EP1199350A1 - Use of quaternary polysiloxanes in detergent compositions - Google Patents

Use of quaternary polysiloxanes in detergent compositions Download PDF

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EP1199350A1
EP1199350A1 EP01123706A EP01123706A EP1199350A1 EP 1199350 A1 EP1199350 A1 EP 1199350A1 EP 01123706 A EP01123706 A EP 01123706A EP 01123706 A EP01123706 A EP 01123706A EP 1199350 A1 EP1199350 A1 EP 1199350A1
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radical
carbon atoms
alkyl
radicals
general formula
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German (de)
French (fr)
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EP1199350B1 (en
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Michael Fender
Sascha Dr. Oestreich
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Evonik Goldschmidt Rewo GmbH
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Goldschmidt Rewo GmbH
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds

Definitions

  • the invention relates to the use of quaternary Polysiloxanes in detergent formulations.
  • Drum washing machines like those in European households are common, usually wash in two steps.
  • the Main wash is the laundry first with the help of a Detergent (powder or liquid) cleaned. Subsequently there are several rinses with clear water. The last one these rinses can be used as fabric softener for after-treatment be added. This should give the laundry a soft, Give a fluffy feel.
  • the wash cycle and Fabric softener cycle usually carried out at different times.
  • the consumer should now have a product that is easier to handle be given to hand, which repeated dosing processes replaced by a single dose.
  • EP-A-0 151 938 describes so-called “two in One "detergent formulations, wherein anionic surfactants and quaternary alkylammonium surfactants with the aid of carrier materials be combined.
  • Polydimethylsiloxanes can also be used as plasticizers Component used in "Two in One" detergent formulations become. If you want to combine the washing and softening process, however, such formulations have the disadvantage that Polydimethylsiloxanes due to their high hydrophobicity and oleophobicity on deposits and "build-up" effects in washing machines and run on the laundry.
  • Quaternary polysiloxanes are also known and for example in EP-A-0 282 720 and in DE-A-37 19 086. Such connections are so far especially for their conditioning properties known in hair cosmetics.
  • the object of the present invention was Provide detergent formulations that the laundry and Combine the softener process and a clear after washing leave a measurable softening effect in the textiles.
  • radical M a divalent hydrocarbon radical with at least 4 carbon atoms, which has a hydroxyl group and which can be interrupted by at least one oxygen atom, the N atom of the radical Z with the radical M via that to the C-OH group in the radical M adjacent carbon atom are connected
  • the two Z radicals have the same or different meaning.
  • radicals R 1 , R 2 , R 3 the alkyl radicals having 1 to 22 carbon atoms or alkenyl radicals having 2 to 22 carbon atoms, where the alkyl or alkenyl radicals can have hydroxyl groups and at least one of the radicals R 1 , R 2 , R 3 has at least 10 carbon atoms, are alkyl radicals such as the methyl, ethyl, octyl, dodecyl, hexadecyl or octadecyl radical; Hydroxyalkyl radicals, such as the hydroxyethyl radical; Alkenyl residues, such as the allyl or vinyl residue.
  • radicals R 4 , R 5 , R 7 , R 9 , R 10 the alkyl radicals with 1 to 22 carbon atoms or alkenyl radicals with 2 to 22 carbon atoms, where the alkyl or alkenyl radicals can have hydroxyl groups, are alkyl radicals, such as methyl -, ethyl, octyl, dodecyl, hexadecyl or octadecyl; Hydroxyalkyl radicals, such as the hydroxyethyl radical; Alkenyl residues, such as the allyl or vinyl residue.
  • R 8 the alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms or hydrogen radical, are the hydrogen radical; Alkyl radicals such as the methyl, ethyl, isopropyl or butyl radical and hydroxyalkyl radicals such as the hydroxyethyl radical.
  • a - an inorganic or organic anion, which derives from a common physiologically compatible acid HA, are Cl - , Br - , SO 4 2- , HSO 4 - , H 3 CSO 4 - , H 3 CCO 2 - , citrate and tosylate.
  • radical Z 1 examples are H-, HO-, H 3 C-CH 2 O-, (H 3 C) 2 CHO-, H 3 C (CH 2 ) 7 -,
  • Examples of Y a divalent hydrocarbon radical with at least 2 carbon atoms, which have a hydroxyl group and which can be interrupted by at least one oxygen or nitrogen atom, are - (CH 2 ) 2 -, - (CH 2 ) 3 -, - (CH 2 ) 6 -, - (CH 2 ) 12 -, - (CH 2 ) 2 -O- (CH 2 ) 2 -, -CH 2 -O-CH 2 -,
  • R 11 , R 12 , R 13 , R 14 which are the same or different and are alkyl radicals having 1 to 4 carbon atoms or benzyl radicals, or R 11 and R 13 or R 12 and R 14 can each be constituents of a bridging alkylene radical are alkyl radicals such as methyl, ethyl, isopropyl or butyl radicals and benzyl radicals such as the benzyl radical. If R 11 and R 13 or R 12 and R 14 are constituents of a bridging alkylene radical, this part of the molecule can have the following structure:
  • R 11 , R 12 , R 13 , R 14 radicals are the methyl and ethyl radicals.
  • R 15 an alkyl radical having 1 to 20 carbon atoms
  • alkyl radicals such as the methyl, ethyl, octyl, dodecyl, hexadecyl or octadecyl radical.
  • Detergents are the formulations that are commercially available in this field in the form of powders, granules, pearls, tablets, Pastes, gels or liquids. They are mostly considered Heavy duty detergent formulated with a universal range of uses essentially contain solid or liquid carriers and various functional ingredients such as surfactants, inorganic polymeric builders, enzymes, bleaching systems, optical brighteners, soil release polymers, foam inhibitors, Fillers, process aids, stabilizers.
  • the surfactants used are predominantly anionic compounds such as alkylbenzenesulfonates (LAS), optionally in combination with fatty alcohol polyglycol ethers, fatty alcohol sulfates, ⁇ -olefin sulfonates, ester sulfates and more recently also alkylpolyglycosides (APG) and fatty acid glucamides (GA); Zeolites, polycarboxylates, polyvinylpyrrolidones and amorphous anhydrous sodium silicates and layered silicates are also used as builders, with citric acid often being used as a co-builder; Components of the bleaching systems are in particular perborates and sodium percarbonate with the use of N-acetyl compounds, N, N, N ', N'-tetraacetylethylene diamine or p-nonyloxybenzenesulfonate as activators; Stilbenes and distyrylbiphenyls are used as optical brighten
  • the test formulations used are composed as follows: Liquid detergent base (component A): Anionic surfactants (Na-alkylbenzenesulfonate) 21.75% Soap 16.50% nonionic surfactants 10.60% amphoteric surfactants 1.40% 1,2 propylene glycol 11.20% water ad 100% Powder detergent base: (component B): Anionic surfactants (Na-alkylbenzenesulfonate) 15% Pentanatriumpyrophosphat 30% sodium 28% Optical brightener 0.1% carboxymethylcellulose 0.5% water glass 3.0% foam inhibitors 2.0% EDTA 0.2% Perfume 0.1% dye 0.7% Sodium sulfate and adjusting agents 17% water ad 100%
  • component B 85 parts of component B were mixed with 15 parts of one Mixture consisting of 33.33% by weight of a silica (Sipernat 50, Degussa) and 66.66 wt .-% of a Talgamidoethylimidazoliniummethosulfats.
  • test the textiles were washed in a normal household washing machine.
  • the detergent dosage varied depending on the type of base, but was based on the usual dosage recommendations for water hardness range II and normally soiled laundry.
  • the laundry was dried statically (on the clothesline) and examined and evaluated using a test panel.
  • test conditions apparatus Miele washing machine W 715, W 719, W 918 Test fabric Cotton terry fabric, Frottana, col. 901; 100 x 50 cm ballast fabric smooth cotton fabric laundry detergent Liquid detergent base (component A) Powder detergent base (component B) Reference detergent (Ref): dosage according to the dosage recommendation for normally soiled laundry aftercare no drying time 24 hours under air-conditioned standard conditions
  • test panel After the terry towels have dried, they are cut into 10 individual lobes and stored in an air-conditioned room until they are finally evaluated by the test panel.
  • the maximum rating is a result of 50.

