DE10304923A1 - Use of linear or branched polyamino- and-or polyammonium-polysiloxane copolymers in the production and-or treatment of dyed hair, e.g. in shampoos, rinses, styling gels, hair sprays and conditioners - Google Patents

Abstract

New linear or branched polyamino- and/or polyammonium-polysiloxane copolymers are used in the production and/or treatment of dyed hair. The use of (b1) linear or branched polyamino- and/or polyammonium-polysiloxane copolymers with repeat units of formula -[Q-V]- (I) (in which the positive charges associated with ammonium groups are neutralized with organic or inorganic acid anions) or their acid addition salts and optionally (b2) amino- and/or ammonium-polysiloxane compounds in the production and/or treatment of dyed hair. Q : -NR-, -N +>R 2-, a saturated or unsaturated diamino-functional heterocycle of formula (Q1), (Q2) or (Q3), an aromatic diamino-functional heterocycle of formula (Q4), a trivalent group of formula -N= or -N(R) +>= or a tetravalent group of formula =N +>=, in which Q is not directly attached to a carbonyl carbon; R : H or a monovalent organic group; V : V 1>, V 2>or V 3>; V 2>a divalent, linear, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon residue with up to 1000 C atoms (not including those in the polysiloxane group Z 2>defined below), optionally containing -O-, -CONR 2>-, -CO- and/or -CS- group(s), optionally substituted with hydroxyl group(s) and containing at least one group -Z 2>- of formula -Si(R 1>) 2O-[Si(R 1>) 2O] n1-Si(R 1>) 2-; R 2>H or a monovalent hydrocarbon group (various types as above) with up to 100 C atoms (optionally containing -O-, -NH-, -CO- and/or -CS- group(s), and optionally substituted with OH, optionally substituted heterocyclic groups (preferably with one or more N atoms), amino, (di)alkylamino, ammonium, polyether or polyether-ester residues); R 1>1-22C alkyl, 1-10C fluoroalkyl or 6-10C aryl; n1 : 20-1000; V 1>as for V 2>, optionally substituted with OH and optionally containing a group Z 1>of formula -Si(R 1>) 2O-[Si(R 1>) 2O] n2-Si(R 1>) 2-; n2 : 0-19; V 3>as for V 2>, but optionally containing -O-, -CONH-, -CONR 2>-, -CO-, -CS-, -Z 1>-, -Z 2>- and/or -Z 3>- group(s) and optionally substituted with OH; and Z 3>an organopolysiloxane unit with a valency of 3 or more; with the proviso that the polysiloxane compound contains at least one group V 1>, V 2>or V 3>and at least one group Z 1>, Z 2>or Z 3>, the tri- or tetra-valent groups Q either act as the branching point of the Q-V main chain with the other valencies carrying other branches based on -[Q-V]- units, or these groups are saturated with V 3>groups in a linear main chain with no branches. [Image] Independent claims are also included for the following: (1) a method (M1) for the production of a composition for the production and/or treatment of dyed hair by mixing (b1) and optionally (b2) with nitrogen-free polysiloxane compounds, silicone-free surfactants, coacervate phase formers and carrier substances; and (2) compositions as defined in M1, especially shampoos, hair rinse formulations, hair-care cures, formulations for dyeing or for the care and conditioning of dyed hair, and developers for permanent hair dyeing.

Description

The invention relates to the use of at least one polyamino and / or Polyammonium-polysiloxane copolymer (silicone quat) in various preferably cosmetic formulations, in particular for treatment of substrates containing keratin, such as human and animal Hair, its cleaning and care with so-called rinse-off products, like shampoos and hair conditioners as well as with so-called leave-in products such as lotions, gels, pump sprays and aerosol sprays and with hair dyes, in which the silicone quat is incorporated. It is special here formulations that wash out dyes from or from toned or colored Lessen hair. Another object of the invention is Use of a cosmetic formulation which contains at least one the quaternary Siloxane contains "silicone quats" for simultaneous Improve the conditioning of hair, to reduce the wet and dry combing forces of the Hair, to increase volume and improve the shine of hair. Next to it other colored ones too Keratin and non-keratin fibers with these formulations treated to wash out dyes during washing and reduce cleaning while maintaining a comfortable grip to create.

It is known that polysiloxane-based, polyquaternary compounds can be used advantageously in hair care formulations ( US 4,587,321 . US 4,833,225 . EP 282,720 . US 6,240,929 ). The use of such compounds leads to a silicone-typical soft, smooth and flat handle, the improvement of the dry and wet combing forces, the increase in hair shine and the reduction of electrostatic charge on the treated hair. In general, the substrate is made hydrophobic.

An improved hydrophilicity of the equipped Substrate can e.g. can be achieved if alkylene oxide structures into the molecules introduced become.

There are branched ( US 5,602,224 ) and comb-like structures have also been synthesized ( US 5,098,979 . US 5,153,294 . US 5,166,297 ), which lead to properties similar to those mentioned above. However, the work mentioned above does not contain any indication of how one can reduce the washing out of colors from or from tinted or dyed hair using quaternary silicone compounds.

The use of an acid amide-modified silicone in a cosmetic formulation and its preparation is described US 6,007,801 , The combing forces of hair and their static charge are reduced. A reduction in the washing out of color from dyed hair is not described here.

J. Soc. Cosmet. Chem., 46, 231-245 (September 1995) discloses the use of amino-functional silicones for Reduction of washing out of color from colored hair with simultaneous Improvement of wet and dry combing forces.

US 5,843,193 . US 6,143,286 describe the use of volatile and non-volatile non-ionic silicone oils, silicone resins and semi-solid and solid silicones in the developer solution of hair dyes and hair conditioning agents. Preferred embodiments here are amino-functional silicones and silicone resins (INCI: trimethylsiloxysilicate). Here, their color-preserving properties are described. (INCI: Trimethylsilylamodimethicone and Amodimethicone The abbreviations are explained in the INCI (The Cosmetic, Toiletry and Fragrance Association Washington DC or at http://www.cosmetic-world.com /inci/Incialf.htm).

GB 2138845 describes the use of laterally amino-functionalized silicones and their derivatives in hair dyes. An intensification of the color result of the hair coloring is described. However, no statement is made about the color-preserving effect of such a formulation.

The amino or Ammonmium-functional siloxanes have coherent siloxane bonds in the main chain based on the definition below for the connections b2) are reproduced that are not represented by other units in the Main chain are interrupted. This makes it possible to adapt the solubility Hydrophilicity and the interaction with the substrate as well as with it achievable changed Limited substrate properties.

US 6,432,145 describes a hair dye that contains, among other things, a cyclic silicone and a silicone elastomer. The use of this silicone elastomer leads to a reduction in the washing out of the hair color from the hair colored with the formulation.

It has surprisingly been found that polyamino and / or polyammonium polysiloxane, preferably those according to WO 02/10256, WO 02/10257, WO 02/10259 and DE-OS 100 36 533 . DE-OS 100 36 522 . DE-OS 100 36 532 . EP 282 720 . US 6,240,929 . DE-OS 33 40 708 and the unpublished DE 102 12 470.1 . DE 102 51 525.5 and DE 102 51 526.3 advantageous for formulations for care, conditioning and treatment, cleaning and care of colored or to be colored substrates, preferably keratin-containing substrates such as B. human and animal hair.

The di- and polyquaternized siloxane systems including amino acid segments are also suitable DE 100 36 522 and DE 100 36 532 are known.

Surprisingly, it was found that when using these compounds, in addition to a excellent softness, an increase in volume, combability and shine. In addition, it was also surprisingly found that washing out the color from and from colored or tinted keratin-containing substrates, in particular fibers such. B. wool and human and animal hair, can significantly reduce.

The present invention relates to polyamino and / or polyammonium polysiloxane compounds of claim 1, that is to say compounds according to WO 02/10256, WO 02/10257, WO 02/10259 and DE-OS 100 36 533 . DE-OS 100 36 522 . DE-OS 100 36 532 . EP 282 720 . US 6,240,929 . DE-OS 33 40 708 and the unpublished DE 102 12 470.1 . DE 102 51 525.5 and 102 51 526.3 , to be incorporated into solutions, mixtures, emulsions and microemulsions such as fluids, pastes, creams with a high active content or to be converted into these. These solutions, mixtures, emulsions and microemulsions in turn facilitate the production of cosmetic formulations according to the invention and also increase their storage stability.

The invention also relates to Production and use of formulations to reduce the Wash out the color from and out of colored or to be colored Substrates, reducing the washout of paint from and off colored Substrates with simultaneous increase in volume, combability and the shine, as well as the provision of suitable, easy to handle and storage-stable feedstocks for the production of cosmetic Formulations such as solutions, Mixtures, emulsions and microemulsions. The substrates are there preferably colored substrates containing keratin such as e.g. B. human and animal hair.

Another subject of the present The invention was to use these compounds directly in formulations for hair tinting or coloring consisting of 2 components - color solution and Developer solution - oxidative Incorporate hair colors that can be used during the dyeing process in addition to excellent softness, volume, combability and increase the shine as well as washing the color from and out of colored or to be colored substrates containing keratin such as e.g. B. human and animal Decrease hair significantly without compromising the stability of the formulation i.e. storage stability and negatively affect the color result.

einem aromatischen diaminofunktionellen Heterocyclus der Formel:

einem dreiwertigen Rest der Formel:

einem dreiwertigen Rest der Formel:

einem vierwertigen Rest der Formel,

worin R jeweils Wasserstoff oder einen einwertigen organischen Rest darstellt,
wobei Q nicht direkt an ein Carbonylkohlenstoffatom bindet,
worin R wie oben definiert ist, und V wird aus V¹ und V² ausgewählt.The compositions according to the invention for the treatment of substrates contain at least one linear or branched polyamino and / or polyammonium polysiloxane copolymer b1) of the formula (I) and optionally at least one amino and / or ammonium polysiloxane compound b2) with the repeating units: - [QV] - (I) where Q is selected from the group consisting of:
-NO-,
-N ⁺ R ₂ -
a saturated or unsaturated diaminofunctional heterocycle of the formulas:

an aromatic diamino-functional heterocycle of the formula:

a trivalent radical of the formula:

a trivalent radical of the formula:

a tetravalent radical of the formula,

where R in each case represents hydrogen or a monovalent organic radical,
where Q does not bind directly to a carbonyl carbon atom,
where R is as defined above and V is selected from V ¹ and V ² .

In the used according to the invention Component b) is at least one polyamino and / or Polyammonium polysiloxane compound b1) and optionally at least one amino and / or ammonium polysiloxane compound b2). The polyamino and / or Polyammonium polysiloxane compound b1) is a copolymer compound, which in the polymer main chain amino and / or ammonium repeat units and polysiloxane repeat units having. The amino units contain secondary and / or tertiary nitrogen atoms (2 or 3 organic residues on the neutral nitrogen atom). The ammonium units contain secondary, tertiary and / or quaternary positively charged nitrogen atoms (2, 3, or 4 organic residues on nitrogen). As amino and / or ammonium repeat units can also over two Nitrogen atoms in the polymer chain heterocyclic Leftovers serve.

The difference is that for component b2) polysiloxane compounds in the side groups the polyorganosiloxane main chain amino and / or ammonium groups contain. That is, the amino and / or ammonium groups are not are located in the main chain of polyorganosiloxane repeat units.

Amino- und/oder Ammonium-Polysiloxan-Verbindung b2):

The difference can be illustrated as follows:
Polyamino and / or polyammonium polysiloxane compound b1):

Amino and / or ammonium polysiloxane compound b2):

The components b1) and b2) serve in the formulation according to the invention mainly as substance-giving substance Component.

The components b1) and b2) can in the formulation of the invention alone or together. In a preferred embodiment however, component b1) lies alone, without component b2) in the formulation according to the invention in front. In a likewise preferred embodiment, both components are located b1) and component b2) side by side.

The components b1) or b2) can in any circumstances exist together to each other.

The polyamino and / or polyammonium polysiloxane compound b1) is preferably a polysiloxane compound which contains at least one unit of the formula (I): - [QV] - (I)

einer quaternierten Pyrazoleinheit der Struktur

einer zweifach quaternierten Piperazineinheit der Struktur

einer monoquaternierten Piperazineinheit der Struktur

einer monoquaternierten Piperazineinheit der Struktur

einer zweifach quaternierten Einheit der Struktur

einer monoquaternierten Einheit der Struktur

einer monoquaternierten Einheit der Struktur

einer zweifach quaternierte Einheit der Struktur

einer monoquaternierten Einheit der Struktur

und einer monoquaternierten Einheit der Struktur

worin
t von 2 bis 10 ist,
R wie oben definiert, bevorzugt R² ist, R² wie oben definiert ist, und die Bedeutung von R² von der Bedeutung der obigen Gruppe R² gleich oder verschieden sein kann,
R³ und R⁴ die Bedeutung von R² aufweisen, wobei R² , R³ und R⁴ gleich oder verschieden sein können, oder
R² und R³ gemeinsam mit dem positiv geladenen Stickstoffatom einen fünf- bis siebengliedrigen Heterocyclus bilden, der gegebenenfalls zusätzlich ein oder mehrere Stickstoff-, Sauerstoff- und/oder Schwefelatome aufweisen kann,
R⁵, R⁶, R⁷ gleich oder verschieden sein können und aus der Gruppe ausgewählt werden, die besteht aus: H, Halogen, Hydroxylgruppe, Nitrogruppe, Cyanogruppe, Thiolgruppe, Carboxylgruppe, Alkylgruppe, Monohydroxyalkylgruppe, Polyhydroxyalkylgruppe, Thioalkylgruppe, Cyanoalkylgruppe, Alkoxygruppe, Acylgruppe, Acetyloxygruppe, Cycloalkylgruppe, Arylgruppe, Alkylarylgruppe, und Gruppen des Typs -NHR^W, in denen R^W H, Alkylgruppe, Monohydroxyalkylgruppe, Polyhydroxyalkylgruppe, Acetylgruppe, Ureidogruppe bedeuten, und jeweils zwei der benachbarten Reste R⁵, R⁶ und R⁷ mit denen sie an den Heterocyclus bindenden Kohlenstoffatomen aromatische Fünf- bis Siebenringe bilden können, und
R⁸ die Bedeutung von R² aufweist, wobei R⁸ und R² gleich oder verschieden sein können.In a preferred embodiment of the invention, Q in the linear or branched polyamino and / or polyammonium polysiloxane copolymer b1) is a divalent radical and is selected in the formulas (I) or (I ') from the group consisting of: - [QV] - (I ') -NO-,
-N ⁺ R ₂ -
a quaternized imidazole unit of the structure

a quaternized pyrazole unit of the structure

a double quaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a doubly quaternized unit of structure

a monoquaternized unit of the structure

a monoquaternized unit of the structure

a double quaternized unit of structure

a monoquaternized unit of the structure

and a monoquaternized unit of the structure

wherein
t is from 2 to 10,
R is as defined above, preferably R ² , R ^{2 is} as defined above, and the meaning of R ² can be the same or different from the meaning of the above group R ² ,
R ³ and R ^{4 have} the meaning of R ² , where R ² , R ³ and R ^{4 may be the} same or different, or
R ² and R ³ together with the positively charged nitrogen atom form a five- to seven-membered heterocycle which can optionally additionally have one or more nitrogen, oxygen and / or sulfur atoms,
R ⁵ , R ⁶ , R ^{7 can be the} same or different and are selected from the group consisting of: H, halogen, hydroxyl group, nitro group, cyano group, thiol group, carboxyl group, alkyl group, monohydroxyalkyl group, polyhydroxyalkyl group, thioalkyl group, cyanoalkyl group, alkoxy group, Acyl group, acetyloxy group, cycloalkyl group, aryl group, alkylaryl group, and groups of the type -NHR ^W , in which R ^{W is} H, alkyl group, monohydroxyalkyl group, polyhydroxyalkyl group, acetyl group, ureido group, and two of the adjacent radicals R ⁵ , R ⁶ and R ⁷ each which they can form aromatic five to seven rings on the carbon atoms binding to the heterocycle, and
R ^{8 has} the meaning of R ² , where R ⁸ and R ^{2 may be the} same or different.

oder eine vierwertigen Rest

darstellt, dienen diese Reste bei den linearen Copolymeren der Formel (I') wie oben erwähnt nicht der Verzweigung der Polysiloxan-Copolymere sondern diese Reste sind ausschließlich mit insbesondere dreiwertigen Resten V³ verbunden, wobei cyclische Strukturen ausgebildet werden, die Bestandteil der linearen Hauptkette sind, wie z.B. ein Strukturelement der Formel:

In case Q in b1) is a trivalent remainder of the formulas

or a tetravalent rest

represents, these residues in the linear copolymers of the formula (I '), as mentioned above, do not serve for the branching of the polysiloxane copolymers but these residues are exclusively connected to trivalent residues V ³ in particular, cyclic structures being formed which are part of the linear main chain , such as a structural element of the formula:

einer quaternierten Imidazoleinheit der Struktur

einer quaternierten Pyrazoleinheit der Struktur

einer zweifach quaternierten Piperazineinheit der Struktur

einer monoquaternierten Piperazineinheit der Struktur

einer monoquaternierten Piperazineinheit der Struktur

einer monoquaternierten Einheit der Struktur

In a further preferred embodiment of the composition comprising at least one linear or branched polyamino and / or polyammonium polysiloxane copolymer formula (I) or (I '), group Q is selected as component b1) from:

a quaternized imidazole unit of the structure

a quaternized pyrazole unit of the structure

a double quaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a monoquaternized unit of the structure

einer quaternierten Imidazoleinheit der Struktur

einer quaternierten Pyrazoleinheit der Struktur

worin R², R³, R⁴, R⁵, R⁶, R⁷ und R⁸ wie oben definiert sind

Another preferred embodiment of b1) is characterized in that the unit Q is selected from the group

a quaternized imidazole unit of the structure

a quaternized pyrazole unit of the structure

wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are} as defined above

worin t, R⁵ bis R⁷ wie oben definiert sind

worin R², R³, R⁴, R⁵, R⁶, R⁷ und R⁸ wie oben definiert sind.In further preferred embodiments, R ² furthermore preferably stands for:

wherein t, R ⁵ to R ^{7 are} as defined above

wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are} as defined above.

wherein t, R ² , R ³ and R ^{8 are} as defined above

enthält, worin
R¹ gleich oder verschieden sein kann und aus der Gruppe ausgewählt wird, die besteht aus: C₁ bis C₂₂ Alkyl, Fluor(C₁-C₁₀)alkyl und C₆-C₁₀ Aryl, und
n₁ = 20 bis 1000 bedeutet, besonders bevorzugt 20 bis 300, speziell 20 bis 200.In the compositions, at least one compound containing at least one polyamino and / or polyammonium polysiloxane copolymer b1) of the formulas (I) or (I ') consists of V at least one constituent selected from the group consisting of V ¹ , V ² and V ³ consists in
V ^{2 is} selected from divalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals having up to 1000 carbon atoms (the carbon atoms of the polysiloxane radical Z ² defined below are not counted), which optionally one or more groups selected from
-O-, -CONH-,
-CONR ² -, wherein R ^{2 is} hydrogen, a monovalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 100 carbon atoms, which has one or more groups selected from -O-, -NH-, -C ( O) - and -C (S) -, and optionally by one or more substituents selected from the group consisting of a hydroxyl group, an optionally substituted, preferably containing one or more nitrogen atoms, heterocyclic group, amino, alkylamino, Dialkylamino, ammonium, polyether residues and polyether ester residues can be substituted, where, if there are several -CONR ² groups, these can be the same or different, can contain -C (O) - and -C (S) -,
the radical V ^{2 may} optionally be substituted by one or more hydroxyl groups, and the radical V ² at least one group -Z ² - of the formula

contains what
R ^{1 can be the} same or different and is selected from the group consisting of: C ₁ to C ₂₂ alkyl, fluoro (C ₁ -C ₁₀ ) alkyl and C ₆ -C ₁₀ aryl, and
n ₁ = 20 to 1000, particularly preferably 20 to 300, especially 20 to 200.

In a further preferred embodiment, n _{1 is} between 20 and 50 50 to 80 or between 80 and 200. The number n ₁ is the average degree of polymerization from M _{n of} the diorganosiloxy units in group Z ² .

In the compositions of the at least one linear or branched polyamino and / or polyammonium polysiloxane copolymer, the repeat units [-QV-] containing compounds b1), in which the units V, consist of the units V ¹ , V2 and / or V3, are in In another preferred embodiment of the polysiloxane compounds of the formula (I) or (I ') as component b1) the units V ² selected from a group of the formula -V ^{2 *} -Z ² -V ^{2 *} -, wherein Z ^{2 is} as defined above and V ² * represents a divalent straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 40 carbon atoms, which optionally has one or more groups selected from -O-, -CONH-, - CONR ² -,
wherein R ^{2 is} as defined above, and may contain -C (O) - and -C (S) -, and the radical V ^{2 * may} optionally be substituted by one or more hydroxyl groups.

In the embodiment mentioned above, the branched or linear polysiloxane copolymer b1) according to the invention can have the following repeating units:
- [V ^{2 *} -Z ² -V ^{2 *} -Q] - preferably together with - [V ¹ -Q] -.

V ^{2 *} = a divalent straight-chain, cyclic or branched, saturated, unsaturated C ₃ to C ₁₆ hydrocarbon radical or aromatic C ₈ to C ₂₀ hydrocarbon radical, which optionally has one or more groups selected from -O-, -CONH-, -CONR ² -, -C (O) -, -C (S) - may contain and may be substituted by one or more OH groups, wherein R ^{2 is} as defined above.

R² steht bevorzugt für: H,

mit
R⁴ = geradkettiger, cyclischer oder verzweigter C₁ bis C₁₈ Kohlenwasserstoffrest, der durch eine oder mehrere Gruppen, ausgewählt aus -O-, -NH-, -C(O)-, und -C(S)- enthalten kann und durch eine oder mehrere OH-Gruppen substituiert sein kann, bevorzugt unsubstituierte C₅ bis C₁₇ Kohlenwasserstoffreste, die sich von den entsprechenden Fettsäuren ableiten oder aber hydroxylierte C₃ bis C₁₇ Reste, die auf hydroxylierte Carbonsäuren, speziell Saccharidcarbonsäuren zurückgeführt werden können und ganz speziell

bedeuten.Is particularly preferred
V ^{2 *} for a divalent straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical with up to 16 carbon atoms, which has one or more groups selected from -O-, -CONH-, -CONR ² -,
wherein R ^{2 is} as defined above, can contain -C (O) -, -C (S) - and can be substituted with one or more hydroxyl groups. V ^{2 * is} more preferably selected from groups of the formulas:

R ² preferably represents: H,

With
R ⁴ = straight-chain, cyclic or branched C ₁ to C ₁₈ hydrocarbon radical, which can contain and through one or more groups selected from -O-, -NH-, -C (O) -, and -C (S) - one or more OH groups can be substituted, preferably unsubstituted C ₅ to C ₁₇ hydrocarbon radicals which are derived from the corresponding fatty acids or hydroxylated C ₃ to C ₁₇ radicals which can be attributed to hydroxylated carboxylic acids, especially saccharide carboxylic acids, and very specifically

mean.

The polysiloxane compounds b1) are, for example, linear polysiloxane copolymers of the general formula (I '): - [QV] - (I ') which contain at least one unit of this formula (I '), in which Q is as defined above,
V represents at least one group V ¹ and at least one group V ² , wherein V ¹ and V ^{2 are} as defined above. In addition, V can also represent trivalent or higher, especially trivalent radicals V ³ . In this case, there are also trivalent or tetravalent units Q, as defined above, and the saturation of the trivalent or higher-valent radicals V3 and the trivalent or tetravalent units Q occurs exclusively with one another within the linear main chain with the formation of cyclic structures, as further below explained in more detail. However, this case is less preferred.

• – dass die genannte Polysiloxan-Verbindung mindestens eine Gruppe V¹, V² oder V³ enthält, die mindestens eine Gruppe -Z¹-, -Z²- oder Z³ enthält, und
• – dass die drei- und vierwertigen Reste Q entweder der Verzweigung der aus Q und V gebildeten Hauptkette dienen,

so dass die Valenzen, die nicht der Bindung in der Hauptkette dienen, weitere aus -[Q-V]-Einheiten gebildete Verzweigungen tragen, oder die drei- und vierwertigen Reste Q sättigen sich mit Resten V³ innerhalb einer linearen Hauptkette ohne Bildung einer Verzweigung ab, und worin die aus Ammoniumgruppen resultierenden positiven Ladungen durch organische oder anorganische Säureanionen neutralisiert sind, und deren Säureadditionssalze.The polysiloxanes of the general formula (I) used according to the invention as component b1) can also contain branching units V ³ . The group V ³ represents a trivalent or higher, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical with up to 1000 carbon atoms, which optionally one or more groups selected from
-O-, -CONH-, -CONR ² -, where R ^{2 is} as defined above, -C (O) -, -C (S) -, -Z ¹ -, which is as defined above, -Z ² - which is as defined above, and Z ³ , in which Z ^{3 is} a trivalent or higher onganopolysiloxane unit, and which may optionally be substituted by one or more hydroxyl groups,
where one or more groups V ¹ , one or more groups V ² and / or one or more groups V ³ may be present in the said polysiloxane compound, with the proviso that

• - That said polysiloxane compound contains at least one group V ¹ , V ² or V ³ , which contains at least one group -Z ¹ -, -Z ² - or Z ³ , and
• That the trivalent and tetravalent radicals Q either serve to branch the main chain formed from Q and V,

so that the valences which do not serve for binding in the main chain carry further branches formed from - [QV] units, or the trivalent and tetravalent radicals Q saturate with radicals V ³ within a linear main chain without forming a branch, and wherein the positive charges resulting from ammonium groups are neutralized by organic or inorganic acid anions, and their acid addition salts.

mit v + w ≥ 0.The group Z ³ represents a trivalent or higher-order organopolysiloxane unit. The branching unit V ³ can be silicone-free - that is, without Z ³ . Examples of these include:

with v + w ≥ 0.

worin R¹ wie oben definiert ist, m = 0 bis 1000, und m¹ ≥ 1 und m² ≥ 3 ist,

worin R¹ jeweils wie oben definiert ist.The branching unit V ³ may contain a trivalent or higher organopolysiloxane unit Z ³ , such as:

wherein R ^{1 is} as defined above, m = 0 to 1000, and m ¹ ≥ 1 and m ² ≥ 3,

wherein R ¹ is as defined above.

An example of a Z ³ -containing branching unit V ³ is, for example:

In the general formulas (I) and (I '), the molar ratio of the groups V ¹ and V ² in the polysiloxane compounds V ² / V ^{1 can} in itself assume any value. According to the invention, this also includes the case in which the polysiloxane compound of the formulas (I) or (I ') contains only V ² units, that is to say the polysiloxane compound has the formula - [QV ² ] -. The case in which the polysiloxane compound contains only V ¹ units is also included according to the invention. In this case, however, the V ¹ units must contain Z ¹ siloxane units.

In a preferred embodiment of the invention, however, the polysiloxane compound of the formulas (I) or (I ') contains both V ² and V ¹ units.

ist, worin
R¹ wie oben definiert ist, wobei die Gruppen R¹ in den Gruppen V¹ und V² gleich oder verschieden sein können, und
n₂ = 0 bis 19 bedeutet.In the compositions at least one linear or branched polyamino and / or polyammonium polysiloxane copolymer containing the repeating units [-QV-] compounds b1), in which the units V, consist of the units V ¹ , V2 and / or V3, the group V ¹ selected from divalent, straight-chain, cyclic
or branched, saturated, unsaturated or aromatic hydrocarbon radicals having up to 1000 carbon atoms, which optionally have one or more groups, selected from
-O-, -CONH-,
-CONR ² -, in which R ^{2 is} as defined above, where the groups R ² in groups V ¹ and V ^{2 may be the} same or different,
-C (O) -, -C (S) - and -Z ¹ - may contain, wherein -Z ¹ - a group of the formula

is what
R ^{1 is} as defined above, where the groups R ¹ in groups V ¹ and V ^{2 may be the} same or different, and
n ₂ = 0 to 19 means.

The radical V ¹ can optionally be substituted by one or more hydroxyl groups.

Particularly preferably 0 to 10, especially 0 to 5, more particularly 0. The number n ₂ is the average degree of polymerization from M _{n of} the diorganosiloxy units in group Z ¹ .

The compounds b1) are preferably characterized in that, preferably the units V 'are composed of at least one esterified polyalkylene oxide structural unit of the general formulas:
-AE-, -EA-, -AE-A'- and / or -A'-EA- exist
wherein
A = -CH ₂ C (O) O-, -CH ₂ CH ₂ C (O) O-, -CH ₂ CH ₂ CH ₂ C (O) O-, -OC (O) CH ₂ -, -OC ( O) CH ₂ -, -OC (O) CH ₂ CH ₂ - and / or -OC (O) CH ₂ CH ₂ CH ₂ -
A '= -CH ₂ C (O) -, -CH ₂ CH ₂ C (O) -, -CH ₂ CH ₂ CH ₂ C (O) -, -C (O) CH ₂ -, -C (O) CH ₂ -, -C (O) CH ₂ CH ₂ - and / or -C (O) CH ₂ CH ₂ CH ₂ -
E = a polyalkylene oxide group of the general formulas:
- [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r - and / or
- [OCH (CH ₃ ) CH ₂ ] _r - [OCH ₂ CH ₂ ] _q -
With
q = 1 to 200,
r = 0 to 200,
wherein the terminal oxygen atom of group A to the terminal -CH ₂ group of group E, and the terminal carbonyl carbon atom of group A 'to the terminal oxygen atom of group E each bind with the formation of ester groups,
and / or at least one terminal polyalkylene oxide structural unit of the formula -AER ² where A and E have the meaning given above,
and
R ² = H, straight-chain, cyclic or branched C ₁ -C ₂₀ -hydrocarbon radical which can be interrupted by -O-, or -C (O) - and substituted by -OH and can be acetylenic, olefinic or aromatic,

• – -R⁹-, worin R⁹ einen zweiwertigen, gesättigten oder einfach oder mehrfach ungesättigten, geradkettigen oder verzweigten Kohlenwasserstoffrest mit zwei bis 25 Kohlenstoffatomen darstellt,
• – -(CH₂)_uC(O)O-[(CH₂CH₂O)_q-(CH₂CH(CH₃)O)_r]-C(O)(CH₂)_u
• – -(CH₂)_uC(O)O-R⁹-O-C(O)(CH₂)_u-, worin R⁹ wie zuvor definiert ist,
• – -(CH₂)_u-R¹⁰-(CH₂)_u-, worin R¹⁰ eine aromatische Gruppe ist,
• – -[CH₂CH₂O]_q-[CH₂CH(CH₃)O]_r-CH₂CH₂-,
• – -CH(CH₃)CH₂O[CH₂CH₂O]_q-[CH₂CH(CH₃)O]_r-CH₂CH(CH₃)-
• – -CH₂CH(OH)CH₂-,
• – -CH₂CH(OH)(CH₂)₂CH(OH)CH₂-,
• – -CH₂CH(OH)CH₂OCH₂CH(OH)CH₂OCH₂CH(OH)CH₂- und
• – -CH₂CH(OH)CH₂O-[CH₂CH₂O]_q-[CH₂CH(CH₃)O]_r-CH₂CH(OH)CH₂-

worin
u von 1 bis 3 ist,
q und r von 0 bis 200, bevorzugt von 0 bis 100, bevorzugter von 0 bis 70 und besonders bevorzugt 0 bis 40 ist, und
q + r > 0 ist.In a further embodiment of b1), V ¹ preferably represents

• -R ⁹ -, in which R ^{9 represents} a divalent, saturated or mono- or polyunsaturated, straight-chain or branched hydrocarbon radical having two to 25 carbon atoms,
• - - (CH ₂ ) _u C (O) O - [(CH ₂ CH ₂ O) _q - (CH ₂ CH (CH ₃ ) O) _r ] -C (O) (CH ₂ ) _u
• - - (CH ₂ ) _u C (O) OR ⁹ -OC (O) (CH ₂ ) _u -, in which R ^{9 is} as previously defined,
• - - (CH ₂ ) _u -R ¹⁰ - (CH ₂ ) _u -, wherein R ^{10 is} an aromatic group,
• - - [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -CH ₂ CH ₂ -,
• - -CH (CH ₃ ) CH ₂ O [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -CH ₂ CH (CH ₃ ) -
• - -CH ₂ CH (OH) CH ₂ -,
• - -CH ₂ CH (OH) (CH ₂ ) ₂ CH (OH) CH ₂ -,
• - -CH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH ₂ - and
• - -CH ₂ CH (OH) CH ₂ O- [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -CH ₂ CH (OH) CH ₂ -

wherein
u is from 1 to 3,
q and r is from 0 to 200, preferably from 0 to 100, more preferably from 0 to 70 and particularly preferably 0 to 40, and
q + r> 0.

