EP0674701A1 - Aqueous textile softener dispersions. - Google Patents

Aqueous textile softener dispersions.

Info

Publication number
EP0674701A1
EP0674701A1 EP94902704A EP94902704A EP0674701A1 EP 0674701 A1 EP0674701 A1 EP 0674701A1 EP 94902704 A EP94902704 A EP 94902704A EP 94902704 A EP94902704 A EP 94902704A EP 0674701 A1 EP0674701 A1 EP 0674701A1
Authority
EP
European Patent Office
Prior art keywords
fatty acid
mole
weight
atoms
ethylene oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP94902704A
Other languages
German (de)
French (fr)
Other versions
EP0674701B1 (en
Inventor
Rolf Puchta
Thomas Engels
Theodor Voelkel
Fred Schambil
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0674701A1 publication Critical patent/EP0674701A1/en
Application granted granted Critical
Publication of EP0674701B1 publication Critical patent/EP0674701B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/001Softening compositions
    • C11D3/0015Softening compositions liquid
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/62Quaternary ammonium compounds

Definitions

  • the present invention relates to aqueous fabric softener dispersions which, despite a particularly high content of fabric softening active ingredients, have a low viscosity which does not increase, or increases only insignificantly, even after prolonged storage.
  • Aqueous textile plasticizer dispersions tend to thicken when stored for a long time, especially at temperatures below or above room temperature. This behavior is particularly pronounced in textile softener dispersions with a high active ingredient content.
  • the commercial textile softener concentrates contain about 15 to 25% by weight of active ingredient.
  • To produce storage-stable dispersions a very low starting viscosity is generally set using different electrolytes. With an even higher active ingredient content, however, a noticeable increase in viscosity is observed even in the presence of electrolyte during storage, which either occurs immediately after production or during storage.
  • the object of the present invention was therefore to provide an aqueous textile plasticizer dispersion with a high active ingredient content, the viscosity of which is low and which does not increase significantly even during storage and which can easily be thinned further with cold water.
  • the proportion of nonionic, non-textile softening dispersant should be as low as possible.
  • the textile-softening cationic active ingredient should moreover be present in an amount of more than 15% by weight, it should impart good softness to the treated textiles, not impair the ability to reuse them and be easily and rapidly biodegraded in the waste water.
  • the present invention accordingly relates to an aqueous textile softener dispersion containing quaternary ammonium compounds and nonionic dispersants which soften the textile, characterized in that the dispersion
  • b) contains 0.001-0.5% by weight of nonionic dispersants which are selected from
  • the quaternary ammonium compounds mentioned are readily and rapidly biodegradable because of the ester or acid groups contained in the long residues and have therefore recently gained interest.
  • the compounds mentioned include, for example, the compounds known from DE-A-16 19058, DE-A-19 35499 or US Pat. No. 3,915,867 with 1, 2 or 3 fatty acyloxyalkyl radicals on the nitrogen atom. These compounds can be easily prepared, for example, by esterification of alkanolamines with fatty acid or by transesterification of fatty acid esters with alkanolamine and subsequent quaternization. Corresponding processes for the production on an industrial scale have also been known for a long time; Compounds produced by these processes are commercially available compounds.
  • Compounds which are of particular interest with regard to the stability of the viscosity of the aqueous dispersions prepared therewith are those whose fatty acyl groups are wholly or partly unsaturated.
  • Derive th fatty acids which are at least 30, preferably at least 55% in cis form.
  • Suitable quaternary ammonium compounds are also known from US 5,066,414, EP 0293 953 A2, EP 0 309052 A2 and EP 0345842 A2.
  • Suitable quaternary ammonium compounds also include those derived from dimethylaminopropanediol-1,2 with two ester groups. They are described, for example, in DE-A-27 28841. A manufacturing process leading to such products with a low pour point is the subject of EP-A-420465.
