EP1025198A1

EP1025198A1 - Method for producing scent intensifying washing and cleaning detergents

Info

Publication number: EP1025198A1
Application number: EP98955451A
Authority: EP
Inventors: Kathleen Paatz; Wolfgang Lahn
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1997-10-23
Filing date: 1998-10-14
Publication date: 2000-08-09
Anticipated expiration: 2018-10-14
Also published as: EP1025198B1; PL340036A1; ES2205570T3; US6228833B1; ATE246727T1; JP2001521060A; WO1999021955A1; DE19746781A1; DE59809226D1; CN1276829A; PL188261B1

Abstract

Scent intensifying washing and cleaning detergents or components for these detergents are manufactured in which a solid and essentially water-free premix is produced, said premis being comprised of washing and cleaning detergent compounds and/or washing and cleaning detergent materials. The premix contains at least 0.1 wt. % perfume referring to the premix and is subjected to granulation or compacted agglomeration. By virtue of the water-free method, subsequent drying steps do not apply in which the prefume is entirely or partially vaporized. The homogenous incorporation of the prefume leads to a substantially increased fragrance of both the product as well as the articles which are dampened or dried, especially textiles.

Description

'Process for the production of fragrance-reinforced washing or cleaning agents'

The present invention relates to a method for producing solid, fragrance-reinforced washing or cleaning agents. In particular, the invention relates to a method for producing fragrance-reinforced detergents or cleaning agents with bulk densities above 600 g / 1 by press agglomeration of an essentially water-free premix.

The scenting of solid washing and cleaning agents is a reliable state of the art. On the one hand, these products are perfumed in order to provide the consumer with a recognizable and "unmistakable" agent in addition to the structure and color impression, on the other hand, the incorporation of fragrances should lead to the objects treated with the agents, in particular textiles , are given a long-lasting fragrance, which is rated by the consumer as a performance of the agent in question. Usually, the auxiliaries that do not act directly in the washing or cleaning process are added last to the washing and cleaning agents. This procedure particularly affects the "aesthetic" Components such as colors and fragrances. The perfume is usually incorporated in such a way that the finished solid granules are sprayed with perfume, which is optionally fixed to the surface of the solid composition with powdering components. The disadvantage of this procedure is that the fragrances are not distributed homogeneously over the entire composition and are additionally partially removed in the case of any subsequent drying steps. The fragrance impression of the agents or the treated objects is often not intense enough with this type of perfuming and can only be made satisfactory by using more fragrance.

The production of detergent and cleaning agent granules is widely described in the prior art, and in addition to comprehensive patent literature, from the individual publication in specialist journals to the complete monograph, there is an almost unmanageable number of documents that deal with this topic. Densified detergents and cleaning agents and processes for their preparation are described, for example, in German Offenlegungsschriften DE 39 26 253 and DE 195 19 139 (both Henkel KGaA). These documents describe the extrusion of water-containing solid mixtures with the addition of plasticizers and / or lubricants. Nothing is said in these writings about the use of fragrances; however, since the extrudates produced without perfume contain water and must subsequently be dried, any desired scenting can only be carried out by the conventional method of spraying onto the already dried extrudates.

The older German patent application 196.38.599.7 (Henkel KGaA) describes an extrusion process which is low in water or free of water, in which subsequent drying steps can be dispensed with because an essentially water-free premix is extruded, which preferably has a water content of not more than 15% by weight. %, which water is not in free form. Also in this document nothing is said about the scenting of the extrudates obtained.

To solve the problem of insufficiently scented articles treated with detergents or cleaning agents, the prior art has described, for example, particles containing perfume in which the fragrance is quasi “encapsulated”. In particular, complexes of cyclodextrins and perfume are considered to be strong in the prior art Fragrant and fragrant agents for use in detergents and cleaning agents are described, for example in patent applications and patent specifications EP 602 139, US 5,236,615 and EP 397 245 (all Procter & Gamble). Microencapsulated perfume oils are also used for this purpose, the perfume preferably activated in the dryer: EP 376 385 (Procter & Gamble).

The proposed solutions mentioned in the prior art extend mainly to the scenting of the treated and dried textiles. If it is desired that the product itself or the freshly washed and still wet laundry is more noticeable olfactively, the products must also be in a more conventional manner Be sprayed with perfume, which means a further process step in addition to the production of the fragrance particles.

The present invention is based on the object of providing a method with which fragrance-reinforced detergents or cleaning agents or components therefor can be produced which not only impart a stronger fragrance to dry laundry, but also to moist laundry, and also as an agent per se smell more clearly than the traditionally scented agents.

