WO2003048290A1

WO2003048290A1 - Method for producing coated bleach activator granules

Info

Publication number: WO2003048290A1
Application number: PCT/EP2002/013127
Authority: WO
Inventors: Georg Assmann; Olaf Joachim Blochwitz; Horst-Dieter Speckmann; Jörg Poethkow; Birgit Middelhauve; Gerhard Blasey
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2001-12-04
Filing date: 2002-11-22
Publication date: 2003-06-12
Also published as: DE50206700D1; DE10159388A1; JP2005514467A; EP1451284B1; ATE325182T1; EP1451284A1; ES2260519T3; AU2002365628A1; US20040248754A1

Abstract

The aim of the invention is to improve the stability in storage and pourability of particle-shaped bleach activators of formula (I) in which: R1 represents -H, -CH¿3?, a C2-24 alkyl radical or alkenyl radical, a substituted C2-24 alkyl radical or alkenyl radical having at least one substituent selected from the group comprised of -Cl, -Br, -OH, -NH2, -CN, an alkyl radical or alkenyl aryl radical having a C1-24 alkyl group or represents a substituted alkyl radical or alkenyl aryl radical having a C1-24 alkyl group and at least one additional substituent on the aromatic ring; R?2 and R3¿, selected independent of one another, consist of -CH¿2?-CN, -CH3, -CH2-CH3, -CH2-CH?2-CH¿3, -CH(CH3)-CH3, -CH2-OH, -CH2-CH2-OH, -CH(OH)-CH3, -CH2-CH2-CH2-OH, -CH2-CH(OH)-CH3, -CH(OH)-CH2-CH3, -(CH2CH2-0)nH with n being equal to 1, 2, 3, 4, 5 or 6; R?4 and R5¿, independent of one another, have a meaning previously given for R?1, R2 or R3¿, and; X is a charge-compensating anion. The stability in storage and pourability are improved, essentially by spraying the particle-shaped bleach activators with an acid aqueous solution that, as both a coating and hardening active substance, contains polymeric polycarboxylate and/or phosphonic acid or alkali phosphonate while simultaneously drying them in a fluidized bed apparatus.

Description

Process for the production of coated bleach activator granules

The invention relates to a process for coating bleach activator-containing granules by treatment with an acidic aqueous strengthening solution which contains polymeric polycarboxylate and / or alkali metal phosphonate as the coating and strengthening active ingredient, with simultaneous drying in a fluidized bed apparatus.

In addition to the ingredients that are indispensable for the washing process, such as surfactants and builder materials, detergents and cleaning agents generally contain other ingredients, which can be summarized under the term washing aids and which include such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents and dye transfer inhibitors. Such auxiliaries also include substances that support the surfactant performance through the oxidative degradation of soiling on the textile or such in the fleet. The same applies analogously to cleaning agents for hard surfaces. Inorganic peroxygen compounds, in particular hydrogen peroxide and solid peroxygen compounds which dissolve in water with the liberation of hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfection and bleaching purposes. The oxidation effect of these substances in dilute solutions depends strongly on the temperature; For example, with H ₂ O ₂ or sodium perborate in alkaline bleaching liquors, sufficiently quick bleaching of soiled textiles can only be achieved at temperatures above about 60 ° C. At lower temperatures, the oxidation effect of the inorganic peroxygen compounds can be improved by the addition of so-called bleach activators, for which numerous suggestions, especially from the classes of the N- or O-acyl compounds, for example multiply acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylgly oluril , N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, and also carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular Sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as pentaacetyl glucose, have been contracted in the literature. By adding these substances, the bleaching effect of aqueous peroxide liquors can be increased to such an extent that even at temperatures below 60 ° C essentially the same effects occur as with the peroxide liquor alone at 95 ° C.

