made in its entirety.
A further embodiment of the invention is hair care compositions, in particular hair conditioners, comprising the polyurethanes obtainable according to the invention.
Hair care compositions corresponding to the hair care compositions comprising the polyurethanes obtainable according to the invention are described analogously in WO 2009/135857, p. 59 to p. 67, to which reference is made in its entirety.
A further embodiment of the invention is acidic preparations comprising the polyurethanes obtainable according to the invention.
Numerous cosmetic preparations comprise active ingredients which develop their desired effect in particular at acidic pHs. These include, for example, preparations which comprise alpha-hydroxycarboxylic acids (AHAs) and beta-hydroxycarboxylic acids (BHAs) since these are not effective or not very effective in the neutralized state.
Acidic preparations corresponding to the acidic preparations comprising the polyurethanes obtainable according to the invention are described analogously in WO 2009/135857, p. 67 to p. 69, to which reference is made in its entirety.
A further embodiment of the invention is self-tanning products comprising the polyurethanes obtainable according to the invention.
Standard commercial self-tanning products are generally 0/W emulsions. In these, the water phase is stabilized by emulsifiers customary in cosmetics.
By applying the self-tanning products according to the invention, it is possible to achieve not only a uniform skin coloration, but it is also possible to uniformly color areas of skin that are differently colored by nature or as a result of a pathological change.
According to the invention, the self-tanning substances used are advantageously inter alia glycerol aldehyde, hydroxymethylglyoxal, y-dialdehyde, erythrulose, 5-hydroxy-1,4-naphtoquinone (juglone), and also 2-hydroxy-1,4-naphtoquinine as occurs in henna leaves. Very particular preference is given to 1,3-dihydroxyacetone (DHA), a trivalent sugar which occurs in the human body. 6-Aldo-D-fructose and ninhydrin can also be used as self-tanning agents according to the invention.
For the purposes of the invention, self-tanning agents are also understood as meaning substances which bring about a skin coloration other than a brown shade.

In one preferred embodiment of the invention, such preparations comprise self-tanning substances in a concentration of from 0.1 to 10% by weight and particularly preferably from 0.5 to 6% by weight, in each case based on the total weight of the preparation.
5 Preferably, these preparations comprise 1,3-dihydroxyacetone as self-tanning substance. These compositions further preferably comprise organic and/or inorganic light protection filters. The preparations can also comprise inorganic and/or organic and/or modified inorganic pigments.
10 Further ingredients preferably present in the preparations according to the invention are specified, for example, in DE 103 21 147 in paragraphs [0024] to [0132], to which reference is made at this point in their entirety.
The invention also provides the use of such preparations for coloring the skin of 15 multicellular organisms, in particular the skin of humans and animals, especially for harmonizing the color of differently pigmented areas of skin.
A further embodiment of the invention is preparations for oral and dental care and cleansing which comprise the polyurethanes obtainable according to the invention.
Preparations corresponding to the preparations for oral and dental care and cleansing comprising the polyurethanes obtainable according to the invention are described analogously in WO 2009/135857, p .69 to p. 70, to which reference is made in its entirety.
A further embodiment of the invention is preparations for hair removal which comprise the polyurethanes obtainable according to the invention.
Preparations corresponding to the preparations for hair removal which comprise the polyurethanes obtainable according to the invention are described analogously in WO 2009/135857, p. 70 to p. 71, to which reference is made in its entirety.
A further embodiment of the invention is preparations for permanent hair shaping comprising the polyurethanes obtainable according to the invention.
Preparations corresponding to the preparations for permanent hair shaping which comprise the polyurethanes obtainable according to the invention are described analogously in WO 2009/135857, p. 71 to p. 73, to which reference is made in its entirety.

Examples The invention is illustrated in more detail by reference to the nonlimiting examples below.
Unless stated otherwise, the percentages are percentages by weight.
Determination of the dynamic viscosity The dynamic viscosities of the polyurethanes according to the invention were measured in each case in a 10% strength by weight aqueous solution at 23 C. In the examples listed below, the dynamic viscosity was always determined at shear rates of 100 1/s and 350 1/s. These two values allow a statement about whether the polyurethanes according to the invention exhibit non-Newtonian or Newtonian thickener behavior in aqueous dispersion.
To determine the dynamic viscosity to DIN 53019, the following were used:
- rotary viscometer Physica Rheolab MCI Portable (Anton Paar);
- cylinder measurement system, Z4 DIN cylinder (diameter 14 mm).
The polyols, ethoxylated alcohols and isocyanates used below were used in essentially alkali-free form (potassium content < 5 ppm).
Synthesis example 1: Preparation of a PUR associative thickener A.1 Catalyst: 300 ppm of K as potassium acetate 120.00 g of polyethylene glycol Pluriol0E6000 (BASF SE, molecular weight 6000 g/mol), 9.60 g of LutensoloT010 (BASF SE), 11.10 g of LutensoloAT11 (BASF

