EP0688356B1 - Aqueous textile softener compositions - Google Patents

Aqueous textile softener compositions Download PDF

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EP0688356B1
EP0688356B1 EP94909087A EP94909087A EP0688356B1 EP 0688356 B1 EP0688356 B1 EP 0688356B1 EP 94909087 A EP94909087 A EP 94909087A EP 94909087 A EP94909087 A EP 94909087A EP 0688356 B1 EP0688356 B1 EP 0688356B1
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alkyl
alkenyl
weight
carbon atoms
sulfate salt
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French (fr)
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EP0688356A1 (en
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Rolf Puchta
Fred Schambil
Theodor Völkel
Anneliese Wilsch-Irrgang
Miguel Osset Hernandez
Xavier Closa Cruxens
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Henkel AG and Co KGaA
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/165—Ethers
    • D06M13/17—Polyoxyalkyleneglycol ethers
    • 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
    • C11D1/65—Mixtures of anionic with cationic compounds
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • D06M13/148—Polyalcohols, e.g. glycerol or glucose
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/262—Sulfated compounds thiosulfates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2044—Dihydric alcohols linear
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/50—Modified hand or grip properties; Softening compositions

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Detergent Compositions (AREA)

Abstract

The viscosity of aqueous textile softener compositions containing 1-40 % wt. of a dispersed cationic softener of the quaternary ammonium compound type and at least two fatty residues is increased by the addition of 0.1-5 wt %. of C12-C22alkyl or alkenyl sulphate salts or ester sulphate salts. In addition, an aliphatic, water-soluble diol, polyol or polyalkylene glycol is preferably added.

Description

Die Erfindung betrifft ein Verfahren zur Erhöhung der Viskosität von relativ niedrig konzentrierten wässrigen Textilweichmacher-Dispersionen auf Basis kationischer Weichmacher vom Typ der quartären Ammoniumverbindungen mit wenigstens zwei langen Alkyl-, Alkenyl- oder Acylgruppen durch Zusatz von relativ kleinen Mengen von Alkyl- oder Alkenyl-sulfat-Salzen oder von Alkyl- oder Alkenyl-Ethersulfat-Salzen mit 12-22 C-Atomen in der Alkyloder Alkenylgruppe.The invention relates to a method for increasing the viscosity of relatively low-concentration aqueous textile plasticizer dispersions based on cationic plasticizers of the quaternary ammonium compound type with at least two long alkyl, alkenyl or acyl groups by adding relatively small amounts of alkyl or alkenyl sulfate Salts or of alkyl or alkenyl ether sulfate salts with 12-22 carbon atoms in the alkyl or alkenyl group.

Die in Textilnachspülmitteln gebräuchlichen Textilweichmacher vom Typ der quartären Ammoniumverbindungen mit wenigstens zwei langkettigen Alkyloder Acylgruppen sind in Wasser wenig löslich und liegen daher auch im Bereich niedriger Konzentrationen von weniger als z. B. 10 Gew.-% in Wasser als Dispersion vor. Diese Dispersionen haben die Eigenschaft, daß sie zwar bei höheren Konzentrationen von mehr als 15 gew.-% in Wasser sehr hochviskos und wenig fließfähig sind, im Bereich niedriger Konzentrationen unter 10 Gew.-%, also in den für Haushalts-Wäscheweichmacher üblichen Konzentrationsbereich aber sind diese Disper-sionen sehr dünnflüssig. Dies ist von Nachteil für die Lagerstabilität der Dispersionen und erschwert auch die Handhabung und Dosierung solcher Produkte. Eine Verdickung durch Zusatz bekannter wasserlöslicher Polymerisate wäre zwar möglich, solche Polymeren haben jedoch Nachteile in ihrer Wirkung auf das weichzumachende Textilgewebe und auch in Bezug auf ihre biologische Abbaubarkeit.The fabric softeners of the type of quaternary ammonium compounds with at least two long-chain alkyl or acyl groups which are customary in fabric rinsing agents are not very soluble in water and are therefore also in the range of low concentrations of less than z. B. 10 wt .-% in water as a dispersion. These dispersions have the property that, although they are very highly viscous and poorly flowable in water at higher concentrations of more than 15% by weight, they are below 10% by weight in the range of low concentrations, ie in the concentration range customary for household laundry softeners these dispersions are very thin. This is disadvantageous for the storage stability of the dispersions and also complicates the handling and metering of such products. Thickening by the addition of known water-soluble polymers would be possible, but such polymers have disadvantages in their effect on the textile fabric to be softened and also in their biodegradability.

