WO2010072456A1

WO2010072456A1 - Use of star-shaped polymers having peripheral negatively charged groups and/or peripheral silyl groups for finishing surfaces

Info

Publication number: WO2010072456A1
Application number: PCT/EP2009/064515
Authority: WO
Inventors: Paula Barreleiro; Haitao Rong; Oliver Bedford; Danuta Bedrunka; Daniela Kropp
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2008-12-23
Filing date: 2009-11-03
Publication date: 2010-07-01
Also published as: DE102008063070A1

Abstract

The invention relates to the use of star-shaped polymers having peripheral negatively charged groups and/or peripheral silyl groups and to the use of oligomers of said star-shaped polymers for finishing surfaces, particularly by application in washing and cleaning agents, and to star-shaped polymers having negatively charged peripheral groups and oligomers of said star-shaped polymers and to coatings based on such oligomers.

Description

"Use of star-shaped polymers having peripheral negatively charged groups and / or peripheral silyl groups to finish surfaces"

The present invention relates to the use of star-shaped polymers having peripheral negatively charged groups and / or peripheral silyl groups and to the use of oligomers of such star-shaped polymers for finishing surfaces, in particular by use in detergents and cleaners, and star-shaped polymers having negatively charged peripheral groups and oligomers of these star-shaped polymers and coatings based on such oligomers.

Star-shaped polymers, especially those with hydrophilic arms, have already been described in various publications.

US Pat. No. 5,003,193A1 and DE10330560.2 describe star-shaped polymers having on average at least four hydrophilic arms which carry reactive functional groups at their free ends. As reactive groups here are called isocyanate, (meth) acrylic, oxirane and carboxylic acid ester groups. The star-shaped polymers are used here to form crosslinking reactions hydrogel coatings on surfaces and thereby in particular to effect bacteriostatic finishing of surfaces.

WO2007 / 096056 describes star-shaped polymers having at least three hydrophilic arms which carry reactive alkoxy-silyl groups at their free ends. Again, the star-shaped polymers are used to form hydrogel coatings on surfaces through crosslinking reactions.

According to the invention, it has now surprisingly been found that star-shaped polymers having hydrophilic arms and peripheral negatively charged groups and / or peripheral silyl groups and oligomers of such star-shaped polymers are outstandingly suitable for removing dirt, in particular fat, from surfaces, in particular textiles. Particularly suitable in this case are polymers with hydrophilic arms and negatively charged peripheral groups.

A first subject of the present invention are therefore star-shaped polymers, characterized in that they carry at least one peripheral negatively charged group.

Another object of the present invention are therefore also oligomers or polymers star-shaped polymers, characterized in that at least a part of the star-shaped polymers of the oligomers or polymers are modified by peripheral negatively charged groups. According to the invention, a star-shaped polymer is understood as meaning a molecule which has a central branching unit to which are attached arms which comprise polymer units. The polymeric units of the star-shaped polymer are preferably hydrophilic units, so that the individual arms of the star-shaped polymer preferably each have hydrophilic properties.

A preferred subject of the present invention is therefore a star-shaped polymer having a multilayer structure, from inside to outside comprising: a) a central branching unit, b) at least three, preferably from 3 to 20, hydrophilic arms, c) at least one peripheral negatively charged group at least one of the hydrophilic arms.

In a preferred embodiment, at least one reactive peripheral group, preferably a group -Si (OR ') ₃ , is likewise present on at least one of the hydrophilic arms, the radicals R' being, independently of one another, hydrogen or C 1. ₆ alkyl.

Another preferred subject matter of the present invention are therefore also oligomers or polymers of star-shaped polymers which comprise the abovementioned star-shaped polymers according to the invention and / or consist exclusively of such star-shaped polymers according to the invention.

The central branching unit of star-shaped polymers according to the invention is preferably a low-molecular weight organochemical central unit or an inorganic oxidic nanoparticle.

The low molecular weight organochemical central unit is preferably a polyol having at least 3, preferably 3 to 20, particularly preferably 3 to 10, in particular 3, 4, 5, 6, 7, 8, 9 or 10, OH groups which in the branched molecule preferably form the linkage to the hydrophilic arms. These may in particular be ether or ester bonds. The polyol may in particular be a monomeric or oligomeric and optionally reduced sugar molecule. The polyol may in this case in particular be selected from glycerol, trimethylolpropane, threitol, erythritol, pentaerythritol, arabitol, adonite, xylitol, sorbitol, mannitol, dulcitol, arabinose, ribose, xylose, glucose, mannose, galactose, fructose, rhamnose, fucose, sucrose, Maltose, trehalose, cellobiose, melibiose and gentiobiose. Instead of polyols, any other branching units with reactive groups can also be used, which can be converted into branched molecules by reaction with molecules having complementary reactive groups.

The inorganic oxide nanoparticle is preferably a silica, zinc oxide, alumina, zirconia, calcium carbonate, titania, carbon, magnesia or iron oxide nanoparticle. The nanoparticles are either commercially available or are in-situ or ex-situ, preferably by sol-gel method, precipitation from aqueous and non-aqueous solution, gas phase synthesis (flame pyrolysis, chemical vapor deposition, etc.), mechanical processing (eg grinding, ultrasound ) produced. With particular preference, these have a size of 0.5 to 200 nm, very particularly preferably 0.5 to 20 nm.

In the case of using oxidic nanoparticles as the central unit, the polymer arms are preferably attached via hydrolyzable silyl end groups to the nanoparticle surface. However, attachment may also be via other surface reactive groups such as carboxyl groups, cationic groups (e.g., trialkylammonium groups), phosphonate groups, etc. Particularly suitable for introducing the polymer arms on the nanoparticles are linear polyoxyalkylene diols, the two OH groups of which are reacted with silanes which are reactive toward OH groups, such as, for example, isocyanatosilanes. Other suitable compounds for introducing polymer arms onto the nanoparticle include polyether polyol, for example, VORANOL®, TERRALOX®, SYNALOX® and DOWFAX® from Dow-Chemical Corporation, SORBETH® from Glyco-Chemicals Inc., GLUCAM® from Amerchol Corp., or Lupranol® and Pluronic® from BASF.

The peripheral negatively charged group according to the invention is preferably a unit which comprises 1-5, preferably 3, 4 or 5, acid groups. The acid groups of the peripheral units are preferably selected from carboxylic acid and sulfonic acid groups, more preferably from carboxylic acid groups. The peripheral unit may be corresponding to the carboxylic acid or sulfonic acid group itself. In a preferred embodiment, however, it is a low molecular weight unit comprising at least one, preferably at least two, more preferably 1 to 5, especially 2 to 5, in particular 2, 3, 4 or 5 carboxylic acid and / or sulfonic acid units , In a particularly preferred embodiment, the peripheral unit contains at least one, preferably at least two, particularly preferably 1 to 5, especially 2 to 5, in particular 2, 3, 4 or 5 acetate units. In a most preferred embodiment, the peripheral moiety is an ethylene diamine triacetate moiety covalently attached to one of the arms of the star polymer via one of its nitrogen atoms. The peripheral negatively charged group in a preferred embodiment according to the invention is linked to the hydrophilic arms via a silyl radical having 1 to 20 Si units, the silyl radical preferably being a unit of the formula

where R is independently selected from C- | _6- alkyl, especially methyl or ethyl, and C- |. ₆ alkoxy, in particular methoxy and ethoxy, and o can assume a value of 0 to 20. Preferably, o assumes a value of 0 to 10, more preferably of 0 to 5, in particular a value of 1, 2 or 3, to.

