WO2004055150A1 - Fine particulate agent - Google Patents

Abstract

The invention relates to a fine particulate agent with a significantly improved solubility and a negligible propensity to create dust of 1 %, having a low maximum apparent density of 450 g/l. The surfactant content of said agent represents between 5 and 25 wt. %, in relation to the total weight of the agent. 8 g agent dissolved in 500 ml water with a hardness of 16° dH, at a water temperature of 22° C and a solvency time of 30 seconds produces a dissolved agent fraction of at least 63 wt. % and/or at least 62 wt. % at a water temperature of 10°, after filtration by means of a tinplate-strip filter circle with a pore size of 6.6 νm. The invention also relates to a method for producing the fine particulate agent.

Description

 Fine particulate agent

The present invention relates to a low-dust, fine particulate agent with high dissolving speed, in particular washing, cleaning or care agents, and a method for their production.

Particulate agents, such as washing, cleaning or care agents, are usually produced by spray drying processes. In the production of powdered detergents, an aqueous slurry "slurry" is formed in a first step. The slurry contains thermally stable detergent ingredients which, under the conditions of spray drying, essentially neither volatilize nor decompose, such as surfactants and builders Pumped slurry into a spray tower and sprayed through nozzles located in the upper part of the spray tower. The slurry is dried by means of rising air at high temperature and the adhering water is evaporated so that the detergent components at the outlet of the tower, where temperatures of 80- Occur as a powder at 120 ° C. Other temperature-labile constituents, such as bleaching agents or fragrances, are then mixed into the powder.

The spray-dried agents thus produced according to the prior art, such as washing, care or cleaning agents, have the disadvantage that these agents have a relatively broad grain spectrum with particle sizes up to above 1000 μm, while at the same time there are also dust components with particle sizes below 100 μm , The coarser particles can result from agglomeration of the primary particles. They can be identified microscopically as particles with raspberry-like structures. Dust components are not desirable for the known reasons. However, spray-drying products usually not only have a very non-uniform grain spectrum, the bulk density also depends to a large extent on the grain spectrum. By changing the spray drying conditions and the contents of the compositions to be spray dried, bulk densities of 600 g / l could be obtained over the years, whereby higher bulk weights could also be achieved by post-treatment of the direct spray drying products either with liquid components such as nonionic surfactants or by further agglomeration and compression , By sieving the coarser particles, finely divided detergents or cleaning agents, which may also have dust, are available, which have a bulk density of well above 600 g / 1, even 700 g / 1 and more, even without aftertreatment.

Devices for spray drying water-containing compositions are known from the prior art. Frequently used devices are, for example, spray towers with atomizing nozzles, which are used in particular in the case of liquid starting materials, such as solutions, suspensions or melts, to provide a powdery product. The aqueous liquid is usually atomized with pressure nozzles and then dried with hot gas in cocurrent or countercurrent. The dry product is then separated by cyclones or filters. If a melt is atomized and solidified in the cold gas, one speaks of a prill tower.

Disk spray towers are further known spray dryers. Like the nozzle towers, these are short-term dryers. They use rotating disks for atomization and are compact compared to the nozzle tower. The advantage of the atomizer disc is its insensitivity to clogging of the "nozzles" and highly variable liquid throughputs.

Spray dryers with an integrated fluidized bed are also known. By installing a fluidized bed at the bottom of the spray tower, the product can be dried and sifted there. The drying gas with the fine dust is drawn off, for example, in the upper part of the tower at the tower head and the fine dust is returned to the tower after separation. Therefore, comparatively sticky and slow-drying educts can also be processed. Easily dispersible agglomerates are obtained as the product, which are larger and therefore usually less dusty than the powders of the nozzle towers and in particular the disk towers.

In a broader sense, the spray dryers also include fluidized bed spray granulators (“agglomeration dryers”) which are used in the production of granules Serve in the range from 0.3 mm to several mm from atomizable solutions, suspensions and melts. Two-substance nozzles are used for atomization. The product is usually compact and abrasion-resistant and is characterized by a relatively high bulk density. The rate of dissolution is therefore lower compared to other spray drying products. Such a granulator can also be used for coating granules, so-called "coating", in which case it is usually operated discontinuously.

International patent application WO 99/29829 (EP-A1 0 96 90 82) describes fine-particle detergents or cleaning agents with rapid dissolution kinetics and an average particle diameter of 150 to 500 μm, which have a bulk density of at least 500 g / l. In contrast, the subject of the present invention relates to agents with a surfactant content of 5 wt .-% to 25 wt .-%, lower bulk density, less tendency to dust and with improved dissolution kinetics.

The international patent applications WO 00/77148 (EP-A1 1 10 48 03), WO 00/77149 (EP-A1 1 10 48 04), WO 00/77158 (EP-A1 1 10 48 06), WO 00/23560 ( EP-A1 1 04 11 39), WO 98/10052 (EP-A1 0 93 62 69) describe granules as a carrier material for surfactants and detergents. The bulk weights of the agents disclosed in these patent applications make up at least 500 g / l.

Accordingly, the object of the invention was to provide a fine particulate agent with a low bulk density, such as washing, cleaning and / or care agent, with a high dissolving rate and reduced dissolving residue.

The invention in a first embodiment relates to a finely particulate agent, in particular washing, cleaning and / or care agent, wherein

the surfactant content of the composition is 5% by weight to 25% by weight, preferably 10% by weight to 24% by weight, based on the total weight of the composition,

- the bulk density of the agent a maximum of 450 g / l,

- the dust value of the product is less than 1%,

- The dissolved medium proportion, based on 8 g of medium in 500 ml of water with 16 ° dH at a water temperature of 22 ° C and a dissolution time of 30 seconds, after filtering through a round white tape filter with a pore size of 6.6 μm at least 63 wt .-% and / or at least 62% by weight at a water temperature of 10 ° C. The fine particulate agent in the sense of this invention is in particular a direct spray drying product.

In the context of the present invention, a direct spray drying product is understood to mean a product which is obtained by spray drying without further aftertreatment. In particular with regard to the fine particle size of the product, reference is made to the fact that the particle size distributions given relate to the direct spray-drying product. It is particularly advantageous here that the agent according to the invention exhibits a relatively large degree of uniform grain spectrum without the need for further customary aftertreatments known from the prior art, such as crushing and / or screening larger components or screening off dust particles. Such measures always lead to a complexization of the process in large-scale production, which is usually accompanied by a reduction in the product yield and thus an increase in the price of the product.

The fine particulate agent in the sense of this invention can, however, also contain or consist of direct spray-drying products which are subsequently post-treated or mixtures of direct spray-drying product and post-treated spray-drying product.

Although fine particulate agents with a low bulk density usually have poor dissolution kinetics, since the particles are mostly sticky and / or agglomerate into larger particles, it has now been found that the fine particulate composition according to the invention despite a low bulk density of at most 450 g / l, in particular 200 g / 1 to 400 g / l, preferably 210 g / l to 350 g / l and preferably 230 g / l to 320 g / l, has an improved dissolution rate compared to fine particulate agents known in the art with the same bulk density.

The fine particulate agent according to the invention can have primary and secondary particles. Primary particles are particles that do not agglomerate into larger diameter particles during spray drying. In contrast, secondary particles are particles that agglomerate into larger particles as the diameter increases. It has been found that the solubility of the fine particulate agent can be further improved by preventing or reducing agglomeration of the primary particles of the direct spray-drying product, if possible, by appropriate treatment. For example, the direct spray product can be dried very quickly at high temperatures. This measure makes it possible to ensure that there is little or no agglomeration of particles of the direct spray-drying product into secondary particles.

The fine particulate agent according to the invention has at least 50% by weight, preferably at least 70% by weight, preferably at least 80% by weight and further preferably at least 90% by weight of primary particles. The proportion of primary particles in the fine particulate agent according to the invention can make up more than 95% by weight or even more than 99% by weight. The person skilled in the art can determine the proportion of primary particles in a manner known per se by determining the number of sieves for the fine particulate agent.

Without being bound to any particular theory, it is assumed that, among other things, the solubility of the fine particulate agent is increased due to the high proportion of primary particles.