  • the quaternary ammonium compounds mentioned can surprisingly also be processed into viscosity-stable aqueous dispersions if the content of quaternary ammonium compounds is particularly high, ie for example 15 to 60% by weight, based on the aqueous dispersion, preferably 20 to 40% by weight .-%. This has been achieved by the selection according to the invention of nonionic dispersants * even at contents of less than 0.5% by weight of the dispersants.
  • Hydroxy fatty acids are understood in particular to mean ricinole fatty acid and 9-hydroxystearic acid. Also suitable as hydroxy fatty acids in the sense of this invention are hydroxyl-containing fatty acids which are obtained by epoxidation of palmitoleic acid, oleic acid or erucic acid and subsequent epoxy ring opening with protic reagents such as e.g. Water, alcohols or carboxylic acids are available.
  • the adducts of 3-100 moles of ethylene oxide with 1 / mole of a polyol fatty alcohol ester include, for example, ethoxylates of fatty acids. remono- and -diglycerides, of sorbitan mono-, di- and sesquiesters of Ci2-C22 fatty acids, on mono- and di-fatty acid esters of di- and triglycerol as well as on triglycerides such as castor oil.
  • ethylene oxide addition products on ring opening products of epoxidized triglycerides such as those e.g. are obtained by epoxidation of soybean oil, hydrogenation or reaction (epoxy ring opening) with protic compounds such as e.g. with H2O, carboxylic acids or alcohols with 1 - 10 C atoms and subsequent addition of ethylene oxide.
  • protic compounds such as e.g. with H2O, carboxylic acids or alcohols with 1 - 10 C atoms and subsequent addition of ethylene oxide.
  • Such products are e.g. known from DE 39 23 394 AI.
  • ethylene oxide adducts of fatty acid (Ci2-C22) - me methyl ester are preferred.
  • Ethylene oxide addition products which additionally contain 1-10 oxypropyl groups and which are obtained by addition of propylene oxide and ethylene oxide, simultaneously or in succession, are also suitable.
  • the selected dispersants to be used according to the invention are already in an added amount of 0.001 to 0.1% by weight in preferred textile plasticizer dispersions capable of markedly reducing the viscosity and preventing subsequent thickening during storage to such an extent that the flow and Pourability and good further dilutability with water are maintained.
  • RCO is an oleoyl residue derived from tallow fatty acid
  • only 0.01-0.1% by weight of the dispersant is required to stabilize the viscosity of a dispersion containing 20-40% by weight of the quaternary ammonium compound.
  • aqueous textile softener dispersions do not have a low initial viscosity, for example through the use of quaternary ammonium compounds of a suitable structure, it is advisable to set a low viscosity by adding an electrolyte.
  • Suitable electrolytes are, for example, sodium chloride, sodium acetate, magnesium sulfate or calcium chloride and in particular magnesium chloride. Small amounts are also sufficient to set a low initial viscosity by adding an electrolyte.
  • the electrolyte is present in the dispersion in concentrations of 0.01 to 3% by weight, based on the finished dispersion.
  • the dispersions mentioned are distinguished by the fact that their initial viscosity does not increase or only increases slightly after production, even after prolonged storage in a wide temperature range, that they have a high active ingredient content, and that they can easily be diluted with cold water, which is particularly noticeable when washing it in automatic washing machines, and that the textiles treated with it do not only Chen grip but also have good rewettability, which is particularly important for textiles that are worn on the skin.
  • aqueous textile plasticizer dispersions the 34% by weight of a compound of the formula I (Stepante ⁇ (R) - VS90 as a textile-softening, quaternary ammonium compound), an esterification product of triethanolamine quaternized with dimethyl sulfate with two Moles of tallow fatty acid), have high viscosity stability when very small amounts of non-ionic dispersants are added.
  • the comparative batches without dispersant or with fatty alcohol ethoxylates with only 5 or 7 moles of ethylene oxide (example 9V, 10V) already show an unacceptable increase in viscosity after 1 week of storage.
  • the viscosity (Pas) was measured in all cases using a Brookfield rotary viscometer with spindle 2 and 20 revolutions per minute at 20 ° C.
  • the textile softener dispersions tested have the following composition:
  • Viscosity (20 ° C)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Colloid Chemistry (AREA)

