DE10214290A1 - Formulations for treating skin, hair and textile fibres, especially to increase volume and improve combability of hair, containing quaternized polysiloxane compounds - Google Patents

Abstract

Formulations (A) for the cleansing and care of skin, hair and textile fibres contain at least one quaternized polysiloxane (silicone quat') compound (I) Formulations (A) for the cleansing and care of skin, hair and textile fibres contain at least one polysiloxane compound (I) comprising: (1) at least one polyalkylene oxide unit of formula -A-E-, -E-A-, -A-E-A'- and/or -A'-E-A- and/or at least one terminal polyalkylene oxide unit of formula -A-E-R2; (2) at least one di- or trivalent organic group containing ammonium group(s); (3) at least one polysiloxane unit of formula -K-S-K-; and (4) at least one organic or inorganic acid residue for neutralizing the charge of the ammonium group(s). A = -(CH2)a-COO- or -OCO-(CH2)a-; A' = -(CH2)a-CO- or -CO-(CH2)a-; a = 1-3; E = polyalkylene oxide group of formula -(CH2CH2O)q-(CH2CHMeO)r or -(OCH2CHMe)r-(OCH2CH2)q- (provided that the terminal O of A is bonded to the terminal CH2 of E and the terminal CO of A' is bonded to the terminal O of E, in each case forming an ester group); q = 1-200; r = 0-200; R2 = H or linear, branched or cyclic 1-20C hydrocarbyl, optionally (i) interrupted by O or CO, (ii) substituted by OH and/or (iii) acetylenic, olefinic or acetylenic; S = -(Si(R1)2-O)n-Si(R1)2-; R1 = 1-22C alkyl, 1-22C fluoroalkyl or aryl; n = 1-1000; K = di- or trivalent, linear branched or cyclic 2-40C hydrocarbon residue, optionally interrupted by O, NH, N, NR1, CO, CS, N+(R3) or N+(R1)(R3) (where R groups are optionally replaced by a bond to a divalent group R3) and optionally substituted by OH; where in a trivalent group K the third valency is saturated by a bond to a group (b); R3 = di- or trivalent, linear branched or cyclic 1-20C hydrocarbon residue (optionally interrupted by O, NH, CO or CS and optionally substituted by OH); or -A-E-R2. Independent claims are also included for the following: (1) a variant of the composition (A), in which (I) consists of groups of formulae (IA) and (IB); and (2) the preparation of (A), by mixing (I) with other surfactants and auxiliaries to give an emulsion. X = at least 4C hydrocarbylene, containing a hydroxy group and optionally interrupted by O; Y = at least 2C hydrocarbylene, containing a hydroxy group and optionally interrupted by one or more O and/or N; Q1 - Q4 = 1-4C alkyl or benzyl; or Q1 +Q3 or Q2 + Q4 = bridging alkylene group; Q6 = H or 1-20C alkyl (optionally substituted by O); E' = -B-O-(EOx)v-(POx)B-; EOx = ethylene oxide unit; POx = propylene oxide unit; B = 2-6C alkylene; v, w = 0-200, but not both 0; An- = inorganic or organic anion.

Description

The invention relates to the use of at least one Silicone quat in cosmetic formulations for treatment substrates containing keratin such as e.g. B. hair and skin. It is special are formulations for the cleaning and care of hair and skin with so-called rinse-off products such as shampoos, Hair rinses and body wash as well as with so-called leave-in Products such as lotions, gels, pump sprays and aerosol sprays. On Another object of the invention is the use of a cosmetic formulation which is at least one of the quaternary Silioxane contains "silicone quats" to improve conditioning of skin and hair, to reduce wet and Dry combing forces of the hair, to increase the volume of the hair and to improve the shine of hair. Besides that, too other non-keratin fibers with these formulations be treated to a comfortable grip, a puffy, fluffy To create texture or "fluffy feeling".

It is known that polysiloxane-based polyquats are advantageous in Hair care formulations can be used (EP 282.720, US 6,240,929). The use of such compounds leads to one Typical silicone soft, smooth and flat handle. Generally there is one Hydrophobization of the substrate.

This improves the hydrophilicity of the finished substrate achieved when alkylene oxide structures are introduced into the molecules.

There are branched (US 5,602,224) and comb-like Structures have been synthesized (US 5,098,979, US 5,153,294, US 5,166,297).

WO 02-10257 and WO 02-10259 are also hydrophilic Silicone softeners are known, which also have washing resistance. These are connections that are about Alkylene oxide units in the main chain, in side chains or as Have chain stoppers.

It has been found that the compounds according to WO 02-10257 and WO 02-10259 advantageous for formulations for treatment substrates containing keratin such as e.g. B. hair and skin.

It was also surprisingly found that among compounds of the structure types disclosed in WO 02-10257 and WO 02-10259 Connections that, in addition to excellent softness on fibers at the same time an outstanding significant increase in volume and the combability - both wet and dry combability - after Apply to fibrous substrates.

Is of particular importance for increasing the volume given structure type of the silicone quat the ratio of Siloxane arc length to the length of the alkylene oxide block.

It has been found that siloxane sheets of 15 to 90 diorganosiloxy units, ie D ₁₅ to D ₉₀ , in combination with alkylene oxide blocks made of ethylene oxide or propylene oxide units EO / PO of 10 to 100 are particularly suitable. The length of the siloxane sheet is preferably D ₂₅ to D ₈₀ and the length of the alkylene oxide block EO or PO 10 to 50. In a particularly advantageous embodiment of the invention, siloxane sheets of the chain length range D ₂₅ to D ₅₀ with alkylene oxide blocks EO / PO of length 10 to 40 combined.

Within the various by WO 02-10257 and WO 02-10259 described connection types, it is possible that the Alkylene oxide units on both sides in proximity to the siloxane block, however are also positioned between quat structures. When positioning on both sides of the siloxane block it should be noted that the sum of the Lengths of the two alkylene oxide blocks must be considered.

The statements made above regarding the preferred chain lengths of the siloxane sheets or alkylene oxide units relate to strictly alternating block structures of the type (AB) _n or ABA.

In statistically distributed block products of the type (-A-B-A-C-A-C-A-B- etc.) with more than two recurring units, an adjustment of the ratios of siloxane block length according to the invention Alkylene oxide block lengths also take place in that, on the one hand, quaternary Units by amine-terminated alkylene oxide units, e.g. B. difunctional Jeffamine, partially replaced. On the other hand, it is too this purpose is also possible by partially suitable siloxane units to replace functionalized alkylene oxide units. It is essential here that one to the absolute lengths of the Equivalent effective block length by alkylene oxide blocks The degree of installation is taken into account.

The subject of the invention was suitable formulations and To provide processes for their preparation, in particular the Wet and dry combability as well as the volume and grip of Improve keratin fibers.

• a) mindestens einer Polyalkylenoxid-Struktureinheit der allgemeinen Formeln:
  
  -A-E-, -E-A-, -A-E-A'- und/oder -A'-E-A-
  
  worin
  A = -CH₂C(O)O-, -CH₂CH₂C(O)O-, -CH₂CH₂CH₂C(O)O-, -OC(O)CH₂-, -OC(O)CH₂-, -OC(O)CH₂CH₂- und/oder -OC(O)CH₂CH₂CH₂-
  A' = -CH₂C(O)-, -CH₂CH₂C(O)-, -CH₂CH₂CH₂C(O)-, -C(O)CH₂-, -C(O)CH₂-, -C(O)CH₂CH₂- und/oder -C(O)CH₂CH₂CH₂-
  E = eine Polyalkylenoxidgruppe der allgemeinen Formeln:
  
  -[CH₂CH₂O]_q-[CH₂CH(CH₃)O]_r- und/oder
  
  -[OCH(CH₃)CH₂]_r-[OCH₂CH₂]_q-
  
  mit
  q = 1 bis 200,
  r = 0 bis 200,
  wobei das endständige Sauerstoffatom der Gruppe A an die endständige -CH₂-Gruppe der Gruppe E, und das endständige Carbonyl-Kohlenstoffatom der Gruppe A' an das endständige Sauerstoffatom der Gruppe E jeweils unter Ausbildung von Estergruppen binden,
  und/oder mindestens eine endständige Polyalkylenoxid- Struktureinheit der Formel
  
  -A-E-R²
  
  worin A und E die oben genannte Bedeutung aufweisen, und
  R² = H, geradkettiger, cyclischer oder verzweigter C₁-C₂₀- Kohlenwasserstoffrest, der durch -O- oder -C(O)- unterbrochen und mit -OH substituiert und acetylenisch, olefinisch oder aromatisch sein kann,
• b) mindestens ein zweiwertiger oder dreiwertiger organischer Rest, der mindestens eine Ammoniumgruppe enthält,
• c) mindestens eine Polysiloxan-Struktureinheit der allgemeinen Formel:
  