Studies have shown that the fine particulate agent according to the invention has a very high solubility. For example, the dissolved proportion of medium, based on 8 g of fine particulate medium in 500 ml of water with 16 ° dH at a water temperature of 22 ° C and a dissolution time of 30 seconds, after filtration through a round white tape filter with a pore size of 6.6 μm 63% by weight and / or at a water temperature of 10 ° C at least 62% by weight.

In a preferred embodiment of the fine particulate agent, the dissolved agent fraction after 30 seconds at a water temperature of 22 ° C. is at least 68% by weight.

In an even more preferred embodiment of the fine particulate agent, the dissolved agent fraction after 30 seconds at a water temperature of 10 ° C. even amounts to at least 67% by weight. Samples 1 to 8 of the fine particulate agent according to the invention listed below in Tables I to IV are of the same composition, the agent comprising, based on the total weight of the fine particulate agent: 5-25% by weight alkylbenzenesulfate,

- 0 - 10% by weight fatty alcohol C ₁₂ -C ₁₈ + 4.5-7.0 EO, 0 - 7% by weight soaps,

- 0 - 10% by weight of silicate,

10 - 60% by weight sulfate,

0-20% by weight sodium carbonate, the proportions by weight of the respective components being chosen so that the total weight of the fine particulate agent does not exceed 100% by weight.

In Table I, for a fine particulate agent not post-treated according to the invention, depending on the spray temperature and atomization pressure, the residues and the dissolved fraction for the respective samples 1 to 8, for a dissolving time of 30 seconds of 8 g agent in 500 ml city water with 16 ° dH (+/- 2 ° dH) and a water temperature of 22 ° C.

Table I

In Table II, depending on the spray temperature and the atomization pressure for an inventive, non-aftertreated, fine particulate agent, the residues for the respective samples 1 to 8, for a dissolving time of 30 seconds, of 8 g agent in 500 ml city water at 16 ° dH (+/- 2 ° dH) and a water temperature of 10 ° C. Table II

Determination of solubility

The solubility for samples 1 to 8 of Tables I and II was determined as follows:

In a 2 liter beaker, 500 ml of city water with 16 ° dH (+/- 2 ° dH) was placed, which had previously been heated to 22 ° C or 10 ° C. Then the propeller stirring head of a laboratory stirrer, approximately 1.5 cm from the beaker bottom, was inserted in the center. The agitator motor was now switched on and set to 800 rpm (+/- 10 rpm). With a constant stirring rate, 8 g of the fine particulate agent to be examined were then placed in water and stirred for 30 seconds. After the time had elapsed, the stirrer was switched off, removed and rinsed briefly with a little city water. A tared MN 640 m round ribbon filter from Macherey-Nagel GmbH & Co. KG with a diameter of 11 cm and a pore size of 6.6 micrometers was then inserted into a porcelain filter chute. The slightly cloudy solution of the fine particulate agent to be examined was then sucked off with the aid of a 1 L suction bottle over the round white tape filter. After filtering the entire solution, the suction filter was sucked dry, carefully removed from the suction filter and dried at 120 ° C. to constant mass in the drying cabinet. By weighing the dry and cooled filter, the mass of the undissolved residue could then be determined. It was also observed that the dissolving speed and the dissolving residue of the fine particulate agent according to the invention could be further improved by setting a certain particle size distribution as a function of the spray temperature and the spray pressure.

In a preferred embodiment, at least 80% by weight, preferably at least 90% by weight, and preferably at least 95% by weight, of the particles of the fine particulate agent, based on the total weight of the fine particulate agent, have a particle diameter of 0.8 mm - 0.1 mm and preferably with a particle diameter of 0.6 mm - 0.2 mm.

In a further preferred embodiment of the fine particulate agent:

0 to 5% by weight, preferably more than 0% by weight, of the particles having a particle diameter of <0.1 mm,

5 to 40% by weight of the particles have a particle diameter of <0.2 mm to 0.1 mm,

20 to 55% by weight of the particles have a particle diameter of <0.4 mm to 0.2 mm,

20 to 70% by weight of the particles have a particle diameter of <0.8 mm to 0.4 mm,

3 to 20% by weight of the particles have a particle diameter of <1.6 mm to 0.8 mm; and

0 to 5% by weight, preferably more than 0% by weight, of the particles have a particle diameter of at least 1.6 mm or> 1.6 mm.

According to a further embodiment of the fine particulate agent:

0.5 to 3% by weight of the particles have a particle diameter of <0.1 mm,

4 to 20% by weight of the particles a particle diameter of <0.2 mm to 0.1 mm,

25 to 50% by weight of the particles have a particle diameter of <0.4 mm to 0.2 mm,

30 to 50% by weight of the particles have a particle diameter of <0.8 mm to 0.4 mm,

6 to 15% by weight of the particles have a particle diameter of <1.6 mm to 0.8 mm; and

0 to 2% by weight, preferably more than 0% by weight, of the particles have a particle diameter of at least 1.6 mm or> 1.6 mm.

According to another embodiment of the fine particulate agent:

1 to 2% by weight of the particles have a particle diameter of <0.1 mm,

8 to 18% by weight of the particles have a particle diameter of <0.2 mm to 0.1 mm,

30 to 47% by weight of the particles have a particle diameter of <0.4 mm to 0.2 mm,

33 to 45% by weight of the particles have a particle diameter of <0.8 mm to 0.4 mm,

5 to 10% by weight of the particles have a particle diameter of <1.6 mm to 0.8 mm, and 0 to 0.5% by weight, preferably more than 0% by weight, of the particles have a particle diameter of at least 1.6 mm or> 1.6 mm.

The particle diameters of the particles of the fine particulate agent were determined using sieve numbers. Here the particle diameter can be determined based on the sieve sizes used for the respective sieve residue.

It was also found that, in a preferred embodiment of the present invention, the particles of the fine particulate agent can have an internal cavity, the cavity preferably having a diameter of at least 50 μm and at most 150 μm, preferably of at least 70 μm and particularly preferably of at least 100 μm.

In addition, such particles of the fine particulate agent can have an outer particle shell with a wall thickness of at least 5 μm and at most 40 μm, preferably at most 30 μm and preferably at most 20 μm.

Due to the particle cavity and the small particle wall thickness, the dissolution rate of the fine particulate agent can be increased even further.

In light microscopic examinations of the fine particulate agent according to the invention, it was found that the particles of the fine particulate agent have an essentially smooth surface. The term "substantially" as used in the present specification means that at least 50% of the outer particle surface is smooth.

The term smooth in the sense of this invention means that the outer particle surface appears to the viewer as a smooth, non-rough surface when magnified 200 times by light microscopy.

In preferred embodiments, at least 10% by weight, in particular at least 30% by weight, preferably at least 50% by weight, preferably at least 70% by weight and more preferably at least 90% by weight, of the particles of the fine particulate agent a 200-fold magnification under light microscopy, an essentially smooth surface. It was also found that the proportion of primary particles with an essentially smooth outer surface is often greater than that of secondary particles.

Surprisingly, the content of particles with an essentially smooth particle surface has no adverse effect on the dust value of the fine particulate agent. The fine particulate agent according to the invention thus has a low dust value.

Due to the low dust level, contacting of the user with the agent, in particular when adding detergent to the washing machine, can be significantly reduced or even avoided. Reduced dustiness is also of particular importance for the manufacture of finished products and in connection with the portioning, storage and transport of such products. Measurements have shown that the dust value of the fine particulate agent is usually 0%, in particular> 0% and at most 0.5%, preferably at most 0.1% and preferably at most 0.06%.

In the context of the present invention, dust is understood to mean particles with a particle size of 10 to 100 μm (according to Vauck, Müller, Basic Operations in Chemical Process Engineering, DVG, Stuttgart 2000).