Abstract

Washing agents having a softening effect contain at least one quaternary polysiloxane compound. Washing agents (I) having a softening effect contain at least one quaternary polysiloxane compound of formula (1), (2a) or (2b). M = divalent hydrocarbon having at least 4C atoms and a hydroxyl group, optionally containing an O atom whereby the N atom of Z is bonded to M via the C-OH group of the neighboring carbon atom in M; Z = -N<+)<R<1>)(R<3>)-R<2>, -N<+)<R<4>)(R<5>)-(CH2)x-R<6>-C(=O)-R<7>, formula (3); R<1>-R<3> = 1-22C alkyl or 2-22C alkenyl optionally having hydroxyl groups whereby at least one of R<1>-R<3> comprises at least 10C; R<4>,R<5>,R<7>, R<9>,R<10> = 1-22C alkyl or 2-22C alkenyl optionally containing hydroxyl groups; R<6> = -O or -NR<8>' R<8> = 1-4C alkyl, hydroxyalkyl or H; x = 2-4; n = 0-200; A = inorganic or organic anion of a physiologically compatible acid HA; Z<1> = H, OH, alkyl or alkoxy or an at least 4C hydrocarbon optionally having hydroxyl groups and containing -O- or is of formula -M-N<+)<R<11>)(R<12>)-Y-N(R<13>)(R<14>).A<-> or -M-N<+)<R<11>)(R<12>)-R<15> .A<->; Z<2> = -SiO(CH3)(CH3)-(SiO(CH3)(CH3))n-Si(CH3)(CH3)-Z<1>; Y = a divalent at least 2C hydrocarbon having one hydroxyl group and optionally containing oxygen or nitrogen linkages; R<11>-R<14> = 1-4C alkyl or benzyl or R<11> and R<13> or R<12> and R<14>=1-4C alkyl or benzyl or R<11> and R<13> or R<12> and R<14> form a bridged alkenyl group; R<15> = 1-20C alkyl; m ≥ 1.

Description

Die Erfindung betrifft die Verwendung von quaternären Polysiloxanen in Waschmittelformulierungen.The invention relates to the use of quaternary Polysiloxanes in detergent formulations.

Trommelwaschmaschinen, wie sie in europäischen Haushalten üblich sind, waschen in der Regel in zwei Arbeitsgängen. Im Hauptwaschgang wird die Wäsche zunächst mit Hilfe eines Waschmittels (Pulver oder flüssig) gereinigt. Anschließend erfolgen mehrere Spülgänge mit klarem Wasser. Dem letzten dieser Spülgänge kann ein Weichspüler zur Nachbehandlung zugesetzt werden. Dieser soll der Wäsche einen weichen, flauschigen Griff verleihen.Drum washing machines like those in European households are common, usually wash in two steps. in the Main wash is the laundry first with the help of a Detergent (powder or liquid) cleaned. Subsequently there are several rinses with clear water. The last one these rinses can be used as fabric softener for after-treatment be added. This should give the laundry a soft, Give a fluffy feel.

Es ist bekannt, dass Waschmittelformulierungen auf Basis von anionischen, nichtionischen und/oder amphoteren Tensiden die Wäsche zwar reinigen, jedoch keinen ausreichenden weichmachenden Effekt auf die Textilien haben. Wünscht der Verbraucher weiche Textilien nach der Wäsche, so müssen die Textilien nach dem Hauptwaschgang einen weiteren Weichspülgang durchlaufen.It is known that detergent formulations based on anionic, nonionic and / or amphoteric surfactants Clean laundry, but do not use sufficient softening agents Have an effect on the textiles. The consumer wishes soft textiles after washing, so the textiles have to go through another fabric softener cycle in the main wash cycle.

Versuche, beide Wäschebehandlungen in einem Arbeitsgang zu vereinen, um der Hausfrau ein Mehrfachdosieren zu ersparen, sind bereits in großer Zahl unternommen worden.Try to do both laundry treatments in one go unite in order to save the housewife from having to dose several times, have already been undertaken in large numbers.

Verschiedene Klassen von Verbindungen können eingesetzt werden, um einen weichmachenden Effekt in Textilien hervorzurufen. Zumeist werden aber kationische Tenside eingesetzt, da sie billig herzustellen sind und selbst in geringsten Konzentrationen einen weichmachenden Effekt auf den Textilien bewirken.Different classes of connections can be used to create a softening effect in textiles. However, cationic surfactants are mostly used because they are cheap to produce and even in the slightest Concentrations have a softening effect on the textiles cause.

Setzt man kationische und anionische Tenside gleichzeitig ein, um sowohl einen reinigenden als auch einen weichmachenden Effekt während der Wäsche zu erzielen, bilden sich jedoch in der Regel Anionen-Kationen-Komplexe, die zum einen die Reinigungswirkung des Waschmittels herabsetzen und zugleich die erwünschte weichmachende Wirkung verringern.If cationic and anionic surfactants are used at the same time, around both a cleansing and a softening To achieve effect during the wash, however, form in usually anion-cation complexes, on the one hand the Reduce the cleaning effect of the detergent and at the same time the Reduce the desired softening effect.

Um die Komplexbildung zu vermeiden, werden daher Waschgang und Weichspülgang üblicherweise zeitlich getrennt durchgeführt.In order to avoid the formation of complexes, the wash cycle and Fabric softener cycle usually carried out at different times.

Dem Verbraucher soll nun ein einfacher zu handhabendes Produkt an die Hand gegeben werden, welches mehrmalige Dosierungsvorgänge durch eine nur einmalig vorzunehmende Dosierung ersetzt.The consumer should now have a product that is easier to handle be given to hand, which repeated dosing processes replaced by a single dose.

Die EP-A-0 151 938 beschreibt zum Beispiel sogenannte "Two in One"-Waschmittelformulierungen, worin anionische Tenside und quaternäre Alkylammoniumtenside mit Hilfe von Trägermaterialien kombiniert werden.For example, EP-A-0 151 938 describes so-called "two in One "detergent formulations, wherein anionic surfactants and quaternary alkylammonium surfactants with the aid of carrier materials be combined.

Hierbei wird der direkte Kontakt von anionischen und quaternären Tensiden dadurch vermieden, dass die quaternären Tensiden auf den Trägermaterialien adsorbiert vorliegen. Das System Träger/Quat, welches im Waschvorgang auf der Faser aufgezogen ist, wird erst nach dem Ausspülen der anionischen Tenside getrennt.Here the direct contact of anionic and quaternary surfactants avoided in that the quaternary Surfactants are present adsorbed on the carrier materials. The System carrier / Quat, which is on the fiber in the washing process is raised, is only after rinsing the anionic Separate surfactants.