  -K-S-K-,
  
  mit
  S =
  
  
  worin R¹ = C₁-C₂₂-Alkyl, C₁-C₂₂-Fluoralkyl oder Aryl,
  n = 1 bis 1000, und wenn mehrere Gruppen S in der Polysiloxanverbindung vorliegen, diese gleich oder verschieden sein können,
  K = ein zweiwertiger oder dreiwertiger geradkettiger, cyclischer oder verzweigter C₂- C₄₀-Kohlenwasserstoffrest, der durch -O-, -NM-
  
  
  -NR¹ -, -C(O)-, -C(S)-,
  
  
  unterbrochen und mit -OH substituiert sein kann,
  worin
  R¹ wie oben definiert ist, oder gegebenenfalls eine Bindung zu einem zweiwertigen Rest R³ darstellt,
  R³ einen einwertigen oder zweiwertigen geradkettigen, cyclischen oder verzweigten C₁-C₂₀- Kohlenwasserstoffrest, der durch -O-, -NH-, -C(O)-, -C(S)- unterbrochen und mit -OH substituiert sein kann, oder -A-E-R² darstellt, worin A, E und R² wie oben definiert ist,
  wobei die Reste K gleich oder verschieden voneinander sein können, und im Falle, dass K einen dreiwertigen Rest darstellt, die Absättigung der dritten Valenz über eine Bindung an den vorstehend genannten organischen Rest, der mindestens eine Ammoniumgruppe enthält, erfolgt,
• d) mindestens einen organischen oder anorganischen Säurerest zur Neutralisation der aus der(n) Ammoniumgruppe(n) resultierenden Ladungen.

These formulations for the cleaning, care of skin, hair and textile fibers, containing at least one quaternary polysiloxane compound, which consists of:

• a) at least one polyalkylene oxide structural unit of the general formulas:
  
  -AE-, -EA-, -AE-A'- and / or -A'-EA-
  
  wherein
  A = -CH ₂ C (O) O-, -CH ₂ CH ₂ C (O) O-, -CH ₂ CH ₂ CH ₂ C (O) O-, -OC (O) CH ₂ -, -OC ( O) CH ₂ -, -OC (O) CH ₂ CH ₂ - and / or -OC (O) CH ₂ CH ₂ CH ₂ -
  A '= -CH ₂ C (O) -, -CH ₂ CH ₂ C (O) -, -CH ₂ CH ₂ CH ₂ C (O) -, -C (O) CH ₂ -, -C (O) CH ₂ -, -C (O) CH ₂ CH ₂ - and / or -C (O) CH ₂ CH ₂ CH ₂ -
  E = a polyalkylene oxide group of the general formulas:
  
  - [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r - and / or
  
  - [OCH (CH ₃ ) CH ₂ ] _r - [OCH ₂ CH ₂ ] _q -
  
  With
  q = 1 to 200,
  r = 0 to 200,
  where the terminal oxygen atom of group A binds 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,
  and / or at least one terminal polyalkylene oxide structural unit of the formula
  
  -AER ²
  
  wherein A and E have the meaning given above, and
  R ² = H, straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which can be interrupted by -O- or -C (O) - and substituted by -OH and can be acetylenic, olefinic or aromatic,
• b) at least one divalent or trivalent organic radical which contains at least one ammonium group,
• c) at least one polysiloxane structural unit of the general formula:
  
  -KSK-,
  
  With
  S =
  
  
  wherein R ¹ = C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ fluoroalkyl or aryl,
  n = 1 to 1000, and if there are several groups S in the polysiloxane compound, these may be the same or different,
  K = a divalent or trivalent straight-chain, cyclic or branched C ₂ - C ₄₀ hydrocarbon residue, which by -O-, -NM-
  
  
  -NR ¹ -, -C (O) -, -C (S) -,
  
  
  interrupted and substituted with -OH,
  wherein
  R ^{1 is} as defined above, or optionally represents a bond to a divalent radical R ³ ,
  R ^{3 is} a monovalent or divalent straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which can be interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted by -OH , or -AER ² , wherein A, E and R ^{2 are} as defined above,
  where the radicals K can be identical or different from one another, and in the event that K represents a trivalent radical, the third valence is saturated by binding to the above-mentioned organic radical which contains at least one ammonium group,
• d) at least one organic or inorganic acid residue for neutralizing the charges resulting from the ammonium group (s).

In these polysiloxane compounds is preferred
K = a divalent or trivalent straight-chain, cyclic or branched C ₂ -C ₄₀ hydrocarbon radical which is represented by -O-, -NH-,


-NR ¹ -, -C (O) -, -C (S) - can be interrupted and substituted by -OH, in which R ^{1 is} as defined above, and where the radicals K can be identical or different from one another.

It is further preferred that the polysiloxane compounds, in which the aforementioned organic radical, which contains at least one ammonium group, as component b)
a remainder of the general formula:

-N ¹ -FN ¹ -

wherein N ^{1 is} a quaternary ammonium group of the general formula


is what
R ^{4 represents} a monovalent or divalent straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which is interrupted by -O-, -NH-, -C (O) -, -C (S) - and is substituted by -OH can
R ^{5 represents} a monovalent straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which can be interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted by -OH, or represents a single bond to a divalent radical R ⁴ or a tetravalent radical F, and the radicals R ⁴ and R ⁵ within the group -N ¹ -FN ¹ - and in the polysiloxane compound can be identical or different from one another,
F = represents a divalent or tetravalent straight-chain, cyclic or branched C ₂ -C ₃₀ hydrocarbon radical which is represented by -O-, -NH-,


-C (O) -, -C (S) -, a siloxane chain S, where the abovementioned references apply to S, can be interrupted and substituted by -OH, a radical of the general formula:


wherein R ⁶ = a monovalent or divalent straight-chain, cyclic or branched C ₁ -C ₃₀ hydrocarbon radical which is interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted with -OH can be, or can represent a single bond to a trivalent radical K,
R ^{7 is} a monovalent straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which can be interrupted by -O-, -NH- -C (O) -, -C (S) - and substituted by -OH, or - AER ² , in which -AER ^{2 has} the meaning given above,
or represents a single bond to a divalent radical R ⁶ or to a trivalent radical K,
and the radicals R ⁶ and R ^{7 can be} identical or different from one another,
or a residue of the formula

-N ⁵ -F ¹ -N ⁵ -

is what
N ^{5 is} an ammonium group of the general formula


is what
R ^{23 represents} hydrogen, a monovalent or divalent straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which is interrupted by -O-, -NH-, -C (O) -, -C / S) - and with -OH can be substituted
R ^{24 represents} hydrogen, a monovalent straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which is interrupted by -O-, -NH-, -C (O) -, -C (S) - and is substituted by -OH , or represents a single bond to a divalent radical R ²³ , and the radicals R ²³ and R ²⁴ within the group -N ⁵ -F ¹ -N ⁵ - and in the polysiloxane compound can be identical or different from one another,
F ¹ = represents a divalent straight-chain, cyclic or branched hydrocarbon radical which is represented by -O-, -NH-,


-C (O) -, -C / S) - or can be interrupted by a group -E-,
and wherein a plurality of the groups N ⁵ and F ^{1 can} each be the same or different from one another,
contains.

Polysiloxanes of the general formula (I) are also preferred,

- [BN ¹ -FN ¹ ] _m - (I)

wherein
m = 2 to 500,
B = -AEKSKEA- and additionally optionally -AE- A'- or -A'-EA-,
wherein S, K, -AE-, -EA-, -AE-A'- and -A'-EA- and -N ¹ -FN ¹ - are as defined above, and
the proportion of the group -AE-A'- or -A'-EA- in group B can be chosen so that the mass of -AE-A'- or -A'- EA- 0 to 90% of Mass of the polysiloxane portion S in the polymer.

Polysiloxane compounds of the general formula (II) are also preferred,

R ² -EAN ² -KSKN ² -AER ² (II)

wherein
S, K, -AE-, -EA- and R ^{2 have} the meanings given above, and
N ^{2 is} an organic radical which contains at least one quaternary ammonium group of the general formula


is what
R ⁸ = a monovalent or divalent straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which is interrupted by -O-, -NH-, -C (O) -, -C (S) - and is substituted by -OH can
R ^{9 is} a monovalent straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which can be interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted by -OH, or represents a single bond to a divalent radical R ⁸ or to a trivalent radical K, and the radicals R ⁸ and R ⁹ within the polysiloxane compound of the general formula (II) can be identical or different from one another.

Also preferred are polysiloxane compounds of the general formula (III),

[KSKN ³ ] _m - (III)

in the
S, K and m are as defined above,
N ^{3 is} an organic radical containing at least one quaternary ammonium group of the general formula


is what
R ^{10 is} a monovalent straight-chain, cyclic or branched C ₁ -C ₃₀ hydrocarbon radical which can be interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted by -OH or one Represents single bond to K,
R ¹¹ = -AER ² , wherein -AER ^{2 has} the meaning given above.