Principle of dust value determination

50 g of the fine particulate agent were applied to a shaking trough, the frequency of the shaking trough being 50 Hz and the opening gap being set so that the agent had passed through the shaking trough in 1 minute so that the agent passed through the funnel and the filler tube into the cylinder falls and collects in the vessel while the dust collects on the bottom plate outside of this vessel. Any remaining remains in the funnel were transferred into the cylinder by carefully tapping the funnel into the cylinder. After a settling time of 2 minutes, the dust deposited on the polished base plate was transferred to a weighing pan with a spatula and weighed out.

The design of the experimental apparatus for determining the dust value was such that fine particulate matter could be dropped into a closed cylinder via a filler tube via a shaking channel and funnel, the drop height, measured 50 cm from the filler pipe outlet opening to the upper outer base plate. While coarse fractions of the product were collected in a collecting vessel with a height of 10 cm and a diameter of 18 cm located vertically and centrally under the funnel, the fine fractions - dust - were distributed over the entire base plate of the cylinder. After the dust was allowed to sit in the cylinder, the dust was pushed together with a spatula on the base plate of the cylinder, collected in a vessel and weighed.

Measurements have shown that the dust value for samples 1 to 8 of the fine particulate agent is in the range from 0 to 0.06%.

The dust content was given in% based on the weight.

equipment

A laboratory shaker was used, manufacturer AEG type DR 50 220 V, 50 Hz, 0.15 A.

The used iron sheet funnel with a wall thickness of 2 mm had an upper diameter of 15 cm and the diameter of the outlet was 1.8 cm. The length of the funnel tube was 8 cm.

The brass filler tube used with a wall thickness of 1mm had a length of 30 cm and a diameter of 2.5 cm. The immersion depth of the tube in the outer cylinder was 20 cm. The immersion depth of the tube is kept constant by a brass disc with a diameter of 15 cm and a thickness of 1mm, which is soldered to the outer wall of the filler tube.

The cylinder used was 70 cm high, 40 cm in diameter, closed at the top, open at the bottom. The cover plate of the cylinder was provided in the middle with a circular opening, about 3 cm in diameter, for receiving the funnel outlet pipe. The lower edge of the cylinder was flared and soldered to remove the sharp edge. The cylinder was made of galvanized sheet steel with a wall thickness of 1 mm. The vessel used had a height of 10 cm and a diameter of 18 cm. The vessel was open at the top and closed at the bottom. The lower edge of the vessel was flared and soldered out to remove the sharp edge. The vessel was made of galvanized sheet steel with a wall thickness of 1 mm.

The base plate made of bare aluminum with a thickness of 1 mm had a round shape with a diameter of 48 cm.

The iron spatula used with a thickness of 2 mm had a working surface width of 11 cm.

The analytical balance used had an accuracy of 0.01 g.

A laboratory weighing dish was used to determine the weight of the dust content.

It has also been shown that fine particulate agents with a high n-octane oil number have good solubility. The oil number can be used as a measure of the porosity of the particles of the fine particulate agent. It is easy to understand that pores promote the penetration of water into the interior of the particle, which is associated with improved dissolution kinetics. Accordingly, preferred fine particulate agents according to the invention, preferably comprising direct spray-drying product particles and / or post-treated direct spray-drying product particles, have an n-octane number of at least 140 ml / 100g, in particular 180 ml / 100g to 340 ml / 100g, preferably 200 ml / 100g to 320 ml / 100g, preferably from 220 ml / 100g to 300 ml / 100g, a very good solubility.

Table III below shows the oil number for the above-mentioned samples 1 to 8, depending on the spray temperature and the atomization pressure. Table III

Determination of the oil number

According to DIN ISO 787/5 oil were determined numbers for samples 1 to 8 of the same composition of the fine particulate material of the invention by 0.5 g each fine particulate means of Samples 1 to 8 einwog a rectangular glass plate, and ^'from a 50 ml burette then added dropwise n-octane to the fine particulate agent. During the addition of the octane, powder and liquid were mixed thoroughly with a spatula. As soon as the sample stopped absorbing liquid and a soft paste had formed, the metering in of octane was stopped and the respective octane consumption was read off from the burette. A duplicate determination was carried out for each sample, the respective oil number indicating the mean value determined.

It has also been found that fine particulate matter with a high proportion of primary particles can improve solubility. In a preferred embodiment, the fine particulate agent is based on at least 30% by weight, in particular at least 50% by weight, preferably at least 70% by weight, preferably at least 80% by weight and further preferably at least 90% by weight of primary particles , based on the total weight of the fine particulate agent.

The proportion of secondary particles of the fine particulate agent should preferably be at most 70% by weight, in particular at most 50% by weight, preferably at most 30% by weight account for a maximum of 20% by weight and more preferably a maximum of 10% by weight, based on the total weight of the fine particulate agent.

The finely particulate agent, in particular the particles of the direct spray-drying product and / or the post-treated direct spray-drying product, can have at least one, preferably several components, selected from the group comprising anionic surfactants, cationic surfactants, amphoteric as washing, care and / or cleaning agents Surfactants, non-ionic surfactants, builder substances, bleaching agents, bleach activators, bleach stabilizers, bleaching catalysts, enzymes, polymers, cobuilders, alkalizing agents, acidifying agents, anti-redeposition agents, silver preservatives, colorants, optical brighteners, UV protective substances, fabric softeners, perfumes and perfumers, or foam inhibitors, foam inhibitors. and, if appropriate, further admixed components.

The particles of the direct spray drying product can be aftertreated with at least one component, the amount of component preferably making up up to 15% by weight, in particular 2 to 15% by weight, in each case based on the total weight of the agent containing the aftertreated particles.

Such fine particulate agents, such as detergents, cleaning agents and / or care agents, can contain inorganic and, if appropriate, organic builder substances and, if appropriate, further conventional ingredients, in which the inorganic constituents present are in particular water-soluble.

Fine particulate agents which can be produced according to the invention, in particular washing and cleaning agents, preferably have surfactants, inorganic and optionally organic builder substances and, if appropriate, further conventional ingredients, the inorganic constituents present preferably being water-soluble.

The finely particulate agent and / or finished product produced according to the invention have at least one, preferably several components, selected from the group comprising, as washing, care and / or cleaning active substances, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, builder substances, bleaching agents, Bleach activators, bleach stabilizers, bleach catalysts, enzymes, polymers, cobuilders, alkalizing agents, acidifying agents, anti-redeposition agents, silver preservatives, colorants, optical brighteners, UV protection Substances, fabric softener and / or rinse aid, as well as any other ingredients that may be added.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C ₉ . _13- Alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates such as are obtained, for example, from C ₁₂ . ₁₈ -monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration. Alkanesulfonates which are derived from C ₁₂ are also suitable. ₁₈ -alkanes can be obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

The alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-alkyl sulfates can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 mol of ethylene oxide. ₂₁ alcohols, such as 2-methyl-branched C ₉ . _ιr alcohols with on average 3.5 mol ethylene oxide (EO) or C _12-18 fatty alcohols with 1 to 4 EO, are also suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _{8-0 8} fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

The content of the anionic surfactants mentioned in the direct spray-drying products is preferably 2 to 30% by weight and in particular 5 to 25% by weight, concentrations above 10% by weight and even above 15% by weight being particularly preferred ,

In addition to the anionic surfactants mentioned, soaps can be included. Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. The content of soap in the direct spray-drying products is preferably not more than 3% by weight and in particular 0.5 to 2.5% by weight.

The anionic surfactants and soaps can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. They are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts. Anionic surfactants and soaps can also be produced in situ by introducing the anionic surfactant acids and optionally fatty acids into the spray-dried composition, which are then neutralized by the alkali carriers in the spray-dried composition. Nonionic surfactants are usually only present in minor quantities in direct spray-dried products, if at all. For example, their content can be up to 2 or 3% by weight. For a more detailed description of the nonionic surfactants, reference is made to the description of the aftertreated spray drying products below.

Cationic surfactants

The cleaning and washing agents according to the invention can optionally also contain cationic surfactants. Suitable cationic surfactants are, for example, surface-active quaternary compounds, in particular with an ammonium, sulfonium, phosphonium, iodonium or arsonium group, as described, for example, by KH Wallhäußer in "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Industrial Hygiene" (5th ed. - Stuttgart; New York: Thieme, 1995) as antimicrobial agents By using quaternary surface-active compounds with an antimicrobial effect, the agent can be designed with an antimicrobial effect or its antimicrobial effect which may already be present due to other ingredients can be improved.

