EP1560973A2

EP1560973A2 - Formulations used for the treatment of substrate surfaces

Info

Publication number: EP1560973A2
Application number: EP03811391A
Authority: EP
Inventors: Horst Lange; Christopher Roos; Roland Wagner; Martin Kropfgans; Andrew Russell Graydon; Richard Timothy Hartshorn; Jean-Pol Boutique; Patrick Firmin August Delplanque; James Pyott Johnston
Original assignee: GE Bayer Silicones GmbH and Co KG
Current assignee: Momentive Performance Materials GmbH
Priority date: 2002-11-04
Filing date: 2003-10-31
Publication date: 2005-08-10
Also published as: CN1735729A; JP2006505716A; US7585494B2; MXPA05004750A; CN1735729B; AU2003302035A1; WO2004046452A2; CA2504914A1; US20060163524A1; WO2004046452A3; BR0315997A

Abstract

The invention relates to formulations containing at least one nitrogen-free polysiloxane compound, at least one polyamino polysiloxane and/or polyammonium polysiloxane compound, and/or at least one amino polysiloxane and/or ammonium polysiloxane compound, and an optional silicone-free cationic surfactant, a coacervate phase-forming agent, and carrier substances. Also disclosed are a method for the production of the inventive formulations and the use thereof for treating natural and synthetic fibrous materials.

Description

FORMULATIONS FOR SURFACE TREATMENT OF

SUBSTRATES

DESCRIPTION:

The invention relates to formulations based on polysiloxane, processes for their preparation and their use, in particular for the treatment of textiles and other natural and synthetic fibrous materials.

Polysiloxanes containing amino groups are known as textile plasticizers (EP 441530). The introduction of amino structures modified by ethylene oxide / propylene oxide units as side chains brings about an improvement in the effect (US Pat. No. 5,591,880, US Pat. No. 5,650,529). The alkylene oxide units allow the targeted adjustment of the hydrophilic-hydrophobic balance. It has also been proposed to react ω-epoxy-modified siloxanes with ω-amino-functionalized alkylene oxides and to use these products as hydrophilic plasticizers (US Pat. No. 5,807,956, US Pat. No. 5,981,681).

Attempts have been made to improve the substantivity by introducing quaternary ammonium groups into alkylene oxide-modified siloxanes. Branched alkylene oxide-modified polysiloxanquats (“polysiloxanquats”

= polysiloxanes containing quaternary ammonium groups) have been synthesized from oc, ω-OH-terminated polysiloxanes and trialkoxysilanes by condensation. The quaternary ammonium structure is introduced via the silane, the quaternary nitrogen atom being substituted by alkylene oxide units (US Pat. No. 5,602,224).

Strictly comb-like alkylene oxide-modified polysiloxanquates have also been described. The hydroxyl groups of comb-substituted polyether siloxanes are converted into the corresponding chlorine derivatives using epichlorohydrin (US Pat. No. 5,098,979) or chloroacetic acid (US Pat. No. 5,153,294, US Pat. No. 5,166,297). This is followed by quaternization with tertiary amines. No. 6,242,554 describes α, ω-di_functional siloxane derivatives which each have a separate quaternary ammonium and alkylene oxide unit. These materials are characterized by improved compatibility with polar environments. The reaction of oc, ω-diepoxides with tertiary amines in the presence of

Acids provide α, ω-diquartary siloxanes, which can be used for hair care purposes (DE-A-37 19 086). In addition to tetraalkyl-substituted quaternary ammonium structures, aromatic imidazolinium derivatives are also claimed. A reduction in the washability from hair can be achieved if the oc, ω-diepoxides are reacted with di-tertiary amines in the presence of acids to form long-chain polyquaternary polysiloxanes (EP-A-282 720). Aromatic quaternary ammonium toctures are not disclosed.

Such polyquaternary imidazolinium derivatives are treated in US 6,240,929. These cationic compounds are said to have a further increased compatibility compared to the anionic surfactants present in cosmetic formulations. However, the washout resistance from hair refers to the short-term attack of primarily water and very mild surfactants that do not irritate the skin, while wash-resistant, hydrophilic plasticizers for textiles have to withstand the attack of concentrated surfactant solutions with high fat and dirt-dissolving properties. To make matters worse, modern detergents contain strongly alkaline complexing agents, oxidative bleaching agents and complex enzyme systems and the fibers are often exposed to the effects for hours at elevated temperatures. Highly charged, very hydrophilic synthetic polycationic compounds are also able to improve the compatibility with anionic surfactant systems (US Pat. No. 6,211,139) or to associate them with fibers in the presence of solutions of anionic surfactants (WO 99/14300). The latter document describes, inter alia, polyimidazolinium derivatives. Mixtures of cationic polysaccharide derivatives with polysiloxanes have also been investigated (JVGruber et. Al., Colloids and Surfaces B: Biointerfaces 19 (2000) 127-135). It is also known to combine hydrocarbon-based quats, which are used extensively in fabric softeners, for example, with polysiloxanes.

It has been proposed to emulsify silicone oils of certain viscosities with cationic surfactants and to incorporate these emulsions in fabric softener formulations which contain further cationic surfactants (WO 00/71806 and WO 00/71807). In US 4,961,753 hydrocarbon quats are combined with a mixture of high-viscosity and low-viscosity polysiloxanes. Emulsions of hydrocarbon-based quats (silicone-free quaternaries

Ammonium compounds with hydrocarbon residues) with highly branched or cross-linked! Polydimethylpolysiloxane (PDMS) are claimed in US 4,908,140. According to US 4,978,462, straight-chain PDMS should advantageously be added to such a system. The combination of hydrocarbon-based quats with OH-terminated

Polysiloxanes as textile softeners are claimed in WO 98/50502.

Combinations of hydrocarbon-based quats with siloxanes from the groups of the unfunctionalized polydimethylsiloxanes, aminosiloxanes or polyether siloxanes are described in WO 95/24460 as constituents of fabric softener formulations.

According to US Pat. No. 5,852,110 and US Pat. No. 6,090,885, aminosiloxane emulsions are prepared by alkaline polymerization in the presence of cationic surfactants.

Finally, it is known from GB 1 549 180 to combine emulsions of unfunctionalized polysiloxanes obtained by alkaline polymerization in the presence of cationic surfactants with further hydrocarbon quat. Alternatively, the hydrocarbon-based quats should also be used together with ω-diquaternary polysiloxanes or comb-like substituted polyquaternary polysiloxanes or aminosiloxanes. None of the suggestions dealt with provides a satisfactory solution for that

The problem is the soft touch of textile materials that is fundamentally possible due to the use of silicones directly during the washing process with modern detergent systems based on anionic surfactants.

WO 02/10256, WO 02/10257 and WO 02/10259 claim silicone materials which enable textiles to be softened during the washing process with such detergent systems. The US patent application 2002/0103094 deals with the use of the silicone materials mentioned in textile care formulations.

A further improvement in the performance of the siloxane systems described above with regard to the achievable softness of the treated fibers, in particular with the same or improved substantivity (adhesion of the siloxane systems to the fiber), the flexibility in the formulation of the siloxane systems and the dosage form, in particular in the direction of reducing the necessary ones Amounts used and material costs are very desirable. It is therefore an object of the invention to formulate

Polysiloxane base especially for the treatment of textiles and other natural and synthetic fibrous materials such as To provide paper fibers and hair which gives such materials or substrates, preferably textile materials, a silicone-typical softness, improved elasticity and reduced tendency to crease, in particular in the presence of anionic surfactants or other anionic surface-active agents for fiber pretreatment, such as e.g. occurs when used in detergent systems and when finishing pretreated fibers. At the same time, the formulations should have a high substantivity on the substrate surfaces. It is another object of the invention to use this

Formulations as a component of separate plasticizer systems after the washing of fibers, as a component of plasticizer systems for nonwovens, such as paper and textiles, as a component of systems for original textile finishing, as an ironing aid and as a means of preventing or reversing textile creases and as a component of cosmetic systems to treat hair and skin. Another object of the invention is to provide formulations based on polysiloxane, which can be flexibly adjusted to the type of substrates to be treated and the treatment conditions by simply varying the composition ratios of the components they contain. can be. Furthermore, the formulations should make it possible to reduce the amounts required to achieve the desired properties of the substrates to be treated and / or to use expensive polysiloxane components, such as so-called polysiloxane quats, without the desired properties of the substrates to be treated being impaired ,

It has surprisingly been found that certain multicomponent formulations of, in particular, polysiloxane-containing compounds can achieve the above object and are inexpensive and nevertheless extremely effective agents for the treatment of certain materials, such as in particular fiber materials.

The present invention thus provides a formulation which contains: a) at least one nitrogen-free polysiloxane compound, b) at least one polyamino and / or polyammonium polysiloxane compound bl) and / or at least one amino and / or ammonium polysiloxane - Compound b2), c) optionally one or more silicone-free surfactants, d) optionally one or more coacervate phase formers, e) optionally one or more carrier substances.

The formulation according to the invention preferably contains 5 to 99% by weight of component a) and 1 to 95% by weight of component b), based on the total amount of components a) and b). The amount of component a) is more preferably 20 to 90% by weight and the amount of component b) is 10 to 80% by weight, particularly preferably the amount of component a) is 30 to 90% by weight and the amount of Component b) 10 to 70 wt .-%, each based on the total amount of components a) and b). The optionally present carrier substances of component e) are preferably selected from solid carrier substances f) and / or liquid carrier substances g), which are described in more detail below.

The formulation according to the invention preferably contains 0 to 1500, more preferably 0 to 1000, more preferably 0 to 500, even more preferably 0 to 300 and most preferably 0 to 150 parts by weight of the optionally present components c), d) and e), based on 100 parts by weight of components a) and b).

Component c) is preferably added in amounts of 0 to 70, more preferably 0 to 50 and particularly preferably 0 to 30 parts by weight per 100 parts by weight of the total amount of components a) and b). If component c) is present in the formulation according to the invention, it is present in amounts of> 0 parts by weight, preferably> 0.1 part by weight per 100 parts by weight of the total amount of components a) and b). Component d) is preferably added in amounts of 0 to 10, more preferably 0 to 3, particularly preferably 0 to 1.5 and most preferably 0 to 0.9 parts by weight per 100 parts by weight of the total amount of components a) and b). If component d) is present in the formulation according to the invention, it is present in amounts of> 0, preferably> 0.01 parts by weight, preferably at most up to 1 part by weight, per 100 parts by weight of the total amount of components a) and b).

Component f) is preferably added in amounts of 0 to 710, more preferably 0 to 300 and particularly preferably from 0 to 100 parts by weight per 100 parts by weight of the total amount of components a) and b). If component f) is present in the formulation according to the invention, it is present in amounts of> 0 parts by weight, preferably> 5 parts by weight per 100 parts by weight of the total amount of components a) and b).

Component g) is preferably added in amounts of 0 to 710, more preferably 0 to 300 and particularly preferably from 0 to 100 parts by weight per 100 parts by weight of the total amount of components a) and b). If component g) is present in the formulation according to the invention, it is in quantities of> 0 parts by weight, preferably> 5 parts by weight per 100 parts by weight of the total amount of components, a) and b).

Component e), i.e. component f) and / or g) is preferably added in amounts of 0 to 1420, more preferably 0 to 600 and particularly preferably from 0 to 200 parts by weight per 100 parts by weight of the total amount of components a) and b).