Solche Systeme haben jedoch den Nachteil, dass der weichmachende Effekt im Vergleich zu der getrennten Dosierung von Wäscheweichmachern nur eingeschränkt zu beobachten ist. Es ist weiterhin wünschenswert homogene Systeme zur Verfügung zu stellen, in denen die Trägermaterialien nicht durch weitere Hilfsstoffe dauerhaft stabilisiert werden müssen.However, such systems have the disadvantage that the softening effect compared to the separate dosage can only be observed to a limited extent by laundry softeners. It is still desirable to have homogeneous systems available places in which the carrier materials are not replaced by other Auxiliaries must be stabilized permanently.

Weiterhin können Polydimethylsiloxane als weichmachende Komponente in "Two in One"-Waschmittelformulierungen eingesetzt werden. Will man den Wasch- und Weichspülvorgang kombinieren, haben solche Formulierungen jedoch den Nachteil, dass Polydimethylsiloxane durch ihre hohe Hydrophobie und Oleophobie zu Ablagerungen und "Build-up"-Effekten in Waschmaschine und auf der Wäsche führen.Polydimethylsiloxanes can also be used as plasticizers Component used in "Two in One" detergent formulations become. If you want to combine the washing and softening process, However, such formulations have the disadvantage that Polydimethylsiloxanes due to their high hydrophobicity and oleophobicity on deposits and "build-up" effects in washing machines and run on the laundry.

Auf der Wäsche hat das den Effekt, dass die Benetzungsfähigkeit der Faser durch die Körperfeuchtigkeit stark verringert wird und bereits nach einigen Anwendungen auf der Haut ein unangenehmes "schmieriges" Gefühl vermitteln.This has the effect on the laundry that it can be wetted the fiber is greatly reduced by body moisture and already after a few applications on the skin convey an unpleasant "greasy" feeling.

Quaternäre Polysiloxane sind ebenfalls bekannt und zum Beispiel in der EP-A-0 282 720 und in der DE-A-37 19 086 beschrieben. Solche Verbindungen sind bisher insbesondere für ihre konditionierenden Eigenschaften in der Haarkosmetik bekannt.Quaternary polysiloxanes are also known and for example in EP-A-0 282 720 and in DE-A-37 19 086. Such connections are so far especially for their conditioning properties known in hair cosmetics.

Der Fachmann erwartet nicht, dass sich solche quaternären Polysiloxane mit anionischen Tensiden kombinieren lassen, da auch hier Anionen-Kationen-Komplexe auftreten sollten.Those skilled in the art do not expect such quaternaries Let polysiloxanes be combined with anionic surfactants, because Anion-cation complexes should also occur here.

Die Aufgabe der vorliegenden Erfindung bestand darin, Waschmittelformulierungen bereitzustellen, die den Wasch- und Weichspülvorgang kombinieren und nach der Wäsche einen deutlich messbaren weichmachenden Effekt in den Textilien hinterlassen.The object of the present invention was Provide detergent formulations that the laundry and Combine the softener process and a clear after washing leave a measurable softening effect in the textiles.

Überraschenderweise wurde nun gefunden, dass der Zusatz von quaternären Polysiloxanen in anionischen Waschmittelformulierungen einen deutlich messbaren weichmachenden Effekt auf den Textilien hinterlässt, aber keinen sichtbaren Niederschlag von Anionen-Kationen-Komplexen oder "Build-Up"-Effekt auf der behandelten Wäsche zeigt. Ein weiterer Vorteil besteht darin, dass die erfindungsgemäß mitverwendeten quaternären Polysiloxane mit den üblicherweise verwendeten waschaktiven Substanzen verträglich sind und normalerweise keine zusätzlichen Hilfsmittel für die Einarbeitung erfordern.Surprisingly, it has now been found that the addition of quaternary polysiloxanes in anionic detergent formulations a clearly measurable softening effect leaves the textiles, but no visible precipitation of anion-cation complexes or "build-up" effect on the treated laundry shows. Another advantage is that the quaternary polysiloxanes used in accordance with the invention with the commonly used detergent substances are tolerated and usually no additional Require tools for familiarization.

Der Gegenstand der vorliegenden Erfindung besteht somit in der Verwendung von quaternären Polysiloxanen der allgemeinen Formel (I)

Figure 00040001
und/oder
cyclischen quaternären Polysiloxanen der allgemeinen Formel (IIa)
Figure 00040002
und/oder
linearen quaternären Polysiloxanen der allgemeinen Formel (IIb)
Figure 00050001
wobei

M
ein zweiwertiger Kohlenwasserstoffrest mit mindestens 4 Kohlenstoffatomen ist, der eine Hydroxylgruppe aufweist und der durch mindestens ein Sauerstoffatom unterbrochen sein kann, wobei das N-Atom des Restes Z mit dem Rest M über das zur C-OH-Gruppe im Rest M benachbarte Kohlenstoffatom verbunden ist,
Z
ein Rest
Figure 00050002
ist,
R1, R2, R3 =
Alkylreste mit 1 bis 22 Kohlenstoffatomen oder Alkenylreste mit 2 bis 22 Kohlenstoffatomen, wobei die Alkyl- oder Alkenylreste Hydroxylgruppen aufweisen können und mindestens einer der Reste R1, R2, R3 mindestens 10 Kohlenstoffatome aufweist,
R4, R5, R7, R9, R10 =
Alkylreste mit 1 bis 22 Kohlenstoffatomen oder Alkenylreste mit 2 bis 22 Kohlenstoffatomen, wobei die Alkyl- oder Alkenylreste Hydroxylgruppen aufweisen können,
R6 =
-O- oder -NR8- Rest,
R8 =
Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen oder Wasserstoffrest,
x =
2 bis 4,
n =
eine Zahl von 0 bis 200,
A-=
ein anorganisches oder organisches Anion, das von einer üblichen physiologisch verträglichen Säure HA herrührt,
Z1 =
ein H-, OH-, ein Alkyl- oder Alkoxyrest ist, oder die Bedeutung eines Kohlenwasserstoffrestes mit mindestens 4 Kohlenstoffatomen hat, der eine oder mehrere Hydroxylgruppe(n) aufweist und durch ein oder mehrere Sauerstoffatome unterbrochen sein kann oder die Bedeutung des Restes
Figure 00060001
hat,
Z2 =
die Gruppe
Figure 00060002
bedeutet,
Y =
ein zweiwertiger Kohlenwasserstoffrest mit mindestens 2 Kohlenstoffatomen ist, der eine Hydroxylgruppe aufweisen und der durch mindestens ein Sauerstoff- oder Stickstoffatom unterbrochen sein kann,
R11,R12,R13,R14 =
gleich oder verschieden sind und Alkylreste mit 1 bis 4 Kohlenstoffatomen oder Benzylreste bedeuten oder jeweils R11 und R13 oder R12 und R14 Bestandteile eines verbrückenden Alkylenrestes sein können,
R15 =
ein Alkylrest mit 1 bis 20 Kohlenstoffatomen ist,
m =
ganze Zahl größer oder gleich 1 ist,
in Waschmittelformulierungen.The object of the present invention thus consists in the use of quaternary polysiloxanes of the general formula (I)
Figure 00040001
and or
cyclic quaternary polysiloxanes of the general formula (IIa)
Figure 00040002
and or
linear quaternary polysiloxanes of the general formula (IIb)
Figure 00050001
in which
M
is a divalent hydrocarbon radical having at least 4 carbon atoms, which has a hydroxyl group and which can be interrupted by at least one oxygen atom, the N atom of the radical Z being connected to the radical M via the carbon atom adjacent to the C-OH group in the radical M. .
Z
a rest
Figure 00050002
is
R 1 , R 2 , R 3 =
Alkyl radicals with 1 to 22 carbon atoms or alkenyl radicals with 2 to 22 carbon atoms, where the alkyl or alkenyl radicals can have hydroxyl groups and at least one of the radicals R 1 , R 2 , R 3 has at least 10 carbon atoms,
R 4 , R 5 , R 7 , R 9 , R 10 =
Alkyl radicals with 1 to 22 carbon atoms or alkenyl radicals with 2 to 22 carbon atoms, where the alkyl or alkenyl radicals can have hydroxyl groups,
R 6 =
-O- or -NR 8 - rest,
R 8 =
Alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms or hydrogen radical,
x =
2 to 4,
n =
a number from 0 to 200,
A - =
an inorganic or organic anion derived from a common physiologically acceptable acid HA,
Z 1 =
is an H, OH, an alkyl or alkoxy radical, or has the meaning of a hydrocarbon radical with at least 4 carbon atoms, which has one or more hydroxyl group (s) and can be interrupted by one or more oxygen atoms, or the meaning of the rest
Figure 00060001
Has,
Z 2 =
the group
Figure 00060002
means
Y =
is a divalent hydrocarbon radical with at least 2 carbon atoms, which have a hydroxyl group and which can be interrupted by at least one oxygen or nitrogen atom,
R 11 , R 12 , R 13 , R 14 =
are identical or different and are alkyl radicals having 1 to 4 carbon atoms or benzyl radicals or R 11 and R 13 or R 12 and R 14 can each be constituents of a bridging alkylene radical,
R 15 =
is an alkyl radical with 1 to 20 carbon atoms,
m =
integer is greater than or equal to 1,
in detergent formulations.