In a particularly preferred embodiment according to the invention, the peripheral negatively charged group is a silyl group of the general formula (I)

-CR ^a ₂ -Si (OR ^b ) _r (R ^c ) ₃ - _r (I),

in which

R ^{a is} hydrogen or C- |. _6- alkyl,

R ^{b is} -Si (R ^d ) _t (R ^e ) ₃ _-t

R ^c d ₆ alkyl, C- |. ₆ -alkoxy or hydroxy, preferably C-. ₆ -alkoxy or hydroxy,

R ^{d is} a negatively charged group,

R ^e d- ₆ alkyl, C- |. ₆ -alkoxy or hydroxy, preferably C-. ₆ -alkoxy or hydroxy, r is an integer from 1 to 3, preferably 1, t is a number from 1 to 3, preferably 1.

R ^d preferably represents a moiety comprising 1-5, preferably 3, 4 or 5, acid groups, in particular carboxylic acid groups.

Particularly preferably, R ^{d is} a group -TUVW, where

T is a bivalent CI_ ₆ alkyl radical, preferably ethyl, propyl or butyl group,

U is N-CH ₂ -COOH,

V for a divalent C | |. _6- alkyl radical, preferably ethyl, propyl or butyl,

W stands for N (-CH ₂ -COOH) ₂ . In a particularly preferred embodiment according to the invention, the star-shaped polymer according to the invention is a molecule of the general formula (II)

_n (R ² -Y ² -A ² -X ² -) Z (-X ¹ -A ¹ -Y ¹ -R ¹ ) _m (II)

wherein

Z stands for the low molecular weight central unit, which is the maximum number of arm of the star-shaped

Determines polymers,

A ¹ and A ² independently of one another represent a hydrophilic polymer arm,

X ¹ , X ² , Y ¹ and Y ² independently of one another for a chemical bond or a bivalent, low molecular weight organic, optionally containing hetero atoms radical preferably

1 to 50, in particular 2 to 20 C atoms,

R ¹ for the aforementioned silyl group of the general formula (I)

-CR ^a ₂ -Si (OR ^b ) _r (R ^c ) ₃ - _r (I)

where R ^a , R ^b and R ^{c have} the meanings given above,

R ^{2 is} OH or a group crosslinkable with substrates, entities and / or self-crosslinkable groups, and m and n are each integers, where m> 1 and n> 0 and m + n can assume a value of 3 to 500,000 , and the m X ¹ -A ¹ -Y ¹ -R ¹ groups and the n X ² -A ² -Y ² -R ² groups may each independently have different meanings.

In the case where the central unit is a low-molecular weight organochemical central unit, m + n preferably has a value of 3 to 100, in particular 3 to 50, particularly preferably 3 to 20, in particular 3 to 10, above all a value of 3, 4, 5, 6, 7, 8, 9 or 10, to.

In a preferred embodiment, m + n here coincides with the number of arms of the star-shaped polymer. However, depending on the manufacturing conditions, it is also possible that complete conversion has not occurred. In this case it is possible that about only 90 or 95% or possibly also a smaller percentage of the arms of the central unit have a structure of the formula (R ² -Y ² -A ² -X ² -) or (-X ¹ -A ¹ -Y ¹ -R ¹ ), so that the sum of m + n is correspondingly smaller in this case. In the event that the central unit is an inorganic oxide nanoparticle, m + n preferably assumes a value of 3 to 500,000, in particular 5 to 250,000, especially 10 to 100,000.

In a particular embodiment n is 0, with the arms of the star-shaped polymer being completely peripherally modified with negatively charged groups. In the case n> 0, the ratio n / m moves between 99/1 and 1/99, preferably 49/1 and 1/49, and especially 9/1 and 1/9.

In a particularly preferred embodiment, m = 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 and n = 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9 and m + n = 3, 4, 5, 6, 7, 8, 9 or 10.

Very particular preference is therefore given to the following combinations of m and n (m / n):

(3/0), (4/0), (5/0), (6/0), (7/0), (8/0), (9/0), (10/0), (2 / 1), (3/1), (4/1), (5/1), (6/1), (7/1), (8/1), (9/1), (1/2 ), (2/2), (3/2), (4/2), (5/2), (6/2), (7/2), (8/2), (1/3), (2/3), (3/3), (4/3), (5/3), (6/3), (7/3), (1/4), (2/4), (3 / 4), (4/4), (5/4), (6/4), (1/5), (2/5), (3/5), (4/5), (5/5 ), (1/6), (2/6), (3/6), (4/6), (1/7), (2/7), (3/7), (1/8), (2/8), (1/9).

In the case of the hydrophilic arms of the star-shaped polymer according to the invention, and in particular those of residues A ¹ and A ² , these are preferably units which comprise and / or consist of hydrophilic polymer units, the hydrophilic polymer units preferably being selected from poly-C ₂ -C ₄ -alkylene oxides, polyoxazolidones, polyvinyl alcohols, homopolymers and copolymers which contain at least 50% by weight of N-vinylpyrrolidone in copolymerized form, homo- and copolymers containing at least 30% by weight of acrylamide and / or methacrylamide copolymerized, homopolymers and copolymers containing at least 30 wt .-% of acrylic acid and / or methacrylic acid in copolymerized form. Polymer arms which consist of polyethylene oxide or ethylene oxide / propylene oxide copolymers are particularly preferred. If the very particularly preferred ethylene oxide / propylene oxide copolymers are used, a propylene oxide content of at most 60% by weight, preferably at most 30% by weight and particularly preferably 10-25% by weight, is recommended.

The hydrophilic arms preferably have a molecular weight of 500 to 30,000 g / mol, more preferably from 1000 to 25,000 g / mol, especially from 2000 to 20,000 g / mol, in particular from 2000 to 5000 g / mol or from 15,000 to 20,000 g / mol. Examples of divalent, low molecular weight organic radicals which may be X ¹ , X ² , Y ¹ and Y ² are aliphatic, heteroaliphatic, araliphatic, heteroaraliphatic, cycloaliphatic, cycloheteroaliphatic and aromatic and heteroaromatic radicals. The low molecular weight radicals can be linear or branched and in particular comprise nitrogen atoms and carbonyl groups. Particularly preferred are short-chain aliphatic and heteroaliphatic radicals. Examples of suitable radicals are the radicals -ethyl, propyl, -butyl, -aminoethyl, -aminopropyl, -aminobutyl, -N- (2-aminoethyl) (3-aminopropyl) -, -3-methacryloxypropyl- , Methacryloxymethyl, -3-acryloxypropyl, -3-isocyanatopropyl, - isocyanatomethyl, -butyraldehyde, -3-glycidoxypropyl, -propylsuccinic anhydride, -chloromethyl, -3-chloropropyl and -hydroxymethyl.