Particularly preferred cationic surfactants are the quaternary, partly antimicrobial ammonium compounds (QAV; INCI Quaternary Ammonium Compounds) according to the general formula (R ¹ ) (R ¹¹ ) (R ^III ) (R ^IV ) N ⁺ X ^~ , in which R ¹ to R ^{ι the} same or different Cι_ ₂₂ alkyl radicals, C ₇ . ₂₈ aralkyl radicals or heterocyclic radicals, where two or, in the case of an aromatic integration, such as in pyridine, even three radicals together with the nitrogen atom form the heterocycle, for example a pyridinium or imidazolinium compound, and X ^"are halide ions, sulfate ions, hydroxide ions or similar anions For an optimal antimicrobial effect, at least one of the residues preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.

QAV can be prepared by reacting tertiary amines with alkylating agents such as methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide. The alkylation of tertiary amines with a long alkyl radical and two methyl groups is particularly easy, and the quaternization of tertiary amines with two long radicals and one methyl group can also be carried out using methyl chloride under mild conditions. Amines that have three long alkyl residues or substituted alkyl radicals are not very reactive and are preferably quaternized with dimethyl sulfate.

Suitable QAC are, for example, benzalkonium chloride (N-alkyl-N, N-dimethyl-benzylammonium chloride, CAS No. 8001-54-5), benzalkon B (mp-dichlorobenzyldimethyl-C ₁₂ -alkylammonium chloride, CAS No. 58390-78 -6), benzoxonium chloride (benzyl dodecyl bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl ammonium bromide, CAS No. 57-09-0), benzetonium chloride (N, N -Dimethyl-N- [2- [2- [p- (1, 1, 3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS No. 121-54-0), dialkyldimethylammonium chlorides such as di-n- decyl-dimethyl-ammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyl-dimethyl-ammoniumchloric, 1-cetylpyridinium chloride (CAS No. 123-03-5) and Thiazoline iodide (CAS No. 15764-48-1) and mixtures thereof. Preferred QACs are the benzalkonium chlorides with C ₈ -C ₁₈ -alkyl radicals, in particular C ₁₂ -C ₁₄ -alkyl-benzyl-dimethyl-ammonium chloride. A particularly preferred QAV cocospentaethoxymethylammonium methosulfate (INCI PEG-5 Coco onium methosulfate; Rewoquat ^® CPEM).

To avoid possible incompatibilities of the antimicrobial cationic surfactants with the anionic surfactants contained according to the invention, anionic surfactant-compatible and / or as little cationic surfactant as possible is used or, in a particular embodiment of the invention, no cationic surfactants with an antimicrobial effect are used entirely. Parabens, benzoic acid and / or benzoate, lactic acid and / or lactates can be used as antimicrobial substances. Benzoic acid and / or lactic acid are particularly preferred.

The cleaning and washing agents according to the invention can contain one or more cationic surfactants in amounts, based on the total composition, of 0 to 5% by weight, greater than 0 to 5% by weight, preferably 0.01 to 3% by weight, in particular Contain 0.1 to 1 wt .-%.

Amphoteric surfactants

The cleaning and washing agents according to the invention can also contain amphoteric surfactants. Suitable amphoteric surfactants are, for example, betaines of the formula (R ¹ ) (R ² ) (R ³ ) N ⁺ CH ₂ CO ^~ in which R ^{1 is} an alkyl radical with 8 to 25, preferably 10 to 21, carbon atoms which is optionally interrupted by heteroatoms or heteroatom groups and R ² and R ^{3 are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₂₂ alkyldimethylcarboxymethylbetaine and Cn-C ₁₇ - alkylamidopropyldimethylcarboxymethylbetaine. Furthermore, the use of Alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids or biosurfactants are conceivable as amphoteric surfactants in the cleaning and washing agents according to the invention.

The cleaning and washing agents according to the invention can contain one or more amphoteric surfactants in amounts, based on the total composition, of 0 to

5% by weight, greater than 0 to 5% by weight, preferably 0.01 to 3% by weight, in particular 0.1 to 1% by weight.

Other ingredients of the direct spray drying product can be inorganic and optionally organic builder substances. The inorganic builder substances also include non-water-insoluble ingredients such as aluminosilicates and in particular zeolites. The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, for example, zeolite MAP ^(R) (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Of particular interest is also a cocrystallized sodium / potassium aluminum silicate made of zeolite A and zeolite X, which as VEGOBOND AX ^® (commercial product from Condea Augusta SpA) im Trade is available. This product is described in more detail below. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its production. In the event that the zeolite is used as a suspension, it can contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Zeolites of the faujasite type can be mentioned as further particularly suitable zeolites. Together with the zeolites X and Y, the mineral faujasite belongs to the faujasite types within the zeolite structure group 4, which are characterized by the double six-ring subunit D6R (compare Donald W. Breck: "Zeolite Molecular Sieves", John Wiley

6 Sons, New York, London, Sydney, Toronto, 1974, page 92). The zeolite structure group 4 includes the minerals chabazite and gmelinite in addition to the faujasite types mentioned as well as the synthetic zeolites R (chabazite type), S (gmelinite type), L and ZK-5. The latter two synthetic zeolites have no mineral analogues.

Faujasite-type zeolites are made up of ß-cages which are tetrahedrally linked via D6R subunits, the ß-cages being arranged similarly to the carbon atoms in the diamond. The three-dimensional network of the zeolites of the faujasite type suitable according to the invention has pores of 2.2 and 7.4 A, the unit cell also contains 8 cavities with a diameter of approximately 13 A and can be determined using the formula Na ₈₆ [(AIO ₂ ) ₈₆ (SiO ₂ ) ₁₀ 6] '264 H ₂ O describe. The network of zeolite X contains a void volume of approximately 50%, based on the dehydrated crystal, which represents the largest empty space of all known zeolites (zeolite Y: approx. 48% void volume, faujasite: approx. 47% void volume). (All data from: Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, pages 145, 176, 177).

In the context of the present invention, the term “zeolite of the faujasite type” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4. In addition to the zeolite X, zeolite Y and faujasite and mixtures of these compounds are also suitable according to the invention, where the pure zeolite X is preferred.

Mixtures or cocrystallizates of faujasite-type zeolites with other zeolites which do not necessarily have to belong to structure group 4 of the zeolite are also suitable according to the invention, preferably at least 50% by weight of the zeolites being faujasite-type zeolites.

The suitable aluminum silicates are commercially available and the methods for their preparation are described in standard monographs.

Examples of commercially available X-type zeolites can be described by the following formulas:

Na ₈₆ [(AIO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] ^• x H ₂ O, K ₈₆ [(AIO ₂ ) ₈ 6 (SiO ₂ ) ₁₀ 6] ^■ x H ₂ O, Ca ₄₀ Na ₆ [(AIO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] ^• x H ₂ O, Sr ₂₁ Ba ₂₂ [(AIO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] ^' x H ₂ O, in which x can have values greater than 0 to 276. These zeolites have pore sizes of 8.0 to 8.4 A.

Also suitable, for example, is the zeolite A-LSX described in European patent application EP-A-816 291, which corresponds to a co-crystallizate of zeolite X and zeolite A and, in its anhydrous form, has the formula (M _{2 n} O + M ' _{2 / π} O) -AI ₂ O ₃ -zSiO, where M and M 'can be alkali or alkaline earth metals and z is a number from 2.1 to 2.6. This product is commercially available under the brand name VEGOBOND AX from CONDEA Augusta SpA

Y-type zeolites are also commercially available and can be expressed, for example, by the formulas

Na ₅₆ [(AIO ₂ ) ₅ 6 (SiO ₂ ) ₁₃ 6] ^■ x H ₂ O, K ₅ 6 [(AIO ₂ ) ₅₆ (SiO ₂ ) ₁₃ 6] ^■ x H ₂ O,

in which x stands for numbers greater than 0 to 276. These zeolites have pore sizes of 8.0 A.