In einer bevorzugten Auführungsform der vorliegenden Erfindung sind die quaternären Polysiloxane dadurch gekennzeichnet, dass

n
für eine Zahl im Bereich von 0 bis 150, insbesondere 5 bis 100,
x
für eine Zahl im Bereich von 2 bis 4,
m
für eine Zahl im Bereich von 1 bis 10, insbesondere 1 bis 5 steht.
In a preferred embodiment of the present invention, the quaternary polysiloxanes are characterized in that
n
for a number in the range from 0 to 150, in particular 5 to 100,
x
for a number in the range from 2 to 4,
m
stands for a number in the range from 1 to 10, in particular 1 to 5.

Es ist dem Fachmann geläufig, dass die Verbindungen in Form eines Gemisches mit einer im wesentlichen durch statistische Gesetze geregelten Verteilung vorliegen. Die Werte für die Indices n und m stellen deshalb Mittelwerte dar.It is known to the person skilled in the art that the compounds are in the form of a Mixed with an essentially by statistical laws regulated distribution. The values for the Indices n and m therefore represent mean values.

Beispiele für den Rest M, einen zweiwertigen Kohlenwasserstoffrest mit mindestens 4 Kohlenstoffatomen, der eine Hydroxylgruppe aufweist und der durch mindestens ein Sauerstoffatom unterbrochen sein kann, wobei das N-Atom des Restes Z mit dem Rest M über das zur C-OH-Gruppe im Rest M benachbarte Kohlenstoffatom verbunden ist, sind

Figure 00070001
Figure 00070002
Figure 00080001
Figure 00080002
Figure 00080003
Figure 00080004
Examples of the radical M, a divalent hydrocarbon radical with at least 4 carbon atoms, which has a hydroxyl group and which can be interrupted by at least one oxygen atom, the N atom of the radical Z with the radical M via that to the C-OH group in the radical M adjacent carbon atom are connected
Figure 00070001
Figure 00070002
Figure 00080001
Figure 00080002
Figure 00080003
Figure 00080004

Innerhalb der erfindungsgemäßen Verbindungen können die beiden Reste Z gleiche oder unterschiedliche Bedeutung haben.Within the compounds according to the invention, the two Z radicals have the same or different meaning.

Beispiele für die Reste R1, R2, R3, die Alkylreste mit 1 bis 22 Kohlenstoffatomen oder Alkenylreste mit 2 bis 22 Kohlenstoffatomen, wobei die Alkyl- oder Alkenylreste Hydroxylgruppen aufweisen können und mindestens einer der Reste R1, R2, R3 mindestens 10 Kohlenstoffatome aufweist, sind Alkylreste, wie der Methyl-, Ethyl-, Octyl-, Dodecyl-, Hexadecyl- oder Octadecylrest; Hydroxyalkylreste, wie der Hydroxyethylrest; Alkenylreste, wie der Allyl- oder Vinylrest.Examples of the radicals R 1 , R 2 , R 3 , the alkyl radicals having 1 to 22 carbon atoms or alkenyl radicals having 2 to 22 carbon atoms, where the alkyl or alkenyl radicals can have hydroxyl groups and at least one of the radicals R 1 , R 2 , R 3 has at least 10 carbon atoms, are alkyl radicals such as the methyl, ethyl, octyl, dodecyl, hexadecyl or octadecyl radical; Hydroxyalkyl radicals, such as the hydroxyethyl radical; Alkenyl residues, such as the allyl or vinyl residue.

Beispiele für die Reste R4, R5, R7, R9, R10, die Alkylreste mit 1 bis 22 Kohlenstoffatomen oder Alkenylreste mit 2 bis 22 Kohlenstoffatomen, wobei die Alkyl- oder Alkenylreste Hydroxylgruppen aufweisen können, sind Alkylreste, wie der Methyl-, Ethyl-, Octyl-, Dodecyl-, Hexadecyl- oder Octadecylrest; Hydroxyalkylreste, wie der Hydroxyethylrest; Alkenylreste, wie der Allyl- oder Vinylrest.Examples of the radicals R 4 , R 5 , R 7 , R 9 , R 10 , the alkyl radicals with 1 to 22 carbon atoms or alkenyl radicals with 2 to 22 carbon atoms, where the alkyl or alkenyl radicals can have hydroxyl groups, are alkyl radicals, such as methyl -, ethyl, octyl, dodecyl, hexadecyl or octadecyl; Hydroxyalkyl radicals, such as the hydroxyethyl radical; Alkenyl residues, such as the allyl or vinyl residue.

Beispiele für R8, den Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen oder Wasserstoffrest, sind der Wasserstoffrest; Alkylreste, wie der Methyl-, Ethyl-, Isopropyl- oder Butylrest und Hydroxyalkylreste, wie der Hydroxyethylrest.Examples of R 8 , the alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms or hydrogen radical, are the hydrogen radical; Alkyl radicals such as the methyl, ethyl, isopropyl or butyl radical and hydroxyalkyl radicals such as the hydroxyethyl radical.

Beispiele für A-, ein anorganisches oder organisches Anion, das von einer üblichen physiologisch verträglichen Säure HA herrührt, sind Cl-, Br-, SO4 2-, HSO4 -, H3CSO4 -, H3CCO2 -, Citrat und Tosylat.Examples of A - , an inorganic or organic anion, which derives from a common physiologically compatible acid HA, are Cl - , Br - , SO 4 2- , HSO 4 - , H 3 CSO 4 - , H 3 CCO 2 - , citrate and tosylate.

