EP1802733B1 - Absorptive particles - Google Patents

Abstract

A method to obtain particles which can absorb large quantities of perfume. The resulting particles are mechanically stable, flow freely, and have no tendency to stick together even when being charged with a great quantity of perfume. The perfume can be stabilized in the particles in such a way that the contained fragrances essentially do not decompose. Also disclosed are the aftertreatment of such particles as well as a detergent composition containing the inventive particles.

Description

The present invention relates to a process for the production of particles by drying, in particular by spray drying or fluidized bed process, wherein during the drying process in the material to be dried carbon dioxide is generated. It also relates to particles which can be prepared by such a process and which are aftertreated. It also relates to a detergent composition containing such particles and also to surfactants and optionally further ingredients, and to a process for fabric laundering using the detergent composition.

Fragrances, essences and aromas, which, especially when they are fragrant to humans, are summarized under the concept of fragrances have always been a human cultural asset and are generally used to create fragrances or to mask unpleasant odors. Their application is today in many products of daily life.

For example, in the field of food and beverages, the aromas and essences are of considerable importance. These are generally concentrated preparations of odorants or flavors intended to give food a better or more intense smell or taste. By adding flavors and essences, therefore, the acceptance of food and stimulants by consumers can be further increased.

Even with detergents and cleaning agents and the like fragrances are often added, although usually have no or only relatively low cleaning properties, but also increase the users' product acceptance, since both the self-scenting of the product, as well as the overlap disturbing side odors from the wash liquor, as well as the Textilbeduftung on the product are desired. If z. B. in the textile fragrances are transferred from the detergent to the textile, so the consumer perceives this usually very positive and associated with the fragrance of the laundry whose cleanliness, such. B. in which he states that a shirt smells like freshly washed.

In the textile washing, treatment and aftertreatment, it is therefore very common today, the detergents and aftertreatment agents to mix certain amounts of perfume, which serve the washing or rinsing eye itself, but also the treated with the washing or rinsing liquor Textile to give a pleasant fragrance. In addition to color and appearance, the scenting of washing and cleaning and after-treatment agents is an important aspect of the aesthetic product impression and thus an important factor in the consumer decision for or against a particular product. For perfuming the perfume can either be incorporated directly into the agent or fed in an additional step the washing or rinsing eye. The first way determines a certain product characteristic, while the second way the consumer can decide on different offered fragrance variants on "his" fragrance individually, comparable to the choice of an Eau de Toilette or aftershave.

Perfume moldings and methods for scenting washing and rinsing eyes are accordingly broadly described in the prior art. So revealed the DE 41 33 862 (Henkel ) Tablets containing excipients, fragrances and optionally further customary in detergents and cleaners ingredients, being used as the carrier material sorbitol and additionally 20 to 70 wt .-% of an effervescent system of carbonate and acid. These tablets, which can be added, for example, to the after-rinse and fabric conditioning cycle in the textile washing in a household washing machine, contain about 3 to 15, preferably 5 to 10,% by weight of perfume. Due to the high explosive content of the tablets, they are sensitive to atmospheric moisture and must be stored appropriately protected.

From the DE 39 11 363 (Baron Freytag von Loringhoven ) discloses a process for producing a fragrance-enriched washing or rinsing liquor and a fragrance adding agent for this purpose. The additives, which are in the form of capsules or tablets, contain the fragrance together with an emulsifier in liquid form (capsules) or bound to fillers and carriers (tablets), with sodium aluminum silicates or cyclodextrins being mentioned as carriers. The perfume content of the capsules or tablets is at least 1 g, the volume of the means being more than 1 cm ³ . Preference is given to tablets or capsules containing more than 2.5 g of fragrance and a volume of at least 5 cm ³ . During storage such tablets or capsules must be provided with a gas and water-tight coating layer to protect the ingredients. Further details on the preparation and the physical properties of suitable tablets are not included in this document.

The international application WO 94/25563 (Henkel-Ecolab ) describes a process for the preparation of washing and cleaning active moldings using the microwave technique, which operates without high pressure compression. The moldings produced in this way are characterized by an extremely high dissolution rate or decay rate while breaking strength, without a disintegrant is necessary. At the same time they are stable in storage and can be stored without any additional precautions. It can also be prepared in this way, moldings, the usual for washing and cleaning agent content of perfume oils between 1 and 3 % By weight. Perfume oils are usually volatile and therefore could evaporate already under the influence of microwave irradiation. If higher proportions of volatile liquid substances are to be used, a two-component system consisting of a component produced by microwave technology and a component containing the sensitive liquid substances is therefore described.

Particulate additives for scenting washing liquors and for use in detergents and cleaners, and processes for their preparation are described in the international patent applications WO97 / 29176 and WO97 / 29177 (Procter & Gamble). According to the teaching of these publications, porous carrier materials (eg sucrose mixed with zeolite X) are mixed with perfume and finally coated with a coating material (carbohydrates) and brought to the desired particle size distribution.

The German patent application DE 197 35 783 A1 (Henkel ) describes high-dose perfume moldings containing carrier material (s), 20 to 50 wt .-% perfume (s) and optionally further customary in detergents and cleaning agents and excipients, the moldings after deduction of the amount of perfume to at least 50 wt .-% of their weight consist of fatty acids and fatty acid salts. These perfume moldings are suitable both for the scenting of detergents and cleaners and for the scenting of textiles in a washing machine.

A method for applying fragrances to textiles in a washing machine is disclosed in US Pat DE 195 30 999 (Henkel ). In this process, a fragrance-containing molded article prepared by irradiation with microwaves is used in the rinse cycle of a washing machine. The preparation of the preferably spherical moldings with diameters above 3 mm and bulk densities up to 1100 g / l succeeds according to the teaching of this document by filling a mixture of predominantly water-soluble excipients, hydratised substances, optionally surfactants and perfume in suitable forms and sintered with the help of microwave radiation. The perfume contents of the moldings are between 8 and 40 wt .-%, as excipients find starches, silicas, silicates and disilicates, phosphates, zeolites, alkali metal salts of polycarboxylic acids, oxidation products of polyglucosans and polyaspartic acids use. An essential condition of the molding process described in this document is that in the mixture which is sintered with the aid of microwave radiation to form bodies, at least partially bound water is present, that is, a portion of the starting materials in hydrated form.

The proposed solutions in the prior art either require additional blocking or coating layers in order to fix the perfume on the carrier, or are not equally for scenting detergents and cleaners and for direct use as the sole fragrance, for example, for the rinse cycle in one Washing machine suitable.

Against this background, the object of the present invention was to make it possible to provide particles which can take up large quantities of fragrance and can be incorporated into other agents, such as detergents and cleaners, without a gas-tight coating layer.

This object is achieved by particles as defined in claim 1.

For the purposes of this invention, pastes are preferably solid dispersions in liquids with very liquid to very pasty, ie. meant tough consistency. For the purposes of this invention, a preferred paste is a slurry, ie a preferably aqueous slurry of solids having a very liquid to pasty or pasty consistency.

By drying is meant in the broadest sense any technical drying capability with which water and / or other solvents can be removed from the pastes to such an extent that at the end of drying particles, i. particulate solids occur. Solids are substances with a solid outer shape. Of course, these particles need not be completely solvent-free and / or anhydrous, for example, they may still contain significant amounts of solvent and / or water, but preferably they have water contents below 30 wt .-%, advantageously below 25 wt .-%, in particular below 20 wt .-%, in each case based on the obtained at the end of the drying solid. The water content may also be lower, if desired, for example below 15% by weight or below 10% by weight or below 5% by weight, based in each case on the solid obtained at the end of the drying.

For drying, the products to be dried are advantageously supplied with heat. The drying can preferably be carried out in cocurrent, countercurrent or crossflow. Depending on the type of heat supply, a distinction is made between contact dryers, convection dryers and radiation dryers. Depending on the pressure prevailing in the dryer can be divided into overpressure, normal pressure and vacuum dryer. In convection drying, the heat is transferred to the material to be dried mainly by hot gases (air or inert gas), which is preferred. For this purpose, channel, chamber, belt, shaft, fluidized bed and atomizing dryers are used, which is preferred. In the contact drying, which is also preferred, the heat transfer takes place via heat exchanger surfaces. The contact dryers include the roller, tube and cabinet dryers. Floor, plate, drum and paddle dryers work according to both principles of heat supply.

A very preferred drying method according to the invention is spray-drying. Also preferred for drying are fluidized bed processes.

The paste to be processed according to the invention contains substance (s) which release carbon dioxide at elevated temperatures, preferably selected from bicarbonate compounds, citric acid and / or aconitic acid. In the bicarbonate compounds, the sodium bicarbonate is preferred.

According to a further preferred embodiment of the invention, the paste to be processed according to the invention contains 0 to 40% by weight, preferably 0.1 to 4% by weight, in particular 1 to 3% by weight of citric acid, or 0 to 50% by weight. , preferably 0.1 to 5 wt .-%, in particular 1 to 4 wt .-% of bicarbonate compound, or 0 to 40 wt .-%, preferably 0.1 to 10 wt .-%, in particular 1 to 5 wt. % Aconitic acid.

It may also be advantageous to use mixtures of bicarbonate compounds, citric acid and / or aconitic acid, the total amount of such a 50 wt .-%, preferably 40 wt .-%, advantageously 20 wt .-%, but especially 10 wt .-% not should exceed, and wherein a minimum total amount of 0.1 wt .-%, preferably 1 wt .-% should not fall below, in each case based on the total paste.

The (spray) drying of aqueous preparations of recyclables, which are suitable, for example, for use in detergents and cleaners, and the drying of aqueous preparations of agents such as detergents and cleaners as such for the preparation of appropriate agents in pourable and pourable powder form is a well-known technical area. From the extensive literature, reference is merely made here by way of example K. Masters "Spray Drying Handbook", Longman Scientific & Technical 1991, ISBN 0-582-06266-7 , The fluidized bed drying, which can be carried out in the context of the invention in conventional systems, is a well-known technical field and therefore need not be further explained here.

To carry out the spray-drying process, it is also possible to use conventional equipment, for example those already used for the production of conventional sprayed detergent components or detergents. Such systems usually consist of towers of round cross-section, which are equipped in the upper part with annular spray nozzles. They also have feeders for the dry gases and dedusting systems for the exhaust air. The drying gas can be used for countercurrent drying or DC drying. In the so-called countercurrent drying, the drying gas is introduced into the lower part of the tower and fed to the product stream, while in the DC drying, the supply of dry gases takes place in the head of the drying tower. The spray-drying plant is operated with hot air or hot combustion gases, which are preferably introduced tangentially into the tower, resulting in a certain swirl effect.