The radical R ² is preferably selected from the group consisting of isocyanate radicals, (meth) acrylate radicals, oxirane radicals, alcoholic OH groups, primary and secondary amino groups, thiol groups and silane groups, oxazoline groups, carboxylic acid groups, carboxylic ester, lactone , Lactam, carboxylic anhydride groups, carboxylic acid and sulfonic acid halide groups, active ester groups, free-radically polymerizable C =C double bonds, eg. B. in addition to the above (meth) acrylic groups and vinyl ether and vinyl ester groups, further activated C = C double bonds, activated C≡C triple bond and N = N double bonds with allyl groups in the sense of an ene reaction or with conjugated diolefin - React groups in the sense of a Diels-Alder reaction. Examples of groups which can react with allyl groups in the sense of an ene reaction or with dienes in the sense of a Diels-Alder reaction are maleic acid and fumaric acid groups, maleic acid ester and fumaric acid ester groups, cinnamic acid ester groups, propiolic acid (ester) groups, Maleic acid amide and fumaric acid amide groups, maleimide groups, azodicarboxylic acid ester groups, and 1, 3,4-triazoline-2,5-dione groups. In a particularly preferred embodiment according to the invention is the radical R ² is a group -Si (OR ') _3, wherein R' is hydrogen or independently of one another CI_ ₆ alkyl.

The star-shaped polymer of the coatings of the invention preferably has a number average molecular weight in the range of 1000 to 100,000, more preferably 2000 to 50,000 and most preferably 5,000 to 30,000 g / mol. The star-shaped polymer further preferably contains at least 0.05% by weight, more preferably at least 0.1% by weight and most preferably at least 0.15% by weight of silicon.

In a preferred embodiment according to the invention, star-shaped polymers according to the invention are characterized in that at least 5%, preferably at least 10, 20 or 25%, in particular at least 30, 40 or 50% of the hydrophilic arms, a peripheral negatively charged group, in particular a radical R ¹ , is bound.

In a further preferred embodiment according to the invention star-shaped polymers according to the invention are characterized in that at least 5%, preferably at least 10, 20 or 25%, in particular at least 30, 40 or 50% of the hydrophilic arms a radical R ² , in particular a group is bonded -Si (oR ') _3, wherein R' is hydrogen or independently of one another CI_ ₆ alkyl.

The preparation of the star-shaped polymers according to the invention is preferably carried out by functionalization of suitable star-shaped polymer precursors in analogy to known functionalization processes of the prior art.

The polymer precursors of the polymers according to the invention are preferably in turn star-shaped polymers which already have the above-described star-shaped structure, ie at least three hydrophilic polymer arms, and which at the ends of the polymer arms each have a suitable functional group R ³ , in the aforementioned reactive groups Y ¹ -R ¹ or Y ² -R ² can be converted in a single or multi-stage process.

Examples of possible functional groups R ³ include OH groups bound to aliphatic or aromatic carbon atoms, thiol groups, primary or secondary amine groups and halogen atoms such as chlorine, bromine or iodine. A particularly preferred precursor relates to the primary and secondary OH groups, the so-called star-shaped polyether polyols. These polymer precursors are prepared by polymerization of the appropriate monomers using multifunctional small molecules such as sorbitol, glycerol or sucrose as initiator and may optionally be further modified to generate at their ends a group -R ^{3 of the} invention. Due to the statistical nature of the polymerization reaction, the above information on the polymer arms of the polymers according to the invention, in particular with regard to the arm length, the number of arms and the values of m and n, are to be understood as a statistical average.

As starting materials for the conversion of the end groups R ^{3 of} the star-shaped polymer precursor into the groups Y ¹ -R ¹ and Y ² -R ² are generally all functional silane derivatives in question, which have a functional group which opposite to the end groups of Polymer precursor is reactive. Examples are amino silanes such as (3-aminopropyl) triethoxysilane and N- (2-aminoethyl) (3-aminopropyl) trimethoxysilane, (meth) acrylate silanes such as (3-methacryloxypropyl) trimethoxysilane, (methacryloxymethyl) triethoxysilane (methacryloxymethyl) methyldimethoxysilane and (3- Acryloxypropyl) trimethoxysilane, isocyanato-silanes such as (3-isocyanatopropyl) trimethoxysilane, (3-isocyanatopropyl) triethoxysilane, (isocyanatomethyl) -nethyl-dinethoxysilane and (isocyanato-methyl) -trinnethoxysilane, aldehyde-silanes such as triethoxysilylundecanal and

Triethoxysilyl butyraldehydes, epoxy silanes such as (3-glycidoxypropyl) trimethoxysilane, anhydride silanes such as 3- (triethoxysilyl) propylsuccinic anhydride, halo-silanes such as chloromethyltrimethoxysilane, 3-chloropropylmethyldinnethoxysilane, hydroxylsilanes such as hydroxymethyltrietoxysilanes, and tetraethylsilicate (TEOS), which are commercially available from, for example, Wacker Chemie GmbH (Burghausen), Gelest, Inc. (Morrisville, USA) or ABCR GmbH & Co. KG (Karlsruhe) are available or can be prepared by known methods. Particular preference is given to reacting isocyanato silanes or anhydride silanes with hydroxy-terminated (R ³ = OH) star-shaped polymers. Complete conversion of all hydroxy ends with isocyanatosilanes gives star-shaped polymers of the invention which carry exclusively peripheral silane radicals. The groups Y ¹ and Y ² in such a case contain a urethane group and the atomic group which is in the starting isocyanatosilane between the isocyanato group and the silyl group. In a complete reaction of all hydroxy endings with anhydride silanes, for example 3- (triethoxysilyl) propylsuccinic anhydride, star-shaped polymers according to the invention are likewise obtained which carry exclusively peripheral silane radicals. The groups Y ¹ and Y ² in such a case contain an ester group and the atomic group which is in the starting anhydride silane between the anhydride group and the silyl group.

In a further step, the reaction of this intermediate can now be carried out into star-shaped polymers having peripheral negatively charged groups by reacting the peripheral silyl groups obtained in the preceding step completely or partially with a negatively charged group which also comprises a reactive group with the silyl groups can be reacted reactively. The reactive group is again preferably a silyl group. In a particularly preferred embodiment, the compound is N- [trimethoxysilylpropyl] -ethylenediaminetriacetic acid trisodium salt.

If star-shaped polymers of the general formula (II) according to the invention are prepared which carry both Y ¹ -R ¹ and Y ² -R ² groups, this can be achieved by negative in the above-mentioned further reaction step for the introduction of the peripheral charged group only a partial reaction takes place, so that unreacted silyl groups remain as crosslinkable radicals R ² in the molecule in addition to the peripheral negatively charged groups R ¹ . In a particular embodiment, not all R ³ groups of the polymer precursor are reacted, but only a part. In this way, functional OH groups are retained in the molecule. This is the special case that the radical R ² coincides with the radical R ³ . The hydrophilic arms modified with silyl groups can now themselves be completely or partially modified with negatively charged groups. If only a part of the silyl groups are modified with negatively charged groups, a mixture of different radicals R ^{2 is obtained} , the radicals R ^{2 being formed} by hydroxyl groups and silyl groups.

Another object of the present invention are derivatives of the star-shaped polymers according to the invention, which are obtained by reaction of the groups R ² with the abovementioned Entites. Entities are foreign materials of organic, inorganic or natural origin. The term "entity" is further explained below under "Coatings".

In the oligomers or polymers of star-shaped polymers according to the invention in which at least some of the star-shaped polymers have been modified by peripheral negatively charged groups, in a preferred embodiment these are those in which the star-shaped polymers in the oligomer or polymer each have a (R 'O) ₂ Si-O-Si (OR') ₂ bridge, wherein the radicals R 'are independently hydrogen or C |. _6- alkyl, bridged with each other, the peripheral ends of hydrophilic arms of different star-shaped polymers linked together.