Aryl- oder Alkylarylen, wie
bevorzugt sindPreferred variants of V ¹ are structures of the formula:
-CH ₂ C (O) O- [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -C (O) CH ₂ -,
-CH ₂ CH ₂ C (O) O- [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -C (O) CH ₂ CH ₂ -,
-CH ₂ CH ₂ CH ₂ C (O) O- [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -C (O) CH ₂ CH ₂ CH ₂ -,
esterified alkylene, alkenylene, alkynylene units, especially the structures
-CH ₂ C (O) O- [CH ₂ ] _o -OC (O) CH ₂ -,
-CH ₂ CH ₂ C (O) O- [CH ₂ ] _o -OC (O) CH ₂ CH ₂ -,
-CH ₂ CH ₂ CH ₂ C (O) O- [CH ₂ ] _o -OC (O) CH ₂ CH ₂ CH ₂ -
-CH ₂ C (O) O-CH ₂ C≡CCH ₂ -OC (O) CH ₂ -,
-CH ₂ CH ₂ C (O) O-CH ₂ C≡CCH ₂ -OC (O) CH ₂ CH ₂ -,
-CH ₂ CH ₂ CH ₂ C (O) O-CH ₂ C≡CCH ₂ -OC (O) CH ₂ CH ₂ CH ₂ -,
-CH ₂ C (O) O-CH ₂ CH = CHCH ₂ -OC (O) CH ₂ -,
-CH ₂ CH ₂ C (O) O-CH ₂ CH = CHCH ₂ -OC (O) CH ₂ CH ₂ -,
-CH ₂ CH ₂ CH ₂ C (O) O-CH ₂ CH = CHCH ₂ -OC (O) CH ₂ CH ₂ CH ₂ -,
further variants of V1 are
Alkylene, alkenylene, alkynylene and aryl units, especially the structures:
- [CH ₂ ] _o -
with o = 2 to 6,
C2 to C10 alkenylene, alkynylene, such as
-CH ₂ C≡CCH ₂ -, -CH ₂ CH = CHCH ₂ -, -CH (CH ₃ ) CH ₂ CH ₂ -, and C6 to C22

Aryl or alkylarylene, such as
are preferred

In another particularly preferred embodiment, V ^{1 is} selected from polyalkylene oxide units of the structures
- [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -CH ₂ CH ₂ -,
-CH (CH ₃ ) CH ₂ O [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -CH ₂ CH (CH ₃ ) -
With
mono-, di- or polyhydroxy-functional units, of the formulas
-CH ₂ CH (OH) CH ₂ -, -CH ₂ CH (OH) (CH ₂ ) ₂ CH (OH) CH ₂ -,
-CH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH ₂ -,
-CH ₂ CH (OH) CH ₂ O- [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -CH ₂ CH (OH) CH ₂ -
and wherein the chain length of the polyether units are the indices
q = 0 to 200 and
have r = 0 to 200.

Q = 1 to 50, in particular, are preferred 2 to 50, especially 1 to 20, very specifically 1 to 10, and 1 or 2, r = 0 to 100, in particular 0 to 50, especially 0 to 20, entirely especially 0 to 10, as well as 0 or 1 or 2. It is particularly preferred that in units V1 different groups V1 side by side in one molecule present the solubility properties or specifically adjust the hydrophilicity of the treated substrate to be able to.

The polysiloxane compounds b1) which contain at least one unit of the formula (I) can be terminated by monofunctional groups -QR and / or -VR. These result from the saturation of one of the two binding sites of Q or V by a monovalent group R or hydrogen, which is defined as above. This results in Q ^* , QR or VR groups.

The polysiloxane compounds that contain at least one unit of the formula (I), in the sense of Invention also include the case where only one unit - [Q-V] - is present, so that compounds of the formulas R-V- [Q-V] -R or R- [Q-V] -Q-R, in which R can also be replaced by H. are.

The polyamino and / or polyammonium polysiloxane compounds b1) are, for. B. described in WO 02/10257, WO 02/10259, DE-OS 100 36 522 . DE-OS 100 36 532 . DE-OS 100 36 533 and the unpublished DE application 102 12 470.1 are preferably suitable. The connections according to US 6,240,929 can basically also be used. In the compositions which contain at least one linear or branched polyamino and / or polyammonium polysiloxane copolymer with the repeating units [-QV-] of the type of the compounds b1) in which the units V, from the units V ¹ , V2 and / or V3 exist, the properties according to the invention can be varied within wide limits by selecting groups V1 to V2 or V3.

In the event that V2 in the polysiloxane compounds b1) of the formula (I) or (I ') from the units -V ^{2 *} -Z ² -V ^{2 *} - is selected in which Z ^{2 is} as defined above and V ^{2 * represents} a divalent straight-chain, cyclic or branched, saturated, unsaturated or aromatic radical as defined above, the preferred compounds b1) have selected molar ratios of the repeating units - [V ^{2 *} - Z ² -V ^{2 *} -Q] - to - [V ¹ -Q] -, ie the ratio V ² / V ¹ , as mentioned above.

In a preferred embodiment, the ratio V ² / V ¹ = 1, but in another embodiment it is preferably not equal to 1, more preferably <0.9, even more preferably <0.8, even more preferably <0.3. In the cases V ² / V ¹ <1, the linear polysiloxane copolymers mentioned - [QV] - necessarily contain blocks which contain more than one - [V ¹ -Q] unit linked to one another.

As will be explained in more detail below in connection with the process for the preparation of the linear polysiloxane copolymers described above, the block-like sequences which have more than one - [V ¹ -Q] unit linked to one another can, depending on the method of preparation, regularly with the V ² -Q units or irregularly connected to the V ² -Q units. This means the following:
In the case of the regular compound, in which, for example, a prepolymer corresponding to the group -Q- [V ¹ -Q] _x is reacted with monomer units corresponding to V ² in a molar ratio of 1: 1, the linear polysiloxane copolymers can be prepared as follows: - {V ² -Q- [V ¹ -Q] _x -} -.

x can be 1 to 2000 and is the average of the distribution. The linear polysiloxane copolymers represented by the formula - {V ² -Q- [V ¹ -Q] _x -} - are characterized in that they have essentially no linked -V ² -Q units or, in other words, are in these preferred variants, two -V ² -Q units are always interrupted by at least one -V ¹ -Q unit.

In the irregular connection, in which, for example, Q units corresponding monomers with V ¹ corresponding monomer units and V ² corresponding monomer units in the ratio Q / (V ¹ + V ² ), for example V ² / V ¹ <1, are preferred <0.5, implemented from 1: 1, the linear polysiloxane copolymers can be represented as follows: -Q- (V ¹ , V ² ) -, where V is the ratio V ² / V ¹ <1 or <0.5. The groups V ¹ and V ^{2 are} statistical about the copoly Merkette distributed. In contrast to the linear polysiloxane copolymer produced by the regular connection, this copolymer can also have adjacent -QV ² units.

und worin X = V^2*, F oder Y = V¹ und n = n₁, n₂ ,n₃, R¹, R², R³, wie oben definiert sind und letztere vorzugsweise Methyl sind. Vorzugsweise sind F oder Y verschieden und stellen bevorzugt AEA' , EA oder einen α,ω-alkylenendständig gebundenen Polyether und C₁-C₁₂-Alkylenreste dar.In a preferred embodiment, in which the ratio V ² / V ¹ = 1, the groups V consist in the repeating units [QV] of the polyamino and / or polyammonium polysiloxane copolymers, these having at least one group V ¹ and V ² or V ^{2 *} contain and the groups V1 have different units Y and F, the connection of which is represented by the formulas (II) and (III) and have linear or cyclic siloxane structures.

and wherein X = V ^{2 *} , F or Y = V ¹ and n = n ₁ , n ₂ , n ₃ , R ¹ , R ² , R ³ as defined above and the latter are preferably methyl. F or Y are preferably different and are preferably AEA ', EA or an α, ω-alkylene-terminated polyether and C ₁ -C ₁₂ -alkylene radicals.

und worin X = V^2*, F oder Y = V¹ und n = n₁, n₂ ,n₃, R¹, R², R³, wie oben definiert sind und letztere vorzugsweise Methyl sind. Dabei sind für F und Y die zuvor benannten Gruppen für V¹ = AEA' , EA oder ein α,ω-alkylenendständig gebundener Polyether und C₁-C₁₂-Alkylenreste bevorzugt.In a further embodiment, these polyamino and / or polyammonium polysiloxane copolymers with the repeating units [QV] as chain end groups contain at least partially tertiary or quaternary monoamines Q ^* from the group of Q units, the group Q ^* via the group X on V ^{2 *} binds to V ² in formulas (IV) to (VII).

and wherein X = V ^{2 *} , F or Y = V ¹ and n = n ₁ , n ₂ , n ₃ , R ¹ , R ² , R ³ as defined above and the latter are preferably methyl. For F and Y, the groups mentioned above for V ¹ = AEA ', EA or an α, ω-alkylene-terminated polyether and C ₁ -C ₁₂ -alkylene radicals are preferred.

wobei
M = V^2* bedeutet und wie oben definiert ist
U steht für einen zweiwertigen organischen Rest, bevorzugt E, F, EA, AEA oder eine Bindung
Z = Q^* ist und ausgewählt wird aus
r wie in V² definiert ist ( = n₁, n₂ oder n₃) und
s = 1 bis 24 und
B^– für ein anorganisches oder organisches Anion ist, wie oben unter A^– definiert steht

In an additional, preferred embodiment, the compositions in the repeating units [QV] contain the compounds of the formula QV ² or Q ^* V ² Q ^* corresponding to the general formula (IX)

in which
M = V ^{2 *} means and is as defined above
U stands for a divalent organic radical, preferably E, F, EA, AEA or a bond
Z = Q ^* and is selected from
r is as defined in V ² (= n ₁ , n ₂ or n ₃ ) and
s = 1 to 24 and
B ^{- is} an inorganic or organic anion, as defined above under A ^-

The linear or branched polyamino and / or polyammonium polysiloxane copolymers b1) Formula - [QV-] and amino and optionally ammonium polysiloxane compounds b2) preferably have as anions A ^- physiologically acceptable organic and inorganic residues from the group consisting of chloride, bromide, hydrogen sulfate, sulfate, or organic residues from the Group consisting of acetate, propionate, octanoate, decanoate, dodecanoate, tetradecanoate, hexadecanoate, octadecanoate, oleate.

It is further preferred that the compounds b2) are present in protonated form as amine salts.

Such linear amine or tetraorgano-ammonium compounds have been described, for example, in WO 02/10257, WO 02/10259, EP 282 720 . DE 102 12 470.1 . DE 102 51 525.5 and 102 51 526.3 . 102 51 524.7 or US 5,981,681 , The polysiloxanes of WO 02/10259 and WO 02/10257, which are hereby expressly incorporated by reference, and which belong to the disclosure content of the present application are particularly preferred.

In a further embodiment ( DE 102 51 526.3 ) of the linear polysiloxane compounds of the formula (I) or (I '), V ² / V ^{1 is} not equal to 1, preferably V ² / V ¹ <1, more preferably <0.9, more preferably V ² / V ¹ fulfills the relationship
0.0005 <V ² / V ¹ <0.5,
even more preferred
0.0005 <V ² / V ¹ <0.3.

The group R is preferably selected from the groups R ² .

In an additional alternative ( DE 102 51 524.7 ) the compositions are selected in such a way that the group V, which consists of the repeating units V2 and V1 or - [V ^{2 *} -Z ² -V ^{2 *} -Q] - and - [V ¹ -Q] - is a molar Ratio of repeat units - [V ^{2 *} -Z ² -V ^{2 *} -Q] - to - [V ¹ -Q] - according to the ratio V ² / V ¹
0.0005 <V ² / V ¹ <1000,
0.005 <V ² / V ¹ <1 or
0.01 <V ² / V ¹ <1.

Compounds b1) with the formulas (I) or (I ') in which the R ¹ = methyl are preferred.

In a further preferred embodiment ( DE 102 51 526.3 ) of the linear polysiloxane compounds b1) of the formula (I ') of the present invention, the molar ratio V ² / V ¹ fulfills the relationship
0.0005 <V ² / V ¹ <0.5, (= 2 <V ¹ / V ² <2000)
preferred the relationship
0.005 <V ² / V ¹ <0.4, (= 2.5 <V ¹ / V ² <200)
the relationship even more preferred
0.01 <V ² / V ¹ <0.3 (= 3.3 <V ¹ / V ² <100).

Another alternative embodiment are compounds b1) in which the group V consists of the repeating units V2 and V1 or - [V ^{2 *} -Z ² -V ^{2 *} -Q] - and - [V ¹ -Q] - and the ratio
1 <V ² / V ¹ <1000,
1 <V ² / V ¹ <100 or
1 <V ² / V ¹ <20.

The variation of the ratio V1 / V2 allows the solubility of the siloxane copolymers to be within wide limits and specifically adjust the hydrophilicity of the substrates treated with it.

• a) mindestens eine Aminverbindung, ausgewählt aus einer Diamin-Verbindung und/oder einer primären oder sekundären Monoaminverbindung, mit mindestens zwei difunktionellen, zur Reaktion mit den Aminofunktionen der Amin-Verbindung befähigten organischen Verbindungen umgesetzt werden, wobei das molare Verhältnis der organischen Verbindungen so gewählt wird, dass das gewünschte Verhältnis V²/V¹ erhalten wird,
• b) mindestens zwei Mol einer Aminverbindung, ausgewählt aus einer Diamin-Verbindung und/oder einer primären oder sekundären Monoaminverbindung, mit einem Mol einer difunktionellen, zur Reaktion mit den Aminofunktionen der Aminverbindung befähigten organischen Verbindung unter Bildung einer Diaminverbindung (Monomer) umgesetzt wird, die anschließend mit mindestens einer Aminverbindung, ausgewählt aus einer Diamin-Verbindung und/oder einer primären oder sekundären Monoaminverbindung, und mindestens einer weiteren difunktionellen zur Reaktion mit den Aminofunktionen der Aminverbindungen befähigten organischen Verbindung umgesetzt wird,
• c) eine Aminverbindung, ausgewählt aus einer Diamin-Verbindung und/oder einer primären oder sekundären Monoaminverbindung, mit einer difunktionellen, zur Reaktion mit den Aminofunktionen der Aminverbindungen befähigten organischen Verbindung unter Bildung einer Diaminverbindung (aminoterminiertes Oligomer) umgesetzt wird, die anschließend mit mindestens einer difunktionellen zur Reaktion mit den Aminofunktionen der Diamin-Verbindungen befähigten organischen Verbindung umgesetzt wird,
• d) eine Aminverbindung, ausgewählt aus einer Diamin-Verbindung und/oder einer primären oder sekundären Monoaminverbindung, mit einer difunktionellen, zur Reaktion mit den Aminofunktionen der Aminverbindung befähigten organischen Verbindung unter Bildung einer difunktionellen, zur Reaktion mit Aminofunktionen befähigten Verbindung (difunktionelles Oligomer) umgesetzt wird, die anschließend mit mindestens einer Aminverbindung, ausgewählt aus einer Diamin-Verbindung und/oder einer primären oder sekundären Monoaminverbindung, und mindestens einer weiteren zur Reaktion mit Aminofunktionen befähigten Verbindung umgesetzt wird, wobei gegebenenfalls monofunktionelle, bevorzugt tertiäre Monoamine oder geeignete, zur Kettenfortpflanzung nicht befähigte Monoamine und/oder monofunktionelle, zur Reaktion mit Aminofunktionen befähigten Verbindungen als Kettenabbruchsmittel hinzugesetzt werden können, und die Stöchiometrie der Aminofunktionen und der zur Reaktion mit Aminofunktionen befähigten funktionellen Gruppen in der letzten Stufe der Umsetzung stets etwa 1 : 1 beträgt, und wobei gegebenenfalls vorhandene Aminofunktionen protoniert oder quaterniert werden können.

The linear polysiloxanes of the formulas (I) and (I ') can be prepared, for example, by a process in which

• a) at least one amine compound selected from a diamine compound and / or a primary or secondary monoamine compound are reacted with at least two difunctional organic compounds capable of reacting with the amino functions of the amine compound, the molar ratio of the organic compounds being chosen in this way the desired ratio V ² / V ^{1 is} obtained,
• b) at least two moles of an amine compound selected from a diamine compound and / or a primary or secondary monoamine compound are reacted with one mole of a difunctional organic compound capable of reacting with the amino functions of the amine compound to form a diamine compound (monomer) which subsequently reacted with at least one amine compound selected from a diamine compound and / or a primary or secondary monoamine compound and at least one further difunctional organic compound capable of reacting with the amino functions of the amine compounds,
• c) an amine compound selected from a diamine compound and / or a primary or secondary monoamine compound with a difunctional organic compound capable of reacting with the amino functions of the amine compounds to form a diamine compound (amino-terminated oligomer), which is then reacted with at least one difunctional organic compound capable of reacting with the amino functions of the diamine compounds is reacted,
• d) an amine compound selected from a diamine compound and / or a primary or secondary monoamine compound, with a difunctional one, for reaction with the amine functions of the amine compound dung capable organic compound to form a difunctional, capable of reacting with amino functions (difunctional oligomer), which is then reacted with at least one amine compound selected from a diamine compound and / or a primary or secondary monoamine compound, and at least one other is reacted with a compound capable of amino functions, wherein optionally monofunctional, preferably tertiary monoamines or suitable monoamines and / or monofunctional compounds which are not capable of chain propagation and capable of reacting with amino functions can be added as chain terminators, and the stoichiometry of the amino functions and that of the reaction with amino functions enabled functional groups in the last stage of the reaction is always about 1: 1, and any amino functions that may be present can be protonated or quaternized.