The first step of a spray-drying process is generally in the production of an aqueous slurry (paste, in particular slurry), more or less thermally stable ingredients that usually do not volatilize or decompose under the conditions of spray drying in the majority. This paste is then usually transported via pumps in the spray tower and sprayed there in the head thereof usually through nozzles or by means of a rapidly rotating atomizer disk to a fine mist.

This spray is dried with a gaseous drying medium such as preferably hot air or an inert gas in cocurrent or countercurrent. If the paste contains very temperature-sensitive constituents, then the supply of the drying gas is usually operated in direct current from above. For example, around the 250 ° C up to 350 ° C hot air evaporates the adhering water or solvent, so that the other paste components are obtained at the tower outlet (temperatures preferably 80-120 ° C) as a powder. The thus spray-dried powder can now be used directly, it can be aftertreated and it can be mixed with other components, in particular with temperature-labile components, such as in the case of detergents, for example fragrances.

The heat of the drying gas, whose temperature is preferably> 100 ° C, advantageously> 150 ° C, more preferably> 180 ° C, more preferably> 200 ° C, with an upper limit of 400 ° C, preferably of 350 ° C, advantageously of 300 ° C, in particular of 250 ° C should not be exceeded, causes not only the adhering water or solvent evaporates, but that during drying in the material to be dried advantageously carbon dioxide is generated. The carbon dioxide is released by substances contained in the paste. Substances which have the potential to release carbon dioxide under such conditions are preferably selected from bicarbonate compounds, citric acid and / or aconitic acid.

Surprisingly, it has been found that in such cases, in which carbon dioxide is released during the drying, particles result, which are distinguished by a significantly increased absorption capacity for fragrances. For the purposes of this invention, the term fragrances encompasses the entirety of the fragrances, flavors, essences, perfume oils and perfumes, these terms, in particular the terms fragrances and perfume, being used synonymously in the further course. Perfumes are understood to be i.d.R. alcoholic solutions of suitable fragrances.

The direct drying product, especially the direct spray-drying product, is capable of receiving larger quantities of perfumes in a subsequent treatment step than usual. Surprisingly, it has been found that the flow properties of such scented particles are very good. The flow properties remain very good even with very high perfume loading. The same applies to the mechanical stability. It is surprising that these scented particles also have a more lasting scent effect have, ie the particles smell at least the same scent intensity longer than conventional (spray) drying products, which were otherwise scented analog.

A further advantage of the invention is that the fragrance note or perfume note of the particles according to the invention, which has been loaded with fragrances, does not change adversely even during prolonged storage. It is often the case that perfume which is incorporated in a carrier material decomposes at least partially, more or less slowly, in the carrier material. In contrast, this decomposition is at least delayed in a particle according to the invention. Thus, a perfumery stabilizing effect is achieved by the invention. This is especially true when the particles are incorporated into an object, such. B. in a detergent formulation, which is rather detrimental to the stability of perfume by their object property, such as their alkalinity. Here, the perfuming stabilizing effect has a particularly favorable effect.

The subject invention provides even more benefits. It could be found that the particles according to the invention, after being loaded with perfume, compared to conventional particles, in the drying process no carbon dioxide is formed, lead to a more intense fragrance experience in the consumer with the same perfume loading, for example, when one laundry Detergent formulation which contains the particles according to the invention washes. It was surprisingly found that the consumer perceives a more intense scent of the washed laundry as compared to laundry washed with a conventionally scented detergent formulation, even though the contained absolute amount of the perfume was the same. In this respect, a fragrance-enhancing effect is made possible by the invention, which directly affects the particles, as well as objects into which these particles are incorporated, for example, detergent formulations, as well as things such. As textiles, which are treated with the objects (here: detergent formulation).

Furthermore, it was surprisingly found that the fragrance impression resulting from the particles according to the invention, which were loaded with perfume, indirectly and immediately longer holds. "Immediately" in this context means that the particles of the invention smells over a longer period of time than an otherwise comparable particle, but in the drying no CO _{2 was} released. "Indirect" in this context means that objects (eg, detergent formulation) containing the particles of the invention have a longer odor, and even when these objects are used (eg, detergent formulations for laundering textiles), the things treated therewith ( here: washed textile) smell longer. By the invention, therefore, a fragrance (impression) with sustained release effect is achieved, with this fragrance-retard effect (ie the temporal extent of the fragrance impression) both on the particles, as on the particles containing objects, such as those with these objects relates to treated things.

It is highly preferred according to the invention that the carbon dioxide in the (spray) drying material essentially only forms when it is exposed to the hot drying gas stream. Preferably, before the paste is subjected to drying conditions, the paste is substantially free of carbon dioxide.

In the case of spray-drying, the drying gas stream may be opposite to the atomized material or, as is preferred, have the same direction of movement as the particles to be dried. In accordance with the invention, the temperature of the gas heating stream in the case of spray drying when entering the relaxation space is preferably at least 150 ° C., but advantageously a temperature of 350 ° C. should not be exceeded, as already mentioned above.

Drying, in particular spray drying, has not only been found in the manufacture of detergents, cleaners and care products, but also in the manufacture of a variety of other goods, e.g. from foodstuffs such as dry milk, instant coffee, yeast, egg, fruit juice dry powder or other goods such as wood sugar, tannins, dry blood powder, polyvinyl and polyethylene powder, glue, serums to pharmaceutical preparations proven. For the production of all these goods, but especially of detergents, cleaners, care, food, stimulants and pharmaceutical preparations, the inventive method is particularly suitable. In the case of foodstuffs, a very high loading of aromas and essences can advantageously be achieved. In the case of pharmaceutical preparations, a very high loading of essential oils or liquids, in particular of a hydrophobic nature, can advantageously be achieved.

In all cases, an increase in the loading capacity is achieved with fragrances, the very good flow properties of the particles are maintained and also does not deteriorate the mechanical stability of the particles and in each case a change in the fragrance does not take place during storage.

Most advantageous method of the invention is with regard to the production of detergents, cleaners and care products, so that the invention to be processed paste preferably includes one or more ingredients, which may usually be included in detergents, cleaning and care products. Such ingredients will be further described below.

However, it is also preferred if the paste to be processed according to the invention comprises such ingredients which are customarily contained in foods and stimulants, pharmaceutical preparations or other technical (spray) dried goods. The ingredients in question depend on the intended use of the particles and are familiar to the expert or refer to relevant reference works, such. As regards food, " Paperback for food chemists and technologists ", Vol. 1 and 2, Wolfgang Frede, 1991 , to which reference is made in full. It is surprising that in the case of foods and / or food components which are produced by means of the process according to the invention, the aroma can be obtained longer than usual after it has been applied. Thus, not only larger amounts of aroma can be introduced without secondary particle properties such as mechanical stability or Rieselvermögen would be affected, the introduced flavor is also noticeable longer.

According to a preferred embodiment of the invention, the paste to be processed according to the invention contains organic carrier material, as is known from the prior art, in particular in connection with detergents and cleaners.

• Zeolith-Sulfat, Zeolith-Sulfat-Carbonat, Zeolith-Sulfat-Carbonat-Silikat, Zeolith-Sulfat-Carbonat-Silikat-Kieselsäure, Zeolith-Carbonat, Zeolith-Carbonat-Silikat, Zeolith-Car-bonat-Silikat-Kieselsäure, Zeolith-Silikat, Zeolith-Silikat-Sulfat, Zeolith-Silikat-Carbonat, Zeolith-Silikat-Kieselsäure, Zeolith-Kieselsäure, Zeolith-Kieselsäure-Sulfat, Zeolith-Kiesel-säure-Carbonat, Sulfat-Carbonat, Sulfat-Carbonat-Silikat, Sulfat-Carbonat-Silikat-Kiesel-säure, Sulfat-Silikat, Sulfat-Kieslsäure, Carbonat-Silikat, Carbonat-Kieslsäure. Das in der Paste enthaltene anorganische Trägermaterial besteht dabei in einer weiteren bevorzugten Ausführungsform entsprechend zumindest zu 30 Gew.-%, vorzugsweise zumindest zu 40 Gew.-%, insbesondere zumindest zu 60 Gew.-% aus Zeolith, vorzugsweise Zeolith X, Y, A, P, MAP und/oder Mischungen dieser, bezogen auf das gesamte, enthaltene Trägermaterial.

The paste to be processed according to the invention contains inorganic carrier material, preferably selected from the group comprising zeolites, sulfates, carbonates, silicates, silicic acid and / or mixtures thereof. Preferred combinations of these support materials here are the following:

• Zeolite sulfate, zeolite sulfate carbonate, zeolite sulfate carbonate silicate, zeolite sulfate carbonate silicate silica, zeolite carbonate, zeolite carbonate silicate, zeolite carbonate silicate, zeolite Silicate, zeolite-silicate-sulphate, zeolite-silicate-carbonate, zeolite-silicate-silica, zeolite-silicic acid, zeolite-silicic-sulphate, zeolite-silicic acid-carbonate, sulphate-carbonate, sulphate-carbonate-silicate, sulphate Carbonate-silicate-silicic acid, sulphate-silicate, sulphate-silicic acid, carbonate-silicate, carbonate-silicic acid. In a further preferred embodiment, the inorganic carrier material contained in the paste is accordingly at least 30% by weight, preferably at least 40% by weight, in particular at least 60% by weight, of zeolite, preferably zeolite X, Y, A. , P, MAP and / or mixtures thereof, based on the total, contained carrier material.

According to a further preferred embodiment of the invention, the paste to be processed according to the invention contains both organic and inorganic carrier material.

The zeolite which can be used according to the invention is advantageously zeolite A and / or P. The zeolite P used is, for example, zeolite ^MAP® (commercial product from Crosfield). Y-type zeolite is also preferred. Also, zeolite X and mixtures of A, X and / or P, for example, a co-crystal of zeolites A and X, the VEGOBOND ^® AX (commercial product of Condea Augusta SpA) are preferred.

Zeolites which are preferably usable according to the invention, such as those mentioned above, are described further below. Particularly suitable zeolites are faujasite-type 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-membered subunit D6R (cf. Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974 . Page 92). In addition to the faujasite types mentioned, the zeolite structural group 4 also includes the minerals chabazite and gmelinite as well as the synthetic zeolites R (chabazite type), S (gmelinite type), L and ZK-5. The latter two synthetic zeolites have no mineral analogs.

Faujasite-type zeolites are composed of β-cages linked tetrahedrally via D6R subunits, with the β-cages resembling the carbon atoms in the diamond. The three-dimensional network of faujasite-type zeolites useful in this invention has pores of 2.2 and 7.4 Å, and the unit cell also contains 8 wells of approximately 13 Å in diameter and can be represented by the formula Na ₈₆ [(ALO ₂ ) ₈₆ (SiO ₂ ) ₁₀₈ ]. 264 H ₂ O describe. The network of zeolite X contains a void volume of about 50%, based on the dehydrated crystal, which represents the largest void space of all known zeolites (zeolite Y: about 48% void volume, faujasite: about 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 "faujasite type zeolite" 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, the pure zeolite X being preferred.

