EP0881279B2 - Granules containing cationic surfactant - Google Patents

Granules containing cationic surfactant Download PDF

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Publication number
EP0881279B2
EP0881279B2 EP98108983A EP98108983A EP0881279B2 EP 0881279 B2 EP0881279 B2 EP 0881279B2 EP 98108983 A EP98108983 A EP 98108983A EP 98108983 A EP98108983 A EP 98108983A EP 0881279 B2 EP0881279 B2 EP 0881279B2
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Prior art keywords
cationic surfactant
weight
granules
alkyl
citric acid
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German (de)
French (fr)
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EP0881279A3 (en
EP0881279A2 (en
EP0881279B1 (en
Inventor
Rene-Andres Dr. Dipl.-Chem. Artiga Gonzalez
Monika Dr. Dipl.-Chem. Böcker
Christian Dr. Dipl.-Chem. Block
Stefan Hammelstein
Heinke Jebens
Judith Dr. Dipl.-Chem. Scherler
Berthold Dr. Dipl.-Chem. Schreck
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Cognis IP Management GmbH
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Cognis IP Management 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets

Definitions

  • the invention is in the field of production of cationic surfactant-containing granules, as used for example in special detergents and cleaners, but also in fabric softeners.
  • Cationic surfactants are used in special detergents and cleaners, but especially in laundry aftertreatment agents, such as fabric softeners, in order to give the textiles treated with the corresponding compositions a soft, fluffy feel and pleasant wear properties.
  • the cationic surfactant applied to the fabrics facilitates ironing and results in an antistatic effect, which in turn improves the wearing properties.
  • the cationic surfactants are incorporated in the form of dispersions in the mostly liquid to pasty agent.
  • Solid preparation forms which contain only cationic surfactant and no other surfactants as the active substance are comparatively rare.
  • German Offenlegungsschrift DE 32 43 983 (Degussa AG) describes a free-flowing plasticizer concentrate which consists of one or more cationic surfactants which, if appropriate in admixture with one or more solubilizers, are applied to synthetic silica.
  • the preparation of the agent is carried out by mixing a melt or a solution of the cationic surfactant in isopropanol with the precipitated and spray-dried silica.
  • Powdered laundry softeners which contain cationic surface-active substances adsorbed on highly absorbent silicic acid are also described in German Offenlegungsschrift DE 34 02 437 (REWO Chemische Werke GmbH).
  • the cationic surfactants are applied as a melt or solution in isopropanol to the silicic acid introduced in the mixer and then granulated under shear.
  • the first two methods have the disadvantage that the cationic surfactant is applied in the form of its isopropanolic solution or as a melt to an insoluble carrier.
  • extensive occupational safety and security measures are required and, in addition, the isopropanol must later be removed by evaporation, since alcohols adversely alter the powder properties of detergent compositions.
  • an energy expenditure for melting the cationic surfactant is required.
  • silica in high amounts leads, when used in detergents and fabric softeners, to formation of residues in the treated textiles. All the processes of the prior art have in common the disadvantage that they provide products which are only sparingly or not residue-free soluble. The latter method also provides products of undesirable low bulk density.
  • the object of the invention was therefore to provide a process for the preparation of cationic surfactant-containing granules which overcomes said process and product disadvantages.
  • the cationic surfactant can be added directly to the mixer in its delivery form, or can be sprayed onto the solid carrier in the form of a liquid to pasty cationic surfactant formulation.
  • Such cationic surfactant formulations can be prepared, for example, by mixing commercial cationic surfactants with excipients such as nonionic surfactants, polyethylene glycols or polyols. Also, lower alcohols such as ethanol and isopropanol can be used, and the amount of such lower alcohols in the liquid cationic surfactant preparation should be below 10% by weight for the reasons mentioned above.
  • solid cationic surfactants are simply added and act on the carrier in the course of granulation; Cationic surfactant forms of other states of aggregation are added, poured or atomized depending on the viscosity.
  • carriers are selected from the group of alkali metal sulfates, carbonates, silicates, citrates, aluminum silicates and citric acid. Particularly preferred are water-soluble excipients and, among these, especially the sodium sulfate.
  • natural polysaccharides such as cellulose and starch and their derivatives are preferred support materials.
  • These include in particular cellulose and starch itself, but also cellulose and starch derivatives obtainable by polymer-analogous reactions of cellulose or starch.
