WO2012098176A1

WO2012098176A1 - Dendritic polyether-polyurethane thickeners

Info

Publication number: WO2012098176A1
Application number: PCT/EP2012/050750
Authority: WO
Inventors: Holger TÜRK; Volker Wendel; Anna Cristadoro; Daniel STADLER; Markus Buchmann
Original assignee: Basf Se
Priority date: 2011-01-20
Filing date: 2012-01-19
Publication date: 2012-07-26
Also published as: JP2014504668A; EP2665759A1; CN103328524A; JP2017095727A; JP6312870B2; BR112013018538A2; KR20140005253A; CN103328524B; KR101924770B1

Abstract

The invention relates to associative polyether-polyurethane thickeners, into which dendritic polyether polyols are polymerized, to the production of said thickeners, and to the use of said thickeners, in particular in cosmetic preparations.

Description

Dendritic polyether polyurethane thickeners

The present invention relates to associative polyether-polyurethane thickeners in which dendritic polyether polyols are copolymerized, the preparation of these thickeners and their use, in particular in cosmetic preparations.

Polyurethane-based associative thickeners are state of the art. They are described in detail, for example, in US 4,079,028 and in US 4,155,892.

The "star-shaped products" (group B) and "complex polymers" (group C) described in US Pat. No. 4,079,028 comprise polyurethanes in which polyhydric alcohols are copolymerized. These polyhydric alcohols are low molecular weight compounds such as, for example, trimethylolpropane, pentaerythritol, sorbitol, erythritol, mannitol or dipentaerythritol.

EP 1566393 (Cognis) describes thickeners based on an aqueous preparation of nonionic, water-dispersible or water-soluble polyurethanes which can be prepared by reacting (a) one or more polyfunctional isocyanates with (b) one or more polyether polyols , (c) one or more monofunctional alcohols and (d) if desired one or more polyfunctional alcohols, the compounds (d) containing no further functional groups apart from the OH groups. The polyfunctional alcohols (d) contain at least predominantly trifunctional alcohols, such as, for example, glycerol or preferably trimethylolpropane.

EP 1765900 (Cognis) describes thickening agents based on an aqueous preparation of nonionic, water-dispersible or water-soluble polyurethanes of special structure. The particular structure of these polymers is due to the presence of allophanate bonds, which are generated by the use of an excess of isocyanate. As component (a) it is possible to use hydrophilic polyols having at least 2 OH groups, which may also contain ether groups. EP 1584331 A1 (Shiseido) describes polyurethane thickeners for cosmetic preparations. The polyurethanes may also be branched. The underlying polyols and their alkoxylated derivatives are described in Sections [38] and [39]. EP 725097 A1 (Bayer) also describes thickeners based on polyurethanes. Branches may optionally be introduced into the polyurethanes by component a4). A4) are 3 to 6-hydric alcohols of the molecular weight Weight range 92 to 600, preferably 92 to 400 and particularly preferably 92 to 200 such as glycerol, trimethylolpropane, pentaerythritol and / or sorbitol. Preferably, if any, glycerol or trimethylol propane is used. EP 978522 (National Starch) describes branched polyurethane thickeners having the following formula

(XY ₁ Z) _n -A- {ZY ₂ X ^, ) _ni

Therein A is a hydrophilic polyol and is preferably selected from trimethylolpropane, [2-ethyl-2- (hydroxymethyl) -1, 3-propanediol], pentaerythritol, glycerin and sorbitol.

US 2009/0286940 A1 (DIC Corp.) describes the preparation of hyperbranched polyether polyols by ring-opening polymerization of hydroxyalkyloxetanes and monofunctional epoxides and polyurethanes based on these hyperbranched polyether polyols.

US 2009/0082483 A1 describes polyurethane foams based on the reaction products of polyisocyanates and polyglycerol, which is hydrophobically modified prior to urethanization by transesterification with naturally occurring polyol esters.

WO 2009/101 141 A1 describes a process for preparing dendritic polyetherols by reacting at least one tri- or higher-functional alcohol and optionally further di- and / or monofunctional alcohols and / or modifying reagents with the aid of acidic catalysts. Furthermore, the use of these polyetherols is described as possible building blocks for the preparation of polyaddition or polycondensation polymers.

DE 1021 1664 A1 describes the synthesis of hyperbranched polyglycerols by ring-opening polymerization of glycidol.

Object of the present invention was to provide suitable for cosmetic applications thickener, which are distinguished from the known thickeners by

A) accessibility of higher viscosities compared to conventional assoziaziv thickeners;

B) increasing water solubility;

C) Adaptation of the molecular structure to different requirements. The present invention relates to polymers comprising in copolymerized form

a) at least one polyisocyanate

b) at least one alcohol of the general formula I.

R-O-R-OH (I) where

R ^{1 is} selected from C ₆ -C ₄₀ -alkyl, C ₆ -C ₄₀ -alkenyl, C ₃ -C 10 -cycloalkyl, C ₆ -C 30 -aryl, C ₇ -C ₄₀ -arylalkyl,

R ^{2 is} selected from C 2 -C 10 -alkylene, C ₆ -C 10 -arylene, C ₇ -C 10 -arylene, n 0 to 200

c) at least one dendritic polyether polyol,

d) optionally containing at least one of b) and c) different compound having a molecular weight M _n of at least 300 g / mol

i. at least two OH groups and

ii. at least two groups selected from ether groups and ester groups, e) optionally further compounds having in the range of 1 to 9 against isocyanate-reactive groups per molecule.

In a preferred embodiment, the polymer according to the invention is water-soluble or water-dispersible.

"Water-soluble" in the context of this invention means that at least 1 gram, preferably at least 10 grams of the substance known as water-soluble, ie for example the polymer according to the invention, in 1 liter of deionized water are clearly soluble to the human eye.

"Water-dispersible" in the context of this invention means that at least 1 gram, preferably at least 10 grams of the substance known as water-dispersible, ie, for example, the polymer of the invention in 1 liter of deionized water without sediment with maximum average particle size 1 μιη are dispersible.

In a preferred embodiment, the polymer according to the invention is uncrosslinked. In the context of this invention, "uncrosslinked" means that a degree of crosslinking of less than 15% by weight, preferably less than 10% by weight, in particular less than 5% by weight, determined via the insoluble fraction of the polymer, is present is. The insoluble fraction of the polymers is determined by extraction for four hours with the same solvent as used for gel permeation chromatography to determine the molecular weight distribution of the polymers, ie tetrahydrofuran, dimethylacetamide or hexafluoroisopropanol, depending on the solvent in which the polymer is more soluble, in a Soxhlet apparatus and after Dry the residue to constant weight Weigh the remaining residue.

In a preferred embodiment, the polymer according to the invention is water-soluble or water-dispersible and uncrosslinked. a) polyisocyanate

According to the present invention, polyisocyanates are compounds having at least two to at most four isocyanate groups per molecule. Suitable polyisocyanates preferably contain on average 2 (diisocyanates) to at most 4 NCO groups per molecule, with diisocyanates being particularly preferred.

Examples which may be mentioned as suitable isocyanates are 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI), 4,4'-diphenyldimethylmethane diisocyanate, di- and tetraalkyldiphenylmethane diisocyanate, 4 , 4-Dibenzyldiisocyanat, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, the isomers of toluene diisocyanate (TDI), optionally in admixture, 1-methyl-2,4-diisocyanato-cyclohexane, 1, 6- diisocyanato-2 , 2,4-trimethylhexane,

1-isocyanatomethyl-S-isocyanato-1-trimethylcyclohexane, 4,4'-diisocyanatophenylperfluoroethane, tetramethoxybutane-1,4-diisocyanate, butane-1,4-diisocyanate, hexane-1,6-diisocyanate (HDI), isophorone diisocyanate ( IPDI), dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate, ethylene diisocyanate, phthalic acid bis-isocyanatoethyl ester.

In a preferred embodiment, the polymers according to the invention contain polymerized (condensed in) cycloaliphatic or aliphatic diisocyanate radicals, particularly preferably aliphatic diisocyanate radicals.

Examples of condensed aliphatic diisocyanates 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-trimethylhexamethylene diisocyanate and in particular hexamethylene diisocyanate (hexane-1,6-diisocyanate, HDI).

Examples of condensed cycloaliphatic diisocyanates are: isophorone diisocyanate (IPDI), 2-isocyanatopropylcyclohexyl isocyanate, 4-methylcyclohexane-1,3-diisocyanate (H-TDI) and 1,3-bis (isocyanatomethyl) cyclohexane. Also called H 12-MDI or "saturated MDI" called diisocyanates, such as 4,4'-methylene-bis (cyclohexyl isocyanate) (alternatively also called dicyclohexyl methane-4,4'-diisocyanate) or 2,4 ' -Methylenebis (cyclohexyl) diisocyanate may be contained as radicals in the polyurethanes of the invention.

In a preferred embodiment, a) comprises or comprises hexamethylene diisocyanate. In another preferred embodiment, a) is or comprises isophorone diisocyanate.

Of course, mixtures of polyisocyanates can also be used as a). b) alcohol of the general formula I

In one embodiment, R ^{1 is} C 6 -C 40 -alkyl. In a preferred embodiment, this is a C6-C30-alkyl radical, more preferably a Ce-Cao-alkyl radical, and most preferably a Ci2-C3o-alkyl radical.

R ¹ is selected, for example, from radicals of linear or branched alkanes such as hexane, heptane, octane, 2-ethylhexane, nonane, decane, undecane, dodecane, tridecan, isotridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, noadecan , Eicosan, henicosan, docosan, tricosane, isotricosane, tetracosane, pentacosan, hexacosan, heptacosan, octacosan, nonacosan, triacontane, 2-octyldodecane, 2-dodecylhexadecane, 2-tetradecyloctadecane, 2-decyltetradecane, or monomethyl-branched isooctadecane.

In one embodiment, R ^{1 is} C 6 -C 40 alkenyl. Suitable C6-C4o-alkenyl radicals may be straight-chain or branched. These are preferably predominantly linear alkenyl radicals, as they also occur in natural or synthetic fatty acids and fatty alcohols and oxo alcohols, which are mono-, di- or polyunsaturated. These include, for example, n-hexenyl, n-heptenyl, n-octenyl, n-nonenyl, n-decenyl, n-undecenyl, n-dodecenyl, n-tridecenyl, n-tetradecenyl, n-pentadecenyl, n-hexadecenyl, n-heptadecenyl , n-octadecenyl, n-nonadecenyl.

In one embodiment, R ^{1 is} C ₃ -C ₃ cycloalkyl. Cycloalkyl is preferably cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. In one embodiment, R ^{1 is} C 6 -C 30 -aryl. Aryl includes unsubstituted and substituted aryl groups and is preferably phenyl, tolyl, xylyl, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl and especially phenyl, tolyl, xylyl or mesityl. In one embodiment, R ^{1 is} C 7 -C 40 arylalkyl. Arylalkyl represents groups which contain both alkyl and aryl radicals, these arylalkyl groups being linked either via the aryl or via the alkyl radical to the compound carrying them. For example, R ¹ may be an arylalkyl radical as described in EP 761780 A2, p. 4, Z. 53-55.

In a preferred embodiment, R ² in the general formula (I) is selected from -CH ₂ -CH ₂ -, -CH (CH 3) -CH ₂ - and mixtures thereof, more preferably -CH ₂ - CH ₂ -.

In a preferred embodiment, in the general formula (I), n is selected from the range 2 to 150. In one embodiment, R ^{1 is} a branched alkyl radical. The side chains of such branched alkyl radicals are likewise preferably alkyl radicals or alkenyl radicals, particularly preferably alkyl radicals, in particular unbranched alkyl radicals.