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

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

• Na₈₈[(AlO₂)₈₆(SiO₂)₁₀₈] · x H₂O_,
  
          K₈₈[(AlO₂)₈₈(SiO₂)₁₀₈] · x H₂O,
  
          Ca₄₀Na₆[(AlO₂)₈₆(SiO₂)₁₀₆] · x H₂O,
  
          Sr₂₁Ba₂₂[(AlO₂)₈₆(SiO₂)₁₀₈] · x H₂O,
  
  

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

• Na ₈₈ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₈ ] .xH ₂ O _,
  
  K ₈₈ [(AlO ₂ ) ₈₈ (SiO ₂ ) ₁₀₈ ] .xH ₂ O,
  
  Ca ₄₀ Na ₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] xH ₂ O,
  
  Sr ₂₁ Ba ₂₂ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₈ ] x H ₂ O,
  
  

where x can take values greater than 0 to 276. These zeolites have pore sizes of 8.0 to 8.4 Å.

Also suitable, for example, in the European patent application EP-A-816,291 described zeolite A-LSX, which corresponds to a cocrystal of zeolite X and zeolite A and in its anhydrous form has the formula (M _{2 / n} O + M ' _{2 / n} O) · Al ₂ O ₃ zSiO ₂ , wherein M and M 'may be alkali or alkaline earth metals and z is a number from 2.1 to 2.6. Commercially available this product is under the brand name VEGOBOND AX by the company CONDEA Augusta SpA

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

Na ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] xH ₂ O,

K ₅₆ [(AlO ₂ ) ₅₈ (SiO ₂ ) ₁₃₆ ] xH ₂ O,

where x is numbers greater than 0 to 276. These zeolites have pore sizes of 8.0 Å.

The particle sizes of the suitable faujasite-type zeolites 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, in each case measured using standard particle size determination methods.

Also preferred are the silicates, in particular amorphous silicates and crystalline phyllosilicates.

Particular support materials according to the invention are also layered sodium silicates of the general formula 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 and y is a number from 0 is up to 20 and preferred values for x are 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 added to the direct or post-treated spray-drying product. Such crystalline layered silicates are described, for example, in the European patent application EP-A-0 164 514 described. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred. Such compounds are commercially available, for example, under the name ^SKS® (from Clariant). Thus, it is mainly SKS-6 ^® is a δ-sodium having the formula Na ₂ Si ₂ O ₅ · yH ₂ O, SKS-7 ^® primarily the β-sodium disilicate. By reaction with acids (for example citric acid or carbonic acid), the δ-kanemite NaHSi ₂ O ₅ · yH ₂ O, im_Handel under the names of SKS-9 ^® and SKS-10 ^® (Fa. Clarlant). It may also be advantageous to use chemical modifications of these phyllosilicates. For example, the alkalinity of the layered silicates can be suitably influenced. Phyllosilicates doped with phosphate or with carbonate have altered crystal morphologies compared to the δ-sodium disilicate, dissolve faster and show increased calcium binding capacity compared to δ-sodium disilicate. Thus, phyllosilicates of the general empirical formula x Na ₂ O • ySiO ₂ • zP ₂ O ₅ in which the ratio x to y a number 0.35 to 0.6, the ratio x to z a number of 1.75 to 1200 and the Ratio y to z of a number from 4 to 2800 corresponds to the patent application DE-A-196 01 063 described. The solubility of the layered silicates can also be increased by using particularly finely divided layered silicates. Also compounds from the crystalline layer silicates with other ingredients can be used. In particular, compounds with cellulose derivatives which have advantages in the disintegrating action, and compounds with polycarboxylates, for example citric acid, or polymeric polycarboxylates, for example copolymers of acrylic acid, may be mentioned.

The preferred support materials also include amorphous sodium silicates having a modulus of Na ₂ O: SiO _{2 of} 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 are delay-delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. It may be advantageous if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which likewise have a dissolution delay compared to the conventional water glasses, are described, for example, in the German patent application DE-A-44 00 024 described. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates. Suitable support materials are furthermore phyllosilicates of natural and synthetic origin. Such sheet silicates are, for example, from the patent applications DE-B-23 34 899 . EP-A-0 026 529 and DE-A-35 26 405 known. Its usability is not limited to any particular composition or structural formula. However, smectites, in particular bentonites, are preferred here.

Layer silicates which can be used as carrier material and belong to the group of water-swellable smectites are, for example, montmorillonite, hectorite or saponite. In addition, small amounts of iron may be incorporated in the crystal lattice of the layered silicates according to the above formulas. In addition, the phyllosilicates, because of their ion-exchanging properties of hydrogen, alkali, alkaline earth ions, in particular contain Na ⁺ and Ca ^2+. The amount of water of hydration is usually in the range of 8 to 20 wt .-% and is dependent on the swelling state or the type of processing. Useful phyllosilicates are for example off US Patent No. 3,966,629 . EP-A-0 026 529 and EP-A-0 028 432 known. Preferably, phyllosilicates are used, which are largely free of calcium ions and strong coloring iron ions due to an alkali treatment.

Particularly preferred support materials are alkali metal carbonates and alkali metal bicarbonates, with sodium and potassium carbonate and especially sodium carbonate being among the preferred embodiments.

Particularly preferred support materials are also the sulfates, preferably alkali metal, and alkaline earth metal sulfates, with sodium and magnesium sulfate being clearly preferred.

Particularly preferred support materials are also the silicic acids, preferably the precipitated silicas, in particular the silica gels (silica gels, silica gels), which are advantageously hydrophobic or hydrophilic.

It has been found that such slurries containing the aforementioned carrier materials in the process according to the invention lead to particularly perfume-receptive particles whose stability and flowability is very high and which can not only absorb large amounts of perfume, but in which the perfume effect also in time holds longer.

It has been observed that the decomposition of fragrances in the particles produced according to the invention is greatly slower than comparable particles. Even when incorporating the particles according to the invention into strongly alkaline matrices, the fragrances contained in the particle are surprisingly stable. It is easily possible to incorporate the particles according to the invention, which may be loaded with high amounts of fragrances, without a gas-tight coating layer in other means, such as detergents and cleaning agents. Moreover, since the particles of the invention loaded with fragrances are free-flowing and do not stick together, incorporation into detergents and cleansers or comparable compositions is effortless.

The paste to be processed according to the invention may preferably also contain non-ionic surfactant, which corresponds to a preferred embodiment of the invention. According to a further preferred embodiment of the invention, the nonionic surfactant is selected from the group consisting of the alkoxylated alcohols, the alkylphenol polyglycol ethers, the alkoxylated fatty acid alkyl esters, the polyhydroxy fatty acid amides, the alkyl glycosides, the alkyl polyglucosides, the amine oxides and / or the long-chain alkyl sulfoxides.

However, nonionic surfactants are preferably only present in minor amounts in the direct (spray) dried products. For example, their content can be up to 2 or 3% by weight. be. According to another preferred embodiment of the invention, the directly dried, in particular directly spray-dried, products are even free of nonionic surfactants, ie they contain less than 1% by weight, preferably less than 0.5% by weight and in particular no nonionic surfactant at all. For a more detailed description of the nonionic surfactants, reference is made to the description of the post-treated (spray) drying products below.

It has surprisingly been found that the presence of nonionic surfactant in the paste, especially in minor amounts, leads to a further increase in the absorption capacity of the particles resulting in the process according to the invention. Advantageously, however, the absorbency of the particles is significantly higher when nonionic surfactant is applied to the direct (spray) drying product in an aftertreatment step.

If nonionic surfactant is present in the paste, then according to a further preferred embodiment of the invention at least partially alkoxylated alcohol is present as nonionic surfactant, preferably in amounts of at least 40% by weight, advantageously of at least 50% by weight, more advantageously Of at least 60% by weight, most advantageously at least 70% by weight, more preferably at least 80% by weight, in particular at least 90% by weight, most advantageously in amounts of 100% Wt .-%, each based on the total amount of nonionic surfactant contained in the paste, which are advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18, in particular 12 to 18 carbon atoms, and preferably an average of 1 to 12 mol Alkylene oxide, preferably ethylene oxide, per mole of alcohol.

According to a further preferred embodiment of the invention, the paste contains anionic or cationic surfactant, preferably in small amounts, advantageously in amounts of less than 10 wt .-%, preferably less than 8 wt .-%, in particular less than 5 wt .-%, based on the Paste. The use of such a small amount of anionic or cationic surfactant is able to further increase the perfume-loading capacity of the resulting particles. The resulting particles are still free-flowing and do not stick together. The perfume is stabilized in the particles and a decomposition of the fragrances does not take place or is very stak delayed. Particularly suitable anionic or cationic surfactants are described below.

Another object of the invention is a particle which can be produced by a process according to the invention, wherein the particles of the direct (spray) drying product is aftertreated. The particles resulting directly from the process according to the invention are referred to as particles of the direct (spray) drying product. Such can be post-treated according to the invention, which is advantageous. In this case, the aftertreatment can take place both with solid and with flowable or sprayable substances as well as combined. Under aftertreatment with solids z. B. to understand the dusting of the particles with very fine particulate matter. Under aftertreatment with flowable or sprayable substances, z. As the impregnation (preferably soaking) of the particles with a liquid, such as perfume to understand. Preference is given to aftertreatment first with the liquid, then with the solid substances. Post-treatment is also understood to mean the mechanical rounding of the particles.

The aftertreatment by rounding represents a preferred measure according to the invention. The rounding of the direct (spray) drying product can be carried out in a conventional milling machine. Preferably, the rounding time is not longer than 4 minutes, especially not longer than 3.5 minutes. Rounding times of a maximum of 1.5 minutes or less are particularly preferred. The rounding achieves a further standardization of the spectrum.

The direct (spray) drying product produced according to the invention can advantageously be treated before (optional) rounding, in particular with nonionic surfactants and perfume or preparation formulations containing these ingredients, preferably with amounts of up to 40% by weight of active substance, in particular with amounts of 2 to 35 wt .-% of active substance, in each case based on the aftertreated product, in a conventional manner, preferably in a mixer or optionally a fluidized bed, aftertreat. It is preferred if the direct (spray) drying product is first impregnated with nonionic surfactant and then loaded with perfume. Of course, the direct (spray) drying product can also be immediately loaded with perfume, d. H. the impregnation with nonionic surfactant is eliminated. Likewise, the direct (spray) drying product can also be aftertreated with a preparation which is a mixture of nonionic surfactant and perfume and optionally other constituents.

The particles produced according to the invention are aftertreated with nonionic surfactants and / or perfume or preparation forms containing these ingredients.