SE), and 106 mg of potassium acetate (= 300 ppm of potassium based on total mixture) were introduced as initial charge under nitrogen in a 2 liter polymerization reactor and then heated to 100 C. By applying a vacuum of ca. 10 mbar for 6 hours, traces of water were removed until ultimately the water content of the mixture was 230 ppm. The mixture was then cooled to 80 C. By adding 5.88 g of hexamethylene diisocyanate, the polymerization was started and the mixture was stirred at a temperature of 80 C for 50 minutes until an isocyanate content of 0.0% was reached.
The yellow colored residue was then dissolved in 586.3 g of water and the aqueous solution was immediately admixed with 7.33 g of EuxyloK701 (Schulke & Mayr) and 70 mg of the stabilizer 4-hydroxy-TEMPO. The mixture was cooled to room temperature (25 C). The polymer A.1 (Mr, = 11 700 g/mol; Mw = 26 900 g/mol) was thus obtained in the form of a clear, pale yellow colored solution which had a solids content of 20.8%.
The viscosity of a 10% strength by weight aqueous solution of the polyether polyurethane A.1 was 1550 mPa*s (shear rate 100 1/s) and 1360 mPa*s (shear rate 350 1/s).
Synthesis example 2: Preparation of a PUR associative thickener A.2 Catalyst: 600 ppm of K as potassium acetate 120.00 g of polyethylene glycol Pluriol0E6000, 9.60 g of LutensoleT010, 11.10 g of LutensoloAT11, and 212 mg of potassium acetate (= 600 ppm of potassium based on total mixture) were introduced as initial charge under nitrogen in a 2 l polymerization reactor and then heated to 100 C. By applying a vacuum of ca. 10 mbar for 5 hours, traces of water were removed until ultimately the water content of the mixture was 225 ppm. The mixture was then cooled to 80 C. By adding 5.88 g of hexamethylene diisocyanate, the polymerization was started and the mixture was stirred at a temperature of 80 C for 50 minutes until an isocyanate content of 0.0% was reached.
The yellow colored residue was then dissolved in 586.3 g of water and the aqueous solution was immediately admixed with 7.33 g of EuxyloK701 and 70 mg of the stabilizer 4-hydroxy-TEMPO. The mixture was cooled to room temperature (25 C).
The polymer A.2 (M, = 12 300 g/mol; Mw = 29 700 g/mol) was thus obtained in the form of a clear, pale yellow colored solution which had a solids content of 20.1%. The viscosity of a 10% strength by weight aqueous solution of the polyether polyurethane A.2 was 3700 mPa*s (shear rate 100 1/s) and 3000 mPa*s (shear rate 350 1/s).
Synthesis example 3: Preparation of a PUR associative thickener A.3 Catalyst: 900 ppm of K as potassium acetate 120.00 g of polyethylene glycol Pluriol0E6000, 9.60 g of Lutensoler1010, 11.10 g of Lutensol AT11, and 318 mg of potassium acetate (= 900 ppm of potassium based on total mixture) were introduced as initial charge under nitrogen in a 2 l polymerization reactor and then heated to 100 C. By applying a vacuum of ca. 10 mbar for 4 hours, traces of water were removed until ultimately the water content of the mixture was 242 ppm. The mixture was then cooled to 80 C. By adding 5.88 g of hexamethylene diisocyanate, the polymerization was started and the mixture was stirred at a temperature of 80 C for 55 minutes until an isocyanate content of 0.0% was reached.
The yellow colored residue was then dissolved in 586.3 g of water and the aqueous solution was immediately admixed with 7.33 g of the preservative EuxyleK701 and 70 mg of the stabilizer 4-hydroxy-TEMPO. The mixture was cooled to room temperature (25 C). The polymer A.3 (Mn = 12 700 g/mol; Mw = 33 000 g/mol) was thus obtained in the form of a clear, pale yellow colored solution which had a solids content of 20.6%.
The viscosity of a 10% strength by weight aqueous solution of the polyether polyurethane A.3 was 6000 mPa*s (shear rate 100 1/s) and 4400 mPa*s (shear rate 350 1/s).
Synthesis example 4: Preparation of a PUR associative thickener A.4 Catalyst: 2000 ppm of K as potassium acetate 90.00 g of polyethylene glycol Pluriol0E6000, 7.20 g of LutensoloT010, 8.33 g of LutensoloAT11, and 530 mg of potassium acetate (= 2000 ppm of potassium based on total mixture) were introduced as initial charge under nitrogen in a 21 polymerization reactor and then heated to 100 C. By applying a vacuum of ca. 10 mbar for 5 hours, traces of water were removed until ultimately the water content of the mixture was 210 ppm. The mixture was then cooled to 80 C. By adding 4.41 g of hexamethylene diisocyanate, the polymerization was started and the mixture was stirred at a temperature of 80 C for 55 minutes until an isocyanate content of 0.0% was reached.
The yellow colored residue was then dissolved in 439.7 g of water and the aqueous solution was immediately admixed with 5.50 g of the preservative EuxyloK701 and 50 mg of the stabilizer 4-hydroxy-TEMPO. The mixture was cooled to room temperature (25 C). The polymer A.4 (Mn = 12 500 g/mol; Mw = 31 300 g/mol) was thus obtained in the form of a clear, pale yellow colored solution which had a solids content of 20.6%.
The viscosity of a 10% strength by weight aqueous solution of the polyether polyurethane A.4 was 5200 mPa*s (shear rate 100 1/s) and 3800 mPa*s (shear rate 350 1/s).
Synthesis example 5: Preparation of a PUR associative thickener A.5 Catalyst: 200 ppm of K as potassium acetate 100.00 g of polyethylene glycol (Merck KGaA, molecular weight 10 000 g/mol), 10.02 g of 2-decy1-1-tetradecano1-20 EO, and 55 mg of potassium acetate (= 200 ppm of potassium based on total mixture) were introduced as initial charge under nitrogen in a 2 I polymerization reactor and then heated to 100 C. By applying a vacuum of ca. 10 mbar for 6 hours, traces of water were removed until ultimately the water content of the mixture was 190 ppm. The mixture was then cooled to 80 C. By adding 2.52 g of hexamethylene diisocyanate, the polymerization was started and the mixture was stirred at a temperature of 80 C for 40 minutes until an isocyanate content of 0.0% was reached. The yellow colored residue was then dissolved in 450.2 g of water and the aqueous solution was immediately admixed with 5.63 g of the preservative EuxyleK701 and 60 mg of the stabilizer 4-hydroxy-TEMPO. The mixture was cooled to room temperature (25 C). The polymer A.5 (Mn = 19 100 g/mol; Mw = 48 500 g/mol) was thus obtained in the form of a clear, pale yellow colored solution which had a solids content of 20.7%. The viscosity of a 5% strength by weight aqueous solution of the polyether polyurethane A.5 was >20 000 mPa*s (shear rate 100 1/s) and >20 000 mPa*s (shear rate 350 1/s).
Comparative example 1: Preparation of a PUR associative thickener A.6 Without catalyst 120.00 g of polyethylene glycol Pluriol0E6000, 9.60 g of Lutenso10-1010, and 11.10 g of Lutensol AT11 were introduced as initial charge under nitrogen in a 2 l polymerization reactor and then heated to 100 C. By applying a vacuum of ca. 10 mbar for 5 hours, traces of water were removed until ultimately the water content of the mixture was 250 ppm. The mixture was then cooled to 80 C. By adding 5.88 g of hexamethylene diisocyanate, the polymerization was started and the mixture was stirred at a temperature of 80 C for a total of 32 hours until an isocyanate content of 0.0% was reached. The yellow colored residue was then dissolved in 586.3 g of water and the aqueous solution was immediately admixed with 7.33 g of the preservative Euxyl and 70 mg of the stabilizer 4-hydroxy-TEMPO. The mixture was cooled to room temperature (25 C). The polymer A.6 (Mn = 10 000 g/mol; Mw = 23 200 g/mol) was thus obtained in the form of a clear, pale yellow colored solution which had a solids content of 18.8%. The viscosity of a 10% strength by weight aqueous solution of the polyether polyurethane A.6 was 100 mPa*s (shear rate 100 1/s) and 100 mPa*s (shear rate 350 1/s).
Comparative example 2: Preparation of a PUR associative thickener A.7 Without catalyst 100.00 g of polyethylene glycol (Merck KGaA, molecular weight 10 000 g/mol), and 10.02 g of 2-decy1-1-tetradecano1-20 EO were introduced as initial charge under nitrogen in a 2 l polymerization reactor and then heated to 100 C. By applying a vacuum of ca. 10 mbar for 6 hours, traces of water were removed until ultimately the water content of the mixture was 185 ppm. The mixture was then cooled to 80 C.
By adding 2.52 g of hexamethylene diisocyanate, the polymerization was started and the mixture was stirred at a temperature of 80 C for a total of 12 hours until an isocyanate content of 0.0% was reached. The yellow colored residue was then dissolved in 450.2 g of water and the aqueous solution was immediately admixed with 5.63 g of the preservative Euxyl0K701 and 60 mg of the stabilizer 4-hydroxy-TEMPO. The mixture was cooled to room temperature (25 C). The polymer A.7 (Mn = 5200 g/mol; Mw =
14 500 g/mol) was thus obtained in the form of a clear, pale yellow colored solution which had a solids content of 18.5%. The viscosity of a 10% strength by weight aqueous solution of the polyether polyurethane A.7 was <100 mPa*s (shear rate 100 1/s) and <100 mPa*s (shear rate 350 1/s).

