EP0881279A2 - Process for making granules containing cationic surfactant - Google Patents

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

The invention is in the field of the production of cationic surfactant-containing granules such as for example in special detergents and cleaning agents, but also in Fabric softeners are used.

Cationic surfactants are used in special detergents and cleaning agents, but especially in Laundry post-treatment agents such as fabric softeners are used to achieve the appropriate agents treated textiles a soft, fluffy feel and to give pleasant wearing properties. This also makes it easier on the textiles applied cationic surfactant ironing and leads to an antistatic effect that in turn, the wearing properties improved.

The cationic surfactants are usually in the form of dispersions liquid to pasty agent incorporated. Solid preparation forms, which as Active substance containing only cationic surfactant and no other surfactants are included comparatively rare.

Nevertheless, there was no shortage of tests, cationic surfactants also in the form of more solid ones to prepare storage-stable preparation forms, so optionally also solid ones To be able to produce detergent compositions or fabric softener.

For example, German published patent application DE 32 43 983 (Degussa AG) describes a free-flowing plasticizer concentrate which consists of one or more cationic surfactants which, if appropriate in a mixture with one or more solubilizers, are applied to synthetic silica. The agents are prepared by mixing a melt or a solution of the cationic surfactant in isopropanol with the precipitated and spray-dried silica.

Powdery fabric softening agents which contain cationic surface-active substances adsorbed on highly absorbent silica 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 silica in the mixer and then granulated under shear.

The German patent specification DE 43 08 794 (Henkel KGaA) describes special solid cationic surfactant preparation forms which are obtained by alkylation of triethanolamine esters in the presence of suitable dispersants (in particular fatty alcohols). The products obtained in this way have a flake-like structure and low bulk densities.

The first two methods have the disadvantage that the cationic surfactant is in the form its isopropanol solution or as a melt on an insoluble carrier is applied. In the first case there are extensive occupational safety and health Safety measures are required, and additionally the isopropanol has to be used again later be removed by evaporation, since alcohols have the powder properties of Change detergent compositions negatively. In the second case it is a Energy required to melt the cationic surfactant. The use of silica in large amounts also leads to the use in detergents and fabric softeners to form residues in the treated textiles. The disadvantage of all prior art processes is that they are products deliver that are only poorly soluble or not soluble without residues. The latter Process also delivers products with an undesirable low Bulk density.

The object of the invention was to provide a method for manufacturing to provide cationic surfactant-containing granules which the process and Overcomes product disadvantages.

a) 5 bis 40 Gew.-% eines oder mehrerer kationischer, textilweichmachender Mittel der Formeln I, II oder III:

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, - Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- 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

c) 0 bis 5 Gew.-% eines oder mehrerer Granulierhilfsmittel,

jeweils bezogen auf das Gewicht des Granulats, enthält.The invention relates to a solid, cationic surfactant-containing granules

a) 5 to 40% by weight of one or more cationic, fabric softening agents of the formulas I, II or III:

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; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5,

b) 50 to 90 wt .-% of a solid carrier from the group of alkali metal sulfates, carbonates, silicates, citrates and aluminum silicates and citric acid and

c) 0 to 5% by weight of one or more granulation aids,

each based on the weight of the granules.

The invention further relates to a process for the preparation of cationic surfactants Granules, in which a solid carrier in a mixer under low Energy input with a cationic surfactant and then with the addition of Water or an aqueous solution of one or more granulating aids under high Granular energy input.

The cationic surfactant can be added directly to the mixer in its delivery form, or in the form of a liquid to pasty cationic surfactant preparation form on the solid Carriers are injected. Such forms of cationic surfactants can be for example by mixing commercially available cationic surfactants with auxiliaries such as Manufacture non-ionic surfactants, polyethylene glycols or polyols. Even lower ones Alcohols such as ethanol and isopropanol can be used, the amount of such lower alcohols in the liquid cationic surfactant preparation form from the reasons mentioned above should be less than 10% by weight.

The cationic active substance can also by the procedure according to the invention can be introduced directly into the process, without first being melted or in solution to be brought. Solid cationic surfactants are simply added and act on the carrier in the course of the granulation; Forms of cationic surfactants other states of matter are added, poured in or depending on the viscosity atomized. All are solid carriers to which the cationic surfactant is applied Carriers or builders usually used in detergents and cleaning agents suitable, carriers from the group of alkali metal sulfates, carbonates, silicates, citrates, aluminum silicates and citric acid are preferred. Are particularly preferred water-soluble carriers and in particular the sodium sulfate.