Abstract

In order to produce highly concentrated textile softener dispersions based on quaternary ammonium compounds with ester groups in their molecules and having a substantially constant viscosity over a large temperature range, small amounts of selected non-ionic dispersing agents are added thereto.

Description

"Wäßrige Textilweichmacher-DispersJonen" "Aqueous textile softener dispersions"
Die vorliegende Erfindung betrifft wäßrige Textilweichmacher-Disper- sionen, die trotz eines besonders hohen Gehaltes an textilweichma- chenden Wirkstoffen eine geringe Viskosität aufweisen, die sich auch nach längerer Lagerzeit nicht oder nur unwesentlich erhöht.The present invention relates to aqueous fabric softener dispersions which, despite a particularly high content of fabric softening active ingredients, have a low viscosity which does not increase, or increases only insignificantly, even after prolonged storage.
Wäßrige Textilweichmacher-Dispersionen neigen bei längerer Lagerung, insbesondere bei Temperaturen unterhalb oder oberhalb der Raumtempe¬ ratur, zur Verdickung. Besonders ausgeprägt ist dieses Verhalten bei Textilweichmacher-Dispersionen mit hohem Wirkstoffgehalt. Die markt¬ üblichen Textilweichmacher-Konzentrate enthalten ca. 15 bis 25 Gew.-% Wirkstoff. Zur Herstellung lagerstabiler Dispersionen wird in der Regel mit Hilfe unterschiedlicher Elektrolyte eine sehr niedrige Ausgangsviskosität eingestellt. Bei einem noch höheren Wirkstoffge¬ halt beobachtet man aber auch in Gegenwart von Elektrolyt bei der Lagerung eine nennenswerte Viskositätserhöhung, die entweder unmit- telbar nach der Herstellung oder aber während der Lagerung auftritt.Aqueous textile plasticizer dispersions tend to thicken when stored for a long time, especially at temperatures below or above room temperature. This behavior is particularly pronounced in textile softener dispersions with a high active ingredient content. The commercial textile softener concentrates contain about 15 to 25% by weight of active ingredient. To produce storage-stable dispersions, a very low starting viscosity is generally set using different electrolytes. With an even higher active ingredient content, however, a noticeable increase in viscosity is observed even in the presence of electrolyte during storage, which either occurs immediately after production or during storage.
Der Zusatz von ethoxylierten Fettalkoholen zur Verbesserung der Ver- dünnbarkeit bzw. Auflösbarkeit konzentrierter Dispersionen in der Spülflotte ist bereits in mehreren Druckschriften vorgeschlagen wor¬ den, z.B. in EP 0 040 562 Bl, EP 0 280 550 Bl, EP 0 503 221 AI, EP 0 507478 AI oder EP 0 523 922 A2. Die dort vorgeschlagenen Eth- oxylate müssen jedoch in Konzentrationen von mehr als 1 Gew.- ein¬ gesetzt werden, um in konzentrierten Dispersionen mit mehr als 15 Gew.-% des kationischen Textilweichmachers eine ausreichende Visko¬ sitätsstabilisierung -und Dispergierbarkeit zu gewährleisten. Aufgabe der vorliegenden Erfindung war daher die Bereitstellung einer wäßrigen Textilweichmacher-Dispersion mit hohem Wirkstoffge¬ halt, deren Viskosität niedrig ist und die auch bei Lagerung nicht wesentlich ansteigt und die sich leicht mit kaltem Wasser weiterver¬ dünnen läßt. Dabei soll der Anteil an nichtionischem, nicht textil- weichmachendem Dispergiermittel möglichst niedrig sein. Der textil- weichmachende kationische Wirkstoff soll darüber hinaus in einer Menge von mehr als 15 Gew.-% vorliegen, er soll den behandelten Tex¬ tilien eine gute Weichheit verleihen, das Wiederbenutzungsvermögen nicht beeinträchtigen und im Abwasser leicht und rasch biologisch abgebaut werden.The addition of ethoxylated fatty alcohols to improve the dilutability or dissolvability of concentrated dispersions in the washing liquor has already been proposed in several publications, for example in EP 0 040 562 B1, EP 0 280 550 B1, EP 0 503 221 A1, EP 0 507478 AI or EP 0 523 922 A2. However, the ethoxylates proposed there must be used in concentrations of more than 1% by weight in order to ensure adequate viscosity stabilization and dispersibility in concentrated dispersions with more than 15% by weight of the cationic textile softener. The object of the present invention was therefore to provide an aqueous textile plasticizer dispersion with a high active ingredient content, the viscosity of which is low and which does not increase significantly even during storage and which can easily be thinned further with cold water. The proportion of nonionic, non-textile softening dispersant should be as low as possible. The textile-softening cationic active ingredient should moreover be present in an amount of more than 15% by weight, it should impart good softness to the treated textiles, not impair the ability to reuse them and be easily and rapidly biodegraded in the waste water.
Es wurden nun spezielle nichtionische Dispergatoren gefunden, die bereits in Mengen von weniger als 0,5 Gew.-% solchen Dispersionen eine gute Viskositätskonstanz und ein gutes Kaltwasser-Dispergier- vermögen verleihen.Special nonionic dispersants have now been found which, even in amounts of less than 0.5% by weight, give such dispersions good viscosity constancy and good cold water dispersing capacity.