Beispiele für den Rest Z1 sind H-, HO-, H3C-CH2O-, (H3C)2CHO-, H3C(CH2)7-,

Figure 00090001
Figure 00090002
Figure 00090003
Examples of the radical Z 1 are H-, HO-, H 3 C-CH 2 O-, (H 3 C) 2 CHO-, H 3 C (CH 2 ) 7 -,
Figure 00090001
Figure 00090002
Figure 00090003

Beispiele für Y, einen zweiwertigen Kohlenwasserstofffrest mit mindestens 2 Kohlenstoffatomen, der eine Hydroxylgruppe aufweisen und der durch mindestens ein Sauerstoff- oder Stickstoffatom unterbrochen sein kann, sind -(CH2)2-, -(CH2)3-, - (CH2)6-, -(CH2)12-, -(CH2)2-O-(CH2)2-, -CH2-O-CH2-,

Figure 00100001
Figure 00100002
Examples of Y, a divalent hydrocarbon radical with at least 2 carbon atoms, which have a hydroxyl group and which can be interrupted by at least one oxygen or nitrogen atom, are - (CH 2 ) 2 -, - (CH 2 ) 3 -, - (CH 2 ) 6 -, - (CH 2 ) 12 -, - (CH 2 ) 2 -O- (CH 2 ) 2 -, -CH 2 -O-CH 2 -,
Figure 00100001
Figure 00100002

Beispiele für die Reste R11,R12,R13,R14, die gleich oder verschieden sind und Alkylreste mit 1 bis 4 Kohlenstoffatomen oder Benzylreste bedeuten oder jeweils R11 und R13 oder R12 und R14 Bestandteile eines verbrückenden Alkylenrestes sein können, sind Alkylreste, wie Methyl-, Ethyl-, Isopropyl- oder Butylreste und Benzylreste, wie der Benzylrest. Wenn jeweils R11 und R13 oder R12 und R14 Bestandteile eines verbrückenden Alkylenrestes sind, so kann dieser Molekülteil folgende Struktur annehmen:

Figure 00100003
Examples of the radicals R 11 , R 12 , R 13 , R 14 , which are the same or different and are alkyl radicals having 1 to 4 carbon atoms or benzyl radicals, or R 11 and R 13 or R 12 and R 14 can each be constituents of a bridging alkylene radical are alkyl radicals such as methyl, ethyl, isopropyl or butyl radicals and benzyl radicals such as the benzyl radical. If R 11 and R 13 or R 12 and R 14 are constituents of a bridging alkylene radical, this part of the molecule can have the following structure:
Figure 00100003

Besonders bevorzugte Beispiele für die Reste R11,R12,R13,R14 sind der Methyl- und Ethylrest.Particularly preferred examples of the R 11 , R 12 , R 13 , R 14 radicals are the methyl and ethyl radicals.

Beispiele für R15, einen Alkylrest mit 1 bis 20 Kohlenstoffatomen, sind Alkylreste, wie der Methyl-, Ethyl-, Octyl-, Dodecyl-, Hexadecyl- oder Octadecylrest.Examples of R 15 , an alkyl radical having 1 to 20 carbon atoms, are alkyl radicals, such as the methyl, ethyl, octyl, dodecyl, hexadecyl or octadecyl radical.

Beispiele für die erfindungsgemäß mitverwendeten quaternären Polysiloxane sind

Figure 00110001
Figure 00110002
Figure 00110003
Figure 00110004
Figure 00110005
Figure 00110006
Examples of the quaternary polysiloxanes used in accordance with the invention are
Figure 00110001
Figure 00110002
Figure 00110003
Figure 00110004
Figure 00110005
Figure 00110006

Beispiele für die erfindungsgemäß mitverwendeten cyclischen quaternären Polysiloxane sind

Figure 00120001
Figure 00120002
Figure 00120003
Figure 00120004
Examples of the cyclic quaternary polysiloxanes used according to the invention are
Figure 00120001
Figure 00120002
Figure 00120003
Figure 00120004

Beispiele für die erfindungsgemäß mitverwendeten linearen quaternären Polysiloxane sind

Figure 00130001
Figure 00130002
Figure 00130003
Figure 00130004
Figure 00130005
Figure 00130006
Figure 00140001
Figure 00140002
Examples of the linear quaternary polysiloxanes used in accordance with the invention are
Figure 00130001
Figure 00130002
Figure 00130003
Figure 00130004
Figure 00130005
Figure 00130006
Figure 00140001
Figure 00140002

Waschmittel sind die auf diesem Gebiet handelsüblichen Formulierungen in Form von Pulvern, Granulaten, Perlen, Tabletten, Pasten, Gelen oder Flüssigkeiten. Sie werden überwiegend als Vollwaschmittel mit universeller Einsatzbreite formuliert und enthalten im wesentlichen feste oder flüssige Trägerstoffe und verschiedene funktionelle Inhaltsstoffe wie Tenside, anorganische polymere Gerüststoffe (Builder), Enzyme, Bleichsysteme, optische Aufheller, Soil-Release-Polymere, Schauminhibitoren, Füllstoffe, Prozeßhilfen, Stabilisatoren.Detergents are the formulations that are commercially available in this field in the form of powders, granules, pearls, tablets, Pastes, gels or liquids. They are mostly considered Heavy duty detergent formulated with a universal range of uses essentially contain solid or liquid carriers and various functional ingredients such as surfactants, inorganic polymeric builders, enzymes, bleaching systems, optical brighteners, soil release polymers, foam inhibitors, Fillers, process aids, stabilizers.

Als Tenside werden überwiegend anionische Verbindungen wie Alkylbenzolsulfonate (LAS) gegebenenfalls in Kombination mit Fettalkoholpolyglykolethern, Fettalkoholsulfate, α-Olefinsulfonate, Estersulfate und neuerdings auch Alkylpolyglycoside (APG) und Fettsäureglucamide (GA) eingesetzt;
als Builder werden Zeolithe, Polycarboxylate, Polyvinylpyrrolidone und amorphe wasserfreie Natriumsilicate und Schichtsilikate mitverwendet, wobei vielfach Citronensäure als Co-Builder zum Einsatz kommt;
Bestandteile der Bleichsysteme sind insbesondere Perborate und Natriumpercarbonat unter Mitverwendung von N-Acetyl-Verbindungen, N,N,N',N'-Tetraacetylethylendiamin oder p-Nonyloxybenzolsulfonat als Aktivatoren; als optische Aufheller kommen Stilbene und Distyrylbiphenyle und als Enzyme Proteasen, Amylasen, Cellulasen und zum Teil auch Lipasen zum Einsatz.The surfactants used are predominantly anionic compounds such as alkylbenzenesulfonates (LAS), optionally in combination with fatty alcohol polyglycol ethers, fatty alcohol sulfates, α-olefin sulfonates, ester sulfates and more recently also alkylpolyglycosides (APG) and fatty acid glucamides (GA);
Zeolites, polycarboxylates, polyvinylpyrrolidones and amorphous anhydrous sodium silicates and layered silicates are also used as builders, with citric acid often being used as a co-builder;
Components of the bleaching systems are in particular perborates and sodium percarbonate with the use of N-acetyl compounds, N, N, N ', N'-tetraacetylethylene diamine or p-nonyloxybenzenesulfonate as activators; Stilbenes and distyrylbiphenyls are used as optical brighteners and proteases, amylases, cellulases and sometimes also lipases are used as enzymes.