Other preferred carrier materials are natural polysaccharides such as cellulose and Starch and its derivatives. These include, in particular, cellulose and starch itself, however also cellulose and starch derivatives, which are made from cellulose by polymer-analogous reactions or starch are available. Such chemically modified celluloses or starches include, for example, products from esterifications or etherifications in which Hydroxy hydrogen atoms have been substituted. But also celluloses or starches, in which the hydroxyl groups against functional groups that do not have a Oxygen atoms are bound, have been replaced, can be used as a carrier material. In the group of these derivatives includes, for example, alkali celluloses, Carboxymethyl cellulose (CMC) and starch (CMS), cellulose and starch esters and - ether and aminocelluloses and starches.

As a particularly preferred carrier material from this group of washing and Starch is used in detergent ingredients.

Preferably the amount of solid carrier in the resulting granules 50 to 80 wt .-% of the weight of the resulting granules.

Cationic surfactants used for the process according to the invention are all customary surface-active substances into consideration, with cationic surfactants with fabric softening Effect are clearly preferred.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO-oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.The agents according to the invention contain, as cationic active substances with a fabric softening effect, 5 to 40% by weight of one or more cationic fabric softening agents of the formulas I, II or III:

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; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO-or -CO-O- and n is an integer from 0 to 5.

The granules are produced by placing the solid support in a mixer and then applied the cationic surfactant with low energy input. Then one or more granulation aids in the form of an aqueous Solution added and the mixture wet granulated with high energy input.

Haufwerksmischen" durchgeführt wird. bei dem das Mischgut im Mischer in Drehrichtung angehoben wird. Hoher Energieeintrag bedeutet im Sinne des erfindungsgemäßen 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 according to the invention means slow-running mixing tools or the omission of the use of additional chopping units. This low energy input is further characterized in that the agitator shaft of the mixer does not swirl the mix, but rather a kind

Haufwerksmischen "is carried out. In which the mix in the mixer is raised in the direction of rotation. In the sense of the method according to the invention, high energy input means a rapid rotation of the mixing tools or the use of additional comminution units. Here, particles from the bed of material are whirled into the free mixing space and the Mixing 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 ". As the speeds continue to increase, the product is finally hurled onto the mixer wall in the form of a mixing material ring, which rotates there.

The process according to the invention can be carried out in both high-intensity and slow-running mixers, the high-intensity mixers being operated slowly in the first process step and the energy input required for the second process step being provided by the slow-moving mixers by means of additional units such as knife rings. 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 slow-speed mixer granulators are the Drais® KT 160 and the Lödige® KM 300. The latter is often called Lödige ploughshare mixer ".

As a granulation aid in the second stage of the process in the form of aqueous solutions are added are all of the auxiliaries commonly used in wet granulation usable. The process according to the invention particularly advantageously uses aqueous solutions Solutions of carboxymethyl cellulose (CMC), water glass or citric acid. In The aqueous solutions have a dependency on the particular granulation aid different concentrations of the substances used. This is how CMC for example in 0.2 to 5% by weight aqueous solutions, water glass in the form 10 to 40 wt .-% warmer solutions and citric acid than 5 to 30 wt .-% aqueous Solution used.

The method according to the invention can also be used as pure water without dissolved ingredients Use granulation aids without losing their advantages. The water or the aqueous solutions of the granulation aids are used in amounts of 1 to 5, preferably from 2 to 4% by weight, based on the weight of the resulting granules, added in the second stage of the process.

The granulated particles that arise in the process according to the invention can subjected to customary post-treatment steps for detergents and cleaning agents will. For example, drying of the granules in the fluidized bed is Connection to the granulation preferred. Also powdering, rounding or a different surface treatment can be applied directly to the granulation or to a connect any drying

The cationic surfactant-containing granules according to the invention contain 5 to 40% by weight of one or several textile softening agents of the above formulas I, II or III, 50 up to 90% by weight of a solid carrier from the group of alkali metal sulfates, carbonates, silicates, citrates and aluminum silicates and citric acid and 0 to 5, preferably 0.1 to 5 wt .-% of one or more granulation aids, each based on the Weight of the granulate.

Granules containing cationic surfactants are preferred in which the Cationic surfactant component a) is a quaternized triethanolamine ester. Preferred Granules containing cationic surfactants contain sodium sulfate as solid carrier component b). As Granulation aids c) are preferably one or more substances selected from the Group of cellulose derivatives, water glasses or organic salts used.