In one embodiment, the side chains of the branched alkyl radicals R ^{1 have} a chain length of at most 6, preferably of at most 4 carbon atoms.

In one embodiment, the branches are significantly shorter than the main chain. In one embodiment, each branch of R ^{1 has} a chain length equal to at most half the chain length of the backbone of R ¹ . In one embodiment, the branches are significantly shorter than the main chain. In a preferred embodiment, the branched R ^{1 is} iso- and / or neo-AI kylreste. In a preferred embodiment, R ¹ radicals of isoalkanes are used as branched alkyl radicals. Particularly preferred is a Ci3-alkyl radical, in particular an iso-Ci3-alkyl radical. In another embodiment, R ¹ comprises branched alkyl radicals whose side chains have a chain length of at least 4, preferably of at least 6, carbon atoms.

In general, b) may also be a mixture of different alcohols.

In a preferred embodiment of the invention, at least one alcohol b) is selected from alkoxylated alcohols. Preferred alkoxylated alcohols are ethoxylated alcohols (R ² = -CH ₂ -CH ₂ -), propoxylated alcohols (R ² = -CH (CH ₃ ) -CH ₂ -), and alcohols that are both ethoxylated and propoxylated. The ethylene oxide and propylene oxide units can be distributed randomly or in blocks. Suitable alcohols b) are, for example, the alkoxylated, preferably ethoxylated

linear alcohols from natural sources or from the Ziegler synthesis reaction of ethylene in the presence of aluminum alkyl catalysts. Examples of suitable linear alcohols are linear C6-C _o-3 alcohols, especially Ci2-C ₃ o-alcohols. Particularly preferred alcohols are: n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, n-eicosanol, n-docosanol, n-tetracosanol, n-hexacosanol, n-octacosanol, and / or n-triacontanol, and mixtures of the aforementioned alcohols, for example NAFOL ^® types such NAFOL ^® 22+ (Sasol). Oxo alcohols are, for example, isoheptanol, isooctanol, isononanol, isodecanol, I-soundecanol, isotridecanol (for example Exxal® grades 7, 8, 9, 10, 11, 13).

- Alcohols branched in the 2-position; these are the Guerbet alcohols known to those skilled in the art, which are accessible by dimerization of primary alcohols via the so-called Guerbet reaction. Particularly preferred alcohols are here: lsofol ^® 12 (Sasol), Rilanit ^® G16 (BASF SE). Alcohols which are obtained by Friedel-Crafts alkylation with oligomerized olefins and which then contain an aromatic ring in addition to a saturated hydrocarbon radical. Particularly preferred alcohols which may be mentioned here are: i-octylphenol and i-nonylphenol.

- Alcohols of the general formula (4) of EP 761780 A2, S.4

4H 6

R -C-ROH

\ 5

R or alcohols of the general formula (5) of EP 761780 A2, S.4

7 H

R-C-OH

\ ₈

R

in which

R ⁴ , R ⁵ , R ⁷ and R ⁸ independently of one another have the meaning described in EP 761780 A2, p. 4, lines 45 to 58; R ⁴ , R ⁵ , R ⁷ and R ^{8 are} independently of one another alkyl radicals having at least 4 carbon atoms and the total number of carbon atoms of the alcohols is at most 30,

R ^{6 is} an alkylene radical such as -CH ₂ -, -CH ₂ -CH ₂ -, -CH ₂ -CH (CH ₃ ) -;

For example, 2-decyl-1-tetradecanol may be mentioned here as suitable alcohol.

In one embodiment, at least one alcohol b) is a mixture of ethoxylated linear Ci6-Ci8 fatty alcohols.

In one embodiment, at least one alcohol b) is a linear, nonionic compound of the structural formula RO (CH ₂ CH ₂ O) _x H, where R is a linear C 16 -C 18 -alkyl radical and x is selected from 3, 5, 7, 8, 11, 13, 18, 25 or 80, preferably x = 1. Commercially such ethoxylated linear fatty alcohol, for example, as Lutensol ^® AT1 1 (BASF SE) available.

In one embodiment, at least one alcohol b) is selected from compounds having the structural formula RO (CH ₂ CH ₂ 0) _x H, wherein R is a linear C8-C ₃ -alkyl radical, preferably linear Ci6-CI8 alkyl group, and x 2 is up to 30. In one embodiment, particularly when no connection d) is einpolymierisert, at least one alcohol b) is selected from compounds having the structural formula RO (CH ₂ CH ₂ 0) x H, wherein R is a linear C8-C ₃ -alkyl radical, preferably linear C16 C18 alkyl and x is from 30 to 150. In one embodiment b) comprises a C ₂ -C ₃ -alcohol ethoxylated with 3 to 100 moles of ethylene oxide per mol. In one embodiment of the invention, b) is selected from mixtures of ethoxylated linear and ethoxylated branched long-chain alcohols, in particular mixtures of the abovementioned types. In another embodiment, b) is selected from ethoxylated 1SO-C13 oxo alcohols and mixtures thereof.

In one embodiment, at least one alcohol b) is a branched, nonionic compound of the structural formula RO (CH 2 CH 2 O) _x H, where R is a C 13 -alkyl radical, preferably an isoC 13 -alkyl radical, and where x = 3, 5, 6, 6.5, 7, 8, 10, 12, 15 or 20, preferably x = 10 used. Commercially such ethoxylated alkyl-branched alcohol, for example, as Lutensol TO10 ^® (BASF SE) available.

In a further embodiment, b) is selected from mixtures comprising ethoxylated C 16-18 fatty alcohols and ethoxylated C 3-3 oxo alcohols.

In a further embodiment, b) is selected from the above-described alcohols of the general formulas (4) or (5) of EP 761780 A2, p.4 in their ethoxylated form. c) Dendritic polyether polyol

The polymers according to the invention contain in polymerized form at least one dendritic polyether polyol c). In the context of the present invention, the term "dendritic" polyether polyols quite generally encompasses polyether polyols which have a branched structure and a high functionality. For the purposes of the invention, "dendritic polymers" include dendrimeric polyether polyols, hyperbranched polyether polyols and structures derived therefrom.

"Dendrimers" are molecularly uniform macromolecules with a highly symmetric structure. They are structurally derived from star polymers, with the individual chains each branched in a star shape. Dendrimers arise from small molecules through a repetitive sequence of reactions, resulting in ever-increasing branches, each terminating with functional groups, which in turn are the starting point for further branching. Thus, with each reaction step, the number of monomer end groups increases, resulting in a spherical tree structure at the end. A characteristic feature of dendrimers is the number of reaction stages used to build them up, commonly referred to as "generations." Due to their uniform structure, dendrimers generally have a very narrow molecular weight distribution. Preferred dendritic polyetherpolyols c) according to the invention are hyperbranched polyetherpolyols which are molecular and structurally nonuniform and have side chains of different length and branching as well as a molecular weight distribution. For the definition of hyperbranched polymers, reference is also made to PJ Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, No. 14, 2499.

For the synthesis of hyperbranched polymers, in particular so-called AB _X monomers are suitable. These have two different functional groups A and B, which can react with each other to form a linkage. The functional group A is contained only once per molecule, the functional group B two or more times. The reaction of said AB _x monomers with one another produces substantially uncrosslinked polymers with regularly arranged branching sites. The polymers have almost exclusively B groups at the chain ends. Further details can be found, for example, in Journal of Molecular Science, Rev. Macromol. Chem. Phys., C37 (3), 555-579 (1997).

In the context of this invention, dendritic polyether polyols c) are polyether polyols which, in addition to the ether groups which form the polymer backbone, have on average at least 3, preferably at least 4, more preferably at least 5 and in particular at least 6 OH groups per molecule. The dendritic polyetherols c) of the present invention have on average not more than 500, preferably not more than 250, more preferably not more than 100, and in particular not more than 50 terminal or pendant functional OH groups per molecule.

The dendritic polyether polyol c) is preferably a condensation product of on average at least 3, more preferably at least 4, in particular at least 5, and most preferably at least 6 di-, tri- or higher-functional alcohols.

Preferably, the dendritic polyether polyol c) is the condensation product of on average at least 3, particularly preferably at least 4, especially at least 5 and in particular at least 6 tri- or higher-functional alcohols. Preferred dendritic polyether polyols c) in the context of this invention are hyperbranched polyether polyols. Dendritic polyether polyols are preferably uncrosslinked polymer molecules having hydroxyl and ether groups which are either structurally and molecularly nonuniform (hyperbranched polyether polyols) or structurally and molecularly uniform (dendrimeric polyether polyols).

Hyperbranched polyether polyols can be constructed starting from a central molecule analogously to dendrimers, but with nonuniform chain length of the branches. On the other hand, they can also have linear regions with functional side groups.

In the context of the present invention, "hyperbranched" means that the degree of branching (for the definition of the "degree of branching" see H. Frey et al., Acta Polym. 1997, 48, 30), ie the average number of dendritic linkages plus average number of end groups per molecule divided by the sum of the average number of dendritic, linear and terminal linkages per molecule multiplied by 100, 10 to 99.9%, preferably 20 to 99%, particularly preferably 20 to 95 % is.

The hyperbranched polyether polyols c) used according to the invention preferably have a degree of branching of from 10 to 99.9%, preferably from 20 to 99%, particularly preferably from 20 to 95%.

"Dendrimer" in the context of the present invention means that a polymer molecule has a degree of branching of more than 99.9 to 100%.

The preparation of dendritic polyether polyols starting from glycerol is known.

US 3,932,532 and DE 10307172 describe the preparation of hyperbranched polyether polyols from glycerol by alkali catalysis.

DE 10307172 describes the polycondensation of glycerol in the presence of acidic catalysts, for example HCl, H 2 SO 4, sulfonic acid or H 3 PO 4.

WO 2004/074346 describes the alkaline polycondensation of glycerol and the subsequent reaction of the resulting condensation product under acidic conditions with a fatty alcohol. A polyglycerol modified with fatty alcohol is thereby obtained.

Reference is made to the aforementioned disclosures.

Suitable dendritic polyether polyols c) according to the invention are dendritic polyglycerols, ie hyperbranched polyglycerol and polyglycerol dendrimers.

Suitable hyperbranched polyglycerols are, for example, glycidol-based polyglycerol ethers as described in DE 19947631 and DE 1021 1664. The preparation takes place by ring-opening reaction of glycidol, optionally in the presence of a polyfunctional starter molecule. These disclosures are referred to. Polyglycerol dendrimers are described, for example, by Haag et al., J. Am. Chem. Soc. 2000, 122, 2954-2955, to which reference is hereby made.

According to the invention as dendritic polyether polyols c) are also suitable in

WO 00/56802 disclosed polyether polyols, to which reference is hereby made. The dendritic polyether polyols c) described therein are obtainable by ring-opening Polymerization of 1-ethyl-1-hydroxymethyl-oxetane with special catalysts. The resulting polymer backbone consists of trimethylolpropane units.

Also suitable according to the invention as dendritic polyether polyols c) are those described by Nishikubo et al., Polymer Journal 2004, 36 (5) 413, to which reference is hereby made. The dendritic polyether polyols c) described therein can be obtained by ring-opening polymerization of 3,3-bis (hydroxymethyl) oxetane.

Also suitable according to the invention as dendritic polyether polyols c) are the polyether polyols obtainable by joint ring-opening polymerization of 1-ethyl-1-hydroxymethyl-oxetane and 3,3-bis (hydroxymethyl) oxetane, as described by Chen et. al, J. Poly. Be. Part A: Polym. Chem. 2002, 40, 1991, which is incorporated herein by reference. Suitable dendritic hyperbranched polyether polyols are also described, for example, in WO 2009/101 141 A1.