Comparative example 3: Preparation of a PUR associative thickener A.8 Catalyst: Dibutyltin dilaurate 90.00 g of polyethylene glycol Pluriol0E6000, 7.20 g of Lutensol0T010, 8.33 g of Lutensol AT11, and 144 mg of dibutyltin dilaurate (DBTL) (= 300 ppm of Sn based on total mixture) were introduced as initial charge under nitrogen in a 2 l polymerization reactor and then heated to 100 C. By applying a vacuum of ca. 10 mbar for 5 hours, 10 traces of water were removed until ultimately the water content of the mixture was 250 ppm. The mixture was then cooled to 80 C. By adding 4.41 g of hexamethylene diisocyanate, the polymerization was started and the mixture was stirred at a temperature of 80 C for 60 minutes until an isocyanate content of 0.0% was reached.
The yellow colored residue was then dissolved in 440.3 g of water and the aqueous 15 solution was immediately admixed with 5.50 g of the preservative Euxyl K701 and 60 mg of the stabilizer 4-hydroxy-TEMPO. The mixture was cooled to room temperature (25 C). The polymer A.8 (Mn = 10 100 g/mol; Mw = 22 000 g/mol) was thus obtained in the form of a clear, pale yellow colored solution which had a solids content of 20.4%. The viscosity of a 10% strength by weight aqueous solution of the polyether 20 polyurethane A.8 was 720 mPa*s (shear rate 100 1/s) and 660 mPa*s (shear rate 350 1/s).
Comparative example 4: Preparation of a PUR associative thickener A.9 25 Catalyst: DABCO
120.00 g of polyethylene glycol Pluriol0E6000, 9.60 g of Lutensol0T010, 11.10 g of Lutensol AT11, and 36 mg of 1,4-diazabicyclo[2.2.2]octane (DABCO; = 300 ppm based on total mixture) were introduced as initial charge under nitrogen in a 2 l 30 polymerization reactor and then heated to 100 C. By applying a vacuum of ca. 10 mbar for 5 hours, traces of water were removed until ultimately the water content of the mixture was 230 ppm. The mixture was then cooled to 80 C. By adding 5.88 g of hexamethylene diisocyanate, the polymerization was started and the mixture was stirred at a temperature of 80 C for a total of 13 hours until an isocyanate content of 35 0.0% was reached. The yellow colored residue was then dissolved in 586.5 g of water and the aqueous solution was immediately admixed with 7.33 g of the preservative Euxyl K701 and 70 mg of the stabilizer 4-hydroxy-TEMPO. The mixture was cooled to room temperature (25 C). The polymer A.9 (Mr, = 8500 g/mol; M = 17 400 g/mol) was thus obtained in the form of a clear, pale yellow colored solution which had a solids 40 content of 18.7%. The viscosity of a 10% strength by weight aqueous solution of the polyether polyurethane A.9 was 105 mPa*s (shear rate 100 1/s) and 105 mPa*s (shear rate 350 1/s).

