WO2000037594A2

WO2000037594A2 - Solid hydrophobic liquids for use in detergent and cleaning agents with high apparent density

Info

Publication number: WO2000037594A2
Application number: PCT/EP1999/009838
Authority: WO
Inventors: Kathleen Paatz; Wolfgang Lahn
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1998-12-21
Filing date: 1999-12-11
Publication date: 2000-06-29
Also published as: WO2000037594A3; DE19858807A1; EP1141184A2

Abstract

The invention aims at improving workability of liquid hydrophobic components in a method for producing granular detergents and cleaning agents with high apparent density by conducting extrusion on perforated molds and subsequently chopping the extruded material using a cutting device. This is essentially achieved in that the hydrophobic liquid is encapsulated in dextrin.

Description

Solid hydrophobic liquids for use in detergents and cleaning agents with high bulk density

The invention relates to a process for the production of granular detergents with high bulk density, which contain hydrophobic active ingredient components which are liquid at the manufacturing temperature in encapsulated form, and correspondingly encapsulated liquid active ingredient components.

From European patent EP 0 684 984, compositions are known which contain mixtures of sparingly water-soluble oil, which is located on an inorganic carrier material, with a substance which is encapsulated in a water-sensitive matrix. The substance encapsulated in the water-sensitive matrix is a perfume, a flavor, a cosmetic active ingredient or an organometallic complex. Starch, maltodextrin, cyclodextrin, rubber, and resins come as the material for the water-sensitive matrix. Polyvinylpyrrolidone, polyvinyl alcohol, cellulose esters and their mixtures in question. The encapsulation in the water-sensitive matrix is carried out essentially for reasons of stability.

Granular detergents with a high bulk density can be prepared according to the process of European patent EP 0 486 592. This involves the strand-shaped pressing of a homogeneous premix of detergent ingredients, which can optionally be carried out with the addition of a plasticizer, via hole shapes, which preferably have an opening width of 0.5 mm to 5 mm, subsequent comminution of the extrudate by means of a cutting device and subsequent treatment in a rounding machine, which results in largely uniform spherical products. However, jagged surfaces of the extrudate and length differences are sometimes observed, especially in the case of formulations rich in surfactants Discount, which leads to a non-optimal increase in bulk density due to the extrusion step, to increased fine and coarse fractions and generally to a deterioration in the product image. If such surfactants are nonionic surfactants that are relatively hydrophobic, in some cases a non-optimal solubility and reduced flushability of the agent are observed. In particular for incorporation into such extruded compositions, there is a need for a solid composition which contains such liquid ingredients which can cause problems when incorporated in liquid form. The mentioned problems can also have other means, for example washing and cleaning agents with a high bulk density obtainable by granulation processes.

Surprisingly, it has now been found that hydrophobic ingredients which are liquid at the processing temperatures of the abovementioned production process can be incorporated into extruded detergents with a high bulk density, in particular, without disadvantageous changes in solubility, if the hydrophobic ingredient is encapsulated in optionally hydrophobicized dextrin before the extrusion step. On the contrary, the use of hydrophobic liquids encapsulated in dextrin leads to an improvement in the dissolving behavior of such detergents and cleaning agents.

A first subject of the invention is therefore a non-ionic surfactant encapsulated in dextrin. Such a particulate encapsulation product preferably has a nonionic surfactant content in the range from 10% by weight to 60% by weight, in particular 15% by weight to 50% by weight. It preferably contains 40% by weight to 90% by weight, in particular 50% by weight to 85% by weight of dextrin or a mixture of dextrin and inorganic salts in which the content of inorganic salt is up to 50% by weight. %, in particular 5 wt .-% to 30 wt .-% of the mixture of dextrin and inorganic salt. Examples of suitable inorganic salts here are alkali metal chlorides, alkali metal carbonates, alkali metal sulfates, alkali metal silicates and silicas and mixtures thereof. In addition, the encapsulation product can contain small amounts, preferably not more than 5% by weight, contain in particular 1% by weight to 3% by weight of water. It preferably has an average particle diameter in the range from 0.05 mm to 1 mm, in particular 0.2 mm to 0.8 mm.