Polysiloxane compounds of the general formula (IV) are also preferred,

- [N ⁴ -KSKN ⁴ -AE-A '] _m - or - [N ⁴ -KSKN ⁴ -A'-EA] _m - (IV)

wherein
m, K, S, -AE-A'- and -A'-EA- are as defined above, and
N ^{4 is} an organic radical which contains at least one quaternary ammonium group of the general formula


is what
R ¹² = a monovalent or divalent straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which can be interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted by OH .
R ^{13 can have} the meanings of R ¹² , or represents a single bond to K or R ¹² ,
and the radicals R ¹² and R ^{13 may be the} same or different from one another.

A further preferred embodiment is represented by quaternary polysiloxane compounds for cleaning, care of skin, hair and textile fibers, containing at least one polysiloxane compound of the general formula (V)

- [N ⁵ -F ¹ -N ⁵ -Y-] _m (V)

wherein
Y is a group of the formula

-KSK-

and
AE-A'- or -A'-EA-,
wherein m, K, S, -AE-A'- and -A'-EA- are as defined above, the groups K, S, -AE-A'- and -A'-EA- within the polysiloxane compounds of the general formula (V) may be the same or different from one another, and the molar ratio of the group -KSK- and the group -AE-A'- or -A'-EA- in the polysiloxane compound of the general formula (V) of
Is 100: 1 to 1: 100,
N ^{5 is} an ammonium group of the general formula


is what
R ^{23 represents} hydrogen, a monovalent or divalent straight-chain, cyclic or branched C ₁ -C ₂₀ - hydrocarbon radical which is interrupted by -O-, -NH-, -C (O) -, -C (S) - and with -OH can be substituted
R ^{24 represents} hydrogen, a monovalent straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which is interrupted by -O-, -NH-, -C (O) -, -C (S) - and is substituted by -OH , or represents a single bond to a divalent radical R ²³ , and the radicals R ²³ and R ²⁴ within the group -N ⁵ -F ¹ -N ⁵ - and in the polysiloxane compound can be identical or different from one another,
F ¹ = represents a divalent straight-chain, cyclic or branched hydrocarbon radical which is represented by -O-, -NH-,


-C (O) -,
-C (S) - or can be interrupted by a group -E-, in which E is as defined above,
and wherein a plurality of N ⁵ and F ^{1 may} each be the same or different from each other.

• a) mindestens eine Polyalkylenoxid-Struktureinheit der allgemeinen Formeln:
  
  -A-E-, -E-A-, -A-E-A'- = und/oder -A'-E-A-
  
  worin A = -CH₂C(O)O-, -CH₂CH₂C(O)O-, -CH₂CH₂CH₂C(O)O-, -OC(O)CH₂-, -OC(O)CH₂-, -OC(O)CH₂CH₂- und/oder -OC(O)CH₂CH₂CH₂-
  A' = -CH₂C(O)-, -CH₂CH₂C(O)-, -CH₂CH₂CH₂C(O)-, -C(O)CH₂-, -C(O)CH₂-, -C(O)CH₂CH₂- und/oder -C(O)CH₂CH₂CH₂-
  E = eine Polyalkylenoxidgruppe der allgemeinen Formeln:
  
  -[CH₂CH₂O]_q-[CH₂CH(CH₃)O]_r- und/oder
  
  -[OCH(CH₃)CH₂]_r-[OCH₂CH₂]_q-
  
  mit
  q = 1 bis 100,
  r = 0 bis 99,
  q + r = 10 bis 100
  wobei das endständige Sauerstoffatom der Gruppe A an die endständige -CH₂-Gruppe der Gruppe E, und das endständige Carbonyl-Kohlenstoffatom der Gruppe A' an das endständige Sauerstoffatom der Gruppe E jeweils unter Ausbildung von Estergruppen binden,
  und/oder mindestens eine endständige Polyalkylenoxid- Struktureinheit der Formel
  
  -A-E-R²
  
  worin A und E die oben genannte Bedeutung aufweisen,
  und R² = H, geradkettiger, cyclischer oder verzweigter C₁-C₂₀- Kohlenwasserstoffrest, der durch -O- oder -C(O)unterbrochen und mit -OH substituiert und acetylenisch, olefinisch oder aromatisch sein kann,
• b) mindestens ein zweiwertiger oder dreiwertiger organischer Rest, der mindestens eine Ammoniumgruppe enthält,
• c) mindestens eine Polysiloxan-Struktureinheit der allgemeinen Formel:
  
  
  mit S =
  worin R¹ = C₁-C₂₂-Alkyl, C₁-C₂₂-Fluoralkyl oder Aryl,
  n = 14 bis 89, und wenn mehrere Gruppen S in der Polysiloxanverbindung vorliegen, diese gleich oder verschieden sein können,
  K = ein zweiwertiger oder dreiwertiger geradkettiger, cyclischer oder verzweigter C₂-C₄₀- Kohlenwasserstoffrest, der durch -O-, -NH-,
  
  
  -NR¹-, -C(O)-, -C(S)-,
  
  
  unterbrochen und mit -OH substituiert sein kann, worin
  R¹ wie oben definiert ist, oder gegebenenfalls eine Bindung zu einem zweiwertigen Rest R³ darstellt,
  R³ einen einwertigen oder zweiwertigen geradkettigen, cyclischen oder verzweigten C₁-C₂₀- Kohlenwasserstoffrest, der durch -O-, -NH-, -C(O)-, -C(S)- unterbrochen und mit -OH substituiert sein kann, oder -A-E-R² darstellt,
  worin A, E und R² wie oben definiert ist,
  wobei die Reste K gleich oder verschieden voneinander sein können, und im Falle, dass K einen dreiwertigen Rest darstellt, die Absättigung der dritten Valenz über eine Bindung an den vorstehend genannten organischen Rest, der mindestens eine Ammoniumgruppe enthält, erfolgt,
• d) mindestens einen organischen oder anorganischen Säurerest zur Neutralisation der aus der(n) Ammoniumgruppe(n) resultierenden Ladungen, zur gleichzeitigen Erhöhung des Volumens und der Kämmbarkeit
  faserartiger Substrate bei der textilen Erstausrüstung, der separaten Behandlung von Textilien nach dem Waschprozeß mit kationischen Weichmachern und der Behandlung von Haaren mit
  Haarpflegeprodukten, wie Shampoos, Conditionern, Gelen, Pumpsprays und Aerosolsprays führen.

According to the invention, it was specifically found that the task is solved particularly well by quaternary polysiloxane compounds which contain:

• a) at least one polyalkylene oxide structural unit of the general formulas:
  
  -AE-, -EA-, -AE-A'- = and / or -A'-EA-
  
  wherein A = -CH ₂ C (O) O-, -CH ₂ CH ₂ C (O) O-, -CH ₂ CH ₂ CH ₂ C (O) O-, -OC (O) CH ₂ -, -OC (O) CH ₂ -, -OC (O) CH ₂ CH ₂ - and / or -OC (O) CH ₂ CH ₂ CH ₂ -
  A '= -CH ₂ C (O) -, -CH ₂ CH ₂ C (O) -, -CH ₂ CH ₂ CH ₂ C (O) -, -C (O) CH ₂ -, -C (O) CH ₂ -, -C (O) CH ₂ CH ₂ - and / or -C (O) CH ₂ CH ₂ CH ₂ -
  E = a polyalkylene oxide group of the general formulas:
  
  - [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r - and / or
  
  - [OCH (CH ₃ ) CH ₂ ] _r - [OCH ₂ CH ₂ ] _q -
  
  With
  q = 1 to 100,
  r = 0 to 99,
  q + r = 10 to 100
  where the terminal oxygen atom of group A binds 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,
  and / or at least one terminal polyalkylene oxide structural unit of the formula
  
  -AER ²
  
  where A and E have the meaning given above,
  and R ² = H, straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which can be interrupted by -O- or -C (O) and substituted by -OH and can be acetylenic, olefinic or aromatic,
• b) at least one divalent or trivalent organic radical which contains at least one ammonium group,
• c) at least one polysiloxane structural unit of the general formula:
  
  
  with S =
  wherein R ¹ = C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ fluoroalkyl or aryl,
  n = 14 to 89, and if there are several groups S in the polysiloxane compound, these may be the same or different,
  K = a divalent or trivalent straight-chain, cyclic or branched C ₂ -C ₄₀ hydrocarbon radical which is represented by -O-, -NH-,
  
  
  -NR ¹ -, -C (O) -, -C (S) -,
  
  
  interrupted and substituted with -OH, wherein
  R ^{1 is} as defined above, or optionally represents a bond to a divalent radical R ³ ,
  R ^{3 is} a monovalent or divalent straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which can be interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted by -OH , or -AER ² ,
  wherein A, E and R ^{2 are} as defined above,
  where the radicals K can be identical or different from one another, and in the event that K represents a trivalent radical, the third valence is saturated by binding to the above-mentioned organic radical which contains at least one ammonium group,
• d) at least one organic or inorganic acid residue to neutralize the charges resulting from the ammonium group (s), to simultaneously increase the volume and combability
  fibrous substrates in the initial textile finishing, the separate treatment of textiles after the washing process with cationic plasticizers and the treatment of hair with
  Lead hair care products such as shampoos, conditioners, gels, pump sprays and aerosol sprays.