The component a) of the formulation according to the invention provides a nitrogen-free polysiloxane compound is These are preferably straight-chain, cyclic, branched or partially crosslinked polydiorganosiloxane siloxanes wherein the organo group is preferably selected from:. C _\ to C ₆ alkyl groups, polyalkyleneoxy groups whose End groups can be hydroxyl, ether or ester groups, and which are preferably bonded to the silicon via alkylene groups, and aryl groups, and where the polydiorganosiloxanes on the silicon can optionally have functional groups, in particular hydroxyl and alkoxy groups, with the exception of nitrogen-containing groups. The organo groups are particularly preferably selected from methyl, ethyl, butyl, phenyl, poly (ethyleneoxy) and copoly (ethyleneoxy) (propyleneoxy) groups. Most preferred are polydialkylsiloxanes, especially polydimethylsiloxanes. The nitrogen-free, functionalized or unfunctionalized polysiloxane compounds according to component a), in particular the polydimethylsiloxanes, expediently have a viscosity in the range from 100 to 50,000,000 mPa.s, preferably from 10,000 to 20,000,000 mPa.s, more preferably from 10,000 to 10,000 .000 mPa.s, more preferably between 100,000 and 10,000.00 mPa.s. such as between 100,000 and 1,000,000 mPas and between 1,000,000 and 10,000,000 mPas at 25 ° C and a shear rate gradient of D = 1 s ^"1 .

The polysiloxane compounds according to component a) which have functional groups are, for example, co-dihydroxy-terminated polydimethylsiloxanes. The amount of component a), based on the total amount of

Formulation, is preferably in the range from 0.3% by weight to 99% by weight, preferably from 1.2% by weight to 90% by weight, more preferably from 1.8% by weight to 80% by weight, and most preferably from 5% by weight to 70% by weight.

Examples of the polysiloxane compounds according to the definition of component a) are described, for example, in "Silicone Surfactants", ed.: R. M. Hill, Surfactant Science Series, Vol. 86, Marcel Dekker, Inc., 1999.

Preferred polysiloxane compounds as defined in component a) include, for example, silicone polymers of the formulas (II) to (III):

and mixtures thereof, in which R ^{24 is in} each case selected independently of one another from the group consisting of: hydroxyl groups, linear, branched or cyclic alkyl groups having 1 to 22 carbon atoms, linear, branched or cyclic alkenyl groups having 2 to 22 carbon atoms, linear, branched or cyclic alkoxy groups with 1 to 8 carbon atoms, phenyl; Alkylaryl groups of 7 to 20 carbon atoms; Arylalkyl groups with 7 to 20 carbon atoms, a poly (ethylene oxide / propylene oxide) copolymer group of the general formula (IV):

-R ²⁵ -O (C ₂ H4θ) _c (C ₃ H ₆ O) _d -R ²⁶

(IV) wherein R is a straight chain, branched or cyclic alkanediyl group having 3 to 22 carbon atoms, which may optionally be interrupted by one or more oxygen atoms, and R 26 is independently selected from the group consisting of hydrogen, alkyl having 1 to 16 carbon atoms and an acetyl group, in which the index a is expediently chosen such that the viscosity of the nitrogen-free silicone polymer of the formula (II) for the derivatives of this class which are liquid at 25 ° C. is between 1 is up to 20 mPa-s and the index b is expediently chosen such that the viscosity of the nitrogen-free silicone polymer of the formula (III) for the derivatives of this class which are liquid at 25 ° C. is between 1 and 50,000,000 mPa-s. The index "a" or the average degree of polymerization as M _n is preferably 3 to 6 and the index "b" or the average degree of polymerization as M _n is preferably 300 to 5000; wherein the viscosity values given in the present application are measured at a temperature of 25 ° C and a shear rate gradient of D = 1 s ^"1 ; and wherein c + d = 1 to 10,000, and c = 1 to 10,000 and d = 0 to 100 and the ethyleneoxy and propyleneoxy groups are random or block-like, preferably randomly arranged Examples of the nitrogen-free silicone polymers of the formula (III) are the so-called Silwet® compounds from OSi Specialties from Crompton, Middlebury, Connecticut, USA, or Tegostab from Goldschmidt, Essen or the SF PU foam stabilizer types from GE Bayer Silicones GmbH & Co KG, Leverkusen, further examples of the compounds of the formulas (II) and (III) are

Polydimethylsiloxane oils e.g. from GE Bayer Silicones GmbH & Co. KG of the Baysilone M series or silicone oils from the 200 series from Dow Corning.

The preferred amount of component a) in the formulation, based on the total amount of the formulation, is 5 to 99, preferably 10 to 80, more preferably 10 to 40% by weight.

Component b) used according to the invention is at least one polyamino and / or polyammonium polysiloxane compound b1) and / or at least one amino and / or ammonium polysiloxane compound b2). The polyamino and / or polyammom ^' polysiloxane compound bl) is a copolymer compound which has amino and / or ammonium repeating units and polysiloxane repeating units in the polymer main chain. The amino units contain secondary and / or tertiary Nitrogen atoms (2 or 3 organic residues on the neutral nitrogen atom). The ammonium units contain secondary, tertiary and / or quaternary positively charged nitrogen atoms (2, 3 or 4 organic residues on the nitrogen). Amino and / or ammonium repeat units can also serve as heterocyclic radicals integrated into the polymer chain via two nitrogen atoms.

In contrast to this, component b2) is

Polysiloxane Nerbindungen that in the side groups of

Polyorganosiloxane backbone contain amino and / or ammonium groups.

That is, the amino and / or ammonium groups are not in the main chain of polyorganosiloxane repeating units.

The difference can be illustrated as follows: polyamino and / or polyammonium polysiloxane linkage bl):

- amino / ammonium — j— polyorganosiloxane - amino / ammonium ^ polyorganosiloxane

Amino and / or ammonium polysiloxane linkage b2):

- Polyorganosiloxane ette

Amino / ammonium containing residue

In the formulation according to the invention, components bl) and b2) serve mainly as a substantivity-giving component.

Components bl) and b2) can be present alone or together in the formulation according to the invention. In a preferred embodiment, component bl) 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.

The polyamino and / or polyammonium polysiloxane linkage bl) is preferably a polysiloxane linkage which contains at least one unit of the formula (I):

- [Q-V] - (I)

where Q is selected from the group consisting of:

-NO-,

-N ⁺ R ₂ - a saturated or unsaturated diεiminofunctional 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,

ι + ^• N—

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

where Q does not bind 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-, -CONH-,

-CONR -, wherein R represents hydrogen, a monovalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 100 carbon atoms, which has one or more groups selected from -O-, -NH-, -C (O) - and -C (S) -, and 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, Ammonium, polyether residues and polyether ester residues can be substituted, where there are several -CONR groups, these can be the same or different,

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

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

the radical V has at least one group -Z - of the formula

contains what R ^{1 may be the} same or different and is selected from the group consisting of: Ci to C ₂₂ alkyl, fluoro -C ₁₀ ) alkyl and C ₆ -Cι ₀ aryl, and nι = 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-, -CONH-,

-CONR ² -, wherein R ^{2 is} as defined above, where the groups R ² in groups V and V can be the same or different,

-C (O) -, -C (S) - and -Z ¹ - may contain, wherein -Z ¹ - a group of the formula

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

and the radical V ^{1 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-, -CONR ² -, wherein R ^{2 is} as defined above, -C (O) -, -C (S) -, -Z -, which is as defined above, -Z - which as is defined above, and Z, wherein Z is a trivalent or higher organopolysiloxane unit, and

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

wherein in the said polysiloxane compound in each case one or more

Groups V ¹ , one or more groups V ² and / or one or more

Groups V ³ may be present, with the proviso that the polysiloxane compound mentioned has at least one group V ¹ ,

V ² or V ³ 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, further from - [Q-V] -

Units are branched or the trivalent and tetravalent radicals Q are saturated with radicals V within a linear main chain without formation of a branch, and in which the positive charges resulting from ammonium groups are neutralized by organic or inorganic acid anions, and their acid addition salts.

The polysiloxane compounds which contain at least one unit of the formula (I) are terminated by monofunctional groups -QR and / or -VR, ie for example by amino groups. These result from the saturation of one of the two binding sites of Q or V by a monovalent group R or hydrogen, which is as defined above, and subsequently also become V ^st or Q ^st called. Instead of V ^{st there} can also be other unreacted reactive groups, such as epoxy or haloalkyl groups.

For the purposes of the invention, the polysiloxane compounds which contain at least one unit of the formula (I) are also intended to include the case where only one unit - [QV] - is present, so that compounds of the formulas RV- [QV] -R or R- [QV] -QR, in which R can also be replaced by H, are included.

Suitable polyamino and / or polyammonium polysiloxane compound bl) are, for. B. described in WO 02/10257, WO 02/10259, DE-OS 100 36 522,

DE-OS 100 36 532, DE-OS 100 36 533 and the unpublished DE application 102 12 470.1. Furthermore, it can be connections according to US 6240929.

The polysiloxane compounds which contain at least one unit of the formula (I) are, for example, linear polysiloxane copolymers of the general formula (F):

- [Q-V] - (I ')

where Q is as defined above,

V represents at least one group V 1 and at least one group V 9, wherein V and V are as defined above. In addition, V can also represent trivalent or higher, especially trivalent radicals V ³ . In this case, there are also trivalent or tetravalent units Q, as defined above, and the saturation of the trivalent or higher-valent radicals V3 and the trivalent or tetravalent units Q occurs exclusively with one another within the linear main chain with the formation of cyclic structures, as further below explained in more detail. However, this case is less preferred.

In a preferred embodiment of the polyamino and / or polyammonium polysiloxane copolymers B1) of the formulas (I) or (V), Q is therefore selected from the group consisting of:

-NR-, -N ⁺ Rz- a saturated or unsaturated diaminofunctional heterocycle of the formulas:

an aromatic diamino-functional heterocycle of the formula:

1 wherein R is as defined above, and V is selected from V and V.

In the general formulas (I) and (P), the molar ratio of

Groups V 1 and V9 in the polysiloxane compounds V 9 / V 1 take on any value per se. According to the invention, this also includes the case in which the polysiloxane compound of the formulas (I) or (F) contains only V ² units, that is to say the polysiloxane compound has the formula - [QV ² ] -. The case in which the polysiloxane compound contains only V ^ units is also included according to the invention. In this case, however, the V ¹ units must contain Z ^ siloxane units. In a preferred embodiment of the invention, however, the polysiloxane compound of the formulas (I) or (F) contains both V ² and V ¹ units.

In a further preferred embodiment of the present invention, the molar ratio of groups V ¹ and V ² in the polysiloxane compounds of the general formulas (I) and (F) is:

V ² N '= 1.

Such linear amine or tetraorgano-ammonium compounds are e.g. have been described in WO 02/10257, WO 02/10259, EP 282720 or US 5,981,681. Particularly preferred are the polysiloxanes of WO 02/10259 and WO 02/10257, the polysiloxane polymers defined in claims 1 of which are hereby expressly referred to and which belong to the disclosure content of the present application.

In a further embodiment of the linear polysiloxane compounds of the formula (I) or (F), VVV ^{1 is} not equal to 1, preferably VVV ¹ <1, more preferably <0.9, even more preferably VVV ¹ fulfills the relationship

0.0005 <V ² / N ¹ <0.5, more preferred

0.0005 <V ² / V ¹ <0.3.

The group R is preferably selected from the groups R.