The particle sizes of the suitable zeolites of the faujasite type are in the range from 0.1 μm to 100 μm, preferably from 0.5 μm to 50 μm and in particular from 1 μm to 30 μm, each measured using standard particle size determination methods.

In another basic embodiment of the invention, however, the inorganic constituents contained are said to be water-soluble. In these embodiments, builders other than the zeolites mentioned are therefore used.

In cases where a phosphate content is tolerated, phosphates can also be used, in particular pentasodium triphosphate, optionally also pyrophosphates and orthophosphates, which act primarily as precipitants for lime salts. Phosphates are mainly used in machine dishwashing detergents, but sometimes also in detergents.

Alkali metal phosphates is the general term for the alkali metal (in particular sodium and potassium) salts of the various phosphoric acids, in which metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PÖ in addition to higher molecular weight laren representatives can distinguish. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 like ^"3 , melting point 60 °) and as a monohydrate (density 2.04 like ^{" 3} ). Both salts are white, water-soluble powders that lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 ^"3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO, is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly ^"3 , water loss at 95 °), 7 mol. (Density 1, 68 gladly ^{" 3} , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1, 52 like ^"3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na P ₂ O ₇ when heated more. Disodium hydrogenphosphate is used by neutralizing phosphoric acid with soda solution produced by phenolphthalein as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals that like a dodecahydrate a density of 1.62 ^"3 and a melting point of 73-76 ° C (decomposition), as a decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C. and, in anhydrous form (corresponding to 39-40% P ₂ O ₅ ), a density of 2.536 ^{″ 3} . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or three-base potassium phosphate), K ₃ PO, is a white, deliquescent, granular powder with a density of 2.56 ^"3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It occurs, for example, when heated of Thomas slag with coal and potassium sulfate At a higher price, the more soluble, therefore highly effective potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na P ₂ O ₇ , exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also given 880 °) and as decahydrate (density 1, 815-1, 836 like ^{" 3} , melting point 94 ° with water loss). Both substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), KP ₂ O _7, exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^"-3, which is soluble in water, the pH of the 1% solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. About 17 g of the salt of water free of water of crystallization dissolve in 100 g of water at room temperature, about 20 g at 60 ° and around 32 g at 100 °; after heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O) ^" . The potassium polyphosphates are found in Detergent and cleaning agent industry wide Use. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH ^• »Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

According to the invention, these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

In a preferred embodiment of the invention, however, in particular carbonates and silicates are used as inorganic builder substances.

Crystalline, layered sodium silicates of the general formula are to be mentioned here

NaMSi _x O _{2x + 1} -yH ₂ O, where M is sodium or hydrogen, x is a number from 1.6 to 4, preferably 1.9 to 4.0 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. However, since such crystalline silicates at least partially lose their crystalline structure in a spray drying process, crystalline silicates are preferably subsequently mixed into the direct or aftertreated spray drying product. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate

Na ₂ Si ₂ O ₅ yH ₂ O is preferred. Such compounds are commercially available, for example, under the name ^SKS® (from Clariant). SKS-6 ^{® is} primarily a δ-sodium disilicate with the formula Na ₂ Si ₂ O ₅ yH ₂ O, and SKS-7 ^{® is} predominantly ß-sodium disilicate. Reaction with acids (eg citric acid or carbonic acid) produces δ-sodium disilicate Kanemit NaHSi ₂ O ₅ yH ₂ O, commercially available under the names SKS-9 ^® and SKS-10 ^® (from Clariant). It can also be advantageous to use chemical modifications of these layered silicates. For example, the alkalinity of the layered silicates can be suitably influenced. Layered silicates doped with phosphate or carbonate have changed crystal morphologies compared to the δ-sodium disilicate, dissolve faster and show in comparison to δ- Sodium disilicate has an increased calcium binding capacity. Layer silicates of the general empirical formula x Na ₂ O • y SiO ₂ • z P ₂ O _{5 are those} in which the ratio x to y is a number from 0.35 to 0.6 and the ratio x to z is a number from 1.75 to 1200 and the ratio y to z corresponds to a number from 4 to 2800 described in patent application DE-A-196 01 063. The solubility of the layered silicates can also be increased by using particularly finely divided layered silicates. Compounds made from crystalline layered silicates with other ingredients can also be used. Compounds with cellulose derivatives which have advantages in their disintegrating action and compounds with polycarboxylates, for example citric acid, or polymeric polycarboxylates, for example copolymers of acrylic acid, are to be mentioned in particular.

The preferred builder substances also include amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which have secondary washing properties. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred. The content of the (X-ray) amorphous silicates in the zeolite-free direct spray drying products is preferably 1 to 10% by weight.

However, particularly preferred inorganic water-soluble builders are alkali metal carbonates and alkali metal bicarbonates, sodium and potassium carbonate and in particular sodium carbonate being among the preferred embodiments. The content of the alkali metal carbonates in the zeolite-free direct Spray drying products can vary within a very wide range and is preferably 5 to 40% by weight, in particular 8 to 30% by weight, the content of alkali metal carbonates usually being higher than that of (X-ray) amorphous silicates.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their alkali metal and in particular sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids,

Aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

Polymeric polycarboxylates are also suitable as organic builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol. In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Your relative Molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The content of organic builder substances in the direct spray-drying products can also vary within a wide range. Contents of 2 to 20% by weight are preferred, with contents of at most 10% by weight being particularly well received for reasons of cost.

From the remaining groups of conventional detergent components, components from the classes of graying inhibitors (dirt carriers), neutral salts and textile-softening auxiliaries are particularly suitable for use in the spray drying according to the invention and in particular by means of the device according to the invention.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, preference is given to cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition, used.

Sodium sulfate, mentioned above, is a typical example of a suitable representative of the neutral salts. It can be used in amounts of, for example, 2 to 45% by weight.

Suitable plasticizers are, for example, swellable sheet silicates of the type of corresponding montmorillonites, for example bentonite. The water content in the direct spray drying product is preferably 0 to less than 10% by weight and in particular 0.5 to 8% by weight, values of at most 5% by weight being particularly preferred. The water adhering to any aluminosilicates such as zeolite was not included.

The direct spray drying products according to the invention have an excellent flow behavior.

The particles of the direct spray drying product produced according to the invention can be post-treated, for example by rounding the particles of the direct spray drying product. The direct spray drying product can be rounded in a conventional rounder. The rounding time is preferably not longer than 4 minutes, in particular not longer than 3.5 minutes. Rounding times of at most 1.5 minutes or less are particularly preferred. The rounding further unifies the grain spectrum, since any agglomerates that may have formed are comminuted.

The direct spray drying product produced according to the invention can be rounded off with nonionic surfactants, perfume and / or foam inhibitors or preparation forms which contain these ingredients, preferably in amounts of up to 20% by weight of active substance, in particular in amounts of 2 to 18% by weight. % Of active substance, based in each case on the post-treated product, in a conventional manner, preferably in a mixer or, if appropriate, a fluidized bed.

In particular, the direct spray drying product produced according to the invention can subsequently be treated with solids, preferably in amounts of up to 15% by weight, in particular in amounts of 2 to 15% by weight, in each case based on the total weight of the aftertreated agent.

Solids which can preferably be used are bicarbonate, carbonate, zeolite, silica, citrate, urea or mixtures thereof, in particular in amounts of 2 to 15% by weight, based on the total weight of the aftertreated product. The aftertreatment can advantageously be carried out in a mixer and / or by means of a rounder. In the aftertreatment step it is therefore possible to powder the direct spray-drying product with a solid, for example silicas, zeolites, carbonates, bicarbonates and / or sulfates, citrates, urea or mixtures thereof, as is sufficiently known from the prior art. This can be done either immediately after leaving the direct spray drying product from the tower in a mixer or in the fillet. It is preferred to use solids, in particular bicarbonate and soda, in amounts of up to 15% by weight and in particular in amounts of 2 to 15% by weight, based in each case on the aftertreated product.