Gegenstand der vorliegenden Erfindung ist dementsprechend eine wä߬ rige Textilweicher-Dispersion mit einem Gehalt an textilweichmachen- den quartären Ammoniumverbindungen und nichtionischen Dispergatoren, dadurch gekennzeichnet, daß die DispersionThe present invention accordingly relates to an aqueous textile softener dispersion containing quaternary ammonium compounds and nonionic dispersants which soften the textile, characterized in that the dispersion
a) 15 - 60 Gew.-% quartäre Ammoniumverbindungen mit zwei oder drei über Ester- oder Amidbindungen damit verknüpften linearen Alkyl- oder Acylgruppen mit jeweils 12 - 22 C-Atomena) 15-60% by weight of quaternary ammonium compounds with two or three linear alkyl or acyl groups linked to them via ester or amide bonds, each having 12-22 carbon atoms
b) 0,001 - 0,5 Gew.-% nichtionische Dispergatoren enthält, die aus¬ gewählt sind ausb) contains 0.001-0.5% by weight of nonionic dispersants which are selected from
Anlagerungsprodukten von 40 - 200 Mol Ethylenoxid an 1 Mol linearen Fettalkohol mit 12 - 22 C-Atomen Anlagerungsprodukten von 10 - 150 Mol Ethylenoxid an 1 Mol einer linearen Fettsäure oder Hydroxyfettsäure mit 12 - 22 C-Atomen, an ein Mol eines linearen Fettalkylamins mit 12 - 22 C-Atomen oder an ein Mol eines Ci-C-j-Niedrigalkylesters einer Fettsäure oder Hydroxyfettsäure mit 12 - 22 C-AtomenAddition products of 40-200 moles of ethylene oxide with 1 mole of linear fatty alcohol with 12-22 carbon atoms Addition products of 10-150 moles of ethylene oxide with 1 mole of a linear fatty acid or hydroxy fatty acid with 12-22 C atoms, with one mole of a linear fatty alkylamine with 12-22 C atoms or with one mole of a Ci-Cj-lower alkyl ester of a fatty acid or hydroxy fatty acid with 12 - 22 carbon atoms
Anlagerungsprodukten von 3 - 100 Mol Ethylenoxid an 1/m Mol eines Polyol-fettsäureesters aus m Mol einer Fettsäure oder Hydroxyfettsäure mit 12 - 22 C-Atomen und einem Mol eines Polyols mit 1 - 6 C-Atomen und 2 - 6 Hydroxylgruppen, wobei m einen Wert von 1 bis 6 annehmen kann, oderAddition products of 3-100 moles of ethylene oxide with 1 / m mole of a polyol fatty acid ester from m moles of a fatty acid or hydroxy fatty acid with 12-22 C atoms and one mole of a polyol with 1-6 C atoms and 2-6 hydroxyl groups, where m can have a value from 1 to 6, or
Gemischen aus solchen Ethylenoxid-Anlagerungsprodukten.Mixtures of such ethylene oxide addition products.
Die genannten quartären Ammoniumverbindungen sind wegen der darin in den langen Resten enthaltenen Ester- oder A idgruppen biologisch leicht und schnell abbaubar und haben deswegen in letzter Zeit an Interesse gewonnen. Zu den genannten Verbindungen zählen beispiels¬ weise die aus der DE-A-16 19058, der DE-A-19 35499 oder der US 3^915,867 bekannten Verbindungen mit 1, 2 oder 3 Fettacyloxyal- kylresten am Stickstoffatom. Man kann diese Verbindungen beispiels¬ weise leicht durch Veresterung von Alkanolaminen mit Fettsäure oder durch Umesterung von Fettsäureestern mit Alkanolamin und anschlie¬ ßender Quaternierung herstellen. Entsprechende Verfahren zur Her¬ stellung in großtechnischem Maßstab sind ebenfalls seit langem be¬ kannt; nach diesen Verfahren hergestellte Verbindungen sind handels¬ übliche Verbindungen.The quaternary ammonium compounds mentioned are readily and rapidly biodegradable because of the ester or acid groups contained in the long residues and have therefore recently gained interest. The compounds mentioned include, for example, the compounds known from DE-A-16 19058, DE-A-19 35499 or US Pat. No. 3,915,867 with 1, 2 or 3 fatty acyloxyalkyl radicals on the nitrogen atom. These compounds can be easily prepared, for example, by esterification of alkanolamines with fatty acid or by transesterification of fatty acid esters with alkanolamine and subsequent quaternization. Corresponding processes for the production on an industrial scale have also been known for a long time; Compounds produced by these processes are commercially available compounds.
Hinsichtlich der Stabilität der Viskosität der damit hergestellten wäßrigen Dispersionen besonders interessante Verbindungen sind sol¬ che, deren Fettacylgruppen sich ganz oder teilweise von ungesättig- ten Fettsäuren ableiten, die zu wenigstens 30, vorzugsweise zu we¬ nigstens 55 % in cis-Form vorliegen.Compounds which are of particular interest with regard to the stability of the viscosity of the aqueous dispersions prepared therewith are those whose fatty acyl groups are wholly or partly unsaturated. Derive th fatty acids, which are at least 30, preferably at least 55% in cis form.
Geeignete quartäre Ammoniumverbindungen sind auch aus US 5,066,414, EP 0293 953 A2, EP 0 309052 A2 und EP 0345842 A2 bekannt.Suitable quaternary ammonium compounds are also known from US 5,066,414, EP 0293 953 A2, EP 0 309052 A2 and EP 0345842 A2.
Zu den geeigneten quartären Ammoniumverbindungen zählen auch die von Dimethylaminopropandiol-1,2 abgeleiteten Verbindungen mit zwei Estergruppen. Sie werden beispielsweise in der DE-A-27 28841 be¬ schrieben. Ein Herstellungsverfahren, das zu derartigen Produkten mit einem niedrigen Fließpunkt führt, ist Gegenstand der EP-A-420465.Suitable quaternary ammonium compounds also include those derived from dimethylaminopropanediol-1,2 with two ester groups. They are described, for example, in DE-A-27 28841. A manufacturing process leading to such products with a low pour point is the subject of EP-A-420465.