In a preferred embodiment of the invention, Q is a divalent radical and is selected in the formulas (I) or (F) from the group consisting of:

-NO-,

-K? R ₂ - a quaternized imidazole unit of the structure

a quaternized pyrazole unit of the structure

a double quaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a doubly quaternized unit of structure

a monoquaternized unit of the structure

a doubly quaternized unit of structure

a monoquaternized unit of the structure

and a monoquaternized unit of the structure

R8

I (CH ₂ ) t

R2 _ ^ _ R3

wherein

t is from 2 to 10,

R is as defined above, preferably R ² , R ^{2 is} as defined above, and the meaning

9 9 of R may be the same or different from the meaning of the above group R,

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

R ² and R ³ together with the positively charged nitrogen atom form a five- to seven-membered heterocycle which can optionally additionally have one or more nitrogen, oxygen and / or sulfur atoms, R, R, R may be the same or different and are selected from the group consisting of: H, halogen, hydroxyl group, nitro group, cyano group, thiol group, carboxyl group, alkyl group, monohydroxyalkyl group, polyhydroxyalkyl group, thioalkyl group, cyanoalkyl group, alkoxy group, acyl group, acetyloxy group , Cycloalkyl group, aryl group, alkylaryl group, and groups of the type

-NHR ^W , in which R ^{w is} H, alkyl group, monohydroxyalkyl group, polyhydroxyalkyl group, acetyl group, ureido group, and in each case two of the adjacent radicals R, R and R 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 may be the} same or different.

In case Q is a trivalent remainder of the formulas

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

In a preferred embodiment of the polysiloxane compounds of the formula (I) or (F) as component bl), V ^{2 represents} a group of the formula -V ² * -Z ² -V ² * -, in which Z ^{2 is} as defined above and V ² * represents a divalent straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical with up to 40 carbon atoms, which optionally contains one or more groups selected from -O-, -CONH-, -CONR ² -, in which R ^{2 is} as defined above, may contain -C (O) - and -C (S) -, and the radical V ² * may optionally be substituted by one or more hydroxyl groups.

In the embodiment mentioned above, the linear polysiloxane copolymer according to the invention can have the following repeating units:

- [V ² * -Z -V ² * -Q] - preferably together with - [V ^ Q] -.

The molar ratio of the repeat units - [V ² * -Z -V ² * -Q] - to

1 9 1 - [V -Q] - _. that is, the NN ratio can be 1, as mentioned above, but in one embodiment it is preferably not equal to 1, more preferably <0.9, even more preferably <0.8, even more preferably <0.3. In the cases Wv ¹ <1, the linear polysiloxane copolymers mentioned - [QV] - necessarily contain blocks which contain more than one - [V ^ Q] unit linked to one another. As will be explained in more detail below in connection with the process for the preparation of the linear polysiloxane copolymers described above, the block-like sequences which have more than one - [N ^ Q] unit linked to one another can, depending on the method of preparation, be used regularly with the N ² - Q units or irregularly connected to the N ² -Q units. This means the following:

In the case of the regular compound, in which, for example, a prepolymer corresponding to the group -Q-IN'-Qj _{x is} reacted with monomer units corresponding to N ² in a molar ratio of 1: 1, the linear polysiloxane copolymers can be prepared as follows:

x can be 2 to 2000 and is the average of the distribution. The through the

Formula - {V ² -Q- [V ¹ -Q] _X -} - linear polysiloxane copolymers shown are characterized in that they essentially have no interlinked -

9 9

V -Q units, or in other words, two -N -Q units are always interrupted by at least one -N ^ Q unit. With the irregular connection, for example with Q units

1 9 corresponding monomers with V corresponding monomer units and V

1 9 corresponding monomer units in the ratio Q / (V + N), with, for example, Wv ¹ <1, preferably <0.5, of 1: 1, the linear polysiloxane copolymers can be prepared as follows:

-QO ^ N ² ) -,

where N is the ratio NVV ¹ <1 or <0.5. The groups N ¹ and N ^{2 are} statistically distributed over the copolymer chain. In contrast to the linear polysiloxane copolymer produced by the regular connection, this copolymer can also have adjacent -QV ² units.

In a preferred embodiment of the polysiloxane compound of formula (I) or (F) as component bl) used according to the invention, group V ^{1 is} selected from divalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals with up to 600, preferably up to 400 carbon atoms, optionally one or more groups selected from -O-, -COΝH-, -COΝR ² -, wherein R ^{2 is} as defined above, -C (O) -, -C (S) - and -Z ¹ - can contain, wherein -Z ¹ - a group of the formula

is what

R ¹ -C -C ₈ alkyl, which may optionally be substituted with one or more fluorine atoms, or is phenyl, and n _{2 is} as defined above.

In a further preferred embodiment of the polysiloxane compounds of the formula (I) or (F) as component bl), the group Q is selected from:

a quaternized imidazole unit of the structure

a quaternized pyrazole unit of the structure

a double quaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

, a monoquaternized piperazine unit with the structure rxY {2

-N + N-

a monoquaternized unit of the structure wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are} as defined above.

In a further preferred embodiment of the linear polysiloxane compounds of the formula (F) as component bl) of the present

9 1

Invention, the molar ratio N / N satisfies the relationship

0.0005 <N ^l <0.5, (= 2 <V 'V ² <2000)

preferred the relationship

0.005 <VW <0.4, (= 2.5 <VW ² <200)

the relationship even more preferred

0.01 <V7V ¹ <0.3 (= 3.3 <VW <100).

In formulas (I) and (F) are preferred:

R ¹ = Ci to Cis alkyl, especially methyl, ethyl, trifluoropropyl and phenyl,

n = 20 to 400, particularly preferably 20 to 300, especially 20 to 200. In a further preferred embodiment, ni is between 20 and 50 or between 80 and 200. The number ni is the average degree of polymerization from M _{n of} the diorganosiloxy units in the Group Z. n = 0 to 15, particularly preferably 0 to 10, especially 0 to 5, more particularly 0. The number n ₂ is the average degree of polymerization from M _{n of} the diorganosiloxy units in group Z ¹ .

V ² = a divalent straight-chain, cyclic or branched, saturated, unsaturated C ₃ to C ₆ hydrocarbon radical or aromatic C ₈ to C ₀ hydrocarbon radical, which optionally has one or more groups selected from -O-, -CONH-, -CONR ² - ,, -C (O) -, -C (S) - may contain and may be substituted by one or more OH groups, wherein R ^{2 is} as defined above.

a quaternized imidazole unit of the structure

a double quaternized piperazine unit of the tract

a monoquaternized piperazine unit of the structure

a monoquaternized unit of the structure

-N-

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

Is particularly preferred

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

- (CH ₂ ) 3θCH CHCH ₂ - - (CH ₂ ) 3θCH ₂ CH OH CH ₂ OH

- (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 (O) CH ₂ -, -CH ₂ CH ₂ CH ₂ OC (O) CH ₂ CH ₂ -,

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

CH ₃

-CH ₂ CH ₂ CH ₂ (OCH CH ₂ ) _V '(OCH ₂ CH) _w OC (O) CH -

CH ₃

-CH ₂ CH ₂ CH ₂ (OCH CH ₂ ) _v (OCH ₂ CH) _w OC (O) CH ₂ CH ₂ -

CH ₃

-CH = CHCH ₂ (OCH ₂ CH ₂ ) _v ι (OCH ₂ CH) _w OC (O) CH ₂ -

CH

-CH = CHCH ₂ (OCH ₂ CH ₂ ) _v ι (OCH ₂ CH) _w OC (O) CH ₂ CH ₂ - CH ₃

-CH = CHCH ₂ CH ₂ (OCH CH ₂ ) _v (OCH ₂ CH) _w OC (O) CH ₂ .

CH ₃

-CH = CHCH ₂ CH ₂ (OCH ₂ CH ₂ ) _v (OCH ₂ CH) _w OC (O) CH ₂ CH ₂ -

C 1 H3 - "

- (CH) ioC (O) (OCH ₂ CH ₂ ) _v (OCH ₂ CH) _w OC (O) CH CH ₂ .

CH3

- (CH) ioC (O) (OCH ₂ CH ₂ ) _v (OCH ₂ CH) _iw OC (O) CH ₂ -

it v + w> 0,

- (CH ₂ ) 3θCH ₂ CHCH ₂ - - (CH ₂ ) 3θCH ₂ CH- OH i; H ₂ OH

- (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 (O) CH ₂ -, - CH ₂ CH ₂ CH ₂ OC (O) CH ₂ CH ₂ -

R preferably stands for: H,

-CH ₃ , -CH ₂ CH ₃ , - (CH ₂ ) ₂ CH ₃ , - (CH ₂ ) ₃ CH ₃ , - (CH ₂ ) ₅ CH ₃ , -CH ₂ CH ₂ OH, With

R ⁴ = straight-chain, cyclic or branched to Cι ₈ hydrocarbon radical, which can contain one or more groups selected from -O-, -NH-, -C (O) - and -C (S) - and one or several OH groups can be substituted, especially unsubstituted C ₅ to C ₁ hydrocarbon radicals which are derived from the corresponding fatty acids or hydroxylated C ₃ to C 1 radicals which can be attributed to hydroxylated carboxylic acids, especially saccharide carboxylic acids, and very specifically

mean. R 2 furthermore stands for:

w "" or "i, nt, R _π ³ ₅ to R ^{8 are} as defined above, wherein t, R> 5 to R are as defined above,

wherein t, R, R and R are as defined above.

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 ) _u C (O) O - [(CH ₂ CH ₂ O) _q - (CH ₂ CH (CH ₃ ) O) _r ] -C (O) (CH ₂ ) _u - ■ - (CH ₂ ) _u C (O) OR ⁹ -OC (O) (CH ₂ ) _u -, where R ^{9 is} as previously defined,

- (CH ₂ ) _u -R ¹⁰ - (CH2) u-, where R ^{10 is} an aromatic group, - [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -CH ₂ CH ₂ -, -CH (CH ₃ ) CH ₂ O [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -CH ₂ CH (CH ₃ ) - -CH ₂ CH (OH) CH ₂ - , ^■ -CH ₂ CH (OH) (CH ₂ ) ₂ CH (OH) CH ₂ -,

-CH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH ₂ - and -CH ₂ CH (OH) CH ₂ O- [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -CH ₂ CH (OH) CH ₂ - wherein u is from 1 to 3, q and r from 0 to 200, preferably from 0 to 100, more preferably from 0 to 70 and particularly preferably 0 to Is 40 and q + r> 0.

Preferred variants of V ¹ are structures of the formula: -CH ₂ C (O) O- [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -C (O) CH ₂ -,

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

-CH ₂ CH ₂ CH ₂ C (O) O- [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -C (O) CH ₂ CH ₂ CH ₂ -, esterified alkylene, Alkenylene, alkynylene units, especially the structures

-CH ₂ C (O) O- [CH ₂ ] ₀ -OC (O) CH ₂ -,

-CH ₂ CH ₂ C (O) O- [CH ₂ ] ₀ -OC (O) CH ₂ CH ₂ -,

-CH ₂ CH ₂ CH ₂ C (O) O- [CH ₂ ] ₀ -OC (O) CH ₂ CH ₂ CH ₂ -

-CH ₂ C (O) O-CH ₂ C≡CCH ₂ -OC (O) CH ₂ -, -CH ₂ CH ₂ C (O) O-CH ₂ C≡CCH ₂ -OC (O) CH ₂ CH2- .