The nonionic surfactant is preferably selected from the group consisting of the alkoxylated alcohols, the alkylphenol polyglycol ethers, the alkoxylated fatty acid alkyl esters, the polyhydroxy fatty acid amides, the alkyl glycosides, the alkyl polyglucosides, the amine oxides and / or the long-chain alkyl sulfoxides.

It is further preferred that the nonionic surfactant used for the post-treatment comprises alkoxylated alcohol, which are advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18, in particular 12 to 18 carbon atoms and preferably on average 1 to 12 moles of alkylene oxide, preferably Ethylene oxide, per mole of alcohol.

In particular, the direct (spray) drying product produced according to the invention may preferably be after (optional) rounding and / or (optional) aftertreatment with free-flowing or sprayable substances with solids, preferably in amounts of up to 15% by weight, in particular in amounts of 2 to 15 wt .-%, in each case based on the total weight of the aftertreated agent, post-treat, ie powder. Unexpectedly, however, the particles according to the invention are not tacky even if they contain a high degree of loading perfume or the like, so that a powdering advantageously can even be omitted altogether.

Hydrogen carbonate, carbonate, zeolite, silica, citrate, urea or mixtures thereof, in particular in amounts of from 2 to 15% by weight, based on the total weight of the aftertreated product, can preferably be used as solids for the powdering. The aftertreatment can be carried out in an advantageous manner in a mixer and / or by means of Verrunder.

In a preferred post-treatment step, it is possible to scavenge the direct (spray) drying product with a solid, for example silicic acids, zeolites, carbonates, bicarbonates and / or sulfates, citrates, urea or mixtures of 2 or more of the substances mentioned. This can be done either directly after leaving the direct spray-drying product from the tower in a mixer or in the malting machine.

In a very preferred embodiment of the invention, the direct (spray) drying product with nonionic surfactants, which may contain, for example, optical brightener and / or hydrotropes and perfume, or preparation forms, which may contain these ingredients, aftertreated. Advantageously, it is first aftertreated with the nonionic surfactants and then with the perfume. Preferably, these ingredients or formulations containing these ingredients are applied in liquid, molten or pasty form to the direct (spray) drying product. Advantageously, the direct (spray) drying products with up to 40 wt .-% of active ingredient of the ingredients mentioned are post-treated. The quantity is based on the aftertreated product. It is preferred that the aftertreatment with the substances mentioned here take place in a conventional mixer. Such post-treated products may have a bulk density of from 300 to 1000 g / l, preferably from 450 to 850 g / l, in particular from 500 to 750 g / l.

It is surprising and unexpected that the flowability of the product is not affected by such measures. Starting from a direct (spray) drying product, the flowability remains essentially constant even after aftertreatment of this product with, for example, up to 35% by weight, based on the aftertreated product, nonionic surfactant and perfume.

According to a preferred embodiment of the invention, therefore, nonionic surfactant is added to the direct (spray) drying product in the course of the aftertreatment. Preferably, alkoxylated, vorteithafterweise ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or contain linear and methyl-branched radicals in the mixture, as they are usually present in O-xoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, palm kernel, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ -alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ -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 of these, 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 means which, for a particular product, may be an integer or a fractional number. 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 include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

Surprisingly, it has been found that especially the alkoxylated alcohols are very advantageous in order to further maximize the perfume absorption capacity of the particles, to promote the stability of the perfume in the particles and to promote said scent-retard effect and the fragrance-enhancing effect.

According to a further preferred embodiment, the nonionic surfactants which are particularly suitable for the aftertreatment are a mixture of at least two different nonionic surfactants, preferably of at least two different alkoxylated, advantageously ethoxylated, especially primary alcohols, the distinguishing feature with respect to the alkoxylated alcohols preferably in the degree of alkoxylation lies.

If in this mixture of at least two different nonionic surfactants at least one alkoxylated, preferably ethoxylated alcohol having a degree of alkoxylation of less than 7, advantageously not greater than 6, more preferably not greater than 5, in particular not greater than 4.5 and at least one further alkoxylated, advantageously ethoxylated Alcohol with a degree of alkoxylation of at least 7 before, then it is another preferred embodiment of the invention.

According to a further preferred embodiment of the invention, the ratio of lower alkoxylated alcohol to higher alkoxylated alcohol is in the range from 5: 1 to 1: 5, preferably from 4: 1 to 1: 4, advantageously 3: 1 to 1: 3, in particular 2: 1 to 1: 2.

However, it is also possible with preference to use alkyl glycosides of the formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol is which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number from 1 to 10; preferably x is 1.1 to 1.4.

Another class of preferred nonionic surfactants 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 from 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as described for example in the Japanese patent application JP 58/217598 are described or preferably according to the in the international patent application WO 90/13533 be prepared described methods. Particularly preferred are C ₁₂ -C ₁₈ fatty acid methyl esters having an average of 3 to 15 EO, in particular having an average of 5 to 12 EO.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

According to a preferred embodiment, in the after-treatment alkoxylated alcohol is used as nonionic surfactant, preferably in amounts of at least 40 wt .-%, advantageously of at least 50 wt .-%, more preferably of at least 60 wt .-%, in a very advantageous Of at least 70% by weight, more preferably of at least 80% by weight, in particular of at least 90% by weight, most advantageously in amounts of 100% by weight, based in each case on the total amount of nonionic surfactant, which is fed in the course of the aftertreatment.

An inventive particle contains inorganic carrier material in a total amount of at least 30 wt .-% based on the total particle, perfume, which is ad / absorbed on / in the carrier material, and at least 0.5 wt .-% of nonionic surfactant, based on the entire post-treated particle.

According to a further preferred embodiment, the amount of perfume adsorbed in / on the carrier material of a particle according to the invention is at least 5% by weight, advantageously more than 10% by weight, more preferably more than 15% by weight, more advantageously Way more than 20 wt .-%, in particular more than 25 wt .-%, based on the total post-treated particles.

Further conceivable additives, in particular for the aftertreatment of the products, are foam inhibitors, for example foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane. The use of mixtures of these agents is possible. As additives which are solid at room temperature, paraffin waxes, silicic acids, which may also be hydrophobized in a known manner, and in particular bismuth derivatives which are derived from C _2-7 -diamines and C _12-22 -carboxylic acids are suitable.

Suitable foam-inhibiting paraffin oils for use in admixture with paraffin waxes are generally complex mixtures without a sharp melting point. For characterization, the melting range is usually determined by differential thermal analysis (DTA) as described in "The Analyst". 87 (1962), 420, and / or the solidification point. This is the temperature at which the paraffin passes from the liquid to the solid state by slow cooling. Paraffins with less than 17 carbon atoms are less useful according to the invention, their proportion in the paraffin oil mixture should therefore be as low as possible and is preferably below the limit significantly measurable by conventional analytical methods, for example gas chromatography. Preferably paraffins are used which solidify in the range of 20 ° C to 70 ° C. It should be noted that even at room temperature appearing paraffin wax mixtures may contain different proportions of liquid paraffin oils. In the case of the paraffin waxes which can be used according to the invention, the liquid fraction at 40 ° C. is as high as possible, without already being 100% at this temperature. Preferred paraffin wax mixtures have at 40 ° C a liquid content of at least 50 wt .-%, in particular from 55 wt .-% to 80 wt .-%, and at 60 ° C, a liquid content of at least 90 wt .-% to. This has the consequence that the paraffins are flowable and pumpable at temperatures down to at least 70 ° C, preferably down to at least 60 ° C. It should also be ensured that the paraffins contain as far as possible no volatile components. Preferred paraffin waxes contain less than 1 wt .-%, in particular less than 0.5 wt .-% at 110 ° C and atmospheric pressure vaporizable fractions. Paraffins which can be used according to the invention can be obtained, for example, under the trade names Lunaflex® from Fuller and Deawax® from DEA Mineralöl AG.

The paraffin oils may contain at room temperature solid bisamides derived from saturated fatty acids containing 12 to 22, preferably 14 to 18, carbon atoms and alkylenediamines having 2 to 7 carbon atoms. Suitable fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof, such as those obtainable from natural fats or hardened oils, such as tallow or hydrogenated palm oil. Examples of suitable diamines are 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 mixtures thereof and the corresponding derivatives of hexamethylenediamine.

According to a further embodiment of the invention, said foam inhibitors may also be present in the direct (spray) drying product.

1. a) Trägermaterial, vorzugsweise anorganisches Trägermaterial, in Mengen von mindestens 30 Gew.-%, vorteilhafterweise In Mengen von 50 bis 95 Gew.-%, vorzugsweise 60 bis 90 Gew.%
2. b) Parfüm in Mengen von 5 bis 40 Gew.-%, vorzugsweise von 1 bis 35 Ges.-%
3. c) nichtionisches Tensid in Mengen von 0,5 - bis 5 Gew.-%

sowie optional weitere Bestandteile.An inventive aftertreated particle contains

1. a) support material, preferably inorganic support material, in amounts of at least 30 wt .-%, advantageously in amounts of 50 to 95 wt .-%, preferably 60 to 90 wt.%
2. b) perfume in amounts of from 5 to 40% by weight, preferably from 1 to 35% by weight
3. c) nonionic surfactant in amounts of from 0.5 to 5% by weight

as well as optional further components.

The other constituents may advantageously be typical ingredients of detergents and cleaners. Particles which can be prepared according to the invention and are intended in particular for use in or as detergents and cleaners can contain typical ingredients, in particular selected from the group comprising washing, care and / or cleaning substances such as surfactants, builders, bleaches, bleach activators, bleach stabilizers. Bleach catalysts, enzymes, polymers, cobuilders, alkalizing agents, Acidifizierungsmittel, Antiredepositionsmittel, silver protectants, colorants, optical brighteners, UV protectants, fabric softeners and / or rinse aid, and optionally contain further ingredients, which are described in detail below. The described and all other suitable conventional ingredients may be contained directly in the (spray) dried product, but preferably also be applied in the course of a post-treatment on the particles. Likewise, the particles may be mixed together with components containing such and / or other conventional ingredients.

The anionic surfactants used are preferably those of the sulfonate and sulfates type. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable. Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as used in the preparation obtained 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 sulfated 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.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example 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 these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. 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 _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 . Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of from 1 to 5% by weight, based on the total agent, in particular detergents.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

The content of the agents, preferably detergents and cleaners, which contain the particles according to the invention, in particular the aftertreated (spray) drying products, of said anionic surfactants is preferably from 2 to 30% by weight and in particular from 5 to 25% by weight. , with concentrations above 10 wt% and even above 15 wt% being particularly preferred in each case based on the total mean. By contrast, the particles according to the invention as such, in particular the aftertreated (spray) drying product, preferably contains only small amounts of anionic surfactant, advantageously less than 10% by weight. In a further advantageous manner less than 8 wt .-%, preferably less than 5 wt .-% and in particular 1 to 4 wt .-%, based on the particles of the invention, in particular the aftertreated (spray) drying product.