Diese und weitere Bestandteile und ihre Formulierungen gehören zum bekannten Stand der Technik und enthalten je nach Anwendungsgebiet die funktionellen Inhaltsstoffe in entsprechenden Mengen. Die typische Zusammensetzung von Universalwaschmitteln in Westeuropa 1998 ist in der folgenden Tabelle wiedergegeben Bestandteil Flüssig-Waschmittel [%] A Pulver-Waschmittel [%] B Tenside 20-50 10-15 Builder 1-15 25-50 Co-Builder 0-5 3-5 Bleichmittel - 10-25 Bleichmittelaktivatoren - 1-3 Antiredepositationsadditive 0-1 0-1 Korrosionsinhibitoren 2-6 2-6 Stabilisatoren 0-1 0-1 Schauminhibitoren - 0,1-4,0 Enzyme 0,5-2 0,3-0,8 Optischer Aufheller 0,1-0,3 0,1-0,3 Soil Repellents +/- +/- Füllstoffe/Prozesshilfe - 5-30 Wasser ad 100 ad 100 These and other constituents and their formulations belong to the known state of the art and, depending on the field of application, contain the functional ingredients in appropriate amounts. The typical composition of universal detergents in Western Europe in 1998 is shown in the following table component Liquid detergent [%] A Powder detergent [%] B surfactants 20-50 10-15 Builder 1-15 25-50 Co-Builder 0-5 3-5 bleach - 10-25 Bleach activators - 1-3 Antiredepositationsadditive 0-1 0-1 corrosion inhibitors 2-6 2-6 stabilizers 0-1 0-1 foam inhibitors - 0.1-4.0 enzymes 0.5-2 0.3-0.8 Optical brightener 0.1-0.3 0.1-0.3 Soil repellents +/- +/- Fillers / legal aid - 5-30 water ad 100 ad 100

Anwendungstechnischer Vergleich:Application comparison:

Die eingesetzten Testformulierungen setzen sich wie folgt zusammen: Flüssigwaschmittelbase (Komponente A): Anionische Tenside (Na-alkylbenzolsulfonat) 21,75 % Seife 16,50 % nichtionische Tenside 10,60 % amphotere Tenside 1,40 % 1,2 Propylenglykol 11,20 % Wasser ad 100 % Pulverwaschmittelbase: (Komponente B): Anionische Tenside (Na-alkylbenzolsulfonat) 15 % Pentanatriumpyrophosphat 30 % Natriumperborat 28 % Optischer Aufheller 0,1 % Carboxymethylcellulose 0,5 % Wasserglas 3,0 % Schauminhibitoren 2,0 % EDTA 0,2 % Parfüm 0,1 % Farbstoff 0,7 % Natriumsulfat und Stellmittel 17 % Wasser ad 100 % The test formulations used are composed as follows: Liquid detergent base (component A): Anionic surfactants (Na-alkylbenzenesulfonate) 21.75% Soap 16.50% nonionic surfactants 10.60% amphoteric surfactants 1.40% 1,2 propylene glycol 11.20% water ad 100% Powder detergent base: (component B): Anionic surfactants (Na-alkylbenzenesulfonate) 15% Pentanatriumpyrophosphat 30% sodium 28% Optical brightener 0.1% carboxymethylcellulose 0.5% water glass 3.0% foam inhibitors 2.0% EDTA 0.2% Perfume 0.1% dye 0.7% Sodium sulfate and adjusting agents 17% water ad 100%

Referenzwaschmittel:Reference Detergent:

85 Teile der Komponente B wurden versetzt mit 15 Teilen einer Mischung, bestehend aus 33,33 Gew.-% einer Kieselsäure (Sipernat 50, Degussa) und 66,66 Gew.-% eines Talgamidoethylimidazoliniummethosulfats. 85 parts of component B were mixed with 15 parts of one Mixture consisting of 33.33% by weight of a silica (Sipernat 50, Degussa) and 66.66 wt .-% of a Talgamidoethylimidazoliniummethosulfats.

Als erfindungsgemäß mitverwendete quaternäre Polysiloxane wurden Verbindungen mit den folgenden Strukturen eingesetzt:

Figure 00170001
Compounds with the following structures were used as quaternary polysiloxanes used in accordance with the invention:
Figure 00170001

Es ist dem Fachmann geläufig, dass die vorgenannten Verbindungen in Form eines Gemisches mit einer im wesentlichen durch statistische Gesetze geregelten Verteilung vorliegen. Die vorgenannten Formeln können daher nur Mittelwerte wiedergeben. It is known to the person skilled in the art that the aforementioned Compounds in the form of a mixture with an essentially distribution regulated by statistical laws. The the above formulas can therefore only represent mean values.

Die vorgenannten Verbindungen werden in einem industriellen Prozess entsprechend den Angaben in der EP-A-0 282 720 und in der DE-A-37 19 086 hergestellt.The aforementioned compounds are used in an industrial Process according to the information in EP-A-0 282 720 and in DE-A-37 19 086.

Es ist dem Fachmann weiterhin geläufig, dass die Endgruppen Z* und Z**, bedingt durch Nebenreaktionen, strukturellen Variationen unterliegen und daher hier nur beispielhaft wiedergegeben sind.It is also known to the person skilled in the art that the end groups Z * and Z **, due to side reactions, structural variations are subject to and are therefore only shown here as examples are.

Beispiele:Examples:

(1)(1) Komponente A)Component A) 95 %95% Formel (III)Formula (III) 5 %5% (2)(2) Komponente A)Component A) 97,5 %97.5% Formel (III)Formula (III) 3,5 %3.5% (3)(3) Komponente B)Component B) 97,5 %97.5% Formel (III)Formula (III) 3,5 %3.5% (4)(4) Komponente B)Component B) 97,5 %97.5% Formel (V)Formula (V) 3,5 %3.5% (5)(5) Komponente A)Component A) 95 %95% Formel (IV)Formula (IV) 5 %5% (6)(6) Komponente A)Component A) 97,5 %97.5% Formel (IV)Formula (IV) 2,5 %2.5% (7)(7) Komponente B)Component B) 97,5 %97.5% Formel (IV)Formula (IV) 2,5 %2.5% (8)(8th) Komponente B)Component B) 97,5 %97.5% Formel (VI)Formula (VI) 2,5 %2.5%

Prüfungen:Exams:

Zur Prüfung der Weichheit des behandelten Gewebes wurden die Textilien in einer normalen Haushaltswaschmaschine gewaschen. Die Waschmitteldosierung war je nach Art der Base unterschiedlich, orientierte sich jedoch an den üblichen Dosierempfehlungen für den Wasserhärtebereich II und normal verschmutzter Wäsche. Nach dem Waschvorgang wurde die Wäsche statisch (auf der Wäscheleine) getrocknet und mittels eines Testpanels untersucht und bewertet. Prüfbedingungen: Apparatur Miele Waschmaschine W 715, W 719, W 918 Prüfgewebe Baumwollfrottiergewebe, Fa. Frottana, Fb. 901; 100 x 50 cm Ballastgewebe glattes Baumwollgewebe Waschmittel Flüssigwaschmittelbase (Komponente A) Pulverwaschmittelbase (Komponente B) Referenzwaschmittel (Ref): Dosiermenge gemäß Dosierempfehlung für normal verschmutzte Wäsche Nachbehandlung keine Trocknungsdauer 24 Stunden unter klimatisierten Standardbedingungen To test the softness of the treated fabric, the textiles were washed in a normal household washing machine. The detergent dosage varied depending on the type of base, but was based on the usual dosage recommendations for water hardness range II and normally soiled laundry. After the washing process, the laundry was dried statically (on the clothesline) and examined and evaluated using a test panel. test conditions: apparatus Miele washing machine W 715, W 719, W 918 Test fabric Cotton terry fabric, Frottana, col. 901; 100 x 50 cm ballast fabric smooth cotton fabric laundry detergent Liquid detergent base (component A) Powder detergent base (component B) Reference detergent (Ref): dosage according to the dosage recommendation for normally soiled laundry aftercare no drying time 24 hours under air-conditioned standard conditions

