EP3177266A1

EP3177266A1 - Polyurethane urea solutions for hair-styling compositions

Info

Publication number: EP3177266A1
Application number: EP15712140.1A
Authority: EP
Inventors: Sophie Viala; Sebastian Dörr; Paula Cristina Alves Rodrigues
Original assignee: Covestro Deutschland AG
Current assignee: Covestro Deutschland AG
Priority date: 2014-08-05
Filing date: 2015-03-26
Publication date: 2017-06-14
Also published as: US20170224606A1; WO2015075280A1; CN106659669A

Abstract

The invention relates to a hair-styling composition, containing at least one propellant gas and/or a thickener, characterized in that the hair-styling composition also contains a polyurethane urea, which has no ionic hydrophilizing groups and which is dissolved in a solvent or solvent mixture, the solvent being composed exclusively of one or more monohydroxy-functional alcohols or a solvent mixture consisting of exclusively organic solvents, which solvent mixture contains ≥ 50 wt% of at least one monohydroxy-functional alcohol, with respect to the total mass of the solvent mixture. The invention further relates to the use of the hair-styling composition to shape, solidify, and/or fix hair and to a method for shaping, solidifying, and/or fixing hair by using the polyurethane urea solution. The invention further relates to a method for producing a hair-styling composition, in which method the polyurethane urea solution is used.

Description

Polyurethane urea solutions for hair compositions

The present invention relates to a hair styling composition comprising at least one thickener and / or a propellant and a specific polyurethaneurea, as well as the use of the hair styling composition for shaping, strengthening and / or fixing the hair and a method for shaping. Firming and / or fixing the hair using the special polyurethaneurea. Another object of the invention is a process for the preparation of a Haarstyiing composition wherein a special Polyurethanhamstoff is used, and a polyurethaneurea obtainable by the process according to the invention.

Hair styling products are often present as aerosol containers, squeeze bottles or by a pumping, spraying or frothing sprayable preparations which consist predominantly of an alcoholic solution of film-forming natural or synthetic polymers.

As good film-forming polymers for hair styling compositions, inter alia, aqueous dispersions of Polyurethanharnsto ffen known, as described for example in WO 2009/1 18105 AI, WO 2012/130683 AI and WO 2012/130682 AI. Hair styling compositions containing the described aqueous polyurethane urea dispersions have some advantages, such as a good fixation of hairstyles in on. However, the known aqueous dispersions of polyurethaneureas have some disadvantages in hairstyling compositions based predominantly on alcoholic solvents. Thus, the film formers described in WO2009 / 1 18105 Al, WO 2012/130683 Al, WO 2012/130682 Al and WO 2014/095164 AI form a clear mixture only with Alkohoi / water mixtures, but are incompatible, for example, with pure ethanol and tarnish the Composition. This is perceived as disturbing for many applications. Another disadvantage is that the polyurethane ureas according to the prior art have hydrophilicizing, in particular ionically hydrophilic, groups which are introduced into the polymers by expensive compounds which carry these groups.

In addition, polyurethaneureas bearing ionic hydrophilizing groups generally do not form clear solutions in alcohols, making them less suitable for use in transparent, cosmetic compositions.

It is also known that the polyurethane-based film formers known from the prior art are poorly compatible with propellant gas mixtures, such as, for example, propane / butane, which are used in aerosol formulations.

Hydrophilicizing groups, in particular polyurethane film formers carrying ionic hydrophilizing groups, are also described, for example, in DE 4241 118 A1. It is generally known that due to their structure, polyurethane ureas tend to precipitate or crystallize from organic solutions. It is therefore problematic to prepare organic solutions of polyurethane ureas which have a sufficiently high molecular weight without the polyurethane ureas precipitating out of the solvents and thus no clear, storage-stable solutions being obtained.

To prevent this crystallization solvent mixtures are recommended; the solvents, which are counted in the meantime due to the growing toxicological findings to the questionable solvents include, such as toluene. or xylo !.

However, the use of such cosolvents is not possible for polyurethane ureas for use in cosmetic products alone for reasons of regulatory approval.

The object of the present invention was therefore to provide a transparent, alcohol-based hairstyling composition based on polyurethane ureas as film formers, wherein the film formers have good compatibility with propellant mixtures such as propane butane and are thus well suited for aerosol formulations. In addition, the compositions should cause a good fixation of the hair.

This object is achieved according to the invention by a hair styling composition comprising at least one propellant gas and / or a thickener, characterized in that it further contains a polyurethaneurea which has no ionically hydrophilicizing groups and which is dissolved in a solvent or solvent mixture, wherein the Solvent exclusively of one or more monohydroxyfunktioneilen alcohols or a solvent mixture consisting of exclusively organic solvents, which contains> 50 wt .-%, based on the total mass of the solvent mixture, of at least one monohydroxyfunkti- onellen alcohol is used. The polyurethaneurea used is composed of at least one aliphatic, araliphatic and / or cycloaliphatic diisocyanate, at least one polyether polyol having a number average molecular weight Mn> 400 and <6000 g / mol and a hydroxyl functionality of> 1, 5 and <4, at least one amino-functional compound having at least two isocyanate-reactive amino groups,

optionally at least one alcohol having at least two hydroxyl groups and a molecular weight> 60 and <399 g mol, e) optionally at least one compound which has an isocyanate-reactive group, and

f) optionally <20 wt .-%, based on the total mass of the Polyur ethanharnsto ffs, at least one Poiyol having a number average molecular weight Mn> 500 and <6000 g / mol and a hydroxyl functionality of> 1, 5 and <4, which varies is from b).

The dissolved polyurethaneurea used according to the invention, including the solvent or solvent mixture, is also referred to below as polyurethaneurea solution. It has surprisingly been found that transparent, alcohol-based hair setting compositions can be obtained by the use of polyurethane urea solutions in monohydroxy-functional alcohols or solvent mixtures of organic solvents and monohydroxy-functional alcohols, the film formers having good compatibility with propellant mixtures such as propane / butane and thus good for aerosol formulations - are suitable. In addition, the compositions cause a good fixation of the hair.

The invention further provides a process for producing a hairstyling composition, which comprises using at least one polyurethaneurea which has no ionically hydrophilicizing groups and which is dissolved in a solvent or solvent mixture, the solvent consisting exclusively of one or more ren monohydroxyfunktionellen alcohols or a solvent mixture consisting exclusively of organic solvents, which contains> 50 wt .-%, based on the total weight of the solvent mixture, of at least one monohydroxyfunktionellen alcohol.

The Polyur ethanharnsto ff used is composed of at least one aliphatic, araliphatic and / or cycloaliphatic diisocyanate, at least one polyether polyol having a number average molecular weight Mn> 400 and <6000 g / mol and a hydroxyl functionality of> 1, 5 and <4, at least one amino-functional compound having at least two isocyanate-reactive amino groups,

optionally at least one alcohol having at least two hydroxyl groups and a molecular weight> 60 and <399 g / mol,

optionally at least one compound which has a reactive group with respect to I, and

optionally <20% by weight, based on the total mass of the polyurethane urethane resin, of at least one polyol having a number-average molecular weight Mn> 500 and <6000 g / mol and a hydroxyl functionality of> 1 .5 and <4, which is different from b).

Likewise provided by the invention is the hairstyling composition obtainable by the process according to the invention.

Another object of the invention is the use of a Polyurethanharnsto ff, which has no ionic hydrophilicizing groups and which is dissolved in a solvent or Lösemitte mixed, wherein the solvent consists exclusively of one or more monohydroxy-functional alcohols or a Lösemitteischisch consisting exclusively of organic Solvents containing> 50 wt .-%, based on the total mass of the solvent mixture, of at least one monohydroxy-functional alcohol, for the preparation of a hair styling composition. The polyurethaneurea used is composed of at least one aliphatic, araliphatic and / or cycloaliphatic diisocyanate, at least one polyether polyol having a number average molecular weight Mn> 400 and <6000 g / mol and a hydroxyl functionality of> 1, 5 and <4, at least one amino-functional compound containing at least two isocyanate-reactive

Having amino groups,

optionally at least one compound which has an isocyanate-reactive group and

optionally <20 wt .-%, based on the total mass of the Polyurethanharnsto ffs, at least one Polyo! having a number average molecular weight Mn> 500 and <6000 g / mol and a hydroxyl functionality of> 1, 5 and <4, which is different from b).

The invention likewise relates to the use of a polyurethaneurea which has no ionically hydrophilicizing groups and is more loosely dissolved in a solvent or solvent mixture, the solvent consisting exclusively of one or more monohydroxy-functional alcohols or a solvent mixture consisting exclusively of organic solvents which is> 50% by weight .-%, based on the total mass of the solvent mixture, of at least one monohydroxyfunktionell en alcohol, for shaping, consolidation and / or fixation of the hair. The polyurethaneurea used is composed of a) at least one aliphatic, aliphatic and / or cycloaliphatic diisocyanate, b) at least one polyether polyol having a number average molecular weight Mn> 400 and <6000 g / mol and a hydroxyl functionality of> 1.5 and <4, c) at least one amino-functional compound, the at least two isocyanate-reactive

Having amino groups,

d) optionally at least one alcohol having at least two hydroxyl groups and a molecular weight> 60 and <399 g mol,

e) optionally at least one compound which has an isocyanate-reactive group, and

f) optionally <20% by weight, based on the total mass of the polyurethane urethane resin, of at least one polyol having a number-average molecular weight Mn> 500 and <6000 g / mol and a hydroxyl functionality of> 1, 5 and <4, which varies is from b).

Dissolved means in the context of the invention that at 23 ° C is homogeneous, single-phase liquid mixtures of at least two substances that are clear. In the context of the present invention, clear means that the turbidity values of the solution are <200 NTU (Nephelometry Turbidity Unit), preferably <50 NTU, more preferably <10 NTU and most preferably <5 NTU. The haze values are determined by a scattered light measurement at a 90 ° angle (nephelometry) at a wavelength of the measuring radiation 860 nm in accordance with DIN EN ISO 7027, carried out at 23 ° C. using a laboratory haze meter model 2100 AN from HA (II LANGE GmbH, Berlin, Germany.

Polyurethane ureas in the context of the invention are polymeric compounds which contain at least two preferably at least three urethane groups-containing repeat units

O

- - ^ - O-

H and also have urea group-containing repeating units:

O

- - ^ - -

HH Ionically hydrophilicizing groups in the sense of the invention are those which could be introduced into the polyurethaneurea, for example, by suitable anionic or potentially anionic hydrophilizing compounds which have at least one isocyanate-reactive group, such as a hydroxyl group or amino group, and at least one functionality such as, for example, -C (X. > M. -SCVNT, KX OM ^' with ^" for example equal to metal cation, H ⁺ , NH ₄ ⁺ , NMR. ^' , Where R is in each case a C 1 -C 12 -alkyl radical, C 5 -C 6 -cycloalkyl radical and / or a C 2 -C C.sub.4- may be hydroxyalkyl radical which, upon interaction with aqueous media, undergoes a pH-dependent dissociation equilibrium and may thus be charged in a negative or neutral form Suitable anionic or potentially anionic hydrophilizing compounds are mono- and dihydroxycarboxylic acids, mono- and dihydroxysulfonic acids, and mono- and dihydroxyphosphonic acids and their salts, examples of such anionic or potentially ionic hydrogenating agents are dimethylolpropionic acid, dimethylolbutyric acid, hydroxypivalic acid, malic acid, citric acid, glycolic acid, lactic acid and the propoxylated adduct of 2-butenediol and NaHSO-, as described in DE-A 2 446 440, page 5 - 9, formula II is described. Within the context of this invention, potentially anionic (and generally also potentially ionic) groups are to be understood as meaning those groups which can be converted by neutralization into an anionic (ionic) group.