In a preferred embodiment of the invention, the direct spray-drying product is aftertreated with nonionic surfactants, which can contain, for example, optical brighteners and / or hydrotropes, perfume, a solution of optical brighteners and / or foam inhibitors or preparation forms which may contain these ingredients. These ingredients or preparation forms which contain these ingredients are preferably applied to the direct spray-drying product in liquid, melted or pasty form. The direct spray drying products are advantageously used with up to 20% by weight. aftertreated advantageously with 2 to 18% by weight and in particular with 5 to 15% by weight of active substance of the ingredients mentioned. The quantities are based on the post-treated product. It is preferred that the aftertreatment with the substances mentioned here is carried out in a conventional mixer, only for example in a 2-shaft mixer within a maximum of 1 minute, preferably within 30 seconds and for example within 20 seconds, the times being given simultaneously for Addition and mixing time is done. It is not surprising to a person skilled in the art that such measures can impair the free-flowing properties of the product.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, palm kernel, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁ - Alcohols with 3 EO or 4 EO, Cg-Cn alcohols with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number from 1 to 10; x is preferably 1.1 to 1.4.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533. C ₁₂ -C ₁₈ fatty acid methyl esters with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO, are particularly preferred.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them. In principle, all surfactants are suitable as surfactants for automatic dishwashing. However, the nonionic surfactants described above, and above all the low-foaming nonionic surfactants, are preferred for this purpose. The alkoxylated alcohols are particularly preferred, especially the ethoxylated and / or propoxylated alcohols. Here, the skilled person generally understands alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the sense of the present invention, the long-chain alcohols (C ₁ 0 -C _18, preferably C ₁₂ to C _16, such as C _ιr, C ₁₂ -, C ₁₃ -, C ₁ - C- _I5 -, C ₁₆ -, C- | ₇ - and C ₁₈ -alcohols). As a rule, a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. A further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. If desired, final etherification with short-chain alkyl groups, such as preferably the butyl group, can also give the class of "closed" alcohol ethoxylates, which can also be used for the purposes of the invention. For the purposes of the present invention, very particularly preferred are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.

Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexyl benzylatepylpionate, allyl cyclohexyl propyl pionate. The ethers include, for example, benzylethyl ether, the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones include, for example, the jonones, oc-isomethylionone and methyl cedryl ketone , the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

Other conceivable additives are foam inhibitors, for example foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane. Mixtures of these active ingredients are also possible. At room temperature and solid additives, particularly in the above-mentioned foam-inhibiting agents, paraffin waxes, silicas, which may have been rendered hydrophobic in a known manner, and of C ₂ - ₇ -diamines and C _{12th 22-} carboxylic acid-derived bisamides in question.

Foam-inhibiting paraffin oils that can be used, which may be present in a mixture with paraffin waxes, are generally complex substance mixtures without a sharp melting point. For characterization, the melting range is usually determined by differential thermal analysis (DTA), as in "The Analyst" 87 (1962), 420, and / or the freezing point. This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling. Paraffins with less than 17 carbon atoms cannot be used according to the invention, their proportion in the paraffin oil mixture should therefore be as low as possible and is preferably below the limit which is significantly measurable with customary analytical methods, for example gas chromatography. Paraffins which solidify in the range from 20 ° C. to 70 ° C. are preferably used. It should be noted that even paraffin wax mixtures that appear solid at room temperature can contain different proportions of liquid paraffin oils. In the paraffin waxes that can be used according to the invention, the liquid content is as high as possible at 40 ° C. without being 100% at this temperature. Preferred paraffin wax mixtures have a liquid fraction of at least 50% by weight, in particular from 55% by weight to 80% by weight, at 40 ° C. and a liquid fraction of at least 90% by weight at 60 ° C. The consequence of this is that the paraffins are flowable and pumpable at temperatures down to at least 70 ° C., preferably down to at least 60 ° C. It is also important to ensure that the paraffins do not contain any volatile components. Preferred paraffin waxes contain less than 1% by weight, in particular less than 0.5% by weight, of parts which can be evaporated at 110 ° C. and normal pressure. Paraffins which can be used according to the invention can be obtained, for example, under the trade names Lunaflex® from Füller and Deawax® from DEA Mineralöl AG. The paraffin oils can contain bisamides which are solid at room temperature and which are derived from saturated fatty acids with 12 to 22, preferably 14 to 18 C atoms and from alkylenediamines with 2 to 7 C atoms. Suitable fatty acids are lauric acid, myristic acid, stearic acid, arachic acid and behenic acid and mixtures thereof, as can be obtained from natural fats or hydrogenated oils, such as tallow or hydrogenated palm oil. Suitable diamines are, for example, ethylenediamine 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine. Preferred diamines are ethylenediamine and hexamethylenediamine. Particularly preferred bisamides are bis-myristoyl-ethylenediamine, bispalmitoyl-ethylenediamine, bis-stearoyl-ethylenediamine and their mixtures and the corresponding derivatives of hexamethylene-diamine.

In some embodiments of the invention, said foam inhibitors can also be included in the direct spray drying product.

In a further embodiment of the invention, the product which has been aftertreated and optionally rounded with the stated ingredients is aftertreated with solids, preferably bicarbonate and / or soda, in particular in amounts of from 2 to 15% by weight, based on the aftertreated product. Here too, the aftertreatment with the solids advantageously takes place in a fillet.

The post-treatment measures rounding, treatment with liquid to pasty and / or solid ingredients with or without rounding show a number of post-treated products with good flow properties.

The agents according to the invention and manufactured according to the invention also have the advantage that they are quickly soluble.

In a further embodiment of the invention, the direct spray-drying products and / or the post-treated products described above can be processed, in particular mixed, with further constituents of washing, care and / or cleaning agents for the production of the finished product, it being advantageous that Components can be added that are not accessible to spray drying. From the broad prior art it is generally known which ingredients of washing or cleaning agents are not accessible to spray drying and which raw materials are usually mixed in. Reference is made to this general literature put referenced. Only high-temperature-sensitive mixture components of detergents or cleaning agents, such as bleaching agents based on per compounds, bleach activators and / or bleaching catalysts, enzymes from the class of proteases, lipases and amylases; or bacterial strains or fungi, foam inhibitors in optionally granular and / or compounded form, perfumes, temperature-sensitive dyes and the like, which are expediently mixed with the previously dried compositions and optionally post-treated products.

UV absorbers, which are absorbed onto the treated textiles and improve the lightfastness of the fibers and / or the lightfastness of other formulation constituents, can also be added subsequently. UV absorbers are understood to mean organic substances (light protection filters) which are able to absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, for example heat. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4- position. Substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid are also suitable. The biphenyl and, above all, stilbene derivatives described, for example in EP 0728749 A and are available as Tinosorb FD ^{® ®} or Tinosorb FR ex Ciba commercially. 3-Benzylidene camphor or 3-benzylidene norcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor, are to be mentioned as UV-B absorbers, as described in EP 0693471 B1; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene); Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomethyl ester; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of

Benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives, such as 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3,5-triazine and Octyl triazone as described in EP 0818450 A1 or dioctyl butamido triazone (Uvasorb® HEB); Propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione; Ketothcyclo (5.2.1.0) decane derivatives, as described in EP 0694521 B1. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-benzylidene camphor, such as 4- (2-oxo-3-bornylidene methyl) benzene sulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.

Derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl-, are particularly suitable as typical UV-A filters. 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds as described in DE 19712033 A1 (BASF). The UV-A and UV-B filters can of course also be used in mixtures. In addition to the soluble substances mentioned, insoluble light-protection pigments, namely finely dispersed, preferably nanoized metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. Silicates (talc), barium sulfate or zinc stearate can be used as salts. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably from 5 to 50 nm and in particular from 15 to 30 nm. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or a shape which differs in some other way from the spherical shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobicized. Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. Micronized zinc oxide is preferably used. Further suitable UV light protection filters can be found in the overview by P.Finkel in SÖFW-Journal 122, 543 (1996). The UV absorbers are usually used in amounts of from 0.01% by weight to 5% by weight, preferably from 0.03% by weight to 1% by weight. In exceptional cases, they can also be contained in the direct spray drying product.