Bewertung:Rating:

Nach der Trocknung der Frotteehandtücher werden diese in 10 einzelne Läppchen zerschnitten und bis zur endgültigen Bewertung durch das Testpanel im klimatisierten Raum gelagert. Die Bewertung der einzelnen Testformulierungen wird immer im direkten Vergleich zur Referenz (Marktprodukt = MP) vorgenommen. Die Prüfer können zur Bewertung der Weichheit Noten vergeben, wobei 5 die beste Bewertung darstellt und 0 die schlechteste. After the terry towels have dried, they are cut into 10 individual lobes and stored in an air-conditioned room until they are finally evaluated by the test panel. The individual test formulations are always evaluated in direct comparison to the reference (market product = MP ). Examiners can give grades to assess softness, with 5 being the best and 0 being the worst.

Bei zehn Testpersonen, die ein Produkt in einem Screeningtest bewerten, ist die maximale Benotung also ein Ergebnis von 50.With ten test persons who tested a product in a screening test rating, the maximum rating is a result of 50.

Claims (9)

Verwendung von quaternären Polysiloxanen der allgemeinen Formel (I)
Figure 00210001
und/oder
cyclischen quaternären Polysiloxanen der allgemeinen Formel (IIa)
Figure 00210002
und/oder
linearen quaternären Polysiloxanen der allgemeinen Formel (IIb)
Figure 00210003
   wobei
M
ein zweiwertiger Kohlenwasserstoffrest mit mindestens 4 Kohlenstoffatomen ist, der eine Hydroxylgruppe aufweist und der durch mindestens ein Sauerstoffatom unterbrochen sein kann, wobei das N-Atom des Restes Z mit dem Rest M über das zur C-OH-Gruppe im Rest M benachbarte Kohlenstoffatom verbunden ist,
Z
ein Rest
Figure 00220001
ist,
R1, R2, R3 =
Alkylreste mit 1 bis 22 Kohlenstoffatomen oder Alkenylreste mit 2 bis 22 Kohlenstoffatomen, wobei die Alkyl- oder Alkenylreste Hydroxylgruppen aufweisen können und mindestens einer der Reste R1, R2, R3 mindestens 10 Kohlenstoffatome aufweist,
R4, R5, R7, R9, R10 =
Alkylreste mit 1 bis 22 Kohlenstoffatomen oder Alkenylreste mit 2 bis 22 Kohlenstoffatomen, wobei die Alkyl- oder Alkenylreste Hydroxylgruppen aufweisen können,
R6 =
-O- oder -NR8- Rest,
R8 =
Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen oder Wasserstoffrest,
x =
2 bis 4,
n =
eine Zahl von 0 bis 200,
A-=
ein anorganisches oder organisches Anion, das von einer üblichen physiologisch verträglichen Säure HA herrührt
Z1 =
ein H-, OH-, ein Alkyl- oder Alkoxyrest ist, oder die Bedeutung eines Kohlenwasserstoffrestes mit mindestens 4 Kohlenstoffatomen hat, der eine oder mehrere Hydroxylgruppe(n) aufweist und durch ein oder mehrere Sauerstoffatome unterbrochen sein kann oder die Bedeutung des Restes
Figure 00230001
hat,
Z2 =
die Gruppe
Figure 00230002
bedeutet,
Y =
ein zweiwertiger Kohlenwasserstoffrest mit mindestens 2 Kohlenstoffatomen ist, der eine Hydroxylgruppe aufweisen und der durch mindestens ein Sauerstoff- oder Stickstoffatom unterbrochen sein kann,
R11,R12,R13,R14 =
gleich oder verschieden sind und Alkylreste mit 1 bis 4 Kohlenstoffatomen oder Benzylreste bedeuten oder jeweils R11 und R13 oder R12 und R14 Bestandteile eines verbrückenden Alkylenrestes sein können,
R15 =
ein Alkylrest mit 1 bis 20 Kohlenstoffatomen ist,
m =
ganze Zahl größer oder gleich 1 ist
in Waschmittelformulierungen. Use of quaternary polysiloxanes of the general formula (I)
Figure 00210001
and or
cyclic quaternary polysiloxanes of the general formula (IIa)
Figure 00210002
and or
linear quaternary polysiloxanes of the general formula (IIb)
Figure 00210003
in which
M
is a divalent hydrocarbon radical having at least 4 carbon atoms, which has a hydroxyl group and which can be interrupted by at least one oxygen atom, the N atom of the radical Z being connected to the radical M via the carbon atom adjacent to the C-OH group in the radical M. .
Z
a rest
Figure 00220001
is
R 1 , R 2 , R 3 =
Alkyl radicals with 1 to 22 carbon atoms or alkenyl radicals with 2 to 22 carbon atoms, where the alkyl or alkenyl radicals can have hydroxyl groups and at least one of the radicals R 1 , R 2 , R 3 has at least 10 carbon atoms,
R 4 , R 5 , R 7 , R 9 , R 10 =
Alkyl radicals with 1 to 22 carbon atoms or alkenyl radicals with 2 to 22 carbon atoms, where the alkyl or alkenyl radicals can have hydroxyl groups,
R 6 =
-O- or -NR 8 - rest,
R 8 =
Alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms or hydrogen radical,
x =
2 to 4,
n =
a number from 0 to 200,
A - =
an inorganic or organic anion derived from a common physiologically acceptable acid HA
Z 1 =
is an H, OH, an alkyl or alkoxy radical, or has the meaning of a hydrocarbon radical with at least 4 carbon atoms, which has one or more hydroxyl group (s) and can be interrupted by one or more oxygen atoms, or the meaning of the rest
Figure 00230001
Has,
Z 2 =
the group
Figure 00230002
means
Y =
is a divalent hydrocarbon radical with at least 2 carbon atoms, which have a hydroxyl group and which can be interrupted by at least one oxygen or nitrogen atom,
R 11 , R 12 , R 13 , R 14 =
are identical or different and are alkyl radicals having 1 to 4 carbon atoms or benzyl radicals or R 11 and R 13 or R 12 and R 14 can each be constituents of a bridging alkylene radical,
R 15 =
is an alkyl radical with 1 to 20 carbon atoms,
m =
integer is greater than or equal to 1
in detergent formulations. Verwendung von quaternären Polysiloxanen der allgemeinen Formel (I) gemäß Anspruch 1, dadurch gekennzeichnet, dass
n
für eine Zahl im Bereich von 0 bis 150, insbesondere 5 bis 100,
x
für eine Zahl im Bereich von 2 bis 4
steht.Use of quaternary polysiloxanes of the general formula (I) according to Claim 1, characterized in that
n
for a number in the range from 0 to 150, in particular 5 to 100,
x
for a number in the range from 2 to 4
stands. Verwendung von quaternären Polysiloxanen der allgemeinen Formel (II a) und / oder Verwendung von quaternären Polysiloxanen der allgemeinen Formel (II b), gemäß Anspruch 1, dadurch gekennzeichnet, dass
n
für eine Zahl im Bereich von 0 bis 150, insbesondere 5 bis 100,
x
für eine Zahl im Bereich von 2 bis 4,
m
für eine Zahl im Bereich von 1 bis 10, insbesondere 1 bis 5
steht.Use of quaternary polysiloxanes of the general formula (II a) and / or use of quaternary polysiloxanes of the general formula (II b), according to claim 1, characterized in that
n
for a number in the range from 0 to 150, in particular 5 to 100,
x
for a number in the range from 2 to 4,
m
for a number in the range from 1 to 10, in particular 1 to 5
stands. Verwendung von quaternären Polysiloxanen nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, dass der Rest M ausgewählt ist aus der Gruppe
Figure 00240001
Figure 00240002
Figure 00240003
Figure 00250001
Figure 00250002
Figure 00250003
Use of quaternary polysiloxanes according to claims 1 to 3, characterized in that the radical M is selected from the group
Figure 00240001
Figure 00240002
Figure 00240003
Figure 00250001
Figure 00250002
Figure 00250003
 Verwendung von quaternären Polysiloxanen nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, dass Z ein Rest der allgemeinen Formel
Figure 00250004
ist,
worin x = 3, R6 = -NH- und R7 = ein Alkylrest mit 8 bis 18 Kohlenstoffatomen ist. Use of quaternary polysiloxanes according to claims 1 to 4, characterized in that Z is a radical of the general formula
Figure 00250004
is
wherein x = 3, R 6 = -NH- and R 7 = an alkyl radical with 8 to 18 carbon atoms. Verwendung von quaternären Polysiloxanen nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, dass Y ein zweiwertiger Kohlenwasserstoffrest mit 3 bis 12 Kohlenstoffatomen ist.Use of quaternary polysiloxanes according to Claims 1 to 5, characterized in that Y is a divalent hydrocarbon radical with 3 to 12 carbon atoms. Waschmittel mit weichmachender Wirkung, enthaltend eine wirksame Menge mindestens einer der Verbindungen der allgemeinen Formel (I), (II a) oder (II b). Detergent with a softening effect, containing one effective amount of at least one of the compounds of the general formula (I), (II a) or (II b). Waschmittel mit weichmachender Wirkung, enthaltend mindestens eine der Verbindungen der allgemeinen Formel (I), (II a) oder (II b) und mindestens ein festes Trägermaterial.Detergent with a softening effect, containing at least one of the compounds of the general formula (I), (II a) or (II b) and at least one solid Support material. Waschmittel mit weichmachender Wirkung gemäß Anspruch 8, dadurch gekennzeichnet, dass die festen Trägermaterialien ausgewählt sind aus der Gruppe der Kieselsäuren, Silicate, Natriumsilicate, Bentonite, Schichtsilicate, Zeolithe und Montmorillonite.Detergent with a softening effect according to claim 8, characterized in that the solid carrier materials are selected from the group of silicas, silicates, sodium silicates, bentonites, sheet silicates, zeolites and montmorillonites.
EP01123706A 2000-10-16 2001-10-04 Use of quaternary polysiloxanes in detergent compositions Expired - Lifetime EP1199350B1 (en)

