DE2352393A1 - PROCEDURE FOR GRANULATING A DETERGENT COMPOSITION - Google Patents

Description

PATENT LAWYERS ■

DR. INC. A. VAN DERWERTH DR. FRANZ LEDERER

21 HAMBURG 9O ' ₈ MUNICH 80

WILSTORFER STR 32 TEL. (040) 770861 LUCILE-CRAHN-STR. 22 TEL. (08 1 1) 47 29 47

Munich, Oct. 18, 1973 C486 London

UNILEVER NV

Burgemeester s'Jacobplein 1 ₉ Rotterdam, the Netherlands

Method of granulating a detergent composition

The invention relates to a process for the granulation of detergent compositions ο When a solid detergent composition is produced for marketing, it is usually converted into a granular solid before packaging Formation of granules with a diameter of about 0.3 mm to about 30 mm. These procedures can be used in combination, for example an ingredient can be dry blended into a spray-dried product. Further proposals are described in US Pat. No. 3,588,950

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The invention relates to a method for granulating a detergent composition to form granules preferably in the range from about 0.3 mm to about 3? 0 dm the components in powder form, which is characterized by the fact that the components form a practically horizontal, circular, rotating bed in contact with a liquid binding agent, which is preferably released from a constituent during the erosion, in a device, which comprises a roughened, rotating table within a cylinder with a smooth wall, formed ν / earth. The binder can be added to the constituents of the batch or the formulation before or, preferably, during the rotation are added in the annular bed, but a special feature of the process according to the invention is the release of a binder material from the components of the formulation during rotation. The particles have one Relative movement to each other and to the container containing them ", Some granules may be outside the desired size range, but they are useful as a commercial product.

Possible mechanisms that lead to the release of the binder can be the rise in temperature in the bed, which would, for example, release water from a hydrate or melt a solid with a low melting point, or mechanical forces that act on a liquid / porous solid system. An example of the last-mentioned possibility would be a liquid, non-ionic, cleaning agent-active material! ■ which is absorbed on porous, solid particles. The liquid used in the granulation step can remain in the particles after they are formed, or it can be allowed to evaporate. The liquid used can-solidify at room temperature, or in the finished, formed particles it could be absorbed on the solid material or as a hydrate _o The liquid can have a specific binary mean effect on the solid particles, the liquid used

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must be chemically compatible with the solid material. It it is possible to carry out the granulation at the same time as the chemical reaction between the solid material and the liquid used occurs. In this way, a neutralization reaction can be carried out while the solid material is granulating will. , ■

The main advantage of the process according to the invention lies in the speed of granulation. The procedure delivers Particles with a relatively narrow size distribution and with tight compositional tolerances. The one on the solid The treatment carried out on the material during granulation is practically constant as the material becomes round on the circumference moved around an axis in a closed circle. As a result of this constant treatment of the particles, the device is when using powder to produce the granulate particularly powerful. The process enables a practically spherical end product to be formed in a simple manner Manner that has a negligible amount of fine abrasion. The process can be carried out at ambient temperature However, the device may be used to enable granulation to be carried out at high temperature below With the help of suitable jackets and heating devices be adjusted. The procedure can also be used at temperature lower than ambient temperature. Under normal operating conditions, the temperature rise is relatively low in the device as a result of processing. Therefore, when processing at · ambient temperature

is started, the temperature rise above this value is relatively slow compared to working methods using from heat, e.g. B. Spray drying. However, the temperature rise is sufficiently large for the binder to be released in situ. Materials which are adversely affected by higher temperatures can therefore be used in the single-stage granulation process

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be included. During processing, the Size of the particles of the final product can be classified by providing an overflow system in the device. The method according to the invention also enables the incorporation of materials which are decomposed by water can e.g. B. a percarbonate, and thus of substances, which »not entered in a slurry process can be. Such an overflow system enables the removal of particles above the specific, i.e. H. desired size. Furthermore, devices can be provided in the device, which ensure that the solid Material not on moving or stationary parts the machine · bakes firmly during processing.