In a preferred embodiment of the process according to the invention, the polyurethaneurea used has no hydrophilicizing groups, ie neither ionic nor nonionic hydrophilicizing groups.

Nonionic hydrophilicizing groups in the context of the invention are those which could be introduced into the polyurethaneurea, for example by suitable non-ionic hydrophilicizing compounds, such as polyoxyalkylene ethers containing at least one hydroxy or amino group. Examples are the monohydroxy-functional, on average 5 to 70, preferably 7 to 55 ethylene oxide units per molecule having polyalkylene oxide polyether alcohols, as they are accessible in a conventional manner by alkoxylation of suitable starter molecules (eg in Ulimann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, Verlag Chemie, Weinheim pp 31-38 described). These compounds are either pure polyethylene oxide ethers or mixed polyalkylene oxide ethers, but then they contain at least 30 mol%, preferably at least 40 mol%, based on all alkylene oxide units contained in ethylene oxide units. The polyurethaneureas of the present invention are used in the hairstyling compositions according to the invention and in the process of the invention for preparing the cosmetic compositions dissolved in a solvent or solvent mixture, and thus as polyurethane urea solutions and not as an aqueous dispersion.

The polyurethaneurea used according to the invention, composed of at least one aliphatic, araliphatic and / or cycloaliphatic diisocyanate,

at least one polyether polyol having a number average molecular weight Mn>

400 and <6000 g / mol and a hydroxyl functionality of> 1 .5 and <4, at least one amino-functional compound which has at least two isocyanate-reactive amino groups,

optionally at least one compound which has an isocyanate-reactive group and

optionally <20 wt .-%, based on the total mass of the polyurethane urea, on at least one Po Ivo! having a number average molecular weight Mn> 500 and <6000 g / mol and a hydroxyl functionality of> 1 .5 and <4, which is different from b).

The number average molecular weight in the context of this application is always determined by gel permeation chromatography (GPC) versus polystyrene standard in tetrahydrofuran at 23 ° C. The procedure according to DIN 55672-1 is "gel permeation chromatography, Part 1 - tetrahydrofuran as eluent" (SECurity GPC system from PSS Polymer Service, flow rate 1, 0 ml / min, columns: 2 × PSS SDV linear M, 8 × 300 mm, 5 μηι; RID detector). This polystyrene samples of known molecular weight are used for calibration. The calculation of the number average molecular weight is software-based. Baseline points and evaluation limits are defined in accordance with DIN 55672 Part 1.

Further preferably, the polyurethaneurea is composed of> 5 and <60 wt .-% of component a),> 30 and <90 wt .-% of component b),> 2 and <25 wt .-% of component c),> 0 and <10 wt .-% of component d),> 0 and <10 wt .-% of component e) and> 0 and <20 wt .-% of component f), each based on the total mass of the polyurethane urea, wherein the components a) to f) add up to 100% by weight. The polyurethaneurea is particularly preferably composed of> 10 and <40 wt .-% of component a),> 55 and <85 wt .-% of component b),> 5 and <20 wt .-% of component c),> 0 and <3 wt .-% of component d),> 0 and <3 wt .-% of component e) and> 0 and <1 wt .-% of component f), each based on the total mass of the polyurethane urea, wherein the components a) to f) add up to 100% by weight.

Compounds suitable as component a) are, for example, 1,4-butylene diisocyanate, 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (I DI), 2,2,4- and / or or 2,4,4-trimethyl-hexa ^"Tnethy ^~ len ⁱ ^{~~ ~} ^~ x xliiso; Yanat, the isomeric bis (4,4'-isocyanatocyclo ^ hexyl ^ methanes or their mixtures of any isomer'gehalts (Hl 2-MDI), 1,4-cyclohexylenediisocyanate, 4-isocyanatomethyl-1,1-octanediisocyanate (nonantriisocyanate), 1,3- and / or 1,4-bis- (2-isocyanato-prop-2- yl) -benzene (TMXDI), 1,3-bis (isocyanato- methyl) benzene (XDI) and also alkyl 2,6-diisocyanatohexanoate (lysine ^™ xliisocyanate) with C1-C8-alkyl groups.

In addition to the abovementioned polyisocyanates, it is also possible proportionally to use modified diisocyanates or triisocyanates having isocyanurate, urethane, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures.

Preference is given to polyisocyanates or polyisocyanate mixtures of the type mentioned above having an average NCO functionality of> 2 and <4, preferably> 2 to 2.6 and more preferably> 2 and <2.4.

The component a) is preferably selected from aliphatic, araliphatic and / or cycloaliphatic diisocyanates which have at least one isocyanate group which is bonded to a secondary and / or tertiary carbon atom.

The component a) is particularly preferably selected from IPDI and / or H12-MDI.

Preference is furthermore given to using no aromatic polyisocyanates for the preparation of the polyurethaneurea.

The component a) is preferably used in amounts of> 5 and <60 wt .-%, particularly preferably> 10 and <40 wt .-% and most preferably of> 1 5 and <35 wt .-%, based on the total weight of the polyurethaneurea. The component b) consists of one or more polyether polyols having a number average molecular weight Mn> 400 and <6000 g mol and a hydroxyl functionality of> 1, 5 and

<4, preferably having a number average molecular weight Mn> 500 and <2500 g mol and a hydroxyl functionality of> 1, 9 and <3, and more preferably having a number average molecular weight Mn> 1000 and <2000 g / mol and a hydroxyl functionality of> 1, 9 and <2, 1.

Suitable polyether polyols of component b) are, for example, the poly (tetramethylene glycol) polyether polyols known per se in polyurethane chemistry, such as are obtainable by polymerization of tetrahydrofuran by means of cationic ring opening. Also suitable polyether polyols are the per se known addition products of styrene oxide, ethylene oxide, propylene oxide, butylene oxide and / or epichlorohydrin to di- or polyfunctional starter molecules. Thus, in particular polyalkylene glycols, such as polyethylene, polypropylene and / or Polybutylengiykole be applicable, in particular with the above-mentioned preferred molecular weights. The polyether polyols preferably have a proportion of groups obtained from ethylene oxide of <50% by weight, preferably <30% by weight.

As suitable starter molecules, it is possible to use all compounds known from the prior art, such as, for example, water, butyldiglycol, glycerol, diethylene glycol, trimethylolpropane, propylene glycol, sorbitol, ethylenediamine, triethanolamine, 1,4-butanediol.

The component b) is preferably selected from polypropylene glycols and / or poly (tetra methylene glycol) polyether polyols, more preferably selected from poly (tetra methylene glycol) polyether polyols.

In a preferred embodiment of the invention, component b) is one or more poly (tetramethylene glycol) polyether polyols having a number average molecular weight Mn> 500 and <2500 g / mol and a hydroxyl functionality of> 1, 9 and

<2, 1.

In a particularly preferred embodiment, component b) is a mixture of poly (tetramethylene glycol) polyether polyols I having a number average molecular weight M _n of> 400 and <1500 g / mol, more preferably of> 600 and <1200 g / mol, completely particularly preferably of 1000 g / mol and poly (tetramethylene glycol) polyether polyols II having a number-average molecular weight M _n of> 1500 and <8000 g / mol, more preferably of> 1800 and

<3000 g / mol, most preferably from 2000 g / mol.

The weight ratio of the poly (tetramethylene glycol) polyetherpolyols I to the poly (tetramethylene glycol) polyetherpolyols 11 is preferably in the range of> 0.1 and <10, in particular ders preferred in the range of> 0.2 and <8, most preferably in the range of> 1 and <6.

Component b) is preferably used in amounts of> 30 and <90% by weight, more preferably> 50 and <85% by weight, very preferably> 55 and <75% by weight, based on the total weight of Polyurethanurea, used.

Component c) is one or more amino-functional compounds which have at least two isocyanate-reactive amino groups. Suitable components c) are, for example, di- or polyamines, such as 1,2-ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 2,2,4- and 2, 4,4-trimethylhexamethylenediamine, 2-methyl pentamethylene diamine, diethylene triamine, triaminononane, 1, 3- and 1, 4-xylylene, a, a, a ^', ^a' -tetramethyl-l, 3- and - 1, 4-xylylenediamine and 4 '4 ^' - Diaminodicyclohexylmethane (H12-MDA), I sophoronediamine (IPDA) and / or 1,2-dimethylethylenediamine.

Component c) is preferably selected from ethylenediamine, IPDA and / or H12-MDA, more preferably from isophoronediamine and / or H12-MDA and most preferably component c) is H 1 2-MDA. The compounds of component c) preferably contain no hydrophilicizing groups, in particular no ionic or potentially ionic hydrophilicizing groups.

In a particularly preferred embodiment of the invention, component c) is selected from amines which have at least two isocyanate-reactive amino groups which are bonded to primary and / or secondary C atoms.

Further preferably, component c) is selected from symmetrically constructed diamines. Most preferably, component c) is selected from symmetrical diamines which have at least two amino groups which are bonded to primary and / or secondary carbon atoms, particularly preferably component c) H1 2-MDA.

Component c) is preferably used in amounts of> 2 and <25% by weight, more preferably> 5 and <20% by weight and very particularly preferably> 9 and <16% by weight, based on the total weight of the polyurethaneurea, used. In a preferred embodiment of the invention, either component a) is H12-MDI or component c) is H12-MDA or component a) is H12-MDI and component c) is H12-MDA.

Optionally, the polyurethaneurea is also built up from component d), one or more alcohols having at least two hydroxyl groups and a molecular weight of> 60 and <399 g / mol, such as polyols of said molecular weight range having up to 20 carbon atoms, such as ethylene glycol, diethylene glycol , Triethylene glycol, 1, 2-propanediol. 1,3-propanediol. 1, 4-butanediol, 1,3-butyiene glycol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, neopentyl glycol, hydroquinone dihydroxyethyl ether, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), hydrogenated bisphenol A, (2,2-bis (4-hydroxycyclohexyl) propane), trimethylolpropane. Glycerine, pentaerythritol.

Component d) is preferably used in amounts of> 0 and <10% by weight, more preferably> 0 and <3% by weight, based on the total weight of the polyurethaneurea, and most preferably not at all.