Es bestand daher die Aufgabe, wässrige Textilweichmacher-Zubereitungen auf Basis quartärer Ammoniumverbindungen durch geeignete, biologisch abbaubare Zusatzstoffe zu verdicken.The task was therefore to thicken aqueous textile plasticizer preparations based on quaternary ammonium compounds by means of suitable, biodegradable additives.

Aus DE-24 32 296 B2 war bekannt, daß Alkylethersulfate die Viskosität wässriger Zubereitungen von Fettsäure-alkanolamin-Kondensaten erniedrigen.From DE-24 32 296 B2 it was known that alkyl ether sulfates make the viscosity more aqueous Reduce preparations of fatty acid alkanolamine condensates.

Aus GB-A-2 054 635 sind Waschmittel-Zusammensetzungen mit einem Zusatz von kationischen Tensiden und Alkylethersulfaten bekannt, in denen ein Alkylethersulfat in einer Menge von 1 - 3 Gewichtsteilen pro Gewichtsteil kationischer Tenside sowie bis zu 50 Gew.-% weitere anionische, amphotere oder nichtionische Tenside enthalten sind.GB-A-2 054 635 discloses detergent compositions with the addition of cationic surfactants and alkyl ether sulfates, in which an alkyl ether sulfate in an amount of 1-3 parts by weight per part by weight of cationic surfactants and up to 50% by weight of further anionic, amphoteric or nonionic surfactants are included.

Überraschend wurde festgestellt, daß Zusätze von Alkylsulfat-Salzen und Alkyl-Ethersulfatsalzen zu Dispersionen von Textilweichmachem des Typs der quartären Ammoniumverbindungen deren Viskosität erhöhen.Surprisingly, it was found that additions of alkyl sulfate salts and alkyl ether sulfate salts to dispersions of textile plasticizers of the quaternary ammonium compound type increase their viscosity.

Obwohl diese verdickende Wirkung der Zusätze von Alkylsulfat-Salzen und Alkyl-Ethersulfat-Salzen in wäßrigen Zubereitungen mit niedriger Konzentration von etwa 0,1 - 10 Gew.-% des dispergierten kationischen Weichmachers besonders wünschenswert ist, stellt man auch bei höherkonzentrierten Textilweichmacher-Dispersionen mit bis zu 40 Gew.-% des dispergierten kationischen Weichmachers eine stabilisierende Wirkung dieses Zusatzes fest.Although this thickening effect of the additions of alkyl sulfate salts and alkyl ether sulfate salts is particularly desirable in aqueous preparations with a low concentration of about 0.1-10% by weight of the dispersed cationic plasticizer, the same is also done with higher-concentration textile plasticizer dispersions up to 40 wt .-% of the dispersed cationic plasticizer a stabilizing effect of this additive.

Es wurde darüber hinaus beobachtet, daß Zusätze von Alkylsulfat-Salzen zu kationischen Textilweichmachem den damit nachbehandelten Textilien eine gewisse schmutzabweisende Ausrüstung verleihen, so daß die danach erfolgenden Anschmutzungen leichter und vollständiger ausgewaschen werden können.It has also been observed that additions of alkyl sulfate salts to cationic textile softeners give the textiles aftertreated with a certain dirt-repellent finish, so that the soiling that follows can be washed out more easily and completely.

Gegenstand der Erfindung sind daher wässrige Textilweichmacher-Zusammensetzungen, dieThe invention therefore relates to aqueous textile plasticizer compositions which

(A) 1-40 Gew.-% eines dispergierten kationischen Weichmachers vom Typ der quartären Ammoniumverbindungen mit wenigstens zwei Alkyl-, Alkenyl-, Acyloxyalkyl- oder Acylaminoalkyl-gruppen mit 12-22 C-Atomen in der Alkyl-, Alkenyl- oder Acylgruppe und zur Erhöhung der Viskosität(A) 1-40% by weight of a dispersed cationic plasticizer of the quaternary ammonium compound type with at least two alkyl, alkenyl, acyloxyalkyl or acylaminoalkyl groups with 12-22 C atoms in the alkyl, alkenyl or acyl group and to increase the viscosity (B) 0,1-5 Gew.-% eines Alkyl- oder Alkenylsulfat-Salzes oder eines Alkyl- oder Alkenyl-Ethersulfat-Salzes mit 12-22 C-Atomen in der Alkyl- oder Alkenylgruppe enthalten.(B) 0.1-5 wt .-% of an alkyl or alkenyl sulfate salt or an alkyl or alkenyl ether sulfate salt with 12-22 carbon atoms in the alkyl or alkenyl group.

Das Gewichtsverhältnis von kationischem Weichmacher (A) und Alkyl- oder Alkenylsulfat-Salz bzw. Alkyl- oder Alkenylethersulfat-Salz (B) sollte dabei größer als (A) : (B) = 5:1 sein.The weight ratio of cationic plasticizer (A) and alkyl or alkenyl sulfate salt or alkyl or alkenyl ether sulfate salt (B) should be greater than (A): (B) = 5: 1.

