WO2004069137A2 - Use of polyamino and/or polyammonium-polysiloxane copolymers - Google Patents

Abstract

The invention relates to the use of linear or cross-linked polyamino and/or polyammonium-polysiloxane copolymers comprising repeater units of formula (I): -[Q-V]- in the production and/or treatment of dyed hair in addition to compositions for the production and/or treatment of dyed hair.

Description

Use of polyamino and / or polyammonium polysiloxane copolymers

The invention relates to the use of linear or branched polyamino and / or polyammonium polysiloxane copolymers in the production and / or treatment of colored hair and compositions for the production and / or treatment of colored hair.

The invention relates in particular to the use of at least one polyamino and / or polyammonium polysiloxane copolymer (silicone quat) in various, preferably cosmetic formulations, in particular for the treatment of substrates containing keratin, such as human and animal hair, their cleaning and care with so-called rinse-off products, such as shampoos and hair rinses and with so-called leave-in products such as lotions, gels, pump sprays and aerosol sprays in the manufacture and / or treatment of colored hair. Specifically, these are formulations that reduce the washing out of dyes from tinted or dyed hair. Another object of the invention is the use of a cosmetic formulation which contains at least one of the quaternary siloxanes 'Silikoπquats' to improve the conditioning of hair at the same time, to reduce the wet and dry combing forces of the hair, to increase the volume and to improve the shine of hair. In addition, other dyed keratin and non-keratin fibers can be treated with these formulations in order to reduce washout of dyes during washing and cleaning and at the same time to produce a pleasant handle.

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 the hair shine and the reduction of electrostatic charge on the treated hair. In general, the substrate is made hydrophobic.

An improved hydrophilicity of the finished substrate can e.g. can be achieved if alkylene oxide structures are introduced into the molecules.

For this purpose, branched (US 5,602,224) and also comb-like structures have been synthesized (US 5,098,979, US 5,153,294, US 5,166,297), which lead to similar properties to those mentioned above. However, the work mentioned above does not contain any information on how to reduce the washout of colors from tinted or colored hair using quaternary silicone compounds. US 6,007,801 describes the use of an acid amide-modified silicone in a cosmetic formulation and its production. 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 to reduce the washout of color from colored hair while at the same time improving the 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

Haarkonditioπierungsmittein. Preferred embodiments are here amino functional silicones and silicone resins (INCI: trimethylsiloxysilicate). Here, their color-retaining properties are described (INCI: trimethylsilylamodimethicone and amodimethicone). The abbreviations are used in INCI (The Cosmetic, Toiletry and Fragraπce

5 Associatioπ Washington DC) explained.

GB 2138845 describes the use of laterally amino-functionalized silicones and their derivatives in hair colorants. An intensification of the color result of the hair coloring is described. A statement about the color-preserving effect of such

10 No wording is made here.

The amino or ammonmium-functional siloxanes mentioned here have contiguous siloxane bonds in the main chain, as are given, for example, in the following definition for the compounds ι ₅ b2) which are not interrupted by other units in the main chain. This limits the possibility of adapting the solubility properties, hydrophilicity and the interaction with the substrate and the altered substrate properties that can be achieved thereby.

20

No. 6,432,145 describes a hair colorant which contains, inter alia, 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.

2 ₅

It has surprisingly been found that polyamino and / or polyammonium-polysiloxane copolymers are 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 30 3340 708 and the unpublished DE 102 12470.1, DE 102 51 525.5 and DE 102 51 526.3 advantageous for formulations for care, conditioning and treatment, cleaning and care colored or to coloring substrates preferably keratin-containing substrates such. B. human and animal hair.

Also suitable are the di- and polyquaternatedπ siloxane systems with the inclusion of amino acid segments, which are known from DE 100 36 522 and DE 100 36 532.

Surprisingly, it was found that using these compounds, in addition to excellent softness, an increase in volume, combability and gloss can be achieved. 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.

15

The present invention relates to polyamino and / or polyammonium polysiloxane compounds according to the definition of component b1) of claim 1, in particular compounds according to WO 02/10256, WO 02/10257, WO 02/10259 and DE-OS 100 36

20 533, DE-OS 100 36 522, DE-OS 100 36 532, EP 282720, US 6,240,929, DE-OS 33 40 708 and the unpublished DE 102 12470.1, DE 102 51 525.5 and 102 51 526.3, in solutions, mixtures, Incorporate or transfer emulsions and microemulsions such as fluids, pastes, creams with a high active content. These solutions,

Mixtures, emulsions and microemulsions in turn facilitate the production of cosmetic formulations according to the invention and additionally increase their storage stability.

The invention also relates to the manufacture and use of

30 formulations for reducing the washout of the color from and from colored or to be colored substrates, the reduction of the

Wash out the color from and from colored substrates simultaneous increase in volume, combability and gloss, 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 micro-emulsions. The substrates are preferably colored keratin-containing substrates such as. B. human and animal hair.

Another object of the present invention was to incorporate these compounds directly into formulations for hair tinting, hair coloring or two-component formulations - color solution and developer solution - oxidative hair colors, which can be used during the coloring process in addition to excellent softness, volume, to increase the combability and the shine, and to wash out the color from and from colored or to be colored substrates containing keratin, such as e.g. B. to significantly reduce human and animal hair without compromising the stability of the formulation i.e. To influence storage stability and the color result negatively.

The present invention relates to the use of at least one linear or branched polyamino and / or polyammonium polysiloxane copolymer b1) with the repeating units of the formula (I):

- [Q-V] - (i)

where Q is selected from the group consisting of:

-NO-,

a saturated or unsaturated, diaminofunctional heterocycle of the formulas:

-N N -

, such as

an aromatic, diamino-functional heterocycle of the formula:

10

a trivalent radical of the formula:

/

-

a trivalent radical of the formula:

^R , or

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,

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 having up to 1000 carbon atoms (the carbon atoms of the polysiloxane radical Z ² defined below not being counted), which optionally one or more groups selected from

-O-,

-CONR ² -,

wherein R ^{2 is} hydrogen, a monovalent, straight chain, cyclic or branched, saturated, unsaturated or aromatic

Represents 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 - CONR ² are present, these can be the same or different,

-C (O) - and -C (S) -

may contain and

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: Ci to C22 alkyl, fluoro (G.-Cιo) alkyl and C ₆ -Cια aryl, and ni = 20 to 1000,

V ^{1 is} selected from divalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals with up to 1000 carbon atoms, optionally one or more groups selected from -O-,

-CONR ² -, wherein R ^{2 is} as defined above, the groups R ² in the

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 in groups V ¹ and V ^{2 can be the} same or different, and n ₂ = 0 to 19,

and the radical V ^{1 may} optionally be substituted by one or more hydroxyl groups, and

V ^{3 represents} a trivalent or higher-chain, 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 , where Z ^{3 is} a trivalent or higher organopolysiloxane unit,

may contain, 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 ,

- That said polysiloxane compound contains at least one group -Z ¹ -, -Z ² - or Z ³ , and - that the trivalent and tetravalent radicals Q either the

Branching of the main chain formed from Q and V serve 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 branching, and in which the positive charges resulting from ammonium groups are neutralized by organic or inorganic acid anions, and their acid addition salts, and optionally at least one amino and / or ammonium polysiloxane compound b2) in the preparation and / or treatment of colored hair. - u

Q in the linear or branched polyamino and / or polyammonium polysiloxane copolymer b1) is preferably selected from the group consisting of: an amino unit of the formula:

R2

-N-

an ammonium unit of the formula:

R ²

-t- R ^{3 of} a quaternized imidazoleiπheit 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

R2

-N Λ i

10 a double quaternized unit of the structure

15 a monoquaternized unit of the structure

a monoquaternized unit of the structure

a doubly quaternized unit of structure

10 a monoquaternized unit of the structure

a monoquaternized unit of the structure

-N K-

I (CH ₂ ) t

R2_ _I ! _r _ R3

where t is from 2 to 10, R ^{2 is} as defined above,

R ^{3 has} the meaning of R ² , where R ² and R ^{3 can 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 also has one or more nitrogen, Can have 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, mono-hydroxyalkyl group, polyhydroxy alkyl group, thioalkyl group, cyano-alkyl 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, acetyl group, Mean ureido group, and in each case two of the adjacent radicals R ⁵ , R ⁶ and R ⁷ with which they can form aromatic five- to seven-membered rings to the heterocycle, and R ^{8 has} the meaning of R ² , where R ⁸ and R ^{2 are the} same or can be different.

In a preferred embodiment, the group Q consists of trivalent radicals of the formulas

or or a tetravalent radical, and these radicals do not serve for the branching of the polysiloxane copolymers, but they are exclusively connected to trivalent radicals V ³ , cyclic structures being formed which are part of the linear main chain. Likewise in this case, the trivalent radicals V ³ do not serve to branch the linear polysiloxane copolymers. Cyclic structures which are formed and are part of the linear main chain are, for example, those of the formula:

In a preferred use of the invention, the units V in the repeating units [QV] contain units V ¹ which contain at least one esterified polyalkylene oxide structural unit of the general formulas:

-A-E-, -E-A-, -A-E-A'- and / or -A'-E-A-

have wherein

A = -CH ₂ C (0) 0-, -CH ₂ CH ₂ C (0) 0-, -CH ₂ CH ₂ CH ₂ C (0) 0-,

-OC (0) CH ₂ -, -OC (0) CH ₂ -, -OC (0) CH ₂ CH ₂ - and / or -OC (0) CH ₂ CH ₂ CH ₂ - A '= -CH ₂ C (0) -, -CH ₂ CH ₂ C (0) -, -CH ₂ CH ₂ CH ₂ C (0) -, -C (0) CH ₂ -, -C (0) CH ₂ -, -C ( 0) CH ₂ CH ₂ - and / or -C (0) CH ₂ CH ₂ CH ₂ -

E = a polyalkylene oxide group of the general formulas: - [CH ₂ CH ₂ 0] _q - [CH ₂ CH (CH ₃ ) 0] _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 bind to the terminal -GH ₂ group of group E, and the terminal carbonyl carbon atom of group A 'to the terminal oxygen atom of group E, each with the formation of ester groups.

In a further embodiment of the use according to the invention, the units V in the repeating units contain [QVj units V ¹ , which are selected from:

- [CH ₂ CH ₂ 0] _q - [CH ₂ CH (CH ₃ ) 0] _r CH ₂ CH ₂ -, -CH (CH ₃ ) CH ₂ 0 [CH ₂ CH ₂ 0] _q - [CH ₂ CH ( CH3) 0] rCH2CH (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 -, -CH ₂ CH (OH) CH ₂ O- [CH ₂ CH ₂ 0] _q - [CH ₂ CH (CH ₃ ) 0] r and

-CH ₂ CH (0H) CH ₂ - and wherein q = 0 to 200, r = 0 to 200.

In a further preferred use according to the invention, the groups V consist of the repeating units V ² and V ¹ , and the molar ratio V ² / V ¹ is from 0.0005 to 1000, more preferably from 0.01 to 100, even more preferably from 0 , 1 to 10 more preferably from 0.8 to 1, 2. In a further preferred use according to the invention, the groups V consist of the repeating units V ² and V ¹ , and the molar ratio V ² / V ¹ is 1.

In a further preferred use according to the invention there are at least two different groups V ¹ .

In a further preferred use according to the invention, V ^{2 is} a group of the formula -V ² * -Z -V ² *, in which Z ^{2 is} as defined above and V ² * is selected from divalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals with up to 40 carbon atoms, optionally one or more groups selected from

-O-,

-CONR ² -, in which R ^{2 is} as defined above, can contain -C (O) - and -C (S) -,

and the radical V ² * can optionally be substituted by one or more hydroxyl groups.