Furthermore, the polyurethaneurea may be composed of component e), one or more compounds which have an isocyanate-reactive group, in particular compounds which have an amino or hydroxyl group. Suitable compounds of component e) are, for example, methylamine, ethylamine, propylamine. Butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine. Dibutylamine, N-methylaminopropylamine, diethyl (methyl) aminopropylamine, morpholine. Piperidine, methanol, ethanol, i-o-propanol. n-propanol, n-butanol, ethylene glycol monobutyl ether, diethylglycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, 2-ethylhexanoi, 1-octanol, 1-dodecanol. hexadecanol.

Component e) preferably comprises no monofunctional polyether polyols which have a proportion of groups of ethylene oxide of> 30% by weight, preferably> 50% by weight. The monohydroxy-functional alcohol used as solvent for the polyurethaneurea can likewise serve as structural component e) for the polyurethaneurea.

The component e) is, preferably in amounts of> 0 and <10 wt .-%, particularly preferably> 0 and <3 wt .-%, based on the total weight of the polyurethane urea, and very particular ders preferably not used, in which case the monohydroxy-functional alcohol used as a solvent for the polyurethane urea as component e) remains unconsidered.

The monohydroxy-functional alcohol which serves as a solvent for the polyurethaneurea makes preferably> 0 and <5 wt .-%, particularly preferably> 0.01 and <3 wt .-% and most preferably> 0.01 and <2 wt. % of the total mass of the polyurethaneurea.

Optionally, the polyurethaneurea may also be composed of the component f), one or more polyols having a number average molecular weight Mn> 500 and <6000 g mol and a hydroxyl functionality of> 1 .5 and <4, where the polyols are different from b) ,

The component f) is preferably used in amounts of> 0 and <20 wt .-%, particularly preferably> 0 and <10 wt .-%, based on the total weight of the polyurethaneurea, and most preferably not at all.

Preferably, the polyols of component f) have a number average molecular weight Mn> 1000 and <3000 g mol and a hydroxyl functionality of> 1, 8 and <3.

Polyols suitable as component f) are the polyester polyols known per se in polyurethane coating technology, polyacrylate polyols, polyurethane polyols. Polycarbonate polyols, polyester polyacrylate polyols, polyurethane polyacrylate polyols. Polyurethane polyester polyols, Polyurelhanpoly- ether polyols, Polyurethanepolycarbonatpolyole, Polyetherpolycarbonatpolyole and / or polyester polycarbonate polyols, in particular polyester polyols and / or Poiycarbonatpolyoie.

Polyester polyols are, for example, the known polycondensates of di- and optionally tri- and tetraols and di- and optionally tri- and tetracarboxylic acids or hydroxy carboxylic acids or lactones. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols for the preparation of the polyesters.

Examples of suitable diols are ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, P o 1 ya 1 ky 1 en 1 vko 1 e as Polyethylenglvkol. 1, 2-propanediol. 1, 3-propaniliol. Butanediol (l, 3), butanediol (l, 4), hexanediol (l, 6) and isomers, neopentyl glycol or Hvdroxypi- valinsäureneopentylglykolester, with hexanediol (l, 6) and isomers, neopentyl glycol and hydroxypivalinsäureneopentylglykolester are preferred. In addition, polyols can also be used Trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate can be used.

As dicarboxylic acids, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, suberic acid, 2-methyl-succinic acid, 3.3- et i et hy 1 I in arsän e and / or 2,2-dimethylsuccinic acid. The acid source used may also be the corresponding anhydrides.

If the average hydroxyl functionality of the polyol to be esterified is greater than 2, it is additionally possible to use monocarboxylic acids, such as benzoic acid and hexanecarboxylic acid.

Preferred acids are aliphatic or aromatic acids of the abovementioned type. Particular preference is given to adipic acid, isophthalic acid and, if appropriate, trimellitic acid, very particular preference to adipic acid.

Hydroxycarboxylic acids which can be used as reactants in the preparation of a polyester polyol having terminal hydroxyl groups are, for example, hydroxycarbonic acid, hydroxybutyric acid, hydroxydecanoic acid, hydroxystearic acid and the like. Suitable lactones are caprolactone, butyrolactone and homologs. Preference is given to caprolactone.

In component f) it is also possible to use hydroxyl-containing polycarbonates, preferably polycarbonatediols, having number-average molecular weights Mn of from 400 to 8000 g / mol, preferably from 600 to 3000 g / mol. These are obtainable by reaction of carbonic acid derivatives, such as diphenyl carbonate, dimethyl carbonate or phosgene, with Po Kolon, preferably diols.

Examples of such diols are ethylene glycol, 1, 2 and 1, 3-propanediol. 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane, 2-methyl-1,3-propanediol, 2,2,4-trimethylpentanediol-1 3, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A and lactone-modified diols of the abovementioned type. The hydroxyl-containing polycarbonates are preferably of linear construction.

In a preferred embodiment of the invention, the polyurethane urea sto ff used in the invention is composed of a) at least one aliphatic, araliphatic and / or cycloaliphatic diisocyanate having at least one isocyanate group which is bonded to a secondary and / or tertiary carbon atom, at least one polyether polyol having a number average molecular weight Mn> 500 and <2500 g mol and a hydroxyl functionality of> 1, 9 and <3, at least one amino-functional compound which has at least two (isocyanate-reactive) amino groups and is selected from ethylenediamine, IPDA and / or II! 2- M DA

optionally at least one compound which has an isocyanate-reactive group and

optionally <20% by weight, based on the total mass of the polyurethaneurea, of at least one polyol having a number average molecular weight Mn> 500 and <6000 g mol and a hydroxyl functionality of> 1 .5 and <4, which is different from b).

Further preferably, the polyurethaneurea in this aforementioned embodiment is composed of> 5 and <60 wt .-% of component a),> 30 and <90 wt .-% of component b),> 2 and <25 wt .-% of the component c),> 0 and <10 wt .-% of component d),> 0 and <10 wt .-% of component e) and> 0 and <20 wt .-% of component f), each based on the total mass the polyurethaneurea, wherein the components a) to f) add up to 100 wt .-%.

Particularly preferably, the polyurethaneurea in this aforementioned embodiment is composed of> 10 and <40 wt .-% of component a),> 55 and <85 wt .-% of component b),> 5 and <20 wt .-% of the component c),> 0 and <3 wt .-% of component d),> 0 and <3 wt .-% of component e) and> 0 and <1 wt .-% of component f), each based on the total mass the polyurethaneurea, wherein the components a) to f) add up to 100 wt .-%.

In a particularly preferred embodiment of the invention, the polyurethaneurea used according to the invention is composed of at least one diisocyanate selected from IPDI and / or H12-MDI,

at least one polyether polyol having a number average molecular weight Mn> 500 and <2500 g mol and a hydroxyl functionality of> 1, 9 and <3, selected from polypropylglycols and / or poly (tetramethylene glycol) polyetherpolyols, at least one amino-functional compound selected from IPDA and / or H12-MDA,

optionally at least one compound which has an isocyanate-reactive group and

optionally <20% by weight, based on the total mass of the polyurethaneurea, of at least one polyol having a number-average molecular weight Mn> 500 and <6000 g mol and a hydroxyl functionality of> 1, 5 and <4, which is different from b) ,

The polyurethaneurea in this aforementioned embodiment is particularly preferably composed of> 10 and <40% by weight of component a),> 55 and <85% by weight of component b),> 5 and <20% by weight. the component c),> 0 and <3 wt .-% of component d),> 0 and

<3% by weight of component e) and> 0 and <1% by weight of component f), in each case based on the total mass of the polyurethaneurea, wherein components a) to f) add up to 100% by weight. The polyurethaneurea is preferably exclusively composed of the components a) to c) and optionally d) to f), particularly preferably exclusively of the components a) to c).

Advantageously, the polyurethaneurea has a number average Molelculargewicht Mn> 2000 and

<50,000 g / mol, particularly advantageously> 3,000 and <30,000 g mol.

The polyurethaneurea is preferably prepared by reacting the components a) and b) and optionally d) and f) in a first step to form an NCO-terminated prepolymer, which then in a subsequent step with the component c) and optionally the components d) and e) is implemented. For the preparation of the polyurethane ureas are preferably the components a) and b) and optionally d) and f) for the preparation of an NCO-terminated prepolymer completely or partially presented, optionally diluted with an isocyanate-inert solvent and to temperatures in the range of 50 to 120 ° C heated. To accelerate the Isocyanatadditionsreaktion known in polyurethane chemistry catalysts can be used. In a preferred variant, however, work is carried out without the addition of urethanization catalysts.

Subsequently, the constituents of a) and b) optionally added at the beginning of the reaction and optionally d) and f) are metered in. In the preparation of the NCO-terminated prepolymers from components a) and b) and optionally d) and f), the molar ratio of isocyanate groups to isocyanate-reactive groups is generally> 1.05 and <3.5, preferably> 1 , 1 and <3.0, more preferably> 1.1 and <2.5.

Isocyanate-reactive groups are to be understood as meaning all groups reactive toward isocyanate groups, such as, for example, primary and secondary amino groups, hydroxyl groups or thiol groups.

The reaction of components a) and b) and optionally d) and f) to form the prepolymer takes place partially or completely, but preferably completely. There are so polyurethane prepolymers. contain the free isocyanate groups, obtained in bulk or in solution.

Preferably, we prepared the NCO-terminated prepolymer exclusively from components a) and b).

Following is preferably in a further process step, if not yet done or only partially done, the resulting prepolymer with the aid of one or more organic solvents. The solvent used here is preferably likewise a solvent or solvent mixture, the solvent consisting exclusively of one or more monohydric functional alcohols or a solvent mixture consisting exclusively of organic solvents,> 50% by weight, based on the total mass of the Solvent mixture containing at least one monohydroxyfunktionellen alcohol is used. The following preferred embodiments for the solvent or the solvent mixture also apply to the solvent or solvent mixture in which the polyurethane urethane resin is dissolved. The solvent or solvent mixture may also be different from the solvent or solvent mixture in which the polyurethaneurea is later dissolved as the end product. The solvent or solvent mixture is preferably identical to the solvent or solvent mixture in which the polyurethaneurea is later dissolved as the end product.

Preferably, the solvent used in the preparation of one or more monohydroxy-functional alcohols. The ratio of solvent to prepolymer is preferably> 1:10 and <5: 1, more preferably> 1: 2 and <2: 1 parts by weight.

The prepolymer is preferably cooled before dissolution to temperatures of -20 to 60 ° C, preferably 0 to 50 ° C and more preferably from 15 to 40 ° C.

In one, optionally followed by the dissolution of the NCO-terminated prepolymer, further step, the NCO-terminated prepolymer obtained in the first step is then preferably completely or partially reacted with the component c) and optionally the components d) and e). This reaction is generally referred to as chain extension, or in the case of component e) as chain termination.

Preference is given here to the NCO-terminated prepolymer and the components c) and optionally d) and e) are added. Preferably, a partial reaction of the NCO groups of the prepolymer with the components c) and optionally d) takes place first, followed by the chain termination by reaction of the remaining NCO groups with the component e). The components c) and optionally e) can also be added in stages in several steps, in particular in two steps.

