EP2461789A2

EP2461789A2 - Hair treatment product comprising solid particles modified by polyethers and hair-fixing polymers

Info

Publication number: EP2461789A2
Application number: EP10737327A
Authority: EP
Inventors: Matthias Schweinsberg
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2009-08-04
Filing date: 2010-07-29
Publication date: 2012-06-13
Also published as: DE102009028207A1; WO2011015513A2; WO2011015513A3

Abstract

The invention relates to hair treatment products containing solid particles in addition to a hair-fixing polymer, said solid particles being modified on the surface with polyethers. Said polyethers comprise a polyoxyalkylene chain consisting of ethylene oxide unit or ethylene oxides and propylene oxide units, with a maximum part of 50 wt. % of propylene oxide units, in relation to the weight of the polyoxyalkylene chain. Said hair treatment product is suitable for temporary hairstyling. Said solid particles modified with polyethers are suitable for using to prevent greasy skin and/or greasy hair.

Description

"Hair treatment compositions with polyether-modified solid particles and hair-setting polymers"

The present invention relates to hair treatment compositions containing in addition to at least one hair-setting polymer additionally polyether-modified solid particles and the use of this hair treatment agent for temporary hairstyle design and a corresponding hair treatment process.

An attractive-looking hairstyle is now generally considered an indispensable part of a well-groomed appearance. Due to current fashion trends, hairstyles are always considered to be chic, which in many hair types can only be built up using firming agents or can be maintained for a longer period of time up to several days. Therefore, hair treatment agents that serve a permanent or temporary shaping of the hair play an important role. Temporary shapes that should give a good hold, without affecting the healthy appearance of the hair, such as their gloss, can be achieved for example by hair sprays, hair waxes, hair gels, hair mousses, hair drier, etc.

Corresponding temporary shaping agents usually contain synthetic polymers as the shaping component. Preparations containing a dissolved or dispersed polymer can be applied to the hair by means of propellant gases or by a pumping mechanism. In particular, however, hair gels and hair waxes are generally not applied directly to the hair, but distributed by means of a comb or hands in the hair.

The most important property of a composition for the temporary deformation of keratinic fibers, also referred to below as styling agent, is to give the treated fibers in the produced form the strongest possible hold. If the keratin fibers are human hair, it is also referred to as a strong hairstyle or the high degree of retention of the styling agent. The hairstyle hold is essentially determined by the type and amount of synthetic polymer used, but also an influence of the other components of the styling can be given by means of. In addition to a high degree of hold, styling agents must meet a whole range of other requirements. These may be broadly subdivided into properties on the hair, properties of the particular formulation, eg properties of the foam, of the gel or of the sprayed aerosol, and of properties relating to the handling of the styling agent, whereby the properties on the hair are of particular importance. Particularly noteworthy are moisture resistance, low tackiness and a balanced conditioning effect. Furthermore, a styling agent should be universally applicable as possible for all hair types.

Often, a high degree of retention is undesirably accompanied by a high brittleness of the hairstyle. The treated with the appropriate styling hair are rigid, brittle and act unnaturally firm. As a result, they feel rough and unkempt. In addition, the polymer film, which leave the means when applied to the hair in the cases mentioned inflexible so that it breaks under stress. This leads to the formation of so-called Filmpiaken, ie residues that detach during the movement of the hair and give the impression that the user of the corresponding styling agent would dandruff.

Another problem is that the product consistency of such products is viewed negatively by the consumer by these products are considered to be tough, sticky and poorly applied.

Object of the present invention was therefore to provide a means for temporary deformation of keratinous fibers available, which is characterized by a very high degree of hold without the need for flexibility and a neat hair feel and pleasant product feel.

It has now surprisingly been found that styling products with a high degree of hold and a pleasant feeling of care can be provided in the hair by incorporating a combination of specific ingredients into the compositions.

A first subject of the invention is therefore a cosmetic agent containing in a cosmetically acceptable carrier

(a) solid particles modified on the surface with polyethers, the polyethers comprising a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum of 50% by weight of propylene oxide units by weight the polyoxyalkylene chain,

and

(B) at least one film-forming and / or setting polymer. By "solid particles" is meant all particulate solids present at room temperature.

By "polyether" is meant any chemical molecules / structures comprising a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units having a maximum of 50 weight percent of propylene oxide units based on the weight of the polyoxyalkylene chain ,

The term "polyether-modified solid particles" is understood according to the invention to mean solid particles which are surface-modified with polyethers, the polyethers comprising a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum proportion of 50% by weight of propylene oxide Units based on the weight of the polyoxyalkylene chain.

The solid particles (a) are preferably present in the compositions according to the invention in an amount of from 0.01 to 10.0% by weight, more preferably from 0.1 to 2.0% by weight, very particularly preferably from 0.2 to 1 , 0 wt .-%, each based on the weight of the total composition included.

The agents according to the invention preferably contain such modified solid particles which have a particle size of from 0.01 μm to 100 μm, particularly preferably less than 5 μm, very particularly preferably <0.1 μm.

The modification of the surface of the solid particles with the said polyethers can be effected, for example, via a covalent bond between the surface and the polyether or can take place via an electrostatic interaction between the surface and the polyether.

The solid particles are preferably selected from aluminates, silicates, aluminum silicates, zinc oxide, titanium dioxide and SiO ₂ , in particular aluminates, silicates, aluminum silicates and silica gel. Likewise according to the invention are in each case mixtures of these preferred or particularly preferred solid particles.

Particularly preferred aluminates are selected from alpha-alumina, beta-alumina, gamma-alumina and mixtures thereof.

Particularly preferred aluminum silicates (also called aluminosilicates) are selected from phyllosilicates, tectosilicates. Preferred phyllosilicates are selected from kaolins (here in particular kaolinite, dickite, halloysite and nacrite), serpentine, talc, pyrophyllite, montmorillonite, quartz, bentonite, mica (here in particular under illite, muscovite, paragonite, phlogopite, biotite, lepidolite, margarite , Smectite (here in particular montmorillonite, saponite, nontronite, hectorite)).

Preferred tectosilicates are selected from feldspar minerals (especially albite, orthoclase, anorthite, leucite, sodalite, hauyne, labradorite, lasurite, nosean, nepheline), zeolites.

Zeolites are natural or synthetic crystalline aluminum silicates of alkali or alkaline earth metals. Zeolites consist of SiO ₄ and AIO ₄ tetrahedra linked by four, six, eight or twelve oxygen rings, resulting in cavities extending through the entire zeolite crystal. Among the preferred zeolites are the zeolites of the type A, K, L, PL, O, T, X, Y and Ω and mixtures thereof. Particularly preferred zeolites are in particular selected from zeolite A (here in particular under Na ₁₂ [(AIO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]), Ca ₅ Na ₅ [(AIO ₂ ) i ₂ (SiO ₂ ) i ₂ ], [Ki ₂ [(AIO ₂ ) i ₂ (SiO ₂ ) i ₂ ]), zeolite X (here in particular under Na ₈₆ [(AIO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]), Ca ₄ oNa ₆ [(AlO ₂ ) ₈₆ ( Si0 ₂ ) ₁₀ 6)], Sr ₂₁ Ba ₂₂ [(AIO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]), zeolite Y (here in particular under Na ₅₆ [(AIO ₂ ) ₅₆ (SiO ₂ ) i ₃₆ ], Na ₅₆ [(AIO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ]), ZSM-5 (here in particular Na ₃ [(AIO ₂ ) ₃ (SiO ₂ ) 93]), mordenite, silicalite (SiO ₂ ) ₉₆ .

According to the invention, those cosmetic agents are preferred which are contained in a cosmetically acceptable carrier

(A) Polyether-modified solid particles, which are obtained by reacting hydroxy-containing solid particles with at least one polyether of formula (I)

T-K-A-K'-T (I)

wherein

A is a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and

Propylene oxide units, with a maximum proportion of 50% by weight of propylene oxide units, based on the weight of A,

K and K 'independently represent a connectivity selected from a covalent bond or from a molecular fragment having two free valencies, T and T are independently selected for a molecular fragment comprising at least one substituent

anionic residue

wherein R and R 'independently of one another represent a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl),

x stands for 1, 2 or 3 wherein at most one radical from T or T ', in addition, a (C ₁ to C ₆₎ alkyl group, an aryl group, an aryl (d to _C6) alkyl group, a (C ₁ to C ₆₎ alkoxy group or a ( C ₂ to C ₆ ) acyl group may be,

and

(B) at least one film-forming and / or setting polymer.

The polyether-modified solid particles are preferably present in the compositions according to the invention in an amount of from 0.01 to 10.0% by weight, more preferably from 0.1 to 2.0% by weight, very particularly preferably from 0.2 to 1 , 0 wt .-%, each based on the weight of the total composition included.

The polyethers of the formula (I) preferably have a molecular weight of from 1 to 200 kDa, more preferably from 1 to 10 kDa.

These agents according to the invention preferably contain such modified solid particles which have a particle size of from 0.01 μm to 100 μm, particularly preferably less than 5 μm, very particularly preferably <0.1 μm.

The polyethers which can be used in the context of the invention for the preparation of the solid particles of component (a) are obtainable by reacting at least one compound of the formula (II):

X-A-X '(II)

wherein

A represents a polyoxyalkylene chain from ethylene oxide units or ethylene oxide and propylene oxide

Units, with a maximum proportion of 50% by weight of propylene oxide units, based on the weight of A,

X is OH, NH ₂ , NHR, NR ₂ or OR, where the radicals R independently of one another represent a linear or branched alkyl group having 1 to 10 carbon atoms, an alkaryl or

Aralkyl group having 6 to 10 carbon atoms or an aryl group having 5 to 10

Carbon atoms,

X 'is OH, NH ₂ , NHR or NR ₂ , wherein the radicals R independently of one another represent a linear or branched alkyl group having 1 to 10 carbon atoms, an alkaryl or

Aralkyl group having 6 to 10 carbon atoms or an aryl group having 5 to 10

Carbon atoms,

with at least one compound of the formula (III)

Y-K-T (IM)

wherein, Y is a reactive group with respect to -OH, -NH ₂ , -NHR, -NR ₂ ,

K is a connectivity selected from a covalent bond or from a

Molecular fragment with two free valences,

T is a molecule fragment comprising at least one substituent selected from

anionic residue

Rest -Si (OR) _x (R ') ₃ - _x

wherein R and R 'independently of one another represent a (C 1 to C ₄ ) -alkyl group (in particular methyl or ethyl),

x stands for 1, 2 or 3.

It is therefore preferred according to the invention for the synthesis of the polyether-modified solid particles of component (a) to use at least one hydroxyl-containing solid particles in combination with a polyether which has been prepared according to the above H 11 first method. This can also be a mixture of reaction products from the above H first method.

The polyether-modified solid particles produced by the above process are preferably present in the compositions according to the invention in an amount of from 0.01 to 10.0% by weight, particularly preferably from 0.1 to 2.0% by weight, very particularly preferably 0 , 2 to 1, 0 wt .-%, each based on the weight of the total composition included.

The polyethers used to prepare the polyether-modified solid particles preferably have a molecular weight of from 1 to 200 kDa, particularly preferably from 1 to 10 kDa.

As reaction products for the preparation of the compounds of the formula (I), for example, in addition to the polyethers of the formula (I), oligomeric polyethers which conform to the formula (Ia) can be obtained,

T- (KA) _Z -K'-T (Ia)

wherein

z stands for an integer from 2 to 10 and

A, K, K ', T and T are as defined in formula (I).

The ratio of polyethers of formula (I) to oligomers can be controlled, for example, by reaction in the presence of a catalyst, especially in the presence of at least one tertiary amine (such as triethylamine).

According to the above first method for the preparation of the compounds of the formula (I), the compounds of the formula (II) are, for example, dihydroxy-terminated polyoxyalkylene diols, diaminoterminated polyoxyalkylene diamines, monohydroxy monoamine-terminated polyoxyalkylene diamines. Monol monoamines, monohydroxy monoalkoxy-terminated polyoxyalkylene monols or monoamino monoalkoxy-terminated polyoxyalkylene monoamines used, among which the diamines and diols are preferred.

The radicals X and X 'of the formula (II) are preferably, independently of one another, OH, NH ₂ and NHR, particularly preferably OH and NH ₂ .

The radical R in the groups NHR, NR ₂ and OR of the formula (IM) preferably represents a linear or branched alkyl group having 1 to 10, preferably 1 to 6, carbon atoms.

Preferably, the radical Y according to formula (III) is

an isocyanate function,

- a group ^* -Si (OR) _x (R ') ₃ .χ

wherein R and R 'independently of one another are a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl) and x is 1, 2 or 3,

a group ^* -Si (R) _x (R ') ₃ . _x

where R is a halogen atom (preferably chlorine or bromine) and R 'independently of one another are a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl) and x is 1, 2 or 3,

a group TKC (O) -OC (O) - ^* , wherein T and K are defined according to formula (II),

a group ^* -C (O) -hal, where Hal is chlorine or bromine,

an epoxy group,

a formyl group.

The number-average molecular weight of the compound of the formula (II) is preferably 100 to 50,000 g / mol, more preferably 500 to 30,000 g / mol, very preferably 1,000 to 20,000, better still 2,000 to 18,000 g / mol, and can be as in the examples determine by end group determination.

If the group A of the compounds of the formula (I) or formula (II) is a polyoxyalkylene chain composed of ethylene oxide and propylene oxide units, the maximum proportion of propylene oxide units is preferably 40% by weight and more preferably not more than 30% by weight. %, based on the weight of A.

A is therefore preferably a structural fragment of the formula (A1) according to formula (I) or formula (II)

^* - (OCH ₂ CH ₂ ) _n - (OCH ₂ CH (CH ₃ )) _m - ^* (A1)

wherein

n is an integer from 1 to 500,

m is an integer from 0 to 500 and the structural fragment of the formula (A1) has a maximum proportion of 50% by weight of propylene oxide units, based on the weight of the structural fragment (A1).

According to the above formulas and all following formulas, a chemical bond marked with the symbol ^{* stands} for a free valency of the corresponding structural fragment.

The groups A comprising ethylene oxide and propylene oxide units of the formula (I) or of the formula (A1) or of the formula (II) may be randomly distributed or distributed in a gradient or present in at least two blocks.

The radicals K or K 'according to formula (I) or according to formula (III) preferably stand independently of one another for a covalent bond, bond, an oxy group, an imino group or at least one of the following connectivities (K1) to (K10)

* - OC- R- * _* _ _N _ _C _ _R _ _{* *} _Q_O-R- _*

R ¹ Il

⁰ (K1) O ° (K2) ° (K3)

R '"R'"

^* -jj- ^N - ^R - ^* _jj} i- * -O-Si- *

OD ¹ "P '"

u (K4) ^κ (K5) ^κ (K6)

* - R-N-C-N-R "- * * - R-O-C-N-R" - *

R 'Il H Il H

⁰ (K7) ° (K8)

* - R - N - C - O - R "- * * - R - O - C - O - R" - *

R 'Il Il

⁰ (K9) ° (K10)

wherein

R and R "independently of one another represent methylene, ethane-1, 2-diyl, propane-1,2-diyl, propane

1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl or phenylene,

R 'represents a hydrogen atom or a (C ₁ to C ₄ ) -alkyl group,

R '"independently of one another is a (C ₁ to C ₄ ) -alkyl group or an aryl group.

In the context of a first preferred embodiment, at least one molecule fragment T or T of the formula (I) or formula (III) comprises at least one radical -Si (OR) _x (R ') ₃ . _x wherein R and R 'are each independently (C ₁ to C ₄₎ alkyl group is a (particularly methyl or ethyl). This residue (s) -Si (OR) _x (R ') ₃ . _x binds / binds preferably to a hydrocarbon molecule fragment with 1 to 20 carbon atoms or directly to the connectivity K or K '. Corresponding polyethers of the formula (I) for preparing the inventive polyether-modified solid particles of component (a) of the inventive composition of this embodiment are obtainable by reacting at least one compound of the formula (II):

X-A-X '(II)

wherein

Aralkyl group having 6 to 10 carbon atoms or an aryl group having 5 to 10

Carbon atoms,

Aralkyl group having 6 to 10 carbon atoms or an aryl group having 5 to 10

Carbon atoms,

with at least one compound of the general formula (III-1)

YK-Si (OR) _x R '-x ₃ (111-1)

wherein,

Y is an OH, NH ₂ , NHR and / or NR ₂ reactive group (especially for a

Isocyanate group, a halogen atom, a carboxylic anhydride group, a

Halocarbonyl group (especially chlorocarbonyl), an epoxy group, a

Formyl group),

K as defined under formula (I) (or as the aforementioned preferred connectivities),

R is a (C ₁ to C ₄ ) -alkyl group or a (C ₂ to C ₄ ) -acyl group (in particular ethyl or methyl),

R 'is a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl),

x stands for 1, 2 or 3.