In order to obtain starting from star-shaped polymers according to the invention oligomerization or polymerization of star-shaped polymers according to the invention, the star-shaped polymers are characterized in a preferred embodiment - as already described above - by additionally having peripheral reactive groups in addition to the peripheral negatively charged groups crosslink themselves and / or can react to form a covalent bond, so that the formation of oligomers or polymers of inventive star-shaped polymers is possible.

In a preferred embodiment according to the invention, oligomers or polymers of star-shaped polymers according to the invention are also distinguished by the fact that at least some of the star-shaped polymers contain peripheral reactive groups in addition to peripherally negatively charged groups; in a preferred embodiment, the reactive groups are those of Formula -Si (OR ') ₃ , wherein the radicals R' are independently hydrogen or C |. ₆ alkyl. Alternatively, oligomers or polymers of star-shaped polymers according to the invention, in which at least some of the star-shaped polymers of the oligomer or polymer are modified by peripherally negatively charged groups, can also be obtained by initially using star-shaped polymers which do not yet have negatively charged groups, however reactive groups which can crosslink with themselves and / or react to form a covalent bond. Free, ie not yet reacted, reactive groups can be reacted in a subsequent step or simultaneously during the oligomerization or polymerization step with molecules which carry reactive groups and negative charges, so that polymers or oligomers according to the invention are formed.

A further subject of the present invention is therefore a process for preparing oligomers or polymers of star-shaped polymers according to the invention, which are characterized in that at least some of the star-shaped polymers of the oligomer or polymer are modified by peripherally negatively charged groups, comprising the following steps: a) star-shaped polymers Polymers having hydrophilic arms and peripheral reactive groups are initially charged and reacted so that oligomers or polymers of these star-shaped polymers are formed by crosslinking reactions. B) Free reactive groups of the oligomers or polymers according to (a) are reacted with molecules having reactive groups and negative groups Carry loads.

Another object of the present invention is the use of a star-shaped polymer or an oligomer or polymer of two or more star-shaped polymers or of any mixtures of such molecules for finishing fabrics, characterized in that it is in the star-shaped polymer and at least part of the star-shaped polymers of the oligomer or polymer to molecules having a multilayer structure, from inside to outside comprising a) a central branching unit, b) at least three, especially 3 to 20, hydrophilic arms, c) at least one peripheral negatively charged group and / or at least one peripheral group of the formula -Si (OR ') ₃ , where the radicals R' are independently hydrogen or C- | ₆ alkyl, on at least one of the arms.

In a preferred embodiment, the oligomer or polymer here is exclusively from star-shaped polymers having a central branching unit, hydrophilic arms and at least one peripheral negatively charged group and / or at least one peripheral group Formula -Si (OR ') ₃ , wherein the radicals R' are independently hydrogen or C |. ₆ alkyl, constructed.

Preferably, furthermore, the star-shaped polymers in the oligomer or polymer are via a - (R'O) ₂ Si-O-Si (OR ') ₂ bridge, where the radicals R' independently of one another are hydrogen or C ₁ . _6- alkyl, bridged together, the peripheral ends of hydrophilic arms of different star-shaped polymers linked together.

In a further preferred embodiment, at least 10%, in particular at least 20, 30 or 50%, particularly preferably at least 60, 70 or 80%, in particular at least 90 or 95%, of the arms, in particular all arms, of the star-shaped polymer have peripheral negatively charged groups and / or peripheral groups of the formula -Si (oR ') _3, wherein R' is hydrogen or independently of one another CI_ ₆ alkyl, to.

In a most preferred embodiment, at least 10%, preferably at least 20 or 30%, of the arms have peripheral negatively charged groups.

Also in this embodiment, the hydrophilic arms preferably comprise groups selected from poly-C ₂ -C ₄ -alkylene oxides, polyoxazolidones, polyvinyl alcohols, homo- and copolymers which contain at least 50 wt .-% of N-vinylpyrrolidone in copolymerized form, homo- and Copolymers containing at least 30 wt .-% acrylamide and / or methacrylamide in copolymerized form, homopolymers and copolymers containing at least 30 wt .-% of acrylic acid and / or methacrylic acid in copolymerized form.

Also in this embodiment, the peripheral negatively charged group is preferably a group comprising 1-5 acid groups.

Also in this embodiment, in a preferred embodiment, the peripheral negatively charged group is linked to the hydrophilic arm via a silyl moiety having 1 to 20 Si units, with the silyl moiety preferably being one unit

wherein the radicals R are independently selected from Ci_ ₆ alkyl and Ci_ ₆ - alkoxy and o can assume a value of 0 to 20. In a particularly preferred embodiment, the peripheral group is a silyl group R ^{3 of} the general formula

-CR ^a ₂ -Si (OR ^f) _s (R ^c) ₃ - _s (IM),

in which

R ^{a is} hydrogen or C _1-6 -alkyl,

R ^{f is} hydrogen, C _1-6 -alkyl or -Si (R ^d ) _t (R ^e ) ₃ -t,

R ^c is d- ₆ alkyl, CI_ ₆ alkoxy or hydroxy,

R ^{d is} a negatively charged group,

R ^e is de-alkyl, CI_ is ₆ alkoxy or hydroxy, s is a number from 1 to 3, t is a number from to 3. 1

In a preferred embodiment, at least one radical R ^{f stands} for a group - Si (R ^d ) _t (R ^e ) ₃ _-t .

In another preferred embodiment, R ^{d is} a group comprising 2 to 4 carboxylic acid groups.

In a particularly preferred embodiment, R ^{d is} a group -TUVW, where

T is d-e-alkyl,

U is N-CH ₂ -COOH,

V for d_ ₆ alkyl,

W stands for N (-CH ₂ -COOH) ₂ .

In a further very particularly preferred embodiment, a previously mentioned star-shaped polymer according to the invention or a previously mentioned oligomer or polymer of star-shaped polymers according to the invention is used to finish the textile fabrics.

In a further very particularly preferred embodiment, a mixture of different star-shaped polymers is used to finish the textile fabrics, wherein preferably a mixture of such star-shaped polymers is used in which the sum m + n is 3, 4 or 5, preferably 3 such star-shaped polymers is used, in which the sum m + n is 7.8 or 9, preferably 8. Another The present invention therefore also provides such inventively preferred mixtures of star-shaped polymers.

The finishing of the textile fabrics is carried out according to the invention preferably for reducing the adhesion of fat, in particular lipstick or skin fat, on the finished textile fabrics. Another particular subject of the present invention is therefore the use of molecules according to the invention for the removal of greasy stains, in particular for the removal of lipstick or for the removal of skin fat, in particular textile fabrics and in particular in detergents and cleaners.

Detergents and cleaners

Another preferred subject of the invention are detergents and cleaners containing molecules of the invention and the use of molecules according to the invention in detergents and cleaners.

In the context of the invention, detergents and cleaners in the broadest sense are surfactant-containing preparations in solid form (particles, powders, etc.), semi-solid form (pastes, etc.), liquid form (solutions, emulsions, suspensions, gels, etc.) and gas-like form. Aerosols, etc.), which may contain any type of surfactant, with regard to a beneficial effect in the application, usually in addition to other components that are customary for the particular application. Examples of such surfactant-containing preparations are surfactant-containing detergent formulations, surfactant-containing cleaners for hard surfaces, or surfactant-containing Aviviermittelzubereitungen, each of which may be solid or liquid, but may also be present in a form comprising solid and liquid components or subsets of the components side by side.