The component c) and optionally d) and e) are preferably used dissolved in one or more organic solvents. The solvent used is preferably also a solvent or solvent mixture, wherein the solvent consists exclusively of one or more monohydroxy-functional alcohols or a solvent mixture consisting exclusively of organic solvents, soft> 50 wt .-%, based on the total mass of the solvent mixture, at least one monohydroxy-functional alcohol is used. For the solvent and the solvent mixture, the following preferred embodiments also apply to the solvent or solvent mixture in which the polyurethaneurea is dissolved.

The solvent or solvent mixture may also be different from the solvent or solvent mixture in which the polyurethaneurea is later dissolved as the end product. The solvent or solvent mixture is preferably identical to the solvent or solvent mixture in which the polyurethaneurea is later dissolved as the end product.

Preferably, the solvent used for the preparation of component c) consists of one or more monohydroxy-functional alcohols.

When solvents are used as diluents, the diluent content in the components used in the chain extension c), and optionally d) and e) is preferably 1 to 95 wt .-%, more preferably 3 to 50 wt.% based on the total weight of component c) and optionally d) and e) including diluent. The addition of the components c) and optionally d) and e) is preferably carried out at temperatures of -20 to 60 ° C, preferably 0 to 50 and particularly preferably from 15 to 40 ° C.

The degree of chain extension, ie the molar ratio of NCO-reactive groups of the components used for chain extension and chain termination c) and optionally d) and e) to free NCO groups of the prepolymer, is generally> 50 and <120%, particularly preferably> 60 and <100% and most preferably> 70 and <95%.

The molar ratio of the isocyanate-reactive groups of component c) to the free NCO groups of the prepolymer is preferably> 50 and <120%, more preferably> 60 and <100% and very particularly preferably> 70 and <95%.

In a preferred embodiment of the invention, the free NCO groups of the prepolymer are only partially reacted with component c), in which case the molar ratio of the isocyanate-reactive groups of component c) to the free NCO groups of the prepolymer is> 60 and <95 %) and the remaining free NCO groups react with the hydroxyl groups of the solvent to form an NCO-free polyurethaneurea.

Subsequent to the preparation of Polyur ethanharnsto ff, if in the manufacturing process already inventive solvent or solvent mixtures were used, further diluted with a solvent or solvent mixture and thereby dissolved, wherein the solvent consists exclusively of one or more monohydroxy-functional alcohols or a solvent mixture consisting of exclusively organic solvents, which contains> 50% by weight, based on the total mass of the solvent mixture, of at least one monohydroxy-functional alcohol.

If no solvent or solvent mixtures according to the invention were used during the reaction, the polyurethaneurea is then used in a solvent or solvent mixture following the preparation of the polyurethaneurea, the solvent consisting exclusively of one or more monohydroxyfunctional alcohols or a solvent mixture consisting exclusively of organic solvents which 50% by weight, based on the total mass of the solvent mixture, of at least one monohydroxy-functional alcohol.

Dissolution of the polyurethaneurea can be carried out by the usual techniques of shear, for example by stirring with standard stirrers, for example as mentioned in DI N 28131. The polyurethaneurea is preferably dissolved without the additional addition of external emulsifiers. The polyurethane urea solutions used according to the invention preferably comprise no external emulsifiers.

Suitable solvents or constituents of the solvent mixture are, in principle, all monohydroxy-functional, aliphatic alcohols having one to six carbon atoms, such as, for example, methanol, ethanol, n-propanol. isopropanol, n-butanol, sec-butanol and / or butyiglycol. Particularly preferably, the monohydroxy-functional alcohol is ethanol. If a solvent mixture is used, in addition to the monohydroxy-functional alcohols it is also possible to use <50% by weight, based on the total weight of the solvent mixture, of a further organic solvent. Suitable solvents are, for example, esters, e.g. Ethyl acetate, butyl acetate, methoxypropyl acetate or butyrolactone, ketones, e.g. Acetone or methyl ethyl ketone, ethers, e.g. T etrahy dro for an or tert. Butyl methyl ether, aromatic solvents, e.g. Xylene or solvent naphtha. In the case of using ethanol, typical denaturants may be included as additives in the usual amounts added.

The proportion of other organic solvents is preferably <30% by weight, more preferably <5% by weight and very preferably <2% by weight, based on the total weight of the solvent mixture. In a very particularly preferred embodiment, in addition to monohydroxy-functional , aliphatic alcohols contain no further organic solvents. Other unsuitable solvents are physiologically incompatible solvents, for example dimethylformamide, N-methylpyrrolidone or toluene. as they are often used as cosolvents for polyurethanes or polyurethane ureas, these should preferably not be included in cosmetic compositions.

The other solvents are not water either. The polyurethaneurea solution obtained by dissolving the polyurethane urea in the solvents or solvent mixtures used according to the invention is preferably anhydrous, except for the proportions of water which are contained in the organic solvents used as a result of the preparation.

The proportion of water in the polyurethaneurea solution is preferably <10% by weight, particularly preferably <4.5% by weight and very particularly preferably <1% by weight, based on the total mass of the polyurethaneurea solution.

The proportion of the polyurethaneurea (as active substance) in the polyurethaneurea solution used according to the invention (also referred to as solids content) is preferably> 10 and <80% by weight, more preferably> 15 and <60% by weight and very particularly preferably> 20 and <50% by weight, based on the total weight of the polyurethane urea solution. The hairstyling compositions are preferably those which are predominantly alcohol-based, ie> 10 and <90 wt.%, Based on the total mass of the hairstyling composition, preferably> 15 and <70 wt.% And particularly preferably > 20 and

<60% by weight of aliphatic alcohols containing 1 to 6, preferably 1 to 4, carbon atoms. The alcohols are preferably selected from ethanol and isopropanol; Polyol and their

Derivatives such as propylene glycol, dipropylene glycol, butylene-1 .3-glycol. Polypropylene glycol, (ilykol- ethers such as alkyl (Cl-4) ethers of mono-, di- or Tripropyienglykoi or mono-, di- or triethylene glycol, or mixtures thereof Particularly preferably, the alcohols contain or consist of ethanol, very particularly preferably the alcohol used is ethanol.

The hair setting composition may also contain other cosmetically suitable solvents, for example acetone, unbranched or branched hydrocarbons, cyclic hydrocarbons and / or mixtures thereof.

The hair styling compositions are particularly preferably alcoholic solutions.

The hair styling compositions preferably contain a water content of> 0 and

<30 wt .-%, particularly preferably of> 0 and <20 wt .-%, most preferably of> 0 and <5 wt .-% and further preferably> 0 and <2 wt .-%. In particular, the cosmetic compositions are preferably anhydrous, thus containing no more water than what is producible by the raw materials unavoidably introduced into the formulation.

The proportion of the polyurethane urea solution used in the hairstyling composition is preferably> 0.5 and <80 wt .-%, particularly preferably> 1 and <60 wt .-% and most preferably> 2 and <40 wt .-%, based on the total mass of the hairstyling composition. The solids content of the polyurethane urea solution is preferably selected such that the hairstyling compositions are preferably> 0.1% by weight and <30% by weight, more preferably> 0.2 and <20% by weight and very particularly preferably> 0.5 and <10 wt .-% of the polyurethane urea as an active ingredient, based on the total mass of the hairstyling composition. The active ingredient is understood as meaning the polyurethaneurea without solvent or solvent mixture.

The hair setting compositions of the invention are preferably in the form of gels, sprays and aerosols, which are preferably transparent. Transparent in the sense of this invention fertil means that the haze values of the composition are <100 NTU (Nephelometry Turbidity Unit), preferably <50 NTU, more preferably <10 NTU, and most preferably <5NTU. The haze values are determined by a scattered light measurement at a 90 ° angle (nephelometry) at a wavelength of 860 nm according to DIN EN ISO 7027, carried out at 23 ° C. using a model 2100AN laboratory turbidity meter from HACH LANGE GmbH, Berlin , Germany.

Most preferably, the hair setting compositions are in the form of transparent aerosols or sprays.

The hair setting compositions of the invention may advantageously be present in a pump spray or aerosol package. They can also be advantageously foamed with a propellant gas. Accordingly, pump sprays, aerosol packaging and foam dispensers containing the composition of the invention are also part of the invention.

The hair styling compositions according to the invention preferably have a viscosity of> 0.5 and <20,000 mPas. Gel-form compositions particularly preferably have a viscosity of> 2000 and <20 000 mPas and very particularly preferably of> 5000 and <10000 mPas. Sprayable compositions for sprays particularly preferably have a viscosity of> 0.5 and <500 mPas and very particularly preferably> 1 and <200 mPas.

The indicated viscosities are determined by rotational viscometry according to DI 53019 at 23 ° C. using a rotational viscometer from Anton Paar Germany GmbH. Ostfildern, DE, at a shear rate of 10 s ^-1 .

In a preferred embodiment of the invention, the hair styling composition contains at least one propellant gas.

Propellant gases suitable for the hair styling composition of the present invention are hydrocarbons such as propane, isobutane and n-butane and mixtures thereof. Compressed air, hydrofluorocarbons, such as 1,2-difluoroethane (propellant 152A), carbon dioxide, nitrogen, nitrogen dioxide and dimethyl ether, as well as mixtures of all these gases can also be used. Preference is given to using dimethyl ether or mixtures of propane and butane in the hairstyling composition according to the invention.

The propellant gases preferably account for> 20 and <80 wt%, more preferably> 35 and <65 wt%, based on the total weight of the hair styling composition. Thickeners which are advantageous for the hairstyling compositions according to the invention are:

Crosslinked or non-substituted acrylic acid or methacrylic acid homopolymers or copolymers. These include crosslinked homopolymers of methacrylic acid or acrylic acid, copolymers of acrylic acid and / or methacrylic acid and monomers derived from other acrylic or vinyl monomers, such as C10-30 alkyl acrylates, C10-30

Alkyl methacrylates and vinyl acetate.

Thickening polymers of natural origin, for example, based on cellulose, guar gum, xanthan, scleroglucan, gellan gum, rhamsan and karaya gum, alginates, maltodextrin, starch and its derivatives, locust bean gum, hyaluronic acid. Nonionic, anionic, cationic or amphoteric associative polymers e.g. based on polyethylene glycols and their derivatives, or polyurethanes.

Crosslinked or non-crosslinked homopolymers or copolymers based on acrylamide or methacrylamide, such as homopolymers of 2-acrylamido-2-methylpropanesulfonic acid, copolymers of acrylamide or methacrylamide and methacryloyloxyethyltrimethylammonium chloride or copolymers of acrylamide and 2-acryiamido-2-methylpropanesulfonic acid.

Particularly advantageous thickeners are thickening polymers of natural origin, crosslinked acrylic acid or methacrylic acid homo- or copolymers and crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid. Very particularly advantageous thickeners are xanthan gum, such as the products supplied under the names Keltroi ^® and Kelza ^® from Finna CP Kelco or the products from RHODIA with the name Rhodopol and guar gum, as under the name Jaguar ^® HP 105 by the company Rhodia available products.