Compounds of general formula (III-1) include all functional silane derivatives capable of reacting with Y groups of formula (III-1). Examples are acrylate silanes such as (3-acryloxypropyl) trimethoxysilane, (acryloxymethyl) triethoxysilane and (acryloxymethyl) methyldimethoxysilane, isocyanato-silanes such as (3-isocyanatopropyl) trimethoxysilane, (3-isocyanatopropyl) triethoxysilane, (isocyanatomethyl) methyl-dimethoxysilane and (Isocyanato-methyl) trimethoxysilane, aldehyde-silanes such as triethoxysilylundecanal and Triethoxysilyl butyraldehydes, epoxy silanes such as (3-glycidoxypropyl) trimethoxysilane, anhydride silanes such as 3- (triethoxysilyl) propyl succinic anhydride, halogen silanes such as

Chloromethyltrimethoxysilane, 3-Chloropropylmethyldimethoxysilan, and tetraethyl silicate (TEOS), which are commercially available for example from Wacker Chemie GmbH (Burghausen), Gelest, Inc. (Morrisville, USA) or ABCR GmbH & Co. KG (Karlsruhe) or by known methods can be produced. Particular preference is given to isocyanato-silanes or anhydride-silanes. Complete conversion of all hydroxy ends with isocyanatosilanes gives completely silylated polyethers. In such a case, the group K contains only the atomic group which is in the starting isocyanatosilane between the isocyanato group and the silyl group. Complete conversion of all hydroxy ends with anhydride silanes, for example 3- (triethoxysilyl) propyl succinic anhydride, also gives completely silylated polyethers. In such a case, the group K contains only the atomic group which is in the starting anhydride silane between the anhydride group and the silyl group.

If the radicals X and X 'in the general formula (II) are OH, NH ₂ or NHR, the reaction with the compounds of the general formula (III) or (III-1) is usually carried out either with elimination of the compound HY - as for example in the case of the reaction of an OH group with a monohalosilane (K = direct bond) - or under addition - such as in the case of reaction of an OH group with an isocyanatoalkylsilane (formation of a urethane).

The radical R in the groups NHR, NR ₂ and OR of the formula (III-1) preferably represents a linear or branched alkyl group having 1 to 10, preferably 1 to 6, carbon atoms.

In the reaction between the compounds of the formula (I) and the compounds of the formula (II), at least one hydrogen atom, preferably up to four hydrogen atoms of the OH and / or NH ₂ groups with one molecule of the compound of the general formula ( II), so that at least monosilylated, in the case of diamino compounds of general formula (I) up to four times silylated polyether arise.

As a preferred silyl-terminated polyether, at least one polyether of the formula (1-1) is preferably used according to the invention for the preparation of the polyether-modified solid particles according to the invention

RAK-Si (OR ² ) _χ R ³ ₃ _ _x ,

(1-1)

wherein A denotes a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum proportion of 50% by weight of propylene oxide units, based on the weight of A,

K for a covalent bond, an oxy group, an imino group or at least one of the following connectivities (K1) to (K10)

* - O-C- R- * * - M- C- R- * * - C- O- R- *

Il R 'Il Il

⁰ (K1) ° (K2) ° (K3)

R ¹ "R"

* - C- N- R- * _* - si- _{* *} - O- Si- _*

I l R 'I I

O D '"P'"

u (K4) ^κ (K5) ^κ (K6)

* - R - N - C - N - R "- * * - R - O - C - N - R" - *

R 'Il H Il H

⁰ (K7) ° (K8)

* - R - N - C - O - R "- * * - R - O - C - O - R" - *

R '11 Il

⁰ (K9) ° (K10)

wherein

R and R "independently of one another are methylene, ethane-1, 2-diyl, propane-1, 2-diyl, propane-1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, Butane-1, 4-diyl, phenylene and

R 'represents a hydrogen atom or a (C ₁ to C ₄ ) -alkyl group,

R '"independently of one another denotes a (C ₁ to C ₄ ) -alkyl group or an aryl group,

R ^{1 is} a (C ₁ to C ₆ ) -alkyl group, a hydrogen atom or a group R ³ ₃ .χ (R ² O) _x Si-K-,

R ^{2 is} a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl),

R ^{3 is} a (C ₁ to C ₆ ) alkyl group or an aryl group (in particular methyl), x is 1, 2, 3 (in particular 3).

Very particularly preferred polyethers for preparing the polyether-modified solid particles according to the invention are selected from at least one compound of the formulas (I-1a), (I-1 b), (I-1c), (I-1d) or (I-1 e )

_R ^ _ _A _ _κ _{Si (0R2) χ} _χ _R 3 ₃ R ¹ -AROC -NR "-Si (OR ²⁾ _x R ^3. ₃ _x

(Ma) ° (Mb)

R ¹ -ARNCNR "-Si (OR ² ) _x R ³ ₃ .χ

H I l H

° (MC) F £ _Y (R ² O 1 -Si- R "-NCNRARNCNR" -Si (OR ² ) χ R ³ _{3 x}

H Il H H Il H

⁰ ° (Md)

F £ _y (R ² O 1 -Si- R "-NCORAROCNR" -Si (OR) _X R ₃ _ _x

H Il Il H

⁰ ° (Me)

wherein

A is a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and

Propylene oxide units means, with a maximum proportion of 50 wt .-% of

Propylene oxide units, based on the weight of A,

* - O-C- R- * * - M- C- R- * * - C- O- R- *

Il R 'Il Il

⁰ (K1) ° (K2) ° (K3)

R '"R'"

I i

* - C- N- R- * * - Si- * * - O- Si- *

I l R 'I I

O R '"R'"

υ (K4) ^κ (K5) ^κ (K6)

* - R - N - C - N - R "- * * - R - O - C - N - R" - *

R 'il H H H

⁰ (K7) ° (K8)

* - R - N - C - O - R "- * * - R - O - C - O - R" - *

R 'Il Il

⁰ (K9) ° (K10)

wherein

R 'denotes a hydrogen atom or a (C 1 to C ₄ ) -alkyl group,

R '"independently of one another denotes a (C 1 to C ₄ ) -alkyl group or an aryl group.

1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl, phenylene,

R ^{2 is} a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl),

R ^{3 is} a (C ₁ to C ₆ ) alkyl group or an aryl group (in particular methyl), x is 1, 2, 3 (in particular 3). In a second preferred embodiment for producing the polyether-modified solid particles according to the invention, at least one molecule fragment T or T of the formula (I) or formula (III) comprises at least one anionic group.

The molecular fragments T or T of the formula (I) or formula (III) having at least one anionic group are preferably according to the invention a molecule fragment which comprises 1 to 5, preferably 3, 4 or 5, deprotonatable acid groups. The anionic groups or the deprotonatable acid groups of the said molecular fragments T or T of the formula (I) or formula (III) are preferably selected from carboxyl group and / or sulfonic acid group and / or phosphate or their respective salt forms (in particular carboxyl group and / or Sulfonic acid group or their respective salt forms, particularly preferably carboxyl group or its salt form).

In a particularly preferred embodiment, the molecule fragment T or T of the formula (I) or formula (III) contains at least one, preferably at least two, particularly preferably 1 to 5, especially 2 to 5, in particular 2, 3, 4 or 5 carboxymethyl -Units. In a very particularly preferred embodiment, the said molecular fragment is an ethylene diamine triacetate unit which is covalently bonded via one of its nitrogen atoms to the connectivity K of the formula (I) or formula (III).

In a preferred embodiment according to the invention for the preparation of the polyether-modified solid particles according to the invention, the molecule fragment T or T of the formula (I) or formula (III) is a silyl group of the general formula (IV)

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

in which

R ^a is hydrogen or alkyl ₆ CI_,

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

R ^{c is} (C ₁ to C ₆ ) -alkyl, (C ₁ to C ₆ ) -alkoxy or hydroxy, preferably (C ₁ to C ₆ ) -alkoxy or

Hydroxy, stands,

R ^{d is} a negatively charged group,

R ^{e is} (C ₁ to C ₆ ) -alkyl, C- |. ₆ alkoxy or hydroxy, preferably (C ₁ to C ₆ ) alkoxy or

Hydroxy, stands,

r is a number from 1 to 3, preferably 1,

t is a number from 1 to 3, preferably 1.

R ^d preferably represents a moiety comprising 1-5, preferably 3, 4 or 5, acid groups, in particular carboxylic acid groups. R ^{d of} the formula (IV) particularly preferably represents a group

^* -B - [(N (CH ₂ COOM) -B ') _y -N (CH ₂ COOM) ₂ ]

in which

B is a (C ₁ to C ₆ ) -alkylene radical (preferably ethane-1, 2-diyl, propane-1, 2-diyl, propane

1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl),

B 'is a (C ₁ to C ₆ ) -alkylene radical (preferably ethane-1, 2-diyl, propane-1, 2-diyl, propane

1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl),

M is independently of one another a hydrogen atom or one equivalent of a mono- or polyvalent cation,

y is 1 or 2 (preferably 1).

When the above group is acid, the group M is a hydrogen atom. The fragments -COOH in this case form a carboxyl group. When the above group is in its salt form (carboxylate), M is one equivalent of a monovalent or polyvalent cation. The monovalent or polyvalent cation M ^{z +} with a charge number z of one or higher serves merely to compensate for the simply negative charge of the carboxylate present during salt formation, for reasons of electroneutrality. The equivalent of the corresponding cation to be used is 1 / z. The fragment -COOM is in the case of salt formation for the group:

-COO ^" 1 / z (M ^{z +} )

As mono- or polyvalent cations M ^{z +} are in principle all cations in question, which are physiologically compatible. In particular, these are metal cations of the physiologically acceptable metals from groups Ia, Ib, IIa, IIb, MIb, VIa or VIII of the Periodic Table of the Elements, ammonium ions, as well as cationic organic compounds with quaternized nitrogen atom. The latter are formed for example by protonation of primary, secondary or tertiary organic amines with an acid, such as with compounds of the above group R ^d in their acidic form, or by permanent quaternization of said organic amines. Examples of these cationic organic ammonium compounds are 2-ammonioethanol and 2-trimethylammonioethanol. M is preferably a hydrogen atom, an ammonium ion, an alkali metal ion, half an equivalent of an alkaline earth metal ion or half an equivalent of a zinc ion, more preferably a hydrogen atom, an ammonium ion, a sodium ion, a potassium ion, ^Λ A calcium ion, ^Λ A magnesium ion or ^Λ A zinc ion.

A very particularly preferred molecular fragment T and / or T of the formula (I) or formula (III) for the preparation of the polyether-modified solid particles according to the invention follows the general formula

^* -B - [(N (CH ₂ COOM) -B ') _y -N (CH ₂ COOM) ₂ ] in which

1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl),

1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl) or an N, N-BiS (C ₁ to C ₆ ) -alkylene

N-carboxymethyl stands,

y is 1 or 2 (preferably 1).

For the remainder M of the above formula, what has been said above (vide supra) applies.

Particularly preferred agents of this embodiment have polyether-modified solid particles, for their preparation, at least one polyether having at least one molecule fragment T or T of said general formula

* -B - [(N (CH ₂ COOM) -B ') _y -N (CH ₂ COOM) ₂ ].

Particularly preferred molecular fragments T and / or T of the formula (I) or formula (III) of the formula ^* -B - [(N (CH ₂ COOM) -B ') _y -N (CH ₂ COOM) ₂ ] are selected from at least one member of the group formed from 3-N-carboxymethyl-N- (2'-N ', N'-di (carboxymethylamino) ethyl) -aminopropyl (B = propane-1,3-diyl, B' = Ethane-1,2-diyl, y = 1, M as above), 3-N-carboxymethyl-N- (2'-N ', N'-di (carboxymethylamino) ethyl) -N'-carboxymethylaminoethyl) aminopropyl (B = Propane-1,3-diyl, B '= ethane-1,2-diyl, y = 2, M as above) where 3-N-carboxymethyl-N- (2'-N', N'-di (carboxymethylamino) ethyl) aminopropyl very particularly preferred.

Suitable polyethers for preparing the polyether-modified solid particles according to the invention as component (a) of this embodiment are preferably obtainable by reacting at least one compound of the formula (II):

X-A-X '(II)

wherein

X is OH or OR, wherein R is a linear or branched alkyl group having 1 to 10

Carbon atoms, an alkaryl or aralkyl group having 6 to 10 carbon atoms or an aryl group having 5 to 10 carbon atoms, and

X 'stands for OH with at least one compound of the formula (III-2)

(RO) _x R ' ₃ _ _x Si-B- (N (CH ₂ COOM) -B') _y -N (CH ₂ COOM) ₂ (III-2)

wherein,

1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl),

N-carboxymethyl stands,

R 'is a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl),

x is 1, 2 or 3 (especially 2 or 3),

y is 1 or 2 (especially 1).

Very particularly preferred compounds for preparing the polyether-modified solid particles according to the invention are selected from at least one compound of the formulas

(Mf) ₁ (Mg)

wherein

A is a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and

Propylene oxide units means, with a maximum proportion of 50 wt .-% of

Propylene oxide units, based on the weight of A, B is a (C ₁ to C ₆ ) -alkylene radical (preferably ethane-1, 2-diyl, propane-1, 2-diyl,

Propan-1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl),

B 'is a (C ₁ to C ₆ ) -alkylene radical (preferably ethane-1, 2-diyl, propane-1, 2-diyl,

Propan-1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl) or an N, N-BiS (C ₁ to C ₆ ) alkylene-N carboxymethyl stands,

R ^{1 is} a (C ₁ to C ₆ ) alkyl group, a hydrogen atom or a

Group R ³ ₃ .χ (R ² O) _x Si-K- is where

R ² and R ³ independently of one another represent a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl),

x is an integer 1, 2 or 3 (in particular 3),

K stands for a connectivity selected from a covalent bond or from a molecule fragment with two free valences,

R independently of one another is a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl) or a (C ₁ to C ₆ ) -alkoxy group (in particular methoxy or ethoxy).

For the abovementioned formulas (I-1f) and (1-1 g), the preferred embodiments with respect to the aforementioned preferred features apply to A, B, B ', M, R ¹ and R mutatis mutandis.

Another method for preparing the solid particles containing polyethers contained in the agents according to the invention comprises the steps:

i) Reaction of hydroxyl-containing solid particles with at least one epoxysilane and ii) reaction of the epoxy-functionalized solid particles obtained in step i) with at least one polyoxyalkylene monoamine which has only one functional group reactive to the epoxy groups of the epoxy-functionalized solid particles.

For the purposes of the present invention, the term "epoxysilane" is to be understood as meaning a compound which comprises at least one silane group and at least one epoxy group. For the purposes of the present invention, a "silane group" is preferably to be understood as meaning a divalent group which comprises at least one silicon atom which is covalently bonded to at least one oxygen atom and to at least one carbon atom.

Preferred epoxysilanes are selected from epoxysilanes of the general formula (EP-I), R ⁹

o? ^u

H ₂ C / C-CH ₂ -O- (CH ₂ ) -Si I (OR ⁸ ) ₃ . _u

^H formula (EP-I)

wherein R ^{8 is} a linear or branched optionally substituted C 1-4 alkyl group or an optionally substituted C 6-12 aryl group,

R ^{9 is} a linear or branched optionally substituted C 1-6 alkyl group, u is 0, 1 or 2 and k is an integer from 1 to 5.

Specifically, 3-glycidyloxypropyltrimethoxysilane (GLYMO), 3-glycidyloxypropyltriethoxysilane (GLYEO), 3-glycidyloxypropyltri-n-propoxysilane, 3-glycidyloxypropyltriisopropoxysilane, 3-glycidyloxypropyltri-n-butoxysilane and 3-glycidyloxypropyltriisobutoxysilane or mixtures thereof preferred as epoxysilane in the context of the present invention. A most preferred epoxysilane is 3-glycidyloxypropyltrimethoxysilane (GLYMO).