Die genannten quartären Ammoniumverbindungen lassen sich überra¬ schenderweise auch dann zu viskositätsstabilen wäßrigen Dispersionen verarbeiten, wenn der Gehalt an quartären Ammoniumverbindungen be¬ sonders hoch ist, d.h. beispielsweise 15 bis 60 Gew.-%, bezogen auf die wäßrige Dispersion, vorzugsweise 20 bis 40 Gew.-% beträgt. Dies ist durch die erfindungsgemäße Auswahl von nichtionischen Disperga¬ toren* bereits bei Gehalten von weniger als 0,5 Gew.-% der Disperga¬ toren erreicht worden.The quaternary ammonium compounds mentioned can surprisingly also be processed into viscosity-stable aqueous dispersions if the content of quaternary ammonium compounds is particularly high, ie for example 15 to 60% by weight, based on the aqueous dispersion, preferably 20 to 40% by weight .-%. This has been achieved by the selection according to the invention of nonionic dispersants * even at contents of less than 0.5% by weight of the dispersants.
Unter Hydroxyfettsäuren werden insbesondere die Ricinolfettsäure und die 9-Hydroxystearinsäure verstanden. Als Hydroxyfettsäuren im Sinne dieser Erfindung eignen sich aber auch Hydroxylgruppen enthaltende Fettsäuren, die durch Epoxidation von Palmitoleinsäure, Olsäure oder Erucasäure und anschließende Epoxid-Ringöffnung mit protischen Reagenzien wie z.B. Wasser, Alkoholen oder Carbonsäuren erhältlich sind.Hydroxy fatty acids are understood in particular to mean ricinole fatty acid and 9-hydroxystearic acid. Also suitable as hydroxy fatty acids in the sense of this invention are hydroxyl-containing fatty acids which are obtained by epoxidation of palmitoleic acid, oleic acid or erucic acid and subsequent epoxy ring opening with protic reagents such as e.g. Water, alcohols or carboxylic acids are available.
Die Anlagerungsprodukte von 3 - 100 Mol Ethylenoxid an 1/m Mol eines Polyolfettalkoholesters umfassen z.B. Ethoxylate von Fettsäu- remono- und -diglyceriden, von Sorbitanmono-, -di- und -sesquiestern von Ci2-C22-Fettsäuren, an Mono- und Di-fettsäureester des Di- und Triglycerins sowie auch an Triglyceride wie z.B. an Ricinusöl.The adducts of 3-100 moles of ethylene oxide with 1 / mole of a polyol fatty alcohol ester include, for example, ethoxylates of fatty acids. remono- and -diglycerides, of sorbitan mono-, di- and sesquiesters of Ci2-C22 fatty acids, on mono- and di-fatty acid esters of di- and triglycerol as well as on triglycerides such as castor oil.
Besonders gut geeignet sind auch die Ethylenoxid-Anlagerungsprodukte an Ringöffnungsprodukte epoxidierter Triglyceride, wie sie z.B. er¬ halten werden durch Epoxidation von Sojaöl, Hydrierung oder Um¬ setzung (Epoxid-Ringöffnung) mit protischen Verbindungen wie z.B. mit H2O, Carbonsäuren oder Alkoholen mit 1 - 10 C-Atomen und an¬ schließende Ethylenoxid-Anlagerung. Solche Produkte sind z.B. aus DE 39 23 394 AI bekannt.The ethylene oxide addition products on ring opening products of epoxidized triglycerides, such as those e.g. are obtained by epoxidation of soybean oil, hydrogenation or reaction (epoxy ring opening) with protic compounds such as e.g. with H2O, carboxylic acids or alcohols with 1 - 10 C atoms and subsequent addition of ethylene oxide. Such products are e.g. known from DE 39 23 394 AI.
Gut geeignet sind auch die Ethylenoxid-Anlagerungsprodukte an Fett- säure(Ci2-C22)-methylester, von diesen sind insbesondere solche mit 10 - 50 Mol Ethylenoxid bevorzugt. Weiterhin eignen sich auch Ethy- lenoxid-Anlagerungsprodukte, die zusätzlich 1 - 10 Oxypropylgruppen enthalten und die durch Anlagerung von Propylenoxid und Ethylenoxid, gleichzeitig oder nacheinander, erhalten werden. Die ausgewählten, erfindungsgemäß zu verwendenden Dispergatoren sind in bevorzugten Textilweichmacher-Dispersionen bereits in einer Zusatzmenge von 0,001 bis 0,1 Gew.-% in der Lage, die Viskosität merklich zu senken und ein Nachdicken bei Lagerung so weit verhindern, daß die Fließ- und Gießfähigkeit und eine gute Weiterverdünnbarkeit mit Wasser er¬ halten bleiben.Also highly suitable are the ethylene oxide adducts of fatty acid (Ci2-C22) - me methyl ester, of these, particularly those having 10 - 50 mol ethylene oxide are preferred. Ethylene oxide addition products which additionally contain 1-10 oxypropyl groups and which are obtained by addition of propylene oxide and ethylene oxide, simultaneously or in succession, are also suitable. The selected dispersants to be used according to the invention are already in an added amount of 0.001 to 0.1% by weight in preferred textile plasticizer dispersions capable of markedly reducing the viscosity and preventing subsequent thickening during storage to such an extent that the flow and Pourability and good further dilutability with water are maintained.
Überraschend wurde festgestellt, daß bei Verwendung einer textil- weich achenden quartären Ammoniumverbindung des Typs der Formel I (Handelsname: Stepanteχ(R)vS90) CH - CH2 - OHIt was surprisingly found that when a quaternary ammonium compound of the type of the formula I (trade name: Stepanteχ ( R ) vS90) with a soft-soft texture is used CH - CH 2 - OH
RCOO - CH2 - CH - N(+) - CH2 - CH2 - OCOR CH30S03(-) (I),RCOO - CH 2 - CH - N ( + ) - CH 2 - CH 2 - OCOR CH 3 0S0 3 (-) (I),
II.
CH3 CH 3
in der RCO ein von Taigfettsäure abgeleiteter Oleoylrest ist, zur Viskositätsstabilisierung einer Dispersion mit einem Gehalt von 20 - 40 Gew.-% der quartären Ammoniumverbindung nur 0,01 - 0,1 Gew.-% des Dispergators erforderlich sind.in which RCO is an oleoyl residue derived from tallow fatty acid, only 0.01-0.1% by weight of the dispersant is required to stabilize the viscosity of a dispersion containing 20-40% by weight of the quaternary ammonium compound.