The detergents and cleaners may contain constituents usually contained, for example surfactants, in particular anionic, nonionic, cationic and / or amphoteric surfactants, builders, in particular inorganic and organic builders, other polymers (for example those with co-builder properties), foam inhibitors, dyes, fragrances (perfumes ), Bleaching agents (such as peroxy bleach and chlorine bleach), bleach activators, bleach stabilizers, bleach catalysts, enzymes, enzyme stabilizers, grayness inhibitors, optical brighteners, UV absorbers, soil repellents and soil release polymers, binding and disintegration (auxiliary) medium, electrolytes, non-aqueous solvents, pH adjusters, perfume carriers, fluorescers, thickeners, hydrotropes, foam inhibitors, silicone oils, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives ierungsmittel, corrosion inhibitors, antistatic agents, Bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, textile softening components, in particular esterquats, heavy metal complexing agents, abrasives, fillers and / or blowing agents.

With regard to inventively preferably employable builders (builders), surfactants, fabric softening components, in particular esterquats, polymers, bleaches, bleach activators, bleach catalysts, solvents, thickeners, optical brighteners, grayness inhibitors, wrinkle inhibitors, antistatic agents, glass corrosion inhibitors, corrosion inhibitors, "soil repellents", dye transfer inhibitors, Foam inhibitors, abrasives, disintegrating (auxiliary) agents, Acidifizierungsmitteln, dyes, fragrances, antimicrobial agents, UV absorbers and blowing agents and their preferred amounts used reference is made to the published WO2008 / 107346 and WO2009 / 071451.

Liquid and solid detergents are preferred embodiments of the invention. Also particularly preferred are detergents and cleaners which are suitable for delicate washing or gentle treatment of sensitive textiles.

Furthermore, textile care products, especially textile aftertreatment agents, preferably textile conditioners, fabric softeners or dryer sheets, are also particularly suitable embodiments according to the invention.

Coatings and other embodiments

Another object of the present invention are coatings which can be prepared from one another and with the surface of the substrate to be coated crosslinkable star-shaped polymers, wherein the star-shaped polymers have at least three, preferably 3 to 20, hydrophilic polymer arms on one part prior to their crosslinking their free ends peripheral silyl end groups R ^{1 of} the following general formula (I)

-CR ^a ₂ -Si (OR ^b ) _r (R ^c ) ₃ - _r (I)

wear, where

R ^{a is} hydrogen or C _1-6 -alkyl,

R ^{b is} -Si (R ^d ) _t (R ^e ) ₃ _-t

R ^c is C-ι- ₆ alkyl, CI_ ₆ alkoxy or hydroxy, preferably CI_ ₆ alkoxy or hydroxy, group,

R ^{d is} a negatively charged group,

R ^e is C-ι- ₆ alkyl, CI_ ₆ alkoxy or hydroxy, preferably CI_ ₆ alkoxy or hydroxy, r is a number from 1 to 3, preferably 1, t is a number from 1 to 3, preferably 1.

More preferably, R ^d represents a group -TUVW, wherein T d- ₆ alkyl, preferably ethyl, propyl or butyl group, U represents N-CH ₂ -COOH,

V is C-ι- ₆ alkyl, preferably ethyl, propyl or butyl, W is N (CH ₂ -COOH) is _second

For the production of coatings according to the invention, preference is given to using the abovementioned star-shaped polymers according to the invention, in particular star-shaped polymers of the formula (II).

The wettability of the coatings according to the invention with water is a sensitive measure of their hydrophilicity or hydrophobicity. The contact angle of a water droplet on a planar substrate in the surrounding medium air results from the surface energies of the coating and the water as well as the interfacial energy between water and the coating according to the Young's equation. In the case of maximum hydrophilicity, the contact angle approaches 0 °. In the case of maximum hydrophobicity, the contact angle approaches 180 °. In practice, the advancing contact angle and the receding contact angle are often measured dynamically by means of a Wilhelmy balance according to DIN EN 14370. Ideally, the difference between the two should be zero. In reality, there is a difference, also called contact angle hysteresis, which is attributed to surface roughness, inhomogeneities and impurities. The smaller the value of the hysteresis, the better the coating "wears off" from adhering water when pulling out a coated substrate from the water-containing test vessel.

Preferably, the coatings according to the invention have both a progressive and a withdrawing water contact angle of at most 90 °, more preferably at most 60 ° or 55 °, particularly preferably at most 50 ° or 40 ° and very particularly preferably at most 30 °.

Particular preference is given to coatings according to the invention whose dynamic contact angle hysteresis in water, measured according to DIN EN 14370 by means of a Wilhelmy balance, is not more than 15 °, more preferably at most 10 ° and most preferably at most 5 °. However, in further preferred cases, contact angle hysteresis of at most 2 °, 3 ° or 4 ° and less is achieved.

In a particular embodiment, the coating according to the invention additionally contains foreign materials of organic, inorganic or natural origin, which are simply referred to below as entities. An entity is preferably selected from the group consisting of biologically active substances, pigments, dyes, fillers, silicic acid units, nanoparticles, organosilanes, biological cells, receptors or receptor-bearing molecules or cells and physically incorporated in the coating and / or on this or in this covalently bound.

Examples of such entities are bioactive materials such as drugs, biocides, oligonucleotides, peptides, proteins, signaling agents, growth factors, cells, carbohydrates and lipids, inorganic components such as apatites and hydroxylapatites, quaternary ammonium salt compounds, compounds of bisguanidines, quaternary pyridinium salt compounds, compounds of phosphonium salts, thiazoylbenzimidazoles , Sulfonyl compounds, salicylic compounds or organometallic and organometallic compounds. Preference is given to antibacterial substances such as, for example, peptides, metal colloids and quaternary ammonium and pyridinium salt compounds.

Another essential group of entities are organically functionalized silanes (organosilanes) of the type (R ^' ) _{1 +} xSi (OR ^" ) ₃ _.x (x = 0, 1 or 2). Characteristic of this is the simultaneous presence of silicic acid ester groups (US Pat. OR ^" ), which hydrolyze in aqueous solution to silanol groups capable of condensation (Si-OH), as well as of hydrolysis-stable Si-R ^' bonds on the same silicon atom, the latter hydrolysis-stable bond usually being present in a covalent Si-C single bond. Often, the said functionalized silanes are low molecular weight compounds, but also oligomeric or polymeric compounds fall under the term "organically functionalized silanes", it is essential that in the same molecule both silanol-hydrolyzable Si-OR ^" groups and non-hydrolyzable Si-R ^' Groups are present. As a result of the generally organic R ^' groups of the functionalized silanes, it is possible to incorporate the entire range of additional chemical functionalities in the coatings described here. For example, cationic adhesive groups (eg, --NR ^'" ₃ ⁺ groups), anionic adhesive groups (eg, -SO ₃ ^" ), redox active groups (eg, quinone / hydroquinone residues), dye groups (eg, azo dye molecules, stilbene based brighteners), groups with biological / pharmacological Effectiveness (for example, also saccharide or polysaccharide molecular units, peptides or protein units and others organic structural motifs) groups for the covalent attachment to substrates (e.g., epichlorohydrin residuals, cyanuric chloride cystine / cysteine residues and the like), groups having a bactericidal activity (for example, NR ^'_"3 ⁺ groups with very long ^R'" alkyl), catalytically active groups (for example Transition metal complexes with organic ligands) are incorporated in this way in the layer. Other groups introduced via the radical R ^' include, for example, epoxy, aldehyde, acrylate and methacrylate groups, anhydride, carboxylate or hydroxy groups. The functionalities described here are not to be understood as a complete listing in terms of a selection of examples. The organosilanes therefore serve not only as a crosslinking aid, but at the same time as a functionality distributor. This gives directly a hydrogel coating according to the invention with desired functionalities.