Furthermore, preferred epoxysilanes are also selected from epoxysilanes of the general formula (EP-II), Formula (EP-II)

wherein R ⁸ , R ⁹ , k and u are as defined above.

In particular, beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane commercially sold under the tradename Silquest® A-187 ™ by Momentive Performance Materials is preferred.

For surface functionalization of the nanoparticulate cores with epoxy groups, it is also possible to use mixtures of different epoxysilanes in the context of the process according to the invention.

The epoxy silanes of the present invention react at least partially with the hydroxyl groups on the surface of the hydroxyl-containing solid particles to form a covalent bond between the at least one silicon atom of the respective epoxysilane and the OH groups present on the surface of the nanoparticulate cores. The reaction described generally leads to the release of water and / or a low molecular weight alcohol, which is why it is advantageous to carry out the reaction so that water and / or the low molecular weight alcohol is removed from the reaction equilibrium. This can be done for example by the use of a water separator or an ion exchanger. The processing performed in step b) of the inventive epoxy functionalization of the hydroxyl group-containing solid particles is effected in dependence on the used epoxysilane preferably at temperatures of 20 to 120 ⁰ C, at about 40 ⁰ C to 80 ° C. Depending on the epoxysilane used, the reaction time is preferably 10 minutes to 12 hours, in particular 1 hour to 4 hours, it being possible to use water and / or low molecular weight alcohols, for example isopropanol and / or methoxypropanol, as solvent.

In the reaction carried out in step ii) of the process according to the invention, the reaction of the epoxy-functionalized solid particles obtained in step i) with at least one polyoxyalkylene monoamine which has only one reactive functional group to the epoxy groups of the epoxy-functionalized cores, the reaction conditions, such as the pH Value or reaction temperature, advantageously chosen so that at least 10%, preferably at least 40% and most preferably at least 60% of all epoxy groups of the epoxy-functionalized solid particles react with the polyoxyalkylene monoamine or the mixture of different polyoxyalkylene monoamines to form a hydroxyl group.

Preferably, said reactive functional group of the polyoxyalkylene monoamines is a primary amino group.

The polyoxyalkylene monoamines mentioned particularly preferably comprise ethylene oxide and / or

Propylene oxide units.

In the context of the present invention, an ethylene oxide unit (EO) is a unit of the general formula (1)

'-CH ₂ -CH ₂ -O- ^* Formula (1)

and for the purposes of the present invention, a unit of the general formula (2) is understood to mean a propylene oxide unit (PO).

^* -CH ₂ -CH (CH ₃ ) -O- ^* Formula (2)

to understand.

It is known that the hydrophilicity or hydrophobicity of polyoxyalkylene monoamines can be controlled, for example, by the ratio of ethylene oxide units (EO) to propylene oxide units (PO)

Particularly preferred polyoxyalkylene monoamines in the context of the present invention are polyoxyalkylene monoamines of the general formula R ⁶ - (-O- CH ₂ -CH -H-O-CH ₂ - CH 4 -NH ₂

In ! _m

R ⁷ CH ₃

wherein R ⁶ is ₁₀ alkyl group, a linear or branched, optionally substituted CI_, R ⁷ represents hydrogen or a methyl group and m and n each independently represent an integer of 0 to 50, with the proviso that n + m> 1 is.

In a preferred embodiment of the invention, the weight average molecular weight "M _w " of the polyoxyalkylene monoamines of the present invention is in the range of 500 to 10,000 g / mol, preferably in the range of 550 to 5000 g / mol and most preferably in the range of 600 to 2200 g / mol. The weight-average molecular weight can be determined by gel permeation chromatography (GPC) using polystyrene as standard.

Particularly preferred polyoxyalkylene monoamines according to the invention are available from Huntsman Corp. Texas under the brand names Jeffamine® M-600, Jeffamine® M-1000, Jeffamine® M-2005 and Jeffamine® M-2070.

The solid particles obtained by this process modified polyether can be isolated solvent-free, without causing an irreversible crosslinking and / or agglomeration of the individual nanoparticles occurs. As a result of the solvent-free isolation of the nanoparticles according to the invention, they can be stored in a simple manner and transported inexpensively. Subsequently, the nanoparticles mentioned can be easily redispersed, for example, in water and / or low molecular weight alcohols, such as isopropanol, the redispersed nanoparticles having very little or no sedimentation tendencies. By choosing the respective epoxy silanes and polyoxyalkylene monoamines, the process of the invention can be widely varied, whereby new surface-modified nanoparticles are obtained for different applications, which are characterized by good processability in solvents or other carrier media.

"Solid particles containing hydroxyl groups" are understood to mean all solids which are particulate at room temperature and which carry hydroxyl groups, preference being given in particular to corresponding mineral oxide solid particles.

The hydroxyl-containing, mineral oxide solid particles (or the hydroxyl-containing, mineral oxide solid particles) are - regardless of H first method - preferably selected from aluminates, silicates, aluminum silicates, zinc oxide, titanium dioxide and SiO _Σ , in particular aluminates, silicates , Aluminum silicates and silica gel. Likewise according to the invention are in each case mixtures of these preferred or particularly preferred hydroxyl-containing solid particles. Particularly preferred aluminates are selected from alpha-alumina, beta-alumina, gamma-alumina and mixtures thereof.

Particularly preferred aluminum silicates (also called aluminosilicates) are selected from phyllosilicates, tectosilicates.

Preferred phyllosilicates are selected from kaolins (here in particular kaolinite, dickite, halloysite and nacrite), serpentine, talc, pyrophyllite, montmorillonite, quartz, bentonite, mica (here in particular under illite, muscovite, paragonite, phlogopite, biotite, lepidolite, margarite , Smectite (here in particular montmorillonite, saponite, nontronite, hectorite)).

Zeolites are natural or synthetic crystalline aluminum silicates of alkali or alkaline earth metals. Zeolites consist of SiO ₄ and AIO ₄ tetrahedra linked by four, six, eight or twelve oxygen rings, resulting in cavities extending through the entire zeolite crystal. Among the preferred zeolites are the zeolites of the type A, K, L, PL, O, T, X, Y and Ω and mixtures thereof. Particularly preferred zeolites are in particular selected from zeolite A (here in particular under Na ₁₂ [(AIO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]), Ca ₅ Na ₅ I (AIO ₂ ) I ₂ (SiO ₂ ) I ₂ ], [Ki ₂ I (AIO ₂ ) I ₂ (SiO ₂ ) I ₂ ]), zeolite X (here in particular under Na ₈₆ [(AIO ₂ ) ₈₆ (SiO ₂ ) ₁₀ 6]), Ca ₄ oNa ₆ [(AlO ₂ ) ₈₆ (Si0 ₂₎ ₁₀ 6)], Sr ₂₁ Ba ₂₂ [(AIO ₂₎ ₈₆ (SiO ₂₎ _106]), zeolite Y (in particular under Na ₅₆ I (AIO ₂₎ _S6 (SiO ₂₎ _I36], Na ₅₆ [(AIO ₂ ) ₅₆ (SiO ₂ ) i ₃₆ ]), ZSM-5 (here in particular Na ₃ [(AIO ₂ ) ₃ (SiO ₂ ) ₉₃ ]), mordenite, silicalite (SiO ₂ ) ₉₆ .

Basegte preferred embodiments of the hydroxy group-containing (mineral oxide) solid particles can be preferably with the preferred embodiments of the polyether of formula (I), or (1-1), or (l-1a) to (1-1 g), to According to the invention preferably implement in the means contained polyether modified solid particles.

The wettability of the coatings obtained by the agents according to the invention with water is a sensitive measure of their hydrophilicity or hydrophobicity. The contact angle of a water droplet on a planar substrate in the surrounding medium air results from the surface energies of the coating and the water as well as the interfacial energy between water and the coating according to the Young's equation. In the case of maximum hydrophilicity, the contact angle approaches 0 °. In the case of maximum hydrophobicity, the contact angle approaches 180 °. In practice, the advancing contact angle and the retracting one are frequently used (receding) contact angle measured. Ideally, the difference between the two should be zero. In reality, there is a difference, also called contact angle hysteresis, which is attributed to surface roughness, inhomogeneities and impurities.

The coatings according to the invention preferably have a static water contact angle of at most 90 °, better still at most 70 °, particularly preferably at most 55 ° and very particularly preferably at most 45 ° measured by the sessile drop method (for carrying out the example). In many cases, however, water contact angles of 40 ° and less are achieved. The agents according to the invention very particularly preferably comprise polyethers of the formula (I), so that after the treatment of keratin-containing fibers, in particular human hair, with this composition according to the invention, the coating obtained has a contact angle of 20 ° to 60 °.

In addition to the polyether-modified solid particles according to the invention, the composition according to the invention furthermore necessarily contains at least one film-forming and / or setting polymer. These polymers are different from said polyether-modified solid particles.

Film-forming polymers are polymers which leave a continuous film on the skin, the hair or the nails when drying. Such film formers can be used in a wide variety of cosmetic products, such as for example face masks, make-up, hair fixatives, hair sprays, hair gels, hair waxes, hair treatments, shampoos or nail varnishes. Particular preference is given to polymers which have a sufficient solubility in water or water / alcohol mixtures in order to be present in completely completely dissolved form in the agent according to the invention. The film-forming polymers may be of synthetic or natural origin.

According to the invention, film-forming polymers are understood as meaning polymers which, when used in 0.01 to 20% strength by weight aqueous, alcoholic or aqueous-alcoholic solution, are capable of depositing a transparent polymer film on the hair.

Firming polymers contribute to the maintenance and / or build-up of the hair volume and hair fullness of the overall hairstyle. These polymers are at the same time also film-forming polymers and therefore generally typical substances for shaping hair treatment agents such as hair fixatives, hair foams, hair waxes, hair sprays. The film formation can be quite selective and connect only a few fibers.

As a test method for the firming effect of a polymer, the so-called curl retention test or the three-point bending test are often used. Preferred agents according to the invention contain the film-forming and / or setting polymers in an amount of from 0.1% by weight to 20.0% by weight, particularly preferably from 0.2% by weight to 10.0% by weight. -%, most preferably from 0.5 wt .-% to 5.0 wt .-%, each based on the weight of the composition.

The composition of the invention preferably contains as a film-forming and / or setting polymer

at least one cationic film-forming and / or cationic setting polymer and / or

at least one nonionic film-forming and / or nonionic setting polymer and / or

at least one anionic film-forming and / or anionic setting polymer

and or

at least one amphoteric film-forming and / or amphoteric setting polymer.

Within the scope of a preferred embodiment, the agents according to the invention contain as film-forming and / or setting polymer at least one cationic film-forming and / or cationic setting polymer.

The cationic film-forming and / or cationic fixing polymers have at least one structural unit containing at least one permanently cationized nitrogen atom. Permanently cationized nitrogen atoms are to be understood as meaning those nitrogen atoms which carry a positive charge and thereby form a quaternary ammonium compound. Quaternary ammonium compounds are most commonly prepared by reacting tertiary amines with alkylating agents, e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also produced ethylene oxide. Depending on the tertiary amine used, the following groups are known in particular: alkylammonium compounds, alkenylammonium compounds, imidazolinium compounds and pyridinium compounds.

Preferred agents according to the invention comprise the film-forming cationic and / or setting cationic polymers in an amount of from 0.1% by weight to 20.0% by weight, particularly preferably from 0.2% by weight to 10.0 Wt .-%, most preferably from 0.5 wt .-% to 5.0 wt .-%, each based on the weight of the composition.

The cationic film-forming and / or cationic fixing polymers can be selected according to the invention from cationic, quaternized cellulose derivatives.

In the context of this embodiment, those agents are preferred which are contained in a cosmetically acceptable carrier (A) Polyether-modified solid particles, which are obtained by reacting hydroxy-containing solid particles with at least one compound of formula (1-1)

RAK-Si (OR ² J _x R ^ _x

(11--11)

wherein R ¹ , R ² , R ³ , A, K and x are as previously defined

and

(B) at least one film-forming cationic and / or setting cationic polymer selected from the group of cationic, quaternized cellulose derivatives.

In the context of this embodiment, those agents are preferred which are contained in a cosmetically acceptable carrier

(A) Polyether-modified solid particles, which by

i) reaction of hydroxyl-containing solid particles with at least one epoxy silane and

ii) reaction of the epoxy-functionalized solid particles obtained in step i) with at least one polyoxyalkylene monoamine which has only one functional group reactive to the epoxy groups of the epoxy-functionalized solid particles.

to be obtained

and

T-K-A-HC-T (I)

wherein

A is a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and

Propylene oxide units means, with a maximum proportion of 50 wt .-% of

Propylene oxide units, based on the weight of A,

K and K 'independently represent a connectivity selected from a covalent bond or from a molecular fragment having two free valencies, T and T independently represent a group of the general formula

* -B - [(N (CH ₂ COOM) -B ¹ ) _y -N (CH ₂ COOM) ₂ ] where B is a (C ₁ to C ₆ ) -alkylene radical (preferably ethane-1, 2-diyl, propane

1, 2-diyl, propane-1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl), B 'is a (C ₁ to C ₆ ) -Alkylene radical (preferably ethane-1, 2-diyl, propane-1, 2-diyl, propane-1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane 1,4-diyl) or an N, N-BiS (C ₁ to C ₆ ) -alkylene-N-carboxymethyl, M is, independently of one another, a hydrogen atom or one equivalent of a mono- or polyvalent cation,

y is 1 or 2 (preferably 1),

wherein at most one radical of T or T additionally for a (C ₁ to C ₆ ) alkyl group, an aryl group, an aryl (C ₁ -C ₆ ) alkyl group, a (C ₁ to C ₆ ) alkoxy or a (C ₂ to C ₆ ) -acyl group can stand,

and

In general, such cationic, quaternized celluloses prove to be advantageous in the sense of the invention, which carry more than one permanent cationic charge in a side chain.

Of these, among the cationic cellulose derivatives are those which are prepared from the reaction of hydroxyethylcellulose with a dimethyldiallylammonium reactant (in particular dimethyldiallylammonium chloride), if appropriate in the presence of further reactants. Among these cationic celluloses such cationic celluloses with the INCI name Polyquaternium-4 in turn, are particularly suitable, which are sold for example under the names of Celquat ^® H 100, Celquat L 200 ^® by the company National Starch.

Therefore, within the scope of this embodiment, agents according to the invention which are present in a cosmetically acceptable carrier are suitable

(A) Polyether-modified solid particles, which are obtained by reacting hydroxy-containing solid particles with at least one compound of formula (1-1)

RAK-Si (OR ² LR ^ _γ

x ³ - ^χ (1-1)

wherein R ¹ , R ² , R ³ , A, K and x are as previously defined

and

(B) at least one additional film-forming cationic and / or setting cationic polymer selected from cationic, quaternized cellulose derivatives, which are prepared by reaction of hydroxyethyl cellulose with a dimethyldiallylammonium reactants (in particular dimethyldiallylammonium chloride) - optionally in the presence of other reactants. In the context of this embodiment, those agents are preferred which are contained in a cosmetically acceptable carrier

(A) Polyether-modified solid particles, which by

to be obtained

and

(B) at least one additional film-forming cationic and / or setting cationic polymer selected from cationic, quaternized cellulose derivatives, which are prepared by reaction of hydroxyethyl cellulose with a dimethyldiallylammonium reactants (in particular dimethyldiallylammonium chloride) - optionally in the presence of other reactants.

T-K-A-K'-T '(I)

wherein

A is a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and

Propylene oxide units means, with a maximum proportion of 50 wt .-% of

Propylene oxide units, based on the weight of A,

^* -B - [(N (CH ₂ COOM) -B ¹ ) _y -N (CH ₂ COOM) ₂ ] where

B is a (C ₁ to C ₆ ) -alkylene radical (preferably ethane-1, 2-diyl, propane-1, 2-diyl, propane-1, 3-diyl, butane-1, 2-diyl, butane -1, 3-diyl, butane-1, 4-diyl),

B 'is a (C ₁ to C ₆ ) -alkylene radical (preferably ethane-1, 2-diyl, propane-1, 2-diyl, propane-1, 3-diyl, butane-1, 2-diyl, butane 1, 3-diyl, butane-1, 4-diyl) or an N, N-bis (C ₁ to C ₆ ) alkylene-N-carboxymethyl, M is independently of one another a hydrogen atom or one equivalent of a mono- or polyvalent cation,

y is 1 or 2 (preferably 1),

wherein at most one radical of T or T additionally for a (C ₁ to C ₆ ) alkyl group, an aryl group, an aryl (Ci to C ₆ ) alkyl group, a (Ci to C ₆ ) alkoxy group or a (C ₂ to C ₆ ) -acyl group can stand,

and

In the context of these abovementioned embodiments, the abovementioned preferred embodiments of the polyether of the formula (I) are suitable (vide supra). Similarly, all of the above-mentioned preferred quantities with respect to components (a) and (b) of the agent according to the invention are also suitable mutatis mutandis for these embodiments as well.