-CH ₂ CH ₂ CH ₂ C (O) O-CH ₂ C≡CCH2-OC (O) CH2CH ₂ CH2-,

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

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

-CH ₂ CH ₂ CH ₂ C (O) O-CH ₂ CH = CHCH ₂ -OC (O) CH ₂ CH ₂ CH ₂ , alkylene, alkenylene, alkynylene and aryl units, especially the structures:

- [CH ₂ ] ₀ - with o = 2 to 6,

-CH ₂ C≡CCH ₂ -, -CH ₂ CH = CHCH ₂ -, -CH (CH ₃ ) CH ₂ CH ₂ -,

Polyalkylene oxide units, especially the structures

- [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -CH ₂ CH ₂ -, -CH (CH ₃ ) CH ₂ O [CH ₂ CH ₂ θ] _q - [CH ₂ CH (CH ₃ ) O] _r -CH ₂ CH (CH ₃ ) - with mono-, di- or polyhydroxy-functional units, especially the structures -CH ₂ CH (OH) CH ₂ -, -CH ₂ CH (OH) (CH ₂ ) 2CH (OH) CH ₂ -, -CH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH ₂ -, -CH ₂ CH (OH) CH ₂ O- [CH ₂ CH ₂ O] _q - [CH ₂ CH (CH ₃ ) O] _r -CH ₂ CH (OH) CH ₂ - with q = 0 to 200, 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.

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

a) at least one amine compound selected from a diamine compound and / or a primary or secondary monoamine compound are reacted with at least two difunctional organic compounds capable of reacting with the amino functions of the amine compound, the molar ratio of the organic compounds being chosen in this way the desired ratio V ² / V ^! is obtained, b) at least two moles of an amine compound selected from a diamine compound and / or a primary or secondary monoamine compound are reacted with one mole of a difunctional organic compound capable of reacting with the amino functions of the amine compound to form a diamine compound (monomer) which is subsequently reacted with at least one amine compound selected from a diamine compound and / or a primary or secondary monoamine compound and at least one further difunctional organic compound capable of reacting with the amino functions of the amine compounds, c) an amine compound selected from one Diamine compound and / or a primary or secondary monoamine compound, with a difunctional organic compound capable of reacting with the amino functions of the amine compounds to form a diamine compound (amino-terminated oligomer), which on closing with at least one difunctional to react with the Amine functions of the diamine compounds enabled organic

Compound is reacted, 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

Reaction with amino-capable compound (difunctional

Oligomer) is implemented, which then 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 is reacted, where appropriate monofunctional, preferably tertiary monoamines or suitable monoamines and / or monofunctional not capable of chain propagation, Compounds capable of reacting with amino functions as

Chain terminators can be added, and the stoichiometry of the

Amino functions and the functional groups capable of reacting with amino functions in the last stage of the reaction is always about 1: 1, and any amino functions which may be present can be protonated or quaternized.

Variant a), wherein at least one diamine compound selected from a diamine compound and / or a primary or secondary monoamine compound is reacted with at least two difunctional organic compounds capable of reacting with the amino functions of the amine compound, the molar ratio of the organic Connections like that

9 1 is selected so that the desired ratio V / N such as <0.5 is fulfilled, can be represented schematically as follows, for example:

- [Ν-Ν] - + - [N ¹ ] - + - [N ² ] - → - [QO ^ N ² )] - or - [Ν] - + - [V ¹ ] - + - [V ² ] - → - [Q- ^ N ² )] - where - [NN] - a cyclic diamine corresponding to the definition of Q or a -containing diamine - [NV ^ N] - or an N ² -containing diamine - [Ν-N ² -Ν] -, in particular - [NV ² * -Z ² -V ² * -N] - can include, from

1 9 the latter each have two Q units and one V or two N units, and - [N ¹ ] - and

9 1 9

- [V] - should represent monomers corresponding to the repeating units V and V, and - [Ν] - a primary or secondary suitable for chain propagation

Monoamine represents, from the - [Ν-Ν] - and / or - [Ν] units, at least one higher-alkylated amine or quaternary ammonium unit Q is formed, secondary or tertiary amino functions formed in the polymerization possibly being followed the polymerization can be protonated or quaternized in a separate step. The formation of quaternary ammonium units is preferred.

Preferred examples of - [Ν-Ν] - are as described in more detail below: piperazine and imidazole, preferred diamine units - [Ν- -Ν] - include, for example: polymethylene diamines such as tetramethylhexamethylene diamine, α, ω-diamino-terminated polyethers such as Jeffamine, etc. Preferred diamine units - [Ν-V ² * -Z ² -V ² * -Ν] - include, for example

Reaction products of α, co-dihydrogenpolydialkylsiloxane with allylamines. Preferred examples of - [N] - are described in more detail below, e.g. Dimethylamine.

The use of diamines - [N-N] - is preferred per se. Preferred - [V ^ monomers include, for example, epichlorohydrin, bis-

Chloroalkyl esters, bisepoxides or bisacrylates. Mixtures of the mentioned - [N ^ monomers, such as e.g. Mixtures of epichlorohydrin, bis-chloroalkyl esters or bisepoxides are implemented.

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

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

Variant bl)

Step 1): 2 - [Ν-Ν] - + - [N ² ] - or - [N ¹ ] - → - [Ν-Ν-N ^ Ν-Ν] - or - [Ν-Ν-N ² - Ν-Ν] -

Step 2.1): - [NNN ² -NN] - + - [V ¹ ] - + - [NN] - →, Step 2.2): - [N-NΛ ^ -NN] - + - [V ² ] - + - [NN] - ->,

9 1 with the stoichiometry V / V being set as desired. With regard to the preferred monomer units - [NN] -, - [V ¹ ] - and - [N ² ] - that applies to step a).

Variant b2)

Step 1): 2 - [Ν] - + - [V ² ] - or - [V ¹ ] - → - [ΝN'-Ν] - or - [Ν-V ² -Ν] - Step 2.1): - [ NV ² -N] - + - [V ¹ ] - + - [N] ~ →, step 2.2): - [NV ^ N] - + - [V ² ] - + - [N] - →, this variant As mentioned above, it can only be carried out with primary or secondary monoamines and, with regard to the preferred monomer units - [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 cl)

Step 1): - [NN] - + - [V ¹ ] - → - [NN-fN ^ NN ^] - Step 2): - [NN-CV ^ NN) ^ - + - [V ² ] - → where with regard to the preferred monomer units used - [NN] -, - [V ¹ ] - and - [V ² ] - what has been said for step a). Variant c2)

Step 1): - [N] - + - [V ¹ ] - → - [NC ^ - - Step 2): - [NO ^ -N) *] - + - [V ² ] - → being with regard to the preferred ones Monomer units - [N] -, - [V ¹ ] - and - [V ² ] - that applies to step a).

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

Variant dl) step 1): - [V ¹ ] - + - [NN] - → - ^ - (NNV ¹ ) ^] -

Step 2): - ^ - (NNV ¹ ^] - + - [V ² ] - + - [N] - or - [NN] - → with regard to the preferred monomer units - [NN] -,

- [V ¹ ] - and - [V ² ] - that applies to step a).

Variant d2)

Step 1): - [V ¹ ] - + - [N] - → - [^ - (NV ¹ ) *] -

Step 2): - [^ - (NV ¹ ^] - + - [V ² ] - + - [N] - or - [NN] - → with regard to the preferred monomer units - [N] -, - [ NN] -, -

[V ¹ ] - and - [V ² ] - that applies to step a). For all variants shown schematically above, mixtures of

Monoamines - [Ν] - and diamines - [Ν-Ν] - can be used.

The functional groups of the difunctional groups are particularly preferred

Reaction with amino functions enabled Nerb selected from the

Gmppe, which consists of epoxy groups and haloalkyl groups. As a starting point for the syntheses of the used according to the invention

Polysiloxane copolymers of the formulas (I) and (F) are, ω Si-H functionalized

General structure siloxanes

preferred, wherein R ^{1 has} the meaning given above and n, depending on the desired repeat unit, is V ¹ or V ² , n ₂ or n], 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 structure elements V ² * and Q can, for. B. done in two ways.

On the one hand, it is possible to bind unsaturated structures initially carrying tertiary amino functions, for example N, N-dimethylallylamine, directly to the siloxane in the, ω-position by hydrosilylation. This process is well known (B. Marciniec, Comprehensive Handbook on Hydrosilylation, Pergamon Press, Oxford 1992, pp. 122-124).

On the other hand, it is preferred to first generate reactive, functionalized intermediates by hydrosilylation, which can subsequently be converted into ω-tertiary amino structures or 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 alkynes, 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-

Chloropropionic acid propargylester and epoxy-functional alkenes, for example vinylcyclohexene oxide and allyl 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-methylglucamine, cyclic secondary amines, for example morpholine and piperidine, aminoamides which carry secondary amino functions, for example the reaction products of diethylenetriamine or dipropylenetriamine with lactones, such as γ-butyrolone, such as γ-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, to carry out 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 secondary amino groups: reactive groups <10, preferably 1 to 3, especially 1 to 2, very particularly 1. Excess amine may need to be removed.

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

On the one hand, it is preferred to separately produce a strongly hydrophilic, polyquaternary, difunctional precondensate - [V ^ QV ^ _x ] -, which is combined with the α, co-ditertiary aminosiloxanes at a suitable time and reacts to form the polyamino or polyquaternary siloxane copolymers , The production of highly charged, difunctional prepolymers of different chain lengths - [V ^ QV ¹ ^] - is described by way of example in WO 99/14300 (Examples 1 to 7, Table 11). Depending on the molar ratio of N 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 - [Ν-CV ^ - - to the amine function of an α, ω-ditertiary aminosiloxane structure For example, an alkylating or quaternizing, difunctional monomer corresponding to the repeating unit V ¹ - [V 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, co-ditertiary aminosiloxane structure.

In the case of a prepolymer terminated by reactive groups, such as - [V ^ CQ-N ¹ ) -] -, a direct link to the amine function of the .alpha.,. Omega.-ditertiary aminosiloxane structure can be made without a further linker, since an excess of the V ¹ generating component was used.

As an alternative to the separate preparation of a precondensate - [^ - (QN ^ _x ] -, highly charged blocks can be built up parallel to the incorporation into the copolymer. This means that the α, ω-di-tertiary aminosiloxane with the starting components for building up - [V ^ QV ^ _x ] -, ie for example - [V ¹ ] - and mono- or diamines of the meaning mentioned above - [Ν] - and / or

- [Ν-Ν -] - submitted together and brought to reaction. Finally, it is possible to use the α, ω-ditertiary aminosiloxane with long chain

9 1

Siloxane unit Z or short-chain siloxane unit Z or the α, o-difunctional siloxane - [Ν-N ² * -Z ² -N ² * -Ν] - or - [NV ^ N] - in the components presented to build up - [ V ^ QV ^ _x ] - to be gradually metered over a period of time or, conversely, to gradually add these components to the α, ω-di-tertiary aminosiloxane or, ω-difunctional siloxane.

Upstream provision of amino-terminated prepolymers, e.g. - [N-CV ^ - y- opens up the possibility of directly using suitable reactive intermediates, for example epoxy derivatives

To carry out copolymer formation.

It is also preferred to use the reactive intermediates and the

Submit starting components for the construction of - [V ^ QV ¹ ) ^ - together and then react.

Finally, it is possible - the reactive intermediates in the submitted

Components for building up - [V ^ QV ^ _x ] - gradually over a period of time meter or, conversely, 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 functionalities and the groups reactive with them is approximately 1: 1.