European patent application EP 0 464 880 discloses bleach-boosting cationic nitriles of the general formula R'R "R '" N ⁺ -CR ₁ R ₂ -CN X ^" , in which Ri and R _{2 are} hydrogen or a substituent with at least one C- Atom, R 'is a C _1-24 - alkyl, alkenyl or alkyl ether group or a group -CRιR ₂ -CN, and R "and R" are each a C _1-24 - alkyl or hydroxyalkyl group and the counter anion X ^" is an organic sulfonate, an organic sulfate or a carboxylate.

From international patent application WO 98/23719 it is known that compounds of the general formula R ¹ R ² R ³ N ⁺ CH2CN X ^" in which R ¹ , R ² and R ³ independently of one another are an alkyl, alkenyl or aryl group with 1 to 18 carbon atoms, where the groups R ² and R ^{3 can} also be part of a heterocycle including the N atom and optionally further hetero atoms, and X is a charge-balancing anion, used as activators for, in particular, inorganic peroxygen compounds in aqueous cleaning solutions for dishes This results in an improvement in the oxidation and bleaching action, in particular of inorganic peroxygen compounds, at low temperatures below 80 ° C., in particular in the temperature range from about 15 ° C. to 55 ° C. However, the cationic nitriles are in particular in combination with other ingredients detergents and cleaning agents usually have little shelf life and are especially recommended sensitive to moisture.

The international patent application WO 00/50556 discloses the production of solid preparations, which contain cationic nitrile and solid carrier material, by means of a valcuum steam drying process in a mixer.

The object of the invention was to provide a process which makes it possible to granulate, which contain a cationic nitrile, in particulate washing and cleaning agent to incorporate that the cationic nitrile suffers as far as possible no loss of bleach-activating effect even after storage. It has now been found that the preparation of preparations which meet this requirement is possible by means of a swirl chicite coating process. In this way, a protective coating can be applied to the granules in a simple manner, without having to accept a decrease in the bleach activating effect.

The invention relates to the production of a coated particulate preparation containing a compound of the formula (I), R ¹

R ² -N ⁽⁺⁾ - (CR ⁴ R ⁵ ) -CN X ^Θ (I)

R ³ in the R ^{1 represents} -H, -CH ₃ , a C _2-2 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br , -OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a Cι.2 ₄ -alkyl group, or for a substituted alkyl or alkenylaryl radical with a C _1-24 alkyl group and at least one further substituent on the aromatic ring , R and R are independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ - CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) - CH ₂ -CH ₃ , - (CH CH ₂ -O) _n H with n = 1, 2, 3, 4, 5 or 6, R ⁴ and R ⁵ independently of one another have a meaning given above for R, R ² or R ³ and X is a charge-balancing anion, characterized in that the bleach activator of the formula (I) present in solid, in particular powdery form, is desired if necessary, in a mixture with binder and / or solid filler or as prefabricated granules, with simultaneous drying in a fluidized bed apparatus, sprayed with an acidic aqueous strengthening solution which contains polymeric polycarboxylate and / or phosphonic acid or alkali metal phosphonate as coating and strengthening active substance.

This makes it possible to completely coat the bleach activator according to formula (I) or a particle containing it with a coating material. Moreover If the solution containing polymeric polycarboxylate and / or phosphonic acid or alkali metal phosphonate is used, an increase in the grain strength of the bleach activator particle is observed.

Compounds of the formula I can be prepared by known processes or based on these, as described, for example, in the patent literature mentioned or by Abraham in Progr. Phys. Org. Chem. 11 (1974), pp. Lff, or from Arnett in J. Am. Chem. Soc. 102 (1980), p. 5892ff. have been published.

Preference is given to the use of compounds of the formula I in which R ¹ , R ² and R ^{3 are} identical. Among these, preference is given to those compounds in which the radicals mentioned mean methyl groups. On the other hand, preference is also given to those compounds in which at least 1 or 2 of the radicals mentioned are methyl groups and the others have more than one carbon atom.