Also suitable are those cationic film-forming and / or cationic fixing polymers (b) which comprise at least one structural unit of the formula (M-I) and at least one structural unit of the formula (M-VI) and optionally at least one structural unit of the formula (M-V)

wherein

R ¹ and R ⁴ independently of one another represent a hydrogen atom or a methyl group,

A ¹ and A ² are each independently a group of ethane-1, 2-diyl, propane-1, 3-diyl or

Butane-1, 4-diyl,

R ² , R ³ , R ⁵ and R ⁶ independently of one another represent a (C ₁ to C ₄ ) -alkyl group,

R ⁷ is a (C ₈ to C ₃₀ ) alkyl group. To compensate for the positive charge of the monomer (M-VI) are all possible physiologically acceptable anions, such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate, triflate.

For the purposes of the present invention, those agents which are preferably suitable according to the invention are those agents which contain a cosmetically acceptable carrier

RAK-Si (OR ² LR ^ _γ

x ³ - ^χ (1-1)

wherein R ¹ , R ² , R ³ , A, K and x are defined as described above and

(b) at least one additional film-forming cationic and / or setting cationic polymer comprising at least one structural unit of the formula (M-I) and at least one structural unit of the formula (M-VI) and optionally at least one structural unit of the formula (M-V)

wherein

A ¹ and A ² independently of one another are a group of ethane-1, 2-diyl, propane-1, 3-diyl or butane-1, 4-diyl,

R ⁷ is a (C ₈ to C ₃₀ ) alkyl group.

(A) Polyether-modified solid particles, which by

ii) reaction of the epoxy-functionalized solid particles obtained in step i) with at least one polyoxyalkylene monoamine which has only one functional group reactive to the epoxy groups of the epoxy-functionalized solid particles and

wherein

R ² , R ³ , R ⁵ and R ⁶ independently of one another represent a (C 1 to C ₄ ) -alkyl group,

R ⁷ is a (C ₈ to C ₃₀ ) alkyl group.

T-K-A-K'-T (I)

wherein

A is a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and

Propylene oxide units means, with a maximum proportion of 50 wt .-% of

Propylene oxide units, based on the weight of A,

* -B - [(N (CH ₂ COOM) -B ¹ ) _y -N (CH ₂ COOM) ₂ ] where

B is a (C ₁ to C ₆ ) -alkylene radical (preferably ethane-1, 2-diyl, propane-1, 2-diyl, propane-1, 3-diyl, butane-1, 2-diyl, butane -1, 3-diyl, butane-1, 4-diyl), B 'is a (C ₁ to C ₆ ) -alkylene radical (preferably ethane-1, 2-diyl, propane-1, 2-diyl, propane-1, 3-diyl, butane-1, 2-diyl, Butane-1, 3-diyl, butane-1, 4-diyl) or an N ₁ N-BiS (C ₁ to C ₆ ) alkylene-N-carboxymethyl, M is independently a hydrogen atom or an equivalent of a or polyvalent cations,

y is 1 or 2 (preferably 1),

wherein at most one radical of T or T additionally represents a (C ₁ to C ₆ ) alkyl group, an aryl group, an aryl (d to C ₆ ) alkyl group, a (C ₁ to C ₆ ) alkoxy group or a (C ₂ to C ₆ ) acyl group, and

wherein

R ⁷ is a (C ₈ to C ₃₀ ) alkyl group.

To compensate for the positive charge of the monomer (M-Vl), the above applies.

Suitable compounds are, for example, as

Copolymers of dimethylaminoethyl methacrylate quaternized with diethyl sulfate, vinyl pyrrolidone with the INCI name Polyquaternium-11 755 (both from ISP), and Luviquat under the names Gafquat ^® 440, Gafquat ^® 734, Gafquat ^® PQ 11 PN (BASF SE), copolymers from Methacryloylaminopropyllauryldimethylammonium chloride with vinyl pyrrolidone and dimethylaminopropyl with the INCI name Polyquaternium-55 available under the trade name Styleze W-10 ^®, ^® Styleze W-20 (ISP)

available in the stores. In the context of these embodiments, the aforementioned preferred

Embodiments of the polether of the formula (I) as preferred (vide supra).

Similarly, all of the aforementioned preferred quantities of the components apply

(A) and (b) of the agent according to the invention also for these embodiments mutatis mutandis as preferred.

In the context of the invention, film-forming and / or setting polymers selected from cationic polymers containing at least one structural unit which have a permanently cationized nitrogen atom are also particularly preferably those cationic film-forming and / or cationic fixing copolymers (b) which contain at least one structural element of the formula (M 1)

wherein

R is a (C ₁ to C ₄ ) -alkyl group, in particular a methyl group,

and additionally have at least one further cationic and / or nonionic structural element.

Within the meaning of the present invention, those agents which are contained in a cosmetically acceptable carrier are therefore considered to be particularly preferred

RAK-Si (OR ² LFd _γ

x ³ - ^χ (1-1) wherein R ¹ , R ² , R ³ , A, K and x are defined as previously described

and

(b) at least one additional film-forming cationic and / or setting cationic polymer which contains at least one structural element of the formula (M1) as at least one structural unit having a permanently cationized nitrogen atom

R "(M1)

wherein R is a (C ₁ to C ₄ ) -alkyl group, in particular a methyl group,

and additionally comprises at least one further cationic and / or nonionic structural element.

To compensate for the positive polymer charge of component (b) are all possible physiologically acceptable anions, such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate, triflate.

In particular, those agents which are contained in a cosmetically acceptable carrier within the scope of this embodiment are particularly preferred

T-K-A-K'-T (I)

wherein

A is a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and

Propylene oxide units means, with a maximum proportion of 50 wt .-% of

Propylene oxide units, based on the weight of A,

^* -B - [(N (CH ₂ COOM) -B ¹ ) _y -N (CH ₂ COOM) ₂ ] where

B is a (C ₁ to C ₆ ) -alkylene radical (preferably ethane-1, 2-diyl, propane

1, 2-diyl, propane-1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl), B 'is a (C ₁ to C ₆ ) -Alkylene radical (preferably for ethane-1,2-diyl, propane

1, 2-diyl, propane-1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl) or an N, N-BiS (C ₁ to C ₆ ) -alkylene-N-carboxymethyl, M independently of one another represent a hydrogen atom or one equivalent of a mono- or polyvalent cation,

y is 1 or 2 (preferably 1),

wherein at most one radical of T or T additionally represents a (C ₁ to C ₆ ) alkyl group, an aryl group, an aryl (d to C ₆ ) alkyl group, a (C ₁ to C ₆ ) alkoxy group or a (C ₂ to C ₆ ) acyl group can stand,

and (B) at least one cationic film-forming and / or cationic setting polymer containing at least one structural element of the formula (M 1)

"(M 1)

wherein

R is a (C ₁ to C ₄ ) -alkyl group, in particular a methyl group,

(A) Polyether-modified solid particles, which by

to be obtained

and

(B) at least one cationic film-forming and / or cationic setting polymer containing at least one structural element of the formula (M 1)

(M 1)

wherein

R is a (C ₁ to C ₄ ) -alkyl group, in particular a methyl group,

To compensate for the positive polymer charge of component (b), the above applies.

It is again preferred according to the invention, if in the agent according to the invention in addition to the polyether of formula (I) as a cationic film-forming and / or cationic setting polymer (b) this embodiment, at least one copolymer (t> 1) is contained, which in addition to at least one structural element of the formula (M 1) additionally comprises a structural element of the formula (MI)

wherein

R is a (C ₁ to C ₄ ) -alkyl group, in particular a methyl group.

To compensate for the positive polymer charge of the copolymers (b1) are all possible physiologically acceptable anions, such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate, triflate.

Very particularly preferred cationic film-forming and / or cationic fixing polymers as copolymers (b1) contain 10 to 30 mol%, preferably 15 to 25 mol% and in particular 20 mol% of structural units of the formula (M 1) and 70 to 90 Mol .-%, preferably 75 to 85 MoI.-% and in particular 80 mol .-% of structural units according to formula (MI).

It is particularly preferred if the copolymers (b1) in addition to polymer units resulting from the incorporation of said structural units of the formula (M1) and (MI) in the copolymer, a maximum of 5 wt .-%, preferably at most 1 wt .-%, Contain polymer units, which are due to the incorporation of other monomers. The copolymers (b1) are preferably composed exclusively of structural units of the formula (M1) where R "= methyl and (M-I) and can be represented by the general formula (poly)

(PoIyI)

describe, wherein the indices m and p vary depending on the molecular weight of the polymer and should not mean that they are block copolymers. Rather, structural units of the formula (M1) and of the formula (M-I) can be present in the molecule in a statistically distributed manner.

If a chloride ion is used to compensate for the positive charge of the polymer of the formula (poly), these N-methylvinylimidazole / vinylpyrrolidone copolymers are referred to as Polyquaternium-16 according to INCI nomenclature and are disclosed by BASF, for example Trade names Luviquat.RTM ^® Style, Luviquat.RTM ^® FC 370, Luviquat.RTM ^® FC 550, FC 905 and Luviquat.RTM ^® Luviquat.RTM ^® HM 552

Is to compensate the positive charge of the polymer of formula (PoIyI) a methosulfate ion used, then these N-methylvinylimidazole / vinylpyrrolidone copolymers nomenclature as Polyquaternium-44, according to INCI, and are, for example, from BASF under the trade names Luviquat ^® Ultra Care available.

Particularly preferred agents according to the invention comprise a copolymer (b1), in particular of the formula (poly), which has molar masses within a certain range. Here, agents according to the invention are preferred in which the copolymer (b1) has a molecular weight of from 50 to 400 kDa, preferably from 100 to 300 kDa, more preferably from 150 to 250 kDa and in particular from 190 to 210 kDa.

In addition to the copolymer (s) (b1) or at its site, the agents according to the invention may also contain copolymers (b2) which, starting from the copolymer (b1), have structural units of the formula (M-II) as additional structural units

Further particularly preferred agents according to the invention are thus characterized in that they contain as cationic film-forming and / or cationic setting polymer (b) at least one copolymer (b2), the at least one structural unit of formula (M1-a), at least one further structural unit according to formula (MI) and at least one further structural unit according to formula (M-II)

Here too, it is particularly preferred if the copolymers (b2) contain not more than 5% by weight of polymer units which result from the incorporation of the abovementioned structural units of the formula (M1-a), (MI) and (M-II) into the copolymer. , preferably at most 1 wt .-%, contain polymer units, which go back to the incorporation of other monomers. Preferably, the Copolymers (b2) are composed exclusively of structural units of the formulas (M1-a), (MI) and (M-II) and can be defined by the general formula (Poly2)

describe, wherein the indices m, n and p vary depending on the molecular weight of the polymer and should not mean that they are block copolymers. Rather, structural units of said formulas can be present in the molecule in a statistically distributed manner.

To compensate for the positive polymer charge of component (b2) are all possible physiologically acceptable anions, such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate, triflate.

Is to compensate the positive charge of the polymer of formula (Poly2), a methosulfate be used refer to those N-methylvinylimidazole / vinylpyrrolidone / vinylcaprolactam copolymers, according to INCI nomenclature as Polyquaternium-46 and are for example available under the trade names Luviquat ^® Hold by BASF ,

Very particularly preferred copolymers (b2) contain 1 to 20 mol%, preferably 5 to 15 mol% and in particular 10 mol% of structural units of the formula (M1-a) and 30 to 50 mol%, preferably 35 to 45 mol% and in particular 40 mol% of structural units of the formula (I) and 40 to 60 mol%, preferably 45 to 55 mol% and in particular 60 mol% of structural units of the formula (M-II) ,

Particularly preferred agents according to the invention contain a copolymer (b2) which has molecular weights within a certain range. Here, agents according to the invention are preferred in which the copolymer (b2) has a molecular weight of 100 to 1000 kDa, preferably of 250 to 900 kDa, more preferably of 500 to 850 kDa and in particular of 650 to 710 kDa.

In addition to the copolymer (s) (b1) and / or (b2) or at its point, the agents according to the invention may also contain copolymers (b3) as film-forming cationic and / or setting cationic polymer (b), which as structural units structural units of the formulas (M1-a) and (I), as well as further structural units from the group of vinylimidazole units and further structural units from the group of the acrylamide and / or methacrylamide units. Further particularly preferred agents according to the invention are characterized in that they comprise as cationic film-forming and / or cationic setting polymer (b) at least one copolymer (b3) which comprises at least one structural unit of the formula (M1-a), at least one further structural unit of the formula ( MI), at least one further structural unit of the formula (M-VII) and at least one further structural unit of the formula (M-VIII)

(M-VII) (M-VIII).

Here, too, it is particularly preferred if the copolymers (b3) result, in addition to polymer units which result from the incorporation of the abovementioned structural units of the formula (M1-a), (III), (M-VII) and (M-VIII) into the copolymer, not more than 5 wt .-%, preferably at most 1 wt .-%, contain polymer units, which go back to the incorporation of other monomers. Preferably, the copolymers (b3) are composed exclusively of structural units of the formula (M1-a), (M-I), (M-VII) and (M-VIII) and can be represented by the general formula (Poly3)

³ (Poly3)

describe, wherein the indices m, n, o and p vary depending on the molecular weight of the polymer and should not mean that they are block copolymers. Rather, structural units of the formulas (M1-a), (M-I), (M-VII) and (M-VIII) can be present in a statistically distributed manner in the molecule.

Is to compensate the positive charge of the polymer of formula (poly 3) a methosulfate be used refer to those N-methylvinylimidazole / vinylpyrrolidone / vinylimidazole / methacrylamide copolymers, according to INCI nomenclature as Polyquaternium-68 and are, for example, from BASF under the tradename Luviquat ^® Supreme available. Very particularly preferred copolymers (b3) contain 1 to 12 mol%, preferably 3 to 9 mol% and in particular 6 mol% of structural units of the formula (M1-a) and 45 to 65 mol%, preferably 50 to 60 mol% and in particular 55 mol% of structural units of the formula (III) and 1 to 20 mol%, preferably 5 to 15 mol% and in particular 10 mol% of structural units of the formula (M-VII) and 20 to 40 mol%, preferably 25 to 35 mol% and in particular 29 mol% of structural units of the formula (M-VIII).

Particularly preferred agents according to the invention contain a copolymer (b3) which has molecular weights within a certain range. Here, agents according to the invention are preferred in which the copolymer (b3) has a molecular weight of from 100 to 500 kDa, preferably from 150 to 400 kDa, more preferably from 250 to 350 kDa and in particular from 290 to 310 kDa.

Among the additional film-forming cationic and / or setting polymers selected from the cationic polymers (b) having at least one structural element of the above formula (M1), the following are preferred:

Vinylpyrrolidone / i-vinyl-S-methyl-I H-imidazolium chloride copolymers (such as for example that with the INCI name Polyquaternium-16 under the trade names Luviquat ^® Style, Luviquat ^® FC 370, Luviquat ^® FC 550, Luviquat ^® FC 905 and Luviquat ^® HM 552 (BASF SE)),

Vinylpyrrolidone / i-vinyl-3-methyl-I H-imidazolium copolymers (such as for example that with the INCI name Polyquaternium-44 under the trade names Luviquat Care ^® (BASF SE)),

Vinylpyrrolidone / vinyl caprolactam / i-vinyl-S-methyl-I H-imidazolium terpolymer (such as for example that with the INCI name Polyquaternium-46 ^® under the trade names Luviquat Care or Luviquat Hold ^® (BASF SE)),

Vinylpyrrolidone / methacrylamide / vinylimidazole / i-vinyl-S-methyl-I H-imidazoliummethylsulfat- copolymer (such as (with the INCI name Polyquaternium-68 under the trade name Luviquat ^® Supreme BASF)), as well as mixtures of these polymers.

In the context of these embodiments, the abovementioned preferred embodiments of the polyether-modified solid particles are preferred (vide supra).