Entities also include nanoparticulate metal or semimetal oxides. For example, those of silicon, zinc, titanium, aluminum, zirconium are suitable. In particular, silica particles with a diameter of about 1 to 500 nm are preferred. Such SiO ₂ particles, including their surface-modified or -functionalized derivatives, can contribute to improving the mechanical properties of the layers.

Another group of entities are inorganic pigments. The coatings according to the invention having reactive silyl groups readily bind to them via stable covalent bonds. If a hydrogel according to the invention, ie a coating according to the invention which is mixed with pigments, is applied to a surface on which the hydrogel can bind, the result is bound, pigmented surface coatings. If organic pigments are to be incorporated into the hydrogel, or if adhesion of the hydrogel to organic surfaces is to be ensured, organosilanes with corresponding adhesion groups (for example cationic groups as described above) can be incorporated into the coating according to the invention. In this way, means and methods are possible by which pigments can be well anchored, for example, on hair. If, for example, mica or effect pigments (pearlescent pigment) are applied to hair, special optical effects on hair are made possible ("glitter hair"). By using colored inorganic or organic pigments (for example lapis lazuli, pyrolopyrroles), particularly intensive or stable hair colors are obtained.

The incorporation of the entities is preferably carried out by co-adsorption from solutions containing the star-shaped prepolymer and / or the star-shaped prepolymer-nanoparticle complex and the foreign constituent. In addition, the star-shaped prepolymers and / or prepolymer-nanoparticle complexes can be chemically reacted with said bioactive materials be reacted on the surface as a mixture with unmodified star-shaped prepolymers and / or prepolymer-nanoparticle complexes. Of course, it is also possible to selectively apply the foreign substances by physisorption or chemisorption on the finished hydrogel coating according to the invention.

The substrates to be coated with the coatings according to the invention are fundamentally subject to no restrictions. The substrates may have regular or irregularly shaped, smooth or porous surfaces.

Suitable surface materials include glassy surfaces such as glass, quartz, silicon, silica or ceramics, or semiconductor materials, metal oxides, metals and metal alloys such as aluminum, titanium, zirconium, copper, tin and steel. Also composites such as glass fiber reinforced or carbon fiber reinforced plastics (GRP, CFRP), polymers such as polyvinyl chloride, polyethylene, polymethylpentenes, polypropylene, generally polyolefins, elastomeric plastics such as polydimethylsiloxane, polyesters, fluoropolymers, polyamides, polyurethanes, poly (meth) acrylates and copolymers, blends and composites The aforementioned materials are suitable as substrates. In addition, cellulose and natural fibers such as cotton fibers, wool and hair can be used as substrates. But even mineral surfaces, such as paints or grout material can serve as substrates. For polymer substrates, it is advisable in some cases to pretreat the surfaces. Particularly preferred substrate materials are glassy or generally inorganic surfaces, since in these directly a connection via relatively hydrolysis-stable bonds, for example Si-O-Si, or Si-O-Al takes place and thus a surface preparation is not necessary. If, as described above, direct formation (hydrolysis-stable) covalent bonds between the hydrogel and the substrate succeeds, that is, for example in the presence of organic substrate surfaces (Si-O-C bonds are hydrolysis-labile), then the attachment can be advantageously achieved by addition of organofunctional silanes which are via adhesion groups have taken place. Suitable adhesive groups are for example cationic trimethylammonium groups or amino groups. By the simultaneous presence of reactive siloxyl groups, these functional groups are incorporated into the hydrogel and become, as it were, an integral, covalently bound component of the coating.

In particular, in the field of glass, ceramic, plastic and metal substrates offers, for example, an application in the equipment of showers, windows, aquariums, glasses, dishes, sinks, toilets, work surfaces, or kitchen appliances, such as refrigerators or cookers with a light cleanable temporary or permanent equipment that allows for complete drainage of water, as well as repels proteins and bacteria. Another object of the present invention is a process for preparing the coatings of the invention on a substrate, wherein a solution of a star-shaped polymer according to the invention is applied to the substrate to be coated, and before, simultaneously or subsequently an at least partial crosslinking reaction of the reactive groups with each other and / or with the substrate takes place.

The process is preferably carried out with the star-shaped polymers of the general formula (II).

In a preferred embodiment of the method according to the invention, before, during and / or after the application of the solution of the star-shaped polymer to the substrate to be coated, a foreign material, for example an entity selected from the group consisting of biologically active substances, pigments, dyes, fillers, silicic acid units , Nanoparticles, organosilanes, biological cells, receptors or receptor-bearing molecules or cells, or precursors of the aforementioned entity are brought into contact with the star-shaped polymers. The introduced entities may be physically embedded in the network of crosslinked star-shaped polymers or ionically bound to the surface of the coating by van der Waals or hydrogen bonds, or chemically bonded via covalent bonds, preferably via reactive end groups of the star-shaped polymer.

For example, if silicic acid units are introduced into the coating as entities, this may be accomplished by mixing a solution of the star-shaped polymers with a hydrolyzable silica precursor, such as a tetraalkoxysilane (eg, tetraethoxyorthosilane; TEOS), preferably in the presence of a catalyst such as an acid, or the like Base, done. The weight ratio of SiO _{2 of} the introduced silica units based on the polyethylene / polypropylene oxide content in the coating is preferably 0.01 to 100, more preferably 0.5 to 50, and most preferably 1 to 10. The attachment of the silica units to the star-shaped Polymer can be carried out via van der Waals bonds, ionically or via hydrogen bonds. Preferably, however, the bond is covalently via a -C-Si-O-Si constellation (detection Raman or IR) to reactive end groups of the star-shaped polymers used in the coatings of the invention.

If the bond takes place via silyl groups, this can take place in the coating via hydrogen bonds or via ionic interaction. However, covalent -Si-O- Si bridges preferred (detectable by IR). The effect of the TEOS within the layer can be understood as a crosslinking effect, wherein layers without crosslinker (TEOS) are usually more hydrophilic, that is, characterized by a lower contact angle, for example in the range of 30 °. In general, it can be said that the incorporation of additional crosslinkers, for example TEOS or functional alkoxysilanes, represents a further possibility for individually adjusting the properties of the coatings.

The ultra-thin hydrogel coatings are applied to the substrate, for example, by depositing the star-shaped polymer by conventional methods on the surface to be coated from a solution of the polymers which may already be partly precrosslinked therein and simultaneously or subsequently crosslinking the reactive groups with each other and with the substrate surface.

In general, all known coating methods can be used. Examples include dip coating, spin coating, polishing and spraying. In order to achieve the desired properties of the surface layer, the coating measures will be selected so that the coating thickness, preferably does not exceed a value of 500 .mu.m, more preferably 200 .mu.m and most preferably 100 .mu.m. Depending on the application, a coating must simultaneously meet many different requirements in terms of, for example, mechanical properties, water wetting and wetting behavior, protein and bacteria repellency, and the like. In many cases, especially in the household sector, an ultrathin or thin layer with a layer thickness of 0.1 to 100 nm, in particular of 1 to 50 nm is often sufficient to achieve the desired effects, while in applications, for example due to a high mechanical Claiming the surface, thicker layers with a layer thickness of, for example, 50-500 microns are desired, and for some applications, such as those that provide for the presence of nanoparticles in the coating, larger layer thicknesses such as 1000 microns may be desired. In contrast to other hydrophilic hydrogel coatings known from the prior art, the hydrophilicity of the hydrogel coatings of the invention remains largely uninfluenced by the layer thickness. In other words, the dirt, protein and cell repellency properties are retained independent of the thickness of the layer.