In a further preferred use according to the invention, V ^{2 * is} selected from groups of the formulas

• (CH ₂ ) 3θCH2CHCH2- - (CH ₂ ) 3θCH ₂ CH-

CH ₂ OH

-CΕbCΗ .- / V

In a further preferred use according to the invention, group V in the repeating units [QV] of the polyamino and / or polyammonium polysiloxane copolymers b1) consists of repeating units of the formulas (II) and (III): (II):

wherein: the radicals R are identical or different and are as defined above, and R preferably has the meaning of R ² , n, n1 as defined above, or n2 as defined above, preferably n = n1 = 20 to 1000

A = organic or inorganic acid anions,

V ² * is as defined above, V ^{1 is} as defined above,

V ¹ 'has the meaning of V ¹ as defined above, but V ¹ ≠

V ¹ ', where the nitrogen atoms in the formula (II) can optionally be protonated.

In a further preferred use according to the invention, V ^{1 is} selected from residues of the formulas: - [CH ₂ CH ₂ 0] _q - [CH ₂ CH (CH ₃ ) 0] _r CH ₂ CH ₂ -, -CH (CH ₃ ) CH ₂ 0 [CH ₂ CH ₂ 0] _q - [CH ₂ CH ( CH ₃ ) 0] _r CH ₂ CH (CH ₃ ) -, -CH ₂ CH (CH ₃ ) 0 [CH ₂ CH ₂ 0] _q - [CH ₂ CH (CH ₃ ) 0] rCH (CH ₃ ) CH ₂ -, -CH (CH ₃ ) CH ₂ 0 [CH ₂ CH ₂ 0] _q - [CH ₂ CH (CH ₃ ) 0] _r CH (CH ₃ ) CH ₂ -, where q = 0 to 200, r = 0 up to 200

and V ¹ 'is selected from C1-C8-alkylene radicals and (C1-C8-alkyl) aryl (C1-C8-alkyl) radicals.

In a further preferred use according to the invention, the polyamino and / or polyammonium-polysiloxane copolymers b1) with the repeating units - [Q-Vj- as chain end groups have a group of the formula -QR or -VR, in which R is as defined above ,

In a further preferred use according to the invention, the polyamino and / or polyammonium-polysiloxane copolymers b1) which have the end groups -Q-R are selected from the following formulas (IV) to (VIII):

(IV) (V)

(VI) (VII)

wherein: the radicals R are the same or different and are as defined above, and

R preferably has the meaning of R ² , n is as defined above and is preferably n1,

A = organic or inorganic acid anions

V ² * is as defined above,

V ^{1 is} as defined above,

V ¹ 'has the meaning of V ¹ as defined above, but V ¹ ≠

V ¹ ', where the nitrogen atoms can optionally be protonated,

R

- NR I (VIII) R in which the radicals R are as defined above and can be the same or different, and R is preferably selected from radicals R ² .

In a further preferred use according to the invention, the linear or branched polyamino and / or polyammonium polysiloxane copolymer b1) have the formula RQV ² -QR, where R, Q and V ^{2 are} as defined above.

The linear or branched polyamino and / or polyammonium polysiloxane copolymer b1) of the formula RQV ² -QR preferably have the following formula:

wherein R, Q, n, V ² * are as defined above.

In a further preferred use according to the invention, the following additional components are optionally used in a mixture with component b1) and optional component b2): one or more nitrogen-free polysiloxane compounds a) (co-adjuvants), one or more silicone-free surfactants c ), - one or more coacervate phase images d), and one or more carrier substances e).

In a further preferred use according to the invention, the compositions defined above are used for temporary, semi-permanent or permanent hair coloring, for tinting and / or for the care and conditioning of colored hair.

In a further preferred use according to the invention, this comprises the following steps: a) producing a premix by mixing at least one component b1) with one or more components selected from b2), a), c), d) and e) to form solutions, mixtures or emulsions and b) preparation of a composition for the preparation and / or treatment of colored hair by mixing the

Premixing a) and, if appropriate, further surfactants, auxiliaries and other additives or combining steps a) and b), in which the constituents are mixed with stirrers, dissolvers, kneaders, pumps, mixing screws, mixing nozzles and / or low and high-pressure emulsifiers. In a further preferred use according to the invention, the premix mentioned has the following composition:

10 - 50 wt .-% polyamino and / or polyammonium

Polysiloxane copolymers b1)

1 - 35% surfactants

0 - 10% auxiliary substances

0 - 20% solvent to 100% supplemented by water

Component b1) used according to the invention is at least one polyamino and / or polyammonium polysiloxane compound. The polyamino and / or polyammonium polysiloxane compound b1) is a copolymer compound which has amino and / or ammonium repeating units and polysiloxane repeating units in the polymer main chain. The amino units Q expediently contain secondary and / or tertiary nitrogen atoms (2 or 3 organic radicals on the neutral nitrogen atom). The ammonium units expediently contain secondary, tertiary and / or quaternary positively charged nitrogen atoms (2, 3 or 4 organic radicals on the nitrogen). Amino and / or ammonium repeating units can also serve as heterocyclic radicals integrated into the polymer chain via two nitrogen atoms.

In contrast to this, component b2) is polysiloxane compounds which contain amino and / or ammonium groups in the side groups of the main polyorganosiloxane chain. That is, the amino and / or ammonium groups are not in the main chain of polyorganosiloxane repeat units. The difference can be illustrated as follows:

Polyamino and / or polyammonium polysiloxane compound b1): - Amino / Ammonium - f-polyorganosiloxane - Amino / Ammonium- rP yorganosiloxane

Amino and / or ammonium polysiloxane compound b2):

- polyorganosiloxane chain

Amino / ammonium containing residue

Components b1) and b2) can be present alone or together in the application according to the invention. In a preferred embodiment, however, component b1) is present alone, without component b2) in the formulation according to the invention. In a likewise preferred embodiment, both component b1) and component b2) are present side by side.

Components b1) or b2) can be present together in any ratio to one another.

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

R ^{3 of} a quaternized imidazole unit of the structure

a quaternized pyrazole unit of the structure

wherein RR ^J , R ^ö , R ^b , R 'and R ^{ö are} as defined above.

In further preferred embodiments, R ² furthermore preferably stands for:

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

In further preferred embodiments, ni = 20 to 1000, particularly preferably 20 to 300, especially 20 to 200. In a further preferred embodiment, ni is between 20 and 50, 50 to 80 or between 80 and 200. The number ni is the average degree of polymerization from M "of the diorganosiloxy units in group Z ² .

In a further preferred embodiment of the use according to the invention, the units V ^{2 are} selected from a group of the formula

-V ² * -Z ² -V ² * -, in which Z ^{2 is} as defined above and V ² * is a divalent straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 40 carbon atoms, which may be one or more Groups selected from -O-, -CONH-, -CONR ² -, in which R ^{2 is} as defined above, and -C (O) - and -C (S) -, and the radical V ^{2 *} optionally by one or more hydroxyl groups can be substituted.

In the embodiment mentioned above, the branched or linear polysiloxane copolymer b1) used according to the invention can have the following repeating units:

-tV 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 ι ₆ hydrocarbon radical or aromatic C ₈ to C ₂ o hydrocarbon radical, which optionally contains 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.

Is particularly preferred V 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 , -C (O) -, -C (S) - may contain and may be substituted with one or more hydroxyl groups. V ^{2 * is} more preferably selected from groups of the formulas:

- (CH ₂ ) ₃ 0CH ₂ CHCH ₂ - - (CH ₂ ) ₃ 0CH ₂ CH-

OH CH ₂ 0H

- (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ -,

-CH = CHCH ₂ -, -CH = CHCH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ OC (0) CH ₂ -, -CH ₂ CH ₂ CH ₂ OC (0) CH ₂ CH ₂ -,

-CH = CHCH ₂ OC (0) CH ₂ -, -CH = CHCH ₂ 0C (0) CH ₂ CH ₂ -,

CH3 -CH2CH2CH2 (OCH ₂ CH ₂ ) v (OCH2CH) _w OC (0) CH2-

CH3 -CH ₂ CH2CH2 (OCH2CH2) v (OCH2CH) _w OC (0) CH2CH2-

CH3 -CH = CHCH2 (OCH2CH2) v (OCH2CH) _w OC (0) CH2-

CH3 -CH = CHCH2 (OCH2CH2) v (OCH2CH) _w OC (0) CH2CH2-

CH3 -CH = CHCH2CH2 (OCH2CH2) v (OCH2CH) _w OC (0) CH2-

CH3 -CH = CHCH2CH2 (OCH2CH2) v (OCH2CH) _w OC (0) CH2CH2-

CH3 - (CH2) 10C (O) (OCH2CH2) v (OCH ₂ CH) _w OC (O) CH2CH2-

CH3 - (CH2) 10C (O) (OCH2CH2) _v (OCH ₂ CH) _w OC (O) CH2- with v + w ≥ 0,

R ² preferably represents: H,

-CH _3> -CH ₂ CH ₃ , - (CH ₂ ) ₂ CH ₃ , - (CH ₂ ) ₃ CH ₃ , - (CH ₂ ) sCH ₃ , -CH ₂ CH ₂ OH,

H H

-CH2CH2l c-R4 -CH2CH2CH2NC-R4

With

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

mean. The group Z ³ represents a three- or higher-order organopolysiloxane unit. The branching unit V ³ can be constructed without silicon, ie without Z ³ . Examples of these include:

with v + w ≥ 0.

The branching unit V ³ can contain a trivalent or higher organopolysiloxane unit Z ³ , for example:

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 formula (I) the molar ratio of the groups V ¹ and V ² in the polysiloxane compounds b1) V ² / V ^{1 can} in itself assume any value. According to the invention, the case is also included in which the polysiloxane compound of the formula (I) contains only V ² units, the polysiloxane compound b1) thus 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 formula (I) contains both V ² and V ¹ units. In group -Z ¹ -

R ^{1 is} as defined above and n ₂ means 0 to 19, 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 the group Z ¹ .

In a further embodiment of b1), V ¹ preferably stands for

■ -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 ) uC (O) O - [(CH ₂ CH ₂ O) _q - (CH ₂ CH (CH ₃ ) 0) _r ] -C (O) (CH ₂ ) _u -

- (CH ₂ ) _u C (0) 0-R ⁹ -0-C (0) (CH ₂ ) _u -, wherein R ^{9 is} as previously defined,

- (CH ₂ ) _u -R ⁰ - (CH ₂ ) u-, in which R ^{10 is} an aromatic group,

- [CH ₂ CH ₂ 0] _q - [CH ₂ CH (CH ₃ ) 0] _r CH ₂ CH ₂ -,

-CH (CH ₃ ) CH ₂ 0 [CH ₂ CH ₂ 0] _q - [CH ₂ CH (CH ₃ ) 0] _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 - uπd

-CH ₂ CH (OH) CH ₂ 0- [CH ₂ CH ₂ 0] _q - [CH ₂ CH (CH ₃ ) 0] _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.