Within the scope of the invention it is possible to prefer from this

Deviate overall stoichiometry. However, products are then obtained which are no longer the targeted length of the highly charged, hydrophilic block

- [N ^ QN ¹ ) _* ] - and also an excess of an unreacted

Leave start components.

In addition to the overall stoichiometry of the reaction discussed above, for

Characteristics of the products the choice of the component (s) forming the repeat unit V ^{1 is} of great importance.

Suitable difunctional, the repeating units V ¹ underlying

Monomers - [V ¹ ] - are, for example, the halocarboxylic acid esters of the polyalkylene oxide diols.

Preferred starting materials for their synthesis are low molecular weight, oligomeric and polymeric alkylene oxides of the general composition

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

where q and r have the meanings given above, and are statistical or block-like units. Preferred representatives with regard to the alkylene oxide block are ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, the oligoethylene glycols with molecular weights of 200 to 10,000 g / mol, especially 300 to 800, and 1,2-propylene glycol, 1,3-propylene glycol and dipropylene glycol. The esterification of the alkylene oxides is carried out in a manner known per se (organics, basic organic chemical internship, 17th edition, VEB German Publishing House of Sciences, Berlin 1988, pp. 402-408) by reaction with the C ₂ - to C ₄ -halocarboxylic acids, their anhydrides or acid chlorides. To be favoured the acid chlorides of chloroacetic acid and 3-chloropropionic acid used and the

Reaction carried out in the absence of solvents.

In an analogous manner, alkanediols, alkenediols and alkynediols can be converted into the corresponding reactive ester derivatives. Exemplary alcohols are 1,4-butanediol, 1,6-hexanediol, 1,4-but (2-) enol and 1,4-but (2-) inol.

The alkylene, alkenylene, alkynylene and aryl units are preferably introduced starting from the corresponding halides, especially chlorides and bromides. Exemplary representatives are 1,6-dichlorohexane, 1,4-dichlorobut- (2) - ene, 1,4-dichlorobut (2) -in and 1,4-bis (chloromethyl) benzene. Polyalkylene oxide units can also be introduced via the α, ω-dihalo compounds. These are made from the oligomeric and polymeric alkylene oxides of the general composition

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

where q and r have the meanings given above, for example accessible by chlorination of the hydroxyl groups with SOCl ₂ (Organikum, Organischchemisches Grundpraktikum, 17th edition, VEB Deutscher Verlag der Wissenschaften, Berlin 1988, pp. 189-190). Mono-, di- or polyhydroxy-functional units as Gmppe V ¹ can be introduced starting from epoxy derivatives.

Commercial examples are l-chloro-2,3-epoxypropane, glycerol-l, 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, in V ¹ siloxane chains Z ^{1 of} the chain length range n ₂ = 0 to 19, preferably 0 to 15, particularly preferably 0 to 10, especially 0 to 5, more particularly 0, install. Suitable starting materials for installation are, for example, the corresponding α, ü - diepoxides or α, ω-di (monohalocarboxylic acid) ester structures. When reacting epoxides with primary or secondary amines, care must be taken to ensure that one mole of H + per mole of epoxy αV tertiary amine is added for alkyl amines of tertiary amino groups.

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

The use of secondary-tertiary diamines, for example N-methylpiperazine, opens the way to repeat units - [V ^ QV ^ _x ] - in which tertiary and quaternary amine or AiT monium structures are present in a ratio of 1: 1. 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 primary-tertiary diamines, for example N, N-dimethylpropylenediamine and 1- (3-aminopropyl) imidazole, especially in combination with diepoxides, are used, comb-like structures can be built up for which the degree of quaternization can be selected during a final alkylation. In principle, the alkylation quantities can also be set to degrees of quaternization of on average less than one quaternary ammonium group per repeating unit - [V ^ QV ^ _x ]. However, it is preferred to quaternize at least one nitrogen atom per repeat unit. Starting from secondary amines, for example piperazine, N, N'-bis (2-hydroxyethyl) hexamethylene diamine, N, N'-bis (2-hydroxypropyl) hexamethylene diamine, it is also possible in principle to use repeating units - [V ^ QV ¹ ^] - with an average salary of less than one quaternary Ammonium groups can be synthesized. The secondary amines initially provide poly-tertiary amino-modified siloxane copolymers or prepolymers which can be quaternized partially or completely in a final reaction to - [N ^ CQ-N ¹ ); -] -. 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 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 oc, ω-diepoxides and, ω-di (monohalocarboxylic acid) esters have been named as suitable starting materials. The ions A ^″ neutralizing the positive charges resulting from the ammonium groups are preferably the ions formed during the quaternization, such as halide ions, especially chloride and bromide, alkyl sulfates, especially methosulfate, carboxylates, especially acetate, propionate, octanoate, decanoate, dodecanoate, tetradecanoate, hexadecanoate , Octadecanoate, oleate, sufonates, especially toluenesulfonate, but other anions can also be introduced by ion exchange, such as organic anions such as polyether carboxylates and polyether sulfates.

The quaternization reactions are preferably carried out in water, polar organic solvents or mixtures of the two components mentioned. For example, 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 are suitable , Ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, Butyl acetate and 2-ethyl-hexyl 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 which may be present and disrupt 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 end-stop cases are intended to be covered by the aforementioned definition -Q-R and / or -V-R, wherein Q, V and R are as defined above and R may be replaced by hydrogen.

The polysiloxanes of the general formula (I) used according to the invention as component b1) can also contain branching units V. V ^{3 is} a trivalent or higher, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 1000 carbon atoms, which may or may not have one or more groups selected from -O-, -CONH-, - CONR ² -, wherein R ^{2 is} as defined above, -C (O) -, -C (S, -Z ¹ - which is as defined above, -Z ² - which is as defined above, and Z ³ , wherein Z ^{3 is} a trivalent or higher organopolysiloxane unit, branching unit V may be silicone-free, examples of which include:

with v + w> 0.

The branching unit V ³ may contain a trivalent or higher organopolysiloxane unit, such as:

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

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

The polyamino and / or polyarnmonium polysiloxane compounds bl) 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 / 1 at 25 ° C. One or more amino and / or ammonium polysiloxane compounds b2) can be used as 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 carrying primary and / or secondary and / or tertiary amino groups in the side groups, in which the amino groups are optionally protonated or quaternized, and the additional hydrophilic groups, if appropriate can contain. The amino or ammonium groups mentioned are preferably bonded to the siloxane skeleton via carbon. The amino and / or ammonium polysiloxane compounds b2) mentioned are preferably polyalkylsiloxanes with aminoalkyl or aminoarylsiloxane units. The aminoalkyl units can be bound both to the difunctional, tifunctional or monofunctional end groups and can be part of other oxygen-containing side groups, in particular of polyether side groups.

The optionally present additional hydrophilizing groups are preferably those derived from polyalkylene oxides and saccharides.

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

(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 radicals 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 having up to 200 carbon atoms, optionally one or more groups selected from

-O-

9 9

-NR -, wherein R is hydrogen, a monovalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical with up to 100

Represents carbon atoms, which may contain one or more groups selected from -O-, -NH-, -C (O) - and -C (S) -, and optionally by one or more substituents selected from the group consisting from a hydroxyl group, an optionally substituted, preferably one or more

Heterocyclic groups, amino, containing nitrogen atoms

Alkylamino, dialkylamino, ammonium, polyether residues and

Polyetheresterreste can be substituted, where if several groups -NR ² are present, these can be the same or different,

-N-

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

and the remainder optionally selected from hydroxy and by one or more substituents wherein R ¹ , m, m2, as defined above, can be substituted,

Hydroxyl, - a polyether radical with up to 20,000 carbon atoms, which optionally contains one or more amino, mono- or dialkylamino, or arylamino

Can carry groups, a saccharide-containing organic radical, or two substituents R ¹¹ from different Siloxyeinlieiten together form a straight-chain, branched or cyclic alkanediyl radical with 2 to 12 carbon atoms between two silicon atoms, with the proviso that at least one substituent R ¹¹ per molecule of nitrogen contains, ie represents a nitrogen-containing radical R ¹¹ .

R ¹¹ preferably represents alkyl, in particular methyl.

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

OH -CH2CH2CH2NH2 -CH2CH2CH2NHCH2CH2 H2 -CH2CH2CH2OCH2CHCH2NH2

OH OH

I I

-CH2CH2CH20CH2CHCH2 HCH2CH2NH2 -CH2CH2CH20CH2CHCH2 HCH2CH2CH2NH2

-CH2CH2CH2OCH2

OH CH2CH ₂ N (CH ₃ ) 2 OH CH2CH ₂ CH ₂ N (CH3) 2

• CH2CH2CH2OCH2CHCH2 N -CH2CH2CH2OCH2CHCH2N

CH ₂ CH2N (CH ₃ ) 2 CH2CH ₂ CH2N (CH3) 2

Further preferred amino or ammonium-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 ¹¹ include, for example:

CH3

-CH ₂ CH ₂ CH ₂ (OCH ₂ CH) _v (OCH ₂ CH) _w OH

CH3 -CH CH ₂ CH ₂ (OCH ₂ CH ₂ ) _v (OCH ₂ CH) _w OC (O) CH3

CH3 -CH ₂ CH CH (OCH ₂ CH ₂ ) _v (OCH ₂ CH) _w OCH3

CH3 -CH = CHCH2 (OCH ₂ CH) _v (OCH ₂ CH) _w OH

CH3 -CH = CHCH ₂ (OCH2CH ₂ ) v (OCH ₂ CH) _w OC (O) CH3

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

CH3 -CH = CHCH ₂ CH (OCH2CH ₂ ) _v (OCH ₂ CH) _w OH

CH3 -CH = CHCH2CH ₂ (OCH ₂ CH ₂ ) _v (OCH ₂ CH) _w OC (O) CH3

CH3 -CH = CHCH ₂ CH ₂ (OCH CH ₂ ) _v (OCH CH) _w OCH3

CH3

CH = CCH (OCH ₂ CH2) v (OCH ₂ CH) _w OH | CH3 CH ₂ (OCH ₂ CH ₂ ) _v (OCH ₂ CH) _w OH

CH3

CH = CCH2 (OCH CH2) _v (OCH CH) _w OC (O) CH3 I CH3

CH2 (OCH2CH2) v (OCH ₂ tH) _w OC (O) CH3

with v + w> 1.

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

The production of such saccharide-containing polysiloxanes can be found e.g. in DE 4 318 536, DE 4318 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.

The typical nitrogen content of the aminopolysiloxanes b2) used according to the invention is, for example, between 0.005% by weight to 18% by weight, preferably 0.02% by weight to 5% by weight, particularly preferably 0.02% by weight to 1.5% by weight.

The aminopolysiloxanes b2) used can be solid or liquid at 25 ° C. In the event that they are liquid at 25 ° C, the viscosities of the aminopolysiloxanes b2) used according to the invention are preferably between 500 to 500,000 mPa.s at 25 ° C, preferably 1000 to 25000 mPa.s at 25 ° C and with a shear rate gradient from 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.

Some of the inventively used Aminopolysiloxanes b2) described above are available for example as Wacker Finish® WR 1100 and General Electric ^® SF 1,923th

The preferred amount of component b), i.e. bl) + b2), based on the total amount of the formulation, is 1 to 30, preferably 1 to 20% by weight.