Very particularly advantageous thickeners are also re-linked homopolymers of methacrylic or acrylic acid from Lubrizol under the names Carbopol ^® 940, Carbopol ^® 941, Carbopol ^® 980, Carbopol ^® 981, Carbopol ^® ETD 2001, Carbopol ^® EDT 2050, Carbopol ^® 2984, Carbopol 5984 and Carbopol ^® Ultrez 10 ^® by the company 3V under the names synchronous Thalen ^® K, Synthaien ^® L and Synthaien ^® MS and the Finna PROTEX under the names Modarez ^® V 1250 PX. Modarez ^® V2000 PX. Viscaron ^® A1600 PE and Viscaron ^® A700 PE are commercially available.

Very particular advantageous United thicker are further crosslinked copolymers of acrylic acid or methacrylic acid and a C 10-30- Alky lacry lat or C 10-30- Aikylmethacrylat and copolymers of Acrylic acid or methacrylic acid and vinylpyrrolidone. Such copolymers are, for example, by the company Lubrizoi under the names Carbopol ^® 1342, Carbopol ^® 1382, Pemulen ^® TR 1 or Pemulen ^® TR2 and from ISP under the names Ultrathix P-100 (INCI: Aery- lic Acid / VP Crosspolymer) available in the stores. Very particular advantageous thickeners are likewise crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid. Such copolymers are available for example from the Finna Clariant under the names Aristo fi ex ^® AVC (INCI: Ammonium acryloyldimethyltaurate / VP copolymer) available.

Thickeners are generally used in a concentration of> 0 and <2 wt .-%, preferably of> 0.1 and <1 wt .-%.

In the compositions according to the invention may further contain hair-care substances. Panthenol and / or cyclic polydimethylsiloxanes (cyclomethicones) or silicone surfactants (polyether-modified siloxanes) of the dimethicone copolyol or simethicone type may preferably be used as care substances. Cyclomethicones are available, inter alia, under the trade names ^Abil® K4 from Goldschmidt or, for example, DC 244, DC 245 or DC 345 from Dow Corning. Dimethicone copolyols are z. B. under the trade name DC 193 from Dow Corning and Belsil ^® DM 6031 from Wacker offered. The hairstyling compositions according to the invention may, in addition to the polyurethane ureas described above, also contain other suitable film formers, which may in particular also contribute to the strengthening and styling of the hair.

The proportion of one or more further film formers may be from> 0 and <20% by weight and in particular> 0 and <10% by weight, based on the total formulation. Advantageously, the one or more other film formers are selected from the group of nonionic, anionic, amphoteric and / or cationic polymers and mixtures thereof.

Suitable nonionic polymers which may be present in the composition according to the invention either alone or in mixtures, preferably also with anionic and / or amphoteric and / or zwitterionic polymers, are selected from the group: Polyalkyloxazoline;

Vinyl acetate homo- or copolymers, wherein, for example, copolymers of

Vinyl acetate and acrylic esters, copolymers of vinyl acetate and ethylene, copolymers of vinyl acetate and maleic acid esters; - Acrylic acid copolymers such. B. the copolymers of alkyl acrylate and alkyl methacrylate, copolymers of alkyl acrylate and urethanes;

Copolymers of acrylonitrile and nonionic monomer selected from butadiene and (meth) acrylate;

Styrene homopolymers and copolymers, for example, homopolystyrene, copolymers of styrene and alkyl (meth) acrylate, Coplymerisate of styrene, Alkyi-

Methacrylate and alkyl acrylate, copolymers of styrene and butadiene, copolymers of styrene, butadiene and vinylpyridine;

polyamides;

Vinyl lactams homopolymers or copolymers, such as vinylpyrrolidone homo- or copolymers; which include, for example, polyvinylpyrrolidone, polyvinylcaprolactam, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate in various concentration ratios, polyvinylcaprolactam, polyvinylamides and their salts and copolymers of vinylpyrrolidone and dimethylaminoethyl methacrylate, terpolymers of vinylcaprolactam, vinylpyrrolidone and dimethylaminoethyl methacrylate; - polysiloxanes; and

Homopolymers of N-vinylformamide.

Particular preferred nonionic polymers are acrylic acid ester copolymers, homopolymers of vinyl pyrrolidone and copolymers, and polyvinyl caprolactam.

Very particular preferred nonionic polymers are homopolymers of vinylpyrrolidone z. B. Luviskol® K of Finna BASF, copolymers of vinylpyrrolidone and vinyl acetate z. B. Luviskol® VA types from BASF or PVPVA® S630L from ISP. Terpolymers of vinylpyrrolidone, vinyl acetate and propionate such as. B. Luviskol® VAP from BASF and polyvinylcactrolactams e.g. Luviskol® PLUS from BASF.

Advantageous anionic polymers are homopolymers or copolymers with monomer units containing acid groups, which may optionally be copolymerized with comonomers which do not contain acidic groups. are lymerisiert. Suitable monomers are unsaturated, radically polymerizable compounds having at least one Säiiregruppe, and in particular carboxylic acid, sulfonic acid or phosphonic acid.

Examples of anionic polymers which contain carboxylic acid groups are: acrylic or methacrylic acid homo- or copolymers or their salts. These include, for example, the copolymers of acrylic acid and acrylamides and / or their sodium salts, copolymers of acrylic acid and / or methacrylic acid and an unsaturated monomer selected from the group ethylenes, styrene, vinyl esters, acrylic esters, methacrylates, optionally ethoxylated compounds, copolymers of vinylpyrrolidones, acrylic acid and C1-C20 alkyl methacrylates such as Acrylidone LM ^®

Company ISP, copolymers of methacrylic acid, ethyl acrylate and tert-butyl acrylates such as Luvimer ^® 100 P from BASF;

Crotonsäurederivat homo- or copolymers or their salts. These include, for example, vinyl acetate / crotonic, vinyl acetate / acrylate and / or vinyl acetate / Vinylneo- decanoate / crotonic acid copolymers such as Resyn ^® 28-1310 or 28-2930 Resyn ^® Company

AkzoNobei or Luviset ^® CAN from BASF. Sodium acrylate / vinyl alcohol

copolymers; unsaturated C4-C8 carboxylic acid derivatives or carboxylic anhydride copolymers selected from copolymers of maleic acid or maleic anhydride or fumaric acid or fumaric acid or itaconic acid or itaconic anhydride and at least one monomer selected from the group of vinyl esters, vinyl ethers, vinyl halide derivatives, phenylvinyl derivatives, acrylic acid, acrylic acid esters or copolymers of maleic acid or Maleic anhydride or fumaric acid or fumaric anhydride or itaconic acid or itaconic anhydride and at least one monomer selected from the group of allyl esters, methallyl esters and, if appropriate, acrylamides, methacrylamides, alpha-olein. Acrylic acid esters, methacrylic acid esters, vinylpyrrolidones. Further preferred polymers are methylvinylether / maleic acid copolymers, which are formed by hydrolysis of vinyl ether / maleic anhydride copolymers. These polymers can also be partially esterified (ethyl, isopropyl or butyl ester) or partially amidated; water-soluble or dispersible anionic polyurethanes, e.g. B. Luviset ^® PUR the

BASF, which are different from the polyurethanes of the invention.

Advantageous anionic polymers containing sulfonic acid group are Sal / e of polyvinylsulfonic acids, polystyrenesulfonic such. As sodium polystyrenesulfonate or of polyacrylamide sulfonic acids. Particularly advantageous anionic polymers are acrylic acid copolymers, crotonic acid derivative copolymer. Copolymers of maleic acid or maleic anhydride or fumaric acid or fumaric anhydride or itaconic acid or itaconic anhydride and at least one monomer selected from the group consisting of vinyl esters, vinyl ethers, vinyl halide derivatives, phenylvinyl derivatives, acrylic acid, acrylic esters and salts of polystyrenesulphonic acids.

Very particularly advantageous anionic polymers are acrylate copolymers, for example, Luvimer ^® of BASF, ethyl acrylate / N-tert-butylacrylamide / acrylic acid copolymers ULTRAHOLD STRONG from BASF ^®, VA / crotonate / vinyl neodecanoate copolymer such. B. Resyn ^® 28-2930 AkzoNobel, copolymers such. Z. Copolymers of methyl vinyl ether and maleic anhydride partially esterified eg GANTREZ ^® the ISP and sodium polystyrene sulfonates z. B. Flexan ^® 130 AkzoNobel.

Advantageous amphoteric polymers can be selected from polymers containing randomly distributed units A and B in the polymer chain, wherein A represents a moiety derived from a monomer having at least one basic nitrogen atom, and B represents a moiety derived from a acidic monomer having one or more carboxy or sulfonic acid groups. Alternatively, A and B may be groups derived from zwitterionic carboxy-betaine monomers or sulfobetaine monomers. A and B may also be a cationic polymer chain containing primary, secondary, tertiary or quaternary groups, wherein at least one amino group carries a carboxy group or sulfonic acid group bonded via a carbon atom donor group, or A and B are part of a polymer chain with ethylene-α, β-dicarboxylic acid unit in which the carboxylic acid groups have been reacted with a polyamine containing one or more primary or secondary amino groups.

Particular advantageous amphoteric polymers are:

Polymers formed in the copolymerization of a monomer derived from a vinylcarboxy-type vinyl compound such as, in particular, acrylic acid, methacrylic acid, maleic acid, α-chloroacrylic acid, and a basic monomer. The basic monomer is derived from a vinyl compound which is substituted and contains at least one basic atom, such as, in particular, di-1-y-yl-1-yac-1-methacrylate and dialkyl acrylate, dialkylaminoalkylmethacrylamide and -acrylamide. Such compounds have been described in US Pat. No. 3,836,537.

Polymers having units which are selected from: a) at least one monomer selected from acrylamides or methacrylamides substituted on the nitrogen atom by an alkyl group, b) at least one acidic comonomer containing one or more reactive carboxy groups, and c) at least one basic comonomer, such as esters of Acryisäure and methacrylic acid with primary, secondary, tertiary and quaternary amine - substituents and the quaternization of dimethylaminoethyl methacrylate with dimethyl sulfate or diethyl sulfate are derived.

Particularly preferred N-substituted acrylamides or methacrylamides are compounds whose alkyl groups contain 2 to 12 carbon atoms. Very particularly preferred are N-ethylacrylamide, N-t-butylacrylamide, N-t-octylacrylamide, N-O ctylacry lamid, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides.

Suitable acidic comonomers are in particular selected from the group of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid and the alkyl monoesters having 1 to 4 carbon atoms of maleic acid, maleic anhydride, fumaric acid or fumaric anhydride.

Preferred basic comonomers are aminoethyl methacrylate, butylaminoethyl methacrylate, Ν, Ν-dimethylaminoethyl methacrylate, N-t-butylaminoethyl methacrylate.

Crosslinked and fully or partially acylated polyaminoamides, those of polyaminoamides of the following general formula

- [CO-R-CO-Z] - are derived, wherein R is a bivalent group of a saturated dicarboxylic acid, an aliphatic mono- or dicarboxylic acid having ethylenic double bond, an ester of these acids with a lower alkanol with 1 to 6 carbon atoms or a group which results from the addition of one of these acids to a bis primary or bis-secondary amine, and Z is a group which is from a bis-primary, mono- or bis-secondary Pol ya 1 ky I s po I ya min is derived.