Die erfindungsgemäßen Textilweichmacher-Zusammensetzungen weisen eine deutlich erhöhte Viskosität auf, ohne daß in dem erfindungsgemäßen Bereich die Fließfähigkeit der Zubereitungen ungünstig beeinflußt wird. Auch wiesen die erfindungsgemäßen Wäschweichmacher-Dispersionen eine gute Scherstabilität auf. Durch Scherbeanpruchung, wie sie z. B. durch längeranhaltendes Pumpen der Dispersion erfolgt oder durch Lagerung der Dispersionen kommt es zwar noch zu geringfügigen Viskositätszunahmen, insgesamt zeigen die erfindungsgemäßen Weichspüler-Dispersionen jedoch eine hohe Lagerstabilität und ein gutes Anwendungsverhalten.The textile plasticizer compositions according to the invention have a significantly increased viscosity without the flowability of the preparations being adversely affected in the range according to the invention. The laundry plasticizer dispersions according to the invention also had good shear stability. By shear stress as z. B. by prolonged pumping of the dispersion or storage of the dispersions, there are still slight increases in viscosity, but overall, the fabric softener dispersions according to the invention show high storage stability and good application behavior.

Als dispergierte kationische Weichmacher vom Typ der quartären Ammoniumverbindungen (QAV) eignen sich alle hierfür bekannten QAV mit wenigstens zwei langkettigen Alkyl-, Alkenyl- oder Acylgruppen. Beispiele solcher Verbindungen sind z. B. das Distearyl-dimethyl-ammonium-chlorid oder das 1-Methyl-(1-stearoylamino)-ethyl-2-heptadecyl-imidazolinium-methosulfat. Besonders bevorzugt sind erfindungsgemäße Textilweichmacher-Zusammensetzungen, die als QAV eine Verbindung der Formel I

Figure imgb0001
enthalten, in der im Mittel 2 bis 3 der Gruppen R1 bis R4 eine Acyloxyalkylgruppe der Formel R5CO(OCnH2n)x- aufweisen, in der R5CO eine Acylgruppe mit 12-22 C-Atomen, n = 2 oder 3 und x = 1 bis 10 sein kann und daneben eine Alkylgruppe mit 1-4 C-Atomen und/oder eine Hydroxy(alkoxy)-alkylgruppe der Formel H-(OCnH2n)x-, in der n = 2 oder 3 und x = bis 10 sein kann, und A(-) ein Chlorid oder ein CH3OSO3(-) - Anion ist. Bevorzugt sind dabei Verbindungen der Formel I, in der x = 1 und n = 2 ist und die sich von Triethanolamin ableiten. Solche QAV lassen sich. B. durch Umsetzung von Triethanolamin mit Fettsäureestern und anschließende Quaternierung des Umsetzungsprodukts mit Methylchlorid oder Dimethylsulfat herstellen. Als Acylgruppe können dabei solche von natürlichen oder synthetischen Fettsäuren mit 12-22 C-Atomen oder von technischen Gemischen pflanzlicher oder tierischer Fettsäuren, z. B. von Palmölfettsäure oder von Talgfettsäure abgeleitete Acylgruppen enthalten sein. Die Umesterung von Triethanolamin mit Fettsäureestern führt, auch wenn sie im Molverhältnis 1 : 2 bis 1 : 3 durchgeführt wurde, zu Gemischen von Mono-, Di- und Triestern des Triethanolamins, die bezüglich des Gehalts an Acyloxyethylgruppen nur im Mittel dem Umsetzungsverhältnis entsprechen.All known QAVs with at least two long-chain alkyl, alkenyl or acyl groups are suitable as dispersed cationic plasticizers of the quaternary ammonium compound (QAV) type. Examples of such compounds are e.g. B. the distearyl-dimethyl-ammonium chloride or the 1-methyl- (1-stearoylamino) -ethyl-2-heptadecyl-imidazolinium methosulfate. Textile plasticizer compositions according to the invention are particularly preferred which, as QAV, are a compound of the formula I.
Figure imgb0001
 contain in which on average 2 to 3 of the groups R 1 to R 4 have an acyloxyalkyl group of the formula R 5 CO (OC n H 2n ) x -, in which R 5 CO an acyl group having 12-22 C atoms, n = 2 or 3 and x = 1 to 10 and in addition an alkyl group with 1-4 C atoms and / or a hydroxy (alkoxy) alkyl group of the formula H- (OC n H 2n ) x -, in which n = 2 or 3 and x = can be up to 10 and A (-) is a chloride or a CH 3 OSO 3 (-) anion. Compounds of the formula I in which x = 1 and n = 2 and which are derived from triethanolamine are preferred. Such QAV can be. B. by reacting triethanolamine with fatty acid esters and subsequent quaternization of the reaction product with methyl chloride or dimethyl sulfate. As an acyl group, those of natural or synthetic fatty acids with 12-22 carbon atoms or of technical mixtures of vegetable or animal fatty acids, e.g. B. from palm oil fatty acid or tallow fatty acid derived acyl groups. The transesterification of triethanolamine with fatty acid esters leads, even if they are in a molar ratio of 1: 2 to 1: 3 was carried out, to mixtures of mono-, di- and triesters of triethanolamine, which correspond to the reaction ratio with respect to the content of acyloxyethyl groups only on average.