For these volumetric compounds according to the invention are preferred
n = 24 to 79 and especially 24 to 49,
q + r = 10 to 50 and especially 10 to 40,
q = 1 to 99, preferably 1 to 70, and particularly preferably 1 to 40,
r = 0 to 100, preferably 0 to 70, particularly preferably 0 to 40.

Another preferred group of formulations contains at least one of the linear polyquaternary polysiloxane polymers


X is a divalent hydrocarbon radical with at least 4 carbon atoms, which has a hydroxyl group and which can be interrupted by an oxygen atom, and the groups X in the repeating units can be identical or different,
Y is a divalent hydrocarbon radical with at least 2 carbon atoms, which have a hydroxyl group and which can be interrupted by one or more oxygen or nitrogen atoms,
R ¹ , R ² , R ³ and R ^{4 are the} same or different and are alkyl radicals having 1 to 4 carbon atoms or benzyl radicals or the radicals R ¹ and R ³ or R ² and R ⁴ can each be constituents of a bridging alkylene radical,
R ⁶ = H or an alkyl radical with 1 to 20 carbon atoms, which can be oxygen-substituted,
E = the structure -BO- (EOx) v (POx) wB-,
wherein EOx is an ethylene oxide unit and POx is a propylene oxide unit, and
B = straight-chain or branched C2 to C6 alkylene,
v = 0 to 200,
w = 0 to 200
v + w ≥ 1
n = 1 to 1000, in which the n in the repeating units can be the same or different and
A ^{- means} an inorganic or organic anion.

They are preferably linear polysiloxane polymers with the terminal groups


wherein X, R ¹ , R ² , R ³ , R ⁴ , R ⁶ , Y, E, A ^- and n are as defined above,
X 'is a hydrocarbon radical with at least 4 carbon atoms, which has an epoxy group or an epoxy group opened with alcohols, water or amines and which can be interrupted by an oxygen atom, and
R ^{5 is} an alkyl radical having 1 to 20 carbon atoms, and
wherein the terminal groups X in the terminal groups each bind to the terminal nitrogen atoms of the repeating units and the terminal nitrogen atoms in the terminal groups each to the terminal groups X of the repeating units.

Also preferred are cyclic polyquaternary polysiloxane polymers of the general formula (I) in formulations for cleaning, care of skin, hair and textile fibers, containing at least one cyclic polysiloxane compound which contains the following repeating units:


and / or linear compounds of the general formula (II)


wherein
X is a divalent hydrocarbon radical with at least 4 carbon atoms, which has a hydroxyl group and which can be interrupted by an oxygen atom,
Y is a divalent hydrocarbon radical with at least 2 carbon atoms, which have a hydroxyl group and which can be interrupted by one or more oxygen or nitrogen atoms
Z ^{1 is} an H, OH, an alkyl, epoxy or an alkoxy radical, or the meaning of a hydrocarbon radical
has at least 4 carbon atoms, which has one or more hydroxyl group (s) and can be interrupted by one or more oxygen atoms or the meaning of the rest


R ¹ , R ² , R ³ and R ^{4 are} identical or different and are alkyl radicals having 1 to 4 carbon atoms or benzyl radicals or the radicals R ¹ and R ³ or R ² and R ⁴ can each be constituents of a bridging alkylene radical,
where R ^{5 is} an alkyl radical having 1 to 20 carbon atoms,
Z ² the group


R ^{6 is} H or an alkyl radical having 1 to 20 carbon atoms, which may be oxygen-substituted,
E = the structure -B- (OCH ₂ CH ₂ ) _v (OCH ₂ CH (CH ₃ )) _w -OB- with
B = straight-chain or branched C ₂ to C ₆ alkylene,
v = 0 to 200,
w = 0 to 200,
v + w ≥ 1
A ^- an inorganic or organic anion
N = 1 to 1000
m = integer ≥ 1 and
s = an integer ≥ 1.

Specifically, m / (m + s) x100 = 0.1 to 99.9%.
X preferably denotes a radical from the group


Y is a radical - (CH ₂ ) _o -, with o preferably from 2 to 6,
the groups R ¹ , R ² , R ³ , R ⁴ preferably methyl radicals,
R ⁶ preferably hydrogen, -CH ₂ CH ₂ OH and -CH ₃ .
The structural element B is preferably represented by -CH ₂ CH ₂ - and -CH ₂ CH (CH ₃ ) units.

Anions A ^- are preferably physiologically acceptable inorganic residues from the group consisting of chloride, bromide, hydrogen sulfate, sulfate or organic residues from the group consisting of acetate, propionate, octanoate, decanoate, dodecanoate, tetradecanoate, hexadecanoate, octadecanoate, oleate ,

The compounds are preferably in protonated form as Amine salts before.

Another special group of polyquaternary polysiloxane polymers contains cyclic compounds in formulations for cleaning, care of the skin, hair and textile fibers, containing at least one cyclic polysiloxane compound which contains the following repeating units (I) or (II)
(I) cyclic compounds


and / or linear compounds of the general formula (II)


wherein
X is a divalent hydrocarbon radical with at least 4 carbon atoms, which has a hydroxyl group and which can be interrupted by an oxygen atom,
Y is a divalent hydrocarbon radical with at least 2 carbon atoms, which have a hydroxyl group and which can be interrupted by one or more oxygen or nitrogen atoms
Z ^{1 is} an H, OH, an alkyl, epoxy or an alkoxy radical, or has the meaning of a hydrocarbon radical with at least 4 carbon atoms, which has one or more hydroxyl group (s) and can be interrupted by one or more oxygen atoms or the meaning the rest


where R ^{5 is} an alkyl radical having 1 to 20 carbon atoms,
Z ² the group


R ¹ , R ² , R ³ and R ^{4 are} identical or different and are alkyl radicals having 1 to 4 carbon atoms or benzyl radicals or the radicals R ¹ and R ³ or R ² and R ⁴ can each be constituents of a bridging alkylene radical,
where R ^{5 is} an alkyl radical having 1 to 20 carbon atoms,
Z ² the group
R ^{6 is} H or an alkyl radical having 1 to 20 carbon atoms, which may be oxygen-substituted,
E = the structure -B- (OCH ₂ CH ₂ ) _v (OCH ₂ CH (CH ₃ ) _w -OB- with
B = straight-chain or branched C ₂ to C ₆ alkylene,
v = 0 to 200,
w = 0 to 200,
v + w ≥ 10 corresponds
v + w _effectively corresponds to ≥ 10 to 100
A ^- an inorganic or organic anion
n = 9 to 99
m = integer ≥ 1 and
s = an integer ≥ 1.

v + w _effective is the effective length of the alkylene oxide unit in a non-strictly alternating block copolymer, taking into account the frequency of installation. If, in a polymer according to the invention with a silicone chain length n = 50, alkylene oxide blocks with chain length v + w = 160 are additionally incorporated with a frequency of 25% (factor 0.25), then v + w is _effectively = 40.

In these volumetric polysiloxane polymers are preferably
n = 24 to 79, very specifically n = 24 to 49,
v + w _effective = 10 to 50, especially v + w _effective = 10 to 40,
v 0 to 100, preferably 0 to 70, and particularly preferably 0 to 40,
w 0 to 100, preferably 0 to 70, particularly preferably 0 to 40.

The selected residues result in both volume and increase the combability of fibrous substrates in the initial textile finishing, the separate treatment of textiles after the washing process using cationic softeners and treating hair Hair care products, such as shampoos, conditioners, gels, pump sprays and aerosol sprays.

The formulations according to the invention can be in various Dosage forms for fiber treatment are produced. The quaternary polysioxane compounds are preferred as cosmetic formulations for the treatment of substrates containing keratin such as B. hair and skin as pure substance, alcoholic or polyalcoholic solution or incorporated as an emulsion and Application. The use of an alcoholic solution or Emulsion is beneficial. Depending on the raw materials used, Auxiliaries and the mixing process in the manufacture Get clear, cloudy and white formulations. Mixing is preferred the quaternary polysiloxanes in alcoholic solutions or emulsions. The solution can be made using the chemical engineering technique usual stirrers and safety measures in handling Solvents are used (Ullmann's encyclopedia).

The emulsions are produced with the standard emulsifying machines but also z. B. with a high pressure jet disperser. Especially In selected cases, microemulsions may be preferred.

The quaternary polysiloxanes can be used as Emulsifiers are used in formulations for cleaning, skin care, Hair and textile fibers serve at least one quaternary Polysiloxane compounds contain mixtures.