The device used in the method according to the invention comprises a preferably vertically arranged, smooth side wall, for. B. a cylinder which has a rotatable, roughened, preferably horizontal table arranged concentrically within it. This table can rotate or turn around the central axis of the side walls, so that a relative movement occurs between the table and the side wall. The amount of roughening of the table is selected for the particular process, and the table is slightly separated from the side walls, and the roughening can be the roughness resulting from manufacture. A device of this type is manufactured by I ¹ UJi Paudal EE (formerly Fuji Denki Kogyo'KK), Japan under the trade name "Marumerizer". This device is described in German Patent 1,294,351, U.S. Patent 3,277,520 (reissued No. 27214) and Japanese published application 8684- / 1967. In the last-mentioned application, a method for granulating powders with the aid of a binder in a machine is described which has a horizontal rotor at the bottom of a smooth, vertical one

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Cylinder owns. It is surprising, however, that all or some of the ingredients of a detergent composition can be granulated in such a device. In particular, the generation of the binder material is in situ not described in this prior publication ... . -

The invention enables a batch to be granulated in a single stage, these as materials such. B. contains sodium perborate, which are usually metered in dry, d. H. can be added after spray drying. In which According to the method according to the invention, the pulverized, solid material that is to be granulated is arranged within the working volume of a device described above, and after the roughened table has started to be heated the liquid material is added continuously. There are no restrictions on the method of adding liquid, d. h .. this can e.g. B, sprayed on, poured in continuously or added in batches. In some cases it can be beneficial to use some of the liquid with the solid To mix material before placing the latter in the working volume. In such cases it should be in the Device housed powder still free-flowing properties exhibit.

For some applications it is advantageous to use granules having layers of the components, d. H. different components are in layers around one central core of a certain component. ' When such granules are placed in a liquid medium a successive release of the various constituents is brought about according to their dissolution in the liquid. The method according to the invention enables production such granules in a very simple way. After the production of a basic granule containing a component or Starting granules, the second component is formed in the form of a layer on the core by repeating the process.

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The basic granule is left in the work volume and the second component in powdered form is added. When the process is repeated with additional, further liquid, a composite granule is formed which has two components, one as a layer on top of the other. This construction on the granule can be repeated using additional components. The method can also be used to determine the proportion of abrasion »d. h · fine fractions, to be reduced in the case of an already granulated product. The detergent composition to which the method of the present invention is applied contains a detergent active ingredient. This active ingredient or a mixture of such active ingredients is selected from the known groups of anionic, cationic, nonionic, amphoteric and zwitterionic active ingredients. Examples of industrially known active ingredients are alkarylsulfonates, e.g. B. dodecylbenzenesulfonate, CQC ^ Q-alkyl sulfates, sulfonated olefins ( ^c ₁₀ ~ ^C 2Cp ^v ethoxylated (5EO to 9EO) alcohols (C _10-18 ), the latter can be branched or straight-chain, salts of long-chain fatty acids ( ^C x | o "" ^C 2O ^ * ^ ^e common salts are the sodium salts, but potassium salts, ammonium salts or other water-soluble salts can also be used. Examples of such active substances are in "Surface Active Agents and Detergents", Volume II (1958) by Schwartz, Perry and Berch. A liquid detergent active can be used as the binder material.

It should be pointed out that the ^{substances referred to in the description as "cleaning agents 11} " can also be referred to as detergents, the term detergent including both soap-free and soap-containing substances.

Detergent builders may also be present * examples are precipitation builders which contain insoluble calcium salts form, e.g. B. sodium orthophosphate, carbonates and sodium alkyl

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and alkenylsuecinates, sulfonated © fatty acid salts and Malonates and also chelating builders which either organic or inorganic substances, e.g. B. Sodium hydrofuran tetraearboxylate, Sodium pyrophosphate, sodium nitrilotriacetate, - ITatriumäthylendiamint etraac etat, sodium citrate, Sodium tetrate, sodium malate, trisodium carbon, oxymethylo succinate, Sodium oxydiacetate, sodium oxydisuccinate, and also poly

such as sodium polyacrylate and copolyethylene maleate.

Alkaline salts, e.g. B. sodium silicates may also be present. .- "■■■

Bleach, e.g. B. active oxygen releasing compounds such as perborates, percarbonates, may be present, preferably in an amount of about 5 ° / ° to about 30%. Other "additives", which are normally present in relatively small amounts, are agents to prevent redeposition of dirt, fragrances, brighteners and germicides.