Preferred variants of V ¹ are structures of the formula:

-CH ₂ C (O) 0- [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) 0] _r C (0) CH ₂ -,

-CH ₂ CH ₂ C (0) 0- [CH ₂ CH ₂ 0] _q - [CH ₂ CH (CH ₃ ) 0] _I -C (0) CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ C (0) 0- [CH ₂ CH ₂ 0] _q - [CH ₂ CH (CH3) 0] C (0) CH ₂ CH ₂ CH2, esterified alkylene, alkenylene, alkynylene units, especially the structures -CH ₂ C ( O) 0- [CH ₂ ] ₀ -OC (0) CH ₂ -, -CH ₂ CH ₂ C (O) O- [CH ₂ ] ₀ -0C (O) CH ₂ CH ₂ -,

-CH ₂ CH2CH2C (0) 0- [CH ₂ ] ₀ -OC (0) CH ₂ CH ₂ CH ₂ - -CH ₂ C (0) 0-CH ₂ C≡CCH ₂ -OC (0) CH ₂ -, -CH ₂ CH ₂ C (0) 0-CH ₂ C≡CCH ₂ -OC (0) CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ C (0) 0-CH ₂ C≡CCH ₂ -OC ( 0) CH ₂ CH ₂ CH ₂ -, -CH ₂ C (0) 0-CH ₂ CH = CHCH ₂ -OC (0) CH ₂ -,

-CH ₂ CH ₂ C (0) 0-CH ₂ CH = CHCH ₂ -OC (0) CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ C (0) 0-CH ₂ CH = CHCH ₂ -OC ( 0) CH ₂ CH ₂ CH ₂ -,

further variants of V1 are alkylene, alkenylene, alkynylene and aryl units, especially the structures:

- [CHzjo- 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:

In another particularly preferred embodiment, V ^{1 is} selected from polyalkylenotide units of the structures

- [CH ₂ CH ₂ 0] _q - [CH ₂ CH (CH ₃ ) 0] _r CH ₂ CH ₂ -, -CH (CH ₃ ) CH ₂ 0 [CH ₂ CH ₂ 0] _q - [CH ₂ CH (CH ₃ ) 0] rCH ₂ CH (CH ₃ ) - with mono-, di- or polyhydroxy-functional units, 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 0- [CH ₂ CH ₂ θ] _q - [CH ₂ CH (CH ₃ ) 0] _r CH ₂ CH (OH) CH ₂ - and in which the chain lengths of the polyether units are the indices

q = 0 to 200 and r = 0 to 200.

Q = 1 to 50, in particular 2 to 50, especially 1 to 20, very particularly 1 to 10, and 1 or 2, r = 0 to 100, in particular 0 to 50, especially 0 to 20, very particularly 0 to 10, are preferred , as well as 0 or 1 or 2.

It is particularly preferred that ¹ different groups V ¹ coexist in the units V in a molecule, keitseigenschaften the solubility and be able to adjust the hydrophilicity of the treated substrate selectively.

The polyamino and / or polyammonium polysiioxane compounds b1) which, for. B. are 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 in principle also be used.

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

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

Compounds b1) in which the R ¹ = methyl are preferred.

The polysiloxanes of component b1) can be produced, for example, by a process as described in the prior art mentioned above, in particular in which

a) at least one amine compound selected from a diamine compound and / or a primary or secondary monoamine compound with at least two difunctional, for

Reaction with the amino functions of the Amiπ compound capable organic compounds are implemented, the molar ratio of the organic compounds being chosen so that the desired ratio V ² Λt ^{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, 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 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 further difunctional organic compound capable of reacting with the amino functions of the amine compounds is reacted, c) an amine compound selected from a diamine compound and / or primary or secondary monoamine compound, with a difunctional organic compound capable of reacting with the amino functions of the amino compounds is reacted 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, d) 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 compound to form a difunctional compound 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 further compound capable of reacting with amino functions ird, in which case monofunctional, preferably tertiary monoamines or suitable monoamines and / or monofunctional compounds which are not capable of chain propagation and / or which are capable of reacting with amino functions can be added as chain terminators, and the stoichiometry of the amino functions and of the functional groups capable of reacting with amino functions in the functional groups 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 organic compounds is selected so that the desired ratio V ² / V ^{1 is} satisfied, for example <0.5, can be represented schematically, for example, as follows:

- [NN] - + -rV ¹ ] - + -rV ² ] - → - [Q- (V ¹ , V ² )] - or

- [Nj- + -r ¹ ] - + -r ² ] - → - [Q- (v ¹ , v ² ) i-

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 * -Z ² -V ² * -N] - may include, the latter resulting in two Q units and one V ¹ and two V ² units , and - [V ¹ ] - and - [V ² ] - are intended to represent monomers corresponding to the repeat units V ¹ and V ² , and - [N] - is a primary or secondary monoamine suitable for chain propagation,

At least one higher-alkylated amine or quaternary ammonium unit Q is formed from the - [NN] - and / or - [N] units, secondary or tertiary amino functions formed in the polymerization optionally after the polymerization in a separate one Step can be protonated or quaternized. The formation of quaternary ammonium units is preferred.

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, such as Polyethers such as Jeffamine, etc.

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

Preferred examples of - [N] - are, for example, dimethylamine, as described in more detail below. The use of diamines - [NN] - is preferred per se.

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

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

Variant b) can be carried out with diamines, - [N-N] - as well as suitable monoamines - [N] - and can be represented schematically, for example, as follows:

Variant b1)

Step 1): 2 - [NN] - + - [V ² ] - or- [V 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.

With regard to the preferred monomer units - [NN] -, - [V ¹ ] - and -r ² ] - that applies to step a).

Variant b2)

Step 1): 2 - [NJ- + - [V ² ] - or - [V ¹ ] - → - [NVN] - 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 represented schematically, for example, as follows:

Variant d)

Step 1): - [NN] - + - [V ¹ ] - → - [NN- (V ¹ -NN) χ] - Step 2): - [NN- (V ¹ -NN) J- + - [V ² ] - → with regard to the preferred monomer units - [NN] -, -ry ¹ ] - and -ry ² ] - what has been said for step a) applies.

Variant c2) Step 1): - [N] - + - [V ¹ ] - → - [N- (V ¹ -N) „] - Step 2): - [N- (V ¹ -N) χ] - + - [V ² ] - → with respect to the preferred monomer units - [N] ~, - [V ¹ ] - and - [V ² ] - what has been said for step a) applies.

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

Variant d1)

Step 1): - [V ¹ ] - + - [NN] - → -ry ¹ - (NNV ¹ ) J- Step 2): - [^ - (NNV ¹ ) *] - + - [V ² ] - + - [N] - or - [NN] - → with respect to the preferred monomer units - [NN] -, -ry ¹ ] - and - [V ² ] - what has been said for step a) applies.

Variant d2)

Step 1): - [V ¹ ] - + - [N] - -> - [V ¹ - (NV ¹ ), j- Step 2): -ry ¹ - (NV ¹ ), J- + - [V ² ] - + - [N] - or - [NN] - -> with respect to the preferred monomer units used - [N] -, - [NN] -, -ry ¹ ] - and -ry ² ] - what has been said for step a) applies. For all the variants shown schematically above, mixtures of monoamines - [N] - and diamines - [NN] - can also be used.

The functional groups of the difunctional compounds capable of reacting with amino functions are particularly preferably selected from the group consisting of epoxy groups and haloalkyl groups. The starting point for the syntheses of the polysiloxane copolymers b1) used according to the invention are α, ω-Si-H-functionalized siliconoxanes of the general structure

preferred, wherein R ^{1 has} the meaning given above and n, depending on the desired repeating unit, is V ¹ or V ² , n ₂ or ni, 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 initially bind unsaturated structures bearing tertiary amino functions, for example N, N-dimethylallylamine, by hydrosilylation directly to the siloxane in the α.ω position. This process is generally known (B. Marciniec, Comprehensive Handbook on Hydrosilylation, Pergamon Press, Oj Ford 1992, pp. 122-124).

On the other hand, it is preferred to first generate reactive α, ω-functionalized intermediates by hydrosilylation, which subsequently follows in α, ω-ditertiary amino structures or can be converted directly into the quaternary ammonium structures according to the invention. Suitable starting materials for the production of reactive intermediates are, for example, halogenated alkenes or alkanes, especially allyl chloride, allyl bromide, chlorpropine and chlorobutin, unsaturated halocarboxylic acid esters, especially chloroacetic acid allyl esters, chloroacetic acid propargyl esters, 3-chloropropionic acid allyl esters and 3-chloropropylpropylene acid propylene acid, epoxy allyl epoxyhexylpropoxy acid propylene oxyphenyl propylene acid and epoxy-allyl epoxy propylene acid, glycidyl ether. The general implementation of hydrosilylation with representatives of the groups of substances 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-methylgiucamine, cyclic secondary amines, for example morpholine and piperidine, aminoamides which carry secondary amino functions, for example the reaction products of diethylene triamine or dipropylenetriamine with lactones, such as -Butyrolactone, 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.

Particularly suitable as partners for the epoxy derivatives used in one embodiment are the secondary-tertiary diamines mentioned, and also imidazole and pyrazole. In this way, the alkylations can be directed regioselectively and without additional effort to the nitrogen atoms carrying hydrogen atoms. To ensure a quantitative conversion of the reactive groups into tertiary amino structures, the amines are used in a ratio of 1 Σ Σ secondary amino groups: reactive groups 10 10, preferably 1 to 3, especially 1 to 2, very particularly 1. Excess amine may need to be removed.

The attachment of the ω-di-tertiary aminosiloxanes described above to monomer units corresponding to V ¹ - [V ¹ ] - or a prepolymer unit - [V ¹ - (QV ¹ ) J- leads to the formation of further higher alkylated amino units or quarterπaren 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 ) χ] -, which is combined with the α, ω-ditertiary 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 ) χ] - 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) χ] - 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, jV ¹ ] -, selected for example from bisepoxides, epichlorohydin, bishalogenalkyl compounds, can be used. It goes without saying that 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 -ry ¹ - (QV ¹ ) χ] -, a direct link to the amine function of the α, ω-ditertiary aminosiloxane structure can be made without any further 'linker', since an excess of the V ¹ generating component was used.

As an alternative to the separate production of a precondensate -ry ¹ - (QV ¹ ) χ] -, highly charged blocks can be built up parallel to the incorporation in the copolymer. This means that the α, ω-ditertiary aminosiloxane with the starting components for building up - [V ¹ - (QV ¹ ) χ] -, 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-ditertiary aminosiloxane with long-chain siloxane unit Z ² or short-chain siloxane unit Z ¹ or the α, ω-difunctional siloxane - [NN ² * -Z ² -V * -N] - or - [NV ¹ -N] - in the components presented to build -ry ¹ - (QV ¹ ) χ] - gradually dose 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) -] - 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 ) _> J- together and then to react them. Finally, it is possible to gradually dose the reactive intermediates into the components presented to build -ry ¹ - (QV ¹ ) χ] - 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 of whether amino units first terminate the siloxane or the prepolymer, the overall stoichiometry is chosen such that the sum of the amino functions and the groups reactive with them is approximately 1: 1 is.

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 intended length of the highly charged, hydrophilic block -ry ¹ - (QV ¹ ) χ] - 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 0] _q - [CH ₂ CH (CH ₃ ) 0] _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 oligoethylβn-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 alkyl oxides of the general composition

HO [CH ₂ CH ₂ 0] _q - [CH ₂ CH (CH ₃ ) 0] _r H

where q and r have the meanings given above, for example accessible by chlorination of the hydroxyl groups with SOCI ₂ (Orgaπikum, Organic Chemistry Basic Internship, 17th Edition, VEB German Publishing House of Sciences, 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-1,3-bis-glycidyl ether and diethylene glycol diglycidyl ether and neopentyl glycol diglycidyl ether.