Variant a), wherein at least one diamine compound selected from a diamine compound and / or a primary or secondary monoamine compound is reacted with at least two difunctional organic compounds capable of reacting with the amino functions of the amine compound, the molar ratio of the organic Connections are chosen so that the desired ratio V ² / V ^1, such as <0.5, is fulfilled, can be represented schematically, for example, as follows:
- [NN] - + - [V ¹ ] - + - [V ² ] - → - [Q- (V ¹ , V ² )] - or
- [N] - + - [V ¹ ] - + - [V ² ] - → - [Q- (V ¹ , V ² )] -
where - [NN] - a cyclic diamine corresponding to the definition of Q or a V ¹ -containing diamine - [NV ¹ -N] - or a V ² -containing diamine
- [NV ² -N] -, as in particular - [NV ^{2 *} -Z ² -V ^{2 *} -N] - may include, with the latter in each case two Q units and one V ¹ and two V ² units emerge, and - [V ¹ ] - and
- [V ² ] - should represent repeating units V ¹ and V ² corresponding monomers,
and - [N] - represents a primary or secondary monoamine suitable for chain propagation,

From the - [N-N] and / or - [N] units at least one is more alkylated Amine or a quaternary Ammonium unit Q is formed, being formed during the polymerization secondary or tertiary Amino functions optionally after the polymerization in one can be protonated or quaternized in a separate step. Prefers education is quaternary Ammonium units.

Preferred examples of - [NN] - are as described in more detail below: piperazine and imidazole, preferred diamine units - [NV ¹ -N] - include, for example: polymethylene diamines, tetramethyl-hexamethylene diamine, α, ω-diamino-terminated ones, such as polyethers, such as Jeffamine, etc.

Preferred diamine units - [NV ^{2 *} -Z ² -V ^{2 *} -N] - include, for example, reaction products of α, ω-dihydrogenpolydialkylsiloxanes with allylamines.

Preferred examples of - [N] - are as detailed below described e.g. Dimethylamine.

The use of diamines - [N-N] - is preferred in itself.

Preferred - [V ¹ ] monomers include, for example, epichlorohydrin, bis-chloroalkyl esters, bisepoxides or bisacrylates. Mixtures of the - [V ¹ ] monomers mentioned, such as, for example, mixtures of epichlorohydrin, bis-chloroalkyl esters or bisepoxides, can also preferably be reacted.

Preferred - [V ² ] monomers are monomers of the formula - [V ^{2 *} -Z ² -V ^{2 *} ] -, in which Z ^{2 is} as defined above, and - [V ^{2 *} ] a functionalized one corresponding to the repeating unit V ^{2 *} Represents group. Preferred - [V ² ] monomers for forming the V ² repeat units are in particular α, ω-diepoxy-terminated polydialkylsiloxanes.

Variant b) can be used with diamines, - [N-N] -, as well as suitable monoamines - [N] - and let yourself schematically, for example, as follows:

Variant b1)

• Step 1): 2 - [NNV] - + - [V ² ] - or - [VN ¹ ] - → - [NNV ¹ -NN] - or - [NNV ² -NN] -
• Step 2.1): - [NNV ² -NN] - + - [V ¹ ] - + - [NN] - →,
• Step 2.2): - [NNV ¹ -NN] - + - [V ² ] - + - [NN] - →, whereby the stoichiometry V ² / V ^{1 is set} as desired.

Regarding the preferred monomer units - [NN] -, - [V ¹ ] - and
- [V ² ] - applies to what was said for step a).

Variant b2)

• Step 1): 2 - [N] - + - [V ² ] - or - [V ¹ ] - → - [NV ¹ -N] - or - [NV ² -N] -
• Step 2.1): - [NV ² -N] - + - [V ¹ ] - + - [N] - →,
• Step 2.2): - [NV ¹ -N] - + - [V ² ] - + - [N] - →, wherein this variant, as mentioned above, can only be carried out with primary or secondary monoamines and, with regard to the monomer units used - [N] -, - [V ¹ ] - and - [V ² ] - what has been said for step a) applies.

Variant c) can be schematically, for example represent as follows:

Variant c1)

• Step 1): - [NN] - + - [V ¹ ] - → - [NN- (V ¹ -NN) _x ] -
• Step 2): - [NN- (V ¹ -NN) _x ] - + - [V ² ] - → with respect to the preferred monomer units - [NN] -, - [V ¹ ] - and - [V ² ] - that applies to step a).

Variant c2)

• Step 1): - [N] - + - [V ¹ ] - → - [N- (V ¹ -N) _x ] -
• Step 2): - [N- (V ¹ -N) _x ] - + - [V ² ] - → with respect to the preferred monomer units - [N] -, - [V ¹ ] - and - [V ² ] - that applies to step a).

Variant d) can be schematically, for example represent as follows:

Variant d1)

• Step 1): - [V ¹ ] - + - [NN] - → - [V ¹ - (NNV ¹ ) _x ] -
• Step 2): - [V ¹ - (NNV ¹ ) _x ] - + - [V ² ] - + - [N] - or - [NN] - → with regard to the preferred monomer units - [NN] -, - [V ¹ ] - and - [V ² ] - that applies to step a).

Variant d2)

• Step 1): - [V ¹ ] - + - [N] - → - [V ¹ - (NV ¹ ) _x ] -
• Step 2): - [V ¹ - (NV ¹ ) _X ] - + - [V ² ] - + - [N] - or - [NN] - → with regard to the preferred monomer units - [N] -, - [NN] -, - [V ¹ ] - and - [V ² ] - what has been said for step a) applies.

For All of the variants shown schematically above also apply to mixtures of monoamines - [N] - and diamines - [N-N] - can be used.

The functional ones are particularly preferred Groups of difunctional compounds capable of reacting with amino functions selected from the group consisting of epoxy groups and haloalkyl groups.

bevorzugt, wobei R¹ die oben angegebenen Bedeutung hat und n je nach gewünschter Wiederholungseinheit V¹ oder V², n₂ oder n₁ ist, die wie oben definiert sind. Sofern nicht kommerziell erhältlich, können diese Siloxane nach bekannten Verfahren, z.B. durch Äquilibrierung hergestellt werden (Silicone, Chemie und Technologie, Vulkan-Verlag, Essen 1989, S. 82–84).The starting point for the syntheses of the polysiloxane copolymers of the formulas (I) and (I ') used according to the invention are α, ω-Si-H-functionalized siloxanes of the general structure

preferred, wherein R ^{1 has} the meaning given above and n, depending on the desired repeat unit, is V ¹ or V ² , n ₂ or n ₁ , which are as defined above. If not commercially available, these siloxanes can be prepared by known processes, for example by equilibration (Silicone, Chemistry and Technology, Vulkan-Verlag, Essen 1989, pp. 82-84).

The preparation of the precursors of the structural elements V ^{2 *} and Q can, for. B. done in two ways.

On the one hand, it is possible to start with tertiary amino functions bearing unsaturated Structures, for example N, N-dimethylallylamine, by hydrosilylation directly to the siloxane in the α, ω position to tie. This process is generally known (B. Marciniec, Comprehensive Handbook on Hydrosilylation, Pergamon Press, Oxford 1992, pp. 122-124).

On the other hand, it is preferred to first generate reactive α, ω-functionalized intermediates by hydrosilylation, which subsequently are converted into α, ω-ditertiary amino structures or directly into the invention quaternary ammonium structures can be converted. Suitable starting materials for producing reactive intermediates are, for example, halogenated alkenes or alkynes, especially allyl chloride, allyl bromide, chlorpropine and chlorobutin, unsaturated halocarboxylic acid esters, especially chloroacetic acid allyl esters, chloroacetic acid proparyl esters, 3-chloropropionic acid allyl esters and 3-chloropropionic acid and vinyl proparyl allyl ether and epoxyoxy allyl allyl ether and epoxy propyl allyl ether and epoxyoxy allyl allyl ether and epoxy methoxy allyl ethene and epoxy methoxy allyl ethene and epoxy methoxy allyl ethene and epoxy allyl allyl ethene and epoxy propyl allyl ethylenediol and epoxy methoxy allyl allyl and epoxy propyl allyl ethylenediol and epoxy allyl allyl ethylenediol and epoxy propyl allyl for example. The general implementation of hydrosilylation with representatives of the groups mentioned is also known (B. Marciniec, Comprehensive Handbook on Hydrosilylation, Pergamon Press, Oxford 1992, pp. 116-121, 127-130, 134-137, 151-155).

In a subsequent step, the reactive intermediates can then be reacted with compounds bearing secondary amino functions. Suitable representatives are N, N-dialkylamines, for example dimethylamine, diethylamine, dibutylamine, diethanolamine and N-methylglucamine, cyclic secondary amines, for example morpholine and piperidine, aminoamides which carry secondary amino functions, for example the reaction products of diethylenetriamine or dipropylenetriamine with lactones, such as γ-butyrolactone, such as γ-butyrolone , Gluconic acid δ-lactone and glucopyranosylarabonic acid lactone ( DE-OS 43 18 536 , Examples 11a, 12a, 13a), or secondary-tertiary diamines, such as N-methylpiperazine. It is particularly preferred to use corresponding imidazole or pyrazole derivatives, especially imidazole and pyrazole, for introducing tertiary amino functions.

As a partner for that in one embodiment epoxy derivatives preferably used are particularly suitable called secondary-tertiary diamines, as well as imidazole and pyrazole. That way they can Alkylations regioselectively and without additional effort on the hydrogen atoms carrying nitrogen atoms.

To ensure a quantitative conversion of the reactive groups into tertiary amino structures, the amines are used in a ratio of
1 ≤ Σ secondary amino groups: reactive groups ≤ 10, preferably 1 to 3, especially 1 to 2, very particularly 1 used. Excess amine may need to be removed.

The attachment of the α, ω-ditertiary aminosiloxanes described above to monomer units corresponding to V ¹ - [V ¹ ] - or a prepolymer unit - [V ¹ - (QV ¹ ) _x ] - leads to the formation of further higher alkylated amino units or quaternary ammonium units and can again be done in two advantageous ways.

On the one hand, it is preferred to separately produce a strongly hydrophilic, polyquaternary, difunctional precondensate - [V ¹ - (QV ¹ ) _x ] -, which is combined with the α, ω-di-tertiary aminosiloxanes at a suitable time and to form the polyamino- or polyquaternary siloxane copolymers reacted.

The production of highly charged, difunctional prepolymers of different chain lengths - [V ¹ - (QV ¹ ) _x ] - is described by way of example in WO 99/14300 (Examples 1 to 7, Table 11). Depending on the molar ratio of V ¹ and the amine on which Q is based, either a prepolymer terminated by amino groups or terminated by other reactive groups can be produced.

In the case of the attachment of a prepolymer terminated by amino groups - [N- (V ¹ -N) _x ] - to the amine function of an α, ω-ditertiary aminosiloxane structure, an alkylating or quaternizing, difunctional monomer corresponding to the repeating unit V ¹ can, for example, [V ¹ ] -, selected for example from bisepoxides, epichlorohydin, bishalogenalkyl compounds, can be used. Needless to say, different groups V ^{1 can result} in the prepolymer and in the connecting link between prepolymer and α, ω-ditertiary aminosiloxane structure.

In the case of a prepolymer terminated by reactive groups, such as - [V ¹ - (QV ¹ ) _x ] -, a direct link to the amine function of the α, ω-ditertiary aminosiloxane structure can be made without a further “linker”, since an excess is already present in the prepolymer synthesis the V ¹ generating component was used.

As an alternative to the separate production of a pre-condensate - [V ¹ - (QV ¹ ) _x ] - highly charged blocks can be built up parallel to the incorporation into the copolymer. This means that the α, ω-ditertiary aminosiloxane with the starting components for building up - [V ¹ - (QV ¹ ) _x ] -, ie for example - [V ¹ ] - and mono- or diamines of the abovementioned meaning - [N ] - and / or - [NN -] - submitted together and brought to reaction.

Finally, it is possible to use the α, ω-di-tertiary aminosiloxane with long-chain siloxane unit Z ² or short-chain siloxane unit Z ¹ or the α, ω-difunctional siloxane - [NV ^{2 *} -Z ² -V ^{2 *} -N] - or - [ NV ¹ -N] - into the components presented to build up - [V ¹ - (QV ¹ ) _x ] - gradually over a period of time or vice versa these components to the α, ω-di-tertiary aminosiloxane or α, ω-difunctional Add siloxane gradually.

A preliminary provision of prepolymers terminated by amino groups, such as - [N- (V ¹ -N) _x ] - opens up the possibility of carrying out the copolymer formation directly with suitable reactive intermediates, for example epoxy derivatives.

It is also preferred to submit the reactive intermediates and the starting components for the construction of - [V ¹ - (QV ¹ ) _x ] - together and then to react them.

Finally, it is possible to gradually meter the reactive intermediates into the components presented to build up - [V ¹ - (QV ¹ ) _x ] - over a period of time or, conversely, to gradually add these components to the reactive intermediate.

Regardless of the choice of one of the reaction routes described above and the closely related Question whether amino units initially the siloxane or the prepolymer terminate the total stoichiometry chosen so that the sum of the amino functions and the groups reactive with them is about 1: 1.

Within the scope of the invention it is possible to deviate from this preferred overall stoichiometry. However, products are then obtained which no longer have the targeted length of the highly charged, hydrophilic block - [V ¹ - (QV ¹ ) _x ] - and additionally leave an excess of an unreacted starting component.

In addition to the overall stoichiometry of the reaction discussed above, the choice of the component (s) forming the repeat unit V ^{1 is} of great importance for the property profile of the products.

Suitable difunctional monomers on which the repeating units V ^{1 are} based - [V ¹ ] - are, for example, the halocarboxylic acid esters of the polyalkylene oxide diols. Preferred starting materials for their synthesis are low molecular weight, oligomeric and polymeric alkylene oxides of the general composition HO [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r H where q and r have the meanings given above, and are statistical or block-like units. Preferred representatives with regard to the alkylene oxide block are ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, the oligoethylene glycols with molecular weights of 200 to 10,000 g / mol, especially 300 to 800, and 1,2-propylene glycol, 1,3-propylene glycol and dipropylene glycol.

The polyalkylene oxide units used can also be introduced via the α, ω-dihalogen compounds. These are made from the oligomeric and polymeric alkylene oxides of the general composition HO [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r H where q and r have the meanings given above, for example accessible by chlorination of the hydroxyl groups with SOCl ₂ (Organikum, Organochemical basic internship, 17th edition, VEB Deutscher Verlag der Wissenschaften, Berlin 1988, pp. 189-190).

Mono-, di- or polyhydroxy-functional units as group V ¹ can be introduced starting from epoxy derivatives.

Commercial examples are 1-chloro-2,3-epoxypropane, the glycerol-l, 3-bis-glycidyl ether and diethylene glycol diglycidyl ether and neopentyl glycol diglycidyl ether.

If not commercially available, the desired Diepoxides, for example, by reaction of the corresponding diols with 1-chloro-2,3-epoxypropane be synthesized under alkaline conditions.

It is within the scope of the invention to introduce siloxane chains Z ¹ into the structure of V ¹ . This results, among other things, in the possibility of using siloxane chains of different lengths for the construction of the entire molecule. It is a preferred variant to install siloxane chains Z ¹ of chain length range n ₂ = 0 to 19, preferably 0 to 15, particularly preferably 0 to 10, especially 0 to 5, more particularly 0, in V ¹ . Suitable starting materials for installation are, for example, the corresponding α, ω-diepoxides or α, ω-di (monohalocarboxylic acid) ester structures.

When reacting epoxides with primary or secondary amines, care must be taken to ensure that one mole of H ⁺ per mole of epoxide / tertiary amine is added for the alkylation of tertiary amino groups.

The choice of suitable amines as starting components for the formation of Q in the repeating unit - [V ¹ - (QV ¹ ) _x ] - also largely determines the molecular structure. The use of ditertiary amines (corresponding to - [NN] -), for example N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyltetramethylenediamine, N, N, N ', N'-tetramethylhexamethylenediamine, N, N'-dimethylpiperazine leads to products in which each nitrogen atom of the repeat unit is quaternized.

The use of secondary-tertiary diamines, for example N-methylpiperazine, opens the way to repeat units - [V ¹ - (QV ¹ ) _x ] -, in which tertiary and quaternary amine or ammonium structures are present in a 1: 1 ratio. A partial or complete subsequent quaternization of remaining tertiary amino structures is a preferred variant for setting a desired high density of the quaternary ammonium groups. The corresponding aromatic amines imidazole or pyrazole lead to products with a delocalized charge.