Such an encapsulation product is preferably produced by a spray drying process. The procedure is such that the dextrin or the combination of dextrin and inorganic salt is slurried or dispersed in water, then the nonionic surfactant to be encapsulated is added and it is dispersed into very fine drops by intensive mixing. Average drop sizes in the range from 1 μm to 2 μm and a maximum drop size of 10 μm are preferred. The viscous liquid thus obtained is then spray-dried using a device which can be used for this purpose, a so-called spray tower. If desired, the spray product obtained in this way can then be dried further using, for example, a fluidized-bed dryer, or a combination of the two drying methods, as has become known under the name “MSD process” (RA Youngs, ..spray drying encapsulation) - today's view ", Food, January 1986). In a preferred embodiment of the invention, the inorganic salt is not incorporated into the encapsulation product or not in its entirety via the aqueous dispersion to be sprayed, but instead is encapsulated by simultaneous powdering in addition to the spray.

Such a spray drying process, as is known in principle from the above-mentioned European patent EP 0 684 984, can also be used for encapsulating any other hydrophobic liquids, wherein hydrophobic liquids are to be understood as those whose solubility in water at 20 ° C. is less than 5 vol. -% (less than 5 ml in 95 ml of water). Such other hydrophobic liquids can be, for example, perfume oils and / or concentrated enzyme solutions, which can also be used in a mixture with the nonionic surfactants mentioned above. The enzymes used here are the enzymatic active ingredients usually provided for use in detergents or cleaning agents, in particular lipase, Protease, amylase and / or cellulase. They usually have a molecular weight of at least 10,000 g / mol.

Surprisingly, it has been found that the incorporation of such hydrophobic liquids into granular washing or cleaning agents with a high bulk density, which are produced in particular by an extrusion process, is greatly facilitated if they are used in a form encapsulated in dextrin.

Another object of the invention is therefore a process for the production of granular detergents or cleaning agents with a high bulk density by strand-shaped pressing through hole shapes and subsequent comminution of the extrudate by means of a cutting device, which is characterized in that a hydrophobic liquid is encapsulated in dextrin, this encapsulation intermediate mixed with at least one solid and / or solid detergent constituent, extruded through a perforated plate and the extrudate optionally rounded and / or powdered.

As an additional benefit of this procedure, the detergent behavior of detergents with a high bulk density in conventional washing machines is improved.

Another object of the invention is therefore the use of hydrophobic liquids encapsulated in dextrin to improve the washing-in behavior and / or to increase the dissolution rate of detergents with a high bulk density. In a particularly simple embodiment of this aspect of the invention, the encapsulated liquid is mixed with the other solid and / or solid detergent ingredients in the course of the preparation of the agents. The encapsulation product can also be subjected, together with further detergent or cleaning agent components, to a granulation step which is known in principle, and so detergents or cleaning agents with an increased bulk density can be obtained, with preference being given to this. use an anhydrous granulation liquid. In the process according to the invention for the production of detergents and cleaning agents and in the context of the use according to the invention, preferably 1 wt.% To 50 wt.%, In particular 1.5 wt Contain 20 wt .-% of the particulate encapsulation product.

In the context of the present invention, dextrins are to be understood as meaning oligomers or polymers of carbohydrates which are accessible by partial hydrolysis of starch. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molecular weights in the range from 440 to 500,000. The dextrin used in the process according to the invention or in encapsulation products according to the invention is preferably a polysaccharide with a dextrose equivalent (DE) in the range from 0. 5 to 40, in particular from 2 to 30, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both dry glucose syrups (DE 20 to 37) and so-called yellow dextrins and white dextrins with higher average molecular weights in the range from about 2,000 to 30,000 can be used, so-called maltodextrins (DE 3 to 20) being preferred according to the invention. The dextrins can also have been modified to be hydrophobic in a known manner. Another advantage of the invention in this context is that when the dextrins are used, active ingredients are introduced into the finished detergent or cleaning agent, which contribute to the washing result, since dextrins, as known from international patent application WO 97/20905, have a Have a cobuilder effect.

In the context of the present invention, agents with a high bulk density should be understood to mean those with bulk densities of at least 550 g / 1, in particular from 600 g / 1 to 950 g / 1 and preferably from 700 g / 1 to 850 g / 1.

Nonionic surfactants which are contained in the encapsulation product according to the invention include, in particular, the alkoxylates, preferably the ethoxylates and / or propoxylates of alcohols, alkylamines, vicinal diols and / or carboxylic acid amides, which have alkyl groups with 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms. The average degree of alkoxylation of these compounds is generally from 1 to 25, preferably 3 to 18 and particularly preferably 6 to 10. They can be prepared in a known manner by reaction with the corresponding alkylene oxides. Products which can be prepared by alkoxylation of fatty acid alkyl esters with 1 to 4 carbon atoms in the ester part by the process of international patent application WO 90/13533 are also suitable. Preferred among the carboxamide derivatives are the ethanolamide derivatives of alkanoic acids with 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms. The alcohol alkoxylates in question include the ethoxylates and / or propoxylates of linear or branched-chain alcohols having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms. Derivatives of fatty alcohols are particularly suitable, although their branched-chain isomers can also be used to prepare usable alkoxylates. Accordingly, the ethoxylates of primary alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. It is also possible to use corresponding alkoxylates of mono- or polyunsaturated fatty alcohols, which include, for example, oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol and erucalcohol. Nonionic surfactants to be encapsulated according to the invention are liquid, preferably at temperatures not above room temperature.