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US7294611B2 (en) 2002-09-05 2007-11-13 The Procter And Gamble Company Structured liquid fabric treatment compositions
US8268975B2 (en) 2009-04-03 2012-09-18 Dow Agrosciences Llc Demulsification compositions, systems and methods for demulsifying and separating aqueous emulsions
CN105658749A (en) * 2013-09-23 2016-06-08 鲁道夫有限公司 Polysiloxanes with quaternized heterocyclic groups

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MXPA05004805A (en) * 2002-11-04 2005-07-22 Procter & Gamble Fabric treatment compositions comprising oppositely charged polymers.
ES2308036T3 (en) * 2002-11-04 2008-12-01 Momentive Performance Materials Gmbh LINEAR COPOLIMEROS OF POLYAMINO-POLISILOXANO AND / OR OF POLYAMONIO-POLISILOXANO II.
EP1565512B1 (en) * 2002-11-04 2018-07-04 Momentive Performance Materials GmbH Linear polyamino and/or polyammonium polysiloxane copolymers i
DE60316340T2 (en) * 2002-11-04 2008-06-12 The Procter & Gamble Company, Cincinnati LIQUID DETERGENT COMPOSITION
DE10259291B4 (en) * 2002-12-18 2006-02-23 Rudolf Gmbh & Co. Kg Chemische Fabrik Highly concentrated, self-emulsifying preparations containing organopolysiloxanes and alkylammonium compounds and their use in aqueous systems
US7179777B2 (en) * 2002-12-23 2007-02-20 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Laundry treatment compositions comprising a polymer with a cationic and polydialkylsiloxane moiety
DE10316662A1 (en) 2003-04-11 2004-11-11 Ge Bayer Silicones Gmbh & Co. Kg Reactive amino and / or ammonium polysiloxane compounds
US7759408B2 (en) * 2005-12-21 2010-07-20 Bausch & Lomb Incorporated Silicon-containing monomers end-capped with polymerizable cationic hydrophilic groups
US7622512B2 (en) * 2005-12-21 2009-11-24 Bausch & Lomb Incorporated Cationic hydrophilic siloxanyl monomers
US20070161769A1 (en) * 2006-01-06 2007-07-12 Schorzman Derek A Polymerizable silicon-containing monomer bearing pendant cationic hydrophilic groups
US7960447B2 (en) * 2006-04-13 2011-06-14 Bausch & Lomb Incorporated Cationic end-capped siloxane prepolymer for reduced cross-link density
US7468397B2 (en) * 2006-06-30 2008-12-23 Bausch & Lomb Incorporated Polymerizable siloxane-quaternary amine copolymers
US20080152540A1 (en) * 2006-12-22 2008-06-26 Bausch & Lomb Incorporated Packaging solutions
US7691917B2 (en) 2007-06-14 2010-04-06 Bausch & Lomb Incorporated Silcone-containing prepolymers
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WO2003012020A2 (en) * 2001-07-27 2003-02-13 The Procter & Gamble Company Fabric care systems for providing anti-wrinkle benefits to fabric
WO2003012020A3 (en) * 2001-07-27 2003-10-30 Procter & Gamble Fabric care systems for providing anti-wrinkle benefits to fabric
US6818610B2 (en) 2001-07-27 2004-11-16 Procter & Gamble Company Fabric care systems for providing anti-wrinkle benefits to fabric
US7196048B2 (en) 2001-07-27 2007-03-27 The Procter & Gamble Co. Fabric care systems for providing anti-wrinkle benefits to fabric
US7294611B2 (en) 2002-09-05 2007-11-13 The Procter And Gamble Company Structured liquid fabric treatment compositions
US8268975B2 (en) 2009-04-03 2012-09-18 Dow Agrosciences Llc Demulsification compositions, systems and methods for demulsifying and separating aqueous emulsions
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CN105658749A (en) * 2013-09-23 2016-06-08 鲁道夫有限公司 Polysiloxanes with quaternized heterocyclic groups

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US6706680B2 (en) 2004-03-16
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US20020068689A1 (en) 2002-06-06

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