  • Such chemically modified celluloses or starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • celluloses or starches, in which the hydroxy groups against functional Groups that are not bound by an oxygen atom have been replaced can be used as a carrier material.
  • the group of these derivatives includes, for example, alkali celluloses, carboxymethylcellulose (CMC) and starch (CMS), cellulose and starch esters and ethers, and aminocelluloses and starches.
  • Starch is used as the particularly preferred carrier material from this group of detergent ingredients.
  • the amount of solid carrier in the resulting granules accounts for 50 to 80% by weight of the weight of the resulting granules.
  • the granules are prepared by placing the solid support in a mixer and then submerged subjected to low energy input with the cationic surfactant. Subsequently, one or more granulation aids are added in the form of an aqueous solution and the mixture is wet-granulated with high energy input.
  • Low energy input in the sense of the method means slow-running mixing tools or the absence of the use of additional chopping units.
  • This low energy input is further characterized in that the agitator shaft of the mixer does not fluidize the mix, but rather a kind of "cluster mixing" is performed. in which the mix is raised in the mixer in the direction of rotation.
  • High energy input in the sense of the method means a fast rotation of the mixing tools or the use of additional crushing units.
  • particles are increasingly being whirled from the good bed into the free mixing space and the mixture is fluidized more and more. In this state, the particles fill the mixer in the form of a cloud, the so-called "mechanically generated fluidized bed".
  • the product is finally thrown in the form of a Mischgutrings to the mixer wall, which rotates there.
  • the method can be carried out in both high-intensity and low-speed mixers, the high-intensity mixers are operated slowly in the first stage of the process and required for the second stage energy input in the low-speed mixers is provided by additional equipment such as knives.
  • high-speed mixers are the Lödige® CB 30 Recycler, the Schugi® Granulator, the Eirich® Mixer Type R or the Drais® K-TTP 80.
  • Examples of low-speed mixing granulators are the Drais® KT 160 and the Lödige® KM 300. The latter is often referred to as the "Lödige Pflugscharmischer".
  • carboxymethyl cellulosic, water glasses or citric acid are aüsge felicit.
  • the inventive method uses aqueous solutions of carboxymethyl cellulose (CMC), water glass or citric acid.
  • CMC carboxymethyl cellulose
  • the aqueous solutions have different concentrations of the substances used.
  • CMC is used in 0.2 to 5% strength by weight aqueous solutions
  • water glass in the form of 10 to 40% strength by weight aqueous solutions
  • citric acid as 5 to 30% strength by weight aqueous solution.
  • the granulated particles which are formed during the process can be subjected to the aftertreatment steps customary in detergents and cleaners. For example, drying of the granules in the fluidized bed following granulation is preferred. Also a powdering, rounding or other type of surface treatment can be directly connected to the granulation or to a possible drying
  • the cationic surfactant granules according to the invention contain from 5 to 40% by weight of one or more textile-softening quaternized triethanolamine esters of the abovementioned formula I, from 50 to 90% by weight of a solid support selected from the group consisting of alkali metal sulfates, carbonates, silicates, citrates and aluminum silicates and citric acid and natural polysaccharides and derivatives thereof and from 0.1 to 5 wt .-% of one or more granulation aids, each based on the weight of the granules.
  • a solid support selected from the group consisting of alkali metal sulfates, carbonates, silicates, citrates and aluminum silicates and citric acid and natural polysaccharides and derivatives thereof and from 0.1 to 5 wt .-% of one or more granulation aids, each based on the weight of the granules.
  • Preferred cationic surfactant-containing granules contain as solid support component b) sodium sulfate.
  • Granulating agents c) used are one or more substances selected from the group of cellulose derivatives, water glasses or citric acid.
  • compositions of the agents after drying are given in Table 1, the physical properties are given in Table 2.
  • Table 1 Composition [% by weight]: E1 E2 E3 E4 E5 V1 Stepantex® VA 90 23,40 18.47 17,01 27,50 22.54 27,70 sodium sulphate - - 82,99 70.60 75.46 71,30 sodium citrate - 81.53 - - - - citric acid 76.60 - - - - - Zeolite P * - - - 1.90 2.00 1.00
  • Stepantex® VA 90 Methyl N- (2-hydroxyethyl) -N, N-di (tallowacyloxyethyl) ammonium methosulfate, 95% in isopropanol, from Stepan CMC: carboxymethylcellulose *: from powdering / rounding Physical Properties E1 E2 E3 E4 E5 V1 Bulk density [g / l] 920 600 1000 875 1065 910 Screen numbers:

Abstract

A solid granulate is claimed which contains (A) 50-40 wt.% cationic, textile-softening agent of formula (I), (II) and/or (III), where R<1> = 1-6C alkyl, alkenyl or hydroxyalkyl; R<2> = 8-28C alkyl or alkenyl; R<3> = as for R<1> or -(CH2)n-T-R<2>; R<4> = as for R<1> or R<2>, or -(CH2)n-T-R<2>; T = -CH2-, -O-CO- or -CO-O-; and n = 0-5; (B) 50-90 wt.% solid carrier comprising an alkali metal-sulphate, -carbonate, -silicate, -citrate or -aluminium silicate or citric acid; and (C) 0-5 wt.% granulating auxiliaries. Also claimed is production of the granulate by low energy impacting of a solid carrier with a cationic surfactant in a mixer, followed by high energy granulation in the presence of water or an aqueous solution of a granulating auxiliary.

Description

Die Erfindung liegt auf dem Gebiet der Herstellung kationtensidhaltiger Granulate, wie sie beispielsweise in speziellen Wasch- und Reinigungsmitteln, aber auch in Weichspülern eingesetzt werden.The invention is in the field of production of cationic surfactant-containing granules, as used for example in special detergents and cleaners, but also in fabric softeners.

Kationtenside werden in speziellen Wasch- und Reinigungsmitteln, insbesondere aber in Wäschenachbehandlungsmitteln wie Weichspülern eingesetzt, um den mit den entsprechenden Mitteln behandelten Textilien einen weichen, flauschigen Griff und angenehme Trageeigenschaften zu verleihen. Zusätzlich erleichtert das auf die Textilien aufgebrachte Kationtensid das Bügeln und führt zu einem antistatischen Effekt, der wiederum die Trageeigenschaften verbessert.Cationic surfactants are used in special detergents and cleaners, but especially in laundry aftertreatment agents, such as fabric softeners, in order to give the textiles treated with the corresponding compositions a soft, fluffy feel and pleasant wear properties. In addition, the cationic surfactant applied to the fabrics facilitates ironing and results in an antistatic effect, which in turn improves the wearing properties.

Üblicherweise werden die Kationtenside dabei in Form von Dispersionen in die zumeist flüssigen bis pastösen Mittel eingearbeitet. Feste Zubereitungsformen, die als Aktivsubstanz nur Kationtensid und keine anderen Tenside enthalten, sind dabei vergleichsweise selten.Usually, the cationic surfactants are incorporated in the form of dispersions in the mostly liquid to pasty agent. Solid preparation forms which contain only cationic surfactant and no other surfactants as the active substance are comparatively rare.

Dennoch hat es an Versuchen nicht gefehlt, Kationtenside auch in Form fester lagerstabiler Zubereitungsformen herzustellen, um so optional auch feste Waschmittelzusammen setzungen oder Weichspüler herstellen zu können.Nevertheless, there has been no lack of attempts to produce cationic surfactants in the form of solid storage-stable preparation forms, so as to optionally also solid detergent compositions or fabric softeners can produce.

So beschreibt die deutsche Offenlegungsschrift DE 32 43 983 (Degussa AG) ein rieselfähiges Weichmacherkonzentrat, das aus einem oder mehreren Kationtensiden besteht, die, gegebenenfalls in Mischung mit einem oder mehreren Lösungsvermittlern, auf synthetische Kieselsäure aufgebracht werden. Die Herstellung der Mittel erfolgt dabei durch Mischen einer Schmelze oder einer Lösung des Kationtensids in Isopropanol mit der gefällten und sprühgetrockneten Kieselsäure.Thus, German Offenlegungsschrift DE 32 43 983 (Degussa AG) describes a free-flowing plasticizer concentrate which consists of one or more cationic surfactants which, if appropriate in admixture with one or more solubilizers, are applied to synthetic silica. The preparation of the agent is carried out by mixing a melt or a solution of the cationic surfactant in isopropanol with the precipitated and spray-dried silica.

Pulverförmige Wäscheweichspülmittel, die kationische oberflächenaktive Substanzen, adsorbiert auf hochsaugfähiger Kieselsäure, enthalten, sind auch in der deutschen Offenlegungsschrift DE 34 02 437 (REWO Chemische Werke GmbH) beschrieben. Hierbei werden die Kationtenside als Schmelze oder Lösung in Isopropanol auf die im Mischer vorgelegte Kieselsäure aufgegeben und dann unter Scherung granuliert.Powdered laundry softeners which contain cationic surface-active substances adsorbed on highly absorbent silicic acid are also described in German Offenlegungsschrift DE 34 02 437 (REWO Chemische Werke GmbH). Here, the cationic surfactants are applied as a melt or solution in isopropanol to the silicic acid introduced in the mixer and then granulated under shear.

Spezielle feste Kationtensid-Zubereitungsformen, die durch Alkylierung von Triethanolaminestern in Gegenwart von geeigneten Dispergatoren (insbesondere Fettalkoholen) gewonnen werden, beschreibt die deutsche Patentschrift DE 43 08 794 (Henkel KGaA). Die auf diese Weise erhaltenen Produkte haben eine flockenähnliche Struktur und geringe Schüttgewichte.Special solid cationic surfactant preparation forms which are obtained by alkylation of triethanolamine esters in the presence of suitable dispersants (in particular fatty alcohols) are described in German Patent DE 43 08 794 (Henkel KGaA). The products obtained in this way have a flake-like structure and low bulk densities.

Die beiden erstgenannten Verfahren besitzen den Nachteil, daß das Kationtensid in Form seiner isopropanolischen Lösung oder als Schmelze auf einen unlöslichen Träger aufgebracht wird. Im ersten Fall sind umfangreiche Arbeitsschutz- und Sicherheitsmaßnahmen erforderlich, und zusätzlich muß das Isopropanol später wieder durch Verdampfüng entfernt werden, da Alkohole die Pulvereigenschaften von Waschmittelzusammensetzungen negativ verändern. Im zweiten Falle ist ein Energieaufwand zum Aufschmelzen des Kationtensids erforderlich.
Der Einsatz von Kieselsäure in hohen Mengen führt darüber hinaus bei der Verwendung in Wasch- und Weichspülmitteln zu Rückstandsbildungen bei den behandelten Textilien. Allen Verfahren des Standes der Technik ist der Nachteil gemeinsam, daß sie Produkte liefern, die nur schlecht bzw. nicht rückstandsfrei löslich sind. Das letzgenannte Verfahren liefert darüber hinaus Produkte mit einem unerwünschten niedrigem Schüttgewicht.The first two methods have the disadvantage that the cationic surfactant is applied in the form of its isopropanolic solution or as a melt to an insoluble carrier. In the first case, extensive occupational safety and security measures are required and, in addition, the isopropanol must later be removed by evaporation, since alcohols adversely alter the powder properties of detergent compositions. In the second case, an energy expenditure for melting the cationic surfactant is required.
In addition, the use of silica in high amounts leads, when used in detergents and fabric softeners, to formation of residues in the treated textiles. All the processes of the prior art have in common the disadvantage that they provide products which are only sparingly or not residue-free soluble. The latter method also provides products of undesirable low bulk density.