Als Komponente (B) eignen sich die Schwefelsäuremonoester-Salze von Fettalkoholen mit 12-22 C-Atomen oder von Ethylenoxid-Addukten von 1-6 Mol Ethylenoxid an solche Fettalkohole. Als Fettalkohole eignen such hierfür synthetische, auch geringfügig methylverzweigte, gesättigte primäre Alkohole wie sie z. B. durch Hydroformylierung aus Alpha-Olefinen oder durch Ziegler-Aufbausynthese aus Ethylen zugänglich sind. Bevorzugt geeignet sind aber die Sulfatsalze und Ethersulfatsalze von gesättigter und ungesättigten natürlichen Fettalkoholen, wie sie durch Hydrierverfahren aus entsprechenden Fettsäureestern erhältlich sind z. B. auch technische Fettalkoholschnitte, wie sie aus Kokos- oder Talgfettsäure-estern hergestellt werden. Die Alkylsulfate und Alkylethersulfate sollen als wasserlösliche Salze, bevorzugt als Alkali-, Magnesium- oder Ammoniumsalze, vorliegen.Suitable components (B) are the sulfuric acid monoester salts of fatty alcohols with 12-22 carbon atoms or of ethylene oxide adducts of 1-6 mol ethylene oxide with such fatty alcohols. Suitable fatty alcohols for this purpose are synthetic, also slightly methyl-branched, saturated primary alcohols such as, for. B. are accessible by hydroformylation from alpha-olefins or by Ziegler synthesis from ethylene. However, preference is given to the sulfate salts and ether sulfate salts of saturated and unsaturated natural fatty alcohols, as can be obtained by hydrogenation processes from corresponding fatty acid esters, e.g. B. also technical fatty alcohol cuts, such as those made from coconut or tallow fatty acid esters. The alkyl sulfates and alkyl ether sulfates should be present as water-soluble salts, preferably as alkali, magnesium or ammonium salts.

Es hat sich gezeigt, daß die Verdickung der erfindungsgemäßen Textilweichmacher-Zusammensetzung noch weiter gesteigert werden kann, wenn zusätzlich.It has been shown that the thickening of the fabric softening composition according to the invention can be increased even further, if in addition.

(C) 0,1-1 Gew.-% eines aliphatischen Diols oder Polyols mit 2-6 C-Atomen und 2-6 Hydroxylgruppen oder ein wasserlösliches Polyalkylenglycol(C) 0.1-1% by weight of an aliphatic diol or polyol with 2-6 C atoms and 2-6 hydroxyl groups or a water-soluble polyalkylene glycol

bezogen auf die gesamte Dispersion zugesetzt wird. Durch diesen Zusatz von Diol, Polyol oder Polyglycol wird vor allem die Viskositätsstabilität gegenüber Scherbeanspruchungen erheblich verbessert, so daß auch bei der technischen Handhabung der Produkte, z. B. beim Rühren, Pumpen und Fördern keine gravierenden Viskositätsschwankungen auftreten.based on the total dispersion is added. This addition of diol, polyol or polyglycol, especially the viscosity stability against shear stresses is significantly improved, so that also in the technical handling of the products, for. B. when stirring, pumping and conveying no serious viscosity fluctuations occur.

Geeignete Diole sind z. B. Ethylenglycol, 1,2-Propylenglycol, 1,3-Propylenglycol, 1,3-Butandiol; geeignete Polyole sind z. B. Glycerin, Erythrit, Pentaerythrit, Trimethylolpropan und Sorbit, geeignete Polyalkylenglycole z. B. Polyethylenglycole mit Molekulargewichten bis 10 000, insbesondere von 200 bis 1 000.Suitable diols are e.g. B. ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol; suitable polyols are e.g. As glycerol, erythritol, pentaerythritol, trimethylolpropane and sorbitol, suitable polyalkylene glycols such. B. polyethylene glycols with molecular weights up to 10,000, in particular from 200 to 1,000.