Similarly, all of the above-mentioned preferred quantities with respect to the components (a) and (b) of the agent according to the invention are also mutatis mutandis preferred for these embodiments. Within the scope of a preferred embodiment, the agents according to the invention comprise as film-forming and / or setting polymer at least one film-forming nonionic and / or setting nonionic polymer.

According to the invention, a nonionic polymer is understood as meaning a polymer which carries in a protic solvent under standard conditions substantially no structural units with permanently cationic or anionic groups which have to be compensated by counterions while maintaining the electroneutrality. Quaternized ammonium groups, however, do not include protonated amines under cationic groups. Examples of anionic groups include carboxyl and sulfonic acid groups.

The film-forming nonionic and / or setting nonionic polymers are preferably present in the composition according to the invention in an amount of from 0.1% by weight to 20.0% by weight, particularly preferably from 0.2% by weight to 15.0% by weight .-%, most preferably from 0.5 wt .-% to 10.0 wt .-%, each based on the weight of the inventive composition.

Again, the film-forming nonionic and / or setting nonionic polymers are preferably selected from at least one polymer of the group that is formed

Homopolymers and nonionic copolymers of N-vinylpyrrolidone,

nonionic copolymers of isobutene.

Suitable polyvinylpyrrolidones are, for example, commercial products such as Luviskol ^® K 90, or

Luviskol ^® K 85 from BASF SE.

Suitable polyvinyl alcohols are marketed under the trade names Elvanol.RTM ^® from DuPont or Vinol ^® 523/540 by Air Products.

Suitable polyvinyl acetate is marketed under the trade name Vinac ^® as an emulsion from Air Products.

Means comprising as film-forming nonionic and / or setting nonionic polymer at least one polymer selected from the group formed from

polyvinylpyrrolidone,

Copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic acids having 2 to 18 carbon atoms, in particular N-vinylpyrrolidone and vinyl acetate,

Copolymers of N-vinylpyrrolidone and N-vinylimidazole and methacrylamide,

Copolymers of N-vinylpyrrolidone and N-vinylimidazole and acrylamide,

Copolymers of N-vinylpyrrolidone with N, N-di (C 1 -C ₄ ) -alkylamino (C ₂ -C ₄ ) -alkylacrylamide, copolymers of N-vinylpyrrolidone with N, N-di (C 1 -C ₄ ) -alkylamino (C ₂ to C ₄ ) alkylacrylamide are very particularly preferred according to the invention. In particular, those agents which are contained in a cosmetically acceptable carrier within the scope of this embodiment are particularly preferred

RAK-Si (OR ² J _x R ^ _x

(1-1)

wherein R ¹ , R ² , R ³ , A, K and x are as previously defined

and

(b) polyvinylpyrrolidone.

(A) Polyether-modified solid particles, which by

to be obtained

and

(b) polyvinylpyrrolidone.

T-K-A-K'-T '(I)

wherein

A is a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and

Propylene oxide units means, with a maximum proportion of 50 wt .-% of

Propylene oxide units, based on the weight of A,

* -B - [(N (CH ₂ COOM) -B ¹ ) _y -N (CH ₂ COOM) ₂ ] in which

y is 1 or 2 (preferably 1),

and

(b) polyvinylpyrrolidone.

RAK-Si (OR ² ) _χ R ₃ _ _χ

(1-1)

wherein R ¹ , R ² , R ³ , A, K and x are as previously defined

and

(B) at least copolymer, which consists of the monomers N-vinylpyrrolidone and vinyl acetate

- In particular, no further monomers - is produced.

In the context of this embodiment, those agents are very particularly preferred containing in a cosmetically acceptable carrier

(A) Polyether-modified solid particles, which by

to be obtained

and

- In particular, no further monomers - is produced. In particular, those agents which are contained in a cosmetically acceptable carrier within the scope of this embodiment are particularly preferred

T-K-A-K'-T '(I)

wherein

A is a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and

Propylene oxide units means, with a maximum proportion of 50 wt .-% of

Propylene oxide units, based on the weight of A,

^* -B - [(N (CH ₂ COOM) -B ¹ ) _y -N (CH ₂ COOM) ₂ ] where

1, 2-diyl, propane-1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl), B 'is a (Ci to C ₆ ) Alkylene radical (preferably ethane-1,2-diyl, propane

1, 2-diyl, propane-1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl) or an N, N-bis (Ci to C ₆ ) -Alkylene-N-carboxymethyl, M is independently of one another a hydrogen atom or one equivalent of a mono- or polyvalent cation,

y is 1 or 2 (preferably 1),

and

(B) at least copolymer which is prepared from the monomers N-vinylpyrrolidone and vinyl acetate - in particular from no further monomers.

In this case, it is again preferred if the molar ratio of the structural units comprised of the monomer N-vinylpyrrolidone to the structural units of the polymer comprised of the monomer vinyl acetate is in the range from 20:80 to 80:20, in particular from 30:70 to 60:40 ,

Suitable copolymers of vinylpyrrolidone and vinyl acetate are available, for example under the trademark Luviskol ^® VA 37, Luviskol ^® VA 55, Luviskol ^® VA 64 and Luviskol ^® VA 73 from the firm BASF SE. Further preferred agents according to the invention are characterized in that they comprise as nonionic film-forming and / or nonionic fixing polymer at least one copolymer (n1) containing at least one structural unit of formula (MI), at least one further structural unit of formula (M-VII) and at least contains a further structural unit according to formula (M-VIII)

(MI) (M-VII) (M-VIII).

In this case too, it is particularly preferred if, in addition to polymer units resulting from the incorporation of the abovementioned structural units of the formula (M1-a), (I), (VII) and (VIII) into the copolymer, these copolymers have a maximum of 5% by weight, preferably at most 1 wt .-%, polymer units, which go back to the incorporation of other monomers. Preferably, the copolymers (n1) are composed exclusively of structural units of the formula (M1-a), (I), (VII) and (VIII) and can be represented by the general formula (poly4)

describe, wherein the indices m, n, o and p vary depending on the molecular weight of the polymer and should not mean that they are block copolymers. Rather, structural units of the formulas (I), (VII) and (VIII) can be present in the molecule in a statistically distributed manner.

RAK-Si (OR ² LR ^ _γ

x ³ - ^χ (1-1)

wherein R ¹ , R ² , R ³ , A, K and x are as previously defined

and

(b) at least one nonionic film-forming and / or nonionic fixing polymer comprising at least one structural unit of the formula (MI), at least one further structural unit of the formula (M-VII) and at least one further structural unit of the formula (M-VIII) (MI) (M-VII) (M-VIII).

(A) Polyether-modified solid particles, which by

ii) reaction of the epoxy-functionalized solid particles obtained in step i) with at least one polyoxyalkylene monoamine which has only one functional group reactive to the epoxy groups of the epoxy-functionalized solid particles

and

(b) at least one nonionic film-forming and / or nonionic fixing polymer comprising at least one structural unit of the formula (M-I), at least one further structural unit of the formula (M-VII) and at least one further structural unit of the formula (M-VIII)

(M-VII)

(M-VIII).

T-K-A-K'-T (I)

wherein

A is a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and

Propylene oxide units means, with a maximum proportion of 50 wt .-% of

Propylene oxide units, based on the weight of A,

K and K 'independently represent a connectivity selected from a covalent bond or from a molecular fragment having two free valencies, T and T independently represent a group of the general formula ^* -B - [(N (CH ₂ COOM) -B ¹ ) _y -N (CH ₂ COOM) ₂ ] where

1, 2-diyl, propane-1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl), B 'is a (Ci to C ₆ ) Alkylene radical (preferably ethane-1, 2-diyl, propane-1, 2-diyl, propane-1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1 , 4-diyl) or an N, N-bis (C ₁ to C ₆ ) -alkylene-N-carboxymethyl, M independently of one another represent a hydrogen atom or one equivalent of a mono- or polyvalent cation,

y is 1 or 2 (preferably 1),

and

(MI) (M-VII) (M-VIII).

A particularly preferred polymer is selected from the polymers of the INCI name VP / methacrylamide / vinyl imidazole copolymer, which are obtainable, for example, under the trade name Luviset Clear from BASF SE.

Furthermore, it has been found preferable to use, for the purpose of achieving the object, compositions comprising at least one nonionic film-forming and / or nonionic fixing polymer comprising at least one structural unit of the formula (III) and at least one structural unit of the formula (III)

wherein

R ^{1 represents} a hydrogen atom or a methyl group,

X ^{1 represents} an oxygen atom or a group NH,

A ^{1 represents} a group of ethane-1,2-diyl, propane-1,3-diyl or butane-1,4-diyl

R ² and R ³ independently represent a (C ₁ to C ₄ ) alkyl group.

RAK-Si (OR ² LR ^ _γ

x ³ - ^χ (1-1)

wherein R ¹ , R ² , R ³ , A, K and x are as previously defined

and

(b) at least one nonionic film-forming and / or nonionic fixing polymer comprising at least one structural unit of the formula (M-I) and at least one structural unit of the formula (M-III)

wherein

R ^{1 represents} a hydrogen atom or a methyl group,

X ^{1 represents} an oxygen atom or a group NH,

R ² and R ³ independently represent a (C ₁ to C ₄ ) alkyl group. In the context of this embodiment, those agents are very particularly preferred containing in a cosmetically acceptable carrier

(A) Polyether-modified solid particles, which by

to be obtained

and

wherein

R ^{1 represents} a hydrogen atom or a methyl group,

X ^{1 represents} an oxygen atom or a group NH,

R ² and R ³ independently represent a (C ₁ to C ₄ ) alkyl group.

T-K-A-K'-T '(I)

wherein

A is a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and

Propylene oxide units means, with a maximum proportion of 50 wt .-% of

Propylene oxide units, based on the weight of A,

K and K 'independently represent a connectivity selected from a covalent bond or from a molecular fragment having two free valences, T and T independently represent a group of the general formula * -B - [(N (CH ₂ COOM) -B ¹ ) _y -N (CH ₂ COOM) ₂ ] where

1, 2-diyl, propane-1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl), B 'is a (Ci to C ₆ ) Alkylene radical (preferably ethane-1, 2-diyl, propane-1, 2-diyl, propane-1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1 , 4-diyl) or an N ₁ N-BiS (C ₁ to C ₆ ) -alkylene-N-carboxymethyl, M independently of one another represent a hydrogen atom or one equivalent of a mono- or polyvalent cation,

y is 1 or 2 (preferably 1),

and

wherein

R ^{1 represents} a hydrogen atom or a methyl group,

X ^{1 represents} an oxygen atom or a group NH,

R ² and R ³ independently represent a (C ₁ to C ₄ ) alkyl group.

In this case, it is particularly preferred if the above nonionic film-forming and / or nonionic fixing polymer is selected from at least one polymer which fulfills at least one or more of the following features:

R ^{1 represents} a methyl group,

X ¹ stands for a group NH, A ¹ is ethane-1, 2-diyl or propane-1, 3-diyl,

RR ²² and FR ³ , independently of one another represent methyl or ethyl, (particularly preferably for

Methyl).

The nonionic film-forming and / or nonionic fixing polymer of this embodiment is particularly preferably at least one polymer comprising at least one structural unit of the formula (M-I) and at least one structural unit of the formula (M-III-8),

A very particularly preferred nonionic film-forming and / or nonionic setting polymer of this embodiment is a copolymer of N-vinylpyrrolidone and N, N-dimethylaminiopropylmethacrylamide, which, for example, under the INCI name VP / DMAPA acrylates copolymer, for example under the trade name Styleze ^® CC 10 of the Company ISP is sold.

Within the scope of all these embodiments, the aforementioned preferred embodiments of the polyether-modified solid particle are preferred (vide supra).

Similarly, all of the above-mentioned preferred quantities with respect to the components (a) and (b) of the agent according to the invention are also mutatis mutandis preferred for these embodiments.

Within the scope of a preferred embodiment, the agents according to the invention contain as film-forming and / or setting polymer at least one film-forming anionic and / or setting anionic polymer.

According to the invention, an anionic polymer is understood as meaning a polymer which, in standard conditions, contains structural units with anionic groups which have to be compensated by counterions while maintaining the electroneutrality in a protic solvent and has no structural units with permanently cationic or cationizable groups. Anionic groups include carboxyl and sulfonic acid groups. The anionic, film-forming and / or anionic, fixing polymers (b) are preferably present in the composition according to the invention in an amount of 0.1% by weight to 20.0% by weight, particularly preferably of 0.2% by weight. to 15.0 wt .-%, most preferably from 0.5 wt .-% to 10.0 wt .-%, each based on the weight of the inventive composition.

It is preferred according to the invention if the anionic, film-forming and / or anionic, fixing polymer (b) contains at least one structural unit of the formula (S1) which is selected from at least one structural unit of the formulas (S1-1) to (S1-5)

It is preferred according to the invention if the anionic, film-forming and / or anionic, fixing polymer (b) additionally contains at least one structural unit of the formula (S2) in addition to at least one structural unit of the formulas (S1-1) to (S1-5) is made up of at least one structural unit of the formulas (S2-1) to (S2-8)

(S2-1) (S2-2) (S2-3)

wherein

R ^{12 is} a (C ₂ to C ₂ ) acyl group (especially acetyl or neodecanoyl).

Within the scope of a preferred embodiment, such pulverulent compositions according to the invention are preferred as containing at least one polymer having at least one structural unit of the formula (S1-5) and at least one structural unit of the formula (I) as a film-forming and / or setting polymer in the form of particles. S2-8)

wherein R ^{12 is} a (C ₂ to C ₁₂ ) acyl group (in particular acetyl and / or neodecanoyl).

Particularly preferred polymers of this type are selected from at least one polymer of the group formed

- Copolymers of vinyl acetate and crotonic acid.

- copolymers of vinyl propionate and crotonic acid,

- Copolymers of vinyl neodecanoate, vinyl acetate and crotonic acid.

Such copolymers are, for example, from the company Clariant under the trade name Aristoflex A 60 (INCI name: VA / Crotonates copolymer) in an isopropanol-water mixture (60 wt .-% of active substance), from BASF under the trade name Luviset CA 66 (Vinyl acetate / crotonic acid copolymer 90:10, INCI name VA / crotonates copolymer) provided by National Starch under the trade names Resyn 28-2942 and Resyn 28-2930 (INCI name: VA / Crotonates / Vinyl Neodecanoate Copolymer).

RAK-Si (OR ² LR ^ _γ

x ³ - ^χ (1-1)

wherein R ¹ , R ² , R ³ , A, K and x are as previously defined

and

(b) at least one anionic film-forming and / or anionic fixing polymer containing at least one structural unit of the formula (S1-5) and at least one structural unit of the formula (S2-8)

(A) Polyether-modified solid particles, which by

to be obtained

and

(S2-8) wherein R ^{12 is} a (C ₂ to C ₁₂ ) acyl group (in particular acetyl and / or neodecanoyl).

T-K-A-K'-T '(I)

wherein

A is a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and

Propylene oxide units means, with a maximum proportion of 50 wt .-% of

Propylene oxide units, based on the weight of A,

* -B - [(N (CH ₂ COOM) -B ¹ ) _y -N (CH ₂ COOM) ₂ ] where

y is 1 or 2 (preferably 1),

and

wherein R ^{12 is} a (C ₂ to C ₂ ) acyl group (in particular acetyl and / or neodecanoyl).

Within the scope of a preferred embodiment, such pulverulent compositions according to the invention are preferred according to the invention which contain as anionic film-forming and / or anionic setting polymer at least one polymer having at least one structural unit of the formula (S1-1) and at least one structural unit of the formula (S2-5 ) contain

It is again particularly preferred if the present in the form of particles, film-forming and / or consolidating polymer in addition to the above structural units of the formulas (S1-1) and (S2-5) additionally contains at least one structural unit of the formula (S3)

wherein

R ¹⁵ represents a hydrogen atom or a methyl group

R ¹⁶ is a (C 1 to C ₄ ) -alkyl group (in particular a methyl group or an ethyl group).