Die Aufgabe der Erfindung lag nun darin, ein Verfahren zur Herstellung kationtensidhaltiger Granulate bereitzustellen, das die genannten Verfahrens- und Produktnachteile überwindet.The object of the invention was therefore to provide a process for the preparation of cationic surfactant-containing granules which overcomes said process and product disadvantages.

Gegenstand der Erfindung ist ein festes, kationtensidhaltiges Granulat, das

  • a) 5 bis 40 Gew.-% eines oder mehrerer quaternierter Triethanolaminester mit textilweichmachender Wirküng der Formel I,
    Figure imgb0001
     worin jede Gruppe R1 unabhängig voneinander ausgewählt ist aus C1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R2 unabhängig voneinander ausgewählt ist aus C8-28-Alkyl- oder -Alkenylgruppen; T = -O-CO- und n eine ganze Zahl von 0 bis 5 ist,
  • b) 50 bis 90 Gew.-% eines festen Trägers aus der Gruppe der Alkalimetallsulfate, -carbonate, -silikate, -citrate und -aluminiumsilikate und Citronensäure sowie natürliche Poly saccharide und deren Derivate
  • c) 0,1 bis 5 Gew.-% eines oder mehrerer Granulierhilfsmittel, aüsgewahlt aüs der Grüppe der Carboxymethyl cellülose, Wasserglässer oder Citronensäure
jeweils bezogen auf das Gewicht des Granulats, enthält.The invention relates to a solid, cationic surfactant-containing granules
  • a) from 5 to 40% by weight of one or more quaternized triethanolamine esters with textile-softening action of the formula I,
    Figure imgb0001
     wherein each R 1 group is independently selected from C 1-6 alkyl, alkenyl or hydroxyalkyl groups; each R 2 group is independently selected from C 8-28 alkyl or alkenyl groups; T = -O-CO- and n is an integer from 0 to 5,
  • b) 50 to 90 wt .-% of a solid support from the group of alkali metal sulfates, carbonates, silicates, citrates and aluminum silicates and citric acid and natural poly saccharides and derivatives thereof
  • c) 0.1 to 5 wt .-% of one or more granulation, aüsgewahlt aüs the group of carboxymethyl celluless, waterglasses or citric acid
in each case based on the weight of the granules.

Das Kationtensid kann dabei in seiner Lieferform direkt in den Mischer gegeben werden, oder in Form einer flüssigen bis pastösen Kationtensid-Zubereitungsform auf den festen Träger aufgedüst werden. Solche Kationtensid-Zubereitungsformen lassen sich beispielsweise durch Mischen handelsüblicher Kationtenside mit Hilfsstoffen wie nichtionischen Tensiden, Polyethylenglycolen oder Polyolen herstellen. Auch niedere Alkohole wie Ethanol und Isopropanol können eingesetzt werden, wobei die Menge an solchen niederen Alkoholen in der flüssigen Kationtensid-Zubereitungsform aus den obengenannten Gründen unter 10 Gew.-% liegen sollte. Hierbei werden feste Kationtenside einfach zugegeben und beaufschlagen den Trägerstoff im Zuge der Granulation; Kationtensid-Lieferungsformen anderer Aggregatzustände werden je nach Viskosität zugegeben, eingegossen oder verdüst. Als feste Träger, auf die das Kationtensid aufgebracht wird, sind Träger aus der Gruppe der Alkalimetallsulfate, -carbonate, -silikate, -citrate, -aluminiumsilikate und Citronensäure ausgewählt. Besonders bevorzugt sind wasserlösliche Trägerstoffe und hierunter insbesondere das Natriumsulfat.The cationic surfactant can be added directly to the mixer in its delivery form, or can be sprayed onto the solid carrier in the form of a liquid to pasty cationic surfactant formulation. Such cationic surfactant formulations can be prepared, for example, by mixing commercial cationic surfactants with excipients such as nonionic surfactants, polyethylene glycols or polyols. Also, lower alcohols such as ethanol and isopropanol can be used, and the amount of such lower alcohols in the liquid cationic surfactant preparation should be below 10% by weight for the reasons mentioned above. Here, solid cationic surfactants are simply added and act on the carrier in the course of granulation; Cationic surfactant forms of other states of aggregation are added, poured or atomized depending on the viscosity. As solid carriers to which the cationic surfactant is applied, carriers are selected from the group of alkali metal sulfates, carbonates, silicates, citrates, aluminum silicates and citric acid. Particularly preferred are water-soluble excipients and, among these, especially the sodium sulfate.