If not commercially available, the desired diepoxides can be synthesized, for example, by reaction of the corresponding diols with 1-chloro-2,3-epoxypropane 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 in} the chain length range π 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 (monohalogen carboxylic 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 alkylation of tertiary amino groups. The choice of suitable amines as starting components for the formation of Q in the repeat unit -ry ¹ - (QV ¹ ) χ] - also determines the molecular structure to a large extent. The use of di-tertiary amines (corresponding to - [NN] -), for example N, N, N ', N'-

Tetramethylethylenediamiπ, N, N, N ', N'-tetramethyltetramethylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, N, N'-dimethylpiperazine, leads to products in which each nitrogen atom of the repeating unit is quaternized.

The use of secondary-tertiary diamines, for example N-methylpiperazine, opens the way to repeat units - [V ¹ - (QV ¹ ) J-, 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. In principle, the alkylations can also be set to degrees of quaternization of on average less than one quaternary ammonium group per repeating unit -ry ¹ - (QV ¹ ) J-. 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 use repeating units -ry ¹ - (QN ¹ ))!] - 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 are quaternized in a final reaction to - [V ¹ - (QV ¹ ) χ] - can. 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 esters, epoxy derivatives in the presence of H ⁺ and dialkyl sulfates, especially dimethyl sulfate.

In a preferred embodiment, non-commercially available secondary amines are prepared starting from the corresponding diprimary amines, for example hexamethylenediamine, by alkylation with epoxides, such as, for example, ethylene oxide, propylene oxide, isopropylglycidyl ether, using the different reaction rates of primary and secondary amines. It had already been shown that within the scope of the invention it is possible to introduce siloxane chains Z ¹ into the structure of V ¹ . The reactive intermediates α, ω-diepoxides and α, ω-bis (moπohalogenecarboxylic acid) esters were named as examples of suitable starting materials.

The quaternization reactions are preferably carried out in water, polar organic solvents or mixtures of the two components mentioned. 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 ethers of the glycols mentioned, 1, 2-propylene glycol and 1, 3-propylene glycol, Ketoπe, 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, such as nitromethane. The choice of solvent depends essentially on the solubility of the reactants, the desired reaction temperature and any reactivity that may interfere with the reaction.

The reactions are carried out in the range from 20 ° C. to 130 ° C., preferably 40 ° C. to 100 ° C. In order to avoid the formation of gel-like, not completely soluble, linear polyorganosiloxane polymers, the molecular weight is expediently limited.

Limitation of the molecular weight is brought about by the end stop which arises during the reaction between epoxides and any water or alcohol present in the reaction system, or alternatively by the additional use of tertiary amines, such as trialkylamines or monofunctional compounds which are reactive towards amino groups. That is, the polyorganosiloxane polymers can, in addition to the terminal groups naturally resulting from the reaction of the monomeric starting materials, also from monofunctional chain terminators, such as trialkylamines etc. and e.g. resulting ammonium, amino, ether or hydroxy end groups. All cases of end stop Q * are intended to be covered by the definition -Q-R and / or -V-R 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 bearing primary and / or secondary and / or tertiary amino groups in the side groups, in which the amino groups optionally protonated or quaternized, and which may optionally contain additional hydrophilic groups. 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 bound both to the difunctional, trifunctional or monofunctional end groups and can 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.

The aminopolysiloxanes b2) mentioned are linear or branched polysiloxanes which are composed of siloxy units which are selected from the group consisting of:

-O

(Q) (T) (D) (M)

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

R ^{11 contains} at least one nitrogen atom.

The substituents R ¹¹ are preferably selected from the group consisting of: straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical with up to 200

Carbon atoms, optionally one or more groups selected from -O-, -NR ² -, where R ^{2 is} as defined above,

- -

-C (O) - and -C (S) - can contain

and the remainder optionally by one or more 10 substituents selected from hydroxy,

wherein R ¹ and m are as defined above, a polyether radical having up to 20,000 carbon atoms, the

can optionally carry one or more amino, mono- or 15 dialkylamino, or arylamino groups, a saccharide-containing organic radical, or two substituents R ¹¹ from different siloxy units together form a straight-chain, branched or cyclic alkanediyl radical having 2 to 12 20 carbon atoms between two silicon atoms, with the proviso that at least one substituent R ¹ contains nitrogen per molecule, ie represents a nitrogen-containing radical R ¹¹ . R ¹ is preferably alkyl, in particular methyl.

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

OH

-CH ₂ CH ₂ CH ₂ NH ₂ -CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ -CH ₂ CH ₂ CH ₂ OCH2CHCH ₂ NH ₂

OH OH

-CH ₂ CH2CH2θCH ₂ CHCH ₂ NHCH ₂ CH ₂ NH ₂ -CH2CH2CH ₂ OCH ₂ CHCH ₂ NHCH ₂ CH ₂ CH2NH ₂

OH OH

-CH ₂ CH ₂ CH2θCH ₂ CHCH ₂ N N-CH ₃ -CH ₂ CH ₂ CH ₂ OCH2CHCH ₂ NO

OH CH ₂ CH ₂ N (CH ₃ ) ₂ OH CH ₂ CH ₂ CH ₂ N (CH3) ₂

-CH ₂ CH ₂ CH ₂ OCH ₂ CHCH ₂ N -CH ₂ CH ₂ CH2θCH ₂ CHCH ₂

CH ₂ CH ₂ N (CH ₃ ) 2 CH2CH ₂ CH ₂ N (CH ₃ ) ₂

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 result 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. Preferred polyether radicals having up to 20,000 carbon atoms, which can optionally carry one or more amino, mono- or dialkylamino or arylamino groups, for R ¹ include, for example:

CH3 -CH2CH2CH ₂ (OCH2CH2) v (OCH ₂ CH) _w OH

CH3 -CH2CH2CH2 (OCH ₂ CH2) v (OCH2CH) _w OC (0) CH3

CH3 -CH2CH ₂ CH2 (OCH2CH2) v (OCH2CH) _w OCH3

CH3 -CH = CHCH2 (OCH2CH2) _v (OCH2CH) _w OH

CH3 -CH = CHCH2 (OCH2CH2) v (OCH2CH) _w OC (0) CH3

CH3 -CH = CHCH2 (OCH2CH) _V (OCH2CH) _W OCH3

CH3 -CH = CHCH2CH2 (OCH2CH2) v (OCH2CH) _w OH

CH3 -CH = CHCH2CH2 (OCH2CH2) v (OCH2 <H) _w OC (0) CH3

CH3 -CH = CHCH2CH2 (OCH2CH ₂ ) _v (OCH2CH) _w OCH3

CH3

CH = CCH2 (OCH2CH ₂ ) v (OCH2CH) _w OC (0) CH3 CH3

CH2 (OCH2CH ₂ ) _v (OCH2CH) _w OC (0) CH3

with v + w ≥ 1.

Examples of saccharide-containing organic radicals for R are:

The additional hydrophilizing groups which may be present are preferably those which are derived from polyalkylene oxides and saccharides.

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

The average degree of polymerization of the polysilox content of the aminopolysiloxanes b2) used according to the invention, which results from Mn, is advantageously from 1 to 3000, preferably from 200 to 1000. The ratio of the nitrogen-free polyorganosiloxane units to the nitrogen-containing polyorganosiloxane units in the aminopolysiloxanes b2) used according to the invention is advantageously from 1: 1 to 500: 1.

The ratio of the polyether- or saccharide-containing polyorganosiloxane units to the other polyorganosiloxane units can be from 0 to 1.

Solutions. Mixtures. Emulsions and microemulsions as the basis for cosmetic formulations

The compounds b1) and b2) described above can be used as a pure substance, solution, mixture, emulsion or microemulsion in the form of liquids, creams or pastes as a starting material for the production of suitable cosmetic formulations of different viscosities used in accordance with the invention. To distinguish them from the compounds b1) and b2), the silicones are also called co-adjuvants or silicones of category 2) under conditioning agents, which are known from the prior art.

The process for the production of formulations for the treatment of substrates expediently consists of the steps: a) preparation of 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 any further Teπside.Hilfsstoffe and other additives or combining steps a) and b), in which the mixing of

Components with stirrers, dissolvers, kneaders, pumps,

Mixing screw, mixing nozzles, low and high pressure emulsifiers. The processes are carried out using machines and apparatus known in the art (Ullmann ^'s encyclopedia), such as, for. B. any form of Rührerπ in suitable containers, apparatus or mixing devices, as described above, realized.

The direct mixing of all components is possible. However, it is preferred to prepare a premix because it leads to faster and better distribution and is in part inevitable because otherwise the different groups of substances cannot be mixed or emulsified or dispersed with one another in a suitable manner or only with great effort. Suitable premixes or intermediate mixtures can preferably be mixtures in the form of solutions, pastes, creams or other forms of emulsions or dispersions. The production and use of microemulsions with an average particle diameter of 10 to 200 nm in cosmetic formulations is particularly preferred. The formulations according to the invention can be prepared in various dosage forms for hair treatment. The compositions containing quaternary polysiloxane compounds b1) are preferred as cosmetic formulations for the treatment of keratin-containing substrates, such as, for. B. human and animal hair or skin applied as an alcoholic or polyalcoholic solution or as an emulsion. Depending on the raw materials, auxiliary materials and the mixing process used in the production, clear, cloudy and white formulations are obtained.

Composition of the solutions. Premixes and mixtures. Alcoholic and polyalcoholic solvents and their mixtures with water, oil-like substances as carriers e) and conventional silicones (including polydimethylsiloxanes), the latter as nitrogen-free polysiloxane compound a), are preferably suitable for producing the solutions and mixtures used according to the invention. Especially preferred solvents as carriers e) are ethanol, isopropanoi, 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 as carriers e) are mineral oil products and oils of vegetable, animal and synthetic origin. Particularly preferred silicones as component a) are cyclic and linear polydimethylsiloxanes and their mixtures such as, for. B. (INCI) Cyclomethicone, cyclotetra- siloxane, Cyclopentasiloxane, Cyclohexasiloxaπe, Dimethicone with a viscosity range of 0.65 to 60,000,000 mPas at 25 ^Q C and dimethiconol having a 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

Water and non-ionic, cationic and amphoteric silicone-free surfactants as well as surfactant mixtures according to component c) are generally used to prepare emulsions. In addition, emulsions can contain adjuvants such as e.g. B. inorganic and organic acids, bases and buffers, salts, thickeners, stabilizers for emulsions such as ∑. B. ^' xanthan gum ^" , preservatives, foam stabilizers, defoamers and solvents such as alcohols (ethanol, isopropanoi, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycol ether and glycerol and mixtures thereof) The quaternary polysiloxanes according to the invention can also serve as emulsifiers in the preparation of emulsions.

Furthermore, it is also possible to use the quaternary polysiloxanes according to the invention in the preparation of emulsions in the form of the solutions and mixtures described above. A preferred emulsion preferred for the production of cosmetic

Formulations in the manufacture and / or treatment of colored hair contain the following components in% by weight:

10 - 50% polyamino and / or polyammonium polysiloxane copolymers b1)

1 - - 35% surfactants

0 - • 10% auxiliary substances

00 - • 2200 %% solvent to 100% supplemented by water.

microemulsions

The production of microemulsions with a high active content of polyamino and / or polyammonium-polysiloxane copolymers b1) is particularly preferred since, in addition to the possibility of producing clear cosmetic formulations, these also have the advantage of simple process incorporation (“cold process”) It is possible to use the quaternary polysiloxanes according to the invention in the preparation of microemulsions in the form of the solutions and mixtures described above. A preferred active content of quaternary polysiloxanes b1) in the emulsion is between 5 and 60%, particularly preferably are 10-50%.