Particularly preferred polymers of this type are selected from at least one polymer of the group which is formed from copolymers of acrylic acid and ethyl acrylate and N-tert-butylacrylamide. Such copolymers are, for example, from BASF under the trade name Ultrahold ^® strand (INCI name: Acrylates / t-butylacrylamide copolymer, white, pourable granules) or Ultrahold ^® 8 (INCI name: Acrylates / t-butylacrylamide copolymer, white, pourable Granules) provided. In the context of this embodiment, those agents are preferred which are contained in a cosmetically acceptable carrier

RAK-Si (OR ² LR, _γ

x ^{3 "x} (1-1)

wherein R ¹ , R ² , R ³ , A, K and x are as previously defined

and

(b) at least one anionic film-forming and / or anionic setting polymer containing at least one structural unit of the formula (S1-1) and at least one structural unit of the formula (S2-5)

(A) Polyether-modified solid particles, which by

to be obtained

and

In the context of this embodiment, those agents are preferred which are contained in a cosmetically acceptable carrier (A) Polyether-modified solid particles, which are obtained by reacting hydroxy-containing solid particles with at least one polyether of formula (I)

T-K-A-K'-T '(I)

wherein

A is a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and

Propylene oxide units means, with a maximum proportion of 50 wt .-% of

Propylene oxide units, based on the weight of A,

^* -B - [(N (CH ₂ COOM) -B ¹ ) _y -N (CH ₂ COOM) ₂ ] where

y is 1 or 2 (preferably 1),

and

Within the scope of one embodiment, those agents are preferred as being in accordance with the invention which contain at least one polymer as the anionic film-forming and / or anionic setting polymer (b) containing at least one structural unit of the formula (S1-3) and at least one structural unit of the formula (S2-6)

Preferred polymers (b) of this type are selected from at least one polymer of the group formed

Copolymers of 2-acrylamido-2-methylpropanesulfonic acid and acrylamide,

Copolymers of 2-acrylamido-2-methylpropanesulfonic acid, acrylamide and acrylic acid,

- Copolymers of 2-acrylamido-2-methyl-propanesulfonic acid, acrylamide and methacrylic acid.

Polymers of this type are, for example, in an inverse isohexadecane emulsion by the company SEPPIC under the trade name Sepigel ^® 305 (INCI name: Polyacrylamide, C13-14 isoparaffin, laureth-7) or Simulgel ^® 600 (INCI name: Acrylamide / Acryloyldimethyltaurate Copolymer , Isohexadecane, polysorbate-80).

A particularly preferred agent according to the invention is characterized in that it contains as polymer (b) a copolymer (b1).

These copolymers (b1) can be defined by the general formula

describe, wherein the indices m, n and o vary depending on the molecular weight of the polymer and should not mean that they are block copolymers. Rather, structural units can be present in the molecule in a statistically distributed manner.

Particularly preferred agents according to the invention are characterized in that the copolymer (b1) has a molecular weight of from 50 to 500 kDa, preferably from 100 to 450 kDa, more preferably from 150 to 400 kDa and in particular from 200 to 300 kDa. Copolymers of acrylamide with methacrylic acid and acryloyldimethyltaurate are available, for example, under the trade name Acudyne® SCP (Rohm & Haas).

RAK-Si (OR ² LR ^ _γ

x ³ - ^χ (1-1)

wherein R ¹ , R ² , R ³ , A, K and x are as previously defined

and

(b) at least one anionic film-forming and / or anionic setting polymer containing at least one structural unit of the formula (S1-3) and at least one structural unit of the formula (S2-6)

(A) Polyether-modified solid particles, which by

to be obtained

and

T-K-A-K'-T '(I)

wherein

A is a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and

Propylene oxide units means, with a maximum proportion of 50 wt .-% of

Propylene oxide units, based on the weight of A,

^* -B - [(N (CH ₂ COOM) -B ¹ ) _y -N (CH ₂ COOM) ₂ ] where

y is 1 or 2 (preferably 1),

and (b) at least one anionic film-forming and / or anionic setting polymer containing at least one structural unit of the formula (S1-3) and at least one structural unit of the formula (S2-6)

In the context of these embodiments, the aforementioned preferred

Embodiments of the polyether-modified solid particles of the formula (I) as preferred (vide supra).

Within the scope of a preferred embodiment, the agents according to the invention contain as film-forming and / or setting polymer at least one film-forming amphoteric and / or setting amphoteric polymer.

According to the invention, an amphoteric polymer is understood as meaning a polymer which, in standard conditions, carries structural units in a protic solvent with anionic groups which have to be compensated by counterions while maintaining electroneutrality and which additionally has structural units with groups which can be cationized by protonation but is free of permanently cationized groups is. Anionic groups include carboxyl and sulfonic acid groups. Permanently cationized nitrogen atoms are to be understood as meaning those nitrogen atoms which carry a positive charge and thereby form a quaternary ammonium compound.

The amphoteric, film-forming and / or amphoteric, fixing polymers (b) are preferably present in the composition according to the invention in an amount of 0.1% by weight to 20.0% by weight, particularly preferably of 0.2% by weight. to 15.0 wt .-%, most preferably from 0.5 wt .-% to 10.0 wt .-%, each based on the weight of the inventive composition.

It is preferred according to the invention if the amphoteric, film-forming and / or amphoteric, fixing polymer contains at least one structural unit of the formula (S1) which is selected from at least one structural unit of the formulas (S1-1) to (S1-5)

It is particularly preferred according to the invention if the amphoteric, film-forming and / or amphoteric, fixing polymers additionally contain, in addition to at least one structural unit of the formulas (S1-1) to (S1-5), at least one structural unit of the formula (S2) which is selected from at least one structural unit of the formula (S2-9) to (S2-15)

(S2-13) (S2-14)

wherein

X ³ represents an oxygen atom or a group NH.

It is again particularly preferred according to the invention if the amphoteric, film-forming and / or amphoteric, fixing polymers in addition to at least one structural unit of the formulas (S1-1) to (S1-5) and at least one structural unit of the formulas (S2-9) to (S2 -15) additionally comprises at least one structural unit of the formulas (S2-1) to (S2-8)

(S2-8) wherein

R ^{12 is} a (C ₂ to C ₁₂ ) acyl group (in particular acetyl or neodecanoyl).

In a particularly preferred embodiment of the invention, the agent according to the invention contains at least one amphoteric, film-forming and / or amphoteric, consolidating polymer which has at least one structural unit of the formula (S1-1), at least one structural unit of the formula (S2-3) and at least one structural unit of formula (S2-16) (in particular selected from the group formed of the above formulas (S2-5) to (S2 12), with the proviso that X ³ represents an oxygen atom),

wherein X ³ is an oxygen atom or a group NH,

R ¹³ represents a hydrogen atom or a methyl group and

R ¹⁴ is an alkyl group having 4 carbon atoms (especially n-butyl, sec-butyl, iso-butyl or tert-butyl).

In this case, it is again particularly preferred if the amphoteric, film-forming and / or anionic, fixing polymers in addition to the above structural units of the formulas (S1-1), (S2-3) and (S2-16) additionally at least one structural unit of the formula (S3 ) contains

R ¹⁵

* ^*

C = O

¹⁶

κ (S3)

wherein

R ¹⁵ represents a hydrogen atom or a methyl group

R ¹⁶ is a (C ₁ to C ₄ ) -alkyl group (in particular a methyl group or an ethyl group).

Preferred polymers of this type are selected from the group consisting of copolymers of acrylic acid, (C 1 to C ₄ ) -alkyl acrylate, N- (C ₄ -alkyl) aminoethyl methacrylate and N- (C ₈ -alkyl) acrylamide.

An example of a particle-forming, film-forming and / or setting polymer particularly preferably usable in the context of this embodiment is that under Trade name Amphomer ^® sold by the company National Starch polymer having the INCI designation octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer.

In the context of these embodiments, the aforementioned preferred

Embodiments of the polyether of the formula (I) as preferred (vide supra).

RAK-Si (OR ² ) _χ R | _.χ

((i1 - i1 :)

wherein R ¹ , R ² , R ³ , A, K and x are as previously defined

and

(b) at least one amphoteric, film-forming and / or amphoteric, consolidating polymer which has at least one structural unit of the formula (S1-1), at least one structural unit of the formula (S2-3) and at least one structural unit of the formula (S2-16) ( in particular selected from the group consisting of the above formulas (S2-5) to (S2-12) with the proviso that X ^{3 represents} an oxygen atom),

wherein X ³ is an oxygen atom or a group NH,

R ¹³ represents a hydrogen atom or a methyl group and

R ¹⁴ is an alkyl group having 4 carbon atoms (in particular n-butyl, sec-butyl, isobutyl or tert-butyl).

(A) Polyether-modified solid particles, which by i) reaction of hydroxyl-containing solid particles with at least one epoxy silane and

to be obtained

and

(b) at least one amphoteric, film-forming and / or amphoteric, consolidating polymer containing at least one structural unit of the formula (S1-1), at least one structural unit of the formula

(S2-3) and at least one structural unit of formula (S2-16) (in particular selected from the group formed of the above formulas (S2-5) to (S2-12) with the proviso that X ³ represents an oxygen atom contains),

wherein X ³ is an oxygen atom or a group NH,

R ¹³ represents a hydrogen atom or a methyl group and

R ¹⁴ is an alkyl group having 4 carbon atoms (in particular n-butyl, sec-butyl, iso)

Butyl or tert-butyl).

T-K-A-K'-T (I)

wherein

A is a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and

Propylene oxide units means, with a maximum proportion of 50 wt .-% of

Propylene oxide units, based on the weight of A,

K and K 'independently represent a connectivity selected from a covalent bond or from a molecular fragment having two free valencies, T and T independently represent a group of the general formula * -B - [(N (CH ₂ COOM) -B ') _y -N (CH ₂ COOM) ₂ ] where

y is 1 or 2 (preferably 1),

and

wherein X ³ is an oxygen atom or a group NH,

R ¹³ represents a hydrogen atom or a methyl group and

The compositions according to the invention contain the ingredients or active substances in a cosmetically acceptable carrier. Preferred cosmetically acceptable carriers are aqueous, alcoholic or aqueous-alcoholic media with preferably at least 10% by weight of water, based on the total agent. As alcohols, it is possible in particular to include the lower alcohols having 1 to 4 carbon atoms usually used for cosmetic purposes, such as, for example, ethanol and isopropanol.

According to the invention, it is preferred to use at least one (C 1 to C ₄ ) monoalkyl alcohol in the agents according to the invention, in particular in an amount of from 1 to 50% by weight, in particular from 5 to 30% by weight. This is in turn preferred in particular for the packaging as pump foam or aerosol foam.

As additional co-solvents, organic solvents or a mixture of solvents with a boiling point below 400 ⁰ C in an amount of 0.1 to 15 weight percent, preferably from 1 to 10 weight percent be present on the total composition. Particularly suitable as additional co-solvents are unbranched or branched hydrocarbons such as pentane, hexane, isopentane and cyclic hydrocarbons such as cyclopentane and cyclohexane. Further, particularly preferred water-soluble solvents are glycerol, ethylene glycol and propylene glycol in an amount of up to 30% by weight, based on the total agent.

In particular, the addition of glycerol and / or propylene glycol and / or polyethylene glycol and / or polypropylene glycol increases the flexibility of the polymer film formed when the agent according to the invention is used. Thus, if a flexible hold is desired, the compositions according to the invention preferably contain from 0.01 to 30% by weight of glycerol and / or propylene glycol and / or polyethylene glycol and / or polypropylene glycol, based on the total agent.

The agents preferably have a pH of 2 to 11. The pH range between 2 and 8 is particularly preferred. The pH value in the context of this document refers to the pH at 25 ^° C., unless stated otherwise.

The compositions of the invention may further contain the auxiliaries and additives which are usually added to conventional styling agents.

The agents according to the invention preferably additionally contain at least one surfactant, nonionic, anionic, cationic, ampholytic surfactants being suitable in principle. The group of ampholytic or amphoteric surfactants includes zwitterionic surfactants and ampholytes. The surfactants according to the invention may already have emulsifying activity.

The additional surfactants are in the inventive composition preferably in an amount of 0.01 wt .-% to 5 wt .-%, particularly preferably from 0.05 wt .-% to 0.5 wt .-%, each based on the Weight of the agent, included. It has proved to be particularly preferred if the agents according to the invention additionally comprise at least one nonionic surfactant.

Nonionic surfactants contain as hydrophilic group e.g. a polyol group, a polyalkylene glycol ether group, or a combination of polyol and polyglycol ether groups. Such compounds are, for example

Addition products of 2 to 100 moles of ethylene oxide and / or 1 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 carbon atoms

Atoms and alkylphenols having 8 to 15 C atoms in the alkyl group,

with a methyl or C ₂ - C ₆ - alkyl radical end-capped addition products of 2 to 50 moles of ethylene oxide and / or 1 to 5 moles of propylene oxide to linear and branched

Fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 carbon atoms and alkylphenols having 8 to 15 carbon atoms in the alkyl group, such as those among the

Sales names Dehydrol® ^® LS, Dehydrol® ^® LT (Cognis) types,

C ₁₂ -C ₃ o-fatty acid mono- and diesters of addition products of 1 to 30 mol ethylene oxide onto glycerol,

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil,

Polyol fatty acid esters, such as the commercial product Hydagen ^® HSP (Cognis) or

Sovermol - types (Cognis),

alkoxylated triglycerides,

alkoxylated fatty acid alkyl esters of the formula (E4-I)

R ¹ CO- (OCH ₂ CHR ² ) _W OR ³ (E4-I)

in the R ¹ CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or methyl, R ^{3 is a} linear or branched alkyl radical having 1 to 4 carbon atoms and w is a number from 1 to 20 stands,

Amine oxides,

Hydroxy mixed ethers, as described, for example, in DE-OS 19738866, sorbitan fatty acid esters and addition products of ethylene oxide onto sorbitan fatty acid esters, for example the polysorbates,

Sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters, addition products of ethylene oxide onto fatty acid alkanolamides and fatty amines,

Sugar surfactants of the alkyl and alkenyl oligoglycoside type of formula (E4-II),

in which R ^{4 is} an alkyl or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. The alkylene oxide addition products of saturated linear fatty alcohols and fatty acids with in each case 2 to 100 mol of ethylene oxide per mole of fatty alcohol or fatty acid have proven to be very particularly preferred nonionic surfactants. Preparations with excellent properties are also obtained when they contain as nonionic surfactants C ₂ -C ₃₀ fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol and / or addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil ,

In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. By "normal" homolog distribution are meant mixtures of homologs obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alkoxides are used as catalysts. The use of products with narrow homolog distribution may be preferred.

The agents according to the invention as surfactant very particularly preferably contain at least one addition product of from 15 to 100 mol of ethylene oxide, in particular from 15 to 50 mol of ethylene oxide, to a linear or branched (in particular linear) fatty alcohol having from 8 to 22 carbon atoms. These are very particularly preferably Ceteareth-15, Ceteareth-25 or Ceteareth- 50, which are marketed as Eumulgin ^® CS 15 (Cognis), Cremophor A25 (BASF SE) or Eumulgin ^® CS 50 (Cognis).

Suitable anionic surfactants are in principle all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group,

linear and branched fatty acids with 8 to 30 carbon atoms (soaps),

Ethercarbonsäuren the formula R-O- (CH2-CH2O) x-CH2-COOH, in which R is a linear

Alkyl group having 8 to 30 C atoms and x = 0 or 1 to 16, Acylsarcosides having 8 to 24 carbon atoms in the acyl group,

Acyltaurides having 8 to 24 carbon atoms in the acyl group,

Acyl isethionates having 8 to 24 carbon atoms in the acyl group,

Sulfobernsteinsäuremono- and -dialkylester having 8 to 24 carbon atoms in the alkyl group and

Sulfosuccinic acid mono-alkylpolyoxyethylester having 8 to 24 carbon atoms in the alkyl group and

1 to 6 oxyethyl groups,

linear alkanesulfonates having 8 to 24 C atoms,

linear alpha-olefin sulfonates having 8 to 24 C atoms,

Alpha-sulfofatty acid methyl esters of fatty acids having 8 to 30 carbon atoms,

Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -OSO ₃ H, in which R is a preferably linear alkyl group having 8 to 30 C atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates,

sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene glycol ethers,

Sulfonates of unsaturated fatty acids having 8 to 24 carbon atoms and 1 to 6 double bonds,

Esters of tartaric acid and citric acid with alcohols, the addition products of about 2-15

Represent molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms,

Alkyl and / or alkenyl ether phosphates of the formula (E1-I),

O

R ¹ (OCH ₂ CH ₂ ) _n - O - P --OR ² (E1 - I)

OX

in the R ^{1 is} preferably an aliphatic hydrocarbon radical having 8 to 30 carbon atoms, R ^{2 is} hydrogen, a radical (CH ₂ CH ₂ O) _n R ¹ or X, n is from 1 to 10 and X is hydrogen, an alkali metal radical or alkaline earth metal or NR ³ R ⁴ R ⁵ R ⁶ , where R ³ to R ⁶ independently of one another represent hydrogen or a C ¹ to C ⁴ hydrocarbon radical,

sulfated fatty acid alkylene glycol esters of the formula (EΞ 1-11)

R ⁷ CO (AIkO) _n SO ₃ M (E1-II)

in the R ⁷ CO- for a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, Alk for CH ₂ CH ₂ , CHCH ₃ CH ₂ and / or CH ₂ CHCH ₃ , n for numbers from 0.5 to 5 and M is a cation, as described in DE-OS 197 36 906,

At id ethercarbonsäu ren,

Condensation products of C ₈ - C ₃₀ - fatty alcohols with protein hydrolysates and / or amino acids and their derivatives, which are known to the skilled person as protein fatty acid condensates, such as Lamepon ^® - types Gluadin ^® - types Hostapon ^® KCG or Amisoft ^® - types. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the alkyl group and sulfosuccinic acid monoalkylpolyoxyethylester with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, Monoglycerdisulfate, alkyl and Alkenyletherphosphate and Eiweissfettsäurekondensate.