When using primary tertiary diamines, for example N, N-dimethylpropylenediamine and 1- (3-aminopropyl) imidazole, especially in combination with diepoxides, comb-like structures can be built up for which the degree of quaternization can be selected during a final alkylation. Basically you can the alkylations are also set to degrees of quaternization of on average less than one quaternary ammonium group per repeat unit - [V ¹ - (QV ¹ ) _x ] -. However, it is preferred to quaternize at least one nitrogen atom per repeat unit.

Starting from secondary amines, for example piperazine, N, N'-bis (2-hydroxyethyl) hexamethylene diamine, N, N'-bis (2-hydroxypropyl) hexa methylene diamine, it is also possible in principle to repeat units - [V ¹ - (QV ¹ ) _x ] - are synthesized with an average content of less than one quaternary ammonium group. The di-secondary amines initially provide poly-tertiary amino-modified siloxane copolymers or prepolymers, which can be quaternized partially or completely in a final reaction to - [V ¹ - (QV ¹ ) _x ] -. However, it is also preferred in this variant to quaternize at least one nitrogen atom per repeat unit.

Suitable quaternizing agents are the generally known groups of substances such as alkyl halides, halocarboxylic acid esters, epoxy derivatives in the presence of H ⁺ and dialkyl sulfates, especially dimethyl sulfate.

The production is not commercial available disecondary In a preferred embodiment, amines take place starting from the corresponding diprimaries Amines, for example hexamethylenediamine by alkylation with Epoxides, e.g. Ethylene oxide, propylene oxide, isopropyl glycidyl ether taking advantage of the different reaction speeds primary and secondary Amines.

It had already been stated that in Scope of the invention the possibility exists, siloxane chains Z 'in to introduce the structure of V '. As Suitable starting materials were the reactive intermediates α, ω-diepoxides and α, ω-bis (monohalocarboxylic acid) esters named.

The ions A ^- neutralizing the positive charges resulting from the ammonium groups are preferably the ions formed during the quaternization, such as halide ions, especially chloride and bromide, alkyl sulfates, especially methosulfate, carboxylates, especially acetate, propionate, octanoate, decanoate, dodecanoate, tetradecanoate, hexadecanoate , Octadecanoate, oleate, sufonates, especially toluenesulfonate. However, other anions can also be introduced by ion exchange. Examples include organic anions such as polyether carboxylates and polyether sulfates.

The quaternization reactions are preferably in water, polar organic solvents or mixtures both of the above components. Suitable are e.g. alcohols, especially methanol, ethanol, i-propanol and n-butanol, glycols, such as Ethylene glycol, diethylene glycol, triethylene glycol, the methyl, ethyl and Butyl ether of the glycols mentioned, 1,2-propylene glycol and 1,3-propylene glycol, Ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, Butyl acetate and 2-ethylhexyl acetate, ethers such as tetrahydrofuran and nitro compounds, like nitromethane. The choice of the solvent depends essentially on the solubility of the reactants, the desired reaction temperature and any existing the implementation disruptive Reactivity.

The reactions are in the area of 20 ° C up to 130 ° C, preferably 40 ° C up to 100 ° C executed.

To the formation of gel-like, not Completely soluble Avoiding linear polyorganosiloxane polymers becomes the molecular weight expedient after limited above.

A limitation on the molecular weight is caused by the reaction between epoxides, and in the reaction system any existing water or alcohol end stop or alternatively through the additional Use of tertiary Amines such as trialkylamines or monofunctional versus amino groups reactive connections.

In other words, in addition to the terminal groups naturally resulting from the reaction of the monomeric starting materials, the polyorganosiloxane polymers can also have monofunctional chain terminators, such as trialkylamines etc. and, for example, ammonium, amino, ether or hydroxy end groups resulting therefrom. All cases of end stop Q ^* are intended to be included in the definition -QR and / or -VR mentioned above, wherein Q, V and R are as defined above and R can be replaced by hydrogen.

The polyamino and / or polyammonium polysiloxane compounds b1) used can be solid or liquid at 25 ° C. In the event that they are liquid at 25 ° C, the viscosities of the polysiloxanes b1) mentioned are preferably between 500 to 50,000,000 mPa.s at 25 ° C, preferably 1000 to 2,500,000 mPa.s at 25 ° C and with a shear rate gradient of D = 1 s ^–1 . They can have melting points up to 250 ° C, but are water-soluble or dispersible. Their solubility is preferably more than 1 g / l at 25 ° C.

One or more amino and / or ammonium polysiloxane compounds b2) can be used as additional component b2). We have included these above, amino or ammonium groups only in the side groups. The amino and / or ammonium polysiloxane compounds b2) are preferably polysiloxanes which carry primary and / or secondary and / or tertiary amino groups in the side groups, in which the amino groups are optionally protonated or quaternized, and the optionally additional hydrophilic ones Groups can contain. The amino or ammonium groups mentioned are preferably bonded to the siloxane skeleton via carbon. The amino and / or ammonium polysiloxane compounds b2) mentioned are preferably polyalkylsiloxanes with aminoalkyl or aminoarylsiloxane units. The aminoalkyl units can be attached to the difunctional, trifunctional or monofunctional be bound end groups and be part of other oxygen-containing side groups, in particular of polyether side groups. Examples are SF 1708, Baysilone OF 7747 from GE Bayer Silicones GmbH & Co KG.

worin R¹¹ organische Reste darstellt, die gleich oder verschieden voneinander sein können, mit der Maßgabe, dass mindestens einer der Reste R¹¹ mindestens ein Stickstoffatom enthält.The aminopolysiloxanes b2) mentioned are linear or branched polysiloxanes which are composed of siloxy units which are selected from the group consisting of:

wherein R ^{11 represents} organic radicals which may be the same or different from one another, with the proviso that at least one of the radicals R ^{11 contains} at least one nitrogen atom.

• – geradkettigen, cyclischen oder verzweigten, gesättigten, ungesättigten oder aromatischen Kohlenwasserstoffrest mit bis zu 200 Kohlenstoffatomen, der gegebenenfalls eine oder mehrere Gruppen, ausgewählt aus -O-, -NR²-, worin R² Wasserstoff, einen einwertigen, geradkettigen, cyclischen oder verzweigten, gesättigten, ungesättigten oder aromatischen Kohlenwasserstoffrest mit bis zu 100 Kohlenstoffatomen darstellt, der eine oder mehrere Gruppen ausgewählt aus -O-, -NH-, -C(O)- und -C(S)- enthalten kann, und der gegebenenfalls durch eine oder mehrere Substituenten, ausgewählt aus der Gruppe, die besteht aus einer Hydroxylgruppe, einer gegebenenfalls substituierten, bevorzugt ein oder mehrere Stickstoffatome enthaltenden heterocyclischen Gruppe, Amino, Alkylamino, Dialkylamino, Ammonium, Polyetherresten und Polyetheresterresten substituiert sein kann, wobei wenn mehrere Gruppen -NR² vorliegen, diese gleich oder verschieden sein können,
  
  -C(O)- und -C(S)- enthalten kann, und der Rest gegebenenfalls durch eine oder mehrere Substituenten ausgewählt aus Hydroxy und worin R¹, m, m₂, wie oben definiert sind, substituiert sein kann,
  
• – einem Polyetherrest mit bis zu 20000 Kohlenstoffatomen, der gegebenenfalls eine oder mehrere Amino-, Mono- oder Dialkylamino, oder Arylamino-Gruppen tragen kann,
• – einem Saccharid-haltigem organischen Rest,
• – oder zwei Substituenten R¹¹ aus verschiedenen Siloxyeinheiten bilden gemeinsam einen geradkettigen, verzweigten oder cyclischen Alkandiylrest mit 2 bis 12 Kohlenstoffatomen zwischen zwei Siliziumatomen,

mit der Maßgabe, dass mindestens ein Substituent R¹¹ je Molekül Stickstoff enthält, d.h einen stickstoffhaltigen Rest R¹¹ darstellt.The substituents R ¹¹ are preferably selected from the group consisting of:

• - Straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 200 carbon atoms, which optionally has one or more groups selected from -O-, -NR ² -, wherein R ^{2 is} hydrogen, a monovalent, straight-chain, cyclic or branched represents saturated, unsaturated or aromatic hydrocarbon radical having up to 100 carbon atoms, which may contain one or more groups selected from -O-, -NH-, -C (O) - and -C (S) -, and which may be replaced by a or several substituents selected from the group consisting of a hydroxyl group, an optionally substituted, preferably containing one or more nitrogen atoms heterocyclic group, amino, alkylamino, dialkylamino, ammonium, polyether radicals and polyetherester radicals, where if several groups -NR ² are present, these can be the same or different,
  
  -C (O) - and -C (S) -, and the radical may optionally be substituted by one or more substituents selected from hydroxy and in which R ¹ , m, m ₂ , as defined above, can be substituted,
  
• A polyether radical with up to 20,000 carbon atoms which can optionally carry one or more amino, mono- or dialkylamino or arylamino groups,
• An organic residue containing saccharide,
• - or two substituents R ¹¹ from different siloxy units together form a straight-chain, branched or cyclic alkanediyl radical with 2 to 12 carbon atoms between two silicon atoms,

with the proviso that at least one substituent R ¹¹ contains nitrogen per molecule, ie one containing nitrogen R ¹¹ represents.

R ¹¹ preferably represents alkyl, in particular methyl.

Preferred radicals R ¹¹ which have nitrogen are, for example:

Further preferred amino or ammonium group-containing radicals R ¹¹ are, for example:

Corresponding aminopolysiloxanes with such radicals R ¹¹ are disclosed in WO 02/10256, the disclosure content of which belongs to the present application.

The nitrogen-containing radical R ¹¹ is preferably aminopropyl or aminoethylaminopropyl. Further preferred nitrogen-containing radicals R ¹¹ are formed from the reaction of glycidyloxypropylsiloxanes with mono- or dialkylamines. Preferred compounds as component b2) are therefore, for example, aminopolysiloxanes which emerge from the reaction of epoxyalkylsiloxanes with ammonia, primary or secondary amines, such as those obtained from the reaction of glycidyloxypropylsiloxanes with mono- or dialkylamines. Preferred alkoxy radicals for R ¹¹ are methoxy, ethoxy, propoxy, isopropoxy, butoxy, hexyloxy and cyclohexyloxy.

mit v + w ≥ 1.Preferred polyether radicals having up to 20,000 carbon atoms, which may optionally carry one or more amino, mono- or dialkylamino or arylamino groups, for R ¹¹ include:

with v + w ≥ 1.

Examples of saccharide-containing organic radicals for R ¹¹ are:

If there are any additional Hydrophilizing groups are preferably those which derived from polyalkylene oxides and saccharides.

The production of such saccharide-containing polysiloxanes can be found, for example, in DE 4 318 536 . DE 4 318 537 ,

The average degree of polymerization the polysilox content of the aminopolysiloxanes used according to the invention b2), which results from Mn, is expediently from 1 to 3000, preferably at 200 to 1000.

The ratio of nitrogen free Polyorganosiloxane units to the nitrogen-containing polyorganosiloxane units in those used according to the invention Aminopolysiloxanes b2) expedient of 1: 1 to 500: 1.

The ratio of polyether or saccharide-containing Polyorganosiloxane units to the rest Polyorganosiloxane units can range from 0 to 1.

Solutions, mixtures, emulsions and microemulsions as the basis for cosmetic formulations

The connections described above b1) and b2) can as pure substance, solution, Mixture, emulsion or microemulsion in the form of liquids, Creams or pastes as raw materials for the production of suitable cosmetic according to the invention Formulations of different viscosities can be used.

• a) Herstellen einer Vormischung in Form von Lösungen, Mischungen oder Emulsionen aus den erfindungsmäßen Zusammensetzungen und
• b) Herstellung einer weiteren Mischung unter Verwendung der Vormischung a) sowie Zusatz gegebenenfalls weiterer Tenside, Hilfsstoffe und anderer Additive oder Zusammenfassen der Schritte a) und b), in dem man das Vermischen der Bestandteile mit Rührern, Dissolvern, Knetern, Pumpen, Mischschnecken, Mischdüsen, Nieder- und Hochdruckemulgiuergeräten durchführt.

The process for producing formulations for treating substrates consists of the steps

• a) preparing a premix in the form of solutions, mixtures or emulsions from the compositions according to the invention and
• b) Production of a further mixture using the premix a) and addition of further surfactants, auxiliaries and other additives, if appropriate, or combining steps a) and b), by mixing the constituents with stirrers, dissolvers, kneaders, pumps, mixing screws, Mixing nozzles, low and high pressure emulsifiers.

The procedures are the same as in the Technology (Ullmann's Encyclopedia) known machines and apparatus, such as. B. any form of stirrers in suitable containers, Apparatus or mixing devices, as previously described.

The direct mixing of all components is possible.

However, it will make one Pre-mix preferred because it is for faster and better distribution leads and partly inevitable is because the different groups of substances are otherwise not in mixed appropriately or only with great effort or can be emulsified or dispersed. Suitable premixes or intermediate mixes can preferably mixtures in the form of solutions, pastes, creams or other forms of emulsions or dispersions. Especially the production and use of microemulsions is preferred with 10 to 200 nm average particle diameter in cosmetic Formulations. The formulations according to the invention can be in different dosage forms for hair treatment become. The quaternary polysiloxane compounds b1) are preferred containing compositions as cosmetic formulations for Treatment of keratinous substrates such. B. human and animal Hair or skin as an alcoholic or polyalcoholic solution or as Emulsion applied. Depending on the raw materials used, Auxiliaries and the mixing process in the manufacture clear, cloudy and white Received formulations.

Compositions of the solutions, Premixes and blends. For the preparation of the solutions and Mixtures are preferably alcoholic and polyalcoholic solvent as well as their mixtures with water, oily substances and conventional silicones (including polydimethylsiloxanes). Particularly preferred solvents are ethanol, isopropanol, ethylene glycol and ethylene glycol ether, Polyethylene glycols and their ethers, propylene glycol and propylene glycol ether, Polypropylene glycols and their ethers and glycerin. Particularly preferred oil-like Substances are petroleum products as well as oils of vegetable, animal and synthetic origin. Especially preferred silicones are cyclic and linear polydimethylsiloxanes and their mixtures such. B. (according to INCI) cyclomethicones, cyclotetrasiloxanes, Cyclopentasiloxanes, cyclohexasiloxanes, dimethicones with a viscosity range from 0.65 to 60,000,000 mPas at 25 ° C and dimethiconol with one viscosity range from 10 to 60,000,000 mPas at 25 ° C, that do not fall under the definition of compounds b1) and b2) (see definition below).

Preferred solutions and mixtures have the following composition in% by weight: 0.1-99,9% Polyamino and / or polyammonium-polysiloxane copolymers b1) 0.1-99,9% Solvent and / or oil and / or silicone and or water

compositions of the emulsions

For the production of emulsions generally water and nonionic, cationic and amphoteric surfactants as well as surfactant mixtures. Emulsions can also be additives such as B. inorganic and organic acids, bases and buffers, salts, Thickeners, stabilizers for Emulsions such as B. "Xanthan Gum ", preservative, Foam stabilizers, defoamers and solvents such as B. alcohols (ethanol, isopropanol, ethylene glycol, polyethylene glycol, Propylene glycol, polypropylene glycol, glycol ether and glycerin and their mixtures) contain. additionally can the quaternary polysiloxanes according to the invention also serve as an emulsifier in the production of emulsions.

A preferred emulsion, preferably for the production of cosmetic formulations, consists of the following constituents in% by weight, but not limiting the invention: 10-50% Polyamino and / or polyammonium-polysiloxane copolymers b1) 1-35% surfactants 0-10% excipients 0-20% solvent to 100 supplemented by water

microemulsions

The production of microemulsions with a high active content of polya is particularly preferred mino- and / or polyammonium-polysiloxane copolymers b1), since, in addition to the possibility of producing clear cosmetic formulations, these additionally offer the advantage of simple process incorporation (“cold process”) into aqueous formulations. A preferred active content of quaternary polysiloxanes b1) in the emulsion is between 5 and 60%, 10-50% are particularly preferred.

A very particularly preferred microemulsion consists of the following, but not limiting, parts by weight of the invention: 20-50% Polyamino and / or polyammonium-polysiloxane copolymers b1) 10-35% surfactants 0-10% excipients 0-20% solvent to 100% supplemented by water.

Another object of the invention is the use of the polyamino and / or polyammonium polysiloxane copolymer according to the invention b1) prepared solutions, Mixtures or emulsions in a cosmetic formulation, which at least one of the quaternaries Contains silicone compounds.