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% auxiliary substances

0 - 20% solvent to 100% supplemented by water.

Cosmetic formulations here include so-called “rinse-off” products such as, for example, 2-in-1 shampoos, body wash and hair rinses for treating hair during and after cleaning or after dyeing or treating hair before bleaching or curling or uncrimping, 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-drying agents and blow-drying agents. In addition, the formulations also include hair colorants, which can be divided into 3 types - permanent, semi-permanent and temporary hair colorants - depending on the wash resistance of the color result obtained. The term hair includes all fibers containing keratin, but especially human hair.

In addition to components b1) and b2), a distinction is made between the ingredients of the formulations, amino- and ammonium group-free silicones, silicone-free surfactants, auxiliary substances such as coacervate formers and carriers, and ingredients for hair colorants. Each of these ingredients can be used either alone or in combination with other ingredients and stands for additional functions in the formulations, which increase the volume, combability and gloss and reduce the washout of the color from and from colored keratin-containing substrates such as human and animal hair and contain at least one quaternary polysiloxane compound. The abbreviations are explained in the INCI (The Cosmetic, Toiletry and Fragrance Association Washington DC or at http: //www.cosrT.etic- world.com/inci /iπcialf.htm).

Silicone conditioning agents (co-adjuvants

The silicones encompassed here according to component a) are cyclic, linear and branched polydimethylsiloxanes with a viscosity of 0.65-200,000,000 mPa.s at 25 ° C. and also mixtures thereof, such as, for example, octaorganocyclotetrasiloxanes, octamethylcyclotetrasiloxanes, deca-organocyclopentasiloxanes, organodasiloxanes, and dodecaorganocyclines, with dodecaorganocyclocycles being preferred Methyl means, such as SF 1173, SF 1202, SF 1217, SF 1204 and SF 1258 from GE Bayer Silicones, dimethicones such as the Baysilone M oils (M3 to M 2,000,000), SE 30, SF 1214, SF 1236, SF 1276 and CF 1251 from GE Bayer Silicones and Dimethiconole such as Baysilone Abhesive ZWTR / OH from GE Bayer Silicones and DC 1501 and DC 1503 from Dow Corning. The use of the polydimethylsiloxanes described above in the form of non-ionic, anionic and cationic emulsions such as SM 2169, SM 2785, SM 555, SM 2167 and SM 2112 from GE Bayer Silicones in combination with emulsions of the polyamino and / or polyammonium polysiloxane copolymers b1) and amino and / or ammonium polysiloxane compounds b2) and / or the use of mixtures and solutions of the above-described poly-dimethylsiloxanes (co-adjuvants) of category 2 with the polyamino and / or polyammonium polysiloxane copolymers b1 according to the invention ) and amino and / or ammonium polysiloxane compounds b2) is particularly preferred here, since these combinations can be used to derive special properties of hair care products, as has been described extensively in the literature for previously known amino-functional silicone (WO 99/44565 , WO 99/44567, WO 99/49836, WO 99/53889, WO 97/12594, US 6,028,031, EP 0811371, WO 98/18443, WO 98/43599 and US Application 20020182161).

Organofunctional 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, are also suitable. SF 1188A, SF 1288 and SF 1388 from GE Bayer Silicones.

Surfactants Silicon-free surfactants according to component c) as ingredients of cosmetic formulations are described in A. Domsch: Die kosmetische Preparate, Verlag für Chem. Industrie, 4th edition, 1992, in the Cosmetics Yearbook 1995, Verlag für chemischen Industrie, 1995, and H. Stäch, Tensid pocket book, 2nd edition, Carl Hanser Verlag, 1981. They include:

Anionic surfactants:

The following anionic surfactants are suitable, by way of example but not by way of limitation, as a constituent of the formulations: 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 and protein ether phosphates, protein 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.

The alkyl and acyl groups contain 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, polyglycol amides, poly sorbates, glycerol fatty acid ethoxylates, alkyl phenol polyglycol ethers and sugar surfactants such as e.g. Alkylglycosides.

Cationic surfactants:

With cationic surfactants, a distinction is made 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, thiazole salts, salts of amine oxides, sulfone salts.

Cationic polymers:

Cationic polymers are used in particular as coacervaiphase formers d). For '2-in-1' shampoos in particular, cationically modified polymers are used in addition to the pure cationic surfactants. US 5,977,038 and WO 01-41720 A1 provide a comprehensive description of these polymers. Cationic polyacrylamides, cationic protein derivatives and hydroxyalkyl cellulose ethers are preferred and cationic guar derivatives. 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

Auxiliaries as ingredients of cosmetic formulations are described in: A. Domsch, Die kosmetischen Preparate, Verlag für Chem. Industrie, 4th edition, 1992; and in: Cosmetics yearbook 1995, publishing house for chemical industry, 1995.

By way of example, but not by way of limitation, the following auxiliaries are suitable as part of the formulations: inorganic and organic acids, bases and buffers, salts, alcohols such as e.g. Ethanol, isopropanoi, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycol ether and glycerin, thickeners, stabilizers for emulsions such as B. xanthan gum, refatting agents, preservatives, foam stabilizers, defoamers, pearlescent and opacifiers such as e.g. Glycol distearates and titanium dioxide, collagen hydrolyzate, keratin hydrolyzate, silk hydrolyzate, anti-dandruff agents such as e.g. Zinc pyrithioπ, 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 by adding oil- and water-soluble UV filters or combinations of UV filters in cosmetic formulations for the care and treatment of substrates containing keratin, such as human and animal hair, the degradation of dyes and thus the fading and fading of colored substrates containing keratin UV radiation can be significantly reduced or even completely prevented. Ingredients for hair dye

Dyes and other ingredients of hair dyes are described in: A. Domsch, Die kosmetischen Preparate, Publishing House for Former Industry, 4th edition, 1992. Dyes are described in: Regulation on Cosmetics (Cosmetics Regulation), Federal Law Gazette 1997, Part I S . 2412, § 3 and Appendix 3 and in Europeaπ Community (EC) Directive, 76/68 / EEC, Annex IV. In the following, hair dye is divided into permanent, semi-permanent and temporary hair dye.

Permanent hair dye

Permanent dyeing, which can be achieved by washing your hair several times (more than

10) not washed out are caused by chemical reaction between dye precursors under oxidative conditions by hydrogen peroxide. The mixture of the corresponding components determines the color result that can be achieved.

A distinction is made in the preliminary products between oxidation bases (developers) and coupling components (modifiers).

Oxidation bases:

The following oxidation bases are exemplary but not limiting

Part of the formulations suitable: 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-metho-cy-m-phenylenediamine sulfate), o-chloro-p -phenylenediamine sulfate, picaminic acid (2,4-dinitro-6-aminophenol) and 2,4-dinitro-1-naphtol sulfonic acid and their sodium salt. Coupling components:

By way of example but not by way of limitation, the following coupling components are suitable as part of the formulations: hydrochiπon (1,4-dihydroxybenzene), resorcinol (1,3-dihydroxybenzene), pyrocatechol (1,2-dihydroxybenzene), α-naphthol (1-hydroxynaphthalene), Pyrogallol (1, 2,3-trihydroxybenzene) and 2,6-diaminopyridine.

Oxidation bases and coupling components with surfactants are usually incorporated into oil-in-water emulsions, but simple solutions or shampoos are also known as formulations. The formulations also contain antioxidants such as e.g. Sodium sulfite, sodium dithionite, ascorbic acid or thioglycolic acid to stabilize the precursors and are mixed with alkaline substances such as e.g. Ammonia adjusted to a pH value between 8 and 12 (preferably 9-11). In addition, surfactants are added as wetting agents, complexing agents for heavy metals, fragrances to mask the smell of ammonia, conditioners to improve the feeling on the hair and to protect the hair, and solvents such as ethanol, ethylene glycol, glycerol or benzyl alcohol are added.

Typically, permanent hair colorants are offered as 2 component systems consisting of a color solution, cream or shampoo as described above and the developer solution. The developer solution contains between 6-12% hydrogen peroxide and can optionally also be mixed with components of the formulation containing the color components. However, the peroxide solution must be carefully stabilized.

Semi-permanent hair dyes Semi-permanent dyes have been developed to maintain the color for shampooing 6-10 times. 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

In contrast to semi-permanent hair dyes, temporary dyeings, also called tints, contain larger dye molecules that are unable to penetrate the hair. They are designed to maintain the color for 1-6 washes. Typically, azo and basic dyes and azine and thiazine derivatives are used here. The same applies to the composition of the formulations as for semi-permanent and permanent hair dyes. Dyes and other ingredients of hair dyes are described in: A. Domsch, Die kosmetischen Preparate, Publishing House for Former Industry, 4th edition, 1992. Dyes are described in: Regulation on Cosmetics (Cosmetics Regulation), Federal Law Gazette 1997, Part I S . 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, but not limiting the invention, in which each functional active ingredient as a single compound or as a mixture of several compounds can occur in this category, in which each functional active ingredient can appear as a single compound or as a mixture of several compounds in this category. A typical shampoo formulation used according to the invention for the care and conditioning of hair consists of the following components in% by weight:

0.01-10% component b1) and optionally b2)

2-15% anionic surfactant

0-10% amphoteric surfactant

0-15% non-ionic surfactant

0-10% cationic surfactant 0-10% silicone conditioning agent (co-adjuvant)

0-10% excipients to 100% supplemented by water.

A typical shampoo formulation used according to the invention consists of the following components in% by weight:

0.1-12% component b1) and optionally b2) (approx. 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- 12% silicone conditioning agent (co-adjuvants) 0.01-1% disodium EDTA

0.01 - 1% phenoxyethylene (and) methyl paraben (and)

Butylparaben (and) ethylparaben (and) propylparaben

0-1% perfume (fragrance) 0-1% dyes

0-1% citric acid

0-2% sodium chloride to 100% supplemented by water.

A typical hair conditioner used according to the invention for the care and conditioning of hair consists of the following components in% by weight:

0.1-15% component b1) and optionally b2)

0-10% amphoteric surfactant

0.1 - 15% non-ionic surfactant

0-10% cationic surfactant

0-15% silicone conditioning agents (co-adjuvants)

0-20% excipients to 100% supplemented by water.

Another typical hair conditioner used according to the invention consists of the following components in% by weight:

0.5-15% component b1) and optionally b2) (as an approximately 43.5% emulsion in water with nonionic emulsifiers)

0- 15% silicone conditioning agents (co-adjuvants)

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 (fragrance)

0-1% dyes

0-1% citric acid to 100% supplemented by water. A typical hair care cure for the care and conditioning of hair used according to the invention consists of the following components in% by weight:

0.4-20% component b1) and optionally b2)

0-15% non-ionic surfactant

0-10% cationic surfactant

0-20% silicone conditioning agents (co-adjuvants)

0-20% excipients to 100% supplemented by water.

A typical hair care treatment used according to the invention consists of the following components in% by weight:

1-20% component b1) and optionally b2) (as approx. 43.5% emulsion in water with nonionic emulsifiers)

0.5-10% stearyl alcohol (and) steareth-7 (and)

Steareth-10

0- 20% silicone conditioning agents (co-adjuvants)

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) melhylparaben (and)

Butylparaben (and) Ethylparaben (and)

Propylparaben

0-1% perfume (fragrance)

0-1% dyes

0-1% citric acid 0-2% sodium chloride to 100% supplemented by water.