The formulations here comprise so-called "rinse-off" products such as B. 2-in-1 shampoos, body wash and hair conditioners Aftertreatment of hair after cleaning or dyeing or pretreating hair before bleaching the curl 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 fixers, hair sprays, pump sprays, blow dryer and blow dryer. Hair means all fibers containing keratin, but especially human hair.

A distinction is made between the ingredients of the formulations, silicones, Surfactants and auxiliaries. Each of these ingredients can either be used alone or used in combination with other ingredients and stands for additional functions in the formulations for Cleaning, care of skin, hair and textile fibers serve and contain at least one quaternary polysiloxane compound.

silicones

With silicones are cyclic, linear and branched Polydimethylsiloxanes with a viscosity of 0.65-60,000,000 mPas at 25 ° C as well their mixtures such. B. the Baysilone M oils (M5 to M 3,000,000) and SF 1214, SF 1236, SF 1276 and CF 1251 from GE Bayer Silicones understand.

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

Organofunctional silicones, such as alkyl, aryl, Arylalkyl, phenyl, fluoroalkyl, aminoalkyl and polyether modified Silicones such as types SF 1632, SF 1642, SF 1555, Baysilone CF 1301, Baysilone PK 20, FF 157, SF 1708, Baysilone OF 7747, SF 1188A, SF 1288 and SF 1388 from GE Bayer Silicones.

surfactants

Surfactants as ingredients in cosmetic formulations described in A. Domsch: The cosmetic preparations, publisher for Chem. Industry, 4th edition, 1992, in the cosmetic yearbook 1995, publisher for chemical industry, 1995, and H. Stache, Tensid pocket book, 2nd edition, Carl Hanser Verlag, 1981.

Anionic surfactants

The following anionic surfactants are suitable as part of the formulations by way of example but not by way of limitation:
Alkyl sulfates, alkyl ether sulfates, alkaryl sulfates, olefin sulfonates, alkyl amide ether sulfates, acyl isethionates, acyl glutamates, alkyl ether carboxylates, methyl taurides and taurides, sarcosides, sulfosuccinates, protein fatty acid condensates, alkyl phosphates and alkyl ether phosphates. The free acids and their alkali metal, 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 limitation:
Alkyl ethoxylates, aryl ethoxylates, ethoxylated esters, polyglycolamides, polysorbates, glycerol fatty acid ethoxylates, alkylphenol polyglycol ethers and sugar surfactants such as e.g. B. alkyl glycosides.

Cationic surfactants

A distinction is made between pure and cationic surfactants 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 limitation:
Monoalkyl quats, dialkyl quats, trialkyl quats, tetraalkyl quats, benzylammonium salts, pyridine salts, alkanolammonium salts, imidazoline salts, oxazoline salts, thiazoline salts, salts of amine oxides, sulfone salts.

Cationic polymers

In particular for 2-in-1 shampoos, in addition to the pure ones cationic surfactants also used cationically modified polymers. US 5,977,038 provides a comprehensive description of these polymers and WO 01-41720 A1. Cationic are preferred here Polyacrylamides, cationic protein derivatives, hydroxyalkyl cellulose ethers and cationic guar derivatives. Cationic ones are particularly preferred Guar derivatives with the CTFA name guar hydroxypropyltrimonium Chlorides. 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 are used as ingredients in cosmetic formulations described in: A. Domsch, The Cosmetic Preparations, Verlag für chem. Industrie, 4th edition, 1992 and in: Kosmetikjahrbuch 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. As ethanol, isopropanol, 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 opacifying agents, collagen hydrolyzate, keratin hydrolyzate, silk hydrolyzate, antidandruff agents such as. B. zinc pyrithione, salicylic acid, selenium disulfide, sulfur and tar preparations, polymeric emulsifiers, vitamins, dyes, UV filters, bentonites, perfume oils, fragrances, styling polymers, moisturizers, plant extracts and other natural or nature-identical raw materials.

Another object of the invention is the use of a cosmetic formulation containing at least one of the silicone quats contains to improve the conditioning of skin and hair, for Reduction of the wet and dry combing forces of the hair and for Volume increase of the hair.

Examples example 1

• 1a) 211,1 g (0,15 mol Epoxygruppen) eines Epoxysiloxans der durchschnittlichen Zusammensetzung
  
  
  und 15,2 g (0,15 mol) N-Methylpiperazin wurden in 225 ml i-Propanol gelöst und 4 Stunden auf 90°C erhitzt. Nach Beendigung der Reaktion wird das Lösungsmittel durch Destillation im Wasserstrahl- und abschließend Ölpumpenvakuum entfernt. Es werden 217 g eines klaren, gelblichen Produktes der Struktur
  
  
  erhalten.

¹³C-NMR Substruktur shift (ppm) -CH(OH)- 66,07 -CH(OH)-CH₂-N- 60,74 -CH(OH)-CH₂-N-CH₂- 53,20 -CH(OH)-CH₂-N-CH₂-CH₂- 55,10 CH₃-N= 45,87

• 1b) 250 g (0.554 mol OH-Gruppen) eines Polyethylenglycols mit einem mittleren Molekulargewicht von 900 g/mol (ca. 20 Ethylenoxid- Einheiten) wurden unter Stickstoff bei Raumtemperatur vorgelegt. Unter intensiven Rühren wurden innerhalb 30 Minuten 68.8 g g (0.61 mol) Chloressigsäurechlorid zugetropft. Während des Zutropfens stieg die Temperatur auf 80°C an und eine intensive HCl-Entwicklung setzte ein. Nach Beendigung des Zutropfens wurde der Ansatz 60 Minuten auf 110°C erhitzt. Abschließend wurden alle bis 110°C und bei 20 hPa siedenden Bestandteile abdestilliert. Es wurden 273 g einer farblosen, viskosen Flüssigkeit der mittleren Zusammensetzung
  
  ClCH₂C(O)O(CH₂CH₂O)₂₀C(O)CH₂Cl
  
  erhalten, welche nach mehreren Tagen kristallisiert.
• 1c) 75.4 g (25.10^-3 mol) des a,w-Aminosiloxans gemäß Beispiel 1a) und 24.4 g (6,5.10^-3 mol) des a,w-Chloressigsäureesters gemäß Beispiel 1b) wurden unter Stickstoff in 300 ml i-Propanol gelöst und 11 Stunden auf Rückflußtemperatur erhitzt. Nach Beendigung der Reaktion wurden alle bis 40°C bei 20 hPa siedenden Bestandteile entfernt. Es wurden 99.2 g eines bernsteinfarbenen Wachses erhalten.
• 1d) 50 g der erfindungsgemäßen Verbindung wurde mit 29.7 g Renex 36 und 5.1 g Renex 30 (beide erhältlich von Uniquema) versetzt und bei 80°C gerührt. Anschließend wurde innerhalb von 10 Minuten eine Lösung von 1.1 g Eisessig und 0.8 g Natriumacetat in 28.2 g Wasser unter Rühren bei 50°C zugetropft. Nach Abkühlung auf Raumtemperatur wurde eine klare, gelbe Mikroemulsion mit einer Viskosität bei 25°C von 200 mPas (Beispiel 1) erhalten. Die Emulsion war lagerstabil bei 50°C und mit Wasser verdünnbar im Verhältnis 100 Teile Wasser zu einem Teil Emulsion.

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.

<Sup> 13 </ sup> C-NMR substructure shift (ppm) - C H (OH) - 66.07 -CH (OH) - C H ₂ -N- 60.74 -CH (OH) -CH ₂ -N- C H ₂ - 53,20 -CH (OH) -CH ₂ -N-CH ₂ - C H ₂ - 55,10 C H 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. With vigorous stirring, 68.8 g (0.61 mol) of chloroacetic acid chloride were added dropwise within 30 minutes. During the dropping, the temperature rose to 80 ° C and intensive HCl development began. After the dropping had ended, the mixture was heated to 110 ° C. for 60 minutes. Finally, all components boiling up to 110 ° C. and at 20 hPa were distilled off. There were 273 g of a colorless, viscous liquid of the medium composition
  
  ClCH ₂ C (O) O (CH ₂ CH ₂ O) ₂₀ C (O) CH ₂ Cl
  
  obtained, which crystallizes after several days.
• 1c) 75.4 g (25.10 ^-3 mol) of the a, w-aminosiloxane according to Example 1a) and 24.4 g (6.5.10 ^-3 mol) of the a, w-chloroacetic acid ester according to Example 1b) were in nitrogen in 300 ml of i-propanol dissolved and heated to reflux temperature for 11 hours. After the reaction had ended, all components boiling up to 40 ° C. at 20 hPa were removed. 99.2 g of an amber wax were obtained.
• 1d) 29.7 g of Renex 36 and 5.1 g of Renex 30 (both available from Uniquema) were added to 50 g of the compound according to the invention and the mixture was 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, yellow microemulsion with a viscosity at 25 ° C. of 200 mPas (example 1) was obtained. 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 2