Formulation example 1:
Cosmetic formulations based on Cremophor A6/Cremophor A25 The cosmetic formulations shown below were prepared by adding the water phase B to the oil phase A and then admixing the resulting 0/VV emulsion with the preservative (phase C). This gave the following formulations based on a Cremophor A6/Cremophor A25 base.
Table 1.
Formulations based on Cremophore A6/Cremophore A25 Phase Ingredients F.1.1 F.1.2 F.1.3 F.1.4 F.1.6 F.1.8 Phase A CremophoreA 6 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g CremophoreA 25 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g Lanette O 2.5 g 2.5 g 2.5 g 2.5 g 2.5 g 2.5 g Paraffin oil 5.0 g 5.0 g 5.0 g 5.0 g 5.0 g 5.0 g LuvitoleEHO 5.0 g 5.0 g 5.0 g 5.0 g 5.0 g 5.0 g A.1 A.2 A.3 A.4 A.6 A.8 Phase B PUR thickener 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 1,2-Propylene glycol 5.0 g 5.0 g 5.0 g 5.0 g 5.0 g 5.0 g Water 77.5 g 77.5 g 77.5 g 77.5 g 77.5 g 77.5 g Phase C EuxyleK300 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g Formulation example 2:
Cosmetic formulations based on stearate ester The following cosmetic formulations were prepared by adding the water phase B
to the oil phase A and subsequently admixing the resulting ONV emulsion with the preservative (phase C). This gave the following formulations based on a stearate ester base.
Table 2.
Cosmetic formulations based on stearate ester Phase Ingredients F.2.1 F.2.2 F.2.3 F.2.4 F.2.6 F.2.8 Phase A CutinaeGMS 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g Lanettee18 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g Dow Corning 345 3.0 g 3.0 g 3.0 g 3.0 g 3.0 g 3.0 g Fluid Cetiole0E 3.0 g 3.0 g 3.0 g 3.0 g 3.0 g 3.0 g Abile350 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g Dry Flo PC 1.0 g 1.0 g 1.0 g 1.0 g 1.0 g 1.0 g Myrj 52 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g A.1 A.2 A.3 A.4 A.6 A.8 Phase B PUR thickener 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g Glycerol 5.0 g 5.0 g 5.0 g 5.0 g 5.0 g 5.0 g Water 79.0 g 79.0 g 79.0 g 79.0 g 79.0 g 79.0 g Phase C EuxyleK300 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g Viscosities of the cosmetic formulations F.1.1 to F.1.8 as a function of the salt concentration Table 3.
Viscosity [mPa*s]
Formulation with 2.0% NaCI addition F.1.1 12 100 F.1.2 17 100 F.1.3 26 200 F.1.4 17 000 F.1.6 6800 F.1.8 11 400 Viscosities of the cosmetic formulations F.2.1 - F.2.8 as a function of the salt concentration Table 4.
Viscosity [mPa*s]
Formulation with 2.0% NaCI addition F.2.1 16 700 F.2.2 21 800 F.2.3 21 200 F.2.4 18 100 F.2.6 10 000 F.2.8 14 700 Viscosities of the polyurethanes A1 - A.9 in water, as a function of shear rate and concentration Table 5. =
Polymer concentration = Viscosity Polymer in water [mPa*s]
[% by weight] Shear rate 100 1/s Shear rate 350 1/s A.1 = 10 1550 1360 A.2 10 3700 3000 A.3 10 6000 4400 A.4 10 5200 3800 A.5 5 >20 000 >20 000 A.6 10 100 100 A.7 10 <100 <100 A.8 10 720 660 A.9 10 105 105 Figure 1. GPC chromatograms of the polyurethanes A.5 and A.7.