There, a process for the preparation of dendritic polyetherols is described by reacting at least one tri- or higher-functional alcohol and optionally further di- and / or monofunctional alcohols and / or modifying reagents with the aid of acidic catalysts.

As tri- and higher functional alcohols, for example, triols, such as Tnmethylolmethan, trimethylolethane, trimethylolpropane (TMP), 1, 2,4-butanetriol, tris-hydroxymethyl isocyanurate, tris-hydroxyethyl isocyanurate (THEIC) can be used. Likewise, tetrols can be used, such as bis-trimethylolpropane (Di-TM P) or pentaerythritol. Furthermore, higher functional polyols, such as bis-pentaerythritol (di-penta) or inositols can be used. Furthermore, it is also possible to use alkoxylation products of the abovementioned alcohols and of glycerol, preferably with 1 to 40 alkylene oxide units per molecule. Particularly preferred trifunctional and higher-functional alcohols are aliphatic alcohols and in particular those having primary hydroxyl groups, such as trimethylolmethane, trimethylolethane, trimethylolpropane, di-TM P, pentaerythritol, di-penta and their alkoxylates having 1 to 30 ethylene oxide units per molecule and also glycerol -Ethoxylates with 1 -30 ethylene oxide units per molecule. Very particular preference is given to using trimethylolpropane, pentaerythritol and their ethoxylates having on average 1 to 20 ethylene oxide units per molecule and also glycerol ethoxylates having 1 to 20 ethylene oxide units per molecule. Likewise, the alcohols mentioned can be used in a mixture.

The tri- and higher-functional alcohols can also be used in mixture with difunctional alcohols. Examples of suitable compounds having two OH groups include ethylene glycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1, 2, 1, 3 and 1, 4-butanediol, 1, 2-, 1, 3- and 1, 5-pentanediol, hexanediol, dodecanediol, cyclopentanediol, Cyclohexanediol, cyclohexanedimethanol, bis (4-hydroxycyclohexyl) methane, bis (4-hydroxycyclohexyl) ethane, 2,2-bis (4-hydroxycyclohexyl) propane, difunctional polyether polyols based on ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, or polytetrahydrofuran. Of course, the difunctional alcohols can also be used in mixtures.

The diols serve to fine tune the properties of the polyether polyol. If difunctional alcohols are used, the ratio of difunctional alcohols to the tri- and higher-functional alcohols is determined by the person skilled in the art according to the desired properties of the polyether. As a rule, the amount of difunctional or difunctional alcohols is 0 to 99 mol%, preferably 0-80, more preferably 0-75 mol% and very particularly preferably 0-50 mol% with respect to the total amount of all alcohols. It is also possible to obtain block copolyethers, for example diol-terminated polyethers, by alternating addition of tri- and higher-functional alcohols and diols during the course of the reaction.

With regard to the building blocks for preferred dendritic polyether polyols c), reference is made to the disclosure of WO 2009/101 141 p. 4, lines 27 to p. 5, line 42, to which reference is made in its entirety.

With regard to the synthesis of these preferred dendritic polyether polyols c) by acid catalysis, reference is made to the disclosure of WO 2009/101 141 p. 6, lines 1 to p. 7, line 8, to which reference is made in its entirety.

With regard to further reaction conditions of the synthesis of these preferred dendritic polyether polyols c), reference is made to the disclosure of WO 2009/101 141 p. 7, line 10 to p. 8, line 11, to which reference is made in its entirety.

In a preferred embodiment of the invention, the dendritic polyether polyols c) are obtainable by condensation of at least one tri- or higher-functional alcohol and optionally further di- and / or monofunctional alcohols and / or modifying reagents with the aid of acidic catalysts.

In a preferred embodiment of the invention, at least one dendritic polyether polyol c) is the condensation product of on average at least 3 di-, tri- or higher-functional alcohols.

Preferred dendritic polyether polyols c) are obtainable by the acid-catalyzed polycondensation of trimethylolpropane.

Preferred dendritic polyether polyols c) are obtainable by the acid-catalyzed polycondensation of trimethylolpropane, wherein at least a part of the OH groups of the trimethylolpropane is alkoxylated. Preferred dendritic polyether polyols c) are also obtainable by the acid-catalyzed polycondensation of pentaerythritol.

Preferred dendritic polyether polyols c) are also obtainable by the acid-catalyzed polycondensation of pentaerythritol, where at least part of the OH groups of the pentaerythritol is alkoxylated.

Preferred dendritic polyether polyols c) are also obtainable by the acid-catalyzed polycondensation of trimethylolpropane and triethylene glycol.

Preferred dendritic polyether polyols c) are also obtainable by the acid-catalyzed polycondensation of trimethylolpropane and pentaerythritol.

Preferred dendritic polyether polyols c) are also obtainable by the acid-catalyzed polycondensation of triethylene glycol and pentaerythritol.

Preferred dendritic polyether polyols c) have a number average molecular weight Mn of at least 300 g / mol, preferably at least 400 g / mol, more preferably at least 500 g / mol.

Modified dendritic polyether polyols c)

Suitable dendritic polyether polyols c) are also those dendritic polyether polyols c) which, in addition to the hydroxyl groups, contain further functional groups which are preferably obtained by modifying at least part of the hydroxyl groups.

Such further functional groups include mercapto groups, primary, secondary or tertiary amino groups, ester groups, carboxylic acid groups or derivatives thereof, sulfonic acid groups or their derivatives, phosphonic acid groups or their derivatives, silane groups, siloxane groups, aryl radicals or short- or long-chain alkyl radicals. Modification reagents are used for modification. These are compounds which have at least one such additional functional group and at least one alcohol-reactive group.

Examples of alcohol-reactive groups are isocyanate groups, acid groups, acid derivatives or epoxide groups.

Compound c) can be modified prior to the polymerization by reacting at least a portion of its OH groups. This is possible either by the preparation of c) in the presence of modifying reagents or by the modification of compound c) after its preparation. Both possibilities are described in WO 2009/101 141, p. 8, Z.13 to p.9, Z.42, to which reference is hereby made. The modifying reagents can be added before or during the preparation of the polyether polyols c) starting from, for example, tri- or higher-functional alcohols. If the tri- or higher-functional alcohol or the alcohol mixture is reacted in the presence of modifying reagents in one step, a polyether polyol having randomly distributed functionalities other than hydroxyl groups is obtained.

Such a functionalization can be achieved, for example, by addition of modifying reagents which contain mercapto groups, primary, secondary or tertiary amino groups, ester groups, carboxylic acid groups or derivatives thereof, sulfonic acid groups or derivatives thereof, phosphonic acid groups or their derivatives, silver groups, Siloxan groups, aryl radicals or short or long chain alkyl radicals. Mercaptoethanol can be used as modification reagent for the modification with mercapto groups, for example.

Tertiary amino groups can be produced, for example, by incorporation of amino-containing alcohols, such as triethanolamine, tripropanolamine, triisopropanolamine, N-methyldiethanolamine, N-methyldipropanolamine or N, N-dimethylethanolamine.

By adding dicarboxylic acids, tricarboxylic acids, dicarboxylic acid esters, such as, for example, adipic acid, terephthalic acid dimethyl ester or tricarboxylic esters, it is possible to produce ester groups. Furthermore, ester groups can be obtained by reacting the OH groups with lactones, especially with caprolactone. By reaction with long-chain alkanols or alkanediols, long-chain alkyl radicals can be introduced.

The reaction with alkyl or aryl isocyanates, diisocyanates or oligoisocyanates generates corresponding urethane-containing polyethers. Subsequent functionalized dendritic polyether polyols c) are obtainable, for example, by reacting the dendritic polyether polyol in an additional process step with a modifying reagent which is reactive with the OH groups of the dendritic polyether polyol. The dendritic polyether polyols c) can be modified, for example, by adding modifying reagents containing acid, acid halide or isocyanate groups.

Acid-containing dendritic polyether polyols c) are obtainable, for example, by reacting at least a portion of the OH groups with compounds containing anhydride groups. Ester-containing dendritic polyether polyols c) are obtainable, for example, by reacting at least part of the OH groups with caprolactone. The length of the ester chains can be controlled by the amount of caprolactone used. Dendritic polyetherols c) with polyalkylene oxide chains are obtainable by reacting the dendritic polyetherols c) with alkylene oxides, for example ethylene oxide, propylene oxide, butylene oxide or mixtures thereof. An object of the invention are polymers according to the invention, wherein the dendritic polyether polyol c) comprises polyalkylene oxide chains.

The new polyurethane thickeners based on dendritic polyether polyols preferably have a large number of hydrophobic end groups, such as, for example, ethoxylated fatty residues, and therefore have a significantly higher thickening performance in comparison with the known polyurethane thickeners. d) From b) and c) different polyol

If appropriate, the polymers according to the invention in copolymerized form contain at least one compound b) different from b) and c) with a molecular weight of at least 200 g / mol, preferably at least 1500 g / mol.

Compound d) contains at least two OH groups per molecule and at least two groups selected from ether groups and ester groups.

Compound d) is preferably selected from polyetherols, polyesterols and polyesteresterols.

In one embodiment of the invention, compound d) has a number-average molecular weight M _{n of} from 1500 to 20 000 g / mol, preferably from 4000 to 12 000 g / mol. Suitable compounds d) are, for example, the polymerization products of ethylene oxide, its mixed or graft polymerization products and the polyethers obtained by condensation of polyhydric alcohols or mixtures thereof and those obtained by ethoxylation of polyhydric alcohols, amides, polyamides and aminoalcohols. Examples include polyethylene glycols, addition products of ethylene oxide with trimethylolpropane, EO-PO block copolymers, OH-terminated polyesters such as those of the polyfunctional polycaprolactone type.

Preferred compounds d) are polyether polyols. These are polyols which contain at least two OH groups per molecule and at least two functions -O- (ether groups). As a rule, these polyether polyols are so highly hydrophilic that they are water-soluble at room temperature (20 ° C.).

Particularly preferred compounds d) contain on average from 30 to 450 CH.sub.2CH.sub.2 O units (EO units) per molecule. Preferred compounds d) are therefore polyols of the general formula HO- (CH 2 -CH 2 -O) _n -H, where n can assume the values 30 to 450. These are usually condensation products of the ethylene oxide with ethylene glycol or water.

Preferred polyethylene glycols d) have a molecular weight M _n in the range from 1500 to 20 000 g / mol, more preferably from 1500 to 12000 g / mol, in particular from 4000 to 12000 g / mol.

Suitable compounds d) are also ethylene oxide-propylene oxide block copolymers such as EO-PO block copolymers of the general formula HO- (EO) _m - (PO) _n - (EO) oH, where m and o are independently integers in the range of 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 wherein m, n and o are chosen such that HO- (EO) m- (PO) _n - (EO) oH is water-soluble. In one embodiment, the polyetherols d) have a molecular weight M _n in the range of 1500 g / mol to 15000 g / mol.

In a further embodiment, the polyetherols d) have a molecular weight M _n in the range from 4000 g / mol to 12000 g / mol.

In a further embodiment, the polyetherols d) have a molecular weight M _n in the range from 200 g / mol to 1500 g / mol.

In a preferred embodiment, the polyetherols d) have a molecular weight M _n in the range of 6000 g / mol to 12000 g / mol.

In a further preferred embodiment, the polyetherols d) have a molecular weight M _n in the range from 6000 g / mol to 10000 g / mol.