These cosmetic formulations are made using the previously prepared solutions or Emulsions made, they can but can also be generated directly from the individual components.

cosmetic formulations

Cosmetic formulations include so-called "rinse-off" products such as 2-in-1 shampoos, body wash and hair conditioners for the treatment of hair while and after cleaning or after dyeing or treating Hair before bleaching, curling or frizzing, as well as so-called "leave-in" products such as hair treatments, Skin care creams, hairdressing creams, hair gels, hair styling products, hair fixatives, Hair sprays, pump sprays, blow dry agents and hair dryer. About that in addition, the formulations also include hair dyes, depending on the wash resistance of the color result obtained in 3 types - permanent, semi-permanent and temporary Hair dye - differentiated can be. The term hair includes all fibers containing keratin, especially human hair.

With the ingredients of the formulations a distinction is made between silicones, surfactants, auxiliaries and ingredients for hair dye. Each of these ingredients can be used alone or in combination can be used with other ingredients and stands for additional Functions in the formulations, which increase the volume, combability and the gloss and the reduction of the washout of the color colored by and out substrates containing keratin, e.g. human and animal Serve hair and contain at least one quaternary polysiloxane compound. Abbreviations are included in the INCI (The Cosmetic, Toiletry and Fragrance Association Washington DC or at http://www.cosmetic-world.com/inci/Incialf.htm ) explained.

Silicone conditioning agent

The silicones included here, except the polyamino and / or polyammonium-polysiloxane copolymers b1) and amino and / or Ammonium polysiloxane compound b2), are cyclic, linear and branched polydimethylsiloxanes with a viscosity of 0.65-200,000,000 mPa.s at 25 ° C as well their mixtures such as the Baysilone M oils (M5 to M 3,000,000) and SE 30 and SF 1214, SF 1236, SF 1276 and CF 1251 from GE Bayer Silicones, to understand.

Solid silicones are also suitable, so-called MQ resins, such as SR 1000 from GE Bayer Silicones and their solutions in solvents like the above-mentioned silicones and aliphatic solvents such as e.g. Isododecane.

Organofunctional ones are also suitable Silicones such as alkyl, aryl, arylalkyl, phenyl, fluoroalkyl, and Polyether-modified silicones such as types SF 1632, SF 1642, SF 1555, Baysilone CF 1301, Baysilone PK 20, FF 157, SF 1188A, SF 1288 and SF 1388 from GE Bayer Silicones.

surfactants

Surfactants as ingredients of cosmetic Formulations are described in A. Domsch: Die kosmetischen Preparations, Publisher for Chem. Industry, 4th edition, 1992, in the cosmetic yearbook 1995, publisher for chemical Industrie, 1995, and H. Stache, Tensid pocket book, 2nd edition, Carl Hanser Verlag, 1981.

Anionic surfactants:

The following anionic surfactants are suitable as part of the formulations by way of example but not by way of limitation:
Alkyl sulfates, alkyl ether sulfates, alkaryl sulfates, olefin sulfonates, alkyl amide ether sulfates, acyl isethionates, acyl glutamates, alkyl ether carboxylates, methyl taurides and taurides, sarcosides, sulfosuccinates, protein fatty acid condensates, alkyl phosphates and alkyl ether phosphates. The free acids and their alkali metal salts, magnesium, ammonium and mono-, di- and triethanolamine salts can be used here. The alkyl and acyl groups typically contain 8-18 C atoms and can be unsaturated. The alkyl ether sulfates, alkyl amide ether sulfates, alkyl ether carboxylates and alkyl ether phosphates can contain 1-10 ethylene oxide or propylene oxide or a combination of ethylene oxide and propylene oxide units.

Amphoteric surfactants:

The following amphoteric surfactants are suitable as part of the formulations, by way of example but not by way of limitation:
Alkyl betaines, alkyl amido betaines, sulfobetaines, acetates and diacetates, imidazolines, propionates and alkylamine oxides.

Contain the alkyl and acyl groups here 8-19 C-atoms.

Nonionic surfactants:

The following nonionic surfactants are suitable as part of the formulations, by way of example but not by way of limitation:
Alkyl ethoxylates, aryl ethoxylates, ethoxylated esters, polyglycolamides, polysorbates, glycerol fatty acid ethoxylates, alkylphenol polyglycol ethers and sugar surfactants such as alkyl glycosides.

Cationic surfactants:

A distinction is made with cationic surfactants between pure cationic surfactants and cationic polymers.

Pure cationic surfactants:

The following nonionic surfactants are suitable as part of the formulations, by way of example but not by way of limitation:
Monoalkyl quats, dialkyl quats, trialkyl quats, tetraalkyl quats, benzylammonium salts, pyridine salts, alkanolammonium salts, imidazoline salts, oxazoline salts, thiazoline salts, salts of amine oxides, sulfone salts.

Cationic polymers:

For 2-in-1 shampoos in particular, cationically modified polymers are used in addition to the pure cationic surfactants. Provide a comprehensive description of these polymers US 5,977,038 and WO 01-41720 A1. Cationic polyacrylamides, cationic protein derivatives, hydroxyalkyl cellulose ethers and cationic guar derivatives are preferred. Cationic guar derivatives with the CTFA name guar hydroxypropyltrimonium chloride are particularly preferred. These types are available under the trade names Cosmedia Guar C 261 (Henkel), Diagum P 5070 (Diamalt), Jaguar C types and Jaguar EXCEL from Rhodia.

excipients

Excipients as cosmetic ingredients Formulations are described in: A. Domsch, Die kosmetischen Preparations, Publisher for chem. Industry, 4th edition, 1992; and in: Cosmetics Yearbook 1995, Publisher for chemical Industry, 1995.

By way of example but not by way of limitation, the following auxiliary substances are suitable as part of the formulations:
Inorganic and organic acids, bases and buffers, salts, alcohols such as ethanol, isopropanol, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycol ethers and glycerin, thickeners, stabilizers for emulsions such as e.g. B. xanthan gum, refatting agents, preservatives, foam stabilizers, defoamers, pearlescent and opacifiers such as glycol distearates and titanium dioxide, collagen hydrolyzate, keratin hydrolyzate, silk hydrolyzate, anti-dandruff agents such as zinc pyrithione, salicylic acid, selenium disulfide, Sulfur and tar preparations, polymeric emulsifiers, vitamins, dyes, UV filters, bentonites, perfume oils, fragrances, styling polymers, moisturizers, plant extracts and other natural or nature-identical raw materials.

It is known that through the addition from oil and water soluble UV filters or combinations of UV filters in cosmetic formulations for the care and treatment of keratinous substrates such as human and animal hair the degradation of dyes and thus the fading and fading of colored substrates containing keratin significantly reduced by UV radiation or even entirely can be prevented.

Ingredients for hair dye

Dyes and other ingredients of hair dyes are described in: A. Domsch, The Cosmetic Preparations, Publisher for chem. Industrie, 4th edition, 1992. Dyes are described in: Ordinance on Cosmetics (Cosmetics Ordinance), Federal Law Gazette 1997, Part I p. 2412, § 3 and Appendix 3 and in European Community (EC) Directive, 76/68 / EEC, Annex IV.

The following are hair dyes a distinction is made between permanent, semi-permanent and temporary hair dye.

Permanent hair dye

Permanent staining which can also be done by several shampoos (more than 10) not washed out are caused by chemical Reaction between dye precursors under oxidative conditions through hydrogen peroxide. Here, the mixture of the corresponding determines Components the achievable color result.

A distinction is made between the preliminary products between oxidation bases (developer) and coupling components (modifier).

Oxidation bases:

The following oxidation bases are suitable as part of the formulations, by way of example but not by way of limitation:
m- and p-phenylenediamines (diaminobenzenes), their N-substituted derivatives and salts, N-substituted derivatives of o-phenylenediamine, o-, m- and p-toluenediamines (methyl-diaminobenzenes), their N-substituted derivatives and salts, p-aminodiphenylamine, hydrochloride and sulfate, o-, m- and p-aminophenol and hydrochloride, 2,4-diaminoisosulfate (4-methoxy-m-phenylenediamine sulfate), o-chloro-p-phenylenediamine sulfate, picramic acid (2, 4-dinitro-6-aminophenol) and 2,4-dinitro-1-naphtholsulfonic acid and their sodium salt.

Coupling components:

Exemplary but not limiting are the following coupling components as part of the formulations suitable: hydroquinone (1,4-dihydroxybenzene), resorcinol (1,3-dihydroxybenzene), Pyrocatechol (1,2-dihydroxybenzene), α-naphthol (1-hydroxynaphtaline), Pyrogallol (1,2,3-trihydroxybenzene) and 2,6-diaminopyridine.

Usually are oxidation bases and coupling components with surfactants in oil-in-water emulsions incorporated, but there are also simple solutions or shampoos as formulations known. The formulations also contain antioxidants such as e.g. Sodium sulfite, sodium dithionite, ascorbic acid or thioglycolic acid Stabilize the precursors and are made with alkaline substances such as. Ammonia to a pH between 8 and 12 (preferred 9-11) set. Moreover are surfactants as wetting agents, complexing agents for heavy metals, fragrances to cover the smell of ammonia, conditioner to improve the feeling on the hair and to protect the hair and solvents such as ethanol, ethylene glycol, glycerin or benzyl alcohol added.

Typically, permanent Hair Dye Offered as 2 component systems consisting of color solution and cream or shampoo described above and from the developer solution. The developer solution contains here between 6-12 % Hydrogen peroxide and can optionally with components of the the formulation containing color components are added. The peroxide must do this however carefully be stabilized.

Semi-permanent hair dye

Semi-permanent stains have been developed to stain for 6–10 washes with Sham to maintain poo. So-called direct dyes are used, which essentially belong to the group of nitro, azo and anthraquinone dyes. These dyes are small enough to penetrate the hair. Formulations typically used are solutions, creams, shampoos or aerosol foams. The composition is comparable to the formulations containing the color component, which are used as permanent hair colors.

Temporary hair dye

Temporary tints, also called tints, contain in contrast to the semi-permanent hair dye larger dye molecules that are unable to penetrate the hair. They were developed around the coloring for 1-6 washes upright to obtain. Azo and basic dyes are typically used here and, azine and thiazine derivatives used. The following applies to the composition of the formulations with semi-permanent and permanent hair dye said. Dyes and other ingredients in hair dyes are described in: A. Domsch, The Cosmetic Preparations, Publisher for chem. Industrie, 4th edition, 1992. Dyes are described in: Ordinance on Cosmetics (Cosmetics Ordinance), Federal Law Gazette 1997, Part I p. 2412, § 3 and Appendix 3 and in European Community (EC) Directive, 76/68 / EEC, Annex IV.

The following recipes were found to be particularly advantageous for the use of the mixtures containing polyamino and / or polyammonium polysiloxane copolymer b1) in the cosmetic formulations according to the invention:
A typical shampoo formulation according to the invention, but not limiting the invention, for the care and conditioning of hair consists of the following components in% by weight: 0.01-10% Ammonium or quaternary siloxane b1 2-15% Anionic surfactant 0-10% Amphoteric surfactant 0-15% Nonionic surfactant 0-10% Cationic surfactant 0-10% excipients to 100% supplemented by water.

A special shampoo formulation, which however does not limit the invention, consists of the following components in% by weight: 0.1–12% Polyamino and / or polyammonium polysiloxane copolymers b1) (43.5% emulsion in water with nonionic emulsifiers) 20-35% Sodium or ammonium lauryl or laureth sulfate (20-30%) 1-6% Cocoamidopropyl betaine (25-35%) 0-3% Guar hydroxypropyltrimonium chloride 0-5% Polyquaternium-10 0.01-1% Disodium EDTA 0.01-1% Phenoxyethynol (and) methylparaben (and) butylparaben (and) ethylparaben (and) propylparaben 0-1% Perfume 0-1% dyes 0-1% citric acid 0-2% sodium chloride to 100% supplemented by water.

A typical hair rinse according to the invention, but not limiting the invention, for the care and conditioning of hair consists of the following components in% by weight: 0.1-15% Ammonium or quaternary siloxane b1 0-10% Amphoteric surfactant 0.1-15% Nonionic surfactant 0-10% Cationic surfactant 0-20% excipients to 100% supplemented by water.

A special composition of a hair conditioner, but not limiting the invention, consists of the following components in% by weight: 0.5-15% Polyamino and / or polyammonium polysiloxane copolymers b1) (as a 43.5% emulsion in water with nonionic emulsifiers) 0-10% Cetrimonium chloride (25-35%) 0-3% Guar hydroxypropyltrimonium chloride 1-10% Cetearyl alcohol 0-10% glycerin 0.01-1% Phenoxyethynol (and) methylparaben (and) butylparaben (and) ethylparaben (and) propylparaben 0-1% Perfume 0-1% dyes 0-1% citric acid to 100% supplemented by water.

A typical hair care cure for the care and conditioning of hair according to the invention, but not limiting the invention, consists of the following components in% by weight: 0.4-20% Ammonium or quaternary siloxane b1) 0-15% Nonionic surfactant 0-10% Cationic surfactant 0-20% excipients to 100% supplemented by water.

A special hair care treatment, which does not limit the invention, consists of the following components in% by weight: 1–20% Polyamino and / or polyammonium polysiloxane copolymers b1) (as a 43.5% emulsion in water with nonionic emulsifiers) 0.5-10% Stearyl Alcohol (and) Steareth-7 (and) Steareth-10 0-10% Cetrimonium chloride (25 - 35%) 0-3% Guar hydroxypropyltrimonium chloride 0-5% Dimethicone 0-5% paraffin oil 1-10% Stearyl alcohol 0-10% glycerin 0.01-1% Phenoxyethynol (and) methylparaben (and) butylparaben (and) ethylparaben (and) propylparaben 0-1% Perfume 0-1% dyes 0-1% citric acid 0-2% sodium chloride to 100% supplemented by water.

A very special hair care treatment, which does not limit the invention, consists of the following components in% by weight: 2–5% Polyamino and / or polyammonium polysiloxane copolymers b1) (as a 43.5% emulsion in water with nonionic emulsifiers) 0-2% Cetrimonium chloride (25-35%) 0.5–5% glycerin 0.25-2.5% propylene glycol 0.05-0.2% Perfume 0.1-0.5% Polysorbate 20 to 100% supplemented by water.

A typical formulation according to the invention, but not limiting the invention, for temporary, semi-permanent or permanent hair coloring, care and conditioning of the hair consists of the following constituents in% by weight: 0.1-10% Polyamino and / or polyammonium polysiloxane copolymers b1) 1-10% Hair color precursors or dyes depending on the desired hair color 0-15% Anionic surfactant 0-10% Amphoteric surfactant 0-10% Nonionic surfactant 0-10% Cationic surfactant 0-1% sodium 0-5% buffer 0-10% excipients To 100% water

A special color cream according to the invention, but not limiting the invention, for permanent hair coloring consists of the following components in% by weight: 0.1-10% Polyamino and / or polyammonium polysiloxane copolymers b1) (as a 20% emulsion in water with nonionic emulsifiers) 1-5% Hair color precursors or dyes depending on the desired hair color 2-15% Anionic surfactant 0-10% Amphoteric surfactant 0-10% Nonionic surfactant 0-10% Cationic surfactant 0.1-1% sodium 0.1-5% Buffer for pH = 8 12 0-10% excipients To 100% water

A special color solution according to the invention, but not limiting the invention, for permanent hair coloring consists of the following components in% by weight: 0.1-10% Polyamino and / or polyammonium polysiloxane copolymers b1) (as a 20% emulsion in water with nonionic emulsifiers) 1-5% Hair color precursors or dyes depending on the desired hair color 0.1-1% sodium 5-15% propylene glycol 5–15% Ammonia (28%) 10-30% oleic acid 5-15% isopropanol 10-30% alkanolamide to 100% water

A typical developer formulation according to the invention but not limiting the invention permanent hair coloring consists of the following components in% by weight: 0.1-10% Polyamino and / or polyammonium polysiloxane copolymers b1) 10-30% Hydrogen peroxide (30%) 0-15% Anionic surfactant 0 - 10% Amphoteric surfactant 0-10% Nonionic surfactant 0-10% Cationic surfactant 0-5% Buffer or acid for pH = 2-6 0-10% excipients To 100% water

A special developer cream according to the invention, but not limiting the invention, for permanent hair coloring consists of the following components in% by weight: 0.1-5% Polyamino and / or polyammonium polysiloxane copolymers b1) (as a 20% emulsion in water with nonionic emulsifiers) 10-30% Hydrogen peroxide (30%) 1-10% Cetearyl alcohol 0.5-5% Trideceth-2 carboxamide MEA 0.5-5% Ceteareth-30 0.5-5% glycerin 0.05-2% Pentasodium pentetate (pentasodium diethylenetriaminepentaacetate 0.05-2% sodium stannate 0.05-2% tetrasodium pyrophosphate To 100% water

It was recognized that the solutions according to the invention or Mixtures preferably for the production of cosmetic formulations suitable, such as: treatment, conditioning, cleaning and / or Care colored or to be colored Substrates.