A typical hair care treatment used according to the invention consists of the following components in% by weight:

2-5% component b1) and optionally b2) (as an approx. 43.5% emulsion in water with nonionic emulsifiers) 0-5% silicone conditioners (co-adjuvants)

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 dye-containing formulation used according to the invention for temporary, semi-permanent or permanent hair coloring. Care and conditioning of the hair consists of the following components in% by weight:

0.1-10% component b1) and optionally b2)

1-10% hair dye precursor or dyes depending on the desired hair color

0-15% anionic surfactant

0-10% amphoteric surfactant

0-10% non-ionic surfactant

0-10% cationic surfactant

0-1% sodium sulfite

0-5% buffer

0-10% silicone conditioning agents (co-adjuvants) 0-10% excipients on 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% component b1) and optionally b2) (as an approximately 20% emulsion in water with nonionic emulsifiers)

1 - 5% hair dye precursor or dyes depending on the desired hair color

2-15% anionic surfactant

0-10% amphoteric surfactant 0-10% non-ionic surfactant

0-10% cationic surfactant

0.1-1% sodium sulfite

0.1 - 5% buffer for pH = 8 - 12

0-10% silicone conditioning agents (co-adjuvants) 0-10% auxiliaries on 100% water

A typical color solution used according to the invention for permanent hair coloring consists of the following components in% by weight:

0.1-10% component b1) and optionally b2) (as an approximately 20% emulsion in water with nonionic emulsifiers)

1 - 5% hair dye precursors or dyes depending on the desired hair color

0.1-1% sodium sulfite

5-15% propylene glycol 5-15 ammonia (28%)

10-30% oleic acid

5-15% isopropanoi

10-30% alkanolamide

0-10% silicone conditioning agent (co-adjuvants) on 100% water

A typical developer formulation used according to the invention for permanent hair coloring consists of the following components in% by weight:

0.1-10% component b1) and optionally b2)

10-30% hydrogen peroxide (30%)

0-15% anionic surfactant 0-10% amphoteric surfactant

0-10% non-ionic surfactant

0-10% cationic surfactant

0 - 5% buffer or acid for pH = 2 - 6

0 - 10% silicone conditioning agents (co-adjuvants) 0-10% auxiliaries in 100% water

A typical developer cream for permanent hair dyeing used according to the invention consists of the following components in% by weight:

0.1 -5% component b1) and optionally b2) (as an approx. 20% emulsion in water with non-ionic emulsifiers) 10-30% hydrogen peroxide (30%)

0 - 5% silicone condensing agent (co-adjuvants)

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

diethylene

0.05 - 2% sodium stanate

0.05 - 2% tetrasodium pyrophosphate on 100% water

It was recognized here that the solutions or mixtures according to the invention are preferably suitable for the production of cosmetic formulations for coloring hair or for the nourishing and color-preserving treatment of colored hair, such as:

- the treatment, conditioning, cleaning and / or care of colored or to be colored substrates; i.e. 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 sheet-like substrates and if these are colored and their color impression is to be largely retained , the treatment conditioning, cleaning and care 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 to be colored at the same time, such as keratin are suitable for human and animal hair.

- the treatment, cleaning and care of keratin fibers or

Hair before, during and / or after the dyeing process, because the hair dye formulated with it also improves the softness and / or to reduce the wet and dry combing forces and / or to increase the gloss and / or to increase the hair volume 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 setting agents, hair sprays, pump sprays, blow-drying agents or hair-setting agents;

use in permanent, semi-permanent and temporary hair dyes, as this enables the dyeing, care and wash resistance of the resulting color result to be achieved simultaneously.

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

Examples

example 1

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

receive.

0 ¹³ C-NMR:

Substructure shift (pp)

-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 g (0.61 mol) of chloroacetyl chloride were added dropwise with intensive stirring over the course of 30 minutes. During the dropping, the temperature rose to 80 ° C and intensive HCI development began. After the dropping had ended, the mixture was heated to 110 ° C. for 60 minutes. Finally, all the components boiling up to 110 ° C. and at 20 hPa o were distilled off. There were 273 g of a colorless, viscous liquid of the medium composition

CICH ₂ C (0) 0 (CH ₂ CH ₂ 0) ₂ oC (0) CH ₂ CI

5 obtained, which crystallized after several days. 1c) 75.4 g (25 * 10 ^"3 mol) of the α, ω-aminosiloxane according to Example 1a) and 24.4 g (25 * 10 ^{" 3} mol) of the α, ω-chloroacetic acid ester according to Example 1b) were dissolved in 300 ml of i -Propanol dissolved and heated to reflux temperature for 11 hours. After the reaction had ended, all the components boiling at from 5 to 40 ° C. were removed at 20 hPa. 99.2 g of an amber wax were obtained.

1d) 29.7 g Renex 36 and 5.1 g Renex 30 (both available from Uniquema) were added to 50 g of the compound according to the invention and at

10 80 ° C stirred. A solution of 1.1 g of glacial acetic acid and 0.8 g of sodium acetate in 28.2 g of water was then added dropwise with stirring at 50 ° C. within 10 minutes. After cooling to room temperature, a clear, yellow microemulsion with a viscosity at 25 ° C. of 200 mPas (Example 1) was obtained. The emulsion was stable at 50 ° C and with

15 water can be diluted in a ratio of 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 HCI 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. It will

566g of a light yellow oil of the composition

CICH ₂ C (0) OCH ₂ CH ₂ OCH ₂ CH ₂ OC (0) CH ₂ CI

30 received.

The purity of the ester, determined by gas chromatography, is 99.2%. ¹³ C-NMR: substructure shift (ppm)

CICH ₂ -C (0) - 167.1 CICH -C (0) -OCH ₂ - 65.2 CICH ₂ -C (0) -OCH ₂ CH 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 warming the batch to 50 ° C., 194.7 g (0.09 mol epoxy groups) of an epoxysiloxane are obtained within 30 minutes

10 of the average composition

and 1.3 g (0.01 mol of alkyl halide groups) of the ester derivative according to 20 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 V2Λ / 1 25 is smaller here 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)

-CH (OH) -CH ₂ -N ⁺ [(CH ₃ ) ₂ ] -CH ₂ -CH ₂ - 65.3 -CH (OH) -CH ₂ -N ⁺ [(CH ₃ ) ₂ ] -CH ₂ - CH ₂ - 64.6 -CH (OH) -CH ₂ -N ⁺ [(CH ₃ ) ₂ ] -CH ₂ -CH ₂ - 53.1 / 53.3 -CH (OH) -CH ₂ -N ⁺ [ (CH ₃ ) 2] -CH ₂ -CH2- 64.8 -CH (OH) -CH ₂ -N ⁺ [(CH ₃ ) ₂ ] -CH ₂ -CH ₂ - 23.4 -O-CfOJ-CH _∑ -N-KCHsJd-CH ^ CHa- 174.2 -0-C (0) -CH ₂ -N ⁺ [(CH ₃ ) ₂ ] -CH ₂ -CH ₂ - 62.0 -0-C (0) - CH ₂ -N ⁺ [(CH ₃ ) ₂ ] -CH ₂ -CH ₂ - 53.7

2c) 17.8 g of Renex 36, 5.1 g of Renex 30 (both available from Uniquema) and 8.3 g of Crodet S 40 (available from Croda) were added to 50 g of the compound according to the invention and the mixture was stirred at 80 ° C. A solution of 1.1 g of glacial acetic acid and 0.8 g of sodium acetate in 31.8 g of water was then added dropwise with stirring at 50 ° C. within 10 minutes. After cooling to room temperature, a clear, yellow microemulsion with a viscosity at 25 ° C. of 200 mPas (Example 1) receive. The emulsion was stable on storage at 50 ° C. and could be diluted with water in a ratio of 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

with a + b = 3.6

submitted 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 average composition are obtained within 30 minutes

and 30ml 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 ° G / 2mmHg in vacuum, 204g become one Obtain colorless, cloudy material, 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 simplification 5, neither a ratio formula nor a structural formula has been given:

3b) 50 g of the compound according to the invention were mixed with 29.7 g Renex 36 and 5.1 g Renex 30 (both available from Uniquema) and at

10 80 ° C stirred. A solution of 1.1 g of glacial acetic acid and 0.8 g of sodium acetate in 28.2 g of water was then added dropwise with stirring at 50 ° C. within 10 minutes. After cooling to room temperature, a clear, yellow microemulsion with a viscosity at 25 ° C. of 5000 mPas was obtained. The emulsion was stable on storage at 50 ° C. and with water

15 dilutable in a ratio of 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 ) _38ι 7 [OCH ₂ CH (CH ₃ )] _b NH2

with a + b = 6

4b) 0.1g of a 45% aqueous trimethylamine solution (0.76 mmol of tertiary amino groups), 0.76g (3.82 mmol) of dodecanoic acid and 0.23g (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 V ¹ groups in the ratio V ² / V ¹ not equal to 1. The linkage shown should not be understood as limiting. For the sake of simplicity, only a ratio formula but no structural formula was given:

1 CH (CH ₂ ) iθCθO- 1 CH ₃ C00-

4c) 50 g of the compound according to the invention were mixed with 29.7 g Renex 36 and 5.1 g Renex 30 (both available from Uniquema) and stirred at 80.degree. A solution of 1.1 g of glacial acetic acid and 0.8 g of sodium acetate in 28.2 g of water was then added dropwise with stirring at 50 ° C. within 10 minutes. After cooling to room temperature, a clear, slightly yellow microemulsion with a viscosity at 25 ° C. of 20,000 mPas was obtained. The emulsion was stable at 50 ° C and with Water can be diluted in a ratio of 100 parts water to one part emulsion.

Example 5 Preparation of a shampoo

Tab. 1 Production of the shampoos to be tested

[in% by weight]: ^•• Λ. ^: B ^"' xy ^{■:: ;'} D:.;:. ^• E. ^■

Ammonium Lauryl Sulfate (26%) 24 24 24 24 24

Ammonium Lauret Sulfate (28%) 14.3 14.3 14.3 14.3 14.3

Cocoamidopropyl betaines (35%) 11.43 11.43 11.43 11.43 11.43

Polyquaternium-10 0.5 0.5 0.5 0.3 0.5

Guar hydroxypropyltrimonium - - - 0.2 -

Chloride

Example 3 (43.5% silicone) - 4.6 - - -

Example 4 (43.5% silicone) - - 4.6 4.6 -

ABIL Quat 3272 (50% silicone) ^* 4

Water 49.77 45.17 45.17 45.17 45.77 * Commercial silicone quat from Goldschmidt

R (CH ₃ ) ₂ N-CH ₂ -CH (OH) -CH ₂ -0- (CH ₂ ) ₃ - [Si (CH ₃ ) ₂ 0] _x Si (CH ₃ ) ₂ - (CH ₂ ) ₃ - 0-CH ₂ -CH (OH) - CH ₂ -N (CH ₃ ) ₂ R

Combing force measurements were carried out with a Diastron Combing Force Analyzer. For this purpose, a 5 g hair bundle of undyed, naturally brown European hair was prewashed with “Neutrogena” shampoo (pretreated = reserved) and then the wet combing force [combing force (wet, Neutrogena)] was measured for each hair bundle. The hair bundles were then measured with 2 g of the respective test formulation and a hair bundle with "Neutrogena" as reference (wet), washed for 30 seconds, washed for 1 minute with running tap water. The wet combing force [combing force (wet, sample) or combing force (wet, reference)] was then measured After 24 hours of drying at room temperature, the dry combing forces were then measured. The hair bundle washed with “Neutrogena” was also dried as a reference and measured in order to determine its dry combing force [combing force (dry, reference)] compared to 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 for selected products.