However, other constituents, for example so-called speckles, can also be distinguished from one another by their color and / or their shape from the appearance of the direct and / or post-treated spray-drying products. The speckles can on the one hand have a similar to identical grain spectrum as the direct and / or aftertreated spray drying products and have the same composition but a different color. It is also possible that the speckles have the same composition as the directly and / or aftertreated spray drying products, are not colored, but have a different shape. Ultimately, however, it is preferred that speckles, which have the same composition as the direct and / or aftertreated spray drying products, differ from the latter in color and, if appropriate, additionally in their shape. In these cases, the speckles should only help to make the appearance of the finished washing, care and / or cleaning agents even more attractive.

In a further and entirely preferred embodiment of the invention, however, the speckles have a different chemical composition than the direct and / or aftertreated spray drying products. It is precisely here that, based on a different color and / or a different shape, the end consumer can be advised that certain ingredients for specific purposes, for example bleaching or care aspects, are contained in the end product. These speckles can not only be spherical to rod-shaped, they can also represent completely different figures. At this point, reference is made to the disclosure of international applications WO 97/08290 and WO 00/23556.

The added speckles or other ingredients can be spray-dried, agglomerated, granulated, pelletized or extruded, for example. With regard to extrusion processes, reference is made here in particular to the disclosures in European patent EP 0486592 B1 and international patent application WO 98/12299. Since it is an advantage of the direct and / or post-treated spray drying products that they have an excellent dissolving rate even in relatively cold water of 30 ° C., it is of course preferred to add such additional ingredients and / or raw materials to them, which are also excellent Have dissolving speed. In a preferred embodiment of the invention, therefore, raw materials are mixed in which were produced according to the disclosure of international patent application WO 99/28433.

In another embodiment, the present invention thus relates to a finished product, preferably a finished washing, cleaning and / or care product, that the direct spray-drying product according to the invention and / or post-treated direct spray-drying product, in particular in amounts of 5 to 90% by weight, and contains other admixed ingredients.

In embodiments suitable according to the invention, the finished product has at least 10% by weight and a maximum of 100% by weight, preferably at least 30% by weight, preferably at least 40% by weight, more preferably at least 70% by weight, even more preferably at least 90% by weight and most preferably at least 95% by weight of fine particulate agent, based on the total weight of the finished product.

The finished product preferred according to the invention can, in addition to the fine particulate agent, at least one, preferably several components, selected from the group comprising anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, builder substances, bleaching agents, bleach activators as washing, care and / or cleaning agents Bleach stabilizers

Bleaching catalysts, enzymes, polymers, cobuilders, alkalizing agents, acidifying agents, anti-redeposition agents, silver preservatives, coloring agents, optical brighteners, UV protective substances, fabric softeners, perfumes, foam inhibitors and / or rinse aids, and optionally further admixed components.

The subject matter of the present invention is explained in more detail with reference to Examples 1 to 9 below.

In Table IV, examples 1 to 3 show possible compositions for a fine particulate agent according to the invention based on a direct, non-aftertreated spray drying product. Table IV

% By weight * ¹ = the percentages by weight relate to the total weight of the fine particulate agent

Balance * ² = salts. Zeolite A * ³ = zeolite A 80%, ie water content 20% by weight.

In a preferred embodiment, the finished product can consist of the direct, non-aftertreated spray drying product according to Table IV.

In Table V, examples 4 to 6 show compositions for an inventive fine particulate agent based on a post-treated direct spray-drying product. Table V

% By weight * ¹ = the percentages by weight relate to the total weight of the fine particulate agent

Balance * ² = salts zeolite A * ³ = zeolite A 80%, ie water content 20% by weight.

In a further preferred embodiment, the finished product can consist of the direct aftertreated spray drying product according to Table V.

In Table VI, examples 7 to 9 show compositions for a finished product according to the invention. Table VI

% By weight * ¹ = the percentages by weight relate to the total weight of the

finished product

Balance * ² = salts zeolite A * ³ = zeolite A 80%, ie water content 20% by weight

The present invention according to a further embodiment is a spray drying process for the production of fine particulate, low-dust agents with low bulk density, an average particle diameter of 0.1 mm to 0.8 mm and very high dissolving speed, under atmospheric pressure.

The method according to the invention comprises the steps:

- Generation of an aqueous liquid or pasty slurry, preferably a washing, cleaning and / or care slurry with a surfactant content of 5% by weight to 25% by weight, preferably 10% by weight to 24% by weight , based on the direct spray drying product, Setting the slurry to a temperature of 50 ° C. to 160 ° C., preferably 70 ° C. to 120 ° C., preferably 80 ° C. to 95 ° C.,

Atomization of the slurry formed at an atomization pressure of 30 bar to 90 bar, preferably at an atomization pressure of 40 bar to 80 bar, preferably at an atomization pressure of 50 bar to 70 bar, by means of at least one nozzle into a spray chamber with atmospheric pressure,

- The nozzle (s) has a diameter of at least 1.8 mm and at most 5 mm, preferably at least 2 mm and at most 4 mm and preferably at least 2.3 mm and at most 3 mm, and wherein

- The inlet temperature of the air in the spray chamber has a temperature at which the particles formed to a water content of at most 5.5 wt .-%, preferably 2.5 wt .-% to 4.5 wt .-%, preferably 3 wt .-% to 4 wt .-%, based on the fine particulate agent, are dried to form a fine particulate agent, the fine particulate agent optionally being post-treated.

According to the invention, preference is given to finely particulate agents, comprising particles which are produced at a spray temperature of at least 70 ° C. to a maximum of 170 ° C., preferably at least 75 ° C. to a maximum of 155 ° C., and an atomization pressure of at least 40 bar and a maximum of 70 bar.

In addition to surfactant, the slurry can contain other active substances. Active substances in the sense of this invention comprise components which have a nourishing, washing-active and / or cleaning-active effect.

A liquid or pasty solvent-containing slurry composition in the sense of the present invention can be any expedient solution, dispersion or combination of solution and dispersion of an agent, preferably solid (s), in the slurry, water being preferred as the solvent.

Thus, the pressurized slurry of water can preferably be used as a solvent with a maximum of 55% by weight, preferably a maximum of 45% by weight, further preferably a maximum of 35% by weight and also preferably a maximum of 25% by weight, based on the total weight of the Slurry included. The water content can also make up more than 55% by weight. The pressurized slurry can also be anhydrous, ie it contains no water but only organic liquids or only a small amount of water.

For the purposes of this invention, “anhydrous slurry” means that the water content is at most 10% by weight, based on the total weight of the slurry.

In particular, liquid or pasty aqueous slurry compositions are used in the process according to the invention, which can be subjected to evaporation in a spray dryer under atmospheric pressure.

Spray temperatures of at least 75 ° C. and a maximum of 155 ° C. are preferred according to the invention. Further spray temperatures suitable according to the invention are 80 ° C., 85 ° C., 90 ° C. 95 ° C. and 150 ° C. Spray temperatures of 100 ° C. to 140 ° C., in particular from 110 ° C to 130 ° C, have been found to be advantageous.

The spray pressure or the pressure at which the slurry is sprayed through nozzles should preferably be at least 40 bar and a maximum of 70 bar. If necessary, one can also work at a pressure of 50 bar or 60 bar.

Claims

claims

1. Fine particulate agent, in particular washing, cleaning and / or care agent, characterized in that

the surfactant content of the composition is 5% by weight to 25% by weight, based on the total weight of the composition,

- the bulk density of the agent a maximum of 450 g / l,

- the dust value of the product is less than 1%, and

- The dissolved medium proportion, based on 8 g of medium in 500 ml of water with 16 ° dH at a water temperature of 22 ° C and a dissolving time of 30 seconds, after filtering through a round white tape filter with a pore size of 6.6 μm at least 63 wt .-% and / or at least 62% by weight at a water temperature of 10 ° C.