This means that the formulations containing at least one linear or branched polyamino and / or polyammonium polysiloxane copolymer b1) can be used in particular for the cleaning, care and conditioning of fibrous or flat substrates and if these are colored and their color impression is to be largely retained. Compounds b1) are preferred
the treatment conditioning, cleaning and maintenance of keratin-containing substrates, since they are used as cleaning agents for wool, for washing and / or increasing the volume and / or the combability and / or the gloss and / or for reducing the washout of the color from and from dyed or from substrates that are to be colored at the same time, such as human and animal hair, are suitable.
the treatment, cleaning and care of keratin fibers or hair before, during and / or after the dyeing process, since the hair dye formulated with it at the same time improves the softness and / or reduces the wet and dry combing forces and / or increases the gloss and / or to increase the volume of hair and / or to reduce the washing out of dyes from and from tinted and dyed hair.
the use as so-called "rinse-off" products, such as, for example, 2-in-1 shampoos, body wash and hair rinses for the aftertreatment of hair after cleaning or dyeing or the pretreatment of hair before bleaching, curling or uncrimping, and so-called "Leave-in" products, such as hair treatments, skin care creams, hairdressing creams, hair gels, hair styling products, hair fixatives, hair sprays, pump sprays, blow-drying agents or blow-drying agents.
the use of formulations which contain at least one polysiloxane compound b1), particularly preferably in permanent, semi-permanent and temporary hair colorants, since this enables the color result achieved to be colored and cared for, as well as washability.

Accordingly, they are suitable compositions according to the invention preferably compounds b1), in particular for treatment, cleaning and / or colored care or to be colored Substrates.

Examples

example 1

wie folgt synthetisiert.In analogy to Example 8 of WO 02/10257, a polymer of the structure

synthesized as follows.

• 1a) 211.1 g (0.15 mol epoxy groups) of an epoxysiloxane of average composition
  
  and 15.2 g (0.15 mol) of N-methylpiperazine were dissolved in 225 ml of i-propanol and heated to 90 ° C. for 4 hours. After the reaction has ended, the solvent is removed by distillation in a water jet vacuum and then in an oil pump vacuum. There are 217 g of a clear, yellowish product of the structure
  
  ¹³ C-NMR: substructure shift (ppm) -CH (OH) - 66.07 -CH (OH) -CH ₂ -N- 60.74 -CH (OH) -CH ₂ -N-CH ₂ - 53,20 -CH (OH) -CH ₂ -N-CH ₂ -CH ₂ - 55,10 CH ₃ -N = 45.87
• 1b) 250 g (0.554 mol OH groups) of a polyethylene glycol with an average molecular weight of 900 g / mol (approx. 20 ethylene oxide units) were placed under nitrogen at room temperature. 68.8 gg (0.61 mol) of chloroacetyl chloride were added dropwise with vigorous stirring over the course of 30 minutes. During the dropping, the temperature rose to 80 ° C and intensive HCl development began. After the dropping had ended, the mixture was heated to 110 ° C. for 60 minutes. Finally, all components boiling up to 110 ° C. and at 20 hPa were distilled off. There were 273 g of a colorless, viscous liquid of the medium composition ClCH ₂ C (O) O (CH ₂ CH ₂ O) ₂₀ C (O) CH ₂ Cl obtained, which crystallizes after several days.
• 1c) 75.4 g (25 · 10 ^-3 mol) of the α, ω-aminosiloxane according to Example 1 a) and 24.4 g (25 · 10 ^-3 mol) of the α, ω-chloroacetic acid ester according to Example 1 b) were dissolved under nitrogen in 300 ml of i-propanol dissolved and heated to reflux temperature for 11 hours. After the reaction had ended, all components boiling up to 40 ° C. at 20 hPa were removed. 99.2 g of an amber wax were obtained.
• 1d) 50 g of the compound according to the invention was with 29.7 g Renex 36 and 5.1 g Renex 30 (both available from Uniquema) and at 80 ° C touched. Subsequently a solution of 1.1 g of glacial acetic acid and 0.8 g of sodium acetate in 28.2 g of water was added dropwise with stirring at 50 ° C. After cooling down A clear, yellow microemulsion with a viscosity at 25 ° C. of 200 became room temperature Get mPas (Example 1). The emulsion was stable at 50 ° C and with Water dilutable in relation to 100 parts water to one part emulsion.

Example 2

• 2a) 238 g (2.24 mol) of diethylene glycol are placed under nitrogen at room temperature. 558 g (4.93 mol) of chloroacetyl chloride are added dropwise with vigorous stirring over the course of one hour. During the dropping, the temperature rises to 82 ° C and intensive HCl development begins. After the dropping has ended, the batch is heated to 130 ° C. for 30 minutes. Finally, all components boiling up to 130 ° C / 20hPa are distilled off. There are 566 g of a light yellow oil of the composition ClCH ₂ C (O) OCH ₂ CH ₂ OCH ₂ CH ₂ OC (O) CH ₂ Cl receive. The purity of the ester, determined by gas chromatography, is 99.2%. ¹³ C-NMR: substructure shift (ppm) Cl C H ₂ - 40.7 ClCH ₂ - C (O) - 167.1 ClCH ₂ -C (O) -O C H ₂ - 65.2 ClCH ₂ -C (O) -OCH ₂ C H ₂ - 68.6
• 2b) 18 g of water and 8.62 g (0.1 mol of tertiary amino groups) of N, N, N ', N'-tetramethyl-1,6-hexanediamine are placed in a 1 liter three-necked flask at room temperature. 36.0 g (0.09 mol) of dodecanoic acid in the form of a 50% solution in 2-propanol are added within 5 minutes. After the batch has been heated to 50 ° C., 194.7 g (0.09 mol epoxy groups) of an epoxysiloxane of the average composition are obtained within 30 minutes
  
  and 1.3 g (0.01 mol of alkyl halide groups) of the ester derivative according to 11a) in 22.5 ml of 2-propanol were added dropwise. The yellow, cloudy mixture is heated to reflux temperature for 6 hours. After removal of all components that are volatile up to 100 ° C / 2mmHg in vacuum, 210g of a yellow, cloudy material are obtained, which includes the following structural elements from the units QV. The ratio V2 / V1 is less than 1. The relationship shown should not be understood as limiting. For the sake of simplicity, no ratio formula or structural formula has been given:
  
  ¹³ C-NMR: substructure Shift (ppm) - C H (OH) -CH ₂ -N ⁺ [(CH _{3) 2]} -CH ₂ -CH ₂ - 65.3 -CH (OH) - C H ₂ -N ⁺ [(CH ₃ ) ₂ ] -CH ₂ -CH ₂ - 64.6 -CH (OH) -CH ₂ -N ⁺ [( C H ₃ ) ₂ ] -CH ₂ -CH ₂ - 53.1 / 53.3 -CH (OH) -CH ₂ -N ⁺ [(CH ₃ ) ₂ ] - C H ₂ -CH ₂ - 64.8 -CH (OH) -CH ₂ -N ⁺ [(CH ₃ ) ₂ ] -CH ₂ - C H ₂ - 23.4 -O- C (O) -CH ₂ -N ⁺ [( C H ₃ ) ₂ ] -CH ₂ -CH ₂ - 174.2 -OC (O) - C H ₂ -N ⁺ [( C H ₃ ) ₂ ] -CH ₂ -CH ₂ - 62.0 -OC (O) -CH ₂ -N ⁺ [( C H ₃ ) ₂ ] -CH ₂ -CH ₂ - 53.7
• 2c) 50 g of the compound according to the invention was made with 17.8 g Renex 36, 5.1 g Renex 30 (both available from Uniquema) and 8.3 g Crodet S 40 (available von Croda) and at 80 ° C touched. Subsequently a solution of 1.1 g of glacial acetic acid and 0.8 g of sodium acetate in 31.8 g of water were added dropwise with stirring at 50.degree. After cooling down A clear, yellow microemulsion with a viscosity at 25 ° C. of 200 became room temperature Get mPas (Example 1). The emulsion was stable at 50 ° C and with Water dilutable in relation to 100 parts water to one part emulsion.

Example 3

• 3a) In a 1 liter three-necked flask, 24 g of water and 4.18 g (0.048 mol of tertiary amino groups) N, N, N ', N'-tetramethyl-1,6-hexanediamine and 3.8 g (0.012 mol of primary amino groups) become one under the trade name Jeffamin ^® ED 600 available alkylene oxide derivatives of the structure H ₂ NCH (CH ₃ ) CH ₂ [OCH ₂ CH (CH ₃ )] _a (OCH ₂ CH ₂ ) ₉ [OCH ₂ CH (CH ₃ )] _b NH ₂ submitted with a + b = 3.6 at room temperature. 12.0 g (0.03 mol) of dodecanoic acid in the form of a 50% solution in 2-propanol and 1.8 g (0.03 mol) of acetic acid are added within 5 minutes. After the batch has been heated to 50 ° C., 194.1 g (0.06 mol epoxy groups) of an epoxysiloxane of the average composition are obtained within 30 minutes
  
  and 30 ml of 2-propanol were added dropwise. The yellow, cloudy mixture is heated to reflux temperature for 6 hours. After removal of all components volatile up to 100 ° C / 2mmHg in a vacuum, 204g of a colorless, cloudy material are obtained, which contains the following structural elements. The polymer contains different V1 groups in the ratio V2 / V1 equal to 1. The linkage shown should not be understood as limiting. For the sake of simplicity, no ratio formula or structural formula has been given:
  
• 3b) 50 g of the compound according to the invention was with 29.7 g Renex 36 and 5.1 g Renex 30 (both available from Uniquema) and at 80 ° C touched. Subsequently a solution of 1.1 g of glacial acetic acid and 0.8 g of sodium acetate in 28.2 g of water was added dropwise with stirring at 50 ° C. After cooling down A clear, yellow microemulsion with a viscosity at 25 ° C. of 5000 became room temperature Receive mPas. The emulsion was stable at 50 ° C and with Water dilutable in relation to 100 parts water to one part emulsion.

Example 4

• 4a) 49.33 g of 2-propanol, 3.1 g of water and 0.53 g (6.12 mmol of tertiary amino groups) N, N, N ', N'-tetramethyl-1,6-hexanediamine, 0.81 g (0.76 mmol primary amino groups) of a under the trade name Jeffamine ^® ED 2003 available alkylene oxide derivative of structure H ₂ NCH (CH ₃ ) CH ₂ [OCH ₂ CH (CH ₃ )] _a (OCH ₂ CH ₂ ) _38.7 [OCH ₂ CH (CH ₃ )] _b NH ₂ with a + b = 6
• 4b) 0.1 g of a 45% aqueous trimethylamine solution (0.76 mmol of tertiary amino groups), 0.76 g (3.82 mmol) of dodecanoic acid and 0.23 g (3.82 mmol) of acetic acid (3.82 mmol) initially at room temperature. After warming to 50 ° C 50g (7.64 mmol epoxy groups) of an epoxysiloxane of average composition within 15 minutes
  
  dropwise. The cloudy mixture is heated to reflux temperature for 9 hours. 101 g of a cloudy, two-phase material are obtained, which contains a silicone polymer, inter alia, with the following structural elements. The polymer contains different V1 groups in the ratio V2 / V1 not equal to 1. The linkage shown should not be understood as limiting. For the sake of simplification, only one ratio was used formula but no structural formula:
  
• 4c) 50 g of the compound according to the invention was with 29.7 g Renex 36 and 5.1 g Renex 30 (both available from Uniquema) and at 80 ° C touched. Subsequently a solution of 1.1 g of glacial acetic acid and 0.8 g of sodium acetate in 28.2 g of water was added dropwise with stirring at 50 ° C. After cooling down A clear, slightly yellow microemulsion was used at room temperature a viscosity at 25 ° C obtained from 20,000 mPas. The emulsion was stable at 50 ° C and with Water dilutable in relation to 100 parts water to one part emulsion.

Example 5

Making a shampoo

Tab. 1 Production of the shampoos to be tested

Kämmkraftmessungen were performed using a Diastron Combing Force Analyzer. For this For each example examined, a 5 g hair bundle of uncolored, naturally brown European Pre-washed hair with "Neutrogena" shampoo (pretreated = reserved) and then the wet combing force [combing force (wet, Neutrogena)] for every bundle of hair measured. Then the hair bundles with 2 g of the respective test formulation and a hair bundle with "Neutrogena" as reference (wet) for 30 seconds long washed for 1 minute with fluent Washed tap water. This was followed by the wet combing force [combing force (wet, Sample) or combing force (wet, Reference)] measured. After 24 hours Drying at room temperature, the dry combing forces were then measured. The hair bundle washed with "Neutrogena" was also used here Reference dried and measured for its dry combing force [combing force (dry, reference)] opposite to determine the only pretreated samples.

The reduction in the wet combing forces of the investigated examples was then calculated using the following formula, based on the hair bundle washed with “Neutrogena”: Wet combing force reduction,% = 1 - [combing force (wet, sample) / combing force (wet, neutrogena)]

The results of this investigation are shown in Table 2.

Table 2

The reduction in dry combing forces in the examples examined was then calculated using the following formula:

The results of this investigation are shown in Table 3.

Table 3

To measure the hair volume, the Diastron Combing Force Analyzer was equipped with a ring system with a diameter of 16 mm to measure the hair volume. The dry hair bundles were pulled through this ring system and the forces required for this were measured as a force (example). Example E was used here as a reference formulation and the relative volume of the examined example with the force (reference) measured for this reference was determined as follows: Relative volume = force (example) / force (reference)

The results of this investigation are shown in Table 4.

Table 4

Those treated with Formulations A, C and D. and dried hair bundles were about it also a panel consisting of 10 people for evaluation of feeling of volume and gloss. 7 test subjects preferred the feeling Formulation D and 3 Formulation C. Preferred by volume 8 Test subjects formulation C, 1 test subject formulation D and 1 test subject Formulation A. When evaluating the gloss of the submitted hair bundle preferred 6 subjects formulation C and 4 subjects formulation D.

The results clearly show that the use of the silicone quats according to the invention b1) leads to a clearly measurable reduction in wet and dry combing forces. Furthermore leads the Use of the polyamino and / or polyammonium polysiloxane compounds b1) to a measurable increase of hair volume and shine. The additional use of a cationic Polymers like guar hydroxypropyltrimonium chloride lead to one further improve the conditioning of the hair.

Example 6

manufacturing a hair conditioner

Tab. 5 Production of the hair rinses to be tested

The formulations were regarding the wet and dry combing forces as well of the volume examined as described in Example 5. The results are summarized in Table 6.

Table 6

The results clearly show that the use of the silicone quats according to the invention b1) to a clearly measurable Reduction of wet and leads to dry combing forces. Furthermore leads the Use of the silicone quats according to the invention to a measurable Increase in hair volume. A comparison of the hair bundles with the reference washed with "Neutrogena" Example 4 also shows an increase in gloss.

Example 7

Treatment of hair after the coloring

ermittelt. Die Referenzskala wurde durch unterschiedliche Einwirkzeiten (0, 2, 4, ...., 20 Minuten) der Brilliance Intensiv-Color-Creme – Intensvrot 872 – auf Strähnen der oben verwendeten naturblonden Haare hergestellt. Hierbei erhielt 0 Minuten Einwirkzeit den Zahlenwert 1, 2 Minuten den Wert 2 usw. bis 11 für 20 Minuten. Durch den Vergleich mit den vor den Wäschen erzielten Ergebnissen wurde der Wert für die Farberhaltung ermittelt. Gleichzeitig wurden die Testpersonen auch gebeten, die Weichheit der Haarsträhnen auf einer Skala von 1 bis 4 vor und nach den Haarwäschen zu beurteilen, wobei 4 die höchste und 1 die geringste Weichheit darstellt. Zur Ermittlung der relativen Weichheit der Haare wurde dann der Mittelwert aller Probanden bestimmt. Die Ergebnisse dieser Untersuchung sind in Tabelle 8 dargestellt.4 strands of natural blonde hair were dyed red with Poly Brilliance Intensive Color Cream - Intensvrot 872 - consisting of color cream and developer solution. For each tress, 2 g of color cream and 2 g of developer solution were mixed together by stirring. Each of the strands of hair was then dyed with this mixture according to the instructions for use for a contact time of 20 minutes. The locks of hair were then washed 20 times with the formulations listed in Table 7 and the color result by comparison against a reference scale by a 6-person panel Tab. 7 Shampoo formulations to be tested

determined. The reference scale was created by different exposure times (0, 2, 4, ...., 20 minutes) of the Brilliance Intensive Color Cream - Intensvrot 872 - on strands of the natural blonde hair used above. 0 minutes of exposure time were given the numerical value 1, 2 minutes the value 2 etc. to 11 for 20 minutes. The value for color preservation was determined by comparison with the results obtained before the washes. At the same time, the test subjects were also asked to rate the softness of the hair strands on a scale from 1 to 4 before and after washing the hair, 4 being the highest and 1 being the lowest. The mean value of all subjects was then determined to determine the relative softness of the hair. The results of this investigation are shown in Table 8.