Zusätzlich sind natürliche Polysaccharide wie Cellulose und Stärke sowie ihre Derivate bevorzugte Trägermaterialien Hierzu zählen insbesondere Cellulose und Stärke selbst, aber auch Cellulose- und Stärke-Derivate, die durch polymeranaloge Reaktionen aus Cellulose bzw. Stärke erhältlich sind. Solche chemisch modifizierten Cellulosen bzw. Stärken umfassen dabei beispielsweise Produkte aus Veresterungen bzw. Veretherungen, in denen Hydroxy-Wasserstoffatome substituiert wurden. Aber auch Cellulosen bzw. Stärken, in denen die Hydroxy-Gruppen gegen funktionelle Gruppen, die nicht über ein Sauerstoffatom gebunden sind, ersetzt wurden, lassen sich als Trägermaterial einsetzen. In die Gruppe dieser Derivate fallen beispielsweise Alkalicellulosen, Carboxymethylcellulose (CMC) und -stärke (CMS), Cellulose- und Stärkeester und -ether sowie Aminocellulosen und -stärken.In addition, natural polysaccharides such as cellulose and starch and their derivatives are preferred support materials. These include in particular cellulose and starch itself, but also cellulose and starch derivatives obtainable by polymer-analogous reactions of cellulose or starch. Such chemically modified celluloses or starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But also celluloses or starches, in which the hydroxy groups against functional Groups that are not bound by an oxygen atom have been replaced, can be used as a carrier material. The group of these derivatives includes, for example, alkali celluloses, carboxymethylcellulose (CMC) and starch (CMS), cellulose and starch esters and ethers, and aminocelluloses and starches.

Als besonders bevorzugtes Trägermaterial aus dieser Gruppe von Wasch- und Reinigungsmittel-Inhaltsstoffen wird Stärke eingesetzt.Starch is used as the particularly preferred carrier material from this group of detergent ingredients.

Vorzugsweise macht die Menge des festen Trägerstoffs in den entstehenden Granulaten 50 bis 80 Gew.-% des Gewichts des entstehenden Granulats aus.Preferably, the amount of solid carrier in the resulting granules accounts for 50 to 80% by weight of the weight of the resulting granules.

Die Erfindungsgemäßen Mittel enthalten als kationische Aktivsubstanzen mit textilweichmachender Wirkung 5 bis 40 Gew.-% eines oder mehrere quaternierte Triethanolaminester mit textilweichmachender Wirküng Formel I :

Figure imgb0002
worin jede Gruppe R1 unabhängig voneinander ausgewählt ist aus C1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R2 unabhängig voneinander ausgewählt ist aus C8-28-Alkyl- oder -Alkenylgruppen; T = -O-CO- und n eine ganze Zahl von 0 bis 5 ist.The compositions according to the invention contain as cationic active substances with textile-softening action 5 to 40% by weight of one or more quaternized triethanolamine esters with textile softening formula I:
Figure imgb0002
 wherein each R 1 group is independently selected from C 1-6 alkyl, alkenyl or hydroxyalkyl groups; each R 2 group is independently selected from C 8-28 alkyl or alkenyl groups; T = -O-CO- and n is an integer from 0 to 5.

Die Granulate werden hergestellt, indem man den festen Träger in einem Mischer vorlegt und dann unter niedrigem Energieeintrag mit dem Kationtensid beaufschlagt. Anschließend werden ein oder mehrere Granulierhilfsmittel in Form einer wäßrigen Lösung zugegeben und die Mischung unter hohem Energieeintrag naßgranuliert.The granules are prepared by placing the solid support in a mixer and then submerged subjected to low energy input with the cationic surfactant. Subsequently, one or more granulation aids are added in the form of an aqueous solution and the mixture is wet-granulated with high energy input.

Niedriger Energieeintrag im Sinne des Verfahrens bedeutet langsamlaufende Mischwerkzeuge bzw. der Verzicht auf den Einsatz zusätzlicher Zerhack-Aggregate. Dieser niedrige Energieeintrag ist weiterhin dadurch gekennzeichnet, daß die Rührwelle des Mischers das Mischgut nicht verwirbelt, sondern vielmehr eine Art "Haufwerksmischen" durchgeführt wird. bei dem das Mischgut im Mischer in Drehrichtung angehoben wird. Hoher Energieeintrag bedeutet im Sinne des Verfahrens eine schnelle Drehung der Mischwerkzeuge bzw. der Einsatz zusätzlicher Zerkleinerungsaggregate. Hierbei werden vermehrt Teilchen aus dem Gutbett in den freien Mischraum hineingewirbelt und die Mischung mehr und mehr fluidisiert. In diesem Zustand füllen die Teilchen den Mischer in Form einer Wolke, des sogenannten "mechanisch erzeugten Wirbelbettes" aus. Bei weiter steigenden Drehzahlen wird das Produkt schließlich in Form eines Mischgutrings an die Mischerwand geschleudert, der dort umläuft.Low energy input in the sense of the method means slow-running mixing tools or the absence of the use of additional chopping units. This low energy input is further characterized in that the agitator shaft of the mixer does not fluidize the mix, but rather a kind of "cluster mixing" is performed. in which the mix is raised in the mixer in the direction of rotation. High energy input in the sense of the method means a fast rotation of the mixing tools or the use of additional crushing units. In this process, particles are increasingly being whirled from the good bed into the free mixing space and the mixture is fluidized more and more. In this state, the particles fill the mixer in the form of a cloud, the so-called "mechanically generated fluidized bed". At further increasing speeds, the product is finally thrown in the form of a Mischgutrings to the mixer wall, which rotates there.