In addition, soaps may be included. Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. The content of the particles according to the invention, in particular of the aftertreated (spray) drying products on soaps, is preferably not more than 3% by weight and in particular 0.5 to 2.5% by weight, based on the total particles, in particular the after-treated ( spray) drying product.

The anionic surfactants and soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. Preferably, they are in the form of their sodium or potassium salts, especially in the form of the sodium salts. Anionic surfactants and soaps may also be prepared in situ by incorporating into the composition to be dried the anionic surfactant acids and optionally fatty acids, which are then neutralized by the alkali carriers in the (spray) drying composition.

Examples of builders which act as builders according to the invention, such as zeolites or silicates. In addition to builder-builders, other builders may be included.
In cases in which a phosphate content is tolerated, it is also possible to use phosphates, in particular pentasodium triphosphate, if appropriate also pyrophosphates and orthophosphates, which act primarily as precipitants for calcium salts. Phosphates are predominantly used in automatic dishwasher detergents, but in some cases also in detergents.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid 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 (potassium phosphate primary or monobasic potassium phosphate, KDP), KH ₂ PO ₄ , is a white salt of 2.33 gcm ^-3 density, 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 ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , loss of water at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as 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 ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 gcm ^-3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , Both substances are colorless crystals which are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed on heating of 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 agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in Form of trihydrate and represents a colorless, hygroscopic powder having a density of 2.33 gcm ^-3 , which is soluble in water, wherein the pH of the 1% solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ results in higher molecular weight sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches 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 with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are used according to the invention exactly as 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.

Useful organic builders are, for example, also the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is for ecological reasons not to complain about, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycinediacetic acid, sugar acids and mixtures thereof.

The acids themselves can also be used. In addition to their builder effect, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents and cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these may be mentioned here.

Other suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses 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. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1000 to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,200 to 8,000 g / mol, for example 4,500 or 8,000, may again be preferred from this group.

Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers are particularly preferably used in the compositions according to the invention. The sulfonic acid-containing copolymers will be described in detail below.

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. Their molecular weight relative to free acids is generally 2000 to 100000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 30,000 to 80,000 g / mol.

The content of the direct (spray) drying products of (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight, in particular from 2 to 20% by weight, with contents of not more than 10% by weight being used for cost reasons. Find favor.

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,

Further preferred copolymers preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable quantities are from 3 to 15 wt .-% for zeolite-containing and / or silicate-containing direct (spray) drying products.

Other co-builders which may be present together with phosphonates, but also as partial to complete substitutes for phosphonates, are iminodisuccinates (IDS) and their derivatives, for example hydroxyiminodisuccinates (HDIS). It has been known for some years that these raw materials can be used in detergents and cleaning agents as co-builders. Thus, the use of HIDS in detergents and cleaning agents already in the patent applications WO 92/02489 and DE 43 11 440 described. From the European patent application EP 0 757 094 For example, the beneficial use of iminodisucinates in combination with polymers having recurring succinyl moieties is known. More recently, it has been discovered that IDS- or HIDS-containing agents can positively contribute to the color retention of textiles.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds capable of forming complexes with alkaline earth ions may be present as co-builders in the particles of the invention, especially in the direct (spray) drying products.

Also suitable for use in the (spray) drying according to the invention are components from the classes of the grayness inhibitors (soil carriers), the neutral salts and the textile-softening adjuvants and also other customary detergent constituents

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, 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. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful. However, preference is given to cellulose ethers, such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and polyvinylpyrrolidone, for example, in amounts of from 0.1 to 5% by weight, based on the direct ( Spray) drying products used.

Suitable plasticizers are, for example, swellable phyllosilicates of the type of corresponding montmorillonites, for example bentonite.

The content of water in the direct (spray) drying product is preferably 0 to less than 25 wt .-% and in particular 0.5 to 20 wt .-%, with values of at most 15 wt .-% find special preference. Not included here was the water present on any existing aluminosilicates such as zeolite.

As perfume oils or fragrances, individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, Zitronellyloxyacetaldehyd, cyclamen aldehyde, hydroxyzitronellal, Lilial and Bourgeonal, to the ketones such as the Jonone, α-isomethylionone and methyl cedrylketone , to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.

According to a further preferred embodiment, the perfume comprises a perfume fixative, preferably in the form of diethyl phthalates, musk (derivatives) and mixtures thereof, wherein the fixative amount preferably 1 to 55 wt .-%, advantageously 2 to 50 wt .-%, even more advantageous 10 to 45 wt .-%, in particular 20 to 40 wt .-% of the total amount of perfume.

According to a further preferred embodiment, the particles contain a viscosity of liquids, in particular perfume-increasing agent, preferably PEG (polyethylene glycol), advantageously having a molecular weight of 400 to 2000, wherein the viscosity increasing agent in a preferred manner in amounts of 0.1 to 20 wt .-%, advantageously from 0.15 to 10 wt .-%, more preferably from 0.2 to 5 wt .-%, in particular from 0.25 to 3 wt .-% is contained, based on the particles.

It is preferred if the added fragrances also include those systems which have a sustained release action with respect to the release of fragrance. Such systems can be found in the prior art. In this connection, reference should be made in particular to the class of silicic acid esters, in particular to those systems as described in the European applications EP 1112273 and EP 1263405 (both handles), which are incorporated herein by reference in their entirety. These silicic acid esters are characterized, inter alia, by a long-lasting release of fragrance and also cause an extension of the fragrance effect of other fragrances. The European patent applications EP 0 998 911 . EP 0 982 313 and EP 0 982 022 General Electric, to which reference is made in its entirety, describe non-volatile, polymeric, copolymeric or oligomeric siloxanes in which one or more organic substituents are radicals derived from certain alcohols, aldehydes, ketones or esters, which may be both siloxanes and as well as compositions incorporating the corresponding siloxanes, confer certain advantageous properties. Are these alcohols, aldehydes, ketones or esters to fragrant compounds such. As para-anisalcohol, safranal, carvone, citric lyelly, to name only one example of such an alcohol, aldehyde, ketone or ester, the siloxanes in question are also very advantageous in terms of a long-lasting release of fragrance.

The direct (spray) drying products and / or the aftertreated products described above can be prepared in a further embodiment of the invention with other ingredients of detergents and cleaners, in particular mixed, it being advantageous that components can be admixed the (spray) drying are not accessible. From the broad state of the art is generally known which ingredients of detergents and cleaners are not the (spray) drying available and which raw materials are usually mixed. In particular, high-temperature-sensitive mixture constituents of detergents and cleaners are admixed, such as bleaches based on percompounds, bleach activators and / or bleach catalysts, enzymes for example from the classes of proteases, lipases, cellulases and / or amylases, or from bacterial strains or fungi, wherein combinations of 2 or more of the enzyme classes are particularly preferred, foam inhibitors in optionally granular and / or compounded form, perfumes, temperature-sensitive dyes and the like. These may conveniently be mixed with the previously dried compositions and optionally post-treated products.

UV absorbers which are applied to the treated textiles and improve the lightfastness of the fibers and / or the lightfastness of other constituents of the formulation can also be added subsequently. Under UV absorber are organic substances (sunscreen) to understand, which are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, eg heat to give back. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid. Of particular importance are biphenyl and especially Stilbenderivate as described for example in the EP 0728749 A and commercially available as Tinosorb® FD or Tinosorb® FR ex Ciba. As UV-B absorber are 3-benzylidene camphor or 3-Benzylidennorcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor, as in EP 0693471 B1 described; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid ester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate; 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 U.S. Pat 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; Ketotricyclo (5.2.1.0) decane derivatives as described in U.S.P. EP 0694521 B1 described. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, 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-Benzylidencamphers, such as 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.

As a typical UV-A filter in particular derivatives of benzoylmethane are suitable, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1,3-dione, and enamine compounds as described in U.S.P. DE 19712033 A1 (BASF). Of course, the UV-A and UV-B filters can also be used in mixtures. In addition to the soluble substances mentioned, insoluble photoprotective pigments, namely finely dispersed, preferably nano-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. As salts silicates (talc), barium sulfate or zinc stearate can be used. 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 may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. Preferably, micronized zinc oxide is used. Further suitable UV photoprotective filters can be found in the review 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, based on the total resulting agent. In exceptional cases, they may also be contained in the direct (spray) drying product.

However, other constituents, for example so-called speckles, which stand out by their color and / or their shape from the appearance of direct and / or post-treated (spray) drying products. The speckles may once have a similar to identical com spectrum as the direct and / or post-treated (spray) drying products as well as the same composition but a different color. It is also possible that the speckles have the same composition as the direct and / or post-treated (spray) drying products, are not stained but have a different shape. Finally, however, it is preferred that speckles having the same composition as the direct and / or post-treated (spray) drying products differ from the latter in color and optionally additionally in their form. In these cases, the speckles are merely intended to make the appearance of the finished detergents and cleaners even more attractive.

In a further and quite preferred embodiment of the invention, however, the speckles have a different chemical composition than the direct and / or post-treated (spray) drying products. Especially here can be pointed out that certain ingredients for certain purposes, such as bleaching or care aspects are included in the final product due to a different color and / or a different shape of the end user. These speckles can not only be spherical to rod-shaped, they can also represent completely different figures.

The admixed speckles or else other ingredients may for example be spray-dried, agglomerated, granulated, pelletized or extruded. With regard to extrusion processes, particular reference is made here to the disclosures in the European patent EP 0486592 B1 and the international patent application WO 98/12299 directed. Since it is an advantage of the direct and / or post-treatment (spray) drying products to include excellent dissolution rate even with relatively cold water at 30 ° C, it is of course preferred to mix such other ingredients and / or raw materials which also have an excellent dissolution rate. Therefore, in a preferred embodiment of the invention, raw materials are mixed in accordance with the disclosure of the international patent application WO 99/28433 were manufactured.

In another embodiment, the present invention thus provides a life, washing and cleaning agent (detergent composition) or care product in that the direct (spray) drying product and / or aftertreated product according to the invention, advantageously in amounts of from 0.5 to 99, 5 wt .-%, more preferably from 1 to 95 wt .-%, more preferably from 5 to 90 wt .-%, more preferably 10 to 80 wt .-%, preferably 20 to 70 wt. % and in particular 30 to 60 wt .-% and other ingredients added. These further constituents advantageously contain 0.01% by weight to 95% by weight, preferably 5% by weight to 85% by weight, more preferably 3% by weight to 30% by weight, in particular 5% by weight. -% to 22 wt .-% of surfactant (s), based on the total amount of these other components added.