Application examples:
At this point, reference is made in full to the application examples which are disclosed in WO 2009/135857 on pages 87 to 114.
The polyurethanes PU.1 to PU.11 used in the examples therein are replaced for the purposes of this invention by the polyurethanes A.1, A.2, A.3, A.4 or A.5 of the present invention, such that the corresponding cosmetic preparations are obtained analogously.
Further typical preparations according to the invention are described below, without, however, limiting the invention to these examples.
Besides the preparation of the cosmetic preparations described here, the polyurethanes A.1, A.2, A.3, A.4 or A.5 and also combinations thereof can be added to the resulting emulsion also after combining the water phase and oil phase at or to the cooled emulsion at about 40 C.
The invention also provides the subsequent addition of the polyurethanes obtainable according to the invention to a cosmetic preparation in order to establish the desired viscosity.
Unless expressly described otherwise, the percentages are % by weight.
0/VV emulsion Phase Ingredient/INCI F.3.1 F.3.2 F.3.3 F.3.4 F.3.5 A Aqua ad 100 ad 100 ad 100 ad 100 ad 100 Glycerin 3.0 5.50 4.50 5.00 3.5 PUR thickener A.1 3.0 1.5 0.8 2.0 2.5 Hydroxyethyl acrylate/sodium acryloyldimethyl taurate 1.0 0.5 copolymer, squalane, polysorbate 60 Glyceryl stearate citrate 1.80 2.00 3.00 1.50 2 Sucrose stearate 1.00 1.20 2.00 2.20 1.5 Cetearyl alcohol 1.80 2.00 1.50 2.40 2.8 Ethylhexyl palmitate 6.00 5.00 3.50 3.00 5.5 Caprylic/capric triglyceride 5.00 5.00 1.00 2.00 3.5 Octyldodecanol 1.50 3.00 2.40 5.0 4.6 Dimethicone 0.20 0.50 2.00 1.80 1.4 Ammonium acryloyldimethyltaurate/ VP 0.5 0.1 copolymer Carbomer 0.05 0.1 Sodium hydroxide 0.02 0.04 Bisabolol 0.5 0.3 0.20 0.35 1.0 Phenoxyethanol, paraben 1.00 0.60 0.70 0.60 0.5 mixture Perfume 0.05 0.10 0.10 0.05 0.05 Preparation:
5 Heat phases A and B separately to ca. 80 C. Stir phase C into phase B and then stir phase A into phase B/C and briefly homogenize.
Add phase D (when required) and cool with stirring to ca. 40 C. Add components of phase E to the emulsion in succession and cool with stirring to room temperature.
10 Briefly homogenize.
Instead of the 0/W emulsion comprising polyurethane thickener A.1, 0/W
emulsions comprising one or more of the polyurethanes A.2, A.3, A.4 or A.5 are also prepared.
15 Hydrodispersion Phase Ingredients/INCI F.4.1 F.4.2 F.4.3 F.4.4 F.4.5 A Stearyl alcohol 0.5 1.5 2.0 Cetyl alcohol 1.00 2.5 C12-15 Alkyl benzoate 2.5 4.0 Dicapryl ether 4.0 6.0 Butylene glycol 4.0 2.0 1.0 dicaprylate/dicaprate Dicapryl carbonate 2.0 3.0 4.0 Cyclopentasiloxane, 2.0 0.5 cyclohexasiloxane Prunus Amygdalus Dulcis (Sweet 2.0 0.5 Almond) oil Shea butter 2.0 1.0 Hydrogenated polyisobutene 3.0 1.0 7.0 0.5 2.0 Squalane 2.0 0.5 Vitamin E acetate 0.50 0.25 1.00 Acrylate/C10-30 alkyl acrylate 0.3 0.1 0.2 0.15 0.2 crosspolymer Aqua ad ad 100 ad 100 ad 100 ad 100 Polyacrylamide, C13-14 isoparaffin, 1.0 1.5 0.75 Laureth-7 PUR thickener A.1 2.5 2.0 0.9 1.5 3.0 Propylene glycol 3.00 5.0 2.5 7.50 10.0 Sodium hydroxide 0.12 0.04 0.08 0.06 0.08 Niacinamide 0.30 3.0 1.5 0.5 0.20 Aqua 2.0 10.0 5.0 2.0 2.0 DMDM hydantoin 0.60 0.45 0.25 Methylparaben 0.50 0.25 0.15 Phenoxyethanol 0.50 0.40 1.00 Ethylhexylglycerin 1.00 0.80 Ethanol 3.00 2.00 1.50 7.00 Fragrance 0.20 0.05 0.40 Preparation:
Heat phases A and C separately to ca. 80 C.
Stir phase B into phase A and then phase C into phase A/B. Briefly homogenize.
Add phase D and cool with stirring to ca. 40 C. Add phase E and cool with stirring to ca. 30 C. Add phase F and G to the emulsion and cool to room temperature with stirring. Briefly homogenize.
Instead of the hydrodispersion comprising polyurethane thickener A.1, hydrodispersions comprising one or more of the polyurethanes A.2, A.3, A.4 or A.5 are also prepared.
Solids-stabilized emulsion Phase Ingredients/INCI F.5.1 F.5.2 F.5.3 F.5.4 F.5.5 A Mineral oil 4.0 6.0 16.0 10.0 6.0 Octyldodecanol 9.0 9.0 5.0 Ethylhexyl isononanoate 9.0 9.0 6.0 5.0 8.0 lsohexadecane 9.0 5.0 4.0 8.0 Dimethicone 0.5 2.0 1.0 1.5 Cera Microcristallina, Paraffinum 0.35 0.75 3.0 Liquidum Phenyl trimethicone 2.0 1.0 2.5 3.0 Silica 2.5 6.0 2.5 Aluminum starch 2.0 1.0 0.5 octenylsuccinate Tapioca starch 0.5 Titanium dioxide, coated 1.0 0.5 3.0 2.0 4.0 Zinc oxide 5.0 10.0 2.0 3.0 Ammonium acryloyldimethyltaurate/
0.2 1.0 0.5 beheneth-25 methacrylate crosspolymer Aqua ad 100 ad 100 ad 100 ad 100 ad 100 Hydroxypropyl methylcellulose 0.1 0.05 Sorbitol 5.0 7.0 8.5 3.0 4.5 PUR thickener A.1 3.0 5.0 0.9 1.4 2.0 Mixed parabens 0.3 0.6 0.2 0.4 Phenoxyethanol 0.2 0.3 0.4 0.5 0.4 Diazolidinyl urea 0.23 0.2 F Perfume 0.2 0.3 0.1 Preparation:
Heat phase A to 80 C.
Add phase B to phase A and homogenize for 3 min. Stir in phase C.
Allow cellulose (if required) to preswell in water, then add the remaining ingredient of phase D and heat to 80 C.
Stir phase D into phase A+B+C and homogenize. Cool emulsion with stirring to ca. 40 C and add phase E and F. With stirring, cool to RT and homogenize.
Instead of the solids-stabilized emulsion comprising polyurethane-thickener A.1, solids-stabilized emulsions comprising one or more of the polyurethanes A.2, A.3, A.4 or A.5 are also prepared.
Sunscreen cream Phase Ingredients/INCI
F.6.1 F.6.2 F.6.3 F.6.4 F.6.5 A Aqua ad 100 ad 100 ad 100 ad 100 ad 100 Disodium EDTA 0.1 0.1 0.1 0.1 0.1 Glycerin 3.00 7.50 8.0 7.50 5.00 Benzophenone-4 2.0 4.0 Phenylbenzimidazole 0.50 4.00 8.0 sulfonic acid Triethanolamine 1.0 0.25 2.0 2.0 4.0 Panthenol 0.5 0.75 1.0 PUR thickener A.1 2.5g 0.5 g 2.0 g 4.0 1.5 Xanthan gum 0.3 0.15 0.2 Octocrylene 8.0 7.5 Ethylhexyl methoxycinnamate, 5.0 10.0 8.0 3.0 7.0 diethylamino hydroxybenzoyl hexyl benzoate Steareth-21 2.0 3.0 2.5 Steareth-2 1.5 PEG-40 stearate 1.0 2.0 Glycerin monostearate SE 1.0 3.0 1.5 1.5 Dibutyl adipate 3.0 5.0 3.5 2.5 2.0 Cetearyl alcohol 2.0 0.5 3.0 Stearyl alcohol 1.5 3.0 2.5 0.6 2.0 Butyrospermum Parkii 1.0 0.5 1.0 1.5 (Shea Butter) Dimethicone 1.0 0.5 1.5 0.8 2.0 PVP hexadecene copolymer 0.20 0.50 0.8 1.00 Bisabolol 0.2 0.1 0.3 DMDM hydantoin 0.5 0.5 0.5 0.5 0.75 Water, Aloe Barbadensis 0.5 1.0 Leaf Juice Alpha-glucosylrutin 0.60 0.5 0.4 0.25 0.3 Perfume 0.10 0.25 0.30 0.40 0.20 Preparation:
Heat phases A and B separately to ca. 80 C.
Stir phase A into phase B and briefly homogenize.
Cool to ca. 40 C with stirring. Add components of phase C to the emulsion in succession and cool to room temperature with stirring. Briefly homogenize.
Instead of the sunscreen cream comprising polyurethane thickener A.1, sunscreen creams comprising one or more of the polyurethanes A.2, A.3, A.4 or A.5 are also prepared.