It has now been found that agents with the desired properties are obtained if a solid perfume-containing premix is prepared which is essentially water-free and this premix is subjected to press agglomeration.

The invention relates to a process for the production of fragrance-reinforced detergents or cleaning agents or components therefor with bulk densities above 600 g / 1, a solid and essentially water-free premix made from detergent or cleaning agent compounds and / or raw materials being produced contains at least 0.1% by weight of perfume, based on the premix, and subjecting this premix to press agglomeration.

In the context of this invention, “essentially water-free” is understood to mean a state in which the content of liquid water, ie water not present in the form of hydrated water and / or constitutional water, is below 2% by weight, preferably below 1% by weight. and in particular even less than 0.5% by weight, based in each case on the premix. Accordingly, water can essentially only be in chemically and / or physically bound form or as a constituent of the raw materials or compounds present as a solid, but not be introduced as a liquid, solution or dispersion into the process for the production of the premix Advantageously, the premix has a total water content of not more than 15% by weight, this water therefore not in liquid free form, but chemically and / or is physically bound, and it is particularly preferred that the content of not zeolite and / or silicates bound water in the solid premix is not more than 10% by weight and in particular not more than 7% by weight.

Detergents or cleaning agents are understood to mean compositions of this type which can be used for washing or cleaning without usually having to add further ingredients. A component for detergents or cleaning agents, on the other hand, consists of at least 2 components usually used in detergents or cleaning agents; However, components or so-called compounds are normally only used in a mixture with other constituents, preferably together with other compounds.

The ingredients used in the process according to the invention - with the exception of any nonionic surfactants which are liquid at temperatures below 45 ° C. and a pressure of 1 bar - can be separately prepared compounds, but also raw materials which are in powder or particulate form (fine to coarse) . For example, beads or (fluidized bed) granules etc. produced by spray drying can be used as particulate particles. The composition of the compounds per se is insignificant for the invention with the exception of the water content, which must be such that the premix is essentially water-free as defined above and preferably contains no more than 10% by weight of water of hydration and / or constitutional water . In a preferred embodiment, over-dried compounds are used in the premix. Such compounds can be obtained, for example, by spray drying, the temperature control being regulated in such a way that the tower outlet temperatures are above 70 ° C., for example 85 ° C. or above. It is also possible to use solid compounds in the premix which serve as carriers for liquids, for example liquid nonionic surfactants or silicone oil and / or paraffins. These compounds can contain water within the scope specified above, the compounds being free-flowing and remaining free-flowing or at least conveyable even at higher temperatures of at least 45 ° C. In particular, however, it is preferred that compounds with a maximum of 10% by weight and, with particular preference, with a maximum of 7% by weight of water, based on the premix, be used in the premix. Free water, that is water that is not in any form a solid is bound and is therefore "in liquid form", is preferably not contained in the premix at all, since very small amounts, for example around 0.2 or 0.5% by weight, based on the premix, are sufficient to absorb This would result in the melting point or softening point being lowered and the end product losing both its flowability and bulk density.

Surprisingly, it has been shown that it is by no means indifferent to which solid raw material or in which solid compound the water is bound. For example, the water that is bound to builder substances such as zeolite or silicates (for a description of the substances see below), in particular if the water is bound to zeolite A, zeolite P or MAP and / or zeolite X, is to be regarded as less critical. On the other hand, it is preferred that water which is bound to solid constituents other than the builder substances mentioned is preferably present in the premix in amounts of less than 3% by weight. It is particularly advantageous if the premix contains no water that is not bound to the builder substances. However, this is difficult to achieve from a technical point of view, since traces of water are usually always brought in by the raw materials and compounds.

According to the invention, the essentially water-free premixes contain perfume, at least 0.1% by weight of perfume, based on the premix, being added.

By incorporating the perfume into the premix and the subsequent press agglomeration step, a homogeneous distribution of the fragrances is achieved over the entire detergent or cleaning agent or the component therefor. Since an essentially water-free premix is used, there is no need for subsequent drying steps in which perfume could evaporate in whole or in part. The targeted incorporation of the perfume into the agents or components also results in a significantly reduced loss of fragrance during transport or storage. Compared to conventionally scented agents, not only is the perfume distributed much more evenly, but also a more intense fragrance impression of the product. In this way, products with the same olfactory impression can be scented with less perfume or with the same Perfume amount significantly improved fragrance impressions can be achieved. The improvement in the fragrance impression not only comes to light on the scented product, but also on the treated objects, preferably textiles. Both on damp and on dry laundry, the agents leave an increased fragrance impression compared to conventionally scented press agglomerates. The fact that the fragrances are homogeneously distributed over the entire press agglomerate also avoids problems associated with conventional scenting: since the suction of the agglomerates for sprayed-on perfume is low and decreases with increasing degree of compaction, most of the perfume adheres to Powdering agent. The conventionally scented product, which is inevitably moved during transport, loses part of the powdering agent, which carries most of the perfume, due to friction. These loose fines then fall through the coarse-grained solid bed during further movement and collect at the bottom of the containers, so that a certain proportion of fragrance hardly contributes to product scenting and no longer contributes to the scenting of the treated objects. These disadvantages are also avoided by the method according to the invention.