Component c) optionally used is one or more silicone-free, preferably cationic, surfactants. It is preferably at least one constituent which is selected from unpolymerized, organic, quaternary ammonium compounds. They are preferably quaternary ammonium salts or amine salts containing hydrocarbon groups, the hydrocarbon groups preferably being able to contain 8 to 28 carbon atoms.

Examples of component c) are compounds of the following formula:

R ¹² R ¹³ R ¹⁴ R ¹⁵ N + X-,

wherein R ¹² , R ¹³ , R ¹⁴ and R ^{15 are} independently selected from the group consisting of: Cj-C ₂ 8 alkyl, alkenyl, hydroxyalkyl, benzyl, alkylbenzyl, alkenylbenzyl, benzylalkyl and benzylalkenyl, and X is an anion , The hydrocarbon groups R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ can independently be polyalkoxylated, preferably polyethoxylated or polypropoxylated, more preferably with groups of the general formula (C ₂ H4θ) yH where y = 1 to 15, preferably 2 to 5. No more as one of the groups R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ should be benzyl. The groups R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ can independently of one another one or more, preferably two ester

(- [- OC (O) -]; [-C (O) -O-]) and / or amido groups (- [CO-N (R ¹² ) -]; [-N (R ^I2 ) -CO -]) where R ^{12 is} as defined above. The anion X can be selected from halides, methosulfates, acetate and phosphate, preferably from halides and methosulfate. Further examples of component c) are tetraorgano-substituted quaternary ammonium compounds with one or two long-chain C8 to C28 hydrocarbon radicals and two or three short-chain Cl to C6 hydrocarbon radicals. The long-chain radicals C12 to C20 are preferably chains and the short-chain radicals are methyl, ethyl, propyl, butyl, hexyl, phenyl and hydroxyethyl, 2-hydroxypropyl. Preferred counterions are Cl ^" , Br ^" , CH ₃ OSO ₃ ^" , C ₂ H ₅ OSO ₃ ^" , NO ₃ ^" , HCOO ^" and CH ₃ COO ^" .

Examples include: Dodecyl-ethyl-dimethyl-ammonium bromide Didodecyl-dimethyl-ammonium bromide.

In the cationic surfactants, which are only a long chain

19

Containing hydrocarbon group R, the chain length of the long-chain hydrocarbon group is preferably 12 to 15 carbon atoms, and the short-chain radicals R ¹³ , R ¹⁴ and R ¹⁵ are preferably methyl and hydroxyethyl. In the cationic surfactants, the two, three or even four long chain

Containing hydrocarbon groups, the chain length of the long-chain hydrocarbon groups is preferably from 12 to 28 carbon atoms. Preferred ester-containing surfactants have the formula:

{(R ¹⁶ ) ₂ N [(CH ₂ ) _Z ER ¹⁷ ] ₂ } ⁺ X- wherein R ^{16 is} independently selected from Cj_4 alkyl, hydroxyalkyl or C ₂ _4 alkenyl; and wherein R ¹⁷ is independently selected from C 8 ₂ 8 alkyl or alkenyl groups is selected; E is an ester group, ie, -OC (O) - or -C (O) O-, z is an integer from 0 to 8, and X ^"is as defined above. They contain two or three short-chain Cl to C6 hydrocarbon radicals one or two long alkyl radicals per molecule are derived from fatty acids of lengths C8 to C26, preferably CIO to C20, especially C12 to C18, The fatty acids or the cuts in the chain length ranges mentioned can be saturated fatty acids, unsaturated fatty acids, hydroxy-substituted Fatty acids or mixtures thereof act. Examples of the acids mentioned are lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and rhicinoleic acid. Further examples are cuts of tallow fatty acid and coconut fatty acid. Their connection to the quaternized nitrogen is preferably via oxyethyl, 2-oxypropyl or 1, 2- dioxypropyl or oligooxyethylene spacers, preferably the short-chain radicals are methyl, ethyl, propyl, butyl, hexyl, phenyl and hydroxyethyl, 2- Hydroxypropyl. Preferred counterions are Cl ^" , Br ^" , CH ₃ OSO ₃ ^" , C ₂ H ₅ OSO ₃ ^" , NO ₃ ^" , HCOO ^" and CH ₃ COO ^" . Examples include (tallow fatty acid oxyethyl) trimethyl ammonium methosulfate (coconut fatty acid repentaethoxy) trimethyl ammonium methosulfate di (tallow fatty acid oxyethyl) dimethyl ammonium chloride di (tallow fatty acid oxyethyl) hydroxyethyl methyl ammonium methosulfate di (tallow) dimethyl 2-oxy-dimethyl di-methyl-dimethyl-2 ammonium methosulfate 1, 2-ditallow fatty oxyreoxy-3-trimethyl-propane-ammonium chloride Another type of preferred ester-containing cationic surfactants can be represented by the following formula:

{(R ¹⁶ ) ₃ N (CH ₂ ) _Z CH [O (O) CHR ¹⁷ ] [C ^ O ^ CR ¹⁷ ]} ^"1 ^ ^" , wherein R ¹⁶ , R ¹⁷ , X, and z are as defined above ,

Another group of cationic surfactants c) are those of the formula R ¹⁸ A (CH ₂ ) ₂ _ ₄ NR ¹⁹ R ²⁰ where R ^{18 is} C ₆ -C ₂ alkyl;

A is a divalent group selected from -NH-, -CONH-, -COO- or -O-, or A may be absent; R ¹⁹ and R ²⁰ become independent selected from the group consisting of H, -CC ₄ alkyl or (CH -CH ₂ - O (R ²¹ )) wherein R ^{21 is} H or methyl.

Particularly preferred surfactants of this type are decylamine, dodecylamine, C ₈ -C ₂ bis (hydroxyethyl) amine, C ₈ -C ₂ bis (hydroxypropyl) amine, Cs-C ^ amidopropyldimethylamine or salts thereof.

Other surfactants include: fatty acid amides of the formula R ²² C (O) N (R ²³ ) ₂ wherein R ^{22 is} an alkyl group having 8 to 28 carbon atoms and R ^{23 is in} each case a short-chain radical, preferably selected from hydrogen, Cj-Cg alkyl and

Is hydroxyalkyl. Cg-C N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include: Cι ₂ -Ci8 N-

Methylglucamide (see WO 92/06154). Other sugar derivatives include e.g. cg

C28 N- (3-methoxypropyl) glucamide. These also have two or three short-chain Cl to C6 hydrocarbon residues. The one or two long alkyl radicals per molecule are derived from fatty acids of lengths C8 to C26, preferably C10 to C20, especially C12 to C18. The fatty acids or the cuts in the chain length ranges mentioned can likewise be saturated fatty acids, unsaturated fatty acids, hydroxy-substituted fatty acids or mixtures thereof. Examples of the acids mentioned are lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and rhicinoleic acid. Other examples are tall fat acid and coconut fatty acid cuts. Their connection to the quaternized nitrogen is preferably via amidoethyl and 3-amidopropyl spacer. The short-chain radicals are preferably methyl, ethyl, propyl, butyl, hexyl, phenyl and hydroxyethyl, 2-hydroxypropyl. Alternatively, it can also be cyclic radicals, such as imidazolinium radicals, into which fatty alkyl substituents may also be incorporated. Preferred counterions are Cl ^" , B, CH ₃ OSO ₃ ^" , C ₂ H ₅ OSO ₃ ^" , NO ₃ ^" , HCOO ^" and CH ₃ COO ^" . Examples include:

(Undecylenic acid amidopropyl) trimethyl ammonium methosulfate (Rhicinoleic acid amidopropyl) trimethyl ammonium methosulfate 1-methyl-1-tallow fatty acid amidoethyl-2-tallow fatty alkyl-imidazolinium methosulfate 1-methyl-1-oleylamidoethyl-1-oleyl methosulfate bis (1-methyl-2-tallow fatty alkyl imidazolinium) methosxilfate. In addition to the quaternary ammonium compounds, amine salts can also be used. These are salts of primary, secondary or tertiary amines with inorganic or organic acids.

The nitrogen in these amine salts is substituted by one or two long-chain C8 to C28 hydrocarbon radicals, one to three hydrogen atoms and optionally one or two short-chain Cl to C6 hydrocarbon radicals. The one or two long alkyl radicals per molecule are derived, for example, from fatty amines or fatty acids of lengths C8 to C26, preferably CIO to C20, especially C12 to C18. Preferred counterions are Cl ^" , Br ^" , CH ₃ OSO ₃ ^" , C ₂ H ₅ OSO ₃ ^" , NO ₃ ^" , HCOO ^" and CH ₃ COO ^" .

The fatty amines used can be ethoxylated to increase the hydrophilicity. An example is the ethoxylated stearlyamine derivative CH ₃ (CH ₂ ) ₁₇ N1H [(CH ₂ CH ₂ O) ₅ H] ₂ Cl ^" .

The fatty acids or the sections of the chain length ranges mentioned can be the already described saturated fatty acids, unsaturated fatty acids, hydroxy-substituted fatty acids or mixtures thereof. Examples of the acids mentioned are lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and rhicinoleic acid. Other examples are high fat and coconut fatty acid cuts. In the case of esters, they are bound to the amine salt nitrogen preferably via oxyethyl, 2-oxypropyl, 1,2-dioxypropyl-xmd, and in the case of amides preferably via amidoethyl xmd 3-amidopropyl spacer. The short-chain radicals are preferably methyl, ethyl, propyl, butyl, hexyl, phenyl and hydroxyethyl, 2-hydroxypropyl. Preferred counterions are Cl ^" , Br ^" , CH ₃ OSO ₃ ^" , C ₂ H ₅ OSO ₃ ^" , NO ₃ ^" , HCOO ^" and CH ₃ COO ^" . Examples are mentioned

Stearic acid triethanolamine derivative: CH ₃ (CH ₂ ) ₁₆ C (O) OCH ₂ CH2N ⁺ (CH2CHOH) ₂ Cl ^"

Stearic acid amide derivative CH ₃ (CH ₂ ) ι ₆ CONHCH ₂ CH ₂ N1H ₂ CH ₂ CH ₂ N1H ₃ 2C1 ^" stearic acid amide derivative CH ₃ (CH ₂ ) ι ₆ CONHCH ₂ CH ₂ N1H ₂ CH ₂ CH ₂ θH Cl ^" palmitic acid amide derivative CH ₃ (CH ₂ ) ι ₄ CONHCH ₂ CH2CH2N ⁺ H (CH ₃ ) 2 Cl ^" . The amount of component c) optionally used, based on the total amount of the formulation, is from 0 to 30% by weight, preferably 0 to 10% by weight. If component c) is present in the formulation, the amount is preferably between 0.01% by weight and 15% by weight, more preferably 1 to 10% by weight. Component c) in the formulations according to the invention has the

Function to improve the emulsifiability of component a) and, if necessary, to increase the substantivity.

The coacervate baths according to component d) which can be used optionally are expediently cationic copolymers which are based on natural or synthetic polymer structures. This differs from the silicone-free cationic surfactants of component c), which are not based on polymer structures. Combinations of natural and synthetic polymers are also possible. Coacervate generator means complex charged anions or cations, each of which forms a complex salt with changed solubility behavior with a polymer or colloid particle charged in opposite directions.