, Face cream with sodium ascorbyl phosphate Phase Ingredients/INCI F.7.1 F.7.2 F.7.3 F.7.4 F.7.5 A Water ad 100 ad 100 ad 100 ad 100 ad 100 Butylene glycol 5.0 6.5 5.5 3.5 4.0 PUR thickener A.1 3.5 1.5 2.5 5.0 2.0 Xanthan gum 0.25 0.2 0.1 Potassium sorbate 0.1 0.1 0.1 0.1 0.1 Imidazolidinyl urea 0.3 0.2 B Potassium cetyl phosphate 1.5 2.0 1.9 2.5 1.0 Caprylic/capric triglyceride 2.0 5.0 3.0 4.0 2.5 Stearyl alcohol 0.5 1.5 2.0 1.0 3.0 Cetearyl alcohol, dicetyl phosphate, Ceteth-10 1.5 2.0 1.8 1.9 2.1 phosphate Simmondsia Chinensis 3.0 1.5 0.5 1.0 2.5 (Jojoba) seed oil Mineral oil 2.0 5.0 10.0 7.5 4.0 Paraben mixture 0.2 0.2 0.2 0.2 0.2 C Sodium ascorbyl phosphate 5.0 2.0 3.0 4.0 1.5 Lactic acid q.s. q.s. q.s. q.s.
q.s.
Water 10.0 4.0 5.0 10.0 3.0 D Tocopherol 0.1 0.2 Retinol 0.03 0.025 0.05 E Fragrance 0.1 0.05 0.05 0.1 0.15 Preparation Heat phases A and B separately to 80 C.
Stir phase A into phase B and homogenize.
Stir phase C into phase A+B and homogenize.
Cool to ca. 40 C with stirring. Adjust pH of phase C to < 6.5 with lactic acid. Add phase C and cool to ca. 30 C with stirring. Add phase D and E. Cool to room temperature with stirring and briefly homogenize.
Note: adjust pH of the emulsion to < 6.5 with lactic acid.

Instead of the face cream comprising polyurethane thickener A.1, face creams comprising one or more of the polyurethanes A.2, A.3, A.4 or A.5 are also prepared.
Hydroxycarboxyclic acid cream Phase I ng redients/I NCI F.8.1 F.8.2 F.8.3 A Ceteareth-6, stearyl alcohol 2.0 2.5 Ceteareth-25 2.0 2.5 PEG-100 stearate, glyceryl 3.5 0.5 stearate Polyglycery1-3 distearate 2.0 Mineral oil 8.0 3.5 5.0 Cetearyl ethylhexanoate 7.0 5.5 4.0 Sorbitan stearate 0.5 1.5 0.5 Cera Alba 0.5 1.0 Cetyl alcohol 1.5 3.5 4.0 Dimethicone 0.2 2.0 0.5 Panthenol 1.0 0.5 0.3 Propylene glycol 3.0 2.0 5.0 PUR thickener A.1 1.0 3.0 5.0 Hydroxy acid 3.0 7.0 10.0 Aqua ad 100 ad 100 ad 100 Sodium hydroxide q.s. q.s. q.s.
Bisabolol 0.2 0.1 0.3 Preservative q.s. q.s. q.s.
Fragrance q.s. q.s. q.s.

Note Alpha-hydroxy acids: lactic acid, citric acid, malic acid, glycolic acid Dihydroxy acid: tartaric acid Beta-hydroxy acid: salicylic acid Adjust pH to > 3 Preparation Heat phase A and B separately to ca. 80 C. Adjust pH of phase B to >3 if necessary using NaOH. Stir phase B into phase A, briefly homogenize.