Das Verfahren kann sowohl in Hochintensitäts- als auch in langsamlaufenden Mischern durchgeführt werden, wobei die Hochintensitätsmischer in der ersten Verfahrensstufe langsamlaufend betrieben werden und der für die zweite Verfahrensstufe benötigte Energieeintrag bei den langsamlaufenden Mischern durch Zusatzaggregate wie beispielsweise Messerkränze erbracht wird. Beispiele für schnellaufende Mischer sind der Lödige® CB 30 Recycler, der Schugi® Granulator, der Eirich® -Mischer Typ R oder der Drais® K-TTP 80, Beispiele für langsamlaufende Mischgranulatoren sind der Drais® K-T 160 sowie der Lödige® KM 300. Letzterer wird oftmals als "Lödige Pflugscharmischer" bezeichnet.The method can be carried out in both high-intensity and low-speed mixers, the high-intensity mixers are operated slowly in the first stage of the process and required for the second stage energy input in the low-speed mixers is provided by additional equipment such as knives. Examples of high-speed mixers are the Lödige® CB 30 Recycler, the Schugi® Granulator, the Eirich® Mixer Type R or the Drais® K-TTP 80. Examples of low-speed mixing granulators are the Drais® KT 160 and the Lödige® KM 300. The latter is often referred to as the "Lödige Pflugscharmischer".

Als Granulierhilfsmittel, die in der zweiten Verfahrensstufe in Form wäßriger Lösungen zugegeben werden, sind Carboxymethyl cellülose, Wassergläser oder Citronensäure aüsgewählt. Mit besonderem Vorteil verwendet das erfindungsgemäße Verfahren wäßrige Lösungen von Carboxymethylcellulose (CMC), Wasserglas oder Citronensäure. In Abhängigkeit vom jeweiligen Granulationshilfsmittel weisen die wäßrigen Lösungen unterschiedliche Konzentrationen an den eingesetzten Stoffen auf. So wird CMC beispielsweise in 0,2 bis 5 Gew.-%-igen wäßrigen Lösungen, Wasserglas in Form 10 bis 40 Gew.-%iger wäriger Lösungen und Citronensäure als 5 bis 30 Gew.-%ige wäßrige Lösung eingesetzt.As Granulierhilfsmittel which are added in the second stage of the process in the form of aqueous solutions, carboxymethyl cellulosic, water glasses or citric acid are aüsgewählt. With particular advantage, the inventive method uses aqueous solutions of carboxymethyl cellulose (CMC), water glass or citric acid. Depending on the particular granulation aid, the aqueous solutions have different concentrations of the substances used. For example, CMC is used in 0.2 to 5% strength by weight aqueous solutions, water glass in the form of 10 to 40% strength by weight aqueous solutions, and citric acid as 5 to 30% strength by weight aqueous solution.

Die granulierten Teilchen, die im Verfahren entstehen, können den bei Wasch- und Reinigungsmitteln üblichen Nachbehandlungsschritten unterzogen werden. So ist beispielsweise eine Trocknung des Granulats in der Wirbelschicht im Anschluß an die Granulierung bevorzugt. Auch eine Abpuderung, Verrundung oder andersartige Oberflächenbehandlung kann sich direkt an die Granulation oder an eine eventuelle Trocknung anschließenThe granulated particles which are formed during the process can be subjected to the aftertreatment steps customary in detergents and cleaners. For example, drying of the granules in the fluidized bed following granulation is preferred. Also a powdering, rounding or other type of surface treatment can be directly connected to the granulation or to a possible drying

Die erfindungsgemäßen kationtensidhaltigen Granulate enthalten 5 bis 40 Gew.-% eines oder mehrerer, textilweichmachender quaternierte Triethanolaminester der obengenannten Formel I, 50 bis 90 Gew.-% eines festens Trägers aus der Gruppe der Alkalimetallsulfate, -carbonate, -silikate, -citrate und Aluminiumsilikate und Citronensäure sowie natürliche Polysaccharide und deren Derivate sowie 0,1 bis 5 Gew.-% eines oder mehrerer Granulierhilfsmittel, jeweils bezogen auf das Gewicht des Granulats.The cationic surfactant granules according to the invention contain from 5 to 40% by weight of one or more textile-softening quaternized triethanolamine esters of the abovementioned formula I, from 50 to 90% by weight of a solid support selected from the group consisting of alkali metal sulfates, carbonates, silicates, citrates and aluminum silicates and citric acid and natural polysaccharides and derivatives thereof and from 0.1 to 5 wt .-% of one or more granulation aids, each based on the weight of the granules.