The term "coacervate phase" as used according to the invention includes all types of discontinuous phases, as described for example in "B. Jonsson, B. Lindman, K. Holmberg, & B. Kronberb," Surfactants and Polymers In Aqueous Solution ", John Wiley & Sons, 1998 "and in" L. Piculell & B. Lindman, Adv. Colloid Interface Sci., 41 (1992) ". The mechanism of coacervation and its specific forms are described, for example, in" Interfacial Forces in Aqueous Media ", CJ van Oss, Marcel Dekker, 1994, pages 245 to 271. The term "coacervate phase" is sometimes referred to in the literature as a "complex coacervate phase" (complex coacervate phase) or as an "associated phase separation" (associated phase separation).

The coacervate phase former according to component d) optionally present in the formulation according to the invention leads, for example, when encountering anionic surfactants or anionic groups of any other components, for example when using the formulation according to the invention, such as in detergent formulation Fiber treatment formulations or in the treatment of pretreated substrate surface (anionic auxiliaries or dirt particles) to form coacervate phases.

This phase formation is visible, for example, microscopically using dyes.

For the substances according to d), the term “cationic” generally refers to protonated amino compounds or quaternary ammonium compounds (tetraorganoammonium compounds).

Natural copolymers are preferably derived from cellulose, starch or chitosan. The guar Gxxm derivatives modified by quaternary ammonium groups are particularly advantageous. These are commercially available as JAGUAR types from Rhδne-Poulenc (Rhodia).

Synthetic copolymers are preferably based on cationic structures such as polyvinylamines, polyethyleneimines and polydimethyldiallyl εimmonium halides. Alternatively, cationically modified materials can e.g. Based on polyvinylpyrrolidone, polyacrylamide, polymethylacrylamide,

Polyvinylimidazole and aminoalkylimidazole copolymers can be used.

High-molecular poly (vinylamine-vinylformamide) copolymers and high-molecular polyethyleneimines are particularly advantageous within this group.

In general, high molecular weight natural or synthetic coacervate formers are preferable to low molecular weight structure-analogue compounds.

A third group of materials are complexes of polycationic and polyanionic compounds, i.e. complex salts.

Combinations of natural polymers and synthetic polymers are preferred. Specifically, these are combinations of anionic natural polymers with cationic synthetic polymers. The pairing of cationic natural polymer with anionic synthetic polymer is also possible. Examples of preferred combinations are carboxymethyl cellulose / polyethyleneimine, carboxymethyl cellulose / polyvinylamine, Chitosan / polystyrene sulfonic acid, chitosan / polyacrylics,

Chitosan polymethacrylic acid.

Combinations of two oppositely charged natural polymers or synthetic polymers are also preferred. Examples include the combinations carboxymethyl cellulose / chitosan,

Polyethyleneimine / polyacrylic acid xmd polyvinylamine / polystyrene sulfonic acid.

The polycationic compounds can be used in the form of the bases or salts of monovalent anions. The polyanionic compounds can be used in the form of the acids or salts of monovalent cations. Synthetic polycationic and polyanionic compounds can be found in

Form of their copolymers are used, whereby their charge density can be designed variably.

If the complexes treated above are used, care must be taken to ensure that their net charge is cationic. This means that regardless of the specific material combination, an excess of amino or ammonium groups compared to the anionic groups, such as carboxylic acid, sulfonic acid,

Sulfur saxi half-esters or their salts.

As a result of the complexation of polycationic with polyanionic compounds of the type described above, the molecular weight of the coacervate former increases as desired.

If the coacervate former d) is contained in the formulation according to the invention, its preferred amount is 0.001 to 5% by weight, more preferably 0.1 to 1% by weight, based on the total amount of the formulation.

Component e) used in the formulation according to the invention is one or more carrier substances. These are preferably selected from solid carrier substances f) and / or liquid carrier substances g).

In the context of the present invention, this means that the liquid carriers are liquid at 40 ° C., the solid carriers are solid at 40 °.

Preferred liquid carriers g) include aqueous and non-aqueous, and may include: water alone or organic solvents, preferably water-soluble organic solvents alone and / or mixtures thereof with water. Preferred organic solvents include: mono alcohols, Diols, polyols, such as glycerol, glycol, polyethers, such as polyalkylene glycols, such as polyethylene glycols, and mixtures thereof, also with water. Mixtures of solvents, in particular mixtures of lower aliphatic alcohols, such as ethanol, propanol, butanol, isopropanol, and / or diols, such as 1,2-propanediol or 1,3-propanediol, are particularly preferred; or mixtures thereof with glycerin. Suitable alcohols include, in particular, -C ₄ alcohols. 1,2-Propanediol is preferred.

The liquid carrier g) is expediently present in the formulation according to the invention, based on the total amount of the formulation, in an amount of 0 to 95% by weight, preferably 0 to 65% by weight, more preferably 0 to 55% by weight. If the liquid carrier g) is present in the formulation according to the invention, its preferred amount is more than 5, more preferably more than 10, most preferably more than 30 to 70, more preferably up to 60% by weight. The solid carrier f) used as component e) is preferably selected from compounds which are solid at 40 ° C. Particularly preferred are compounds which are selected from the group of water-soluble compounds which have a solubility in water of at least 100 grams / liter at 20 ° C. Examples of the solid carriers include: inorganic or organic salts, polyhydroxy compounds,

Saccharides, amides such as urea, and higher molecular weight polyethylene oxides. The solid carriers f) are preferably compounds which have no significant surface-active effect in the sense of surfactants. Examples of inorganic salts are sodium chloride, potassium chloride, sodium carbonate, sodium sulfate. An example of an organic salt is natriximacetate. Examples of polyhydroxy compounds and saccharides which can be used according to the invention are pentaerythritol, sorbitol, glucamine, N-methylglucamine. Amide derivatives which can be used according to the invention are, for example, urea xmd strongly hydrophilic, saccharide-modified amide derivatives such as ethylenediamine-bisgluconamide, 1,3-propylenediamine-bisgluconamide, 1,2-propylenediamine-bisgluconamide

Diethyletriamine-bisgluconamide, dipropylenetriam-bisgluconamide, N-methyl-dipropylenetriamine-bisgluconamide, N, N-dimethyl-ethylenediamine-gluconamide N, N- Dimethyl-propylene-gluconamide. The latter saccharide-modified amide derivatives can be obtained by regioselective reaction of the primary amino groups of the corresponding amines with saccharide carboxylic acid lactones, such as gluconic acid lactone or glucopyranosylarabinonic acid lactone (DE 4 318 536, DE 4 318 537).

The solid carrier f) is expediently present in the formulation according to the invention, based on the total amount of the formulation, in an amount of 0 to 95% by weight, preferably 0 to 65% by weight, more preferably 0 to 55% by weight , If the solid carrier f) is contained in the formulation according to the invention, its preferred amount is more than 5, more preferably more than 10, most preferably more than 30 to 70, more preferably up to 60% by weight.

The solid carrier f) xmd the liquid carrier g) can be in any ratio to one another. The choice of the ratio depends on whether liquid, pasty or solid compositions of the formulation are desired.

The formulation according to the invention can, depending on the areas of use, contain, in addition to the components a) to g) described above, other other ingredients or auxiliaries.

When used in detergents, e.g. so-called builders, such as Zeolites, silicates, polyphosphates, alkali metal citrates, -2,2-oxydisuccinates, - carboxymethyloxysuccinates, -nitrilotriacetates, and sodium carbonate, enzymes, defoamers, such as silicone compounds and stabilizers. The stabilizers serve, for example, to stabilize component b) by preventing their coagulation and sedimentation. The stabilizers are e.g. 'Gums' and other polysaccharides, such as can'ageen gum, other thickeners or rheological additives. The stabilizer is preferably a crystalline hydroxyl-containing compound, such as trihydroxystearin, a hydrogenated oil or a derivative thereof.

Further auxiliaries which can be contained in particular in detergents are coupling agents, such as hexylamine, octylamine, nonylamine, their C1-C3 secondary or tertiary analogs and alkanediols. Further auxiliaries, which can be contained in particular in detergents, are fragrances adhering to the substrates, chelating agents, other surface-active substances.

The preparation of the formulation according to the invention can include, for example, the production of a homogeneous basic mixture a) + b) and the introduction of the optional components c) to e).

In an advantageous embodiment of the invention, components a) and b) are first mixed homogeneously to form a premix, optionally with the addition of parts of the carrier substance e). In the context of the invention, homogeneous means largely dissolved or else dispersed in transparent, finely divided form. The optional component c) can, for example, be subsequently introduced into this homogeneous premix. Depending on the structure of the premix components a) and b) or component c), this introduction can again lead to a homogeneous mixture or else a visibly coarser disperse distribution of c) in the premix a) + b). Depending on the application, d), (possibly further) e), i.e. f) and / or g) are introduced.

In a further preferred embodiment of the invention, a solution of c) in water e) or a solution of d) in water e) or a mixture of c) and d) is introduced into the premix a) + b). An admixture of c) + d) + e) for premixing a) + b) is also within the scope of the invention.

These different mixing strategies can influence the microscopic distribution of the components in the overall system and thus the product properties. The invention further relates to the use of the invention

Formulation in cosmetic formulations, in detergents or for the surface treatment of substrates.

The invention further relates to the use of the formulation according to the invention for fiber treatment or fiber finishing. The invention further relates to the use of the invention

Formulation for the treatment of textiles and other natural and synthetic fibrous materials, including paper. The formulations according to the invention are particularly suitable for use in the presence of anionic surfactants, in particular in detergent formulations or in the treatment of pretreated fibers.

The invention further relates to the use of the formulation according to the invention as a plasticizer.

The mixtures described above represent formulations which are suitable for the treatment of textiles and other natural and synthetic fibrous materials, in particular in the presence of anionic surfactants from detergent formulations or agents for fiber pretreatment. For this purpose, the formulations according to the invention can be incorporated directly into detergents or can be metered separately into the ongoing washing process. As a result of the use of the formulations according to the invention during the washing process, the treated substrates are given a silicone-typical softness, improved elasticity and reduced Knittemeigx g. Furthermore, the formulations described can be used as a component of separate plasticizer systems after the washing of fibers and textiles. Furthermore, the formulations described can be used for the surface treatment of substrates, such as natural and synthetic fibers, including paper and textiles, as a component of systems for initial textile finishing, as an ironing aid and as a means of preventing or eliminating textile creases. It is furthermore possible to introduce the formxilation rings according to the invention into cosmetic systems for the treatment of hair and skin.

The formulations according to the invention can be in liquid, including pasty or solid form. The Fomiulierxmg can also be present in an encapsulated form in a liquid or solid matrix.

A preferred formulation of the present invention contains: a): 5 to 99, preferably 10 to 80, more preferably 10 to 40, b): 1 to 95, preferably 1 to 30, more preferably 1 to 20, c): 0 to 10, preferably 1 to 10, d): 0 to 1, preferably 0.1 to 1, e): 0 to 70, preferably 30 to 70, the amounts given are% by weight, based on the total amount of the formulation.

Examples

Example 1 (Production of Quat According to WO 02/10259)

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 placed under the tradename Jeffamin ^® ED 600 available alkylene oxide derivatives of the Stniktur

H ₂ NCH (CH ₃ ) CH2 [OCH2CH (CH ₃ )] _a (OCH2CH ₂ ) ₉ [OCH2CH (CH ₃ )] _b NH2

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 xmd 1.8 g (0.03 mol) of acetic acid are added within 5 minutes. After the batch has been heated to 50 ° C., 194.1 g (0.06 mol epoxy groups) of an epoxysiloxane of the average composition are obtained within 30 minutes

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

V ^*

The repetition units Q, V ¹ and V ^{2 are also} shown in the above formula for the purpose of explanation. From the molar ratio

1 9 of the V-Gmppen-containing polysiloxane-free diamino components and the V-Gmppen-containing, long-chain polysiloxane group containing

9 1

The 1: 1 epoxy component gives a V / V ratio of 1: 1.