The detergent formulation preferably contains from about 5% by weight to about 30% by weight of a detergent-active Materials and a builder material for the cleaner in the same area. The amount of active ingredient can be outside of these specific limits. Approaches or formulations lying, d. H. from about 2% by weight to about 40% <each ..-%. The amount of cleaner builder can also be outside of this preferred range, d. H. from about 5 wt% to about 60% by weight, with the larger amounts of builder Are used in formulations ^ which for a relatively low usage concentration are provided, e.g. B ·, when washing fabrics or textile goods.

The process according to the invention is explained in more detail below with the aid of examples. .

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The device used was a Marumerizer apparatus, which had a flat, horizontal table with cylindrical side walls. The diameter was 23 cm. The rotatable one The table had two legs rolled in by depressions, one of which each 1 mm deep wells spaced by. 2 mm arranged at right angles.

example 1

The following ingredients were mixed and placed in the device housed:

Alkyl benzene sulfonate Sodium toluene sulfonate coconut ethanol amide Sodium Metasilicate Pentahydrate Sodium Tripolyphosphate Hexahydrate Sodium sulfate decahydrate sodium carboxymethyl cellulose Brightener

Sodium perborate tetrahydrate

The rotating table was set in motion at 1160 TJpm, and after 5 minutes the granulation was complete, and that Product has been emptied.

It was found that the specific constituent of this formulation or this approach which caused the granulation, which was the sodium sulfate decahydrate. This hydrate gave off water which acted as a binder. The average particle size the ingredients before processing was less than 0.2 mm and after processing it was the average particle size 1 mm. The particular advantage of the method described in this example is that the sodium perborate directly in the detergent formulation can be entered without a subsequent mixing stage, as is the case with a conventional one Spray dry process would be required.

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130 G 12th S. 12th 6th 94 S. 249 6th 36 G 3 S. 3, 5 6 138 G

example 2 - ..

The components of this example were the same as those of Example 1 with the exception that the sodium metasilicate pentahydrate by 54 S powder of anhydrous sodium silicate was replaced. The ingredients with the exception of this sodium silicate powder were in the working volume of the 'device filled in, and the rotating table is set in motion. After 5 minutes at 1160 rpm, granulation had occurred. The speed of rotation of the table was then set to 350 rpm and the anhydrous sodium silicate was added to the bed of granules. After 1 minute the product became emptied.

This example shows how a sequential release can be achieved by means of the process, if the product of this example is dissolved in water, the result is a high Initial pH as the sodium silicate dissolves, and the pH drops when the rest of the ingredients are dissolved will. A washing pH profile of this type is advantageous, for example, in the presence of soils containing catalase. It is known that catalase deactivates sodium perborate * This However, catalase is produced under conditions of high pH deactivated. If.this before the occurrence of the sodium perborate can be brought about in the solution, an economically and technically advantageous use of the perborate is possible.

Example 5 _v

The following ingredients were mixed and placed in the device filled in? ·

Dodecylbenzenesulfonate 36 g

Tallow alcohol-18E0 '36 g

anhydrous sebum soap. 36 .g

Sodium silicate powder, anhydrous 26 g

Sodium tripolyphosphate, anhydrous.

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Sodium sulfate, anhydrous 48 g

Sodium carboxymethyl cellulose 12 g

Brightener 3 p

Sodium toluenesulfonai 9 g ^:

. Sodium percarbonate tetrahydrate. 15Og

The table was set in motion at 1160 rpm, and after Granules of 0.5 to 1.5 mm were formed in 7 minutes. In this An example is the specific component that causes granulation, the non-ionic, active tallow alcohol ISEO. That Product in this example has exceptionally good free-flowing properties Characteristic.

Example 4

Example 1 was repeated using 16 g of anhydrous sodium sulfate instead of the deeahydrate and 50 ml Water has been added to induce granulation * The final product was the same as that made in Example 1.

Example ^ .

It became a dishwashing formulation according to the following Preparation by granulation in the Maruiaerizer device described above manufactured;

Block copolymer of polyethylene

(Hol-, Gew. 1750) and polyoxypropylene

in a ratio of 9: 1 10 g

Sodium tripolyphosphate hydrate 522 g

Sodium metasilicate, anhydrous 425 S

Water 18 g

The metasilicate, which was in the form of granules, was incorporated into the Marumerizer device, which then runs at 1160 rpm in Movement was set. Then the powdered tripolyphosphate

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with the water, which acted as a binder, added. The product formed granules which remained free-flowing after storage for 8 weeks at 37 ^° C. and 70 % humidity. A bleach, e.g. B. Potassium dichloroisocyanuric acid (25 g) can. can be added. The mean particle diameter was now 2.5 and the product was within the desired range . '. - ■ · "" ■.