2. Fine particulate agent according to claim 1, wherein at least 50% of the particles of the agent have an n-octane absorption capacity of at least 140 ml / 100g, in particular from 180 ml / 100g to 340 ml / 100g, preferably from 200 ml / 100g to 320 ml / 100g, preferably from 220 ml / 100g to 300 ml / 100g.

3. Fine particulate agent according to claim 1 or 2, wherein at least 80% by weight, preferably at least 90% by weight, and preferably at least 95% by weight of the particles, based on the total weight of the fine particulate agent, has a particle diameter of 0, 8 mm - 0.1 mm, preferably a particle diameter of 0.6 mm - 0.2 mm.

4. Fine particulate agent according to one of claims 1 to 3, wherein

0 to 5% by weight of the particles a particle diameter of <0.1 mm,

5 to 40% by weight of the particles have a particle diameter of <0.2 mm to 0.1 mm,

20 to 55% by weight of the particles have a particle diameter of <0.4 mm to 0.2 mm,

20 to 70% by weight of the particles have a particle diameter of <0.8 mm to 0.4 mm, - 3 to 20 wt .-% of the particles a particle diameter of <1.6 mm to 0.8 mm, and

- 0 to 5 wt .-% of the particles have a particle diameter of at least 1.6 mm, based on the total weight of the fine particulate agent.

5. Fine particulate agent according to one of claims 1 to 4, wherein

0.5 to 3% by weight of the particles have a particle diameter of <0.1 mm,

4 to 20% by weight of the particles a particle diameter of <0.2 mm to 0.1 mm,

25 to 50% by weight of the particles have a particle diameter of <0.4 mm to 0.2 mm,

30 to 50% by weight of the particles have a particle diameter of <0.8 mm to 0.4 mm,

6 to 15% by weight of the particles have a particle diameter of <1.6 mm to 0.8 mm, and

- 0 to 2 wt .-% of the particles have a particle diameter of at least 1.6 mm, based on the total weight of the fine particulate agent.

6. Fine particulate agent according to one of claims 1 to 5, wherein

1 to 2% by weight of the particles a particle diameter of <0.1 mm,

8 to 18% by weight of the particles have a particle diameter of <0.2 mm to 0.1 mm,

30 to 47% by weight of the particles have a particle diameter of <0.4 mm to 0.2 mm,

33 to 45% by weight of the particles have a particle diameter of <0.8 mm to 0.4 mm,

5 to 10% by weight of the particles have a particle diameter of <1.6 mm to 0.8 mm, and

- 0 to 0.5 wt .-% of the particles have a particle diameter of at least 1.6 mm, based on the total weight of the fine particulate agent.

7. Fine particulate agent according to one of claims 1 to 6, characterized in that the dust value of the agent is 0 to 0.5%, preferably at most 0.1% and preferably at most 0.06%.

8. Fine particulate agent according to one of claims 1 to 7, characterized in that the surfactant content of the agent is 10% by weight to 24% by weight, based on the total weight of the fine particulate agent.

9. Fine particulate agent according to one of claims 1 to 8, characterized in that the dissolved middle portion after 30 seconds at a water temperature of 22 ° C makes up at least 68 wt .-%.

10. Fine particulate agent according to one of claims 1 to 9, characterized in that the dissolved agent portion after 30 seconds at a water temperature of 10 ° C makes up at least 67 wt .-%.

11. Fine particulate agent according to one of claims 1 to 10, characterized in that the agent has a bulk density of 200 g / l to 400 g / l, preferably 210 g / l to 350 g / l and preferably 230 g / l to 320 g / l.

12. Fine particulate agent according to one of claims 1 to 11, characterized in that the agent has particles with at least one internal cavity with a diameter of at least 50 microns and a maximum of 150 microns, preferably at least 70 microns and particularly preferably at least 100 microns ,

13. Fine particulate agent according to claim 12, characterized in that the outer particle shell essentially has a wall thickness of at least 5 μm and at most 40 μm, preferably at least 30 μm, preferably at least 20 μm.

14. Fine particulate agent according to one of claims 1 to 13, characterized in that the agent has at least 30% by weight, in particular at least 50% by weight, preferably at least 70% by weight, preferably at least 80% by weight and further preferably has at least 90% by weight of primary particles, based on the total weight of the fine particulate agent.

15. Fine particulate agent according to one of claims 1 to 14, characterized in that the agent at most 70 wt .-%, in particular at most 50 wt .-%, preferably at most 30 wt .-%, preferably at most 20 wt .-% and further preferably has a maximum of 10% by weight of secondary particles, based on the total weight of the fine particulate agent.

16. Fine particulate agent according to one of claims 1 to 15, characterized in that at least 10% by weight of the primary particles, in particular at least 30% by weight, preferably at least 50% by weight, preferably at least 70% by weight, more preferably at least 90% by weight of the particles of the composition, with a 200-fold magnification under light microscopy, have an essentially smooth surface.

17. Fine particulate agent according to one of claims 1 to 16, characterized in that the agent, in particular the particles, has at least one, preferably several components, selected from the group comprising anionic surfactants as washing, care and / or cleaning agents, cationic surfactants, amphoteric surfactants, nonionic surfactants, builder substances, bleaching agents, bleach activators, bleach stabilizers, bleaching catalysts, enzymes, polymers, cobuilders, alkalizing agents, acidifying agents, anti-redeposition agents, silver preservatives, colorants, optical brighteners, UV protective agents, foaming agents and softeners, softeners Rinse aid and any other ingredients mixed in.

18. Fine particulate agent according to one of claims 1 to 17, characterized in that the fine particulate agent is a direct spray drying product and / or an aftertreated direct spray drying product.

19. Fine particulate agent according to claim 18, characterized in that the particles of the direct spray drying product are then aftertreated with at least one component, the amount of components preferably up to 15% by weight, in particular 2 to 15% by weight, in each case based on the Total weight of the agent containing the post-treated particles.

20. Finished product, in particular washing, cleaning and / or finished care product, characterized in that the finished product has at least 5% by weight and a maximum of 100% by weight, preferably at least 30% by weight, preferably at least 40% by weight. %, more preferably at least 70% by weight, even more preferably at least 90% by weight and most preferably at least 95% by weight of fine particulate agent according to one of claims 1 to 19, based on the total weight of the finished product.

21. Finished product, characterized in that the finished product has, in addition to the fine particulate agent, at least one, preferably several components, selected from the group comprising anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants as washing, care and / or cleaning substances , Builder substances, bleaching agents, bleach activators, bleach stabilizers, bleaching catalysts, enzymes, polymers, cobuilders, alkalizing agents, acidifying agents, anti-deposition agents, silver protection agents, coloring agents, optical brighteners, UV protective substances, fabric softeners, perfumes, foam inhibitors and / or rinse aid ingredients and, if appropriate, and ingredients.

22. Process for the production of fine particulate, low-dust agents with low bulk density, an average particle diameter of 0.1 mm to 0.8 mm and very high dissolving speed, under atmospheric pressure, by

an aqueous liquid or pasty slurry, preferably a washing, cleaning and / or care slurry with a surfactant content of 5% by weight to 25% by weight, preferably 10% by weight to 24% by weight, based on the fine particulate agent,

brings the slurry to a temperature of 50 ° C. to 160 ° C., preferably 70 ° C. to 120 ° C., preferably 80 ° C. to 95 ° C.,

- The slurry formed at an atomizing pressure of 30 bar to 90 bar, preferably at an atomizing pressure of 40 bar to 80 bar, preferably at an atomizing pressure of 50 bar to 70 bar, atomized by means of at least one nozzle into a spray chamber at atmospheric pressure, wherein - The nozzle (s) has a diameter of at least 1.8 mm and at most 5 mm, preferably at least 2 mm and at most 4 mm and preferably at least 2.3 mm and at most 3 mm, wherein

- The inlet temperature of the air in the spray chamber has a temperature at which the particles formed to a water content of at most 5.5 wt .-%, preferably 2.5 wt .-% to 4.5 wt .-%, preferably 3 wt .-% to 4 wt .-%, based on the fine particulate agent, are dried to form a fine particulate agent, the fine particulate agent optionally being post-treated.