The anions X ^" include in particular the halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate, hexafluorophosphate, carbonate, hydrogen carbonate, sulfate, hydrogen sulfate, C _{1- 0} -alkyl sulfate, C. _1-2 o-alkyl sulfonate, optionally C _1-18 alkyl substituted aryl sulfonate, chlorate, perchlorate and / or the anions of C _1-24 carboxylic acids such as formate, acetate, laurate, benzoate or citrate, alone or in any mixtures.

Compounds according to formula I are preferred in which X ^" chloride, sulfate, hydrogen sulfate, ethosulfate, C _12/18 -, C _12/16 - or C _13/15 alkyl sulfate, lauryl sulfate, dodecyl benzene sulfonate, toluenesulfonate, cumene sulfonate, xylene sulfonate or Toluene sulfonate or cumene sulfonate is understood to mean the anion of the ortho-, meta- or /> αra isomer of methylbenzenesulfonic acid or isopropylbenzenesulfonic acid and any mixtures thereof. Αr -Isopropylbenzenesulfonic acid is particularly preferred.

The compound according to general formula I can be packaged in solid form as such or in particulate form, that is to say applied to an organic and / or inorganic carrier material, can be used as starting material in the coating process according to the invention. The compound of the formula (I) can be applied to the support material in such a way that the support material is stirred into a solution of the compound of the formula I, as is obtained in the course of its preparation, and the aqueous solvent, if appropriate, in vacuo, if desired at elevated Temperature, subtracts. However, the solution of the compound of the formula I can also be sprayed onto the support material and, if appropriate, or subsequently, subjected to a drying process. Enveloping the bleach activator granules produced in accordance with the methods disclosed in German patent applications DE 19740 668 or DE 197 40 671 is also possible by means of the method according to the invention and represents a preferred embodiment of the method according to the invention. It is preferred if the particles resulting from the packaging process have one Have diameters in the range of 0.4 mm to 3 mm. Suitable carrier materials are all substances which do not interact in an unacceptably negative way with the compound of the formula I, for example alkali metal sulfonate, surfactants, organic acids and polymers, alkali metal carbonates, alkali metal sulfates, alkali metal hydrogen sulfates,

Alkali hydrogen carbonates, alkali phosphates, alkali dihydrogen phosphates,

Dialkalihydrogenphosphate and alkali silicates and their mixtures. Support materials are preferably used whose inner surface is in the range from 10 m ² / g to 500 m ² / g, in particular 100 m Ig to 450 m ² / g. The silicate carrier materials which are particularly suitable in the context of the present invention include, for example, both alkali silicates and also silicas, silica gels and clays and mixtures thereof. However, the carrier material is preferably free of zeolites. In addition to the silicate component, silicate-containing carrier material optionally contains further particulate inert constituents which do not unreasonably impair the stability of the compounds of the formula I. Silicas which have been produced by a thermal process (flame hydrolysis of SiCl ₄ ) (so-called pyrogenic silicas) can be used as well as silicas produced by wet processes. Silica gels are colloidal silicas with elastic to firm consistency and a largely loose pore structure, which results in a high fluid absorption capacity. They can be made by the action of mineral acids on water glass become. Clays are naturally occurring crystalline or amorphous silicates of aluminum, iron, magnesium, calcium, potassium and sodium, for example kaolin, talc, pyrophyllite, attapulgite, sepiolite, montmorillionite and bauxite. The use of aluminum silicate as a carrier material or as a component of a carrier material mixture is also possible. The carrier material preferably has particle sizes in the range from 100 μm to 1.5 mm.