Table 2

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

Dry combing force 1- combing force (dry, example) ^* combing force (wet, neutrogena)

Combing force (dry, subject to reference) * Combing force (wet, subject to reference)

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 for measuring 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

The hair bundles treated and treated with formulations A, C and D were also presented to a panel consisting of 10 people for evaluating the feeling, the volume and the shine. In terms of feeling, preferred 7 test persons formulation D and 3 formulation C. In terms of volume, preferred 8 test persons formulation C, 1 test person formulation D and 1 test person formulation A. When evaluating the gloss of the hair bundles presented, 6 test persons formulation C and 4 test persons formulation D.

The results clearly show that the use of the silicone quats b1) according to the invention leads to a clearly measurable reduction in the wet and dry combing forces. In addition, the use of the polyamino and / or polyammonium polysiloxane compounds b1) according to the invention leads to a measurable increase in hair volume and gloss. The additional use of a cationic polymer such as guar hydroxypropyltrimonium chloride leads to a further improvement in the conditioning of the hair.

Example 6

Making a hair conditioner

Tab. 5 Production of the hair rinses to be tested [in% by weight] F 7 G: H; -i ^" : .J - ^! -

Cetyl alcohol 3 3 3 3 3

Ceteareth-20 3 3 3 3 3

Example 1 (43.5% silicone) 4.6 - - - -

Example 3 (43.5% silicone) - 4.6 - - -

Example 4 (43.5% silicone) - - 4.6 - -

SE 253 (20% silicone) ^** - - - 10 -

ABIL Quat 3272 (50% silicone) * - - - - 4

Water 89.4 89.4 89.4 84 90

** 20% non-ionic microemulsion from GE Bayer Silicones of an amino-functional silicone oil (amodimethicone; (CH ₃ ) ₃ Si-0 {-Si (CH ₃ ) ₂ -0} _x {-

Si (CH ₃ ) [(CH ₂ ) ₃ ] -NH- (CH ₂ ) ₂ -NH ₂ ] -0} y-Si (CH ₃ ) ₃ ; x = 100-500, y = 3-15)

* Commercial silicone quat from Goldschmidt R (CH ₃ ) ₂ N-CH ₂ -CH (OH) -CH ₂ -0- (CH ₂ ) ₃ - [Si (CH ₃ ) ₂ O] _x Si (CH ₃ ) ₂ -

(CH ₂ ) ₃ -0-CH ₂ -CH (OH) -CH ₂ -N (CH ₃ ) ₂ R

The formulations were examined with regard to the wet and dry combing forces and the volume 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 b1) according to the invention leads to a clearly measurable reduction in the wet and dry combing forces. In addition, the use of silicone quats according to the invention leads to a measurable increase in hair volume. A comparison of the hair bundles with the reference from Example 4 washed with "Neutrogena" also shows an increase in the gloss.

Example 7

The following shampoo formulations were examined:

Tab. 7 Shampoo formulations to be tested

[in% by weight] KL ^" M. N

Sodium lauryl sulfate (27% 35 35 35 35

Cocoamidopropyl betaine 2 2 2 2

Citric acid 0.1 0.1 0.1 0.1

Sodium chloride 1 1 1 1

Phenylparaben (and) methylparaben 0.1 0.1 0.1 0.1 SME 253 (20% silicone) ** - 2 - -

Example 2 (diluted with water to 20% silicone) - - 2 -

Example 3 (diluted with water to 20% silicone) - - - 2

Water 61.8 59.8 59.8 59.8

** 20% non-ionic microemulsion from GE Bayer Silicones of an amino-functional silicone oil (amodimethicone; (CH ₃ ) ₃ Si-0 {-Si (CH ₃ ) ₂ - 03 {-Si (CH ₃ ) [(CH ₂ ) ₃ ] -NH - (CH ₂ ) ₂ -NH ₂ ] -0} y-Si (CH ₃ ) ₃ ; x = 100-500, y = 3-15)

Treatment of hair after coloring

4 strands of natural blonde hair were dyed red with Poly Brilliance Intensive Color Cream - Intensivrot 872 - consisting of color cream and developer. 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 strands of hair were then washed 20 times with the formulations listed in Table 7 and the color result was determined by comparison against a reference scale by a 6-person panel. The reference scale was prepared by different exposure times (0, 2, 4 to 20 minutes) of the Brilliance Intensive Color Cream - Intensive Red 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 the% color retention was determined by comparison with the results obtained before the washes. At the same time, the test subjects were also asked to indicate the softness of the strands of hair on a scale of 1 to 4 and to be judged by the hair washes, 4 being the highest and 1 the least softness. 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

Formulation% color retention Relative softness

K 59 1.33

L 86 1.67

M 100 3.5

N 98 3.5

The results in Table 8 show that the use of the compounds b1) according to the invention in a shampoo leads to a significant improvement in the color retention with at the same time significantly increased softness of the hair.

Example 8

Treatment of hair before coloring

Table 9: Pump spray formulations to be tested

[in% by weight] O P Q R

SME 253 (20% silicone) ** - 4 - -

Example 2 (with water to 20%

Diluted silicone) - - 4 -

Example 3 (with water to 20%

Diluted silicone) - - - 4

Water 100 96 96 96 ** 20% non-ionic microemulsion from GE Bayer Silicones of an amino-functional silicone oil (amodimethicone; (CH ₃ ) ₃ Si-0 {-Si (CH ₃ ) ₂ - OM-Si (CH ₃ ) [(CH ₂ ) ₃ ] -NH- (CH ₂ ) ₂ -NH ₂ ] -0} _y -Si (CH ₃ ) 3; x = 100-500, y = 3-15)

The formulations from Table 9 were filled into a pump atomizer and then each formulation was applied in a controlled manner to 10 strands of natural blond hair by 10 pumps. After drying, each strand of hair was dyed with Poly Brilliance Intensive Color Cream - Intensivrot 872. These locks of hair were then washed 20 times with the shampoo formulation K described in Example 7 in Table 7. The color result and the relative softness were then determined as described in Example 7. The results are described in Table 10.

Table 10

Formulation% color retention Relative softness

O 59 1

P 86 3

Q 95 3

R 98 3

The results in Table 10 clearly show that the use of the compounds b1) according to the invention in a pretreatment before dyeing hair leads to a significant improvement in color retention. At the same time, the hair feels soft.

Example 9

Treatment of hair during coloring

Table 11: Developer formulations to be tested

) ¹ silicone elastomer from GE Bayer Silicones with INCI names Cyclopentasiloxane and

Dimethicone / vinyldimethicone crosspolymer according to US 5,760,116) ² silicone resin from GE Bayer Silicones with INCI names Cyclopentasiloxane and

Trimethylsiloxysilicate {[(CH ₃ ) ₃ Si-Oι _{/ 2} ] _x [Si04 / 2]; x = 0.5-1} ** 20%> non-ionic microemulsion from GE Bayer Silicones of an amino-functional silicone oil (amodimethicone; (CH ₃ ) ₃ Si-0 {-Si (CH ₃ ) ₂ -0} _x {- Si (CH ₃ ) [(CH ₂ ) ₃ ] -NH- (CH ₂ ) 2-NH2] -0} y-Si (CH ₃ ) ₃ ; x = 100-500, y = 3-15)

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

Table 12

Formulation% color retention Relative softness

S 59 1

M 26 -

U 54 -

V 68 2 w 92 3.5

X 90 3.5

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

Claims

claims

1. Use of at least one linear or branched polyamino and / or polyammonium polysiloxane copolymer b1) with the repeating units of the formula (I):

- [Q-V] - (I)

where Q is selected from the group consisting of:

-NO-,

-N ⁺ R ₂ -

a saturated or unsaturated, diaminofunctional

Heterocycle of the formulas:

, such as

an aromatic, diamino-functional heterocycle of the formula:

a trivalent radical of the formula:

/ - N \

a trivalent radical of the formula:

a tetravalent radical of the formula,

15 in which R in each case represents hydrogen or a monovalent organic radical,

where Q does not bind directly to a carbonyl carbon atom,

20

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 having up to 1000 carbon atoms (the carbon atoms of the polysiloxane radical Z ² defined below not being counted), which optionally one or more groups selected from

-O-, -CONR ² -,

10 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 is one or more groups selected from -O-, -NH-, -C (O) -

15 and -C (S) -, and which 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, At the-

20 monium, polyether residues and polyether ester residues can be substituted, where if there are several -CONR ² groups, these can be the same or different,

-C (O) - and 25 -C (S) - may contain, and

the radical V ^{2 can} optionally be substituted by one or more hydroxyl groups, and the radical V ² at least one

Group -Z ² - of the formula

30

contains what

R ^{1 can be the} same or different and is selected from the group consisting of: Ci to C ₂₂ alkyl, fluoro (C-pCιo) alkyl and Cβ-C-io aryl, and ni = 20 to 1000,

V ^{1 is} selected from divalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic

10 hydrocarbon radicals with up to 1000 carbon atoms, optionally one or more groups selected from

-O-, -CONR ² -,

15 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,

-C (O) -,

20 -C (S) - and

-Z ¹ - may contain, wherein -Z ¹ - a group of the formula

25 is what R is as defined above, where the groups R ¹ in groups V ¹ and V / 2 may be the same or different and n = 0 to 19,

and the radical V ^{1 may} optionally be substituted by one or more hydroxyl groups, and

V ^{3 is} a trivalent or higher, straight-chain, cyclic or branched, saturated, unsaturated or aromatic

Represents hydrocarbon radical having up to 1000 carbon atoms, optionally one or more groups selected from

-O-,

-CONH-, 15 -CONR ² -, wherein R ^{2 is} as defined above,

-C (O) -,

-C (S) -,

-Z ¹ - which is as defined above, 20 -Z ² - which is as defined above, and Z ³ , wherein Z ^{3 is} a trivalent or higher organopolysiloxane unit,

may contain, and which may optionally be substituted by one or more hydroxyl groups,

25 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 30 - that the said polysiloxane compound has at least one

Contains group V ¹ , V ² or V ³ , - That said polysiloxane compound contains at least one group -Z ¹ -, -Z ² - or Z ³ , and

- that the trivalent and tetravalent radicals Q either serve for the branching of 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 three - and tetravalent radicals Q are saturated with radicals V ³ within a linear main chain without the formation of a branch, and in which the positive ones resulting from ammonium groups

Charges are neutralized by organic or inorganic acid anions, and their acid addition salts, and optionally at least one amino and / or ammonium polysiloxane compound b2) in the manufacture and / or treatment of colored hair.

2. Use 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:

R2

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

10

a monoquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

20 a doubly quaternized unit of structure

a monoquaternized unit of the structure

a monoquaternized unit of the structure

a double quaternized unit of the structure

a monoquaternized unit of the structure

a monoquaternized unit of the structure

10 where t is from 2 to 10,

R ^{2 is} as defined above,

R ^{3 has} the meaning of R ² , where R ² and R ^{3 may be the} same or different, or

15 R ² and R ³ together with the positively charged nitrogen atom form a five- to seven-membered heterocycle which may optionally have one or more nitrogen, oxygen and / or sulfur atoms, R ⁵ , R ^s , R ^{7 may be the} same or different can and from the group

20 pe can be selected, which consists 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 denotes H, alkyl group, monohydroxyalkyl group, polyhydroxyalkyl group, acetyl group, and ureido group of the adjacent radicals R ⁵ , R ⁶ and R ⁷ with which they can form aromatic five- to seven-membered rings which bind to the heterocycle, and

R ^{8 has} the meaning of R ² , where R ⁸ and R ^{2 may be the} same or different.