Example 6 "■ - .. '■

A formulation for washing tissue in a fiarumerizer device was granulated which had a relatively high Content of non-ionic, active ingredient contained «The formulation consisted of:

Sodium carbonate, anhydrous 33Og

non-ionic, active ingredient

(Tergltol 15-S-9) ■ 1Ί0 g

ITodium metasilicate pentahydrate 88 g

Sodium carboxymethyl cellulose -3g

Ethylene maleic anhydride copoly-

merisat (variety with low viscous'.

sity) 3g

The carbonate, metasillkat and cellulose inventory were placed in the kettle of the Marumerizer and the base plate was rotated at 350 rpm while the nonionic detergent active ingredient (Tergitol-15-S-9) was added to the rotating powder bed was added. The speed was then increased to 1160 rpm until a substantially spherical product of the desired particle size. was formed, this stage requiring about A- minutes. The speed was then reduced to the lower value, while the Gopolymerisat in the form of a 20 wt .-% / wt. aqueous solution was poured before emptying the product. The total processing time was about 5 minutes. The granulation process was repeated with the formulation, soaked 3 6 of a fabric whitening agent added to the initial batch

A Q9.81-9 / 1-021 '■ ·

was added, contained. The copolymer is under the Trademark EMA 11 available from Monsanto Co.

Example 7

A carbonate based formulation containing an amine oxide was prepared using a Marumerizer granulated. The formulation "consisted of:

H, N-Dime thy 1-TT-coconut amine oxide

(50 wt .-% / wt. Solution in water) - 165 g straight-chain alcohols-8E0

(Alfol 1412.8EC) _% 165 G

Alkaline silicate powder 275 g sodium carboxymethyl cellulose 14 g

Sodium carbonate, anhydrous 1705 S

Ethylene-maleic anhydride copolymer (Variety with low viscosity), description of goods EIlA. 11. 27 g

Water (solvent for the amine oxide) 385 S

These materials with the exception of the copolymer. became intimately mixed to disperse the active amine oxide component (trade name Aromox DMCDW) and placed in a marumerizer device filled. The base plate was rotated at 1160 rpm until the desired particle size of 0.5 until 2.0 mm was reached after 9 minutes. Another 110 ml of water was added during the process. The speed was reduced to 500 rpm and the copolymer became! than 20 wt .-% / wt. aqueous solution added. The product was then drained.

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Claims (1)

Patent claims 1. A process for granulating a detergent composition with the formation of "granules in the range from about 0.3 mm to about 3» 0 ^mm from the ingredients in powder form, characterized in that the ingredients form a practically horizontal, circular, rotating bed in Contact with a liquid binder in an apparatus comprising a roughened, rotating table within a smooth-walled cylinder. 2. A method for granulating a detergent composition according to claim Λ , characterized in that the liquid binder is released on a component for contact with the components during rotation. 3 ·. Method according to claim 2, characterized in that that the binder is released by the decomposition of a material as a result of the heat generated in the rotating bed will. 4-, method according to claim 3> characterized, that the binder releases water by decomposing a hydrate. 5- The method according to claim 2 _S, characterized in that the binder is converted into a liquid by melting in the rotating bed 6. The method according to claim 2, characterized in that that the binder in the rotating'Bett is released by mechanical forces. 4098Ί9 / 102 1 Method according to one of the preceding claims, characterized in that one uses a Reinigunersmittelformulieruns which about 5 ° i "to about 30 $ of a detergent-active material and about 5 &7" to about 30 $ of a builder material for the cleaning power umfaßtο 8. The method according to any one of the preceding claims, characterized in that the components of the formulation be granulated one after the other to form layered granules » 9. The method according to any one of the preceding claims, characterized characterized in that one uses a detergent formulation which about 5 Gev /, ~ $ to about 30% by weight of an active, oxygen-releasing material contains " 40981 9/1021