Eine bevorzugte Ausführungsform der erfindungsgemäßen Textilweichmacher-Zusammensetzung enthält

  • (A) 1 - 10 Gew.-% des kationischen Weichmachers
  • (B) 0,1 - 2 Gew.-% eines Alkyl- oder Alkenylsulfat-Alkali-, Magnesiumoder Ammoniumsalzes.
Neben den kennzeichnenden Komponenten (A), (B) und gegebenenfalls (C) können die erfindungsgemäßen Textilweichmacher-Zusammensetzungen noch weitere, in solchen Produkten übliche Zusätze enthalten. Als solche sind vor allen Duftstoffe zu nennen, da neben dem Weichspül-Effekt meist auch eine Beduftung des Textilguts erwünscht ist. Geeignete Parfümöle können z. B. in Mengen von 0,1 bis 1 Gew.-% zugesetzt werden. Zur homogenen Einarbeitung der Duftstoffe kann auch der Zusatz weiterer Hilfsmittel, z. B. von niederen Alkoholen oder von nichtionigenen Emulgatoren oder Solubilisatoren wünschenswert sein, deren Menge aber insgesamt nicht mehr als 5 Gew.-% der Zusammensetzung ausmachen sollte. Schließlich werden Wäsche-Weichspüler für den Gebrauch in Haushalt gern angefärbt, wozu wasserlösliche Farbstoffe in kleinen Mengen zugesetzt werden, die aber nicht auf das Textilgut aufziehen sollten.A preferred embodiment of the fabric softener composition according to the invention contains
  • (A) 1-10% by weight of the cationic plasticizer
  • (B) 0.1-2% by weight of an alkyl or alkenyl sulfate alkali, magnesium or ammonium salt.
In addition to the characteristic components (A), (B) and, if appropriate, (C), the fabric softener compositions according to the invention may also contain further additives which are customary in such products. As such, fragrances should be mentioned above all, since in addition to the fabric softening effect, scenting of the textile goods is usually also desirable. Suitable perfume oils can e.g. B. in amounts of 0.1 to 1 wt .-%. For the homogeneous incorporation of the fragrances, the addition of other auxiliaries, for. B. of lower alcohols or of non-ionic emulsifiers or solubilizers, but the total amount should not make up more than 5% by weight of the composition. Finally, laundry softeners for household use are often dyed, for which water-soluble dyes are added in small amounts, but should not be absorbed by the textile.

Schließlich kann es in Textilweichmacher-Zusammensetzungen mit hohen Gehalten von mehr als 10 Gew.-% an kationischen Weichmacherverbindungen erforderlich sein, zur Verhinderung der Gelbildung strukturbrechende Elektrolyte, z.B. MgCl2 zuzusetzen. Durch kombinierte Anwendung dieser Elektrolyte und des verdickenden Zusatzes von Alkyl-, Alkenyl- oder Ethersulfat-Salzen wird eine besonders gute Stabilität auch höherkonzentrierter Textilweichmacher-Zusammensetzungen erreicht.Finally, in textile plasticizer compositions with high contents of more than 10% by weight of cationic plasticizer compounds it may be necessary to add structurally breaking electrolytes, for example MgCl 2 , to prevent gel formation. The combined use of these electrolytes and the thickening addition of alkyl, alkenyl or ether sulfate salts results in particularly good stability even of highly concentrated textile plasticizer compositions.

Zur Herstellung der erfindungsgemäßen Textilweichmacher-Zusammensetzung werden die Komponenten nacheinander in Wasser gelöst bzw. dispergiert. Bevorzugt erfolgt die Herstellung in der Weise, daß man aus den Komponenten (A), (B) und gegebenenfalls (C) eine homogene Schmelze (Prämix-Lösung) herstellt und diese in Wasser oder in der wässrigen Lösung der übrigen Komponenten dispergiert.To produce the textile plasticizer composition according to the invention, the components are dissolved or dispersed in water in succession. The preparation is preferably carried out by producing a homogeneous melt (premix solution) from components (A), (B) and optionally (C) and dispersing them in water or in the aqueous solution of the other components.

Die folgenden Beispiele sollen den Gegenstand der Erfindung erläutern ohne ihn hierauf zu beschränken.The following examples are intended to explain the subject matter of the invention without restricting it thereto.