1. (a) erfindungsgemäße Partikel,
2. (b) 0, 01 Gew.-% bis 95 Gew.-%, vorzugsweise 5 Gew.-% bis 85 Gew.-%, vorteilhafterweise 3 Gew.-% bis 30 Gew.-%, insbesondere 5 Gew.-% bis 22 Gew.-% zusätzlicher Tensid(e)

sowie optional weitere Bestandteile.A further subject of the invention is a detergent composition (washing and cleaning agent) comprising:

1. (a) particles according to the invention,
2. (b) 0, 01 wt .-% to 95 wt .-%, preferably 5 wt .-% to 85 wt .-%, advantageously 3 wt .-% to 30 wt .-%, in particular 5 wt .-% to 22% by weight of additional surfactant (s)

as well as optional further components.

In the following, further suitable ingredients of a washing and cleaning agent according to the invention are described, wherein these ingredients may be present in the particles according to the invention and / or in the admixing components. Preferably, a washing and cleaning agent according to the invention consists of admixing components and the particles according to the invention.

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

In a preferred embodiment, detergents and cleaners according to the invention are distinguished by the fact that they contain bleaching agents, preferably sodium percarbonate and / or halogen bleach, in amounts of from 0.5 to 80% by weight, preferably from 2.5 to 70% by weight preferably from 5 to 60 wt .-% and in particular from 10 to 50 wt .-%, each based on the total mass of the composition.

In order to achieve an improved bleaching effect during washing at temperatures of 60 ° C. and below, bleach activators may be present in detergents and cleaners according to the invention. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexa-hydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be present in detergents and cleaners according to the invention. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Particularly suitable are bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. Enzyme mixtures, for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but in particular cellulase-containing mixtures, are of particular interest. Peroxidases or oxidases have also proved suitable in some cases. The enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation. The proportion of enzymes, enzyme mixtures or enzyme granules in the detergents and cleaners according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

Detergents according to the invention contain, according to a particularly preferred embodiment, further additives known from the prior art as additives for detergents and cleaners. A preferred group of additives used in the invention are optical brighteners. Can be used here, the usual in detergents optical brightener. Examples of optical brighteners are derivatives of diaminostilbene disulfonic acid or its alkali metal salts. Suitable z. B. salts of 4, 4'-bis (2-anilino-4-morpholino1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed compounds which instead of the MorpholinoGroup a diethanol-amino Group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the type of substituted Diphenylstyryle may be included in the detergent compositions of the invention, for. For example, the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl or 4- (4-chlorostyryl) 4 '- (2 -sulfostyryl-) biphenyl. Mixtures of the aforementioned brightener can be used.

Disintegration aids, preferably a cellulose based disintegration aid, may also be among the relevant ingredients. Well-known disintegration aids are, for example Carbonate / citric acid systems, although other organic acids can be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives. All mentioned disintegration aids can be used according to the invention.

In order to prevent undesirable changes to the detergent and cleaner preparations and / or the treated textiles caused by oxygen and other oxidative processes, the agents may contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

Increased comfort of washed clothing may result from the additional use of antistatic agents. Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges. External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistatic agents for textiles or as an additive to detergents, wherein additionally a softening effect is achieved.

To care for the textiles and to improve the textile properties such as a softer "feel" (avivage) and reduced electrostatic charge (increased wear comfort), the compositions according to the invention may contain softener or softening agent. Preference is given to quaternary ammonium compounds having two hydrophobic radicals, such as, for example, disteraryldimethylammonium chloride, which, however, due to its insufficient biodegradability, is increasingly being replaced by quaternary ammonium compounds which contain ester groups in their hydrophobic radicals as predetermined breaking points for biodegradation (ester quats).

In a preferred embodiment, the additives include preservatives, preferably cationic surfactants, in particular quaternary ammonium compounds.

In a preferred embodiment, the agents according to the invention are characterized in that they contain excipients, preferably cationic surfactant (s), in particular alkylated quaternary ammonium compounds of which at least one alkyl chain is interrupted by an ester group and / or amido group, in amounts of 0, From 5 to 80% by weight, preferably from 2.5 to 70% by weight, especially preferably from 5 to 60 wt .-% and in particular from 10 to 50 wt .-%, each based on the total mass of the composition contains.

wobei in (1) R¹ und R² für einen acyclischen Alkylrest mit 12 bis 24 Kohlenstoffatomen, R³ für einen gesättigten C₁-C₄ Alkyl- oder Hydroxyalkylrest steht, R⁴ entweder gleich R¹, R² oder R³ ist oder für einen aromatischen Rest steht. X^- steht entweder für ein Halogenid-, Methosulfat-, Methophosphat- oder Phosphation sowie Mischungen aus diesen. Beispiele für kationische Verbindungen der Formel (1) sind Didecyldimethylammoniumchlorid, Ditalgdimethylammoniumchlorid oder Dihexadecylammoniumchlorid.Suitable examples are quaternary ammonium compounds of the formulas (1) and (2),

wherein in (1) R ¹ and R ^{2 is} an acyclic alkyl radical having 12 to 24 carbon atoms, R ^{3 is} a saturated C ₁ -C ₄ alkyl or hydroxyalkyl radical, R ^{4 is} either R ¹ , R ² or R ³ or represents an aromatic radical. X ^- is either a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof. Examples of cationic compounds of the formula (1) are didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.

Compounds of formula (2) are so-called ester quats. Compositions of the present invention characterized by containing a quaternary ammonium compound of formula (2) are preferred embodiments of the invention. Esterquats are characterized by excellent biodegradability. Here, R ^{5 is} an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds; R ⁶ is H, OH or O (CO) R ⁶ , R ⁷ is independently of R ^{6 is} H, OH or O (CO) R ⁸ , wherein R ⁸ and R ⁹ are each independently an aliphatic alkyl radical having 12 to 22 carbon atoms having 0, 1, 2 or 3 double bonds, a, b and c may each independently have the value 1, 2 or 3. X ^- may be either a halide, methosulfate, methophosphate or phosphate ion, as well as mixtures of these. Preference is given to compounds which contain the group O (CO) R ⁸ for R ⁶ and for R ⁵ and R ⁸ contain alkyl radicals having 16 to 18 carbon atoms. Particularly preferred are compounds in which R ^{7 is} also OH. Examples of compounds of the formula (2) are methyl N- (2-hydroxyethyl) -N, N-di (tallow acyloxyethyl) ammonium methosulfate, bis (palmitoyl) ethyl hydroxyethyl, methyl ammonium methosulfate or methyl N , N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate. If quaternized compounds of the formula (2) which have unsaturated alkyl chains are used, preference is given to the acyl groups whose corresponding fatty acids have an iodine number between 5 and 80, preferably between 10 and 60 and in particular between 15 and 45 and which have a cis / trans isomer ratio (in wt .-%) of greater than 30: 70, preferably greater than 50: 50 and in particular greater than 70: 30 have. Commercial examples are by Stepan under the tradename Stepantex ^® marketed Methylhydroxyalkyldialkoyloxyalkylammoniummethosulfate or known under Dehyquart ^® products from Cognis or known under Rewoquat ^® products from Goldschmidt-Witco. Further preferred compounds are the diester quats of the formula (3) which are obtainable under the name Rewoquat® W 222 LM or CR 3099.

R ¹⁰ and R ¹¹ are each independently an aliphatic radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.

wobei R¹² für H oder einen gesättigten Alkylrest mit 1 bis 4 Kohlenstoffatomen, R¹³ und R¹⁴ unabhängig voneinander jeweils für einen aliphatischen, gesättigten oder ungesättigten Alkylrest mit 12 bis 18 Kohlenstoffatomen, R¹³ alternativ auch für O(CO)R¹⁵ stehen kann, wobei R¹⁵ einen aliphatischen, gesättigten oder ungesättigten Alkylrest mit 12 bis 18 Kohlenstoffatomen bedeutet, und Z eine NH-Gruppe oder Sauerstoff bedeutet und X^- ein Anion ist, d kann ganzzahlige Werte zwischen 1 und 4 annehmen.In addition to the cationic compounds just described, other known cationic compounds may also be present in the compositions, for example quaternary imidazolinium compounds of the formula (4),

where R ^{12 is} H or a saturated alkyl radical having 1 to 4 carbon atoms, R ¹³ and R ^{14 may} each independently be an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, R ^{13 may} alternatively also be O (CO) R ¹⁵ where R ^{15 is} an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, and Z is an NH group or oxygen and X ^{- is} an anion, d can be integer values between 1 and 4.

wobei R¹⁶, R¹⁷ und R¹⁸ unabhängig voneinander für eine C_1-4-Alkyl-, Alkenyl- oder Hydroxyalkylgruppe steht, R¹⁹ und R²⁰ jeweils unabhängig ausgewählt eine C_8-28-Alkylgruppe darstellt und e eine Zahl zwischen 0 und 5 ist. X^- ist ein passendes Anion, vorzugsweise ein Halogenid-, Methosulfat-, Methophosphat- oder Phosphation sowie Mischungen aus diesen sein. Erfindungsgemäße Mittel, die sich dadurch auszeichnen, daß sie eine quartäre Ammoniumverbindung gemäß Formel (5) beinhalten, sind besonders bevorzugt.Further preferred quaternary cationic compounds are described by formula (5)

wherein R ¹⁶ , R ¹⁷ and R ¹⁸ independently represent a C _1-4 alkyl, alkenyl or hydroxyalkyl group, R ¹⁹ and R ²⁰ each independently represent a C _8-28 alkyl group and e is a number between 0 and 5 is. X ^- is a suitable anion, preferably a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof. Compositions of the invention which are characterized in that they include a quaternary ammonium compound according to formula (5) are particularly preferred.

In addition to the compounds of the formulas (1) and (2) also short-chain, water-soluble, quaternary ammonium compounds can be used, such as trihydroxyethylmethylammonium methosulfate or alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and Trialkylmethylammoniumchloride, z. Cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetylmethyl ammonium chloride.

Also protonated alkylamine compounds which have plasticizing effect, as well as the non-quaternized, protonated precursors of cationic emulsifiers are suitable.