The saturated carboxylic acids are preferably among the acids having 6 to 10 carbon atoms, such as adipic acid, 2,2,4-trimethyl adipic acid and 2,4,4, - trimethyl adipic acid, terephthalic acid; Selected from ethylenic double bond acids such as acrylic acid, methacrylic acid and itaconic acid.

The alkanesultones used in the acylation are preferably propanesultone or butanesultone, the salts of the acylating agents are preferably the sodium salts or potassium salts. Polymers with zwitterionic units of the following formula:

wherein RH is a polymerizable unsaturated group such as acrylate, methacrylate, acrylamide or methacrylamide, y and z are integers of 1 to 3, Rn and RB is a hydrogen atom, methyl, ethyl or propyl. R ₁₄ and R 15 represent a hydrogen atom or an alkyl group selected so that the sum of the carbon atoms RH and R 15 does not exceed 10.

Polymers containing such units may also contain units derived from non-zwitterionic monomers such as dimethyl and diethylaminoethyl acrylate or dimethyl and diethylaminoethyl methacrylate or alkyl acrylates or alkyl methacrylates, acrylamides or methacrylamides or vinyl acetate.

Polymers derived from chitosan containing monomer units corresponding to the following formulas:

wherein the first unit is contained in proportions of 0 to 30%, the second unit in proportions of 5 to 50% and the third unit in proportions of 30 to 90%, with the proviso that in the third unit Ri6 a group of the following Formula means:

I

- (OL-C

where q = 0, the groups R _{! 7} , Ris and R19, identical or different, each represent a hydrogen atom, methyl, hydroxy, acetoxy or amino, a monoalkylamine radical or a dialkylamine radical which is optionally interrupted by one or more nitrogen atoms and / or optionally with one or more groups amino, hydroxyl, carboxy, Alkylthio, sulfonic acid, alkylthio, whose alkyl group carries an amino radical, wherein at least one of the groups Rn, Ris and R19 in this case represents a hydrogen atom; or if q = 1, the groups Rn, Ris and R19 are each a hydrogen atom, as well as the salts which form these compounds with bases or acids.

Polymers which correspond to the following general formula and which are described, for example, in French Patent 1,400,366:

wherein R _{20 is} a hydrogen atom, CH ₃ O, CH ₃ CH ₂ O or phenyl, R _{21 is} a hydrogen atom or a lower alkyl group such as methyl or ethyl, R _{22 is} a hydrogen atom or a lower ( ^' 1-alkyl group such as methyl or ethyl, R23 is a lower C 1-4 alkyl group such as methyl or ethyl or a group of the formula: -R 24- (R ₂ 2) 2, where R 24 is a group -CH 2 -CH _2, -CH ₂ -CH ₂ -CH ₂ - or -CH.-CH (CH - and wherein R22 has the meanings given above.

Polymers which can be formed in the N-carboxyalkylation of chitosan, such as N-carboxymethylchitosan or N-carboxybutylchitosan.

Alkyl (C 1.5) vinyl ether / maleic anhydride copolymers which are partially partially modified by semiamidation with a Ν, Ν-dialkylaminoalkylamine such as Ν, Ν-dimethylaminopropylamine or a Ν, Ν-dialkylaminoalcohol. These polymers may also contain other comonomers, such as vinyl caprolactam.

Very particularly advantageous amphoteric polymers are copolymers of at least one acrylate group-containing monomer with at least one further comonomer, such as, for example, the copolymers of octylacrylamide with t-butylaminomethyl methacrylate, and acrylic acid and / or methacrylic acid and / or their esters (eg INCI: octylacrylamide / Acryiates / Butyiami- no ethyl methacrylate copolymer), which are sold under the names AMPHOMER ^®, AMPHOMER LV ^® 71 or 47 BALANCE ^® of the company AkzoNobel commercially, and methyl methacrylate / methyl -dimethylcarboxyiOethylammoniumethylmethactylat copolymers. It may be advantageous to neutralize the anionic and amphoteric polymers with suitable bases to improve their water solubility or water dispersibility.

As neutralizing agents for polymers containing acid groups, the following bases can be used: hydroxides whose cation is ammonium or an alkali metal such. As NaOH or KOH.

Other neutralizing agents are primary, secondary or tertiary amines, ammoalcohols or ammonia. Preference is given here 2-amino-2-methyl-l, 3-propanediol (AMPD), 2-amino-2-ethyl-1, 3-propanediol (AEPD), 2-amino-2-methyl-l-propanol (AMP ), 2-amino-1-butanol (AB), 2-amino-1,3-propanediol, monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), monoisopropanolamine (MI A), diisopropanolamine (DIPA), triisopropanolamine (TIPA), dimethyl laurylamine (DML), dimethyl myristalamine (DMM), and dimethyl stearamine (DMS).

Neutralization may be partial or complete depending on the application.

Optionally usable but less preferred are cationic polymers, such as polymers containing primary, secondary tertiary and / or quaternary amino groups, which are part of the polymer chain or directly attached to the polymer chain.

Optionally, the usual additives for hair styling compositions may also be included in the composition. These may be, for example, silicones or silicone derivatives, wetting agents, humectants, plasticizers such as glycerol, glycol and phthalic esters and ethers, UV absorbers, dyes, pigments, and other colorants, anticorrosives, neutralizers, detackifiers, combination agents and conditioners, antistatic agents, brighteners, preservatives, proteins and derivatives thereof, amino acids, vitamins, emuigators, surfactants, viscosity modifiers, thickeners and rheology modifiers, gelling agents, stabilizers, surfactants, sequestering agents, chelating agents. Pearlescing agents, aesthetic enhancers, fatty acids, fatty alcohols, triglycerides, botanical extracts and herbal remedies. These additives may be present in total at a concentration of about> 0 and <15% by weight, preferably> 0.01 and <10% by weight, based on the total weight of the composition.

In a preferred embodiment of the invention, the hair styling composition A) contains at least one polyurethane urethane which is dissolved in a solvent or solvent mixture, the solvent consisting exclusively of one or more monohydroxy-functional alcohols or a solvent mixture consisting exclusively of organic solvents Solvents, soft> 50 wt .-%, based on the total mass of Solvent mixture containing at least one monohydroxy-functional alcohol is used,

at least one propellant selected from dimethyl ether and a mixture of propane and butane,

at least one aliphatic alcohol having 1 to 6 C atoms

Hair care substances and

optionally further film formers.

In a particularly preferred embodiment of the invention contains the hairstyling composition

A)> 0.5 and <80 wt .-% at least one polyurethane urea, which is dissolved in a solvent or solvent mixture, wherein the solvent consists exclusively of one or more monohydroxyfunktionellen alcohols or a solvent mixture consisting exclusively of organic solvents, which> 50 wt %, based on the total mass of the solvent mixture, of at least one monohydroxy-functional alcohol is used,

B)> 35 and <65% by weight of at least one blowing agent selected from dimethyl ether and / or a mixture of propane and butane,

C)> 10 and <90% by weight, based on the total composition, of at least one aliphatic alcohol having 1 to 6 C atoms,

D)> 0.01 and <10 wt .-% Haarp (laying substances and

E)> 0 and <20% by weight of further film formers,

in each case based on the total mass of the hairstyling composition, wherein the components A) to E) add up to 100 wt .-%.

The solids content of the polyurethane urea solution is preferably selected such that the hairstyling compositions contain> 0.2 and <20% by weight of the polyurethaneurea as active ingredient, based on the total mass of the hairstyling composition. In a particularly advantageous embodiment, the hairstyling composition contains a further film former E), in particular in a proportion of> 1 and <20 wt .-%, preferably> 1 and <10 wt .-%.

The further film former E) is particularly advantageously copolymers of at least one acrylate group-containing monomer with at least one further comonomer, for example the copolymers of copolymers of octylacrylamide with t-butylaminomethyl methacrylate, and also acrylic acid and / or methacrylic acid and / or esters thereof ( eg INCI: octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer, which is used under the Names AMPHOMER ^®, AMPHOMER LV ^® 71 or 47 BALANCE ^® of the company AkzoNo- bel are commercially available, and / or methyl methacrylate / methyl dimethylcarboxymethylammoniumethylmethacrylat copolymers.

Suitable acrylate-containing monomers are, in particular, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-octyl acrylate, ethylhexyl acrylate, nonyl acrylate, 2-methyl octyl acrylate, 2-tert. Butylheptyl acrylate, 3-isopropyl propyl acrylate, decyl acrylate, undecyl acrylate, 5-methyl undecyl acrylate, dodecyl acrylate, 2-methyldodecyl acrylate, tridecyl acrylate, 5-methyltridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, 2-methylhexadecyl acrylate, Heptadecyl acrylate, 5-iso-propyiheptadecyl acrylate, 5-ethyloctadecyl acrylate, octadecyl acrylate, nona-decyl acrylate, eicosyl acrylate, cycloalkyl acrylates such as cyclopentyl acrylate, cyclohexyl acrylate, 3-vinyl-2-butylcyclohexyl acrylate, cycloheptyl acrylate, cyclooctyl acrylate, bornyl acrylate, Tetrahy dro furfurylacry lat and isobornyl acrylate. Preference is given to ethyl acrylate, n-butyl acrylate, ethylhexyl acrylate, cyclohexyl acrylate and particularly preferred are ethyl acrylate, n-butyl acrylate or ethylhexyl acrylate.

Advantageously, the further monomer is selected from the group of nonionic, anionic, amphoteric and / or cationic monomers or mixtures thereof.

Particularly suitable further monomers, which may be present alone or in mixtures, preferably also with anionic and / or amphoteric and / or zwitterionic monomers, are:

Styrene or its derivatives. vinyl acetate

Acrylic acid or methacrylic acid or its salts. These include for example copolymers of vinyl pyrrolidone, acrylic acid and C1-C20 alkyl methacrylates such as Acrylido- ne ^® LM the company ISP, copolymers of methacrylic acid, ethyl acrylate and tert-butyl acrylates such as Luvimer ^® 100 P from BASF, ethyl acrylate / N-tert , Butylacrylamide / Ac rylsäure-Co | X) mers ULTRAHOLD® ^® STRONG by BASF;

Crotonic acid derivative or its salts. They include vinyl acetate / crotonic acid, vinyl acetate / acrylate and / or vinyl acetate / Vinyineodecanoat / crotonic copolymers to eg Resyn ^® 28-1310 or 28-2930 Resyn ^® Company AkzoNobei or Luv i- set ^® CAN BASF, NatriumacrylaWinylalkohol copolymers; Unsaturated C4-C8 carboxylic acid derivatives or carboxylic anhydride copolymers selected from Copolymeri sate of maleic acid or maleic anhydride or fumaric acid or fumaric anhydride or itaconic acid or itaconic anhydride and at least one acrylic acid esters. Very particularly advantageous polymers are copolymers of maleic anhydride partially esterified eg Methyivinylether and GANTREZ ^®;

Acrylamides or methacrylamides. These include, for example, acrylates / Octylac- rylamide copolymer z. B. Amphomer.RTM ^® HC the company AkzoNobel;

Basic monomers derived from a substituted vinyl compound having at least one basic atom, such as, in particular, dialkylaminoalkyl methacrylate and acrylate, dialkylaminoalkylmethacrylamide and acrylamide. Preferred basic comonomers are aminoethyl methacrylate, butylaminoethyl methacrylate,

N, N-t-butylaminoethyl methacrylate.