Also usable according to the invention are cationic surfactants of the quaternary ammonium compound type, the esterquats and the amidoamines. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides. The long alkyl chains of these surfactants preferably have 10 to 18 carbon atoms, such as. In cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetylmethyl ammonium chloride. Further preferred cationic surfactants are the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83.

Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ⁽⁾ or -SO ₃ ⁽⁾ group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines having in each case 8 to 18 C atoms in the alkyl or acyl group, and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Ampholytes are understood as meaning those surface-active compounds which, apart from a C ₈ -C ₂₄ -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytes are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 24 C atoms in the alkyl group. Particularly preferred ampholytes are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C ₂ - C ₈ - sarcosine. Other suitable auxiliaries and additives are in particular additional care substances.

As a care material, for example, a silicone oil and / or a silicone gum can be used.

Silicone oils or silicone gums which are suitable according to the invention are in particular dialkyl and alkylaryl siloxanes, for example dimethylpolysiloxane and methylphenylpolysiloxane, and also their alkoxylated, quaternized or else anionic derivatives. Preference is given to cyclic and linear polydialkylsiloxanes, their alkoxylated and / or aminated derivatives, dihydroxypoly-dimethylsiloxanes and polyphenylalkylsiloxanes.

The agents contain the silicones preferably in amounts of from 0.01% by weight to 15% by weight, particularly preferably from 0.05 to 2% by weight, based on the total agent.

As a care substance of another class of compounds, the agent may contain, for example, at least one protein hydrolyzate and / or one of its derivatives.

Protein hydrolysates are product mixtures obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins). According to the invention, the term protein hydrolyzates also means total hydrolyzates as well as individual amino acids and their derivatives as well as mixtures of different amino acids. Furthermore, according to the invention, polymers made up of amino acids and amino acid derivatives are understood by the term protein hydrolyzates. The molecular weight of the protein hydrolysates which can be used according to the invention is between 75, the molecular weight for glycine, and 200,000, preferably the molecular weight is 75 to 50,000 and very particularly preferably 75 to 20,000 daltons.

The protein hydrolysates are present in the agents according to the invention, for example, in concentrations of from 0.01% by weight to 20% by weight, preferably from 0.05% by weight to 15% by weight and very particularly preferably in amounts of 0 , 05 wt .-% up to 5 wt .-%, each based on the total application preparation included.

As a care substance, the agent according to the invention may further comprise at least one vitamin, a provitamin, a vitamin precursor and / or one of their derivatives.

According to the invention, such vitamins, provitamins and vitamin precursors are preferred, which are usually assigned to groups A, B, C, E, F and H.

The group of substances called vitamin A includes retinol (vitamin A ₁ ) and 3,4-didehydroretinol (vitamin A ₂ ). The ß-carotene is the provitamin of retinol. As vitamin A component according to the invention, for example, vitamin A acid and its esters, vitamin A aldehyde and vitamin A alcohol and its esters such as the palmitate and the acetate in Consideration. The agents preferably contain the vitamin A component in amounts of 0.05-1% by weight, based on the total application preparation.

The agents according to the invention preferably contain vitamins, provitamins and vitamin precursors from groups A, B, C, E and H.

Panthenol, pantolactone, pyridoxine and its derivatives as well as nicotinic acid amide and biotin are particularly preferred.

Very particular preference is given to using D-panthenol as care substance, if appropriate in combination with at least one of the abovementioned silicone derivatives.

As with the addition of glycerin and / or propylene glycol, the addition of panthenol increases the flexibility of the polymer film formed using the composition of the present invention. If, therefore, a particularly flexible hold is desired, the compositions according to the invention may contain panthenol instead of or in addition to glycerol and / or propylene glycol. In a preferred embodiment, the agents according to the invention contain panthenol, preferably in an amount of 0.05 to 10% by weight, particularly preferably 0.1 to 5% by weight, in each case based on the total agent.

As a conditioner, the compositions according to the invention may further contain at least one plant extract.

Usually these extracts are produced by extraction of the whole plant. However, in individual cases it may also be preferred to prepare the extracts exclusively from flowers and / or leaves of the plant.

The extracts of green tea, oak bark, nettle, witch hazel, hops, henna, chamomile, burdock root, horsetail, hawthorn, lime blossom, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime , Wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root.

As a care substance is still a series of carboxylic acids.

In the context of the invention, short-chain carboxylic acids may in particular be advantageous. Short-chain carboxylic acids and their derivatives in the context of the invention are understood to mean carboxylic acids which may be saturated or unsaturated and / or straight-chain or branched or cyclic and / or aromatic and / or heterocyclic and have a molecular weight of less than 750. For the purposes of the invention, preference may be given to saturated or unsaturated straight-chain or branched carboxylic acids having a chain length of from 1 to 16 C atoms in the chain, very particular preference being given to those having a chain length of from 1 to 12 C atoms in the chain. Furthermore, it is inventively preferred to use 2-pyrrolidinone-5-carboxylic acid and derivatives thereof as the carboxylic acid. Particularly preferred are the sodium, potassium, calcium, Magnesium or ammonium salts in which the ammonium ion in addition to hydrogen carries one to three C ₁ - to C ₄ alkyl groups. The sodium salt is most preferred. The amounts used in the compositions according to the invention are preferably from 0.05 to 10% by weight, based on the total application preparation, particularly preferably from 0.1 to 5% by weight, and particularly preferably from 0.1 to 3% by weight.

Ectoin or ectoine derivatives, allantoin, taurine and / or bisabolol are also suitable as care substances.

The compositions of the invention contain these care substances preferably in amounts of 0.001 to 2, in particular from 0.01 to 0.5 wt .-%, each based on the total application preparation.

Mono- or oligosaccharides can also be used as a care substance in the compositions according to the invention. Both monosaccharides and oligosaccharides, such as cane sugar, lactose and raffinose, can be used. The use of monosaccharides is preferred according to the invention. Among the monosaccharides, in turn, those compounds which contain 5 or 6 carbon atoms are preferred.

The mono- or oligosaccharides are preferably present in the compositions according to the invention in an amount of from 0.1 to 8% by weight, particularly preferably from 1 to 5% by weight, based on the total application preparation.

The agent may further contain at least one lipid as a care substance.

Lipids which are suitable according to the invention are phospholipids, for example soya lecithin, egg lecithin and cephalins, and also the substances known by the INCI names linoleneamidopropyl PG-dimonium chlorides phosphates, cocamidopropyl PG-dimonium chlorides phosphates and stearamidopropyl PG-dimonium chlorides phosphates. These are sold, for example, by the company Mona under the trade names Phospholipid ^EFA® , Phospholipid ^PTC® and Phospholipid ^SV® .

The agents according to the invention preferably contain the lipids in amounts of from 0.01 to 10% by weight, in particular from 0.1 to 5% by weight, based on the total application preparation.

Furthermore, oil bodies are suitable as a care substance.

The natural and synthetic cosmetic oil bodies include, for example: vegetable oils. Examples of such oils are sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheat germ oil, peach kernel oil and the liquid portions of coconut oil. Also suitable, however, are other triglyceride oils such as the liquid portions of beef tallow as well as synthetic triglyceride oils.

liquid paraffin oils, isoparaffin oils and synthetic hydrocarbons and di-n-alkyl ethers having a total of between 12 and 36 carbon atoms, in particular 12 to 24 carbon atoms, such as Example, di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n-undecyl ether, di-n-dodecyl ether, n-hexyl n-octyl ether, n-octyl-n-decyl ether, n-decyl n-undecyl ether, n-undecyl n-dodecyl ether and n-hexyl n-undecyl ether, and di-tert-butyl ether, di-isopentyl ether, di-3-ethyl decyl ether, tert-butyl n-octyl ether, isobutyl Pentyl n-octyl ether and 2-methyl pentyl n-octyl ether. The compounds are available as commercial products 1, 3-di- (2-ethyl-hexyl) -cyclohexane (Cetiol ^® S), and di-n-octyl ether (Cetiol ^® OE) may be preferred.

Esteröle. Ester oils are to be understood as meaning the esters of C ₆ - C ₃₀ fatty acids with C ₂ - C ₃₀ fatty alcohols. The monoesters of the fatty acids with alcohols having 2 to 24 carbon atoms are preferred. Examples of fatty acid components used in the esters are caproic, caprylic, 2-ethylhexanoic, capric, lauric, isotridecanoic, myristic, palmitic, palmitoleic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic Behenic acid and erucic acid and their technical mixtures which are obtained, for example, in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from Roelen's oxo synthesis or the dimerization of unsaturated fatty acids. Examples of the fatty alcohol components in the ester oils are isopropyl alcohol, caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, Gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from the Roelen oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols incurred. According to the invention, particularly preferred are isopropyl myristate (IPM Rilanit ^®), isononanoic acid C16-18 alkyl ester (Cetiol ^® SN), 2-ethylhexyl palmitate (Cegesoft ^® 24), stearic acid-2-ethylhexyl ester (Cetiol ^® 868), cetyl oleate, glycerol tricaprylate, Kokosfettalkohol- caprate / caprylate (Cetiol ^® LC), n-butyl stearate, oleyl erucate (Cetiol ^® J 600), isopropyl palmitate (IPP Rilanit ^®), oleyl Oleate (Cetiol ^®), hexyl laurate (Cetiol ^® A), di-n-butyl adipate (Cetiol ^® B), myristyl myristate (Cetiol ^® MM), cetearyl isononanoate (Cetiol ^® SN), oleic acid decyl ester (Cetiol ^® V).

Dicarboxylic acid esters such as di-n-butyl adipate, di- (2-ethylhexyl) adipate, di- (2-ethylhexyl) succinate and di-isotridecyl acelate, and diol esters such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di (2- ethylhexanoate), propylene glycol diisostearate,

Propylene glycol di-pelargonate, butanediol di-isostearate, neopentyl glycol dicaprylate,

symmetrical, asymmetrical or cyclic esters of carbonic acid with fatty alcohols, for example described in DE-OS 197 56 454, glycerol carbonate or dicaprylyl carbonate (Cetiol ^® CC),

Trifatty acid esters of saturated and / or unsaturated linear and / or branched fatty acids with glycerol, Fatty acid partial glycerides, which are understood to mean monoglycerides, diglycerides and their technical mixtures. With the use of technical products production reasons may still contain small amounts of triglycerides. The partial glycerides preferably follow the formula (D4-I),

CH ₂ O (CH ₂ CH ₂ O) _m R ¹

I

CHO (CH ₂ CH ₂ O) _n R ² (D4-I)

I

CH ₂ O (CH ₂ CH ₂ O) _q R ³

in which R ¹ , R ² and R ³ independently of one another represent hydrogen or a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18, carbon atoms, with the proviso that at least one of these groups represents a Acyl radical and at least one of these groups is hydrogen. The sum (m + n + q) is 0 or numbers from 1 to 100, preferably 0 or 5 to 25. Preferably, R ^{1 is} an acyl radical and R ² and R ^{3 are} hydrogen and the sum (m + n + q) is 0. Typical examples are mono- and / or diglycerides based on caproic, caprylic, 2-ethylhexanoic, capric, lauric, isotridecanoic, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic , Elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Preferably, oleic acid monoglycerides are used.

The amount used of the natural and synthetic cosmetic oil bodies in the compositions according to the invention is usually from 0.1 to 30% by weight, based on the total application preparation, preferably from 0.1 to 20% by weight, and in particular from 0.1 to 15% by weight. %.

Although each of the aforementioned care substances alone already gives a satisfactory result, in the context of the present invention, all embodiments are also included, in which the agent contains a plurality of care substances also from different groups.

By adding a UV filter, both the agents themselves and the treated fibers can be protected from the harmful effects of UV radiation. Preferably, therefore, at least one UV filter is added to the agent. The suitable UV filters are not subject to any general restrictions with regard to their structure and their physical properties. On the contrary, all UV filters which can be used in the cosmetics sector and whose absorption maximum lies in the UVA (315-400 nm), in the UVB (280-315 nm) or in the UVC (<280 nm) range are suitable. UV filters with an absorption maximum in the UVB range, in particular in the range from about 280 to about 300 nm, are particularly preferred. The UV filters preferred according to the invention can be selected, for example, from substituted benzophenones, p-aminobenzoic acid esters, Diphenylacrylsäureestern, cinnamic acid esters, Salicylsäureestern, Benzimidazolen and o-Am inobenzoesäu reestern.

The UV filters are usually contained in amounts of 0.01-5 wt .-%, based on the total application preparation. Amounts of 0.1-2.5 wt .-% are preferred.

In a particular embodiment, the composition according to the invention also contains one or more substantive dyes. This allows the treated keratin fiber not only to be temporarily patterned when the agent is applied, but also dyed at the same time. This may be particularly desirable if only a temporary dyeing is desired, for example, with eye-catching fashion colors, which can be removed again by simple washing from the keratinic fiber. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those having the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) -aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) - amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-

Ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-Amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Preference is given to using cationic substantive dyes. Particularly preferred are

(a) cationic triphenylmethane dyes such as Basic Blue 7,

Basic Blue 26, Basic Violet 2 and Basic Violet 14,

(b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as

(c) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as mentioned, for example, in EP-A2-998 908, which is incorporated herein by reference, in claims 6 to 11. The compounds listed under the INCI names Basic Yellow 87, Basic Orange 31 and Basic

Red 51 are known, are very particularly preferred cationic substantive dyes of

Group (c).

The cationic direct dyes, which are sold under the trademark Arianor ^®, according to the invention are also very particularly preferred cationic substantive

Dyes.

The agents according to the invention according to this embodiment contain the substantive

Dyes preferably in an amount of 0.001 to 20 wt .-%, based on the total agent.

It is preferred according to the invention that the agents according to the invention are free of oxidation dye precursors. Oxidation dye precursors are classified into so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components.

In addition to the components mentioned, the agents may furthermore contain all active ingredients, additives and auxiliaries known for such preparations. Other active ingredients, auxiliaries and additives are, for example

Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. Bentonite, fully synthetic hydrocolloids such as e.g. Polyvinyl alcohol, and optionally crosslinked polyacrylates,

Perfume oils, dimethylisosorbide and cyclodextrins,

Defoamers like silicones,

Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,

Substances for adjusting the pH, such as, for example, customary acids, in particular edible acids, and bases,

Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,

Fats and waxes such as spermaceti, beeswax, montan wax and paraffins,

Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,

Swelling and penetration agents such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates, opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers

Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,

Preservatives,

Antioxidants.

With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art. The formulation of the compositions according to the invention can be carried out in all forms customary for styling agents, for example in the form of solutions which can be applied to the hair as hair lotions or pump or aerosol spray, in the form of creams, emulsions, waxes, gels or surfactant-containing foaming solutions or other preparations suitable for use on the hair.

Hair creams and gels generally contain structurants and / or thickening polymers which serve to give the products the desired consistency. Structurants and / or thickening polymers are typically used in an amount of from 0.1 to 10% by weight, based on the total product. Amounts of 0.5 to 5 wt .-%, in particular 0.5 to 3 wt .-% are preferred.

The agents according to the invention are preferably used as pump spray, aerosol spray, pump foam or aerosol foam.