Bevorzugte kationtensidhaltige Granulate enthalten als feste Trägerkomponente b) Natriumsulfat. Als Granulierhilfsmittel c) werden einer oder mehrere Stoff, ausgewählt aus der Gruppe der Cellulosederivate, Wassergläser oder Citronensäure eingesetzt.Preferred cationic surfactant-containing granules contain as solid support component b) sodium sulfate. Granulating agents c) used are one or more substances selected from the group of cellulose derivatives, water glasses or citric acid.

BeispieleExamples

Verschiedene Trägerstoffe (siehe Tabelle) wurde in einem Lödige-Mischer vorgelegt und bei niedrigem Energieeintrag (ohne Zerhacker) unter Zugabe des Kationtensids gemischt. Anschließend wurden 3 Gew.-% wäßrige Lösungen von Carboxymethylcellulose (1%ig) bzw. Wasserglas (30%ig) bzw. Citronensäure (25%ig), bezogen auf das Gewicht des Granulats, zugegeben und die Mischung bei hohem Energieeintrag granuliert. Im Anschluß an die Granulation erfolgte eine Trocknung der Produkte in der Wirbelschicht bzw. eine Abpuderung/Verrundung. Als Vergleich wurde versucht, ein Kationtensid-Compound durch Imprägnierung der betreffenden Trägerstoffe mit Kationtensid in einem Mischer herzustellen. Die Zusammensetzungen der Mittel nach der Trocknung sind in Tabelle 1 wiedergegeben, die physikalischen Eigenschaften finden sich in Tabelle 2. Tabelle 1: Zusammensetzung [Gew.-%]: E1 E2 E3 E4 E5 V1 Stepantex® VA 90 23,40 18,47 17,01 27,50 22,54 27,70 Natriumsulfat - - 82,99 70,60 75,46 71,30 Natriumcitrat - 81,53 - - - - Citronensäure 76,60 - - - - - Zeolith P * - - - 1,90 2,00 1,00 Stepantex® VA 90:
Methyl-N-(2-hydroxyethyl-)-N,N-di(talgacyloxyethyl)ammoniummethosulfat, 95%ig in Isopropanol, Firma Stepan
CMC: Carboxymethylcellulose *: aus Abpuderung/Verrundung Tabelle 2: physikalische Eigenschaften E1 E2 E3 E4 E5 V1 Schüttgewicht [g/l] 920 600 1000 875 1065 910 Siebzahlen: [%] ** > 1,6 mm 6 25 42 22 10 > 0,8 mm 9 33 47 45 42 > 0,4 mm 18 41 10 23 40 > 0,2 mm 28 1 1 9 7 > 0,1 mm 28 - - 1 1 < 0,1 mm 11 - - - - **: Das Vergleichsmittel ließ sich in der Wirbelschicht nicht trocknen, verklumpte und lieferte dementsprechend kein Kornspektrum. Various excipients (see table) were placed in a Lödige mixer and mixed at low energy input (without chopper) with the addition of the cationic surfactant. Subsequently, 3 wt .-% aqueous solutions of carboxymethyl cellulose (1%) or water glass (30%) or citric acid (25%), based on the weight of the granules added, and granulated the mixture at high energy input. Following the granulation, the products were dried in the fluidized bed or powdered / rounded. As a comparison, it was attempted to prepare a cationic surfactant compound by impregnation of the respective carriers with cationic surfactant in a mixer. The compositions of the agents after drying are given in Table 1, the physical properties are given in Table 2. Table 1: Composition [% by weight]: E1 E2 E3 E4 E5 V1 Stepantex® VA 90 23,40 18.47 17,01 27,50 22.54 27,70 sodium sulphate - - 82,99 70.60 75.46 71,30 sodium citrate - 81.53 - - - - citric acid 76.60 - - - - - Zeolite P * - - - 1.90 2.00 1.00 Stepantex® VA 90:
Methyl N- (2-hydroxyethyl) -N, N-di (tallowacyloxyethyl) ammonium methosulfate, 95% in isopropanol, from Stepan
CMC: carboxymethylcellulose *: from powdering / rounding Physical Properties E1 E2 E3 E4 E5 V1 Bulk density [g / l] 920 600 1000 875 1065 910 Screen numbers: [%] ** > 1.6 mm 6 25 42 22 10 > 0.8 mm 9 33 47 45 42 > 0.4 mm 18 41 10 23 40 > 0.2 mm 28 1 1 9 7 > 0.1 mm 28 - - 1 1 <0.1 mm 11 - - - - **: The comparison agent was not allowed to dry in the fluidized bed, clumped and therefore gave no grain spectrum.