To prepare the solution of the star-shaped polymer for the process according to the invention for producing a coating on a substrate, all solvents which have little or no reactivity with the reactive end groups of the star-shaped polymer are generally suitable. Examples are water, alcohols, water / alcohol mixtures, aprotic solvent or mixtures thereof. Examples of suitable aprotic solvents are, for example, ethers and cyclic ethers such as tetrahydrofuran (THF), dioxane, diethyl ether, tert-butyl methyl ether, aromatic hydrocarbons such as xylene and toluene, acetonitrile, propionitrile and mixtures of these solvents. If star-shaped prepolymers having OH, SH, carboxyl, (meth) acrylic and oxirane groups or similar groups are used as end groups, protic solvents such as water or alcohols, for example methanol, ethanol, n-propanol, 2-propanol, n-propanol Butanol and tert-butanol, as well as their mixtures with aprotic solvents. If star-shaped prepolymers with isocyanate groups are used, water and mixtures of water with aprotic solvents are suitable in addition to the abovementioned aprotic solvents. Preferably, the solvent is water or a mixture of water with aprotic solvents.

Suitable amounts of the star-shaped polymer in the application mixtures used in the coating process according to the invention depend on the layer thicknesses which are most suitable for the respective application. Frequently, amounts of, for example, about 0.005 to 50 wt .-%, preferably 0.1 to 10 wt .-% of. Depending on the affinity of the substrate and the nature of the application, it is also possible to use both application mixtures with a higher or even lower content of star-shaped polymers. The application mixtures may for example also have the form of pastes or creams.

embodiments

Example 1: Preparation of a triethoxysilyl-terminated polyether polyol

The polyether polyol used consists of a 3-arm random poly (ethylene oxide-co-propylene oxide) (glycerol-started) and an 8-arm polyether polyol (cane sugar-started).

The polymer arms are each random poly (ethylene oxide-co-propylene oxides) with an EO / PO-

Ratio of about 75/25. The OH functionality averages 6.9 (by

Endgruppenbestimmung determined), resulting in an average number average

Molecular weight of about 12,000 g / mol. The result is a ratio of 78 wt .-% of 8-arm polyether polyol to 22 wt .-% of 3-armed polyether polyol. The polyether-polyol

Mixture was obtained from DOW Chemicals (Voranol® 4053). Before the reaction, the polyether polyol was heated in vacuo with stirring for 1 h at 80 ⁰ C.

To the dried polyether polyol (209 g, 16.9 mmol) was added (3-isocyanatopropyl) triethoxysilane

(30.3 g, 1, 0 eq.) Was added. The reaction mixture was further stirred under inert gas at 90 ⁰ C until the vibrational band of the NCO group has disappeared in an IR measurement. This gives a product in which in each case a triethoxysilyl group at the free ends of Polymer arms of the two star-shaped prepolymers is present. The product is a colorless viscous liquid.

Example 2: Preparation of a hydrolyzate of the star-shaped polymer of Example 1 The star-shaped polymer (20 g) obtained in Example 1 was dissolved in EtOH (380 ml). To this mixture was added a mixture of 10 ml of acetic acid and 10 ml of distilled water. After two days of stirring at room temperature, one obtained hydrolyzate of the star-shaped polymer with a concentration of about 5% of active substance.

Example 3: Preparation of an anioic modified hydrolyzate of the star-shaped polymer of Example 1

The star-shaped polymer (20 g) obtained in Example 1 was dissolved in EtOH (380 ml). To this mixture was added a mixture of 10 ml of acetic acid and 10 ml of distilled water. After stirring for two days at room temperature, an anioic silane (10 g, N- [trimethoxysilylpropyl] -ethylenediaminetriacetic acid trisodium salt, based on ABCR, 45% in water), water (380 ml) and acetic acid (20 ml) were added. After further stirring at room temperature, a mixture of mixed hydrolyzate with a concentration of about 2.5% of active substance

Example 4: Washing test

A detergent composition comprising:

Fatty alcohol polyethylene oxide 7.0%

LAS 9.0%

Coconut Fatty Acid 4.0%

Boric acid 1, 0%

Citric acid 2.0%

Propylene glycol 6.0%

PTPMP 0.2%

NaOH 3.1%

Protease 0.8%

Amylase 0.1%

Water rest

was mixed in each case with 2 wt .-% of nonionic star polymer according to Example 2 and with anionic star polymer according to Example 3. Subsequently, pure cotton textiles were washed with these detergent compositions as well as for comparison with a detergent composition without the addition of star polymers. For the washing tests, a washing machine Miele W 918 Novotronic was used. Washed according to the standard program with a simple wash at 4O ⁰ C 3.5 kg of clean laundry using water with a water hardness of 16 ° German hardness. The liquid volume was 18 liters. In order to obtain a statistical mean, 5 parallel washing tests were carried out in each case.

The clean textiles were each washed three times under the conditions mentioned above with 100 g each of the abovementioned detergent compositions. After the third wash, the textiles were soiled with lipstick and skin fat. The intensity of the soiling was recorded with a Minolta CR 200 camera and then allowed to stand for 7 days at room temperature. Thereafter, the aged stains were again washed under the conditions mentioned above, then allowed to dry and again determined the intensity values of stains with the camera Minolta CR 200.

In the following, the differences of the intensity values obtained by respectively forming the difference between the obtained intensity values before and after the washing of the soiled fabrics are plotted. The greater the difference, the stronger the lightening achieved.

The results show that by adding both the star-shaped polymers according to Example 2 and the star-shaped polymers according to Example 3 to the detergent composition, it was possible to increase the fat-dissolving power both with regard to the lipstick and with respect to the skin fat. While with the polymers according to Example 2 above all a better detachment of the lipstick could be achieved, with the polymers according to Example 3 above all a better detachment of the skin fat was achieved.

Claims

claims:

Use of a star-shaped polymer or an oligomer or polymer of two or more star-shaped polymers or of any mixtures of such molecules for finishing textile fabrics, characterized in that it is in the star-shaped polymer and at least part of the star-shaped polymers of the oligomer or Polymers are molecules with multi-layer structure is, from the inside out comprising a) a central branching unit, b) at least three hydrophilic arms, c) at least one peripheral negatively charged group and / or at least a peripheral group of the formula -Si (oR ') ₃ on at least one of the arms, wherein the radicals R 'are independently hydrogen or Ci_ ₆ alkyl.

2. The embodiment according to claim 1, characterized in that at least 10% of the arms of the star-shaped polymer have peripheral negatively charged groups or groups of the formula -Si (OR ') ₃ .

3. The embodiment according to any one of the preceding claims, characterized in that the hydrophilic arms comprise groups selected from poly-C ₂ -C ₄ - alkylene oxides, polyoxazolidones, polyvinyl alcohols, homo- and copolymers containing at least 50 wt .-% N -Vinylpyrrolidone copolymerized, homo- and copolymers containing at least 30 wt .-% acrylamide and / or methacrylamide in copolymerized form, homopolymers and copolymers containing at least 30 wt .-% of acrylic acid and / or methacrylic acid in copolymerized form.