In one embodiment, the polyetherols d) have a molecular weight M _n of about 10,000 g / mol.

In a further particularly preferred embodiment, the polyetherols d) have a molecular weight M _n of about 6000 g / mol.

In a further particularly preferred embodiment, the polyetherols d) have a molecular weight M _n of about 9000 g / mol.

In one embodiment of the invention, no compounds d) are used to prepare the polymers of the invention. In this way, polymers according to the invention with low melt viscosity are obtained, which can be handled well in pure form. The increase in viscosity results only after the addition of water. Thus, a readily manageable thickener precursor is first obtained, which has a thickening effect only when water is added, that is, for example when used in a cosmetic preparation. e) other compounds with isocyanate-reactive groups

If appropriate, the polymers according to the invention contain further compounds a) to d) which are different from one another in copolymerized form in the range from 1 to 9 groups which are reactive toward isocyanate groups per molecule.

Compounds having isocyanate-reactive groups are preferably selected from compounds having hydroxyl groups such as alcohols, compounds having amino groups such as amines and compounds having hydroxyl groups and amino groups such as aminoalcohols.

Examples of compounds e) having up to 8 hydroxyl groups per molecule are disclosed, for example, in EP 1584331 A1, paragraph [0039], to which reference is hereby made.

Suitable compounds e) with amino groups are, for example, ethylenediamine, diethylenetriamine and propylenediamine.

Suitable compounds e) having hydroxyl groups and amino groups are, for example, ethanolamine and diethanolamine.

A preferred embodiment of the invention are polymers according to the invention which comprise in copolymerized form

a) at least one polyisocyanate, preferably at least one diisocyanate,

b) at least one alcohol of the general formula I.

R ¹ - OR - OH (I)

in which

R ^{1 is} selected from C 6 -C 40 -alkyl, preferably C 12 -C 30 -alkyl,

R ^{2 is} selected from -CH ₂ -CH ₂ -, CH (CH 3) -CH ₂ - and mixtures thereof, preferably - 3 to 100, preferably 10 to 20,

c) at least one dendritic polyether polyol,

d) containing at least one of b) and c) different compound having a molecular weight M _n in the range of 1500 g / mol to 20,000 g / mol

i) at least two OH groups and

ii) at least two ether groups,

preferably at least one polyethylene glycol having M _n in the range of 1500 g / mol to 12000 g / mol.

a) at least one diisocyanate,

b) at least one alcohol of the general formula I.

R ¹ - OR - OH (I) in which

R ^{1 is} selected from linear and / or branched Ci2-C3o-alkyl,

R ^{2 is} -CH ₂ -CH ₂ -,

n 3 to 100,

c) at least one dendritic polyether polyol having M _{n of} at least 300 g / mol and comprising at least 5 OH groups per molecule,

d) at least one polyethylene glycol having M _n in the range of 1500 g / mol to 12000 g / mol.

The polymers according to the invention comprise components a), b) and c) preferably in the following ratios (mol to mol):

if the polymers according to the invention contain compound (d) in copolymerized form: a: b of 10: 1 to 1: 1, 9; preferably 5: 1 to 1: 1

b: c from 25: 1 to 1: 1; preferably 10: 1 to 1, 5: 1

a: d from 10: 1 to 1: 1, 9; preferably 5: 1 to 1: 1 if the polymers according to the invention do not contain d) in copolymerized form:

a: b from 1.5: 1 to 1: 1, 9; preferably 1, 2: 1 to 1: 1, 5

b: c from 25: 1 to 1: 1; preferably 10: 1 to 1.5: 1 compound e) is preferably copolymerized in such an amount that from 0 to 50 mol%, particularly preferably from 0 to 25 mol%, very particularly preferably from 0 to 10 mol% all of the isocyanate-reactive groups of components b) to e) of e).

In one embodiment, e) is copolymerized in such an amount that from 0 to 1 mol% of all isocyanate-reactive groups of components b) to e) of e) originate.

In a further embodiment, no compound e) is copolymerized.

Process for the preparation

Another object of the present invention are methods for preparing the polymers of the invention. The following describes these methods of the invention. The individual reaction steps are provided with Roman numerals. Steps with higher digits are performed in time after lower-digit steps.

To prepare the polymers according to the invention, the components a) to e) can be polymerized in the presence of a solvent other than a) to e). By "solvent" is meant a compound which is inert to a) to e), in which the starting compounds a) to e), the resulting intermediates and the polymers according to the invention are soluble. Soluble means that at least 1 g, preferably at least 10 g of the relevant compound in 1 liter of solvent under standard conditions for the human eye is clearly resolved.

Examples of suitable solvents are xylene, toluene, acetone, tetrahydrofuran (THF), butyl acetate, N-methylpyrrolidone and N-ethylpyrrolidone.

In one embodiment of the invention, the polymers according to the invention are prepared from the compounds a) to e) essentially in the absence of solvents. Substantially in the absence of solvents means that with respect to the total amount of compounds a) to e), the polymerization in the presence of less than 10 wt .-%, preferably less than 5 wt .-% of a different from a) to e) Solvent is carried out.

In principle, all catalysts customarily used in polyurethane chemistry are suitable for the preparation of the polymers according to the invention.

Such suitable catalysts and their amount, solvent and type of addition are described, for example, in WO 2009/135856, p.1 1, Z.35 to p.12, Z.42, to which reference is hereby made.

Preferred catalysts are zinc carboxylates, in particular selected from zinc 2-ethylhexanoate, zinc n-octanoate, zinc n-decanoate, zinc neodecanoate, zinc ricinoleate and zinc stearate. Especially preferred is zinc neodecanoate.

Suitable catalysts include (alkaline) salts of inorganic acid or of carboxylic acids such as potassium salts of acetic acid, citric acid, lactic acid, oxalic acid. It is preferred according to the invention for all the compounds used in the process to be substantially free of water. "Essentially anhydrous" means that the water content of all the compounds used in the process is less than 5% by weight, preferably less than 1% by weight, particularly preferably is less than 0.1 wt .-%, based on the total amount of the respective compound.

Method of removing water from the compounds before reacting with the NCO

Group-containing compounds are brought into contact, are common and known in the art.

In one embodiment of the invention, for the preparation of the polymers according to the invention

I) d) submitted,

II) the addition of a) started,

II) when reaching an NCO value in the range of 99.9 to 0.1% of the initial value, preferably from 80 to 5% of the initial value, the addition of b) and c) started approximately at the same time. In a preferred embodiment of the invention, for the preparation of the polymers according to the invention

I) d) submitted,

II) the addition of a) started,

III) upon reaching an NCO value in the range from 99.9 to 0.1% of the initial value, preferably from 80 to 5% of the initial value, the addition of b) started, IV) when an NCO value in the range of 95 is reached to 5% of the initial value, preferably 50 to 5% of the initial value, the addition of c) started. Step IV) takes place after step III).

In a further embodiment of the invention, for the preparation of the polymers according to the invention

I) the component b) submitted,

II) the addition of component a) is started,

III) upon reaching an NCO value in the range of 99.9 to 0.1% of the initial value, preferably from 80 to 5% of the initial value, very particularly preferably from 50 to 5% of the initial value, the addition of component c) started. An object of the invention is a process for the preparation of the polymers according to the invention comprising the steps

I) submitting b),

II) addition of a),

III) Beginning of the addition of c) when the NCO value is in the range from 99.9 to 0.1, preferably from 80 to 5, more preferably from 50 to 5% of the starting value.

The polymer obtainable by this particular embodiment preferably has, based on its total weight, less than 5% by weight, more preferably less than 1% by weight and in particular 0% by weight, of compound d) in copolymerized form.

The NCO value (isocyanate content) was determined titrimetrically in accordance with DIN 53185. Polymer-analogous Modification of the Polymers According to the Invention The dendritic polyether polyol c) comprises, in a preferred embodiment, free OH groups after the polymerization. These cause an increased in comparison with conventional associative thickeners solubility of the polymers of the invention in polar solvents, especially in alcohols and water. The free OH groups of the copolymerized compound c) also have a positive influence on the structure and the visual appearance of the preparations containing the polymers according to the invention. In one embodiment of the invention, in the range from 5 to 95 mol%, preferably from 25 to 75 mol%, of the OH groups originally present in c) are still present in the polymers according to the invention after the polymerization, ie not reacted.

The invention thus also relates to polymers according to the invention in which in the range from 5 to 95% of the OH groups present before the polymerization in c) are present even after the polymerization as OH groups. For certain applications sufficient thickening effect can already be achieved from a conversion of only 5 mol% of the originally present in c) OH groups, ie at 95 mol% OH groups still present.

The invention also relates to polymers according to the invention in which in the range from 75 to 95% of the OH groups present in the c) before the polymerization also exist after the polymerization as OH groups.

In another embodiment of the invention, in the range from 0 to 50 mol% of the OH groups originally present in c), they are also present in the inventive polymers.

The invention furthermore relates to polymers which are obtainable by the reaction of at least part of the free OH groups of the copolymerized compound c) of the polymer according to the invention with compounds which are reactive toward OH groups.

The polymerized-in compound c) can be modified by reacting the polymer according to the invention in an additional process step with suitable modifying reagents which can react with the OH groups of c).

The remaining OH groups of copolymerized compound c) can be modified, for example, by adding modifying reagents containing acid, acid halide or isocyanate groups. Functionalization of the copolymerized compound c) with acid groups can be carried out, for example, by reacting their OH groups with compounds containing anhydride groups. Ester groups can be subsequently introduced, for example, by reaction with caprolactone. The length of the ester chains can be controlled by the amount of caprolactone used. Furthermore, the copolymerized compounds c) can also be functionalized by reaction with alkylene oxides, for example ethylene oxide, propylene oxide, butylene oxide or mixtures thereof. The invention also provides polymers obtainable by functionalization of the polymerized-in compound c) with OH-reactive substances which, in addition to at least one group which is reactive toward OH groups, comprise further groups such as carboxylate, sulfonate, diol or polyol. The invention also provides polymers obtainable by functionalizing the polymerized-in compound c) with OH-reactive substances which, in addition to at least one group which is reactive toward OH groups, comprise sugar molecules. The invention also relates to polymers obtainable by functionalization of the polymerized-in compound c) with OH-reactive substances which, in addition to at least one group which is reactive towards OH groups, comprise polar polymer chains such as, for example, polyacrylic acid chains or polyalkylene glycol chains.

The invention also provides polymers obtainable by functionalizing the polymerized-in compound c) with OH-reactive substances which, in addition to at least one group which is reactive toward OH groups, comprise nonpolar polymer chains such as, for example, polyisobutene chains.

The invention also relates to polymers obtainable by functionalization of the polymerized-in compound c) with OH-reactive substances which, in addition to at least one group which is reactive toward OH groups, comprise silicone chains.

The invention also provides polymers obtainable by functionalization of the polymerized-in compound c) with OH-reactive substances which, in addition to at least one group which is reactive toward OH groups, comprise amphiphilic surfactant chains.

The abovementioned polymers are also obtainable by carrying out the functionalization of the copolymerized compound c) in two steps:

I) reaction of at least part of the free OH groups of the copolymerized compound c) with a polyisocyanate, preferably with a diisocyanate, more preferably with an unsymmetrical diisocyanate having 2 differently reactive NCO groups, such as, for example, isophorone diisocyanate or toluene-2, 4-diisocyanate, II) Reaction of the remaining NCO groups with NCO-reactive substances such as hydroxyl groups or preferably amino-containing substances. Functional groups such as carboxylate, sulfonate, diol, sugar, polar and non-polar polymer chains, surfactant chains can thus be bonded via a hydroxyl group or an amino group to the copolymerized, NCO-functionalized compound c).