In addition to solid individual raw materials such as powdered polycarboxylate cobuilders, for example alkali citrate, solid inorganic builder materials such as zeolite-A, the solid and / or solid-form detergent or detergent constituents with which the encapsulation product is mixed prior to strand-like molding include solid individual raw materials. Zeolite-P, Zeolite-X and crystalline phyllosilicates, and other inorganic salts such as alkali carbonate, alkali hydrogen carbonate and alkali silicate, solid bleaching agents based on oxygen, for example alkali perborates, which may be present as so-called monohydrates or tetrahydrates, or alkali percarbonates, also powder-formulated bleach activators, for example a post-bleach activator the procedure of the European Patent EP 0 037 026 produced tetraacetyl methylenediarnine granules, solid form, high-active substance-containing amon surfactant compounds, for example an alkyl sulfate compound produced in accordance with the process of international patent application WO 93/04162, enzymes present in granular form, for example an enzyme according to the process of international patent application WO 92/11347 produced enzyme extrudate or a multi-enzyme granulate produced according to the method of the German patent application DE 43 29463 and / or a powdery, for example, soil release active substance made up according to the method of the German patent application DE 44 08 360. The above-mentioned solid or solid-form detergent ingredients can also, as an alternative to their processing via the premix to be extruded, be mixed with the extrudate in order to obtain a finished detergent or cleaning agent, as long as care is taken to ensure that at least one solid or Detergent ingredient prepared in solid form has found its way into the premix to be extruded together with the encapsulation product. A premix is preferably made from 20% by weight to 70% by weight of a builder and surfactant-containing detergent product produced by spray drying, 3% by weight to 20% by weight of anionic surfactant compound according to WO 93/04162 with a content of more than 80 wt .-%, in particular over 90 wt .-% of alkyl sulfate with alkyl chain lengths in the range of C ₁₂ to C _lg , balance essentially inorganic salts and water, 2 wt .-% to 10 wt .-% powdered, separately added alkali carbonate . 5% by weight to 20% by weight of powdered, separately added polycarboxylate cobuilder, for example alkali citrate, 10% by weight to 20% by weight of peroxobleaching agent, for example sodium perborate monohydrate, and 1% by weight to 20% by weight. % of the encapsulation product and up to 20% by weight, in particular 5% by weight to 20% by weight, of aqueous liquid components, for example water, aqueous alkali silicate and / or polycarboxylate solutions, are produced and extruded, the further one if desired after the extrusion solid or solid detergent ingredients can be added.

The extrusion is carried out under conditions which are known in principle, preferably using an extruder, into which one contains the encapsulation product homogeneous premix and fed under a pressure in the range of preferably 30 bar to 180 bar, in particular 40 bar to 80 bar, through a perforated plate with a hole diameter of preferably 1.2 mm to 2.0 mm, in particular 1.4 mm to 1, 7 mm strand veφresst and crushed to a length that does not differ significantly from the thickness, that is, the hole diameter. The extrudate, if desired with application of powdery solids as described in particular in international patent application WO 94/01526, can then be rounded and deburred in a conventional rounding device, for example a Spheronizer®.

Examples

example 1

A hydrophobized, oxidation-stable dextrin (Narlex® ST2, manufacturer National Starch) was dispersed in water (mixing ratio 1: 1) with stirring. After the dispersion had been heated to approximately 80-90 ° C., the dextrin swelled, and a viscosity of above 20,000 mPa.s was established. The solution was cooled to about 40 ° C. A 7-fold ethoxylated C _{12/18 fatty} alcohol (Dehydol® LT7, manufacturer Henkel KGaA) was added and finely dispersed in the aqueous starch solution using a Supraton® mixer. The composition of the slurry to be sprayed was 42.4% by weight of dextrin, 42.4% by weight of water and 15.2% by weight of nonionic surfactant. It was spray-dried via a two-fluid nozzle with a liquid outlet diameter of 2 mm in a drying tower (manufacturer Niro Atomizer) according to the fountain principle, the throughput of the aqueous slurry being 14 kg / h and the drying gas at a temperature of 150 ° C. from above into the tower entered and left the tower at a temperature of 90 ° C. The encapsulation product obtained had a water content of 2.6% by weight and a nonionic surfactant content of 27% by weight. It was a free-flowing, non-sticky powder with a bulk density of 280 g / 1.