In a further preferred embodiment of the invention, steps a) preparation of an aqueous solution containing cationic nitrile, preferably in amounts of 10% by weight to 90% by weight, in particular 15% by weight, are first carried out % to 50% by weight, and optionally alkali metal sulfonate, in particular sodium cumene sulfonate, b) optionally adjusting the solution to an acidic pH, in particular by adding sulfuric acid and / or citric acid c) spraying and drying the solution in a fluidized bed apparatus, d) optionally powdering the primary granules thus obtained using silica, zeolite and / or alkali metal sulfonate, in particular Na-cumene sulfonate, in the fluidized bed, and the optionally powdered granules obtained in this way with the aqueous strengthening and coating solution with simultaneous drying in the same or, if appropriate, one sprayed downstream second fluidized bed apparatus. The granules can then be discharged from the fluidized bed apparatus and, if necessary, separated into good and coarse / fine particles, in particular by sieving. If appropriate, the return of fine grain and / or ground coarse grain to the fluidized bed in step c) and / or the return of fine grain and / or ground coarse grain to the powdering step d) can follow.

The coated bleach activator granules obtainable by the process according to the invention or the proportion of good grains thereon preferably have average particle diameters in the range from 0.2 mm to 2.5 mm, in particular in the range from 0.4 mm to 2.0 mm. Its bulk density is preferably in the range from 300 g / 1 to 1000 g / 1, in particular in the range from 400 g / 1 to 800 g / 1. The proportion of compound of the formula (I) is preferably in the range from 10% by weight to 90% by weight, in particular from 15% by weight to 50% by weight. It is preferably used for the production of particulate detergents or cleaning agents.

Fluidized bed devices which can be used in a method according to the invention are known, for example, from European Patent EP 0 603 207 B1 or German Patent Application DE 197 50 424. In order to better prevent the granules from falling through the through openings located in the inflow floor, as a result of which they come into contact with surfaces of relatively high temperature, the through openings can be covered by a grid, in particular with mesh sizes of less than 600 μm. The grid can be arranged inside or above the passage openings. However, the grid is preferably located directly below the passage openings of the inflow floor, as is known in principle from German patent application DE 197 50 424. In a practical embodiment, a metal gauze with the appropriate mesh size can be sintered onto the underside of a known inflow floor or attached in some other way. The metal gauze preferably consists of the same material as the inflow floor, in particular of stainless steel. The fine-meshed grid prevents particles from falling through, especially when the system stops unscheduled, but also especially in the case of particularly heavy particles with bulk densities of around 1000 g / l, even during operation. The mesh size of said grid is preferably between 200 and 400 μm. It is also advantageous if the inflow floor used has a pressure loss of at most 10 mbar and in particular at most 6 mbar.

According to the invention, the aqueous strengthening and coating solution is applied in a fluidized bed apparatus. Suitable solidifying agents and coating agents are polymeric polycarboxylates, in particular polymerization products of acrylic acid, methacrylic acid or maleic acid, or copolymers of at least two of these, which can be used in completely or partially neutralized form, in particular in the form of the alkali metal salts. As an alternative or in addition to polymeric polycarboxylate, phosphonic acid or alkali metal phosphonate can be used. In the alkali metal salts mentioned, sodium is the preferred alkali metal in each case. The setting of the solution is preferably as low as possible Viscosity for good droplet distribution when spraying into the fluidized bed while drying. If the pH of the solution is not from the outset in the acidic range, by adding acids compatible with the system, in particular by adding sulfuric acid and / or citric acid, it is brought to acidic values, in particular to values in the pH range from 4 to 4.4 , set. It is preferred that, based on the granules to be coated, so much of the aqueous solution is sprayed on that the coating makes up 1% by weight to 25% by weight, in particular 2% by weight to 15% by weight.

The granules can then be discharged from the fluidized bed in a manner known in principle and, if appropriate, massaged according to the particle size, wherein, as stated above, undesirably small particles (fine particles) and undesirably large particles (coarse particles) can optionally be returned to a granulation process after a grinding step. In a special embodiment of the process according to the invention, the classified good grain can be introduced again into a fluidized-bed apparatus and sprayed onto the hardening and coating solution in order to further improve the product properties of the granulate if necessary.