The invention also relates to the use of the polymers according to the invention for the preparation of aqueous preparations. Preparations which contain 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 are preferred.

Preference is given to preparations containing not more than 95% by weight, more preferably not more than 90% by weight and in particular not more than 85% by weight of water. The preparations containing water may be, for example, solutions, emulsions, suspensions or dispersions.

In addition to the polymers according to the invention, further substances can be used for the preparation of the preparations, such as e.g. conventional auxiliaries (for example dispersants and / or stabilizers), surfactants, preservatives, anti-foaming agents, fragrances, wetting agents, UV filters, pigments, emollients, active ingredients, other thickeners, dyes, plasticizers, humectants and / or other polymers. Cosmetic preparations

Another object of the invention are cosmetic preparations containing at least one inventive polymer.

Preference for use in cosmetic preparations is given to polymers according to the invention which are prepared without using a tin-containing catalyst.

An advantage of the polymers according to the invention, when used in cosmetic preparations, is that their thickening performance also

1) after addition of salts or pigments in an amount of at least 1, preferably at least 2% by weight, based on the preparation,

2) up to temperatures of about 50 ° C and

3) is virtually unchanged with changes in the pH in the range of 2 to 13, respectively. Cosmetic preparations which comprise the polymers according to the invention have a more finely divided structure as compared to preparations which comprise known thickeners by reducing the particle sizes. The free OH groups attributed to the copolymerized dendritic polyetherpolyol cause a higher water solubility.

The use of polymer-like polar modified polymers according to the invention preferably leads to more stable emulsions.

An object of the present invention is the use of polymer-analogous polar modified polymers according to the invention to increase the compatibility with polar solvents such as low molecular weight monohydric alcohols such. Ethanol or low molecular weight polyhydric alcohols such as propylene glycol or glycerol.

Likewise provided by the present invention is the use of polymer-analogous polar modified polymers according to the invention for increasing the solubility of finely water-soluble ingredients such as, for example, hydrophilic UV filters. Another object of the present invention is the use of polymer-polymer polar modified polymers according to the invention for increasing the water-binding capacity in the preparation and after application to the skin (use of the polymers according to the invention as a moisturizer). Another object of the present invention is the use of the polymer analog nonpolar modified polymers of the invention to increase the compatibility with non-polar liquid phases such as cosmetic oils and silicone oils.

The present invention likewise relates to the use of polymer-analogously non-polar modified polymers according to the invention for increasing the solubility of limited oil-soluble constituents, for example hydrophobic UV filters.

A further subject of the present invention is the use of polymer-analogously modified polymers according to the invention for improving the dispersibility of particles in the preparation.

Another object of the present invention is a method for improving the feel of the skin, characterized in that the skin is brought into contact with a preparation comprising a polymer-analogous non-polar modified polymer according to the invention.

By using subsequently amphiphilic modified polymers of the invention, the theological behavior can be adjusted due to the case.

The polymers according to the invention can generally be used instead of the associative thickeners known from the prior art for cosmetic preparations. Cosmetic preparations containing an associative thickener based on polyurethane are described in detail in WO 2009/135857, p. Preparations according to the invention are the preparations described in WO 2009/135857, pp. 87 to 11, with the proviso that the preparations according to the invention contain a polymer according to this invention instead of the polyurethane thickeners designated there.

All formulations described in the publication IPCOM000181520D are also in accordance with the invention, with the proviso that the "Polymer 1" mentioned there is replaced by a polymer according to the present invention.

Also included in the invention are all preparations described in the publication IPCOM000181842D, with the proviso that the "Polymer 1" mentioned therein is replaced by a polymer according to the present invention.

All formulations described in publication IPCOM000183957D are also in accordance with the invention, with the proviso that the "polymer 1" mentioned there is replaced by a polymer according to the present invention.

Examples

The determination of the molecular weights of the inventive polymers A.1 to A.7 and the polymers according to Comparative Examples A.8 and A.9 was carried out by GPC in tetrahydrofuran as a solvent, standard: PMMA.

The determination of the molecular weight of the polyether polyol PE.1 was carried out by GPC in hexafluoroisopropanol + 0.05% trifluoroacetic acid potassium salt as solvent, standard: PMMA.

The OH number was determined in accordance with DIN 53240, Part 2.

All reactions were carried out under a protective gas atmosphere (dried nitrogen). The degree of functionalization in% indicates how many mol% of the OH groups originally present in compound c) were reacted during the polymerization.

Other percentages are always% by weight, unless otherwise stated.

Preparation of a hyperbranched polyether polyol from pentaerythritol and triethylene glycol (PE.1)

The polymerization was carried out in a 4-liter four-neck glass flask equipped with a stirrer, reflux condenser and a vacuum-assisted distillation column. The mixture of 1250.4 g of pentaerythritol (9.00 mol), 1393.3 g of triethylene glycol (9.00 mol) and 6.8 g of trifluoromethanesulfonic acid was evacuated and slowly heated to 200 ° C. by means of an oil bath at a pressure of 200 mbar. After reaching the reaction temperature, the reaction mixture was stirred for 4 h. Thereafter, the reaction mixture was allowed to cool under vacuum. For neutralization, 8.0 g of ethanolic KOH (5 molar) was added to the reaction solution and stirred for 2 hours.

Subsequently, the product was stripped at 130 ° C and a reduced pressure of up to 100 mbar for 4 h. The polyether polyol PE.1 (M _n = 510 g / mol, M _w = 3670 g / mol, OH number 675 mg KOH / g polymer) was finally obtained as a highly viscous, pale brown colored liquid.

Synthesis Example 1 Preparation of a Polymer According to the Invention Containing a Hyperbranched Polyether Polyol, Degree of Functionalization of the OH Groups 25% (A.1) 120.00 g of polyethylene glycol Pluriol E6000 ^® (BASF SE, molecular weight 6000 g / mol) were dissolved in 467.00 g of xylene under nitrogen in a 2-liter polymerization reactor (planned cut glass vessel with anchor stirrer) was dissolved. After heating the solution to about 140 ° C (internal temperature), 200 g of xylene were distilled off. The water content of the reaction mixture was then only about 100 ppm. Now, the polymer solution was cooled to 50 ° C (internal temperature) and treated with 89 mg of acetic acid dissolved in 5 ml of xylene, to neutralize the previously quantitatively determined amount of potassium acetate in polyethylene glycol. By addition of 360 mg of zinc neodecanoate (TIB ^® Cat 616, TIB Chemicals, Mannheim, Germany), dissolved in 5 ml of xylene, and 6.72 g of hexamethylene diisocyanate dissolved in 10 ml of xylene, polymerization was started, and the batch at an internal temperature of 50 ° C to an isocyanate content of 0.40%. Then 16.58 g Lutensol ^® were AT1 1 (BASF SE), dissolved in 20 ml of xylene was added and the reaction mixture while further heated to 50 ° C until the isocyanate content was 0.17%. Now, 5.85 g of the hyperbranched polyether polyol PE.1, dissolved in 20 ml of THF, were added and the reaction mixture was heated further to 50 ° C until the isocyanate content was finally 0%. The solvents xylene and THF were subsequently substantially removed by vacuum distillation at elevated temperature (about 60 ° C) (residual content <100 ppm) and the residue dissolved in 602.4 g of water. The aqueous solution of 7.52 g of the preservative Euxyl K701 ^® and 80 mg of the stabilizer 4-hydroxy-TEMPO were added subsequently. After cooling to room temperature (25 ° C), the polymer A.1 (M "= 14500 g / mol; M _w = 33200 g / mol) was obtained in the form of an aqueous dispersion having a solids content of 20.4%. The viscosity of a 10% strength aqueous solution of the branched polyether polyurethane A.1 was 15,000 mPa * s (shear rate 100 1 / s) or 7,000 mPa * s (shear rate 350 l / s).

Synthesis Example 2: Preparation of a polymer according to the invention containing a hyperbranched polyether polyol, degree of functionalization of the OH groups 50% (A.2)

120.00 g of polyethylene glycol Pluriol E6000 ^® (BASF SE, molecular weight 6000 g / mol) were dissolved in 467.00 g of xylene under nitrogen in a 2-liter polymerization reactor (planned cut glass vessel with anchor stirrer) was dissolved. After heating the solution to about 140 ° C (internal temperature), 200 g of xylene were distilled off. The water content of the reaction mixture was then only about 1 10 ppm. Now, the polymer solution was cooled to 50 ° C (internal temperature) and treated with 107 mg of acetic acid dissolved in 5 ml of xylene, to neutralize the previously quantitatively determined amount of potassium acetate in polyethylene glycol. By addition of 360 mg of zinc neodecanoate (TIB Cat 616, TIB Chemicals, Mannheim), dissolved in 5 ml of xylene, and 6.72 g of hexamethylene diisocyanate, dissolved in 10 ml of xylene, the polymerization was started and the mixture at an internal temperature of 50 ° C to an isocyanate content of 0.40%. Then the 16.58 g Lutensol ^® AT1 1 (BASF SE), dissolved in 20 ml of xylene was added and the reaction mixture while further heated to 50 ° C until the isocyanate content was 0.17%. Now, 2.93 g of the hyperbranched polyether polyol PE.1, dissolved in 20 ml of THF, were added and the reaction mixture was heated further to 50 ° C. until finally the isocyanate content was 0%. The solvents xylene and THF were subsequently largely removed by vacuum distillation at elevated temperature (about 60 ° C) (residual content <100 ppm) and the residue dissolved in 587.8 g of water. The aqueous solution of 7.35 g of the preservative Euxyl K701 ^® and 70 mg of the stabilizer 4-hydroxy-TEMPO were added subsequently. After cooling to room temperature (25 ° C), the polymer A.2 (M "= 15,000 g / mol; M _w = 39,500 g / mol) was obtained in the form of an aqueous dispersion having a solids content of 20.3%. The viscosity of a 10% aqueous solution of the branched polyether polyurethane A.2 was 25,000 mPa * s (shear rate 100 1 / s) or 12,000 mPa * s (shear rate 350 1 / s).

Synthesis Example 3 Preparation of a Polymer According to the Invention Containing a Hyperbranched Polyether Polyol, Degree of Functionalization of the OH Groups 100% (A.3)

120.00 g of polyethylene glycol Pluriol E6000 ^® (BASF SE, molecular weight 6000 g / mol) were dissolved in 467.00 g of xylene under nitrogen in a 2-liter polymerization reactor (planned cut glass vessel with anchor stirrer) was dissolved. After heating the solution to about 140 ° C (internal temperature), 200 g of xylene were distilled off. The water content of the reaction mixture was then only about 100 ppm. Now, the polymer solution was cooled to 50 ° C (internal temperature) and treated with 89 mg of acetic acid dissolved in 5 ml of xylene, to neutralize the previously quantitatively determined amount of potassium acetate in polyethylene glycol. By addition of 360 mg of zinc neodecanoate (TIB ^® Cat 616, TIB Chemicals, Mannheim, Germany), dissolved in 5 ml of xylene, and 6.72 g of hexamethylene diisocyanate dissolved in 10 ml of xylene, polymerization was started, and the batch at an internal temperature of 50 ° C to an isocyanate content of 0.40%. Then 16.58 g Lutensol ^® were AT1 1 (BASF SE), dissolved in 20 ml of xylene was added and the reaction mixture while further heated to 50 ° C until the isocyanate content was 0.16%. Then, 1.46 g of the hyperbranched polyether polyol PE.1, dissolved in 20 ml of THF, were added and the reaction mixture was heated further to 50 ° C. until finally the isocyanate content was 0%. The solvents xylene and THF were subsequently largely removed by vacuum distillation at elevated temperature (about 60 ° C) (residual content <100 ppm) and the residue dissolved in 580.5 g of water. The aqueous solution of 7.26 g of the preservative Euxyl K701 ^® and 70 mg of the stabilizer 4-hydroxy-TEMPO were added subsequently. After cooling to room temperature (25 ° C), the polymer A.3 (M "= 17100 g / mol; M _w = 42300 g / mol) was obtained in the form of an aqueous dispersion having a solids content of 21, 2% had. The viscosity of a 5% aqueous solution of the branched polyether polyurethane A.1 was 9200 mPa * s (shear rate 100 1 / s) and 4600 mPa * s (shear rate 350 1 / s).