BeispieleExamples I. Erhöhung der ViskositätI. Increase in viscosity

Es wurden Textilweichmacher-Dispersionen der folgenden Zusammensetzungen hergestellt (Tabelle) und die Viskositäten mit Hilfe eines Brookfield-Rotationsviskosimeters bestimmt: Tabelle I 1 2 3 4 5 6 7 kationischer Weichmacher (A) 4,5 4,5 4,5 4,5 4,5 4,5 4,5 Talgfettalkohol (C16-18) Sulfat, Na-Salz (B1) - 0,5 - 0,5 - 0,5 - Kokos-Talg (1:1)-fettalkohol (C12-18)-sulfat, Na-Salz (B2) - - 0,5 - 0,5 - 0,5 Polyethylenglycol (MG:400) - - - 0,5 0,5 - - Glycerin - - - - - 0,5 0,5 Parfümöl 0,3 0,3 0,3 0,3 0,3 0,3 0,3 Wasser 95,2 94,7 94,7 94,2 94,3 94,2 94,2 Viskosität (m Pa s) 20 °C, 2 UpM Brookfield-Viskosimeter 20 190 90 360 200 860 840 Tabelle II 8 9 10 kationischer Weichmacher (A) 17,2 17,2 17,2 Talgfettalkohol (C16-18)-Sulfat, Na-Salz (B1) 0,1 0,2 0,3 MgCl2 · 6H2O 0,15 0,15 0,15 Farbstoff (rot) 0,0003 0,0003 0,0003 Parfümöl 0,8 0,8 0,8 Wasser ad 100 ad 100 ad 100 Viskosität (m Pa s) 20 °C, 2 UpM Brookfield-Viskosimeter 103 143 160 Fabric softener dispersions of the following compositions were prepared (table) and the viscosities were determined using a Brookfield rotary viscometer: Table I 1 2nd 3rd 4th 5 6 7 cationic plasticizer (A) 4.5 4.5 4.5 4.5 4.5 4.5 4.5 Tallow fatty alcohol (C 16-18 ) sulfate, Na salt (B1) - 0.5 - 0.5 - 0.5 - Coconut tallow (1: 1) fatty alcohol (C 12-18 ) sulfate, Na salt (B2) - - 0.5 - 0.5 - 0.5 Polyethylene glycol (MG: 400) - - - 0.5 0.5 - - Glycerin - - - - - 0.5 0.5 Perfume oil 0.3 0.3 0.3 0.3 0.3 0.3 0.3 water 95.2 94.7 94.7 94.2 94.3 94.2 94.2 Viscosity (m Pa s) 20 ° C, 2 rpm Brookfield viscometer 20th 190 90 360 200 860 840 8th 9 10th cationic plasticizer (A) 17.2 17.2 17.2 Tallow fatty alcohol (C 16-18 ) sulfate, Na salt (B1) 0.1 0.2 0.3 MgCl 2 .6H 2 O 0.15 0.15 0.15 Dye (red) 0.0003 0.0003 0.0003 Perfume oil 0.8 0.8 0.8 water ad 100 ad 100 ad 100 Viscosity (m Pa s) 20 ° C, 2 rpm Brookfield viscometer 103 143 160

Als kationischer Weichmacher (A) wurde eine Verbindung der Formel

Figure imgb0002
eingesetzt, in der R5CO ein von Talgfettsäure abgeleiteter Oleoylrest war und die im Handel unter der Bezeichnung Stepantex VS 90 (STEPAN) als ca. 90 %ige Isopropanol enthaltende Paste erhältlich ist.As a cationic plasticizer (A) was a compound of the formula
Figure imgb0002
 used in which R 5 CO was an oleoyl residue derived from tallow fatty acid and which is commercially available as a paste containing approx. 90% isopropanol under the name Stepantex VS 90 (STEPAN).

Als Talgfettalkohol-sulfat (B1) wurde das Handelsprodukt Sulfopon T55 (Henkel KGaA), eine ca. 50 %ige wässrige Paste eingesetzt. Als Kokos-Talg (1:1) Fettalkoholsulfat (B2) wurde das Handelsprodukt Sulfopon KT115 (Henkel KGaA), eine ca. 40 %ige wässrige Paste verwendet.The commercial product Sulfopon T55 (Henkel KGaA), an approx. 50% aqueous paste, was used as tallow fatty alcohol sulfate (B1). The commercial product Sulfopon KT115 (Henkel KGaA), an approx. 40% aqueous paste, was used as coconut tallow (1: 1) fatty alcohol sulfate (B2).

Die %-Angaben in der Tabelle beziehen sich auf Wirkstoffgehalte.The percentages in the table relate to active substance contents.