To determine the residue or solubility behavior (L test), 8 g of the agent to be tested are normally sprinkled into a 2-liter beaker while stirring (800 rpm with laboratory stirrer / propeller stirring head 1.5 cm from the beaker bottom) and Stirred at 30 ° C for 1.5 minutes, the experiment being carried out with water having a hardness of 16 ° d. The wash liquor is then poured off through a sieve (80 μm), the beaker is rinsed out with very little cold water over the sieve and the sieve is dried to constant weight at 40 ° C ± 2 ° C and the detergent residue is weighed out. Using the agent prepared as described above in this test resulted in a 0% residue. Even if the dissolution time was reduced to 60 seconds and the water temperature was reduced to 20 ° C, there was no residue.

Example 2

The procedure was as in Example 1, using a perfume oil instead of the nonionic surfactant. The resulting product had the same properties as the product in Example 1.

Claims

claims

1. Liquid nonionic surfactant encapsulated in particulate form in dextrin.

2. Particles according to claim 1, characterized in that it contains 10 wt .-% to 60 wt .-%, in particular 15 wt .-% to 50 wt .-% nonionic surfactant.

3. Particles according to claim 1 or 2, characterized in that there are 40% by weight to 90% by weight, in particular 50% by weight to 85% by weight, of dextrin or a mixture of dextrin and inorganic salts in which the content of inorganic salt can comprise up to 50% by weight, in particular 5% by weight to 30% by weight, of the mixture of dextrin and inorganic salt.

4. Particles according to one of claims 1 to 3, characterized in that the dextrin is a hydrophobic dextrin.

5. Particles according to one of claims 1 to 4, characterized in that the dextrin is a maltodextrin.

6. Particle according to one of claims 1 to 5, characterized in that it contains not more than 5 wt .-%, in particular 1 wt .-% to 3 wt .-% water.

7. Particles according to one of claims 1 to 4, characterized in that it has an average particle diameter in the range from 0.05 mm to 1 mm, in particular 0.2 mm to 0.8 mm.

8. A process for the production of liquid nonionic surfactants encapsulated in particulate form in dextrin, characterized in that dextrin or a combination of dextrin and inorganic salt is slurried or dispersed in water, then the nonionic surfactant to be encapsulated is added and it is mixed vigorously into very fine drops dispersed as well the viscous liquid thus obtained is spray dried using a device which can be used for this purpose.

9. The method according to claim 8, characterized in that the spray product is dried further using, for example, a fluidized bed dryer.

10. A process for the production of washing or cleaning agents with increased bulk density, characterized in that a hydrophobic liquid is encapsulated in dextrin and this encapsulation intermediate is mixed with the other solid and / or solid detergent or cleaning agent ingredients.

11. A process for the production of detergents or cleaning agents with increased bulk density, characterized in that a hydrophobic liquid is encapsulated in dextrin and this encapsulation intermediate together with further detergent or cleaning agent components is subjected to a known granulation step, in particular using an anhydrous granulation liquid.

12. A process for the production of granular detergents or cleaning agents with a high bulk density by strand-shaped pressing through hole shapes and subsequent comminution of the extrudate by means of a cutting device, which is characterized in that a hydrophobic liquid is encapsulated in dextrin, this encapsulation intermediate with at least one solid and / or a detergent or cleaning agent component made up in solid form, extruded through a perforated plate and the extrudate optionally rounded and / or powdered.

13. The method according to any one of claims 10 to 12, characterized in that 1% by weight to 50% by weight, in particular 1.5% by weight to 20% by weight, in the washing or cleaning agent or in the mixture to be extruded. -% are contained in the particulate encapsulation product.

14. The method according to any one of claims 10 to 13, characterized in that the hydrophobic liquid is a nonionic surfactant, a concentrated enzyme solution, a perfume oil or a mixture of these.

15. Use of hydrophobic liquids encapsulated in dextrin to improve the washing-in behavior and / or to increase the dissolution rate of detergents with a high bulk density.

16. Use according to claim 15, characterized in that the hydrophobic liquid is a nonionic surfactant, a perfume oil or a mixture of these.