Further compounds which can be used according to the invention and can be present in the compositions are the quaternized protein hydrolysates.

die Alkylamidoamine in ihrer nicht quatemierten oder, wie dargestellt, ihrer quaternierten Form, sein können. R²¹ kann ein aliphatischer Alkylrest mit 12 bis 22 Kohlenstoffatomen mit 0, 1, 2 oder 3 Doppelbindungen sein, f kann Werte zwischen 0 und 5 annehmen. R²² und R²³ stehen unabhängig voneinander jeweils für H, C_1-4-Alkyl oder Hydroxyalkyl. Bevorzugte Verbindungen sind Fettsäureamidoamine wie das unter der Bezeichnung Tego Amid^®S 18 erhältliche Stearylamidopropyldimethylamin oder das unter der Bezeichnung Stepantex^® X 9124 erhältliche 3-Talgamidopropyl-trimethylammonium-methosulfat, die sich neben einer guten konditionierenden Wirkung auch durch farbübertragungsinhibierende Wirkung sowie speziell durch ihre gute biologische Abbaubarkeit auszeichnen. Besonders bevorzugt sind alkylierte quaternäre Ammoniumverbindungen, von denen mindestens eine Alkylkette durch eine Estergruppe und/oder Amidogruppe unterbrochen ist, insbesondere N-Methyl-N(2-hydroxyethyl)-N,N-(ditalgacyloxyethyl)ammonium-methosulfat und/oder N-Methyl-N(2-hydroxyethyl)-N,N-(palmitoyloxyethyl)ammonium-methosulfat.It is likewise possible to use compounds of the formula (6)

the alkylamidoamines may be in their unquaternized or, as shown, their quaternized form. R ²¹ can be an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds, f can assume values between 0 and 5. R ²² and R ²³ are each independently H, C _1-4 alkyl or hydroxyalkyl. Preferred compounds are fatty acid amidoamines such as Stearylamidopropyldimethylamin available under the name Tego Amid ^® S 18 or 3-Talgamidopropyl-trimethylammonium methosulfate available under the name Stepantex ^® X 9124, which in addition to a good conditioning effect by color transfer inhibiting effect and especially by their good distinguish biodegradability. Particularly preferred are alkylated quaternary ammonium compounds, of which at least one alkyl chain is interrupted by an ester group and / or amido group, in particular N-methyl-N (2-hydroxyethyl) -N, N- (ditalgacyloxyethyl) ammonium methosulfate and / or N-methyl-N (2-hydroxyethyl) -N, N- (palmitoyloxyethyl) ammonium methosulfate.

To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate the ironing of the treated textiles, for example, silicone derivatives can also be used in the compositions according to the invention. These additionally improve the rinsing out of the compositions according to the invention by their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.

Since textile fabrics, in particular of rayon, rayon, cotton and their mixtures, can crumple because the individual fibers against bending, kinking. Pressing and squeezing are sensitive transversely to the fiber direction, the detergents of the invention may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

For controlling microorganisms, the compositions of the invention may contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate. The terms antimicrobial action and antimicrobial active ingredient in the context of the teaching according to the invention have the usual meaning, which is described, for example, by K. H. Wallhäusser in "Practice of Sterilization, Disinfection - Conservation: Germ Identification - Plant Hygiene" (5th edition - Stuttgart, New York: Thieme, 1995) is reproduced, with all substances described there can be used with antimicrobial effect. Suitable antimicrobial agents are preferably selected from the groups of the alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazolines , Phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propyl-butylcarbamate, iodine, iodophores, peroxo compounds, halogen compounds and any mixtures of the above compounds or connection groups.

The antimicrobial active ingredient may be selected from the group of the compounds mentioned below, it being possible to use one or more of the compounds mentioned: ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, Glycerol, undecylenic acid, benzoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N-methylmorpholine-acetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 4,4'-dichloro-2'-hydroxydiphenyl ether (dichlosan), 2,4,4'-trichloro-2'-hydroxydiphenyl ether (trichlosan), chlorhexidine, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl ) urea, N, N '- (1,10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4-chlorophenyl) - 3,12-diimino-2,4,11,13-tetra-azatetradecandiimidamide, glucoprotamines, antimicrobial surface-active quaternary compounds, guanidines including the bi-and polyguanidines, such as 1,6-bis (2-ethylhexyl) biguanido hexane) -dihydro- chloride, 1,6-di- (N ₁ , N ₁ '-phenyl-diguanido-N ₅ , N ₅ ' -) hexane-tetrahydrochloride, 1,6-di- (N ₁ , N ₁ '-phenyl-N ₁ , N _1- methyldiguanido-N ₅ , N ₅ '-) hexane-dihydrochloride, 1,6-di- (N ₁ , N ₁ ' -o-chlorophenyl-diguanido-N ₅ , N ₅ '-) hexane-dihydrochloride, 1,6- Di- (N ₁ , N ₁ '-2,6-dichlorophenyldiguanido-N ₅ , N ₅ ' -) hexane dihydrochloride, 1,6-di- [N ₁ , N ₁ '-beta (p-methoxyphenyl) diguanido-N ₅ , N ₅ -] hexane dihydrochloride, 1,6-di- (N ₁ , N ₁ '-alphamethyl-beta-phenyldiguanido-N ₅ , N ₅ ' -) hexane dihydrochloride, 1,6-di - (N ₁ , N ₁ '- p -nitrophenyldiguanido-N ₅ , N ₅ ' -) hexane dihydrochloride, omega: omega-di- (N ₁ , N ₁ '-phenyldiguanido-N ₅ , N ₅ ' -) di n-propyl ether dihydrochloride, omega: omega'-di- (N ₁ , N ₁ '-p-chlorophenyldiguanido-N ₅ , N ₅ ' -) di-n-propyl ether tetrahydrochloride, 1,6-di- (N ₁ , N ₁ '-2,4-dichlorophenyldiguanido-N ₅ , N ₅ ' -) hexane-tetrahydrochloride, 1,6-di- (N ₁ , N ₁ '-p-methylphenyl-diguanido- N ₅ , N ₅ ' -) hexane dihydrochloride, 1,6-di- (N ₁ , N ₁ '-2,4,5-trichlorophenyldiguanido-N ₅ , N ₅ ' -) hexane-tetrahydro-chloro id, 1,6-di- [N ₁ , N ₁ '-alpha (p-chlorophenyl) ethyldiguanido-N ₅ , N ₅ ' -] hexane dihydrochloride, omega: omega-di- (N ₁ , N ₁ ' -p-chlorophenyldiguanido-N ₅ , N ₅ '-) m-xylene dihydrochloride, 1,12-di- (N ₁ , N ₁ ' -p-chlorophenyldiguanido-N ₅ , N ₅ '-) dodecane dihydrochloride, 1 , 10-di- (N ₁ , N ₁ '-phenyl-diguanido-N ₅ , N ₅ ' -) -decane-tetrahydro-chloride, 1,12-di- (N ₁ , N ₁ '-phen-yldiguanido- N ₅ , N ₅ '-) dodecane-tetrahydrochloride, 1,6-di- (N ₁ , N ₁ ' -o-chlorophenyl-diguanido- N ₅ , N ₅ '-) hexane-dihydrochloride, 1,6-di- (N ₁ , N ₁ '-o-chlorophenyldiguano-nido-N ₅ , N ₅ ' -) hexane-tetrahydrochloride, ethylenebis (1-tolylbiguanide), ethylenebis (p-tolylbiguanide), ethylenebis- (3,5-dimethylphenylbiguanide), ethylenebis ( p-tert-amylphenylbiguanide), ethylenebis (nonylphenylbiguanide), ethylenebis (phenylbifluoride), ethylenebis (N-butylphenylbiguanide), ethylenebis (2,5-diethoxyphenyl-biguanide), ethylenebis (2,4-dimethylphenylbiguanide), Ethylenebis (o-diphenyl-biguanide), ethylenebis (mixed amyl naphthylbiguanide), N-butyl-ethylenebis (phen -ylbiguanide), trimethylenebis (o-tolylbiguanide), N-butyl-trimethylenebis (phenylbifluoride) and the corresponding salts such as acetates, gluconates, hydrochlorides, hydrobromides, citrates, bisulfites, fluorides, polymaleates, N-cocoalkylsarcosinates, phosphites , Hypophosphites, perfluorooctanoates, silicates, sorbates, salicylates, maleates, tartrates, fumarates, ethylenediaminetetraacetates, iminodiacetates, cinnamates, thiocyanates, arginates, pyromellitates, tetracarboxybutyrates, benzoates, glutarates, monofluorophosphates, perfluoropropionates and any mixtures thereof. Also suitable are halogenated xylene and cresol derivatives, such as p-chloro-meta-cresol or p-chloro-meta-xylene, and natural antimicrobial agents of plant origin (eg from spices or herbs), animal and microbial origin. Preferably, antimicrobial surface-active quaternary compounds, a natural antimicrobial Substance of vegetable origin and / or a natural antimicrobial agent of animal origin, most preferably at least one natural antimicrobial agent of plant origin from the group comprising caffeine, theobromine and theophylline and essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial agent of animal origin from the group comprising enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface active quaternary compound having an ammonium, sulfonium, phosphonium, iodonium or Arsoniumgruppe, peroxo compounds and chlorine compounds chlorine compounds. Also substances of microbial origin, so-called bacteriocins, can be used.

Examples of suitable quaternary ammonium compounds (QAVs) as antimicrobial agents are benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B (m, p-dichlorobenzyldimethyl-C 12 -alkylammonium chloride, CAS No. 58390-78-6), benzoxonium chloride (benzyldodecyl-bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethylammonium bromide, CAS No. 57-09-0) , Benzetonium chloride (N, N-dimethyl-N- [2- [2- [ p- (1,1,3,3-tetramethylbutyl) phenoxy] oxy] ethyl] benzylammonium chloride, CAS No. 121- 54-0), dialkyldimethylammonium chlorides such as di- n -decyldimethylammoniumchlorid (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyl dimethyl ammonium chloride, 1-cetylpyridinium chloride (CAS No. 123- 03-5) and thiazoline iodide (CAS No. 15764-48-1) and mixtures thereof. Particularly preferred QACs are the benzalkonium chlorides having C ₈ - to C ₁₈ -alkyl radicals, in particular C ₁₂ - to C ₁₄ -alkylbenzyldimethylammonium chloride.

Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat ^® by Lonza, Marquat® ^® from Mason, Variquat ^® from Witco / Sherex and Hyamine ^® from Lonza Bardac ^® from Lonza Company, as well. Other commercially obtainable antimicrobial agents are N- (3-chloroallyl) hexaminium chloride such as Dowicide and Dowicil ^{® ®} from Dow, benzethonium chloride such as Hyamine ^® 1622 Rohm & Haas, methylbenzethonium as Hyamine ^® 10X from Rohm & Haas, cetylpyridinium chloride such as Cepacol and the company Merrell Labs.

The antimicrobial agents are preferably used in agents according to the invention in amounts of from 0.0001% by weight to 1% by weight, preferably from 0.001% by weight to 0.8% by weight, particularly preferably from 0.005% by weight to 0.3 wt .-% and in particular from 0.01 to 0.2 wt .-% used.