Table 8

The results are shown in Table 8 that the use of the compounds b1) according to the invention in one Shampoo to a significant improvement in color retention while at the same time significantly higher Lead softness of hair.

Example 8

Treatment of hair before coloring

Table 9: Pump spray formulations to be tested

The formulations from Table 9 were in a pump sprayer filled and subsequently each formulation was controlled by 10 puffs on a natural blonde strand of hair applied. After drying, each strand of hair was with Poly Brilliance Intensive-Color-Creme - Intensvrot 872 - colored. This strands of hair were then with the example 7 shampoo formulation K described in Table 7 washed 20 times. Subsequently were the color result and the relative as described in Example 7 Softness determined. The results are described in Table 10.

Table 10

The results are shown in Table 10 clearly that the Use of the compounds according to the invention b1) in a pretreatment before dyeing hair to a clear one Improve color retention. Feel at the same time the hair feels soft.

Example 9

Treatment of hair during the coloring

Table 11: Developer formulations to be tested

The developer solution listed in Table 11 exists According to the package name, from the following ingredients (according to INCI): Aqua, Hydrogen Peroxide, Acrylates Copolymer, Editronic Acid, Sodium Laureth sulfate, 2,6-dicarboxypyridine, disodium pyrophosphate, Dimethicone.

2 g each of those described in Table 11 developer solutions were with 2 g of Brilliance Intensive Color Cream - Intensvrot 872 - color cream by stirring mixed. Then 6 strands natural blonde hair, each with a formulation as described in Example 7 colored. These strands of hair were then with the example 7 shampoo formulation K described in Table 7 washed 20 times. Subsequently were the color result of all and as described in Example 7 the relative softness of those treated with formulation S, V, W and X. strands of hair determined. The results are described in Table 12.

Table 12

The results in Table 12 clearly show that the use of the compounds of the invention gene b1) lead to a significant improvement in color retention in a dye formulation for dyeing hair. At the same time, the hair feels soft.

Claims (26)

Composition for the treatment of substrates, characterized in that they have at least one linear or branched polyamino and / or polyammonium polysiloxane copolymer b1) and optionally at least one amino and / or ammonium polysiloxane compound b2) with the repeating units of the formula (I) - [QV] - (I) contains, wherein Q is selected from the group consisting of: -NR-, -N ⁺ R ₂ - a saturated or unsaturated, diaminofunctional heterocycle of the formulas:

an aromatic, diamino-functional heterocycle of the formula:

a trivalent radical of the formula:

a trivalent radical of the formula:

a tetravalent radical of the formula,

wherein each R represents hydrogen or a monovalent organic radical, wherein Q does not bind directly to a carbonyl carbon atom, V is at least one component selected from the group consisting of V ¹ , V ² and V ³ , wherein V ^{2 is} selected from divalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals with up to 1000 carbon atoms (the carbon atoms of the polysiloxane radical Z ² defined below are not counted), which optionally one or more groups selected from -O-, -CONH -, -CONR ² -, in which R ^{2 represents} hydrogen, a monovalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 100 carbon atoms, which comprises one or more groups selected from -O-, - NH-, -C (O) - and -C (S) - can contain, and optionally by one or more substituents selected from Gr uppe, which consists of a hydroxyl group, an optionally substituted, preferably containing one or more nitrogen atoms, heterocyclic group, amino, alkylamino, dialkylamino, ammonium, polyether radicals and polyetherester radicals, which may be the same or different if there are several CONR ² groups , -C (O) - and -C (S) - may contain, the radical V ^{2 may} optionally be substituted by one or more hydroxyl groups, and the radical V ² at least one group -Z ² - of the formula

contains, wherein R ^{1 may be the} same or different and is selected from the group consisting of: C ₁ to C ₂₂ alkyl, fluoro (C ₁ -C ₁₀ ) alkyl and C ₆ -C ₁₀ aryl, and n ₁ = 20 up to 1000 means V ^{1 is} selected from divalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals with up to 1000 carbon atoms, which optionally have one or more groups selected from -O-, -CONH-, -CONR ² - , wherein R ^{2 is} as defined above, where the groups R ² in groups V ¹ and V ^{2 may be the} same or different, may contain -C (O) -, -C (S) - and -Z ¹ -, wherein -Z ¹ - a group of the formula

in which R ^{1 is} as defined above, where the groups R ¹ in groups V ¹ and V ^{2 may be the} same or different and n ₂ = 0 to 19, and the radical V ^{1 is} optionally substituted by one or more hydroxyl groups can be, and V ^{3 is} a trivalent or higher, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 1000 carbon atoms, which optionally has one or more groups selected from -O-, -CONH-, -CONR ² -, wherein R ^{2 is} as defined above, -C (O) -, -C (S) -, -Z ¹ -, which is as defined above, -Z ² - which is as defined above, and Z ³ , wherein Z ^{3 is} a trivalent or higher organopolysiloxane unit, and which may optionally be substituted by one or more hydroxyl groups, wherein in the polysiloxane compound mentioned one or more groups V ¹ , one or more groups V ² and / or one or more groups V ³ vorli with the proviso that - That said polysiloxane compound contains at least one group V ¹ , V ² or V ³ , which contains at least one group -Z ¹ -Z ² - or Z ³ , and - that the trivalent and tetravalent radicals Q either branching the Main chain formed from Q and V serve so that the valences that do not serve the bond in the main chain carry further branches formed from - [QV] units, or the trivalent and tetravalent residues Q saturate with residues V ³ within one linear main chain without branching, and wherein the positive charges resulting from ammonium groups are neutralized by organic or inorganic acid anions, and their acid addition salts. Compositions according to claim 1, characterized in that Q in the linear or branched polyamino and / or polyammonium polysiloxane copolymer b1) is selected from the group consisting of an amino unit of the formula an amino unit of the formula:

an ammonium unit of the formula:

a quaternized imidazole unit of the structure

a quaternized pyrazole unit of the structure

a double quaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a doubly quaternized unit of structure

a monoquaternized unit of the structure

a monoquaternized unit of the structure

a double quaternized unit of structure

a monoquaternized unit of the structure

a monoquaternized unit of the structure

wherein t is from 2 to 10, R ^{3 has} the meaning of R ² , where R ² and R ^{3 may be the} same or different, or R ² and R ³ together with the positively charged nitrogen atom form a five- to seven-membered heterocycle which optionally may additionally have one or more nitrogen, oxygen and / or sulfur atoms, R ⁵ , R ⁶ , R ^{7 may be the} same or different and are selected from the group consisting of: H, halogen, hydroxyl group, nitro group, cyano group , Thiol group, carboxyl group, alkyl group, monohydroxyalkyl group, polyhydroxyalkyl group, thioalkyl group, cyanoalkyl group, alkoxy group, acyl group, acetyloxy group, cycloalkyl group, aryl group, alkylaryl group, and groups of the type-NHR ^W , in which R ^W H, alkyl group, monohydroxyalkyl group, polyhydroxyalkyl group, acetogyl group, acetogyl group mean, and in each case two of the adjacent radicals R ⁵ , R ⁶ and R ⁷ with the aromatic atoms binding them to the heterocycle che five to seven rings can form, and R ^{8 has} the meaning of R ² , wherein R ⁸ and R ^{2 may be the} same or different. Compositions according to claim 1, characterized in that the group Q from a trivalent radical of the formulas

exists, these residues are not used for the branching of the polysiloxane copolymers, but these residues are exclusively connected to trivalent residues V ¹ or V ² , cyclic structures being formed which are part of the linear main chain, such as a structural element of the formula

and likewise the trivalent radicals V ¹ and V ² do not serve for the branching of the linear polysiloxane copolymers. Compositions according to claim 1, characterized in that the units V in the repeating units [QV] consist of units V ¹ which contain at least one esterified polyalkylene oxide structural unit of the general formulas: -AE-, -EA-, -AE-A 'and / or -A'-EA-, wherein A = -CH ₂ C (O) O-, -CH ₂ CH ₂ C (O) O-, -CH ₂ CH ₂ CH ₂ C (O) O-, -OC (O) CH ₂ -, -OC (O) CH ₂ -, -OC (O) CH ₂ CH ₂ - and / or -OC (O) CH ₂ CH ₂ CH ₂ - A '= -CH ₂ C (O ) -, -CH ₂ CH ₂ C (O) -, -CH ₂ CH ₂ CH ₂ C (O) -, -C (O) CH ₂ -, -C (O) CH ₂ -, -C (O) CH ₂ CH ₂ - and / or -C (O) CH ₂ CH ₂ CH ₂ - E = a polyalkylene oxide group of the general formulas: - [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r - and / or - [OCH (CH ₃ ) CH ₂ ] _r - [OCH ₂ CH ₂ ] _q - with q = 1 to 200, r = 0 to 200, the terminal oxygen atom of group A being attached to the terminal -CH ₂ - Group E group, and the terminal carbonyl carbon atom of group A 'to the terminal oxygen atom of group E each with the formation of ester groups, and / o the at least one terminal polyalkylene oxide structural unit of the formula -AER ² wherein A and E have the meaning given above, and R ² = H, straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which is interrupted by -O-, or -C (O) - and substituted by -OH and acetylenic , can be olefinic or aromatic, Compositions according to claim 1, characterized in that V ¹ consists of polyalkylene oxide units of the structures - [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -CH ₂ CH ₂ -, -CH (CH ₃ ) CH ₂ O [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -CH ₂ CH (CH ₃ ) - with mono-, di- or polyhydroxy-functional units, of the formulas -CH ₂ CH (OH) CH ₂ -, -CH ₂ CH (OH) (CH ₂ ) ₂ CH (OH) CH ₂ -, -CH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH ₂ -, -CH ₂ CH (OH) CH ₂ O- [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -CH ₂ CH (OH) CH ₂ - and in which the chain length of the polyether units is the indices q = 0 to 200, r = 0 to 200. Compositions according to claim 1, characterized in that the group V consists of the repeating units V2 and V1 or - [V ^{2 *} -Z ² -V ^{2 *} -Q] - and - [V ¹ -Q] - and the molar ratio V ² / V ^{1 has} the relationship V ² / V ¹ = 1. Compositions according to claim 1, characterized in that V ^{2 *} - is selected from groups of the formulas

R ² preferably represents: hydrogen, -CH ₃ , -CH ₂ CH ₃ , - (CH ₂ ) ₂ CH ₃ , - (CH ₂ ) ₃ CH ₃ , - (CH ₂ ) ₅ CH ₃ , -CH ₂ CH ₂ OH. Compositions according to claim 1, characterized in that the group V in the repeating units [QV] of the polyamino and / or polyammonium-polysiloxane copolymers b1) contain at least one group V ¹ and V ² and the groups V1 have different units V ¹ = Y and F. , the combination of which is represented by the formulas (II) and (III)

and wherein X = V ^{2 *} , F or Y = V ¹ and n = n ₁ , n ₂ , n ₃ , R ¹ , R ² , R ³ as defined above and the latter are preferably methyl. and Compositions according to claim 1, characterized in that the polyamino and / or polyammonium polysiloxane copolymers with the repeat units [-QV-] as chain end groups have tertiary or quaternary monoamines Q ^* or QR VR from the group of Q units, the group Q ^* binds to V ^{2 *} in formulas (IV) to (VII) to V ² via group X.

and wherein X = V ^{2 *} , F or Y = V ¹ and n = n ₁ , n ₂ , n ₃ , R ¹ , R ² , R ³ as defined above and the latter preferably Are methyl. Compositions according to claim 1, characterized in that the repeating units [-QV-] represent compounds of the formula QV ² or Q ^* V ² Q ^* according to the general formula (IX)

where M = V2 ^* and as defined above U is a divalent organic radical, preferably E, F, EA, AEA or a bond Z = Q ^* and is selected from r as defined in V ² = n ₁ , n ₂ or n ₃ and s = 1 to 24 and B ^{- is} an inorganic or organic anion, as defined above under A ^-

Compositions according to claims 1 to 9, characterized in that the group V2 from a group of the formula -V ^{2 *} -Z ² -V ^{2 *} - in which Z ² , as defined above, and V ^{2 * represents} a divalent straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 40 carbon atoms, which optionally has one or more groups selected from -O-, - CONH-, -CONR ² -, in which R ^{2 is} as defined above, may contain -C (O) - and -C (S) -, and the radical V ^{2 * may} optionally be substituted by one or more hydroxyl groups. Compositions according to claims 1 to 9, characterized in that the group V consists of the repeating units V ² and V ¹ or - [V ^{2 *} -Z ² -V ^{2 *} -Q] - and - [V ¹ -Q] - and have the ratio 1 <V ² / V ¹ <1000, 1 <V ² / V ¹ <100 or 1 <V ² / V ¹ <20. Compositions according to claims 1 to 9, characterized in that the group V consists of the repeating units V2 and V1 or - [V ^{2 *} -Z ² -V ^{2 *} -Q] - and - [V ¹ -Q] - and the molar Ratio of repeat units - [V ^{2 *} -Z ² -V ^{2 *} -Q] - to - [V ¹ -Q] - corresponding to the ratio V ² / V ¹ 0005 <V ² / V ¹ <1000, 0.005 <V ² / V ¹ <1 or 0.01 <V ² / V ¹ <1. Process for the preparation of formulations for Treatment of substrates consisting of the steps a) Manufacture a premix in the form of solutions, Mixtures or emulsions, from the compositions according to claim 1 to 13 and b) Preparation of a mixture using the premix a) and, if appropriate, further surfactants, auxiliaries and other additives or combining steps a) and b) characterized in that the mixing of the ingredients with stirrers, Dissolvers, kneaders, pumps, mixing screws, mixing nozzles, low and high pressure emulsifiers he follows. Compositions according to claims 1 to 14 consisting of the following parts by weight in% by weight: 10-50% Polyamino and / or polyammonium-polysiloxane copolymers b1) 1-35% surfactants 0-10% excipients 0-20% solvent to 100% supplemented by water A shampoo formulation according to claims 1 to 14 for the care and conditioning of the hair consisting of the following components in% by weight: 0.01-10% Ammonium or quaternary siloxane b1 2-15% Anionic surfactant 0-10 Amphoteric surfactant 0-15% Nonionic surfactant 0-10% Cationic surfactant 0-10% excipients to 100% supplemented by water. A hair rinse according to claims 1 to 14 for the care and conditioning of the hair consisting of the following ingredients in% by weight: 0.1-15% Ammonium or quaternary siloxane b1 0-10% Amphoteric surfactant 0.1-15% Nonionic surfactant 0-10% Cationic surfactant 0-20% excipients to 100% supplemented by water. A hair care cure according to claims 1 to 14 for the care and conditioning of the hair consisting of the following components in% by weight: 0.4-20% Ammonium or quaternary siloxane b1) 0-15% Nonionic surfactant 0-10% Cationic surfactant 0-20% excipients to 100% supplemented by water. A hair dye formulation according to claims 1 to 14 for temporary, semi-permanent or permanent hair dyeing, dyeing, care and conditioning of the hair consisting of the following ingredients in% by weight: 0.1-10% Ammonium or quaternary siloxane b1) 1-10% Hair color precursors or dyes depending on the desired hair color 0-15% Anionic surfactant 0-10 Amphoteric surfactant 0-10% Nonionic surfactant 0-10 Cationic surfactant 0-1% sodium 0-5% buffer 0-10% excipients to 100 supplemented by water. A developer formulation for permanent hair dyeing hair dyeing according to claims 1 to 14 for dyeing, maintaining and conditioning the hair, consisting of the following components in% by weight: 0.1-10% Ammonium or quaternary siloxane b1 10-30% Hydrogen peroxide (30%) 0-15% Anionic surfactant 0-10% Amphoteric surfactant 0-10% Nonionic surfactant 0-10% Cationic surfactant 0-5% Buffer or acid for pH = 2-6 0-10% excipients to 100% supplemented by water. Use of formulations according to claim 1 to 20 for treatment, conditioning, cleaning and / or care colored or to be colored Substrates. Use of formulations according to claim 1 to 20 for the treatment, conditioning, cleaning and care of keratin Substrates. Use of formulations according to claim 1 to 20 for the treatment, cleaning and care of keratin fibers or hair before, during and / or after the dyeing process. Use of the formulations according to claim 1 to 20 for the production of so-called "rinse-often" products, such as 2-in-1 shampoos, Body wash and hair rinses for the aftertreatment of hair after cleaning or dyeing or the pretreatment of hair before the equation, the curl or straightening, as well as so-called "leave-in" products, such as hair treatments, Skin care creams, hairdressing creams, hair gels, hair styling products, hair fixatives, Hair sprays, pump sprays, blow dry agents or hair dryers. Use of formulations according to claim 1 to 20 to improve softness and / or decrease the wet and dry combing forces and / or to increase of gloss and / or to increase hair volume and / or to reduce dye washout tinted from and / or colored Hair. Use of formulations containing at least a polysiloxane compound according to claims 1 to 20 in permanent, semi-permanent and temporary hair dye.