Example 2 (preparation of the quat according to WO 02/10257) a) 211.1 g (0.15 mol epoxy groups) of an epoxysiloxane of the 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 end of the reaction, the solvent removed by distillation in a water jet vacuum and finally in an oil pump vacuum. There were 217 g of a clear, yellowish product of the structure

receive.

¹³ C-NMR:

Substructure S shift (ppm)

-CH (OH) - 66.07

-CH (OH) -CH ₂ -N- 60.74

-CH (OH) -CH ₂ -N-CH ₂ - 53.20

-CH (OH) -CH ₂ -N-CH ₂ -CH ₂ - 55.10

CH ₃ -N = 45.87

b) 200 g (1.21 mol) of triethylene glycol monomethyl ether were placed under nitrogen at 20 ° C. room temperature. With intensive stirring, 151 g (1.34 mol) of chloroacetic acid chloride were added dropwise over the course of 30 minutes. During the dropping, the temperature rose to 90 ° C and intensive HCl development started. After the dropping had ended, the mixture was heated to 130 ° C. for 30 minutes. Finally, all components boiling up to 130 ° C. and at 20 hPa were distilled off. There were 301 g of a light yellow, viscous liquid of the composition

O

ClCH ₂ CO (CH ₂ CH ₂ O) ₃ CH ₃

receive. The purity of the ester, determined by gas chromatography, is 99%.

13 ^J C-NMR:

Substructure shift (ppm)

C1CH ₂ - 40.8

ClCH ₂ -C (O) - 167.3

ClCH ₂ -CH ₂ -C (O) -OCH ₂ - 65.2

ClCH ₂ -CH ₂ -C (O) -OCH ₂ CH ₂ - 68.7

-CH ₂ -OCH ₃ 58.8

c) 19.61 g (6.5 * 10 ^" mol) of the α, ω-aminosiloxane according to Example 4a) and 3.12 g (1.3 * 10 ^{" 2} mol) of the chloroacetic acid ester according to Example 4b) were dissolved in nitrogen 50 ml of i-propanol dissolved and heated to reflux temperature for 12 hours. After the reaction had ended, all components boiling up to 70 ° C. and at 20 hPa were removed. 19.7 g of a yellowish-light brown viscous oil of the formula as component bl) were:

receive. A quantitative conversion of the ester was determined by gas chromatography.

13 C-NMR: substructure shift (ppm)

-CH (OH) - 65.9 / 66.1

-CH (OH) -CH ₂ -N- 52.6

-CH (OH) -CH ₂ -N-CH ₂ - 45.4

-CH (OH) -CH ₂ -N-CH ₂ -CH ₂ - 60.5 / 60.6

-CH (OH) -CH ₂ -N-CH ₂ -CH2-N ⁺ -CH ₂ - 61.4 -CH (OH) -CH ₂ -N-CH ₂ -CH ₂ -N ⁺ -CH ₂ -C (O) - 169.6 / 169.9

CHs-N ^ 52.9

-CH ₂ -OCH ₃ 58.6

1 part

According to the C-NMR spectrum, the quaternization takes place selectively on the methyl-substituted nitrogen atoms.

Example 3

153 g (1.5 mol) of H ₂ NCH ₂ CH ₂ CH ₂ N (CH ₃ ) ₂ are placed under nitrogen in a four-necked flask. 412.3 g (1.5 mol) of palmitoyl chloride are added dropwise within 15 minutes. The addition is regulated so that the batch remains in the temperature range from 100 ° C to 120 ° C. After the addition is complete, a vacuum is briefly applied in order to degas the white-yellowish viscous mass formed. 123 g (1.5 mol) of natrix imacetate are added to this viscous mass at 100 ° C. After cooling, 556 g of a white-yellowish, hard mass are obtained. Composition: CH ₃ (CH ₂ ) ₁₄ C (O) NHCH2CH2CH ₂ N ⁺ H (CH3) 2 Cl ^" + CH ₃ COONa

Example 4

Starting from tetrameric cyclodimethylsiloxane or a cyclosiloxane-polydimethylsiloxane diol mixture as well as aminopropylmethyldiethoxysilane, aminopropyldimethylethoxysilane, optionally adding traces of water and hexamethyldisiloxane, the following average alkali-catalyzed equilibration and condensation with the exit of ethanol2 form the amino acid in the exit form of ethanol2)

According to the 1H-NMR spectrum, this material still contains traces of ethoxy groups.

Example 5

The following formulations are produced:

To produce the formulations, the two silicone quats are first mixed for FI or the aminosiloxane and silicone quat for F2. The polydimethylsiloxane is stirred homogeneously into these mixtures. The amine salt is then finely distributed in these premixes. An opaque mass is created in each case. Finally, the water in FI and F2 is slowly stirred in, so that white emulsion-like liquids are obtained. Finally, the aqueous guar gum solution is stirred into the formulations F3 and F4.

Example 6

To demonstrate the softening properties, washing tests are carried out in a drum washing machine with a powdered (Dash® 2inl) xmd liquid (Ariel liquid®) detergent.

Wash trial Wl

40 ° C, 20 min, then rinse 5 times

110g Dash® 2inl matrix without bentonite

2kg laundry (1850g ballast material + 5 terry cloths total 150g)

10 1 water in the machine

13.5g formulation FI washed in immediately after Dash 2in 1 matrix

The 5 terry cloths softened by FI in washing test W1 were compared with 5 cloths, which were washed identically with 'Ariel® liquid' alone. The 5 terry cloths softened by F2 in wash test W2 were compared with 5 cloths, which were washed identically with Ariel liquid alone. The 5 terry cloths softened by F2 in wash test W3 were compared with 5 cloths that were washed identically with Ariel®liquid alone. The 5 terry cloths softened by F3 in wash test W4 were compared with 5 cloths, which were washed identically with Ariel liquid alone. The 5 terry cloths softened by F4 in wash test W5 were compared with 5 cloths, which were washed identically with Ariel liquid alone. On a scale from 0 to 4 points, i.e. 1 = very good, the rags washed according to the invention achieved the following average scores:

Claims

; ₇₈

1) Formulation containing:

a) at least one nitrogen-free polysiloxane compound, b) at least one polyamino and / or polyammonium polysiloxane compound bl) and / or at least one amino and / or arnmonium polysiloxane compound b2), c) optionally one or more silicone-free Surfactants, d) optionally one or more coacervate phase formers, e) optionally one or more carrier substances.

2) Formulation according to claim 1, characterized in that, based on the total amount of components a) and b), 5 to 99% by weight of component a) and

Contains 1 to 95 wt .-% of component b).

3) Formulation according to claim 1 or 2, wherein component e) is selected from solid carrier substances f) and / or liquid carrier substances g).

4) Formulation according to one of claims 1 to 3, characterized in that it contains, based on 100 parts by weight of components a) and b), 0 to 1500 parts by weight of components c), d) and e).

5) Formulation according to one of claims 1 to 4, characterized in that it contains, based on 100 parts by weight of components a) and b), 0 to 70 parts by weight of component c).

6) Formulation according to one of claims 1 to 5, characterized in that it contains, based on 100 parts by weight of components a) and b), 0 to 10 parts by weight of component d). 7) Formulation according to one of claims 1 to 6, characterized in that it contains, based on 100 parts by weight of components a) and b), 0 to 710 parts by weight of component f).

8) Formulation according to one of claims 1 to 7, characterized in that it contains, based on 100 parts by weight of components a) and b), 0 to 710 parts by weight of component g).

9) Formulation according to one of claims 1 to 8, characterized in that component a) is at least one component selected from the group consisting of: straight-chain, cyclic, branched and partially crosslinked polyorganosiloxanes.

10) Formulation according to one of claims 1 to 9, characterized in that the polyamino-xmd / or polyammonium-polysiloxane compound bl) is selected from polysiloxane compounds which contain at least one unit 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:

, such as

an aromatic diamino functional heterocycle of the formula:

a trivalent radical of the formula:

/

IN THE \

a trivalent radical of the formula:

/

- N ⁺ l \

^, or

a tetravalent radical of the formula,

ι + - N— where R in each case represents hydrogen or a monovalent organic radical,

where Q does not bind to a carbonyl carbon atom,

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-, -CONH-,

-CONR ² -, wherein 1? _ Is hydrogen, a monovalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical with up to 100

Heterocyclic group containing nitrogen atoms, amino,

Alkylamino, dialkylamino, ammonium, polyether residues and

Polyetheresterreste can be substituted, wherein if several -CONR ² groups are present, these can be the same or different, -C (0 and -C (S) - may contain

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 C ₂ 2 alkyl, fluoro (Cι-Cιo) alkyl and C _Ö -C _IO aryl, and nι = 20 to 1000,

-O-, -CONH-,

-CONR ² -, wherein R ^{2 is} as defined above, where the groups R in the groups and V ^{2 may be the} same or different,

-C (O) -, -C (S) - and -Z ¹ - may contain, wherein -Z ¹ - a group of the formula is what

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

and the radical V can 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 -, where R- is as defined above, -C (0, -C (S) -, -Z ¹ -, which is as defined above, -Z ² - which as is defined above, and Z ³ , wherein Z ^{3 is} a trivalent or higher organopolysiloxane unit, and

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

where one or more V groups, one or more V ² groups and / or one or more V ³ groups may be present in the said polysiloxane compound, with the proviso that

- That said polysiloxane compound at least one group V ¹ . V ² or V ³ 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 saturate with radicals V ³ within a linear main chain without the formation of a branch, and in which the positive charges resulting from ammonium groups are neutralized by organic or inorganic acid anions, and their acid addition salts.

11) Formulation according to one of claims 1 to 10, characterized in that the amino and / or ammonium polysiloxane compound b2) is a polysiloxane compound which contains amino and / or ammonium groups in the side groups of a polyorganosiloxane main chain.

12) Formulation according to one of claims 1 to 11, characterized in that the silicone-free surfactant as component c) is at least one component which is selected from unpolymerized, organic, quaternary ammonium compounds.

13) Formulation according to one of claims 1 to 12, characterized in that the coacervate phase former contains as component d) at least one component which is selected from cationic, silicone-free polymer compounds.

14) Formulation according to one of claims 3 to 13, characterized in that the solid carrier f) is at least one component which is selected from the group of water-soluble compounds which have a solubility in water of at least 100 grams / liter at 20 ° C. ,

15) Formulation according to one of claims 3 to 14, characterized in that the liquid carrier g) is at least one component which consists of Group is selected, which consists of water and water-miscible organic solvents.

16) formulation according to one of claims 1 to 15, characterized in that it is solid or liquid at 40 ° C.

17) Method for producing the formulation according to one of claims 1 to 16, comprising the steps of: a) mixing components a) and b) to form a homogeneous premix, and b) optionally introducing components c), d) and / or e).

18) Use of the formulation according to one of claims 1 to 16 in cosmetic formulations, in detergents or for the surface treatment of substrates.

19) Use of the formulation according to one of claims 1 to 16 and 18 for fiber treatment or fiber finishing.

20) Use of the formulation according to any one of claims 1 to 16, 18 and 19 as a formulation for the treatment of textiles and other natural and synthetic fibrous materials, including paper.

21) Use of the formulation according to one of claims 1 to 16, 18, 19 and 20 as a plasticizer.