II. Schmutzabweisende WirkungII. Dirt-repellent effect

Proben aus Polyester-Testgewebe wurden je dreimal mit einem handelsüblichen Waschmittel (PERSIL supra, ohne besonderen soil-repellent-Zusatz) bei 40°C in einer Waschmaschine gewaschen. Die Hälfte der Proben wurde mit einem erfindungsgemäßen Wäscheweichspülmittel (gemäß Beispiel 2, Dosierung 100 ml im Nachspülgang der Waschmaschine) gespült.Samples of polyester test fabric were washed three times with a commercially available detergent (PERSIL supra, without special soil repellent additive) at 40 ° C in a washing machine. Half of the samples were rinsed with a fabric softener according to the invention (according to Example 2, dosage 100 ml in the rinse cycle of the washing machine).

Die andere Hälfte der Proben wurde mit dem Vergleichsprodukt (gemäß Beispiel 1) in gleicher Weise gespült. Dann wurden die Proben der erfindungsgemäß weichgespülten Testgewebe und der Vergleichs-Testgewebe mit folgenden Testanschmutzungen beaufschlagt. 1. Motorenöl 5. Margarine 9. Make-up 2. Sonnenblumenöl 6. Hartfett (Palmin(R) 10. Wimperntusche 3. Olivenöl 7. Butter 11. Lippenstift 4. Tiroler Nußöl(R) 8. Baby-Öl The other half of the samples was rinsed in the same way with the reference product (according to Example 1). Then the samples of the test fabric softened according to the invention and the comparison test fabric were subjected to the following test soiling. 1. Motor oil 5. Margarine 9. Make-up 2. Sunflower oil 6. Hard fat (Palmin (R) 10. Mascara 3. Olive oil 7. Butter 11. Lipstick 4. Tyrolean nut oil (R) 8. Baby oil

Dann wurden alle Testgewebe 1 x wie vorher gewaschen und nur mit Wasser gespült.Then all test fabrics were washed once as before and rinsed only with water.

Der Grad der Fleckentfernung wurde visuell wie folgt benotet:

  • 0 = völlige Fleckentfernung
  • 1 = Spuren erkennbar
  • 2 = geringe Fleckreste
  • 3 = deutliche sichtbare Fleckreste
  • 4 = starke Fleckreste
  • 5 = Fleck voll erhalten.
The degree of stain removal was visually graded as follows:
  • 0 = complete stain removal
  • 1 = traces recognizable
  • 2 = minor stain residues
  • 3 = clearly visible stain residues
  • 4 = strong stain residues
  • 5 = stain fully preserved.

Die Noten für die Fleckentfernung wurden über die 11 Testanschmutzungen ermittelt (Durchschnittsnote).The marks for the stain removal were determined on the 11 test stains (average grade).

Es wurden folgende Durchschnittsnoten für die Fleckentfernung erhalten: Weichspüler gemäß Beispiel 2 (Erfindung) : 1,6 Weichspüler gemäß Beispiel 1 (Vergleich) : 2,1 The following average marks for spot removal were obtained: Fabric softener according to Example 2 (invention): 1.6 Fabric softener according to example 1 (comparison): 2.1

In einer weiteren Versuchsreihe wurde das Polyester-Testgewebe wie vorher gewaschen, gespült und angeschmutzt. Es wurde aber ein Waschmittel mit einem "soil-repellent-Wirkstoff (PERSIL supra mit 1 Gew.-% Repel-0-Tex(R)) eingesetzt. Der soil-repellent-Wirkstoff Repel-0-Tex(R) ist ein Polyester aus Dimethylterephthalat, Ethylenglycol und Polyethylenglycol, erhältlich von Fa. Rhone-Poulenc.In a further test series, the polyester test fabric was washed, rinsed and soiled as before. However, a detergent with a "soil repellent active ingredient (PERSIL supra with 1% by weight Repel-0-Tex (R) ) was used. The soil repellent active ingredient Repel-0-Tex (R) is a polyester from dimethyl terephthalate, ethylene glycol and polyethylene glycol, available from Rhone-Poulenc.

Auch bei dieser Versuchsreihe konnte eine zusätzliche schmutzabweisende Wirkung durch die erfindungsgemäße Textilweichmacher-Zusammensetzung festgestellt werden: Weichspüler gemäß Beispiel 2 (Erfindung) : 0,52 Weichspüler gemäß Beispiel 1 (Vergleich) : 1,15. In this series of tests, too, an additional dirt-repellent effect could be determined by the textile plasticizer composition according to the invention: Fabric softener according to Example 2 (invention): 0.52 Fabric softener according to example 1 (comparison): 1.15.