Cool to ca. 40 C with stirring, add components of phase D in succession, homogenize again.
Instead of the hydroxycarboxylic acid cream comprising polyurethane thickener A.1, hydroxycarboxylic acid creams comprising one or more of the polyurethanes A.2, A.3, A.4 or A.5 are also prepared.
Emulsion with deodorant active ingredient Phase Ingredients/I NCI F.9.1 F.9.2 F.9.3 F.9.4 F.9.5 Ceteareth-6, stearyl alcohol 1.5 2.0 1.0 Ceteareth-25 1.5 0.5 1.0 PEG-40 hydrogenated castor 0.5 1.0 2.0 oil Glyceryl stearate 0.5 2.0 1.0 Cetyl alcohol 2.0 1.0 0.5 2.5 0.2 Hydrogenated coco-glycerides 2.0 1.0 0.5 Hydrogenated polyisobutene 10.0 20.0 5.0 3.0 Decyl oleate 3.0 2.0 8.0 5.0 Bis-PEG/PPG-14/14 dimethicone, 3.0 3.5 4.0 2.0 1.5 cyclopentasiloxane Talc 3.0 2.5 1.5 Magnesium aluminum silicate 1.0 0.5 1.0 1.5 Propylene glycol 10.0 5.0 7.5 20.0 15.0 PUR thickener A.1 0.5 1.0 3.0 3.5 2.0 Xanthan gum 0.2 0.1 0.05 Cetyl hydroxyethylcellulose 0.3 0.1 Aluminum chlorohydrate 5.0 10.0 20.0 Aluminum zirconium 15.0 50.0 20.0 tetrachlorohydrex GLY
Aqua ad 100 ad 100 ad 100 ad 100 ad 100 Neutralizing agent q.s. q.s. q.s. q.s.
q.s.
Alcohol 5.0 10.0 25.0 7.5 6.0 Allantoin 0.1 0.1 0.1 0.1 0.1 Preservative q.s. q.s. q.s. q.s.
q.s.
_ Fragrance q.s. q.s. q.s. q.s.
q.s.
Preparation Heat phases A and B separately to ca. 80 C.
Stir phase B into phase A with homogenization. If appropriate, adjust to pH 4-5 using phase C. Cool to ca. 40 C, add phase D and allow to cool to room temperature with stirring. Briefly homogenize.
Note: adjust pH of the emulsion to 4-5 Instead of the emulsion with deodorant active ingredient comprising polyurethane thickener A.1, emulsions with deodorant active ingredient comprising one or more of the polyurethanes A.2, A.3, A.4 or A.5 are also prepared.
Hair removal cream Phase I ngredients/I NCI F.10.1 F.10.2 F.10.3 A Glyceryl stearate 1.0 Ceteareth-12 1.0 2.0 Ceteareth-20 1.0 2.0 Stearyl alcohol 4.0 1.0 Cetyl alcohol 4.0 1.0 Mineral oil 6.0 4.0 Prunus Armeniaca (Apricot) 3.0 1.0 2.0 kernel oil Propylene glycol 1.0 2.0 10.0 Calcium carbonate 10.0 Calcium hydroxide 7.0 Sodium hydroxide 0.4 0.6 Calcium thioglycolate 5.0 3.0 5.0 PUR thickener A.1 3.0 1.5 2.0 Aqua ad 100 ad 100 ad Tocopherol 0.1 0.2 0.15 Bisabolol 0.2 0.1 0.3 Fragrance q.s. q.s. q.s.
Preparation Heat phase A and B separately to ca. 80 C.
Stir phase B into phase A with homogenization, briefly homogenize.
Cool to ca. 40 C, add phase C, cool to RT with stirring and homogenize again.

. .

Note: adjust pH of the emulsion to > 10.
Instead of the hair removal cream comprising polyurethane thickener A.1, hair removal creams comprising one or more of the polyurethanes A.2, A.3, A.4 and A.5 are also prepared.
Self-tanning emulsion Phase Ingredients/I NCI F.11.1 F.11.2 F.11.3 F.11.4 A Isohexadecane 4.0 2.0 3.0 1.0 Dimethicone 1.0 1.0 0.5 1.5 Cetearyl alcohol 2.0 = 2.5 1.5 2.5 Isopropyl myristate 1.0 2.0 3.0 Simnnondsia Chinensis (Jojoba) 2.0 1.0 0.5 0.5 seed oil Polyglycery1-3 methylglucose 3.0 3.5 distearate PEG-40 stearate 2.5 2.0 Lecithin 0.5 1.0 Cetearyl glucoside 0.5 0.5 Sorbitan oleate 0.5 0.5 0.3 B Glycerin 4.0 5.0 Butylene glycol 4.0 3.0 PUR thickener A.1 1.0 3.0 1.5 2.5 Xanthan gum 0.1 0.1 Aqua ad 100 ad 100 ad 100 ad 100 C Dihydroxyacetone 1.5 5.0 Erythrulose 2.0 4.0 Aqua 5.0 10.0 5.0 8.0 Citric acid q.s. q.s. q.s.
q.s.
D Bisabolol 0.3 0.5 0.2 0.4 Tocopheryl acetate 0.7 0.5 0.6 1.0 Preservative q.s. q.s. q.s.
q.s.
Fragrance q.s. q.s. q.s.
q.s.
Preparation Heat phases A and B separately to ca. 80 C.
Stir phase B into phase A and briefly homogenize.