Falls die wäßrigen Textilweichmacher-Dispersionen nicht schon ohne¬ hin eine geringe Ausgangsviskosität haben, beispielsweise durch die Verwendung von quartären Ammoniumverbindungen geeigneter Struktur, ist es zweckmäßig, eine niedrige Viskosität durch den Zusatz eines Elektrolyten einzustellen. Geeignete Elektrolyten sind beispiels¬ weise Natriumchlorid, Natriumacetat, Magnesiumsulfat oder Calciu - chlorid und insbesondere Magnesiumchlorid. Zur Einstellung einer niedrigen Ausgangsviskosität durch Zusatz eines Elektrolyts reichen ebenfalls geringe Mengen aus. Der Elektrolyt liegt beispielsweise in Konzentrationen von 0,01 bis 3 Gew.-%, bezogen auf die fertige Dispersion, in der Dispersion vor.If the aqueous textile softener dispersions do not have a low initial viscosity, for example through the use of quaternary ammonium compounds of a suitable structure, it is advisable to set a low viscosity by adding an electrolyte. Suitable electrolytes are, for example, sodium chloride, sodium acetate, magnesium sulfate or calcium chloride and in particular magnesium chloride. Small amounts are also sufficient to set a low initial viscosity by adding an electrolyte. For example, the electrolyte is present in the dispersion in concentrations of 0.01 to 3% by weight, based on the finished dispersion.
Die genannten Dispersionen zeichnen sich dadurch aus, daß deren Aus¬ gangsviskosität nach der Herstellung- auch bei längerer Lagerung in einem breiten Temperaturbereich nicht oder nur geringfügig ansteigt, daß sie einen hohen Wirkstoffgehalt aufweisen, daß sie auch mit kal¬ tem Wasser leicht verdünnbar sind, was sich besonders beim Einspülen in automatischen Waschmaschinen positiv bemerkbar macht, und daß die damit behandelten Textilien nach dem Trocknen nicht nur einen wei- chen Griff sondern auch eine gute Wiederbenetzbarkeit aufweisen, was insbesondere für Textilien, die auf der Haut getragen werden, von besonderer Bedeutung ist. The dispersions mentioned are distinguished by the fact that their initial viscosity does not increase or only increases slightly after production, even after prolonged storage in a wide temperature range, that they have a high active ingredient content, and that they can easily be diluted with cold water, which is particularly noticeable when washing it in automatic washing machines, and that the textiles treated with it do not only Chen grip but also have good rewettability, which is particularly important for textiles that are worn on the skin.
B e i s p i e l eB e i s p i e l e
In den folgenden Beispielen wird gezeigt, daß wäßrige Textilweich¬ macher-Dispersionen, die als textilweichmachende, quartäre Ammonium¬ verbindung 34 Gew.-% einer Verbindung der Formel I (Stepanteχ(R)- VS90, ein mit Dimethylsulfat quaterniertes Veresterungsprodukt von Triethanolamin mit zwei Mol Taigfettsäure) enthalten, eine hohe Vis¬ kositätsstabilität bei Zusatz von sehr niedrigen Mengen an nicht¬ ionischen Dispergatoren aufweisen. Demgegenüber zeigen die Ver¬ gleichs-Ansätze ohne Dispergator oder mit Fettalkohol-Ethoxylaten mit nur 5 oder 7 Mol Ethylenoxid (Beispiel 9V, 10V) schon nach 1-wöchiger Lagerung einen nicht akzeptablen Viskositätsanstieg.The following examples show that aqueous textile plasticizer dispersions, the 34% by weight of a compound of the formula I (Stepanteχ (R) - VS90 as a textile-softening, quaternary ammonium compound), an esterification product of triethanolamine quaternized with dimethyl sulfate with two Moles of tallow fatty acid), have high viscosity stability when very small amounts of non-ionic dispersants are added. In contrast, the comparative batches without dispersant or with fatty alcohol ethoxylates with only 5 or 7 moles of ethylene oxide (example 9V, 10V) already show an unacceptable increase in viscosity after 1 week of storage.
Die Viskosität ( Pas) wurde in allen Fällen mit einem Brookfield- Rotationsviskosi eter mit Spindel 2 und 20 Umdrehungen pro Minute bei 20 °C gemessen.The viscosity (Pas) was measured in all cases using a Brookfield rotary viscometer with spindle 2 and 20 revolutions per minute at 20 ° C.
Die geprüften Textilweichmacher-Dispersionen weisen folgende Zu¬ sammensetzung auf:The textile softener dispersions tested have the following composition:
Quartäre Ammoniumverbindung (Formel I) 34 Gew.-%Quaternary ammonium compound (formula I) 34% by weight
Dispergator X Gew.-%Dispersant X% by weight
MgCl2 0,8 Gew.-%MgCl2 0.8% by weight
Wasser ad 100,0 Gew.-% Water ad 100.0% by weight
Umsetzungsprodukt von epoxidierte Sojaöl mit Cs/io-Fettsäure (TMOI pro Mol Epoxid-Sauerstoff) und mit 9 Mol E0 (pro Mol Soja¬ öl)Reaction product of epoxidized soybean oil with Cs / io fatty acid (TMOI per mole of epoxy oxygen) and with 9 moles of E0 (per mole of soybean oil)
Die Viskosität (mPas) wurde mit einem Brookfield-Rotationsviskosime- ter (Spindel 2, 20 Umdrehungen pro Minute) bei 20°C frisch, d.h. unmittelbar nach der Herstellung und nach 1 Woche Lagerung gemessen. Viskosität (20°C)The viscosity (mPas) was measured using a Brookfield rotary viscometer (spindle 2, 20 revolutions per minute) fresh at 20 ° C., ie immediately after production and after 1 week of storage. Viscosity (20 ° C)