Claims (4)

  1. Aqueous fabric softener compositions containing
    (A) 1 to 40% by weight of a dispersed cationic softener selected from quaternary ammonium compounds containing at least two alkyl, alkenyl, acyloxyalkyl or acylamidoalkyl groups containing 12 to 22 carbon atoms in the alkyl, alkenyl or acyl group,
    characterized in that, to increase viscosity,
    (B) 0.1 to 5% by weight of an alkyl or alkenyl sulfate salt or an alkyl or alkenyl ether sulfate salt containing 12 to 22 carbon atoms in the alkyl or alkenyl group
    is present in a ratio by weight of cationic softener (A) to alkyl or alkenyl sulfate salt or alkyl or alkenyl ether sulfate salt (B) of greater than 5:1 (A:B).
  2. Aqueous fabric softener compositions as claimed in claim 1, characterized in that they additionally contain
    (C) 0.1 to 1% by weight of an aliphatic diol or polyol containing 2 to 6 carbon atoms and 2 to 6 hydroxyl groups or a water-soluble polyalkylene glycol.
  3. Aqueous fabric softener compositions as claimed in claim 1 or 2, characterized in that the quaternary ammonium compounds correspond to formula I:
    Figure imgb0004
     in which on average 2 to 3 of the groups R1 to R4 correspond to the formula R5CO(OCnH2n)x-, in which R5CO may be an acyl group containing 12 to 22 carbon atoms, n = 2 or 3 and x = 1 to 10 and, in addition, may be an alkyl group containing 1 to 4 carbon atoms and/or a hydroxy(alkoxy)alkyl group corresponding to the formula H-(OCnH2n)x-, in which n = 2 or 3 and x = 1 to 10, and A(-) is a chloride or CH3OSO3 (-) anion.
  4. A process for increasing the viscosity of an aqueous fabric softener composition containing (A) 1 to 40% by weight of a quaternary ammonium compound containing at least two alkyl, alkenyl, acyloxyalkyl or acylamidoalkyl groups bearing 12 to 22 carbon atoms in the alkyl, alkenyl or acyl group in dispersed form, characterized in that (B) 0.1 to 5.0% by weight of an alkyl or alkenyl sulfate salt containing 12 to 22 carbon atoms in the alkyl or alkenyl group and optionally (C) a diol or polyol containing 2 to 6 carbon atoms and 2 to 6 hydroxyl groups or a water-soluble polyalkylene glycol in a quantity of 0.1 to 1% by weight, based on the composition as a whole, is converted together with component (A) into a homogeneous melt which is then dispersed in water by application of shear forces, the cationic softener (A) and the alkyl or alkenyl sulfate salt or alkyl or alkenyl ether sulfate salt (B) being used in a ratio by weight of greater than 5:1 (A:B).
EP94909087A 1993-03-08 1994-02-28 Aqueous textile softener compositions Expired - Lifetime EP0688356B1 (en)

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DE4307186 1993-03-08
DE4307186A DE4307186A1 (en) 1993-03-08 1993-03-08 Aqueous fabric softener composition
PCT/EP1994/000580 WO1994020596A1 (en) 1993-03-08 1994-02-28 Aqueous textile softener compositions

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DE4420514A1 (en) * 1994-06-13 1995-12-14 Henkel Kgaa Aqueous dispersions of anionic and cationic surfactants
WO1997003170A1 (en) * 1995-07-11 1997-01-30 The Procter & Gamble Company Concentrated, water dispersible, stable, fabric softening compositions
BR9609800A (en) * 1995-07-11 1999-07-06 Procter & Gamble Preferably concentrated stable fabric softener composition preferably clear
EP1352948A1 (en) * 1995-07-11 2003-10-15 The Procter & Gamble Company Concentrated, stable, fabric softening composition
BR9710409A (en) * 1996-03-22 1999-08-17 Procter & Gamble Fabric softener composition / compound
DE19629666A1 (en) 1996-07-23 1998-01-29 Henkel Kgaa Process for the hydrophilic finishing of fibers or nonwovens
CA2264087A1 (en) * 1996-08-30 1998-03-05 Hugo Jean-Marie Demeyere Concentrated premix with reduced flammability for forming fabric softening composition
GB9810656D0 (en) * 1998-05-18 1998-07-15 Unilever Plc Stable ammonium compositions
GB9810655D0 (en) * 1998-05-18 1998-07-15 Unilever Plc Stable ammonium compositions

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JPS598392B2 (en) * 1979-06-29 1984-02-24 花王株式会社 cleaning composition
ATE10646T1 (en) * 1979-09-29 1984-12-15 The Procter & Gamble Company DETERGENT COMPOSITIONS.
AU619502B2 (en) * 1987-11-05 1992-01-30 Colgate-Palmolive Company, The Liquid softergent formulations having improved stability and softening properties
US4857213A (en) * 1988-02-08 1989-08-15 The Procter & Gamble Company Liquid detergent containing conditioning agent and high levels of alkyl sulfate/alkyl ethoxylated sulfate

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DE4307186A1 (en) 1994-09-15

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