For this purpose, the agents according to the invention are packaged in a dispensing device, which is either an additionally filled with a propellant compressed gas container ("aerosol container") or a non-aerosol container.

The pressurized gas containers, with the aid of which a product is distributed by the internal gas pressure of the container via a valve, are defined as "aerosol containers". When

"Non-aerosol container" is defined in reverse to the aerosol definition a container under normal pressure, with the aid of which a product is distributed by means of mechanical action by a pumping system.

With particular preference the agents according to the invention are packaged as aerosol hair foam or aerosol hair spray. The agent according to the invention therefore preferably additionally contains at least one propellant. Propellants suitable according to the invention are selected, for example, from N ₂ O, dimethyl ether, CO ₂ , air, alkanes having 3 to 5 carbon atoms, such as propane, n-butane, isobutane, n-pentane and isopentane, and mixtures thereof. Preference is given to dimethyl ether, propane, n-butane, isobutane and mixtures thereof.

According to a preferred embodiment, said alkanes, mixtures of said alkanes or mixtures of said alkanes with dimethyl ether are used as sole blowing agent. However, the invention expressly also includes the concomitant use of propellants of the type of chlorofluorocarbons, but in particular of fluorocarbons.

With regard to the quantity ratio of blowing agent to the other constituents of the preparations, the sizes of the aerosol droplets or of the foam bubbles and the respective size distribution can be set for a given spraying device. The amount of blowing agent used varies in Depending on the specific composition of the agent, the packaging used and the desired product type, such as hair spray or hair foam. When conventional spray devices are used, aerosol foam products preferably contain the blowing agent in amounts of from 1 to 35% by weight, based on the total product. Amounts of 2 to 30 wt .-%, in particular from 3 to 15 wt .-% are particularly preferred. Aerosol sprays generally contain larger amounts of propellant. Preferably, the blowing agent is used in this case in an amount of 30 to 98 wt .-%, based on the total product. Amounts of 40 to 95 wt .-%, in particular from 50 to 95 wt .-% are particularly preferred.

The aerosol products can be prepared in the usual manner. As a rule, all constituents of the respective agent, with the exception of the propellant, are introduced into a suitable pressure-resistant container. This is then closed with a valve. By conventional techniques, finally, the desired amount of blowing agent is introduced.

For the foaming of gel-like agents in a two-chamber aerosol container isopentane is preferably suitable as a propellant, which is incorporated into the compositions according to the invention and is packaged in the first chamber of the two-chamber aerosol container. In the second chamber of the two-chamber aerosol container, at least one further propellant other than isopentane is made up, which builds up a higher pressure in the two-chamber aerosol container than the isopentane. The blowing agents of the second chamber are preferably selected from N ₂ O, dimethyl ether, CO ₂ , air, alkanes having 3 or 4 carbon atoms (such as propane, n-butane, isobutane) and mixtures thereof.

The compositions according to the invention and products which contain these agents, in particular aerosol hair foams or aerosol hair sprays, gels, are distinguished, in particular, by giving treated hair a very strong, lasting hairstyle hold, although the hair remains flexible.

The formulation of the compositions according to the invention can be carried out in all forms customary for styling agents, for example in the form of solutions which can be applied to the hair as hair lotions or pump or aerosol spray, in the form of creams, emulsions, waxes, gels or surfactant-containing foaming solutions or other preparations suitable for use on the hair.

Hair creams and gels generally contain structurants and / or thickening polymers which serve to give the products the desired consistency. Structurants and / or thickening polymers are typically used in an amount of from 0.1 to 10% by weight, based on the total product. Amounts of 0.5 to 5 wt .-%, in particular 0.5 to 3 wt .-% are preferred. The agents according to the invention are preferably used as pump spray, aerosol spray, pump foam or aerosol foam.

The pressurized gas containers, with the aid of which a product is distributed by the internal gas pressure of the container via a valve, are defined as "aerosol containers". As a "nonaerosol container", a container under normal pressure is defined in reverse to the aerosol definition, with the aid of which a product is distributed by means of mechanical action by a pumping system.

With regard to the quantity ratio of blowing agent to the other constituents of the preparations, the sizes of the aerosol droplets or of the foam bubbles and the respective size distribution can be set for a given spraying device.

The amount of blowing agent used varies depending on the specific composition of the composition, the packaging used and the desired product type, such as hair spray or hair foam. When conventional spray devices are used, aerosol foam products preferably contain the blowing agent in amounts of from 1 to 35% by weight, based on the total product. Amounts of 2 to 30 wt .-%, in particular from 3 to 15 wt .-% are particularly preferred. Aerosol sprays generally contain larger amounts of propellant. Preferably, the blowing agent is used in this case in an amount of 30 to 98 wt .-%, based on the total product. Amounts of 40 to 95 wt .-%, in particular from 50 to 95 wt .-% are particularly preferred. The aerosol products can be prepared in the usual manner. As a rule, all constituents of the respective agent, with the exception of the propellant, are introduced into a suitable pressure-resistant container. This is then closed with a valve. By conventional techniques, finally, the desired amount of blowing agent is introduced.

A second object of the invention is the use of the compositions according to the invention for the temporary deformation of hair and / or hair care.

A third object of the invention is the use of polyether-modified

Solid particles according to the first subject of the invention against oily skin and / or greasy

Hair (prefers greasy hair).

The Hautfettschmutzabweisung on the skin and / or on the hair (preferably on the hair) is increased by said polyether.

It is preferred to use cosmetic agents, in addition to at least one of said

Polyether contains at least one surfactant.

It is also preferred according to the invention to use, instead of the polyether of the formula (I), at least one compound which has been prepared by the preparation process described in the first subject of the invention. In this case, a mixture of reaction products from the above manufacturing process can be used.

The polyethers characterized as being preferred according to the first subject of the invention are also preferred here. The same applies to the surfactants mentioned in the first subject of the invention. Here, the presence of at least one anionic surfactant is preferred. A fourth object of the invention is the use of the agent according to the first subject of the invention for improving the hairstyle hold.

The agents according to the invention characterized as being preferred according to the invention are also preferred here.

The following examples are intended to illustrate the subject matter of the present invention without limiting it in any way.

B e i s p e e l e

The molecular weights given in the examples are number-average molecular weights of the alcohols or amines of the general formulas (I) or (III) which were used to prepare the prepolymers. The number-average molecular weight of the alcohols can be determined by end group determination on the basis of the knowledge of the functionality of the compounds or the functionality of the mixture components and the OH number of the compound or mixture (determined according to DIN 53240). In the case of amines or amine mixtures, the end group determination can be carried out by potentiometric titration according to DIN 16945.

Preparation Examples of Suitable Silyl-Terminated Linear Polyethers:

Example 1: Polyether Functionalization of Hydroxy Group-Containing Silica Particles (Particle-1) 450 g of DOWEX HCR-W2 (ion exchanger (Dow, Merck)) was placed in a beaker. While stirring, 110 ml of the aqueous Bindzil dispersion (silica, specific surface area: 220 m ² / g, Akzo-Nobel, d = 1.2 g / cm ³ ) were added within 15 min. It was stirred for 15 min and then the ion exchanger is filtered off.

87.56 g of isopropanol and 87.56 g of the pretreated Bindzil dispersion were placed in a 500 ml round bottom flask and heated to 60 ⁰ C with stirring. 17.51 g were within 2 h 3-glycidoxypropyltrimethoxysilane (GLYMO) (GE Silicones, Silquest A-187) was added and the reaction solution is then stirred for 2 h at 60 ⁰ C.

A clear, low-viscosity dispersion of epoxy-functionalized silica cores was obtained.

The obtained as described above low-viscous dispersion of epoxy-functionalized, silica cores were added to 148,0g of the Polyoxyalkylenmonoamis Jeffamine® M-2070 (Messrs. Huntsman) and then stirred for 20 hours at 2O ⁰ C. After removal of the solvent gave a yellowish, highly viscous substance which can be easily redispersed in both water and isopropanol.

TEM (Transmission Electron Microscopy) images of the polyether-functionalized solid particles show that essentially spherical particles having an average particle diameter of 10 to 80 nm were obtained.

Measurement of static water contact angle and contact angle preventer

The measurements were carried out with a contact angle measuring device from Data Physics GmbH (device type: OCA20; electronic tilting device TBU90E; Syringe module ES; Software: SCA incl. Software update for SCA modules (Version 3.11.6 Build 155)).

The instrument is calibrated before measurement using the instrument's automatic calibration feature. By means of the syringe module, a drop of distilled water (15 μl) is applied to the surface of the slide to be measured. The tilt angle is 0 °, i. the surface to be measured is horizontal. There is a recording of the drops with a video camera. On the frame, the software applies a tangent to the drop cross section at the point where the drop touches the surface. The resulting angle between the tangent and the surface to be measured is called the static contact angle (sessile drop method).

Subsequently, the sample, including the sample table and the camera, is tilted at an angle of 90 ° at the slowest speed permitted by the device (calculated from the device data: 0.62 7 s). During this process, a video of the drop is taken by the camera by means of the software, wherein the tilt angle is recorded at the time of recording. As soon as the drop starts to run off the surface, the measurement is stopped. In the video, the software can then be used to determine the angle of advancement (angle in drop flow direction) and the angle of retraction (on the other side of the drop) by means of the ellipse method of the measuring software at the time the droplet starts to drip from the surface. The difference between the two angles is the contact angle hysteresis (tilting plate method).

Provision of hair care products

The following hair treatment products were prepared by mixing the ingredients:

Table 1: hair gel

Table 2: hair gel

Table 5: Hair show m

washing tests

The prepared according to Example 1, polyether-modified solid particles were mixed in an amount of 2 wt .-% in a commercial shampoo ("Schauma Shampoo 7 herbs", Schwarzkopf).

For comparison, a reference measurement was carried out only with "Schauma Shampoo 7 herbs." To determine the detergency hair strands were contaminated with skin fat and then determined the respective Y values (Y _before ) - Then the hair strands were washed, dried and dried strands again the Y-values (Y _after ) determined. The Y values were determined in all cases with a Minolta CR 200. The resulting wash results (ΔY values) given in Table 1 were obtained.

Table 1: Wash results

Δ ϊ 'after' before

The results shown in Table 1 demonstrate that the washing performance of a conventional detergent is significantly improved by the addition of the nanoparticles according to the invention in relation to the tested test soils.

Claims

Patent claims

1. Cosmetic agent containing in a cosmetically acceptable carrier

and

(B) at least one film-forming and / or setting polymer.

2. Cosmetic composition according to claim 1, comprising in a cosmetically acceptable carrier

(A) Polyether-modified solid particles which are obtained by reacting hydroxy group-containing solid particles with at least one polyether of formula (I)

T-K-A-K'-T (I)

wherein

A is a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and

anionic radical,

x stands for 1, 2 or 3

wherein at most one radical from T or T ', in addition, a (C ₁ to C ₆₎ - alkyl group, an aryl group, an aryl group (d to _C6), a (C ₁ -C ₆₎ - alkoxy group or a ( C ₂ to C ₆ ) acyl group, and

(B) at least one film-forming and / or setting polymer.

3. Cosmetic composition according to claim 1, comprising in a cosmetically acceptable carrier

(a) Polyether-modified solid particles prepared by a method comprising the steps of:

i) reaction of hydroxyl-containing solid particles with at least one epoxy silane and ii) reaction of the epoxy-functionalized solid particles obtained in step i) with at least one polyoxyalkylene monoamine which has only one functional group reactive to the epoxy groups of the epoxy-functionalized solid particles. and

(B) at least one film-forming and / or setting polymer.

4. Composition according to one of claims 1 to 3, characterized in that said polyether-modified solid particles are contained in an amount of 0.01 to 10.0 wt .-% based on the weight of the total composition.

5. Composition according to one of claims 1 4, characterized in that the polyethers have a molecular weight of 1 to 200 kDa.

6. Composition according to one of claims 1 to 5, characterized in that A is therefore preferably a structural fragment of the formula (A1) according to formula (I) or formula (II)

* - (OCH ₂ CH ₂ ) _n - (OCH ₂ CH (CH ₃ )) _m - * (A1)

wherein

n is an integer from 1 to 500,

m is an integer from 0 to 500 and

the structural fragment of the formula (A1) has a maximum proportion of 50% by weight of propylene oxide units, based on the weight of the structural fragment (A1).

7. Composition according to one of claims 1 to 6, characterized in that the radicals K and K 'independently of one another are a covalent bond, an oxy group, an imino group or at least one of the following Konnektivitäten (K1) to (K10)

* - O - C - R - * * - M - C - R - * * - C - O - R - *

Il R ¹ Il Il

⁰ (K1) ° (K2) ° (K3)

^{* ~} Π ^~ _R ^{ΓR ~ *} * -L * * -o-si- *

O D '"R'"

u (K4) ^κ (K5) ^κ (K6)

* - R-N-C-N-R "- * * - R-O-C-N-R" - *

R 'Il H Il H

⁰ (K7) ° (K8)

* - R-N-C-O-R "- * * - R-O-C-O-R" - *

R 'Il Il

⁰ (K9) ° (K10) where

R and R "independently of one another are methylene, ethane-1, 2-diyl, propane-1,2-diyl,

Propan-1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl or phenylene, R 'is a hydrogen atom or a (Ci to C ₄ ) alkyl group, R '"independently of one another is a (C ₁ to C ₄ ) -alkyl group or an aryl group.

8. Composition according to one of claims 1 to 7, characterized in that it contains polyether-modified solid particles, which are obtained by reacting hydroxyl-containing solid particles with at least one compound of formula (1-1) contains

R ¹ -AK-Si (OR ² ) _χ R ³ 3_ _χ .._

(1-1)

wherein

A is a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and

Propylene oxide units means, with a maximum proportion of 50 wt .-% of

Propylene oxide units, based on the weight of A,

* - O-C- R- * * - M- C- R- * * - C- O- R- *

Il R 'Il Il

⁰ (K1) ° (K2) ° (K3)

R ¹ "R"

* - C- N- R- * * _5J_ * _* - o- Si- _*

I l R 'I I

υ (K4) ^κ (K5) ^κ (K6)

* - R - N - C - N - R "- * * - R - O - C - N - R" - *

R 'il H H H

⁰ (K7) ° (K8)

* - R - N - C - O - R "- * * - R - O - C - O - R" - *

R 'Il Il

⁰ (K9) ° (K10)

wherein

R 'represents a hydrogen atom or a (C ₁ to C ₄ ) -alkyl group,

R ^{1 is} a (C ₁ to C ₆ ) -alkyl group, a hydrogen atom or a group R ³ ₃ _x (R ² O) _x Si-K-,

R ^{2 is} a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl),

9. Composition according to one of claims 1 to 6, characterized in that at least one molecule fragment T or T 'of the general formula

* -B - [(N (CH ₂ COOM) -B ') _y -N (CH ₂ COOM) ₂ ] follows, where

B is a (C ₁ to C ₆ ) -alkylene radical (preferably ethane-1, 2-diyl, propane-1, 2-diyl,

Propan-1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl),

Propan-1, 3-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl) or a N ₁ N-BiS (C ₁ to

C ₆ ) -alkylene-N-carboxymethyl,

y is 1 or 2 (preferably 1).

10. Composition according to one of claims 1 to 9, characterized in that the hydroxyl-containing, mineral oxide solid particles are selected from aluminates, silicates, aluminum silicates, zinc oxide, titanium dioxide, SiO ₂ and mixtures thereof.

11. Composition according to one of claims 1 to 10, characterized in that the film-forming and / or setting polymers are contained in an amount of 0.1 wt .-% to 20.0 wt .-% based on the weight of the composition.

12. Composition according to one of claims 1 to 11, characterized in that the polyether-modified solid particles have a particle size of 0.01 .mu.m to 100 .mu.m.

13. Composition according to one of claims 1 to 12, characterized in that is contained as a film-forming and / or setting polymer

at least one cationic film-forming and / or cationic setting polymer and / or

at least one nonionic film-forming and / or nonionic setting polymer and / or

at least one anionic film-forming and / or anionic setting polymer and / or

at least one amphoteric film-forming and / or amphoteric setting polymer.

14. Use of a composition according to any one of claims 1 to 13 for the temporary deformation of hair.

15. Use of solid particles which are surface-modified with polyethers, wherein the polyethers comprise a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum proportion of 50 wt .-% of propylene oxide units, based on the Weight of the polyoxyalkylene chain, against oily skin and / or against greasy hair.