Weitere erfindungsgemäße Mittel, deren Zusammensetzung in der Tabelle 3 angegeben ist, wurden nach der oben beschriebenen Verfahrensweise hergestellt; ihre physikalischen Eigenschaften finden sich in Tabelle 4. Tabelle 3: Zusammensetzung [Gew.-%]: E6 E7 E8 E9 E10 E11 Stepantex® VA 90 25,45 - - - - - Stepantex® VL 90 - - 28,27 27,89 - - Stepantex® DC 90 - - - - 28,27 14,14 Dehyquart® AU 48 - 25,45 - - - 14,14 Stärke 64,27 64,27 - - - - Natriumsulfat - - 70,60 70,42 70,60 70,60 Citronensäure 1,03 1,03 1,13 1,13 1,13 1,13 Carboxymethylcellulose - - - 0,56 - - Zeolith P * - - - - - - Wasser 9,25 9,25 - - - - Stepantex® VA 90:
Methyl-N-(2-hydroxyethyl-)-N,N-di(talgacyloxyethyl)ammoniummethosulfat, 95%ig in Isopropanol, Firma Stepan
Stepantex® VL 90:
Methyl-N-(2-hydroxyethyl-)-N,N-di(talgacyloxyethyl)ammoniummethosulfat, 95%ig in Isopropanol, Firma Stepan
Stepantex® DC 90:
Methyl-N-(2-hydroxyethyl-)-N,N-di(oleyloxyethyl)ammoniummethosulfat, 90%ig in Isopropanol, Firma Stepan
Dehyquart® AU 48:
Methyl-N-(2-hydroxyethyl-)-N,N-di(acyloxyethyl)ammoniummethosulfat, 90%ig in Isopropanol, Firma Pulcra *: aus Abpuderung/Verrundung Tabelle 4: physikalische Eigenschaften E6 E7 E8 E9 E10 E11 Schüttgewicht [g/l] 650 720 610 585 780 730 Siebzahlen: [%] > 1,6 mm 2 21 1 3 1 5 > 0,8 mm 28 45 13 21 33 11 > 0,4 mm 43 22 44 76 24 36 > 0,2 mm 27 12 41 - 41 48 > 0,1 mm - 3 1 - 1 - < 0,1 mm - - - - - - Further agents according to the invention, the composition of which is given in Table 3, were prepared by the procedure described above; their physical properties are shown in Table 4. Table 3: Composition [% by weight]: E6 E7 E8 E9 E10 E11 Stepantex® VA 90 25.45 - - - - - Stepantex® VL 90 - - 28.27 27.89 - - Stepantex® DC 90 - - - - 28.27 14.14 Dehyquart® AU 48 - 25.45 - - - 14.14 Strength 64.27 64.27 - - - - sodium sulphate - - 70.60 70.42 70.60 70.60 citric acid 1.03 1.03 1.13 1.13 1.13 1.13 carboxymethylcellulose - - - 0.56 - - Zeolite P * - - - - - - water 9.25 9.25 - - - - Stepantex® VA 90:
Methyl N- (2-hydroxyethyl) -N, N-di (tallowacyloxyethyl) ammonium methosulfate, 95% in isopropanol, from Stepan
Stepantex® VL 90:
Methyl N- (2-hydroxyethyl) -N, N-di (tallowacyloxyethyl) ammonium methosulfate, 95% in isopropanol, from Stepan
Stepantex® DC 90:
Methyl N- (2-hydroxyethyl) -N, N-di (oleyloxyethyl) ammonium methosulfate, 90% in isopropanol, from Stepan
Dehyquart® AU 48:
Methyl N- (2-hydroxyethyl) -N, N-di (acyloxyethyl) ammonium methosulfate, 90% in isopropanol, Pulcra *: from powdering / rounding Physical Properties E6 E7 E8 E9 E10 E11 Bulk density [g / l] 650 720 610 585 780 730 Screen numbers: [%] > 1.6 mm 2 21 1 3 1 5 > 0.8 mm 28 45 13 21 33 11 > 0.4 mm 43 22 44 76 24 36 > 0.2 mm 27 12 41 - 41 48 > 0.1 mm - 3 1 - 1 - <0.1 mm - - - - - -

Claims (3)

  1. Solid granules containing - based on the weight of the granules -
    a) 5 to 40% by weight of one or more fabric-softening quaternized triethanolamine esters corresponding to formula I:
    Figure imgb0004
     in which the groups R1 independently of the other are each selected from C1-6 alkyl, alkenyl or hydroxyalkyl groups; the groups R2 independently of one another are each selected from C8-28 alkyl or alkenyl groups; T = -O-CO- and n is an integer of 0 to 5,
    b) 50 to 90% by weight of a solid carrier from the group of alkali metal sulfates, carbonates, silicates, citrates and aluminium silicates, citric acid and natural polysaccharides and derivatives thereof,
    c) 0.1 to 5% by weight of one or more granulation aids selected from the group consisting of carboxymethyl cellulose, waterglasses or citric acid.
  2. Granules as claimed in claim 1, characterized in that the solid carrier component b) is sodium sulfate.
  3. Granules as claimed in any of claims 1 to 2, characterized in that the solid carrier component b) is selected from natural polysaccharides and derivatives thereof, starch being preferred.
EP98108983A 1997-05-26 1998-05-18 Granules containing cationic surfactant Expired - Lifetime EP0881279B2 (en)

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EP1502942A1 (en) * 2003-07-29 2005-02-02 Clariant International Ltd. Solid softener composition
US11441106B2 (en) * 2017-06-27 2022-09-13 Henkel Ag & Co. Kgaa Particulate fragrance enhancers
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