In a 1 liter three-necked flask, 24 g of water and 4.18 g (0.048 mol of tertiary amino groups) of N, N, N ', N'-tetramethyl-1,6-hexanediamine and 3.8 g (0.012 mol of primary amino groups) are 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 warming the batch to 50 ° C., 194.1 g (0.06 mol epoxy groups) of an epoxysiloxane of the average composition become within 30 minutes


and 30 ml of 2-propanol were added dropwise. The yellow, cloudy mixture is heated to reflux temperature for 6 hours. After removal of all components volatile up to 100 ° C / 2 mmHg in vacuum, 204 g of a colorless, cloudy material are obtained, which contains the following structural elements


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, yellow microemulsion with a viscosity at 25 ° C. of 5000 mPa.s was obtained. 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

In a 250 ml three-necked flask, 49.33 g 2-propanol, 3.1 g water and 0.53 g (6.12 mmol tertiary amino groups) N, N, N ', N'-tetramethyl-1,6-hexanediamine, 0.81 g (0.76 mmol primary Amino groups) of an alkylene oxide derivative of the structure available under the trade name Jeffamin® ED 2003

H ₂ NCH (CH ₃ ) CH ₂ [OCH ₂ CH (CH ₃ )] _a (OCH ₂ CH ₂ ) _38.7 [OCH ₂ CH (CH ₃ )] _b NH ₂

with a + b = 6
0.1 g of a 45% aqueous trimethylamine solution (0.76 mmol of tertiary amino groups), 0.76 g (3.82 mmol) of dodecanoic acid and 0.23 g (3.82 mmol) of acetic acid (3.82 mmol) at room temperature. After warming to 50 ° C 50 g (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 with the following structural elements


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 on storage at 50 ° C. and could be diluted with water in a ratio of 100 parts water to one part emulsion. Example 4 Preparation of a shampoo Table 1 Preparation of the shampoos to be tested

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

Combing force measurements were made using a Diastron Combing Force Analyzer performed. For this purpose, a 5 g Hair bundles of undyed, naturally brown European hair with "Neutrogena" shampoo prewashed and then the Wet combing force [combing force (wet, neutrogena)] for each hair bundle measured. Then the hair bundles with 2 g of each Test formulation and a bundle of hair with "Neutrogena" as reference 30 Washed for seconds, with running tap water for 1 minute rewashed. This was followed by the wet combing force [Combing force (wet, sample) or combing force (wet, reference)] measured. After drying for 24 hours at room temperature, the Dry combing forces measured. This was also with "Neutrogena" washed hair bundles dried for reference and measured by its dry combing force [combing force (dry, Reference)].

The reduction in the wet combing forces of the examined examples was then calculated according to the following formula based on the hair bundle washed with "Neutrogena":

Wet combing force reduction,% = 1 - [combing force (wet, sample) / combing force (wet, neutrogena)]

The results of this investigation are shown in Table 2. Table 2

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

The results of this investigation are shown in Table 3. Table 3

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

Relative volume = force (example) / force (reference)

The results of this investigation are shown in Table 4. Table 4

Those treated with Formulations A, C and D and dried Hair bundles were also a panel consisting of 10 People to evaluate the feeling, the volume and the shine submitted. In terms of feeling, 7 test subjects preferred formulation D and 3 formulation C. In volume, 8 test subjects preferred Formulation C, 1 test person Formulation D and 1 test person Formulation A. When evaluating the gloss of the submitted Hair bundles preferred 6 subjects formulation C and 4 subjects Formulation D.

The results clearly show that the use of the silicone quats according to the invention leads to a clearly measurable reduction in the wet and dry combing forces. In addition, the use of the silicone quats according to the invention leads to a measurable increase in hair volume and shine. The additional use of a cationic polymer such as guar hydroxypropyltrimonium chloride leads to a further improvement in the conditioning of the hair. Example 5 Preparation of a hair conditioner

R (CH ₃ ) ₂ N-CH ₂ -CH (OH) -CH ₂ -O- (CH ₂ ) ₃ - [Si (CH ₃ ) ₂ O] _x Si (CH ₃ ) ₂ - (CH ₂ ) ₃ - O-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 4. The results are summarized in Table 4. Table 4

The results clearly show that the use of the invention Silicone quats for a clearly measurable reduction in wet and Dry combing forces leads. In addition, the use of silicone quats according to the invention to a measurable increase in Hair volume. A comparison of the hair bundles with that with "Neutrogena" washed reference from Example 4 also shows an increase in Gloss.

Claims (26)

1. Formulations for cleaning, care of skin, hair and textile fibers, containing at least one polysiloxane compound, which consists of: a) at least one polyalkylene oxide structural unit of the general formulas:
- AE-, -EA-, -AE-A'- and / or -A'-EA-
wherein
A = -CH ₂ C (O) O-, -CH ₂ CH ₂ C (O) O-, -CH ₂ CH ₂ CH ₂ C (O) O-, -OC (O) CH ₂ -, -OC ( O) CH ₂ -, -OC (O) CH ₂ CH ₂ - and / or -OC (O) CH ₂ CH ₂ CH ₂ -
A '= -CH ₂ C (O) -, -CH ₂ CH ₂ C (O) -, -CH ₂ CH ₂ CH ₂ C (O) -, -C (O) CH ₂ -, -C (O) CH ₂ -, -C (O) CH ₂ CH ₂ - and / or -C (O) CH ₂ CH ₂ CH ₂ -
E = a polyalkylene oxide group of the general formulas:
- [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r - and / or
- [OCH (CH ₃ ) CH ₂ ] _r - [OCH ₂ CH ₂ ] _q -
With
q = 1 to 200,
r 0 to 200,
wherein the terminal oxygen atom of group A binds 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,
and / or at least one terminal polyalkylene oxide structural unit of the formula
-AER ²
where A and E have the meaning given above,
and
R ² = H, straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which can be interrupted by -O- or -C (O) and substituted by -OH and can be acetylenic, olefinic or aromatic, b) at least one divalent or trivalent organic radical which contains at least one ammonium group, c) at least one polysiloxane structural unit of the general formula:
-KSK-,
With
S =


wherein
R ¹ = C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ fluoroalkyl or aryl,
n = 1 to 1000, and if there are several groups S in the polysiloxane compound, these may be the same or different,
K = a divalent or trivalent straight-chain, cyclic or branched C ₂ -C ₄₀ hydrocarbon radical which is represented by -O-, -NH-


-NR ¹ -, -C (O) -, -C (S) -,


interrupted and substituted with -OH, wherein
R ^{1 is} as defined above, or optionally represents a bond to a divalent radical R ³ ,
R ^{3 is} a monovalent or divalent straight-chain, cyclic or branched C ₁ -C ₂₀ -hydrocarbon radical which can be interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted by -OH , or -AER ² , wherein A, E and R ^{2 are} as defined above,
where the radicals K can be identical or different from one another, and in the event that K represents a trivalent radical, the third valence is saturated by binding to the above-mentioned organic radical which contains at least one ammonium group, d) at least one organic or inorganic acid residue for neutralizing the charges resulting from the ammonium group (s). 2. Formulations for cleaning, care of skin, hair and textile fibers, containing at least one polysiloxane compound according to claim 1, characterized in that preferably K = a divalent or trivalent straight-chain, cyclic or branched C ₂ -C ₄₀ hydrocarbon radical which is formed by - O-, -NH-,


-NR ¹ -, -C (O) -, -C (S) - can be interrupted and substituted by -OH, in which R ^{1 is} as defined above, and where the radicals K can be identical or different from one another. 3. Formulations for cleaning, care of skin, hair and textile fibers containing at least one polysiloxane compound according to claims 1 and 2, characterized in that the aforementioned organic radical, which contains at least one ammonium group, as component b)
a remainder of the general formula:
N ¹ -FN ¹ -
wherein
N ^{1 is} a quaternary ammonium group of the general formula


is what
R ^{4 represents} a monovalent or divalent straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which is interrupted by -O-, -NH-, -C (O) -, -C (S) - and is substituted by -OH can
R ^{5 represents} a monovalent straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which can be interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted by -OH, or represents a single bond to a divalent radical R ⁴ or a tetravalent radical F, and the radicals R ⁴ and R ⁵ within the group -N ¹ -FN ¹ - and in the polysiloxane compound can be identical or different from one another,
F = represents a divalent or tetravalent straight-chain, cyclic or branched C ₂ -C ₃₀ hydrocarbon radical which is represented by -O-, -NH-,