4. The embodiment according to any one of the preceding claims, characterized in that the peripheral negatively charged group is linked to the hydrophilic arm via a SiIyI radical having 1 to 20 Si units.

5. The embodiment of any of the preceding claims, characterized in that it is in the peripheral group is a silyl group R ³ of the general formula -CR ^a ₂ -Si (OR ^f) _s (R ^c) ₃ - _s is (IM), in which

R ^{a is} hydrogen or C- |. _6- alkyl,

R ^{f is} hydrogen, d. ₆ alkyl or -Si (R ^d) _t (R ^e) ₃ - is _t,

R ^c is C-ι- ₆ alkyl, C- |. ₆ -alkoxy or hydroxy, R ^d is a negatively charged group, R ^e is C-ι- ₆ alkyl, C- |. _{6 is} alkoxy or hydroxy, s is a number from 1 to 3, t is a number from 1 to 3.

6. The embodiment according to the preceding claim, characterized in that at least one radical R ^{f is} a group -Si (R ^d ) _t (R ^e ) ₃ - _t .

7. The embodiment according to any one of the preceding claims, characterized in that R ^{d represents} a group comprising 2 to 4 carboxylic acid groups.

8. Embodiment according to one of the preceding claims for reducing the adhesion of grease on the finished textile fabrics.

9. Star-shaped polymer, characterized in that it has at least one negatively charged peripheral group.

10. A star-shaped polymer according to claim 9, characterized in that the negatively charged peripheral group is bound by a hydrophilic arm to the central branching unit of the star-shaped polymer and that the star-shaped polymer has a multilayer structure, comprising from inside to outside: a) a central Branching unit, b) at least three hydrophilic arms, c) at least one peripheral negatively charged group on at least one of the hydrophilic arms.

11. Star-shaped polymer according to claim 10, characterized in that the central branching unit is a low molecular weight organochemical central unit or an inorganic oxidic nanoparticle, wherein the low molecular weight organochemical central unit is preferably a polyol having 3 to 20 OH groups to which the hydrophilic arms are bound.

12. A star-shaped polymer according to claim 10 or 11, characterized in that the hydrophilic arms comprise groups selected from poly-C ₂ -C ₄ -alkylene oxides, polyoxazolidones, polyvinyl alcohols, homopolymers and copolymers containing at least 50% by weight. In copolymerized form containing N-vinylpyrrolidone, homo- and copolymers which contain at least 30 wt .-% acrylamide and / or methacrylamide in copolymerized form, homo- and Copolymers containing at least 30 wt .-% of acrylic acid and / or methacrylic acid in copolymerized form.

Star-shaped polymer according to any one of the preceding claims, characterized in that the peripheral negatively charged group comprises 1-5 acid groups, preferably 3, 4 or 5 carboxylic acid groups.

14. Star-shaped polymer according to one of the preceding claims, characterized in that the peripheral negatively charged group is linked to the hydrophilic arm via a silyl radical having 1 to 20 Si units.

15. Star-shaped polymer according to one of the preceding claims, characterized in that the negatively charged group is a silyl group of the general formula (I)

-CR ^a ₂ -Si (OR ^b ) _r (R ^c ) ₃ - _r (I), where

R ^{a is} hydrogen or C- |. _6- alkyl,

R ^{b is} -Si (R ^d ) _t (R ^e ) ₃ _-t

R ^c is C-ι- ₆ alkyl, C- |. ₆ -alkoxy or hydroxy,

R ^{d is} a negatively charged group,

R ^e is C-ι- ₆ alkyl, C- |. _{6 is} alkoxy or hydroxy, r is a number from 1 to 3, t is a number from 1 to 3.

16. A star-shaped polymer according to the preceding claim, characterized in that R ^{d is} a group -TUVW, wherein

T for CI_ ₆ alkyl,

U is N-CH ₂ -COOH,

V for d. _6- alkyl,

W stands for N (-CH ₂ -COOH) ₂ .

17. Star-shaped polymer according to one of the preceding claims, characterized in that it additionally comprises peripheral -Si (OR ') ₃ groups, wherein the radicals R' are independently hydrogen or C-. ₆ alkyl.

18. Star-shaped polymer according to one of the preceding claims, characterized in that it is a molecule of the general formula (II): _n (R ² -Y ² -A ² -X ² -) Z (-X ¹ -A ¹ -Y ¹ -R ¹ ) _m (II) wherein

Z stands for the low molecular weight central unit, which determines the maximum number of arm of the star-shaped prepolymers,

A ¹ and A ² independently of one another represent a hydrophilic polymer arm,

X ¹ , X ² , Y ¹ and Y ² independently of one another represent a chemical bond or a bivalent, low molecular weight organic radical having preferably 1 to 50, in particular 2 to 20, C atoms,

R ^{1 represents} a silyl group of the following general formula (I)

-CR ^a ₂ -Si (OR ^b ) _r (R ^c ) ₃ - _r (I) wherein

R ^{a is} hydrogen or C- |. _6- alkyl,

R ^{b is} -Si (R ^d ) _t (R ^e ) ₃ _-t

R ^c is C-ι- ₆ alkyl, C- |. ₆ -alkoxy or hydroxy,

R ^{d is} a negatively charged group,

R ^{e is} de-alkyl, d ₆ -alkoxy or hydroxy, r is a number from 1 to 3, t is a number from 1 to 3,

R ^{2 is} OH or one with substrates, entities and / or self-crosslinkable

Group and m and n are each integers, where m> 1 and n> 0 and m + n is a value of 3 to

Has 500,000 and preferably coincides with the arm number of Z, and the m X ¹ -A ¹ -Y ¹ -R ¹ groups and the n X ² -A ² -Y ² -R ² groups independently of one another may have different meanings.

19. oligomer or polymer of star-shaped polymers, characterized in that at least a part of the star-shaped polymers is modified by peripheral negatively charged groups.

20. An oligomer or polymer according to the preceding claim, characterized in that the negatively charged group is a silyl group of the general formula (I) -CR ^a ₂ -Si (OR ^b ) _r (R ^c ) ₃ - _r ( I), where

R ^{a is} hydrogen or C _1-6 -alkyl,

R ^{b is} -Si (R ^d ) _t (R ^e ) ₃ _-t

R ^c is C-ι- ₆ alkyl, CI_ is ₆ alkoxy or hydroxy,

R ^{d is} a negatively charged group, R ^e is C-ι- ₆ alkyl, C- |. _{6 is} alkoxy or hydroxy, r is a number from 1 to 3, t is a number from 1 to 3.

21, washing or cleaning agent, characterized in that it contains at least one star-shaped polymer according to any one of claims 9 to 18 and / or at least one oligomer or polymer star-shaped polymers according to claim 19 or 20.

22. Coatings which can be prepared from star-shaped polymers which can be crosslinked with one another and with the surface of the substrate to be coated, the star-shaped polymers having at least three, preferably from 3 to 20, hydrophilic polymer arms which, at least at their free ends, have peripheral silicone polymers. End groups R ^{1 of} the following general formula (I)

-CR ^a ₂ -Si (OR ^b ) _r (R ^c ) ₃ - carry _r (I), wherein

R ^{a is} hydrogen or C- |. ₆ -alkyl, R ^{b is} -Si (R ^d ) _t (R ^e ) ₃ _-t ,

R ^{d is} a negatively charged group,