It is very particularly preferred if the copolymer comprises or consists of octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer.

Another object of the invention is the use of the hair styling composition according to the invention for shaping, strengthening and / or fixing the hair.

Also a method of shaping, strengthening or fixing the hair using the hair styling compositions of the invention wherein the hair styling composition is applied to the hair is the subject of the invention.

Advantageously, the hair styling compositions remain at least partially on the hair in the inventive method.

The present invention will be illustrated by the following examples.

Example:

Unless otherwise indicated, all percentages are by weight.

Unless otherwise stated, all analytical measurements are based on temperatures of 23 ° C.

The solids contents (non-volatile content) were determined according to DIN-EN ISO 3251.

NCO contents were determined volumetrically in accordance with DIN-EN ISO 1 1909, unless expressly stated otherwise.

The control on free NCO groups was conducted (cm ^" 'band at 2260) by means of IR spectroscopy.

The indicated viscosities were determined by means of rotational viscometry according to DIN 53019 at 23 ° C. with a rotational viscometer from Anton Paar Germany GmbH, Ostfildern, DE.

The number average molecular weight was determined by gel permeation chromatography (GPC) in tetrahydrofuran at 23 ° C. The procedure according to DIN 55672-1 is "gel permeation chromatography, Part 1 - tetrahydrofuran as eluent" (SECurity GPC system from PSS Polymer Service, flow rate 1, 0 ml / min, columns: 2 × PSS SDV linear M, 8 × 300 mm, 5 μιη; RI D detector). This polystyrene samples of known molecular weight are used for calibration. The calculation of the number average molecular weight is software-based. Baseline points and evaluation limits are defined in accordance with DIN 55672 Part 1.

The turbidity values [NTU] were determined by means of a scattered light measurement at a 90 ° angle (nephelometry) at a wavelength of the ss radiation 860 nm in accordance with DIN EN 1 SO 7027, carried out at 23 ° C. using a model 2100AN laboratory turbidity meter from BACH LANGE GmbH, Berlin, Germany. Used substances and abbreviations:

PolyTHF ^® 2000: Polytetramethylenglykolpolyol, OH -value 56 mg KOH / g, / Ahlen average molecular weight 2000 g mol (BASF AG, Ludwigshafen, DE)

PolyTHF ^® 1000: Polytetramethylenglykolpolyol, OH number 1 12 mg KOH / g, number-average number average molecular weight 1000 g / mol (BASF AG, Ludwigshafen, DE)

Ethanol Unless otherwise indicated by MEK

ethanol from the company Nordbrand, Norhausen, DE used.

Isocyanates and the other polymeric polyols were used by Bayer MaterialScience AG, Leverkusen, DE. Other chemicals from Sigma-Aldrich Chemie GmbH, Taufkirchen, DE. Unless otherwise stated, the raw materials were used without further purification or pretreatment.

Example 1 Preparation of a Polyurethane Solution in Ethanol (According to the Invention)

150 g PolyTHF ^® 2000 and 37.50 g PolyTHF ^® 1000 were dewatered in a standard stirred apparatus for one hour at 100 ° C under diaphragm pump vacuum and then placed under nitrogen at 80 ° C. Then 75.06 g of isophorone diisocyanate were added at 80 ° C. over the course of 5 minutes, and the mixture was stirred at 110 ° C. for about 3 hours until the theoretical NCO value had fallen below. The prepolymer was cooled to 40 ° C and it was dissolved in 630.4 g of ethane l (denatured with diethyl phthalate) and then the temperature was reduced to 15 ° C. Then, a solution of 37.6 g of methyl enbis (4-aminocyclohexan) and 270 g of ethanol (denatured with diethyl phthalate) within 30 min added: after a further 30 minutes at 20 ° C I was still detectable isocyanate groups IR spectroscopy. It was further stirred for about 16 hours at 23 ° C until no more free isocyanate groups were detectable by IR spectroscopy.

The resulting clear, storage-stable solution had the following properties:

Lowest salary: 23%

Viscosity (viscometer, 23 ° C): 280 mPas Haze value: 1.2 NTU

Example 2 Preparation of a Polyurethane Solution in Ethanol (Inventive) 300 g PolyTHF ^® 1000 were dewatered in a standard stirred apparatus for one hour at 100 ° C under diaphragm pump vacuum and then placed under nitrogen at 80 ° C. Then 3.44 g of isophorone diisocyanate was added at 80 ° C. over the course of 5 minutes and the mixture was stirred at 110 ° C. (about 3 hours) until the theoretical NCO value had fallen below. The prepolymer was cooled to 40 ° C and it was dissolved in 517 g of ethanol (denatured with MEK) and then the temperature was reduced to 16 ° C. Then a solution of 58.8 g of methylenebis (4-aminocyclohexane) and 222 g of ethanol (denatured with MEK) was metered in over 30 minutes, after which an additional 410 g of ethanol were added. The mixture was stirred until no more free isocyanate groups were detectable by IR spectroscopy.

The resulting clear, storage-stable solution had the following properties:

Solids content: 30.2%

Viscosity (viscometer, 23 ° C): 85000 mPas

Example 3 Preparation of a Polyurethane Solution in Ethanol (Inventive)

300 g PolyTHF ^® 1000 were dewatered in a standard stirred apparatus for one hour at 100 ° C under diaphragm pump vacuum and then placed under nitrogen at 80 ° C. Then 133.44 g of isophorone diisocyanate were added at 80 ° C within 5 min and it was stirred at 110 ° C as long (about 3 hours) until the theoretical NCO value was exceeded. The prepolymer was cooled to 40 ° C and it was dissolved in 498 g of ethanol (denatured with MEK) and then the temperature was reduced to 16 ° C. Then a solution of 40.9 g of isophoronediamine and 2 1 3 g of ethanol (denatured with MEK) was added within 30 min, then another 7.15 g of ethanol was added to isophoronediamine. The mixture was stirred until no more free isocyanate groups were detectable by IR spectroscopy. The resulting clear, storage-stable solution had the following properties:

Solids content: 40.8%

Viscosity (viscometer, 23 ° C): 3850 mPas

Example 4 Preparation of a Polyurethane Solution in Ethanol (Inventive)

250 g PolyTH F '2000 and 62.5 g of PolyTHF ^® 1000 were dewatered in a standard stirred apparatus r for one hour at 100 ° C under diaphragm pump vacuum and then placed under nitrogen at 80 ° C. Then 83.4 g of isophorone diisocyanate was added at 80 ° C within 5 min and it was stirred at 1 10 ° C as long (about 3 hours) until the theoretical NCO value was exceeded. The prepolymer was cooled to 40 ° C and it was dissolved in 425 g of ethanol and then the temperature was reduced to 18 ° C. Then a solution of 9.0 g of ethylenediamine and 180 g of ethanol was metered in within 30 minutes. An additional 0.83 g of ethylenediamine was added and stirring was continued until free isocyanate groups were no longer detectable by IR spectroscopy.

The resulting clear, storage-stable solution had the following properties:

Solids content: 40.7%

Viscosity (viscometer, 23 ° C): 34600 mPas

Step Example! 5: Preparation of a polyurethane solution in ethanol (according to the invention)

21 1 g PolyTHF ^® 2000 and 52.7 g PolyTHF ^® 1000 were dewatered in a standard stirred apparatus envakuum for one hour at 100 ° C in the diaphragm pump, then 5.4 g of neopentyl glycol were added and the mixture was then under nitrogen at 80 ° C submitted. Then 93.4 g of isophorone diisocyanate was added at 80 ° C within 5 min and it was stirred at 110 ° C as long (about 3 hours) until the theoretical NCO value was exceeded. The prepolymer was cooled to 40 ° C and it was dissolved in 420 g of ethanol (denatured with diethyl phthalate) and then the temperature was reduced to 17 ° C. Then a solution of 35.3 g of methylenebis (4-aminocyclohexane) and 180 g of ethanol (denatured with diethyl phthalate) was metered in within 30 min. An additional 0.67 g of methylenebis (4-aminocyclohexane) was added and then further stirred until no more free isocyanate groups were detectable by IR spectroscopy. The resulting clear, storage-stable solution had the following properties:

Solids content: 40.5%

Viscosity (viscometer, 23 ° C): 7060 mPas

Step Example! 6: Preparation of a polyurethane solution in ethanol (ertlndungsgeniäü)

226.2 g Polypropylengiykol having a number average molecular weight of 2000 g / 'mol and 62.5 g Polypropylengiykol having a number average molecular weight of 1000 g / mol were dehydrated in a standard stirrer for one hour at 100 ° C in a diaphragm pump vacuum, the mixture was then submitted under nitrogen at 80 ° C. Then 83.4 g of isophorone diisocyanate was added at 80 ° C within 5 min and it was stirred at 120 ° C for 6 hours until the theoretical NCO value was exceeded. The prepolymer was cooled to 40 ° C and it was dissolved in 280 g of ethanol and then the temperature was reduced to 18 ° C. Then a solution of 34.1 g of methylene-bis (4-aminocyclohexan) and 120 g of ethanol was added within 30 min. An additional 4.5 g of methylenebis (4-aminocyclohexane) were added. and then stirred until no more free isocyanate groups were detectable by IR spectroscopy.