With stirring, cool to ca. 40 C, add phase C and cool to 30 C with stirring.
Add components of phase D in succession and cool to RT with stirring. Briefly homogenize.
Note: adjust pH of the emulsion to 4-5.5 Instead of the self-tanning emulsion comprising polyurethane thickener A.1, self-tanning emulsions comprising one or more of the polyurethanes A.2, A.3, A.4 or A.5 are also prepared.
Conditioner shampoo Ingredients/INCI F.12.1 F.12.2 F.12.3 F.12.4 Aqua ad 100 ad 100 ad 100 ad 100 Sodium laureth sulfate 35.7 30.0 12.0 Cocamidopropyl betaine 13.5 15.0 Disodium 10.0 cocoamphodiacetate Sodium cocoamphoacetate 6.0 Polysorbate 20 5.0 Decyl glucoside 5.0 1.5 Laureth-3 2.0 Sodium laureth sulfate, glycol distearate, cocamide 3.0 2.0 MEA, laureth-10 Coco-glucoside, glyceryl 5.0 oleate Dimethicone 2.0 Conditioning polymer 2.0 0.5 0.75 0.4 PUR thickener A.1 0.75 1.2 0.5 1.0 PEG-150 distearate 3.0 Citric acid q.s. q.s.
Preservative q.s. q.s. q.s. q.s.
Fragrance q.s. q.s. q.s. q.s.
Dye q.s. q.s. q.s. q.s.
Sodium chloride 1.0 1.0 Conditioning polymer is understood as meaning polyquaternium-7, PQ-10, PQ-16, PQ-39, PQ-44, PQ-46, PQ-67, guar hydroxypropyltrimonium chloride, PQ-87, and combinations of these.

41 as Instead of the conditioner shampoo comprising polyurethane thickener A.1, conditioner shampoos comprising one or more of the polyurethanes A.2, A.3, A.4 and A.5 are also prepared.
5 Hair conditioner Phase I ngredients/I NCI F.13.1 F.13.2 F.13.3 F.13.4 F.13.5 A Water ad 100 ad 100 ad 100 ad 100 ad 100 PUR thickener A.1 2.5 1.5 3.0 0.6 2.0 Hydroxyethylcellulose 0.05 0.1 0.2 Propylene glycol 1.0 2.0 0.8 0.5 Panthenol 0.5 0.75 0.25 0.3 B Quaternium-91, cetearyl alcohol, 2.0 1.5 cetrimonium methosulfate Distearoyethyl hydroxyethylmonium 3.0 4.0 methosulfate, cetearyl alcohol Hydrogenated polyisobutene 1.0 1.5 1.0 Cyclopentasiloxane 2.0 1.0 0.5 Isopropyl palmitate 1.0 2.0 Persea Gratissima (Avocado) oil 2.5 Steareth-2 0.75 0.5 Ceteareth-6, stearyl alcohol 1.5 0.5 Ceteareth-25 1.5 Cetearyl alcohol 2.0 1.5 0.5 4.0 C Acrylate/C10-30 alkylacrylate 0.1 0.2 0.15 copolymer D Cetrimonium chloride 1.5 3.0 Conditioning polymer 2.0 6.0 3.0 1.5 0.8 E Preservative q.s.
q.s. q.s. q.s. q.s.
Fragrance q.s. q.s. q.s.
q.s. q.s.
Conditioning polymer is understood as meaning polyquaternium-7, PQ-10, PQ-16, PQ-39, PQ-44, PQ-46, PQ-67, guar hydroxypropyltrimonium chloride, PQ-87, and 10 combinations of these.
Preparation 15 Heat phases A and B separately to ca. 80 C.
Stir phase C into phase B, then stir phase A into phase B/C and briefly homogenize.

With stirring, cool to ca. 50 C, add components of phase D in succession and cool to ca. 30 C with stirring. Add components of phase E in succession and cool to RT
with stirring. Briefly homogenize.
Instead of the hair conditioner comprising polyurethane thickener A.1, hair conditioners comprising one or more of the polyurethanes A.2, A.3, A.4 or A.5 are also prepared.

Claims

1.A process for preparing polyurethanes comprising l) at least two hydrophilic sections S, II) at least one hydrophilic section P different from S, III) at least two terminal hydrophobic sections T, IV) at least two hydrophobic sections D different from T, where a) to each section T is directly attached a section S, b) to each section S on at least one side is attached at least one section D, c) to each section P are attached at least two sections D, wherein the preparation takes place in the presence of at least one carboxylic acid salt of at least one metal selected from the group consisting of the alkali metals, the alkaline earth metals and mixtures thereof.

2. The process according to claim 1, where at least some of the polyurethanes comprise allophanate segments.

3. The process according to at least one of claims 1 and 2, where at least some of the polyurethanes comprise isocyanurate segments.

4. The process according to at least one of claims 1 to 3, wherein the amount of solvents which are different from the substances which introduce the hydrophilic and hydrophobic sections into the polyurethanes, based on the reaction mixture, is in the range from 0 to 10% by weight.

5. The process according to at least one of claims 1 to 4, wherein the process is single-stage.

6. The process according to at least one of claims 1 to 5, wherein polyurethanes are also additionally obtained which comprise l) at least two hydrophilic sections S, II) no hydrophilic section P, III) at least two terminal hydrophobic sections T, IV) at least one hydrophobic section D different from T, where a) to each section T is directly attached a section S, b) to each section S is attached a section D.

7. The process according to at least one of claims 1 to 6, wherein the at least one hydrophilic section P has a number-average molecular weight of from 4000 to 12 000 g/mol.

8. The process according to at least one of claims 1 to 7, wherein the preparation takes place in the presence of at least one potassium carboxylate.

9. The process according to at least one of claims 1 to 8, wherein the preparation takes place in the presence of less than 10 ppm of tin.

10. The process according to at least one of claims 1 to 9, wherein the preparation takes place in the presence of less than 10 ppm of zinc.

11. The process according to at least one of claims 1 to 10, wherein in each case at least - one alkoxylated C4-C30-alcohol, - one polyetherdiol and - one diisocyanate are used for preparing the polyurethanes.

12. The process according to claim 11, wherein - at least one C4-C30-alcohol is a branched C12-C30-alkanol, - at least one polyetherdiol has a molecular weight M n in the range from 4000 to 12 000 g/mol and - at least one diisocyanate is an aliphatic diisocyanate.

13. The use of polyurethanes obtainable by a process according to claims 1 to 12 in aqueous preparations.

14. A preparation comprising at least one polyurethane obtainable by a process according to claims 1 to 12.