Synthesis Example 4 Preparation of a polymer of the invention containing a hyperbranched polyether polyol of functionalization of the OH groups of 50% (A.4) 120.00 g Polyethylene glycol Pluriol E6000 ^® (BASF SE, molecular weight 6000 g / mol) were dissolved in 467.00 g of xylene under Dissolved nitrogen in a 2 liter polymerization reactor (plane glass vessel with anchor stirrer). After heating the solution to about 140 ° C (internal temperature), 200 g of xylene were distilled off. The water content of the reaction mixture was then only about 100 ppm. Now, the polymer solution was cooled to 50 ° C (internal temperature) and treated with 89 mg of acetic acid dissolved in 5 ml of xylene, to neutralize the previously quantitatively determined amount of potassium acetate in polyethylene glycol. By addition of 360 mg of zinc neodecanoate (TIB Kat 616, TIB Chemicals, Mannheim), dissolved in 5 ml of xylene, and 8.89 g of isophorone diisocyanate, dissolved in 10 ml of xylene, the polymerization was started and the approach at an internal temperature from 50 ° C to an isocyanate content of 0.40%. Then 16.58 g Lutensol ^® were AT1 1 (BASF SE), dissolved in 20 ml of xylene was added and the reaction mixture while further heated to 50 ° C until the isocyanate content was 0.17%. 2.93 g of the hyperbranched polyetherpolyol PE.1, dissolved in 20 ml of THF, were then added and the reaction mixture was heated further to 50.degree. C. until finally the isocyanate content was 0%. The solvents xylene and THF were subsequently substantially removed by vacuum distillation at elevated temperature (about 60 ° C) (residual content <100 ppm) and the residue dissolved in 596.5 g of water. The aqueous solution of 7.45 g of the preservative Euxyl K701 ^® and 80 mg of the stabilizer 4-hydroxy-TEMPO were added subsequently. After cooling to room temperature (25 ° C), the polymer was A.4 (M _n = 15100 g / mol; _Mw = 41300 g / mol) obtained in the form of an aqueous dispersion, which had a solids content of 19.8%. The viscosity of a 5% aqueous solution of the branched polyether polyurethane A.4 was 8200 mPa * s (shear rate 100 1 / s) and 3500 mPa * s (shear rate 350 1 / s).

Synthesis Example 5: Preparation of a polymer according to the invention comprising a hyperbranched polyether polyol, degree of functionalization of the OH groups 50% (A.5)

120.00 g of polyethylene glycol Pluriol E6000 ^® (BASF SE, molecular weight 6000 g / mol) were dissolved in 467.00 g of xylene under nitrogen in a 2-liter polymerization reactor (planned polished glass vessel with anchor stirrer). After heating the solution to about 140 ° C (internal temperature), 200 g of xylene were distilled off. The water content of the reaction mixture was then only about 100 ppm. The polymer solution was then cooled to 50 ° C. (internal temperature) and admixed with 89 mg of acetic acid dissolved in 5 ml of xylene in order to neutralize the previously quantitatively determined amount of potassium acetate in the polyethylene glycol. By addition of 360 mg of zinc neodecanoate (TIB Cat 616, TIB Chemicals, Mannheim), dissolved in 5 ml of xylene, and 8.89 g of isophorone diisocyanate, dissolved in 10 ml of xylene, the polymerization was started and the batch at an internal temperature of 50 ° C to an isocyanate content of 0.40%. Then a mixture of 8.29 g was Lutensol®AT1 1 (BASF SE) and 7.17 g Lutensol ^® TO10 (BASF SE), dissolved in 20 ml of xylene were added and the reaction mixture was further heated until at 50 ° C until the Isocyanate content was 0.17%. Now, 2.93 g of the hyperbranched polyether polyol PE.1, dissolved in 20 ml of THF, were added and the reaction mixture was heated further to 50 ° C. until finally the isocyanate content was 0%. The solvents xylene and THF were subsequently largely removed by vacuum distillation at elevated temperature (about 60 ° C) (residual content <100 ppm) and the residue dissolved in 589.1 g of water. The aqueous solution of 7.37 g of the preservative Euxyl K701 ^® and 70 mg of the stabilizer 4-hydroxy-TEMPO were added subsequently. After cooling to room temperature (25 ° C), the polymer was A.5 (M _n = 14900 g / mol; _Mw = 38200 g / mol) obtained in the form of an aqueous dispersion, which had a solids content of 20.4%. The viscosity of a 10% aqueous solution of the branched polyether polyurethane A.5 was 6700 mPa * s (shear rate 100 1 / s) and 4600 mPa * s (shear rate 350 1 / s).

Synthesis Example 6: Preparation of a polymer of the invention containing a hyperbranched polyether polyol of functionalization of the OH groups of 50% (A.6) 374.00 g Lutensol ^® AT25 (BASF SE) were dissolved in 374.00 g of acetone under nitrogen in a 2-liter Polymerization reactor (plane glass vessel with anchor stirrer) solved. Now, the polymer solution was heated to 50 ° C (internal temperature) and treated with 259 mg of acetic acid to neutralize the previously quantitatively determined amount of potassium acetate in Luten sol ^® . By adding 4 mg of zinc neodecanoate (TIB Cat 616, TIB Chemicals, Mannheim) and 55.58 g of isophorone diisocyanate dissolved in 55.58 g of acetone, the reaction was started and the mixture at an internal temperature of 50 ° C to an isocyanate Content of 1, 13% driven. Then, 20.78 g of the hyperbranched polyetherpolyol PE.1, dissolved in 20.78 g of acetone, and a further 1.35 g of zinc neodecanoate (TIB Cat 616, TIB Chemicals, Mannheim) dissolved in 10.00 g of acetone, were added - Added and the reaction mixture further heated to 50 ° C until the isocyanate content was finally 0%. The solvent acetone was subsequently largely removed by vacuum distillation at elevated temperature (about 60 ° C.) (residual <100 ppm) and the residue dissolved in 1000.0 g of water. The aqueous solution of 22.52 g of the preservative Euxyl K701 ^® and 230 mg of the stabilizer 4-hydroxy-TEMPO were added subsequently. After cooling to room temperature (25 ° C), the polymer A.6 (M "= 3700 g / mol; M _w = 6500 g / mol) was obtained in the form of an aqueous dispersion having a solids content of 31.2%. The viscosity of a 10% aqueous solution of the branched polyether-polyurethane A.6 was 1 160 mPa * s (shear rate 100 1 / s) and 930 mPa * s (shear rate 350 1 / s). Synthesis Example 7: Preparation of a polymer according to the invention comprising a hyperbranched polyether polyol, degree of functionalization of the OH groups 50%; Subsequently functionalized with diethanolamine (A.7)

120.00 g of polyethylene glycol Pluriol E6000 ^® (BASF SE, molecular weight 6000 g / mol) were dissolved in 467.00 g of xylene under nitrogen in a 2-liter polymerization reactor (planned cut glass vessel with anchor stirrer) was dissolved. After heating the solution to about 140 ° C (internal temperature), 200 g of xylene were distilled off. The water content of the reaction mixture was then only about 100 ppm. Now, the polymer solution was cooled to 50 ° C (internal temperature) and treated with 89 mg of acetic acid dissolved in 5 ml of xylene, to neutralize the previously quantitatively determined amount of potassium acetate in polyethylene glycol. By addition of 360 mg of zinc neodecanoate (TIB ^® Cat 616, TIB Chemicals, Mannheim, Germany), dissolved in 5 ml of xylene, and 6.72 g of hexamethylene diisocyanate dissolved in 10 ml of xylene, polymerization was started, and the batch at an internal temperature of 50 ° C to an isocyanate content of 0.41%. Then the wur- 16.58 g Lutensol ^® AT1 1 (BASF SE), dissolved in 20 ml of xylene was added and the reaction mixture while further heated to 50 ° C until the isocyanate content was 0.17%. Now, 2.93 g of the hyperbranched polyether polyol PE.1, dissolved in 20 ml of THF, was added and the reaction mixture was heated further to 50 ° C. until finally the isocyanate content was 0%. The resulting polymer solution was subsequently added a further 3.91 g of isophorone diisocyanate dissolved in 10 ml of xylene, and the mixture was driven to an isocyanate content of 0.15% in order to convert the OH groups of the already formed thickener molecule into isocyanate groups. Then, 1.85 g of diethanolamine dissolved in 10 ml of THF was added and the reaction was stopped. The solvents xylene and THF were subsequently substantially removed by vacuum distillation at elevated temperature (about 60 ° C.) (residual content <100 ppm) and the residue was dissolved in 610.9 g of water. The aqueous solution of 7.58 g of the preservative Euxyl K701 ^® and 80 mg of the stabilizer 4-hydroxy-TEMPO were added subsequently. After cooling to room temperature (25 ° C.), the polymer A-functionalized with diol groups (M _n = 13800 g / mol, M _w = 37500 g / mol) was obtained in the form of an aqueous dispersion having a solids content of 20 , 2%. The viscosity of a 10% aqueous solution of the Functionalized, branched polyether polyurethane A.7 was 36,000 mPa * s (shear rate 100 1 / s) (viscosity at shear rate 350 1 / s not measurable).

Comparative Example: Preparation of a PUR-associative thickener containing trimethylolpropane (known structure), degree of functionalization of the OH groups 100% (A.8)

120.00 g of polyethylene glycol Pluriol E6000 ^® (BASF SE, molecular weight 6000 g / mol) were dissolved in 467.00 g of xylene under nitrogen in a 2-liter polymerization reactor (planned cut glass vessel with anchor stirrer) was dissolved. After heating the solution to about 140 ° C (internal temperature), 200 g of xylene were distilled off. The water content of the reaction mixture was then only about 120 ppm. The polymer solution was then cooled to 50 ° C. (internal temperature) and admixed with 89 mg of acetic acid dissolved in 5 ml of xylene in order to neutralize the previously quantitatively determined amount of potassium acetate in the polyethylene glycol. By addition of 360 mg of zinc neodecanoate (TIB ^® Cat 616, TIB Chemicals, Mannheim, Germany), dissolved in 5 ml of xylene, and 6.72 g of hexamethylene diisocyanate dissolved in 10 ml of xylene, polymerization was started, and the batch at an internal temperature of 50 ° C to an isocyanate content of 0.40%. Then 16.58 g Lutensol ^® were AT1 1 (BASF SE), dissolved in 20 ml of xylene was added and the re- action mixture while further to 50 ° C heated until the isocyanate content was 0.18%. Then, 0.79 g of 1,1,1-tris (hydroxymethyl) propane (TMP) dissolved in 20 ml of THF was added, and the reaction mixture was further heated to 50 ° C. until finally the isocyanate content was 0%. The solvents xylene and THF were subsequently largely removed by vacuum distillation at elevated temperature (about 60 ° C) (residual content <100 ppm) and the residue dissolved in 577.1 g of water. The aqueous solution of 7.22 g of the preservative Euxyl K701 ^® and 70 mg of the stabilizer 4-hydroxy-TEMPO were added subsequently. After cooling to room temperature (25 ° C), the polymer was A.8 (M _n = 16500 g / mol; _Mw = 39500 g / mol) obtained in the form of an aqueous dispersion, which had a solids content of 20.5%. The viscosity of a 5% aqueous solution of the branched polyether polyurethane A.8 was 12500 mPa * s (shear rate 100 l / s) and 7500 mPa * s (shear rate 350 l / s).