Claims

Patentansprüche Claims
1. Wäßrige Textilweichmacher-Dispersion mit einem Gehalt an textil- weichmachenden quartären Ammoniumverbindungen und nichtionischen Dispergatoren, dadurch gekennzeichnet, daß die Dispersion1. Aqueous fabric softener dispersion containing textile-softening quaternary ammonium compounds and nonionic dispersants, characterized in that the dispersion
a) 15 - 60 Gew.-% quartäre Ammoniumverbindungen mit zwei oder drei über Ester- oder Amidbindungen damit verknüpften li¬ nearen Alkyl- oder Acylgruppen mit jeweils 12 - 22 C-Atomen unda) 15-60% by weight of quaternary ammonium compounds with two or three linear alkyl or acyl groups linked to them via ester or amide bonds, each having 12-22 carbon atoms and
b) 0,001 - 0,5 Gew.-% nichtionische Dispergatoren enthält, die ausgewählt sind ausb) contains 0.001-0.5% by weight of nonionic dispersants selected from
Anlagerungsprodukten von 40 - 200 Mol Ethylenoxid an 1 Mol linearen Fettalkohol mit 12 - 22 C-AtomenAddition products of 40-200 moles of ethylene oxide with 1 mole of linear fatty alcohol with 12-22 carbon atoms
Anlagerungsprodukten von 10 - 150 Mol Ethylenoxid an 1 Mol einer linearen Fettsäure oder Hydroxyfettsäure mit 12 - 22 C-Atomen, an ein Mol eines linearen Fettalkyl- amins mit 12 - 22 C-Atomen oder an ein Mol eines C1-C4- Niedrigalkylesters einer Fettsäure oder Hydroxyfettsäure mit 12 - 22 C-Atomen oderAddition products of 10-150 moles of ethylene oxide with 1 mole of a linear fatty acid or hydroxy fatty acid with 12-22 C atoms, with one mole of a linear fatty alkyl amine with 12-22 C atoms or with one mole of a C1-C4 lower alkyl ester of a fatty acid or hydroxy fatty acid with 12 - 22 carbon atoms or
Anlagerungsprodukten von 3 - 100 Mol Ethylenoxid an 1/m Mol eines Polyol-fettsäureesters aus m Mol einer Fett¬ säure oder Hydroxyfettsäure mit 12 - 22 C-Atomen und einem Mol eines Polyols mit 1 - 6 C-Atomen und 2 - 6 Hydroxylgruppen, wobei m einen Wert von 1 bis 6 annehmen kann, oderAddition products of 3 to 100 moles of ethylene oxide with 1 / m mole of a polyol fatty acid ester from m moles of a fatty acid or hydroxy fatty acid with 12-22 C atoms and one mole of a polyol with 1-6 C atoms and 2-6 hydroxyl groups, where m can have a value from 1 to 6, or
Gemischen solcher Ethylenoxid-Anlagerungsprodukten. Mixtures of such ethylene oxide addition products.
2. Wäßrige Textilweichmacher-Dispersion nach Anspruch 1, dadurch gekennzeichnet, daß sie als textilweichmachende quartäre Ammo¬ niumverbindung 20 - 40 Gew.-% einer Verbindung der Formel I2. Aqueous fabric softener dispersion according to claim 1, characterized in that it as a fabric softening quaternary ammonium compound 20 - 40 wt .-% of a compound of formula I.
CH2 - CH2 - OH I RC00 - CH2 - CH2 - N(+) - CH2 - CH2 - 0C0R CH3OSO3H (I),CH 2 - CH 2 - OH I RC00 - CH 2 - CH 2 - N ( + ) - CH 2 - CH 2 - 0C0R CH3OSO3H (I),
I -I -
CH3CH3
in der RCO ein von Taigfettsäure abgeleiteter Oleoylrest ist, enthält.in which RCO is an oleoyl residue derived from tallow fatty acid.
Wäßrige Textilweichmacher-Dispersion nach Anspruch 1, dadurch gekennzeichnet, daß der nichtionische Dispergator in einer Menge von 0,001 bis 0,1 Gew.-%, bevorzugt von 0,01 bis 0,1 Gew.-%, enthalten ist.Aqueous textile softener dispersion according to claim 1, characterized in that the nonionic dispersant is contained in an amount of 0.001 to 0.1% by weight, preferably 0.01 to 0.1% by weight.
Textilweichmacher-Dispersion nach Anspruch 1, dadurch gekenn¬ zeichnet, daß zusätzlich ein Elektrolyt, vorzugsweise Magnesium¬ chlorid, in einer Menge von 0,01 bis 3 Gew.-% enthalten ist. Textile plasticizer dispersion according to Claim 1, characterized in that an electrolyte, preferably magnesium chloride, is additionally present in an amount of 0.01 to 3% by weight.
EP94902704A 1992-12-16 1993-12-07 Aqueous textile softener dispersions Expired - Lifetime EP0674701B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4242480 1992-12-16
DE4242480A DE4242480A1 (en) 1992-12-16 1992-12-16 Aqueous textile softener dispersions
PCT/EP1993/003441 WO1994013772A1 (en) 1992-12-16 1993-12-07 Aqueous textile softener dispersions

Publications (2)

Publication Number Publication Date
EP0674701A1 true EP0674701A1 (en) 1995-10-04
EP0674701B1 EP0674701B1 (en) 1997-06-18