A granulate encased by the process according to the invention is stable in storage, has good free-flowing properties and is sufficiently stable to be able to be mixed in a customary manner with other particulate constituents of washing or cleaning agents. Coated granules obtainable by the process according to the invention are used in particular particulate washing or cleaning agents, preferably in amounts such that these agents have contents of 0.1% by weight to 10% by weight, in particular 0.2% by weight. up to 7% by weight of bleach activator according to formula (I).

Examples

example 1

In a fluidized bed apparatus (Glatt® AGT 400 with a diameter of 40 cm) at 400 m ³ / h supply air flow, a supply air temperature of 95 ° C and an exhaust air temperature of 55 ° C from a homogeneous aqueous solution of trimethylammonium acetonitrile methosulfate and Na-cumolsulfonate (mass ratio 1: 1, dry matter content 30%) with a throughput of the solution of 3 kg / h within 5 h, a granulate which was still very sticky. The stickiness could be eliminated by repeated granulation with a 20% aqueous solution of polymeric polycarboxylate (Sokalan® CP45, manufacturer BASF) under the same conditions with regard to the supply air flow, supply air temperature and exhaust air temperature. The polymer content in the granules thus obtained was 5% by weight. The grain size of the granules was in the range from 0.4 mm to 2.0 mm, the bulk density was 700 g / 1. The granules were then sieved and the portion with particle sizes of between 0.8 and 1.6 mm was mixed with the other detergent components of a detergent formulation. The finished detergent could be used without clumping.

Example 2

In a fluidized bed apparatus with a diameter of 1.8 m (Glatt® AGT 1800), primary granules were produced from a 40% strength aqueous solution of the cationic nitrile used in Example 1 while being powdered with Na-cumene sulfonate powder. The supply air volume was 21000 mVh, the supply air temperature was 145 ° C. The exhaust air temperature was set to 65 ° C by water evaporation of the solution. After 1 h the fluidized bed operated in batch was so full that the granulation was ended. The solidification was carried out with the 20% polymer solution used in Example 1 at a supply air temperature of 110 ° C. The polymer content in the finished granulate was 10% by weight. The granules obtained were sieved between 0.8 and 1.6 mm. The bulk density was 730 g / 1. The finished granulate was processed into a particulate detergent using conventional particulate detergent components.

Example 3

In a fluidized bed apparatus with a diameter of 1.8 m (Glatt® AGT 1800), primary granules were produced from a 40% strength aqueous solution of the cationic nitrile used in Example 1 with powdering with silica powder (Thixosil® 38A). The supply air volume was 20,000 m ³ / h, the supply air temperature was 140 ° C. The exhaust air temperature was set to 65 ° C by water evaporation of the solution. After 1 h the fluidized bed operated in batch was so full that the granulation was ended. The solidification was carried out with the 20% polymer solution used in Example 1 at a supply air temperature of 110 ° C. The polymer content in the finished granulate was 7% by weight. The granules obtained were sieved between 0.8 and 1.6 mm. The bulk density was 710 g / 1.

Example 4

The granules obtained according to Example 2 were again introduced into the fluidized bed apparatus and sprayed from the side with the 20% polymer solution already used at 130 ° C. supply air temperature and 65 ° C. exhaust air, so that a 20 percent by weight coating was produced. Likewise, the granules obtained according to Example 3 were again introduced into the fluidized bed apparatus and sprinkled with the 20% polymer solution from the side at 130 ° C. supply air temperature and 65 ° C. exhaust air, so that a 10 percent by weight coating was produced.

Example 5

In a fluidized bed apparatus with a diameter of 15 cm (Glatt® AGT 1800), granules containing trimethylammonium acetonitrile methosulfate were sprayed with the polymer solution used in Example 1 using two-component nozzles arranged below. The supply air volume was 100 m ³ / h, the supply air temperature was 120 ° C and the exhaust air temperature 60 ° C. The two-component nozzles were operated with warm air at 75 ° C; the air factor of the nozzles was 1.5 (kg air / kg solution). The share of

The coating layer on the finished granulate was 10% by weight. A complete coating layer was visible under the milcroscope. The granules obtained consisted of

Particles with diameters in the range from 0.8 mm to 2.0 mm and had a bulk density of 750 g / 1.