In a preferred embodiment, an agent according to the invention contains those active ingredients which are beneficial to the fiber elasticity, shape retention and tear resistance of the textile fibers. Substituting fibers of a medium or high deformation force, for example, by stretching the fiber by 80%, this can result in untreated fibers that the fiber is not or only partially returns to its original shape when the deformation force is eliminated. In certain circumstances can even rip the fiber. Of course, for practical reasons, the consumer desires textile fibers which do not tear or lose their original shape even when exposed to medium or high deformation or stretching forces. It has now been found that certain active substances which can be applied to the textile fibers in a washing process and as a result greatly improve their elasticity, shape retention and tear resistance, so that the fibers are more tear-resistant and elastic, are effective in a particularly advantageous manner, if they contained in the inventive compositions.
These active substances are preferably aminosiloxanes, cellulose derivatives, in particular cellulose ethers and carboxylic acid esters.

Preferred carboxylic acid esters obey the general formula (7)

• i) -C₆H_h(OH)_i, wobei h zwischen 3 und 4, i zwischen 1 und 2 liegt, und wobei die Summe h+i 5 beträgt, insbesondere -C₆H₄OH;
• ii) -CH(OH)-CH(R²⁶)-COO-(-CH₂-CH₂-O-)_j-R²⁷, wobei R²⁶ gleich H oder OH ist, j liegt zwischen 0, was bevorzugt ist, und 20, and R²⁷ ist ein mono-funktionelles Kohlenwasserstoffradikal, vorzugsweise ein Alkylrest mit 6-20, insbesondere 8-18, Kohlenstoff-Atomen;
• iii) -CH(OH)-CH₃

R ^{24 is} -CO-O - (- CH ₂ -CH ₂ -O-) _g -R ²⁵ , where g is between 0, which is preferred, and 20, where R ^{25 is} a monofunctional hydrocarbon radical of 6-20, preferably 8-18, carbon atoms, and wherein R ^{24 is} a mono-functional hydrocarbon radical containing at least one hydroxy group and at least two carbon atoms, preferably selected from the following radicals:

• i) -C ₆ H _h (OH) _i , where h is between 3 and 4, i is between 1 and 2, and where the sum h + i is 5, in particular -C ₆ H ₄ OH;
• ii) -CH (OH) -CH (R ²⁶ ) -COO - (- CH ₂ -CH ₂ -O-) _j -R ²⁷ , where R ²⁶ is H or OH, j is between 0, which is preferred and 20, and R ²⁷ is a mono-functional hydrocarbon radical, preferably an alkyl radical of 6-20, especially 8-18, carbon atoms;
• iii) -CH (OH) -CH ₃

Typical and preferred esters which obey this formula (7) include, but are not limited to, tridecyl salicylate (HO-C ₆ H ₄ -CO-O- (C ₂ H ₂ ) ₁₂ -CH ₃ ), di- ( C ₁₂ -C ₁₃₎ -alkylmalate, alkyltartrate di- (C ₁₂ -C ₁₃₎ and / or di- (C ₁₂ - C ₁₃₎ alkyl lactates.

According to a further preferred embodiment of the invention, the particles according to the invention are at least partially surrounded by a coating which preferably contains at least one at least partially water-soluble or at least partially water-dispersible component which is in particular selected from polyols, carbohydrates, starches, modified starches, starch hydrolysates, Cellulose and cellulose derivatives, natural and synthetic gums, silicates, borates, phosphates, chitin and chitosan, water-soluble polymers, fat components and mixtures of these. For example, waxes and / or resins come into consideration, for. Beeswax, benzoin, carnauba wax, candelilla wax, coumarone-indene resin, copels, shellac, mastic, polyethylene wax oxidates or sandarak resin. Likewise suitable are paraffins or gelatin, in particular cellulose ethers.

According to a further preferred embodiment, the coating has polycarboxylates.

The coating of the particles can be carried out in the manners described in the prior art. The coating material preferably completely encloses the respective particles, although a discontinuous coating may also be desired. Suitable coating materials are, in particular, those which are commonly used in connection with detergents and cleaners.

Materials which can be used as coating materials in the context of the invention are any inorganic and / or organic substances and / or mixtures of substances, preferably those which are sensitive to pH, temperature and / or ionic strength, so that they are dependent on a pH. , Temperature and / or ionic strength change lose their integrity, ie for example, dissolve completely or partially.

Particularly preferred as coating materials are polymers and / or copolymers which have film-forming properties and can preferably be used from aqueous dispersion. Organic solvents are for many reasons (flammability, toxicity, etc.) disadvantageous in the production of pH-sensitive coatings. Aqueous dispersions are characterized by easy handling and the avoidance of all toxicological problems. The decisive factor for the film-forming properties is the glass transition temperature of the film-forming polymer and / or copolymer. Above the glass transition temperature, the polymer or copolymer is elastic, meltable and flowable, while becoming brittle below the glass transition temperature. Only above the glass transition temperature can the polymer be easily processed as required to form a film coating. The glass transition temperature can be influenced by the addition of low molecular weight substances with softening properties, the so-called plasticizers. In addition to the polymer, it is thus also possible to use plasticizers in the aqueous dispersion. Suitable plasticizers are all substances which reduce the glass transition temperature of the polymers and / or copolymers used, preferably pH-sensitive polymers. The polymer can thus be applied at lower temperatures, possibly even at room temperature. Particularly preferred plasticizers are citric acid esters (preferably tributyl citrate and / or triethyl citrate), phthalic acid esters (preferably dimethyl phthalate, diethyl phthalate and / or dibutyl phthalate), esters of organic polyalcohols (preferably glycerol triacetate), polyalcohols (preferably glycerol, propylene glycol) and / or polyoxyethylene glycols (preferably polyethylene glycol ). The plasticizer deposits between the polymer chains, thereby increasing the mobility, reducing the interactions and avoiding abrasion and cracks in the film by reducing the brittleness

It is particularly advantageous if the coating material is a polyacrylate and / or a derivative thereof and / or a corresponding copolymer based on acrylic esters or acrylic acids and other monomers. In particular, copolymers of acrylamide and acrylic acid and / or derivatives thereof are of advantage for the coating material according to the invention.

Another object of the invention is a process for washing textiles, comprising the step of contacting the textiles with an aqueous medium containing an effective amount of a detergent composition according to the invention (detergent composition).

Examples:

In order to detect the increased absorption capacity of the particles according to the invention, various particles were prepared by spray drying (countercurrent nozzle atomization) aqueous slurries, and then the oil number of the particles was determined.
The oil number is a common measure for characterizing the oil absorption capacity of particles. The determination of the oil numbers was carried out according to DIN ISO 787.
The slurrytemperatur before the nozzles was about 70 ° C, in the production of the particle B about 120 ° C. The temperature at the inlet (inlet temperature) was about 210 ° C. The gas consumption was about 150-160 m ³ / l.

Slurry formulation for the preparation of the comparison particles by spray drying: Fatty alcohol C12-C18 + 4.5 EO 1.45% by weight Fatty alcohol C12-C18 + 7 EO 0.50% by weight Zeolite A 76.39% by weight Carboxymethylcellulose sodium salt 2.00% by weight sodium hydroxide 0.48% by weight sodium sulphate 1.70% by weight water 16.75% by weight rest 0.73% by weight

The resulting particles had the following parameters: Bulk density: 480 g / l Oil absorption: 146 ml / 100g d ₅₀ : 0.32 mm (d ₅₀ is the average particle diameter or the feature value at which the distribution sum of the particle diameter assumes the value 0.5 = 50%.) For example, the statement "d ₅₀ = a mm" means that 50 (mass) of the considered good % of the particles have a diameter greater than a mm and 50 (mass)% have a diameter smaller than a mm.)

Slurry formulation for the preparation of particles A by spray drying: Fatty alcohol C12-C18 + 4.5 EO 1.41% by weight Fatty alcohol C12-C18 + 7 EO 0.50% by weight Zeolite A 74.44% by weight Carboxymethylcellulose sodium salt 2.00% by weight sodium hydroxide 0.47% by weight sodium sulphate 1.70% by weight water 16.75% by weight sodium 2.00% by weight rest 0.73% by weight

The resulting particles A had the following parameters: Bulk density: 490 g / l Oil absorption: 160 ml / 100g d ₅₀ : 0.28 mm

Slurry formulation for the preparation of particles B by spray drying: Fatty alcohol C12-C18 + 4.5 EO 1.39% by weight Fatty alcohol C12-C18 + 7 EO 0.50% by weight Zeolite A 73.13% by weight Carboxymethylcellulose sodium salt 2.00% by weight sodium hydroxide 0.46% by weight sodium sulphate 1.70% by weight water 16.75% by weight Hydroxypropane-1,2,3-tricarboxylic acid * 1H ₂ O 3.34% by weight rest 0.73% by weight

The resulting particles B had the following parameters: Bulk density: 500 g / l Oil absorption: 160 ml / 100g d ₅₀ : 0.32 mm

The particles A and B according to the invention thus had oil numbers which were almost ten percent higher than those of the comparison particles.

The comparison particles and particles A and B, whose bulk weights and grain size distribution were all comparable, were also exposed to perfume by mixing the perfume and the respective particles in a standard mixing unit, wherein the weight gain of the particles, the maximum possible perfume absorption of the respective particles was determined. It was found that particles A and B according to the invention could each receive about 10% by weight more perfume than the comparison particles. Despite the high perfume loading particles A and B according to the invention remained free flowing even after prolonged storage and did not stick.

Claims (7)

1. A particle which may be prepared according to a method, wherein a paste containing substances which release carbon dioxide at elevated temperatures, is subjected to drying, wherein carbon dioxide is produced in the material to be dried during the process, wherein the particle of the direct drying product is post-treated with non-ionic surfactants, and/or perfume or preparation forms containing these ingredients,
   wherein the particle contains:

   a) an inorganic carrier material in amounts of at least 30% by weight,

   b) perfume in amounts from at least 5% by weight to 40% by weight,

   c) a non-ionic surfactant in amounts from 0.5 to 5% by weight

   as well as optionally other components.
2. The particle according to claim 1, characterized in that the applied paste contains an inorganic carrier material, preferably selected from the group comprising zeolites, sulfates, carbonates, silicates, silicic acid and/or mixtures thereof.
3. The particle according to any of claims 1 or 2, characterized in that the applied paste contains an anionic or cationic surfactant.
4. The particle according to any of claims 1 to 3, characterized in that the applied paste contains substance(s) which release(s) carbon dioxide at high temperatures, selected from hydrogencarbonate compounds, citric acid and/or aconitic acid.
5. The particle according to any of claims 1 to 4, characterized in that it is surrounded by a coating, wherein the latter preferably has polycarboxylates.
6. A detergent composition, containing:

   (a) a particle according to any of claims 1 to 5,

   (b) 0.01% by weight to 95% by weight, preferably 5% by weight to 85% by weight, advantageously 3% by weight to 30% by weight, in particular 5% by weight to 22% by weight of additional surfactant(s)

   as well as optionally other components.
7. A method for washing textiles, comprising the step of contacting the textiles with an aqueous medium, which contains an effective amount of a detergent composition according to claim 6.