Family

ID=6475439

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94902704A Expired - Lifetime EP0674701B1 (en) 1992-12-16 1993-12-07 Aqueous textile softener dispersions

Country Status (5)

Country Link
EP (1) EP0674701B1 (en)
AT (1) ATE154632T1 (en)
DE (2) DE4242480A1 (en)
ES (1) ES2102809T3 (en)
WO (1) WO1994013772A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5916863A (en) * 1996-05-03 1999-06-29 Akzo Nobel Nv High di(alkyl fatty ester) quaternary ammonium compound from triethanol amine
US5919750A (en) * 1997-07-24 1999-07-06 Akzo Nobel Nv Fabric softener composition
DE10134224B4 (en) 2001-07-13 2012-12-20 Clariant Produkte (Deutschland) Gmbh Additives for inhibiting gas hydrate formation

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2482636A1 (en) * 1980-05-14 1981-11-20 Lesieur Cotelle Et Associes Sa CONCENTRATED SOFTENING COMPOSITION FOR TEXTILE FIBERS
DE3218667A1 (en) * 1982-05-18 1983-11-24 Hoechst Ag, 6230 Frankfurt CONCENTRATED SOFT SOFTENER
DE3501521A1 (en) * 1985-01-18 1986-07-24 Henkel KGaA, 4000 Düsseldorf AQUEOUS CONCENTRATED TEXTILE SOFTENER
GB8818593D0 (en) * 1988-08-04 1988-09-07 Albright & Wilson Fabric conditioners
GB8916307D0 (en) * 1989-07-17 1989-08-31 Unilever Plc Fabric softening composition
GB9115255D0 (en) * 1991-07-15 1991-08-28 Unilever Plc Fabric softening composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9413772A1 *

Also Published As

Publication number Publication date
DE4242480A1 (en) 1994-06-23
WO1994013772A1 (en) 1994-06-23
EP0674701B1 (en) 1997-06-18
ES2102809T3 (en) 1997-08-01
ATE154632T1 (en) 1997-07-15
DE59306802D1 (en) 1997-07-24

Similar Documents

Publication Publication Date Title
EP2563889B1 (en) Textile softening composition
DE2929512C2 (en) Process for the manufacture of absorbent cellulose pulp
EP0675941B1 (en) Aqueous textile softener dispersions
EP1141189B1 (en) Clear softening agent formulations
EP0188242B1 (en) Concentrated aqueous textile softener
DE3612479A1 (en) AQUEOUS CONCENTRATED TEXTILE SOFTENER
DE3602089C2 (en) A durable, aqueous, pourable and water-dispersible fabric softening composition
EP0498050B1 (en) Aqueous emulsions comprising fatty acid esters of N-methyl-N,N,N-trihydroxyethyl-ammonium-methyl-sulfate
DE69532508T2 (en) Fabric softening composition
EP0718275B1 (en) Quaternary fatty-acid triethanolamine esters
DE1794068A1 (en) Preparations for treating textiles
EP0267551A2 (en) Quaternary ammonium compounds, their preparation and use as textile-finishing agents
DE3818061A1 (en) LIQUID, AQUEOUS LAUNDRY TREATMENT AGENT
EP0094655B2 (en) Concentrated laundry softening agents
DE3904754A1 (en) CONCENTRATED SOFT MAKER FOR USE IN CLOTHING PIECES
DE3618944A1 (en) QUARTAERE 2-ALKYLIMIDAZOLINIAL SALTS, METHOD FOR THE PRODUCTION AND USE THEREOF
EP0391392B1 (en) Low-foam, cold-stable aqueous detergents containing nonionic, anionic and cationic surface active agents and their utilization
EP0674701B1 (en) Aqueous textile softener dispersions
WO1993021291A1 (en) Low-viscosity aqueous textile-treatment agents
DE2721847C2 (en)
DE3908008A1 (en) CONCENTRATED AND LIQUID WATER-BASED SURFACTANT COMPOSITION, METHOD FOR THE PRODUCTION AND USE THEREOF
DE1619182A1 (en) Softeners for textiles
DE4229649A1 (en) Aqueous textile softener dispersions
WO1992010481A1 (en) Process for producing fluid imidazolinium tensides by quaternary transformation of 1-hydroxyethyl-2-alkylimidazolines
DE2723525C2 (en) Softeners

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19950607

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR IT LI NL

17Q First examination report despatched

Effective date: 19960531

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR IT LI NL

REF Corresponds to:

Ref document number: 154632

Country of ref document: AT

Date of ref document: 19970715

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

ET Fr: translation filed
REF Corresponds to:

Ref document number: 59306802

Country of ref document: DE

Date of ref document: 19970724

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2102809

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20121205

Year of fee payment: 20

Ref country code: CH

Payment date: 20121213

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20121227

Year of fee payment: 20

Ref country code: IT

Payment date: 20121213

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20121208

Year of fee payment: 20

Ref country code: AT

Payment date: 20121127

Year of fee payment: 20

Ref country code: FR

Payment date: 20130107

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20121217

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59306802

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: NL

Ref legal event code: V4

Effective date: 20131207

BE20 Be: patent expired

Owner name: *HENKEL K.G.A.A.

Effective date: 20131207

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK07

Ref document number: 154632

Country of ref document: AT

Kind code of ref document: T

Effective date: 20131207

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20131210

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20140925

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20131208