-C (O) -, -C (S) -, a siloxane chain S, where the abovementioned references apply to S, can be interrupted and substituted by -OH,
a remainder of the general formula:


wherein R ⁶ = a monovalent or divalent straight chain, cyclic or
branched C ₁ -C ₃₀ hydrocarbon radical which can be interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted by -OH, or represent a single bond to a trivalent radical K. can
R ^{7 is} a monovalent straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which can be interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted by -OH, or -AER ² , in which -AER ^{2 has} the meaning given above,
or represents a single bond to a divalent radical R ⁶ or to a trivalent radical K,
and the radicals R ⁶ and R ^{7 can be} identical or different from one another,
or a residue of the formula
-N ⁵ -F ¹ -N ⁵ -
is what
N ^{5 is} an ammonium group of the general formula


is what
R ^{23 represents} hydrogen, a monovalent or divalent straight-chain, cyclic or branched C ₁ -C ₂₀ - hydrocarbon radical which is interrupted by -O-, -NH-, -C (O) -, -C (S) - and with -OH can be substituted
R ^{24 represents} hydrogen, a monovalent straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which is interrupted by -O-, -NH-, -C (O) -, -C (S) - and is substituted by -OH , or represents a single bond to a divalent radical R ²³ , and the radicals R ²³ and R ²⁴ within the group -N ⁵ -F ¹ -N ⁵ - and in the polysiloxane compound can be identical or different from one another,
F ¹ = represents a divalent straight-chain, cyclic or branched hydrocarbon radical which is represented by -O-,


-NH-, -C (O) -, -C (S) - or can be interrupted by a group -E,
and wherein a plurality of the groups N ⁵ and F ^{1 can} each be the same or different from one another,
contains. 4. Formulations for cleaning, care of skin, hair and textile fibers, containing at least one polysiloxane compound according to claims 1 to 3, characterized in that preferably polysiloxanes of the general formula (I),

- [BN ¹ -FN ¹ ] _m - (I)

wherein
m = 2 to 500,
B = -AEKSKEA- and additionally optionally -AE- A'- or -A'-EA-,
wherein S, K, -AE-, -EA-, -AE-A'- and -A'-EA- and -N ¹ -FN ¹ - are as defined above, and
the proportion of the group -AEA '= or -A'-EA- in group B can be chosen so that the mass of -AE-A'- or -A'- EA- 0 to 90% of the mass of The amount of polysiloxane S in the polymer can be used. 5. Formulations for cleaning, care of skin, hair and textile fibers, containing at least one polysiloxane compound according to claims 1 to 3, characterized in that polysiloxane compounds of the general formula (II),

R ² -EAN ² -KSKN ² -AER ² (II)

wherein
S, K, -AE-, -EA- and R ^{2 have} the meanings given above, and
N ^{2 is} an organic radical which contains at least one quaternary ammonium group of the general formula


is what
R ⁸ = a monovalent or divalent straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which can be interrupted by -O-, -NH- -C (O) -, -C (S) - and substituted by -OH .
R ^{9 is} a monovalent straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which can be interrupted by -O-, -NH- -C (O) -, -C (S) - and substituted by -OH, or one Represents a single bond to a divalent radical R ⁸ or to a trivalent radical K, and the radicals R ⁸ and R ⁹ within the polysiloxane compound of the general formula (II) may be the same or different from one another. 6. formulations for cleaning, care of skin, hair and textile fibers containing at least one polysiloxane compound according to claims 1 to 3, characterized in that polysiloxane compounds of the general formula (III),

- [KSKN ³ ] _m - (III)

in the
S, K and m are as defined above,
N ^{3 is} an organic radical containing at least one quaternary ammonium group of the general formula


is what
R ^{10 is} a monovalent straight-chain, cyclic or branched C ₁ -C ₃₀ hydrocarbon radical which can be interrupted by -O-, -NH-, -C (O) -, -C / S) - and substituted by -OH or one Represents single bond to K,
R ¹¹ = -AER ² , in which -AER ^{2 has} the meaning given above, can be used. 7. formulations for cleaning, care of skin, hair and textile fibers, containing at least one polysiloxane compound according to claims 1 to 3, characterized in that polysiloxane compounds of the general formula (IV),

- [N ⁴ -KSKN ⁴ -AE-A '] _m - or - [N ⁴ -KSKN ⁴ -A'-EA] _m - (IV)

wherein
m, K, S, -AE-A'- and -A'-EA- are as defined above, and
N ^{4 is} an organic radical which contains at least one quaternary ammonium group of the general formula


is what
R ¹² = a monovalent or divalent straight chain, cyclic or
branched C ₁ -C ₂₀ hydrocarbon residue which can be interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted by -OH,
R ^{13 can have} the meanings of R ¹² , or represents a single bond to K or R ¹² ,
and the radicals R ¹² and R ^{13 may be the} same or different from one another. 8. formulations for cleaning, care of skin, hair and textile fibers, containing at least one polysiloxane compound according to claims 1 to 3, characterized in that polysiloxane compounds of the general formula (V)

- [N ⁵ -F ¹ -N ⁵ -Y-] _m (V)

wherein
Y is a group of the formula
-KSK-
and
-AE-A'- or -A'-EA-,
wherein m, K, S, -AE-A'- and -A'-EA- are as defined above, the groups K, S, -AE-A'- and -A'-EA- within the polysiloxane compounds of the general formula (V) may be the same or different from one another, and the molar ratio of the group -KSK- and the group -AE-A'- or -A'-EA- in the polysiloxane compound of the general formula (V) from 100: 1 to Is 1: 100,
N ^{5 is} an ammonium group of the general formula


is what
R ^{23 represents} hydrogen, a monovalent or divalent straight-chain, cyclic or branched C ₁ -C ₂₀ - hydrocarbon radical which is interrupted by -O-, -NH-, -C (O) -, -C (S) - and with -OH can be substituted
R ^{24 represents} hydrogen, a monovalent straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which is interrupted by -O-, -NH-, -C (O) -, -C (S) - and is substituted by -OH , or represents a single bond to a divalent radical R ²³ , and the radicals R ²³ and R ²⁴ within the group -N ⁵ -F ¹ -N ⁵ - and in the polysiloxane compound can be identical or different from one another,
F ¹ = represents a divalent straight-chain, cyclic or branched hydrocarbon radical which is represented by -O-, -NH-,


-C (O) -,
- C (S) - or can be interrupted by a group -E-, in which E is as defined above,
and wherein a plurality of N ⁵ and F ^{1 may} each be the same or different from each other. 9. Formulations for cleaning, care of skin, hair and textile fibers, containing at least one polysiloxane compound according to claims 1 to 8, which consists of: a) at least one polyalkylene oxide structural unit of the general formulas:
AE-, -EA-, -AE-A'- and / or -A'-EA-
wherein
A = -CH ₂ C (O) O-, -CH ₂ CH ₂ C (O) O-, -CH ₂ CH ₂ CH ₂ C (O) O-, -OC (O) CH ₂ -, -OC ( O) CH ₂ -, -OC (O) CH ₂ CH ₂ - and / or -OC (O) CH ₂ CH ₂ CH ₂ -
A '= -CH ₂ C (O) -, -CH ₂ CH ₂ C (O) -, -CH ₂ CH ₂ CH ₂ C (O) -, -C (O) CH ₂ -, -C (O) CH ₂ -, -C (O) CH ₂ CH ₂ - and / or -C (O) CH ₂ CH ₂ CH ₂ -
E = a polyalkylene oxide group of the general formulas:
- [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r - and / or
- [OCH (CH ₃ ) CH ₂ ] _r - [OCH ₂ CH ₂ ] _q -
With
q = 1 to 100,
r = 0 to 99,
q + r = 10 to 100
where the terminal oxygen atom of group A binds 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,
and / or at least one terminal polyalkylene oxide structural unit of the formula
-AER ²
wherein A and E have the meaning given above, and
R ² = H, straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which can be interrupted by -O- or -C (O) and substituted by -OH and can be acetylenic, olefinic or aromatic, b) at least one divalent or trivalent organic radical which contains at least one ammonium group, c) at least one polysiloxane structural unit of the general formula:
-KSK-,
with S =


wherein
R ¹ = C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ fluoroalkyl or aryl,
n = 14 to 89, and if there are several groups S in the polysiloxane compound, these may be the same or different,
K = a divalent or trivalent straight-chain, cyclic or branched C ₂ -C ₄₀ hydrocarbon radical which is represented by -O-, -NH-,