Claims

claims

1. A process for the preparation of a coated particulate preparation comprising a compound of the formula (I),

R ¹

R ² -N ⁽⁺⁾ - (CR ⁴ R ⁵ ) -CN X ^Θ (I)

I

R ³ in the R ^{1 represents} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-2 alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br , -OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a C _1-24 alkyl group, or for a substituted alkyl or alkenylaryl radical with a

and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH, -CH ₂ -CH ₃ , -CH ₂ -CH ₂ - CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H with n = 1, 2, 3, 4, 5 or 6, R ⁴ and R ⁵ independently of one another have the meaning given above for R ¹ , R ² or R ³ and X is a charge-balancing anion, characterized in that the bleach activator according to formula (I) is present in solid, in particular powdery form, if desired in admixture with binder and / or solid filler or as prefabricated granules, with simultaneous drying in a fluidized bed apparatus, sprayed with an acidic aqueous solution which contains polymeric polycarboxylate and / or phosphonic acid or alkali metal phosphonate as the coating and solidifying agent.

2. The method according to claim 1, characterized in that the pH of the aqueous solution is adjusted to acidic values by adding sulfuric acid and / or citric acid.

3. The method according to claim 1 or 2, characterized in that the aqueous solution has a pH in the range from 4 to 4.4.

4. The method according to any one of claims 1 to 3, characterized in that - based on the granules to be coated - sprayed so much of the aqueous solution that the coating 1 wt .-% to 25 wt .-%, in particular 2 wt .-% % to 15% by weight.

5. The method according to any one of claims 1 to 4, characterized in that a polymerizing product of acrylic acid, methacrylic acid or maleic acid or a copolymer of at least two of these and / or phosphonic acid or alkali metal phosphonate is used as the coating and solidifying agent.

6. The method according to any one of claims 1 to 5, characterized in that one uses a compound according to formula 1, in which R ¹ , R ² and R ^{3 are the} same and in particular are methyl groups.

7. The method according to any one of claims 1 to 6, characterized in that one uses a compound according to formula I in which the anion X ^" halide such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate , Metaphosphate, hexafluorophosphate, carbonate, bicarbonate, sulfate, hydrogen sulfate, C _{1-2ö alkyl} sulfate, C _{1- 0} alkyl sulfonate, optionally C _1-18 alkyl substituted aryl sulfonate, chlorate, perchlorate and / or an anion of C _1-24 - Carboxylic acid such as formate, acetate, laurate, benzoate or citrate, alone or in any mixtures.

8. The method according to claim 7, characterized in that one uses a compound according to formula I, in which the anion X ^" chloride, sulfate, hydrogen sulfate, methosulfate ethosulfate, C _12/18 -, C _{12 /} ιe- or C _13/15 Alkyl sulfate, lauryl sulfate, dodecyl benzenesulfonate, toluenesulfonate, cumene sulfonate, xylene sulfonate or mixtures thereof.

9. The method according to any one of claims 1 to 8, characterized in that the coated particulate preparation has an average particle diameter in the range from 0.2 mm to 2.5 mm, in particular in the range from 0.4 mm to 2.0 mm.

10. The method according to any one of claims 1 to 9, characterized in that the bulk density of the coated particulate preparation is in the range from 300 g / 1 to 1000 g / 1, in particular in the range from 400 g / 1 to 800 g / 1.

11. The method according to any one of claims 1 to 10, characterized in that the proportion of compound of formula (I) in the coated particulate preparation in the range of 10 wt .-% to 90 wt .-%, in particular 15 wt .-% % to 50 wt .-% is.

12. Use of the coated particulate preparation, obtainable by the process according to one of claims 1 to 11, for the production of particulate detergents or cleaning agents.