3. Use according to claim 1 or 2, characterized in that the group Q from trivalent radicals of the formulas

is selected and these residues are not used to branch the polysiloxane copolymers, but these residues are exclusively connected to trivalent residues V ³ , cyclic structures being formed which are part of the linear main chain, and likewise the trivalent residues V ^{3 are} not intended to branch serve linear polysiloxane copolymers.

4. Use according to any one of claims 1 to 3, characterized in that the units V in the repeating units [QV] contain units V ¹ , the at least one esterified Polyalkyleπo. id structural unit of the general formulas:

-AE-, -EA-, -AE-A'- and / or -A'-EA- have wherein

A = -CH ₂ C (0) 0-, -CH ₂ CH ₂ C (0) 0-, -CH ₂ CH ₂ CH ₂ C (0) 0-, -OC (0) CH ₂ -, -OC ( 0) CH ₂ -, -OC (0) CH ₂ CH ₂ - and / or -OC (0) CH ₂ CH ₂ CH ₂ -

A '= -CH ₂ C (0) -, -CH ₂ CH ₂ C (0) -, -CH ₂ CH ₂ CH ₂ C (0) -, -C (0) CH ₂ -, -C (0) CH ₂ -, -C (0) CH ₂ CH ₂ - and / or -C (0) CH ₂ CH ₂ CH ₂ -

E = a polyalkylene oxide group of the general formulas:

- [CH ₂ CH ₂ 0] _q - [CH ₂ CH (CH ₃ ) 0] _r and / or - [OCH (CH ₃ ) CH2] _r [OCH ₂ CH2] _q - with q = 1 to 200, r = 0 to 200,

wherein the terminal oxygen atom of group A bind 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 with the formation of ester groups.

5. Use according to one of claims 1 to 4, characterized in that the units V in the repetition units [QV] contain units V ¹ , which are selected from:

- [CH ₂ CH2θ] _q - [CH ₂ CH (CH ₃ ) 0] _r CH ₂ CH ₂ -, -CH (CH ₃ ) CH ₂ θ [CH ₂ CH ₂ 0] _q - [CH2CH (CH ₃ ) 0 ] rCH ₂ CH (CH ₃ ) -, -CH ₂ CH (0H) 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 0- [CH ₂ CH ₂ 0] _q - [CH ₂ CH (CH ₃ ) 0] _r and

-CH ₂ CH (OH) CH ₂ - and wherein q = 0 to 200, r = 0 to 200.

6. Use according to one of claims 1 to 5, characterized in that the group V consists of the repeating units V ² and V ¹ and the molar ratio V ² Λ / ¹

V ² / V ^{1 is} from 0.0005 to 1000.

7. Use according to any one of claims 1 to 6, wherein the molar ratio V ² / V ^{1 is} 0.8 to 1.2.

8. Use according to one of claims 1 to 7, wherein the molar ratio V ² / V ^{1 is} 1.

9. Use according to one of claims 1 to 8, wherein at least two different groups V ¹ are present.

10. Use according to one of claims 1 to 9, wherein V ^{2 is} a group of the formula -v ² * -Z ² -V ² *, wherein Z ^{2 is} as defined above and V ² * is selected from divalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals having up to 40 carbon atoms, optionally one or more groups selected from

-O-,

-CONR ² -, in which R ^{2 is} as defined above, can contain -C (O) - and -C (S) -, and the radical V ² * can optionally be substituted by one or more hydroxyl groups.

11. Use according to one of claims 1 to 10, characterized in that V ^{2 * is} selected from groups of the formulas

- (CH ₂ ) ₃ OCH ₂ CHCH ₂ - - (CH ₂ ) OCH ₂ CH-

OH CH 0H

12. Use according to one of claims 1 to 11, characterized in that the group V in the repeating units [QV] of the polyamino and / or polyammonium polysiioxane copolymers b1) consists of repeating units of the formulas (II) and (III):

the radicals R are identical or different and are as defined above, and R preferably has the meaning of R ² , n, n1 as defined above, or n2 as defined above, A = organic or inorganic acid anions

5 V ² * as defined above,

V ^{1 is} as defined above,

V ¹ 'has the meaning of V ¹ as defined above, but V ¹ ≠ V ¹ ', where the nitrogen atoms in the formula (II) optionally

10 can be protonated.

13. Use according to claim 12, wherein V ^{1 is} selected from radicals of the formulas:

15 - [CH ₂ CH ₂ 0] _q - [CH ₂ CH (CH ₃ ) 0] _r CH ₂ CH ₂ -,

-CH (CH ₃ ) CH ₂ 0 [CH ₂ CH ₂ 0] _q - [CH ₂ CH (CH ₃ ) 0] rCH ₂ CH (CH ₃ ) -, -CH ₂ CH (CH ₃ ) 0 [CH ₂ CH ₂ 0] _q - [CH ₂ CH (CH ₃ ) 0] rCH (CH ₃ ) CH ₂ -, -CH (CH ₃ ) CH ₂ 0 [CH ₂ CH ₂ 0] _q - [CH ₂ CH (CH ₃ ) 0] rCH (CH ₃ ) CH ₂ -, wherein

20 q = 0 to 200, r = 0 to 200 and V ¹ 'is selected from C1-C8-alkylene radicals and (C1-C8-alkyl) aryl (C1-C8-alkyl) radicals.

25 14. Use according to one of claims 1 to 13, characterized in that the polyamino and / or polyammonium polysiloxane copolymers b1) with the repeating units - [Q- V] - as chain end groups, a group of the formula -QR or -VR where R is as defined above.

30

15. Use according to one of claims 1 to 14, characterized in that the polyamino and / or polyammonium Have polysiloxane copolymers b1) -QR end groups, which are selected from the following formulas (IV) to (VIII):

(IV) (V)

(VI) (VII)

wherein: the radicals R are identical or different and are as defined above, and R preferably has the meaning of R ² , n is as defined above,

A = organic or inorganic acid anions

V ² * is as defined above,

V ^{1 is} as defined above, V ¹ 'has the meaning of V ¹ as defined above, but V ¹ ≠ V ¹ ', where the nitrogen atoms can optionally be protonated.

R

I

- NR ^ (VIII) in which the radicals R are as defined above and can be the same or different, and R is preferably selected from radicals R ² .

16. Use according to one of claims 1 to 15, characterized in that the linear or branched polyamino and / or polyammonium polysiloxaπcopolymer b1) have the formula RQV ² -QR, wherein R, Q and V ^{2 are} as defined above.

17. Use according to claim 16, characterized in that the linear or branched polyamino and / or polyammonium polysiloxane copolymer b1) of the formula RQV ² -QR have the following formula:

wherein R, Q, n, V ² * are as defined above.

18. Use according to one of claims 1 to 17, characterized in that the following additional components are optionally used in a mixture with component b1) and optional component b2): one or more nitrogen-free polysiloxane compounds a), one or more silicone-free surfactants c), one or more coacervate phase formers d), and one or more carrier substances e).

19. Use according to one of claims 1 to 18 in compositions for temporary, semi-permanent or permanent hair coloring, for tinting and / or for the care and conditioning of colored hair.

20. Use according to one of claims 1 to 19, characterized in that it comprises the following steps: a) producing a premix by mixing at least one component b1) with one or more components selected from b2), a), c), d) and e) with the formation of solutions, mixtures or emulsions and b) preparation of a composition for the preparation and / or

Treatment of colored hair by mixing the premix a) and, if appropriate, further surfactants, auxiliaries and other additives or combining steps a) and b), in which the mixing of the constituents with stirrers, dissolvers,

Kneaders, pumps, mixing screws, mixing nozzles and / or low and high pressure emulsifiers.

21. Use according to claim 20, characterized in that the premix has the following composition:

10 - 50 wt .-% polyamino and / or polyammonium

Polysiloxane copolymers b1)

1 - 35% surfactants

0 - 10% auxiliary substances

0 - 20% solvent to 100% supplemented by water

22. A method of making a composition in the manufacture and / or treatment of colored hair, wherein a

Composition as defined in claims 18 and 21, with further for the compositions in the manufacture and / or Treatment of colored hair necessary ingredients is mixed.

23. Composition for the manufacture and / or treatment of

5 colored hair, containing at least one component b1) as defined in claim 1, optionally one or more

Components b2) and optionally one or more of the following further components: one or more nitrogen-free polysiloxane compounds a) 10 (co-adjuvants), one or more silicone-free surfactants c), one or more coacervate phase formers d), and one or more carrier substances e) ,

15 24. A composition for the manufacture and / or treatment of colored hair, which is a shampoo formulation containing the following ingredients:

0.01 - 10% component b1),

20 2 - 15% anionic surfactant

0-10% amphoteric surfactant

0 - 15% o non-ionic surfactant

0 - 10% cationic surfactant

0 - 10% auxiliary substances

25 to 100% supplemented by water, in which the quantities are in% by weight.

25. A composition for the manufacture and / or treatment of colored hair, which is a hair rinse formulation containing the following ingredients:

0.1 - 15% at least one component b1), 0-10% amphoteric surfactant

0.1 - 15% non-ionic surfactant

0-10% cationic surfactant

0 - 15% silicone conditioning agent (co-adjuvants),

0 -20% auxiliary substances, to 100% supplemented by water.

where the quantities are in% by weight.

10 26. Composition for the manufacture and / or treatment of colored hair, which is a hair care regimen containing the following ingredients:

0.4 - 20% at least one component b1)

15 0 - 15% non-ionic surfactant

0-10% cationic surfactant

0 - 20% silicone conditioning agent (co-adjuvants),

0 - 20% auxiliary substances to 100% supplemented by water,

20 in which the quantities are in% by weight.

27. A composition for the manufacture and / or treatment of colored hair, which is a hair coloring formulation 25 for temporary, semi-permanent or permanent hair coloring or for the care and conditioning of colored hair, which contains the following components:

0.1 - 10% at least one component b1)

30 1 - 10% hair dye precursors or dyes

0 - 15% anionic surfactant

0-10% amphoteric surfactant 0-10% non-ionic surfactant

0-10% cationic surfactant

0-1% sodium sulfite

0-10% silicone conditioning agent (co-adjuvant),

0-5% buffer

0-10% excipients to 100% supplemented by water

where the quantities are in% by weight.

28. A composition for the manufacture and / or treatment of colored hair, which is a developer formulation for permanent hair dyeing, containing the following ingredients:

0.1-10% at least one component b1)

10-30% hydrogen peroxide (30%)

0-15% anionic surfactant

0-10% amphoteric surfactant

0-10% non-ionic surfactant

0-10% cationic surfactant

0-5% buffer or acid for pH = 2-6

0-10% silicone conditioning agent (co-adjuvant),

0-10% excipients to 100% supplemented by water,

where the quantities are in% by weight.

29. Use according to one of claims 1 to 21 for the treatment, conditioning, cleaning and / or care of colored or to be colored substrates.

30. Use according to one of claims 1 to 21 for the treatment, cleaning and care of keratin fibers or hair before, during and / or after dyeing.

5 31. Use according to any one of claims 1 to 21 for the production of so-called "rinse-off" products, such as 2-in-1 shampoos, body wash and hair rinses for the after-treatment of colored hair after cleaning or dyeing or the pretreatment of Hair before bleaching, curling or

10 crimping, 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-drying agents or blow-drying agents.

15 32. Use according to one of claims 1 to 21 to improve the softness and / or to reduce the wet and dry combing forces and / or to increase the gloss and / or to increase the hair volume and / or to reduce the washing out of dyes from and

20 toned and / or dyed hair.