Comparative Example: Preparation of a PU R-associative thickener containing ethylene glycol (linear structure), degree of functionalization of the OH groups 100% (A.9)

120.00 g of polyethylene glycol Pluriol E6000 ^® (BASF SE, molecular weight 6000 g / mol) were dissolved in 467.00 g of xylene under nitrogen in a 2-liter polymerization reactor (planned cut glass vessel with anchor stirrer) was dissolved. After heating the solution to about 140 ° C (internal temperature), 200 g of xylene were distilled off. The water content of the reaction mixture was then only about 100 ppm. The polymer solution was then cooled to 50 ° C. (internal temperature) and treated with 89 mg of acetic acid dissolved in 5 ml of xylene. to neutralize the previously quantitatively determined amount of potassium acetate in the polyethylene glycol. By addition of 360 mg of zinc neodecanoate (TIB ^® Cat 616, TIB Chemicals, Mannheim, Germany), dissolved in 5 ml of xylene, and 6.72 g of hexamethylene diisocyanate dissolved in 10 ml of xylene, polymerization was started, and the batch at a home temperature of 50 ° C to an isocyanate content of 0.40%. Then 16.58 g Lutensol ^® were AT1 1 (BASF SE), dissolved in 20 ml of xylene was added and the reaction mixture while further heated to 50 ° C until the isocyanate content was 0.18%. Now, 0.55 g of monoethylene glycol dissolved in 20 ml of THF was added and the reaction mixture was further heated to 50 ° C until the isocyanate content was finally 0%. The solvents xylene and THF were subsequently largely removed by vacuum distillation at elevated temperature (about 60 ° C) (residual content <100 ppm) and the residue dissolved in 575.9 g of water. The aqueous solution of 7.20 g of the preservative Euxyl K701 ^® and 70 mg of the stabilizer 4-hydroxy-TEMPO were added subsequently. After cooling to room temperature (25 ° C), the polymer A.9 (M "= 14300 g / mol; M _w = 33500 g / mol) was obtained in the form of an aqueous dispersion having a solids content of 19.9%. The viscosity of a 10% aqueous solution of the branched polyether polyurethane A.9 was 27000 mPa * s (shear rate 100 1 / s) (viscosity at shear rate 350 1 / s not measurable).

Cosmetic preparations based on Cremophor ^® A6 / Cremophor ^® A25 or stearic rat containing the polymers A.1 to A.9 according to Examples (Preparations FA.1.1 - FA.1.9 and FA.2.1 -FA.2.9)

The cosmetic preparations were prepared by adding the water phase B to the oil phase A and then adding the obtained O / W emulsion with the preservative (phase C). The ^® on a Cremophor A6 / A25 basis based formulations were obtained FA.1 -FA.1 .1 .9 (Tab. 1) and based on a stearate based formulations FA.2.1 -FA.2.9 (Tab. 4).

The amounts given for the polymers according to the invention of Examples A.1 -A.9 in the formulations FA.1.1 -FA.1 .9 (Tab.1) and FA.2.1-FA.2.9 (Tab.4) give the amounts of polymer again. Table 1 . Recipe parameters for the Cremophor ^® on a A6 / A25 based-based cosmetic formulations FA.1.1 -FA.1 .9.

Phase Ingredients FA.1 .1 -1.9 ^*

Phase A Cremophor ^® A 6 2.0 g

Cremophor ^® A 25 2.0 g

Lanette ^® 0 2.5 g

Paraffin oil 5.0 g Luvitol ^® EHO 5.0 g

Phase B each one of the polymers A.1 -A.9 0.5 g

1, 2-propylene glycol 5.0 g

Water 77.5 g

Phase C Euxyl K300 ^® 0.5 g

^* FA.1 .8, FA.1.9 are not according to the invention

Table 2. Viscosities of thickeners A.1 -A.9 in water, as a function of the shear rate.

^* not according to the invention

* not according to the invention

Structure in Comparative Example FA.1 .8 very poor (gritty) despite high viscosity. The polymer according to the invention with completely reacted OH groups A.3 achieves the highest viscosity (30.0 Pa * s), ie the same value as polymer A.8. The corresponding preparation FA.1 .8, however, has a much worse structure; the structure of the preparation FA.1 .3 is significantly better due to the copolymerized hyperbranched polyether polyol.

The corresponding linear comparison structure A.9 gives a viscosity (FA.1.9) of 20.0 Pa * s and is thus comparable to the viscosity of the polymer A.2 (FA.1.2) with 19.2 Pa * s. The decisive advantage of the polymer A.2 according to the invention compared to A.9 is comparable viscosity in the possibility of functionalization and tailoring of the polymer architecture, since even 50% of the originally present OH groups of copolymerized compound c) are present as OH groups.

Table 4. Recipe parameters for the stearate-based cosmetic formulations FA.2.1 -FA.2.9.

^* FA.2.8, FA.2.9 are not according to the invention

Table 5. Viscosities of the cosmetic formulation en FA.2.1 -FA.2.9

Viscosity [Pa * s]

formulation

in the presence of 2.0% NaCl

FA.2.1 6,8

FA.2.2 9.0

FA.2.3 8,7

FA.2.4 5.7

FA.2.5 10.0

FA.2.6 not determined

FA.2.7 7.1

FA.2.8 ^* 9.0 FA.2.9 ^* 4.4

^* not according to the invention

Structure in Comparative Example FA.2.8 very poor (gritty) despite high viscosity.

Here, the structures A.2, A.3 (according to the invention) and A.8 (not according to the invention) allow similar viscosities of the cosmetic preparations of about 9 Pa * s. The polymer A.2 according to the invention can be subsequently modified in contrast to A.8. The structure of the preparation obtainable with polymer A.3 is significantly better than that obtained with A.8. Application examples:

In the following, further typical preparations according to the invention are described, but without limiting the invention to these examples.

In addition to the preparation of the cosmetic preparations described here, the polymers A.1, A.2, A.3, A.4, A.5, A.6 or A.7 as well as combinations thereof of the respective emulsion can also be obtained after combination of water and oil phase at 60-80 ° C or the cooled emulsion at about 40 ° C are added.

The invention also relates to the subsequent addition of the polyurethanes obtainable according to the invention to a cosmetic preparation in order to adjust the desired viscosity.

The percentages are% by weight, unless expressly stated otherwise.

O / W 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

Glycerine 3.0 5.50 4.50 5.00 3.5

Polymer A.1 3.0 1, 5 0.8 2.0 2.5

Hydroxyethyl acrylates / sodium Acryloyldimethyl Tau¬

1, 0 0.5

rate copolymer, squalane,

Polysorbate 60

B Glyceryl Stearate Citrate 1, 80 2.00 3.00 1, 50 2

Sucrose stearates 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 Triglycerides 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 acryloyldime

C 0.5 0.1

ethyl taurate / VP copolymer

Carbomer 0.05 0.1 D Sodium Hydroxide 0.02 0.04

E 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

production:

Heat phases A and B separately to approx. 80 ° C. Stir phase C into phase B and then stir in phase A in phase B / C and briefly homogenize.

Add phase D (if needed) and cool to about 40 ° C while stirring. Add the components of phase E successively to the emulsion and cool to room temperature while stirring. Homogenise briefly.

Instead of the O / W emulsion comprising polymer A.1, O / W emulsions containing one or more of the polymers A.2, A.3, A.4, A.5, A.6 or A.7 are also prepared.

Hydro dispersion

Phase Ingredient / 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 dicaprylate / dicaprate 4.0 2.0 1, 0

Dicapryl carbonate 2.0 3.0 4.0

Cyclopentasiloxanes, cyclohexasi-

2.0 0.5 loxanes

Simmondsia chinensis (jojoba)

2,0 0,5

Seed oil

Shea Butter 2.0 1, 0

Hydrogenated polyisobutenes 3.0 1, 0 7.0 0.5 2.0

Squalane 2,0 0,5

Vitamin E Acetates 0.50 0.25 1, 00

B acrylate / C10-30 alkyl acrylate

0.3 0.1 0.2 0.15 0.2 Crosspolymer

C Aqua ad 100 ad 100 ad 100 ad 100 ad 100

Polyacrylamide, C13-14 Isoparaf¬

1, 0 1, 5 0.75 fin, Laureth-7

Polymer A.1 2.5 2.0 0.9 1, 5 3.0

Propylene Glycol 3.00 5.0 2.5 7.50 10.0

D Sodium hydroxides 0.12 0.04 0.08 0.06 0.08 E niacinamide 0.30 3.0 1, 5 0.5 0.20

Aqua 2.0 10.0 5.0 2.0 2.0

F DMDM Hydantoin 0.60 0.45 0.25

Methylparaben 0.50 0.25 0.15

Phenoxyethanol 0,50 0,40 1, 00

Ethylhexylglycerol 1.00 0.80

Ethanol 3.00 2.00 1, 50 7.00

G fragrance 0.20 0.05 0.40

production:

Heat phases A and C separately to approx. 80 ° C.

Stir phase B into phase A and then phase C into phase A / B. Homogenize briefly. Add phase D and cool to about 40 ° C. while stirring. Add phase E and cool to about 30 ° C while stirring. Add phase F and G to the emulsion and cool to room temperature while stirring. Homogenise briefly.

Instead of the hydrodispersion comprising polymer A.1, hydrodispersions comprising one or more of the polymers A.2, A.3, A.4, A.5, A.6 or A.7 are also prepared.

Solid-stabilized emulsion

Phase Ingredient / 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 isononanoates 9.0 9.0 6.0 5.0 8.0

Isohexadecane 9.0 5.0 4.0 8.0

Dimethicone 0.5 2.0 1, 0 1, 5

Cera microcristallina, paraffin

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 Octenylsucci

2.0 1, 0 0.5

nate

Tapioca strength 0.5

B Titanium dioxide, coated 1, 0 0.5 3.0 2.0 4.0

Zinc oxide 5.0 10.0 2.0 3.0

C ammonium acryloyldimethyltaurate / beheneth-25 methacrylate 0.2 1, 0.5

Crosspolymer

D Aqua ad ad 100 ad 100 ad 100 ad 100

100

Hydroxypropyl methylcellulose 0.1 0.05 Sorbitol 5.0 7.0 7.0 3.0 4.5

Polymer A.1 3.0 5.0 0.9 1, 4 2.0

E 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

production:

Heat phase A to 80 ° C. Place phase B in phase A and homogenize for 3 min. Stir in phase C.

Pre-swell cellulose (if needed) in water, then add the remaining ingredients of phase D and heat to 80 ° C.

Stir phase D into phase A + B + C and homogenize. Cool the emulsion to about 40 ° C. with stirring and add phase E and F. Cool to RT while stirring and homogenize.