Examples

Various carriers (see table) were placed in a Lödige mixer and mixed with low energy input (without chopper) with the addition of the cationic surfactant. Then 3% by weight of aqueous solutions of carboxymethyl cellulose (1%) or water glass (30%) or citric acid (25%), based on the weight of the granules, were added and the mixture was granulated with high energy input. Following the granulation, the products were dried in the fluidized bed or powdered / rounded. As a comparison, an attempt was made to produce a cationic surfactant compound by impregnating the relevant carriers with cationic surfactant in a mixer. The compositions of the agents after drying are shown in Table 1, the physical properties can be found in Table 2. 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 sulfate - - 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 (tallow acyloxyethyl) ammonium methosulfate, 95% in isopropanol, Stepan company
CMC: carboxymethyl cellulose

Physical Properties E1 E2 E3 E4 E5 V1 Bulk density [g / l] 920 600 1000 875 1065 910 Sieving numbers: [%] ** > 1.6 mm 6 25th 42 22 10th > 0.8 mm 9 33 47 45 42 > 0.4 mm 18th 41 10th 23 40 > 0.2 mm 28 1 1 9 7 > 0.1 mm 28 - - 1 1 <0.1 mm 11 - - - - **: The comparison agent could not be dried in the fluidized bed, clumped and accordingly did not provide a grain spectrum.

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 can be found in Table 4. 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 sulfate - - 70.60 70.42 70.60 70.60 Citric acid 1.03 1.03 1.13 1.13 1.13 1.13 Carboxymethyl cellulose - - - 0.56 - - Zeolite P - - - - - - water 9.25 9.25 - - - - Stepantex® VA 90:
Methyl-N- (2-hydroxyethyl -) - N, N-di (tallow acyloxyethyl) ammonium methosulfate, 95% in isopropanol, Stepan company
Stepantex® VL 90:
Methyl-N- (2-hydroxyethyl -) - N, N-di (tallow acyloxyethyl) ammonium methosulfate, 95% in isopropanol, Stepan company
Stepantex® DC 90:
Methyl-N- (2-hydroxyethyl -) - N, N-di (oleyloxyethyl) ammonium methosulfate, 90% in isopropanol, Stepan company
Dehyquart® AU 48:
Methyl-N- (2-hydroxyethyl) - N, N-di (acyloxyethyl) ammonium methosulfate, 90% in isopropanol, Pulcra company

Physical Properties E6 E7 E8 E9 E10 E11 Bulk density [g / l] 650 720 610 585 780 730 Sieving numbers: [%] > 1.6 mm 2nd 21 1 3rd 1 5 > 0.8 mm 28 45 13 21 33 11 > 0.4 mm 43 22 44 76 24th 36 > 0.2 mm 27 12th 41 - 41 48 > 0.1 mm - 3rd 1 - 1 - <0.1 mm - - - - - -

Claims (11)

Solid granules containing cationic surfactants a) 5 to 40% by weight of one or more cationic, fabric softening agents of the formulas I, II or III:

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; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5, b) 50 to 90 wt .-% of a solid carrier from the group of alkali metal sulfates, carbonates, silicates, citrates and aluminum silicates and citric acid and c) 0 to 5% by weight of one or more granulation aids, each based on the weight of the granules. Granules containing cationic surfactants according to claim 1, characterized in that the Cationic surfactant component a) is a quaternized triethanolamine ester. Granules containing cationic surfactants according to one of claims 1 or 2, characterized characterized in that the solid carrier component b) is sodium sulfate. Granules containing cationic surfactants according to one of claims 1 to 3, characterized characterized in that the solid carrier component b) is selected from natural Polysaccharides and their derivatives, with starch being preferred. Granules containing cationic surfactants according to one of claims 1 to 4, characterized characterized in that the granulation aid c) one or more of the substances the group of cellulose derivatives, water glasses or organic salts and in Amounts of 0.1 to 5 wt .-% is used. Process for the preparation of granules containing cationic surfactants, thereby characterized in that a solid carrier in a mixer under low Energy input with a cationic surfactant and then under Add water or an aqueous solution of one or more Granulation aid granulated with high energy input. A method according to claim 6, characterized in that the solid support 50 to 80% by weight of the weight of the resulting granules. Method according to one of claims 6 or 7, characterized in that the Application of cationic surfactant by spraying a liquid to pasty Cationic surfactant preparation takes place. Method according to one of claims 5 to 8, characterized in that the aqueous solution of one or more granulation aids in amounts of 1 to 5, preferably 2 to 4 wt .-%, based on the weight of the resulting Granules, is added. Method according to one of claims 5 to 9, characterized in that in After the granulation, the granules are dried in the fluidized bed he follows. Method according to one of claims 5 to 10, characterized in that the resulting granules after granulation by powdering, Rounding or other surface treatment can be treated.