The resulting clear, storage-stable solution had the following properties: Solids content: 49.8%

Viscosity (viscometer, 23 ° C): 1 100 mPas

Example 7 Production of a Polyurethane Solution in Ethanol (According to the Invention)

160 g PolyTHF ^® 2000 and 40.0 g of PolyTHF ^® 1000 were dewatered in a standard stirred apparatus for one hour at 100 ° C under diaphragm pump vacuum and then placed under nitrogen at 80 ° C. Then, at 80 ° C was within 5 min 62.9 g of bis (4,4'-isocyanatocyclo ^ hexyl) ^~ triethane added and as long stirred at 1 10 ° C (about 3 hours) until the theoretical NCO value was below. The prepolymer was cooled to 40 ° C and it was dissolved in 595 g of ethanol and then the temperature was reduced to 19 ° C. Then, a solution of 20.2 g of methylenebis (4-aminocyclohexane) and 255 g of ethanol was added within 30 min. An additional 4.5 g of methylenebis (4-aminocyclohexane) was added and stirring was continued until free isocyanate groups were no longer detectable by IR spectroscopy. The resulting clear, storage-stable solution had the following properties:

Solids content: 25.2%

Viscosity (viscometer, 23 ° C): 3400 mPas

Example 8 Preparation of a Polyurethane Solution in Ethanol (According to the Invention)

200 g PolyTHF ^® 2000 and 50.0 g of PolyTHF ^® 1000 were dewatered in a standard stirred apparatus for one hour at 100 ° C in Membranpumpenvalatum and then placed under nitrogen at 70 ° C. Then 50.4 g of hexamethylene diisocyanate were added at 70 ° C within 5 min and it was stirred at 1 10 ° C as long (about 3 hours) until the theoretical NCO value was below. The prepolymer was cooled to 40 ° C and it was dissolved in 340 g of ethanol and then the temperature was reduced to 18 ° C. Due to the high viscosity, a further 270 g of ethanol were added, then a solution of 25.2 g of methylenebis (4-aminocyclohexane) and 150 g of ethanol was metered in within 30 min. The mixture was then stirred until free isocyanate groups were no longer detectable by IR spectroscopy. The resulting clear, storage-stable solution had the following properties:

Solids content: 30.1%

Viscosity (viscometer, 23 ° C): 15500 mPas

Vergleichsbeispie! 1: Test for producing a Polyurethanharnston ^* - solution in ethanol 100 g PolyTHF ^® 2000, 25.0 g PolyTHF ^® 1000 and 127.5 g of a linear difunctional amorphous Polyestersdiols on adipic acid, 1, 6-hexane diol and having a number average Neopentlyglykol Molecular weight of 1700 g / mol were dehydrated in a standard stirred apparatus for one hour at 100 ° C in a membrane pump vacuum and then under nitrogen at 80 ° C presented. 66.7 g of isophorone diisocyanate were then added at 80 ° C. over the course of 5 minutes, and the mixture was stirred at 110 ° C. (about 3 hours) until the theoretical NCO value had fallen below. The prepolymer was cooled to 40 ° C and it was dissolved in 720 g of ethanol, whereby the product did not dissolve completely and then the temperature was reduced to 17 ° C. Then, a solution of 25.2 g of methylenebis (4-aminocyclohexane) and 310 g of ethanol was metered in over 30 minutes, resulting in a white turbidity. The mixture was then stirred, forming no stable solution but a 2-phase mixture resulted from which deposited the solid phase.

Comparative Example 2: Attempted Preparation of a Polyurethaneurea Solution in Ethanol 200 g of a linear, difunctional, polycarbonate diol based on 1,6-hexanediol having a number average molecular weight of 2000 gmole and 50 g of a linear, difunctional, polycarbonate diol based on 1 , 6-hexanediol, having a number average molecular weight of 1000 g / mol were dehydrated in a standard stirring apparatus for one hour at 100 ° C in a diaphragm pump vacuum and then placed under nitrogen at 80 ° C. 66.7 g of isophorone diisocyanate were then added at 80 ° C. over the course of 5 minutes, and the mixture was stirred at 110 ° C. (about 3 hours) until the theoretical NCO value had fallen below. The prepolymer was cooled to 40 ° C and it was dissolved in 720 g of ethanol, whereby the product did not dissolve completely and then the temperature was reduced to 17 ° C. Then, a solution of 25.2 g of methyl enbis (4-aminocyclohexan) and 310 g of ethanol was added within 30 min, thereby forming a two-phase mixture. The mixture was then stirred, forming no stable solution but a 2-phase mixture resulted from which deposited the solid phase.

Application tests: Compatibility with propellant mixture propane / butane

A mixture of propane and butane (weight ratio 2: 1) with concentrations according to Table 1 with a polyurethane urea solution according to the invention or a polyurethane urea according to the prior art, each containing 2 wt .-% polyurethaneurea, at room temperature for about 10 min with a stirrer mixed. The stability and appearance was determined immediately after mixing at room temperature. Table 1 summarizes the results and shows that stable and transparent mixtures are obtained only with the polyurethaneurea according to the invention.

Table 1 :

Curl retention:

For the so-called "Curl Retention" experiments, commercially available European mixed hairs (useful length: 18 cm, Kerling, weight: 0.7 g) were used. The hair was subjected to a standardized washing procedure before use. For this purpose, the hair soaked in water for 15 minutes was shampooed with 0.2 ml of standard shampoo for one minute, rinsed thoroughly with warm water, cold-dry-puffed and conditioned at 21 ± 1 ° C and 50 ± 5% relative humidity. 0.1 g of a 2 wt% polymeric active material (polyacrylate and / or polyurethane urea) containing solution was applied to the strand. The hairs prepared in this way were wound on 16 mm winder and then conditioned at 21 ± 1 ° C and 50 ± 5% relative humidity for at least 18 hours. The solutions used contained the polyurethane urea solution according to the invention and / or the product octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer (Amphomer der

Akszo Nobel), 100% neutralized with aminomethylpropanediol and dissolved in ethanol, in the mixture indicated in the figures.

The "Curl Retention" experiments were performed in a special air-conditioned chamber at a relative humidity of 90 ± 5%, the temperature in the chamber was 21 ± 1 ° C. The prepared strands were simultaneously hung in the chamber was read at different times on a scale and each experiment was performed with eight strands.

The "Curl Retention" was calculated according to the following formula:

CR = (lf-lt) / (lf-lti) xl 00; in the lf the length of the strand, l _t i original length of the curly strand of hair, and l _t length of the curly strand of hair were at time t. The results of the measurement are shown graphically in FIG. It is clear from this that good curl retention is achieved with the polyurethaneurea used according to the invention, in particular also in combination with polyacrylate film formers according to the prior art.

For the so-called "snap" tests, commercially available European mixed hairs (useful length: 18 cm, Körting, weight: 0.7 g) were used and the hair was subjected to a standardized washing procedure before use Hair soaked with 0.2 l of standard shampoo shampooed for one minute, rinsed thoroughly with warm water, cold dry, and conditioned at 21 ± 1 ° C and 50 + 5% relative humidity.

3 mg of active substance (polyurethaneurea used in accordance with the invention or polyacrylate dissolved in ethanol) / 1 g of hair strand was applied to the tress by means of a pipette. The liquid was distributed evenly on the hair with the help of the finger.

The solutions used contained the polyurethane according to the invention and / or the product octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer (Amphomer der Company Akszo Nobel), 100% neutralized with Am i no me thy lpropanedio 1 and dissolved in ethanol, in the mixture indicated in the figures.

From the hairs prepared in this way, strands were wound on 16 mm winder and then conditioned at 21 + 1 ° C and 50 ± 5% relative humidity for at least 18 hours.

The unwound strand is hung on a device and the initial length is determined using a scale.

The curls were opened with the finger and the length of the strand determined after the time t.

The "curl recovery" was calculated according to the following formula: in the, i _t i original length of the curly strand of hair and l length of the curly strand of hair at the time t were.

The test was repeated 10 times.

FIG. 2 also shows that good curl retention is achieved with the polyurethaneurea used according to the invention, in particular also in combination with polyacrylate film former according to the prior art.

Claims

claims:

1. Hairstyling composition containing at least one propellant and / or a thickener, characterized in that it further contains a polyurethaneurea, which has no ionic hydrophilicizing groups and which is dissolved in a solvent or solvent mixture, wherein the solvent exclusively from one or more monohydroxyfunktionellen Alcohols or a solvent mixture consisting exclusively of organic solvents, which contains> 50 wt .-%, based on the total mass of the Lösemitteigemisches, of at least one monohydroxyfunktionellen alcohol is used, wherein the polyurethaneurea is composed of a) at least one aliphatic, araliphatic and or cycloaliphatic diisocyanate,

b) at least one Polyetherpoiyol having a number average molecular weight Mn> 400 and <6000 g / mol and a hydroxyl functionality of> 1, 5 and <4, c) at least one amino-functional compound having at least two isocyanate-reactive amino groups,

d) if appropriate, at least one alcohol which has at least two hydroxyl groups and a molecular weight of> 60 and <399 g / mol,

e) optionally at least one compound which has an isocyanate-reactive group and

f) optionally <20% by weight, based on the total mass of the polyurethane urea, of at least one polymer having a number-average molecular weight Mn> 500 and <6000 g mol and a hydroxyl functionality of> 1, 5 and <4, which varies is from b).

Hair styling composition according to claim 1, characterized in that the polyurethaneurea has no hydrophilizing groups.

3. Hairstyling composition according to claim 1 or 2, characterized in that the component b) is selected from poly (tetramethylene glycol) polyether polyols.

4. Hairstyling composition according to one of claims 1 or 3, characterized in that the component b) has a number average molecular weight Mn> 500 and <2500 g / mol and a hydroxyl functionality of> 1.9 and <3.

5. hair styling composition according to one of claims 1 to 4, characterized in that the component a) is selected from aliphatic, araliphatic and / or cycloaliphatic diisocyanates having at least one isocyanate group bonded to a tertiary C atom.

6. hair styling composition according to any one of claims I to 5, characterized marked, that the component a) is selected from IPDi and / or H12-MDI.

7. hair styling composition according to any one of claims 1 to 6, characterized in that the component c) is selected from amines having at least two amino groups, which are bound to primary and / or secondary C atoms.

8. Haarstyl in «composition according to one of claims 1 to 7, characterized in that the monohydroxy-functional alcohols are selected from aliphatic alcohols having one to six carbon atoms. 9. Hair styling composition according to one of claims 1 to 8, characterized in that it contains> 0.2 and <20 wt .-% of the polyurethane urea as an active ingredient, based on the total weight of the hair styling composition.

10. Hair styling composition according to one of claims 1 to 9, characterized marked, that it is present as an aerosol, spray or gel.

11. A hair styling composition according to any one of claims 1 to 10, characterized in that it contains a further film former, which is a copolymer of at least one acrylate group-containing monomer with at least one other comonomer.

12. Hair styling composition according to claim 11, characterized in that the copolyester is octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer.

13. Use of the hair styling composition according to one of claims 1 to 12 for

Shaping, strengthening and / or fixing the hair.

A method of shaping, strengthening or fixing the hair using hairstyling compositions according to any one of claims 1 to 12, wherein the hair styling composition is applied to the hair.

15. A process for producing a hair styling composition, characterized in that at least one polyurethaneurea is used which has no ionically hydrophilicizing groups and which is dissolved in a solvent or solvent wherein the solvent consists exclusively of one or more monohydroxy-functional alcohols or a solvent mixture consisting exclusively of organic solvents which contains> 50% by weight, based on the total mass of the solvent mixture, of at least one monohydroxy-functional alcohol, the polyurethaneurea is composed of a) at least one aliphatic, araliphatic and / or cycloaliphatic diisocyanate,

b) at least one polyether polyol having a number average molecular weight Mn> 400 and <6000 g mol and a hydroxyl functionality of> 1, 5 and <4, c) at least one amino-functional compound having at least two isocyanate-reactive amino groups,

e) optionally at least one compound which has an isocyanate-reactive group and

f) optionally <20% by weight, based on the total mass of the polyurethaneurea, of at least one polyol having a number-average molecular weight Mn> 500 and <6000 g / mol and a hydroxyl functionality of> 1.5 and <4, which is different from b) ,