-NR ¹ -, -C (O) -, -C (S) -,


interrupted and substituted with -OH, wherein
R ^{1 is} as defined above, or optionally represents a bond to a divalent radical R ³ ,
R ^{3 is} a monovalent or divalent straight-chain, cyclic or branched C ₁ -C ₂₀ hydrocarbon radical which can be interrupted by -O-, -NH-, -C (O) -, -C (S) - and substituted by -OH , or -AER ² , wherein A, E and R ^{2 are} as defined above,
where the radicals K can be identical or different from one another, and in the event that K represents a trivalent radical, the third valence is saturated by binding to the above-mentioned organic radical which contains at least one ammonium group, d) at least one organic or inorganic acid residue to neutralize the charges resulting from the ammonium group (s), to simultaneously increase the volume and combability of fibrous substrates in the initial textile finishing, the separate treatment of textiles after the washing process with cationic plasticizers and the treatment of hair with hair care products such as shampoos, conditioners, gels, pump sprays and aerosol sprays. 10. Formulations for cleaning, care of skin, hair and textile fibers containing at least one polysiloxane compound according to claim 9, characterized in that preferred for these compounds
n = 24 to 79,
q + r = 10 to 50,
q 1 to 99,
r = 0 to 100,
stand. 11. Formulations for cleaning, care of skin, hair and textile fibers, containing at least one polysiloxane compound, which consists of:


wherein
X is a divalent hydrocarbon radical with at least 4 carbon atoms, which has a hydroxyl group and which can be interrupted by an oxygen atom, and the groups X in the repeating units can be identical or different,
Y is a divalent hydrocarbon radical with at least 2 carbon atoms, which have a hydroxyl group and which can be interrupted by one or more oxygen or nitrogen atoms,
R ¹ , R ² , R ³ and R ^{4 are} identical or different and are alkyl radicals having 1 to 4 carbon atoms or benzyl radicals or the radicals R ¹ and R ³ or R ² and R ⁴ can each be constituents of a bridging alkylene radical,
R ⁶ = H or an alkyl radical with 1 to 20 carbon atoms, which can be oxygen-substituted,
E = the structure -BO- (EOx) v (POx) wB-, where EOx is an ethylene oxide unit and POx is a propylene oxide unit, and
B = straight-chain or branched C2 to C6 alkylene,
v = 0 to 200,
w = 0 to 200
v + w ≥ 1
n = 1 to 1000, in which the n in the repeating units can be the same or different and
A ^{- means} an inorganic or organic anion. 12. Formulations for cleaning, care of skin, hair and textile fibers containing at least one polysiloxane compound according to claim 11, characterized in that it is linear polysiloxane polymers with the terminal groups


wherein X, R ¹ , R ² , R ³ , R ⁴ , R ⁶ , Y, E, A ^- and n are as defined above,
X 'is a hydrocarbon radical with at least 4 carbon atoms, which has an epoxy group or an epoxy group opened with alcohols, water or amines and which can be interrupted by an oxygen atom, and
R ^{5 is} an alkyl radical having 1 to 20 carbon atoms, and
wherein the terminal groups X in the terminal groups each bind to the terminal nitrogen atoms of the repeating units and the terminal nitrogen atoms in the terminal groups each bind to the terminal groups X of the repeating units. 13. Formulations for cleaning, care of skin, hair and textile fibers, containing at least one cyclic polysiloxane compound, which contains the following repeating units:


and / or linear compounds of the general formula (II)




wherein
X is a divalent hydrocarbon radical with at least 4 carbon atoms, which has a hydroxyl group and which can be interrupted by an oxygen atom,
Y is a divalent hydrocarbon radical with at least 2 carbon atoms, which have a hydroxyl group and which can be interrupted by one or more oxygen or nitrogen atoms
Z ^{1 is} an H, OH, an alkyl, epoxy or an alkoxy radical, or has the meaning of a hydrocarbon radical with at least 4 carbon atoms, which has one or more hydroxyl group (s) and can be interrupted by one or more oxygen atoms or the meaning the rest


R ¹ , R ² , R ³ and R ^{4 are} identical or different and are alkyl radicals having 1 to 4 carbon atoms or benzyl radicals or the radicals R ¹ and R ³ or R ² and R ⁴ can each be constituents of a bridging alkylene radical,
where R ^{5 is} an alkyl radical having 1 to 20 carbon atoms,
Z ^{2 is} the group R ⁶ H or an alkyl radical having 1 to 20 carbon atoms, which may be oxygen-substituted,
E = the structure -B- (OCH ₂ CH ₂ ) _v (OCH ₂ CH (CH ₃ )) _w -OB- with
B = straight-chain or branched C ₂ to C ₆ alkylene,
v = 0 to 200,
w = 0 to 200,
v + w corresponds to 1 ≥
A ^- an inorganic or organic anion
N = 1 to 1000
m = integer ≥ 1 and
s = an integer ≥ 1.


14. Formulations for cleaning, care of skin, hair and textile fibers, containing at least one polysiloxane compound according to claims 11 to 13, characterized in that X is preferably a radical from the group


Y is a radical - (CH ₂ ) _o -, with o preferably from 2 to 6,
R ¹ , R ² , R ³ , R ⁴ preferably methyl radicals,
R ⁶ preferably hydrogen, -CH ₂ CH ₂ OH and -CH ₃ ,
B preferably -CH ₂ CH ₂ - and -CH ₂ CH (CH ₃ ) units, m / (m + s) x100 = 0.1 to 99.9%,
the anion A ^- preferably a physiologically acceptable inorganic radical from the group consisting of chloride, bromide, hydrogen sulfate, sulfate or organic radical, from the group consisting of acetate, propionate, octanoate, decanoate, dodecanoate, tetradecanoate, hexadecanoate, octadecanoate, oleate , and the compounds are preferably in protonated form as amine salts. 15. Formulations according to claims 11 to 13, containing at least one polysiloxane compound, which consists of:
cyclic compounds with the repeating units (I)


and / or linear compounds of the general formula (II)


wherein
X is a divalent hydrocarbon radical with at least 4 carbon atoms, which has a hydroxyl group and which can be interrupted by an oxygen atom,
Y is a divalent hydrocarbon radical with at least 2 carbon atoms, which have a hydroxyl group and which can be interrupted by one or more oxygen or nitrogen atoms
Z ^{1 is} an H, OH, an alkyl, epoxy or an alkoxy radical, or has the meaning of a hydrocarbon radical with at least 4 carbon atoms, which has one or more hydroxyl group (s) and can be interrupted by one or more oxygen atoms or the meaning the rest


where R ^{5 is} an alkyl radical having 1 to 20 carbon atoms,
Z ² the group


R ¹ , R ² , R ³ and R ^{4 are} identical or different and are alkyl radicals having 1 to 4 carbon atoms or benzyl radicals or the radicals R ¹ and R ³ or R ² and R ⁴ can each be constituents of a bridging alkylene radical,
where R ^{5 is} an alkyl radical having 1 to 20 carbon atoms,
Z ² the group
R ^{6 is} H or an alkyl radical having 1 to 20 carbon atoms, which may be oxygen-substituted,
E = the structure -B- (OCH ₂ CH ₂ ) _v (OCH ₂ CH (CH ₃ )) _w -OB- with
B = straight-chain or branched C ₂ to C ₆ alkylene,
v = 0 to 200,
w = 0 to 200,
v + w ≥ 10 corresponds
v + w _effectively corresponds to ≥ 10 to 100
A ^- an inorganic or organic anion
n = 9 to 99
m = integer ≥ 1 and
s = an integer ≥ 1. 16. Formulations for cleaning, care of skin, hair and textile fibers containing at least one polysiloxane compound according to claim 15, characterized in that preferred
n = 24 to 79, very specifically n = 24 to 49,
v + w _eff. = 10 to 50, especially v + w _effective = 10 to 40,
v = 0 to 100
w = 0 to 100 mean. 17. Production of formulations according to claims 1 to 16 thereby characterized that the quaternary polysiloxanes with other surfactants and auxiliaries are mixed to form an emulsion. 18. Use of formulations containing at least one Polysiloxane compound according to claims 1 to 17 for treatment substrates containing keratin. 19. Use of formulations containing at least one Polysiloxane compound according to claim 18, wherein the keratin-containing Substrate is human hair. 20. Use of formulations containing at least one Polysiloxane compound according to claim 18, wherein the keratin-containing Substrate is human skin. 21. Use of formulations containing at least one Polysiloxane compound according to Claims 1 to 18, for the production of so-called "rinse-off" products, such as. B. 2-in-1 shampoos, body Wash and conditioners for the after-treatment of hair after the Cleaning or dyeing or pretreating hair before the bleaching of the curl or crimp, as well as so-called "Leave-in" products such as hair treatments, skin care creams, hairdressing creams, Hair gels, hair styling products, hair fixers, hair sprays, pump sprays, Fönwellmittel and Fönfestiger deals. 22. Use of formulations containing at least one Polysiloxane compound according to claims 1 to 20 for improvement the wet combing forces. 23. Use of formulations containing at least one Polysiloxane compound according to claims 1 to 20 for improvement the dry combing forces. 24. Use of formulations containing at least one Polysiloxane compound according to claims 1 to 20 to increase the Hair volume. 25. Use of formulations containing at least one Polysiloxane compound according to claims 1 to 20 to increase the Gloss. 26. Use of formulations containing at least one Polysiloxane compound according to claims 1 to 20 for simultaneous Improvement of wet combing forces and / or improvement of Dry combing forces and / or the increase in hair volume and / or the increase in gloss.