Instead of the solids-stabilized emulsion comprising polymer A.1, solid-stabilized emulsions containing one or more of the polymers A.2, A.3, A.4, A.5, A.6 or A.7 are also prepared. Sunblock

Phase Ingredient / 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

Butylene glycol 3.00 7.50 8.0 7.50 5.00

Benzophenone-4 2,0 4,0

Phenylbenzimidazole sulfone

0.50 4,00 8,0 acid

Triethanolamine 1, 0 0.25 2.0 2.0 4.0

Panthenol 0.5 0.75 1, 0

Polymer A.1 2.5 g 0.5 g 2.0 g 4.0 1, 5

Xanthan gum 0.3 0.15 0.2

B Octocrylene 8.0 7.5

Ethylhexyl methoxycinnamate,

Diethylamino hydroxybenzoyl 5.0 10.0 8.0 3.0 7.0 hexyl benzoates

Steareth-21 2.0 3.0 2.5

Steareth-2 1, 5

PEG-40 Stearate 1, 0 2.0

Glycerol 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 hexadecenes copolymer 0.20 0.20 0.80 0.8 1.00

Bisabolol 0.2 0.1 0.3 c DMDM Hydantoin 0.5 0.5 0.5 0.5 0.75

Water, Aloe Barbadensis Leaf

0.5 1, 0

Juice

Tocopheryl Acetate 0.60 0.5 0.4 0.25 0.3

Perfume 0.10 0.25 0.30 0.40 0.20

production:

Heat phases A and B separately to approx. 80 ° C.

Stir phase A into phase B and homogenise briefly.

Cool with stirring to about 40 ° C. Add the components of phase C to the emulsion in succession and cool to room temperature while stirring. Homogenise briefly.

Instead of the sunscreen cream containing polymer A.1, sunscreen creams containing one or more of the polymers A.2, A.3, A.4, A.5, A.6 or A.7 are also prepared.

silicone emulsion

Phase Ingredient / 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 6.0 3.0 2.0 8.0 5.0

Polymer A.1 3.5 1, 0 0.5 5.0 2.0

Xanthan Gum 0.1 0.15

Imidazolidinyl urea 0.3 0.2

B Cetyl PEG / PPG-10/1 Di¬

2.5 3.5 0.5 2.0 2.5 methicone

PEG-9 Dimethicone 1, 0 1, 5 2.0 0.5

PEG-14 Dimethicone 0.5 2.0 2.5

PEG-1 1 methyl ether Di¬

1, 5 3.0 0.8 0.5

methicone

Polyglyceryl-3 disiloxanes

1, 0 2.0 0.5

Dimethicone

Cyclopentasiloxanes, caprolyl dimethicone ethoxy 0.5 5.0 2.5 3.5 glucosides Phenyl Trimethicone 5.0 3.0 1, 5 7.5

Polymethylsilsesquioxanes 2.0 1, 5 1, 0 0.5

Cyclopentasiloxanes, cyclo-

5.0 3.0 8.0 10.0 hexasiloxane

Cetyl Dimethicone 1, 5 1, 0 2.5 3.0 4.0

Paraben mixture 0.2 0.2 0.2 0.2 0.2 c sodium citrate 0.15 0.15 0.15 0.15 0.15

Monosodium Citrate 0.05 0.05 0.05 0.05 0.05

D Bisabolol 0.2 0.5 0.15 0.3 0.1

Fragrance 0.1 0.05 0.05 0.1 0.15

manufacturing

Heat phases A and B separately to approx. 80 ° C.

Stir phase A into phase B and homogenize.

Stir phase C into phase A + B and homogenize.

Cool with stirring to about 40 ° C. Add phase C and cool to about 30 ° C. while stirring. Add phase D. Cool to room temperature while stirring and homogenize briefly.

Instead of the silicone emulsion comprising polymer A.1, silicone emulsions containing one or more of the polymers A.2, A.3, A.4, A.5, A.6 or A.7 are also prepared.

Hydroxy cream

Phase Ingredient / INCI 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 stearates

Polyglyceryl-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

B Panthenol 1, 0 0.5 0.3

Propylene Glycol 3.0 2.0 5.0

Polymer A.1 1, 0 3.0 5.0

Hydroxy acid 3.0 7.0 10.0

Aqua ad 100 ad 100 ad 100 c Sodium hydroxides qsqsqs

D 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

Di-hydroxy acid: tartaric acid

Beta hydroxy acid: Salicylic acid pH value> 3

manufacturing

Heat phase A and B separately to approx. 80 ° C. If necessary, adjust the pH of phase B to> 3 with NaOH. Stir phase B into phase A, homogenize briefly. Cool to about 40 ° C with stirring, add the components of phase D in succession, homogenize again. Instead of the hydroxycarboxylic acid cream containing polymer A.1, hydroxycarboxylic creams containing one or more of the polymers A.2, A.3, A.4, A.5, A.6 or A.7 are also prepared.

Emulsion with deodorant active ingredient

Phase Ingredient / INCI 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 Cas-

0.5 1, 0 2.0

tor oil

Glyceryl Stearate 0.5 2.0 1, 0

Cetyl Alcohol 2.0 1, 0 0.5 2.5 0.2

Hydrogenated Coco

2.0 1, 0 0.5 glycerides

Hydrogenated polyisobutene

10.0 20.0 5.0 3.0 ne

Decyl Oleate 3.0 2.0 8.0 5.0

Bis-PEG / PPG-14/14 dimethicone, cyclopentasilo- 3.0 3.5 4.0 2.0 1, 5 xane

Tale 3.0 2.5 1, 5

Magnesium Aluminum Sili

1, 0 0.5 1, 0 1, 5 cate B propylene glycol 10.0 5.0 7.5 20.0 15.0

Polymer A.1 0.5 1, 0 3.0 3.5 2.0

Xanthan gum 0.2 0.1 0.05

Cetyl hydroxyethyl cellulose 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

C neutralizing agent q.s. q.s. q.s. q.s. q.s.

D 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.

manufacturing

Heat phases A and B separately to approx. 80 ° C.

Stir phase B into phase A while homogenizing. If necessary adjust with Phase C to pH 4-5. Cool to about 40 ° C, add the phase D and allow to cool to room temperature while stirring. Homogenise briefly.

Note: Adjust the pH of the emulsion to 4-5

Instead of the emulsion with deodorant active ingredient containing polymer A.1, emulsions with deodorant active ingredient containing one or more of the polymers A.2, A.3, A.4, A.5, A.6 or A.7 are also prepared.

depilatory creme

Phase Ingredient / INCI 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 l, 2.0 cot) Kernel Oil

B Propylene Glycol 1, 0 2.0 10.0

Calcium Carbonates 10.0

Calcium hydroxides 7.0

Sodium hydroxides 0.4 0.6

Calcium thioglycolate 5.0 3.0 5.0 Polymer A.1 3.0 1, 5 2.0

Aqua ad 100 ad 100 ad 100 c tocopherol 0.1 0.2 0.15

Bisabolol 0.2 0.1 0.3

Fragrance q.s. q.s. q.s.

manufacturing

Heat phase A and B separately to approx. 80 ° C.

Stir phase B into phase A while homogenizing, briefly homogenize.

Cool to about 40 ° C, add phase C, cool to RT with stirring and homogenize again.

Note: Adjust the pH of the emulsion to> 10

Instead of the depilatory cream containing polymer A.1 depilatory creams containing one or more of the polymers A.2, A.3, A.4, A.5, A.6 or A.7 are also prepared.

Conditioner Shampoo

Ingredient / INCI F.1 1.1 F.1 1.2 F.1 1.3 F.1 1.4

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 Cocoamphodiace-

10.0

tate

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-glucosides, glyceryl

5.0

Oleate

Dimethicone 2.0

Conditioning polymer 2.0 0.5 0.75 0.4

Polymer 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 qsqsqsqs dye qsqsqsqs

Sodium Chloride 1, 0 1, 0

Conditioning polymer is understood to mean polyquaternium-7, PQ-10, PQ-16, PQ-39, PQ-44, PQ-46, PQ-67, guar hydroxypropyltrimonium chlorides, PQ-87, and combinations thereof.

Instead of the conditioner shampoo containing polymer A.1, conditioner shampoos containing one or more of the polymers A.2, A.3, A.4, A.5, A.6 or A.7 are also prepared.

Hair Conditioner

By conditioning polymer is meant polyquaternium-7, PQ-10, PQ-16, PQ-39, PQ-44, PQ-46, PQ-67, guar hydroxypropyltrimonium chlorides, PQ-87 and combinations thereof. manufacturing

Heat phases A and B separately to approx. 80 ° C.

Stir phase C into phase B, then stir in phase A in phase B / C and briefly homogenize.

Cool with stirring to about 50 ° C, add the components of phase D in succession and cool to about 30 ° C with stirring. Add the components of phase E in succession and cool to RT while stirring. Homogenise briefly.

Instead of the hair conditioner containing polymer A.1, hair conditioners containing one or more of the polymers A.2, A.3, A.4, A.5, A.6 or A.7 are also prepared.

Claims

claims

1 . Polymer containing in copolymerized form

a) at least one polyisocyanate

b) at least one alcohol of the general formula I.

O-R-OH (I) where

R ^{1 is} selected from C ₆ -C ₄₀ -alkyl, C ₆ -C ₄₀ -alkenyl, C ₃ -C 10 -cycloalkyl, C ₆ -C ₃₀ -aryl, C ₇ -C ₄₀ -arylalkyl,

c) at least one dendritic polyether polyol,

d) optionally containing at least one of b) and c) different compound having a molecular weight of at least 300 g / mol

i. at least two OH groups and

ii. at least two groups selected from ether groups and ester groups,

e) optionally further compounds having in the range of 1 to 9 isocyanate-reactive groups per molecule.

Polymer according to claim 1, wherein c) is obtainable by condensation of at least one tri- or higher-functional alcohol and optionally further di- and / or monofunctional alcohols and / or modifying reagents with the aid of acidic catalysts.

Polymer according to one of claims 1 to 2, wherein c) is the condensation product of on average at least 3 di-, tri- or higher functional alcohols.

Polymer according to one of claims 1 to 3, wherein c) has a number average molecular weight M _n of at least 300 g / mol.

A polymer according to any one of claims 1 to 4, wherein c) is or comprises polyglycerol.

A polymer according to any one of claims 1 to 5, wherein the polymer is water-soluble or water-dispersible.

A polymer according to any one of claims 1 to 6, wherein in the range from 5 to 95% of the OH groups present in c) before the polymerization, also after the po- lymerisation present as OH groups.

8. Polymer according to one of claims 1 to 7, wherein b) comprises a Ci2-C3o-alcohol, which is ethoxylated with 3 to 100 moles of ethylene oxide per mole.

9. A polymer according to any one of claims 1 to 8, wherein d) is or comprises a polyethylene glycol having a molecular weight M _n in the range of 1500 to 12000 g / mol. 10. A polymer obtainable by reacting at least a portion of the free OH groups of a polymer according to claims 1 to 9 with compounds reactive toward OH groups.

1 1. A process for producing a polymer according to any one of claims 1 to 10, comprising the steps

I) submitting d),

II) addition of a),

III) beginning of the addition of b) when the NCO value is in the range of 80% to 5% of the initial value, and

IV) Beginning of the addition of c) when the NCO value is in the range of 50 to 5% of the initial value.

12. A process for the preparation of a polymer according to any one of claims 1 to 10 comprising the steps

I) submitting b),

II) addition of a),

III) Beginning of the addition of c) when the NCO value is in the range of 80 to 5% of the initial value. 13. Use of a polymer according to any one of claims 1 to 10 as a thickener for aqueous preparations.

14. Cosmetic preparation containing at least one polymer according to one of claims 1 to 10.