In the process according to the invention, individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethyl acetate, benzyl acetate, ethyl methylphenylglycinate, allyl cyclohexylate, methylateylateylate, styrallyl methylylateylate, styrallyl amylateylate, styrallyl methylateylate, The ethers include, for example, benzylethyl ether and ambroxan, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, lilial and bourgeonal, the ketones, for example, the jonones, oc-isomethylionone and Methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel sage oil, chamomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The essentially water-free premix which is pressed agglomerated preferably has no dust-like components and in particular no particles with particle sizes below 200 μm. In particular, those particle size distributions are preferred which have at least 90% by weight of particles with a diameter of at least 400 μm. In a particularly preferred embodiment of the invention, the washing or cleaning agents or components produced by press agglomeration consist of at least 70% by weight, advantageously at least 80% by weight and, with particular preference, up to 100% by weight spherical or almost spherical (pearl-shaped) particles with a particle size distribution which has at least 60% by weight of particles between 0.8 and 2.0 mm.

The solid and essentially water-free premix contains conventional solid detergent and cleaning agent ingredients such as builders, solid surfactants, bleaches, bleach activators, polymers and other conventional ingredients. Here, the ingredients can be used individually or in the form of compounds, as described above, optionally with liquid to pasty detergent and cleaning agent ingredients such as silicone oils, paraffins or liquid nonionic surfactants. Pre-mixtures are preferably used in the context of the present invention, the individual raw materials and / or compounds which are present as a solid at room temperature and a pressure of 1 bar and have a melting or softening point not below 45 ° C. and optionally up to 20% by weight. %, preferably up to 15% by weight and in particular up to 10% by weight, based on the premix, contain liquid nonionic surfactants at temperatures below 45 ° C. and a pressure of 1 bar. The use of alkoxylated alcohols, such as fatty or oxo alcohols, which are usually used in washing and cleaning agents is preferred, so that one is preferred Process is designed in such a way that the premix in addition to the solid constituents up to 20% by weight, preferably up to 15% by weight and in particular up to 10% by weight at temperatures below 45 ° C. and a pressure of 1 bar liquid nonionic surfactants, in particular the alkoxylated alcohols usually used in detergents or cleaning agents, such as fatty alcohols or oxo alcohols with a carbon chain length between 8 and 20 and in particular an average of 3 to 7 ethylene oxide units per mole of alcohol, the addition of the liquid nonionic surfactants preferably in Mix with the perfume.

In order to facilitate the press agglomeration of the premix and to improve the physical properties of the fragrance-reinforced washing or cleaning agents or components obtained by press agglomeration, the premix can contain a raw material or a compound which functions as a binding and disintegration aid. In the case of press agglomeration, these binding and disintegration aids serve as lubricants and adhesives which adhere the solid components of the premix to one another and facilitate the passage of the premix through the pressure zone of the press agglomeration apparatus. As water-soluble binders, they also facilitate the redissolution of the press agglomerates, since they act as disintegrants in aqueous liquors. In a preferred method in the context of the present invention, the premix contains at least one raw material or a compound which is present in solid form at a pressure of 1 bar and temperatures below 45 ° C., but is present as a melt in the press agglomeration, where this melt serves as a polyfunctional, water-soluble binder which, in the preparation of the compositions, performs both the function of a lubricant and an adhesive function for the solid detergent or cleaning agent compounds or raw materials, but disintegrates when the composition is redissolved in an aqueous liquor works.

Binders suitable for use in the process according to the invention are solid at a pressure of 1 bar and temperatures below 45 ° C., but are present as a melt under the process conditions of the press agglomeration. The binders can be incorporated into the premix in such a way that a melt of the binder or binder mixture is sprayed onto the premix or the premix is added dropwise. However, the binder (mixture) can also be incorporated into the premix as a finely divided solid.

The type of suitable binder and the temperature in the compression step of the press agglomeration are dependent on one another. Since it has proven to be advantageous if the binder is distributed as homogeneously as possible in the material to be compacted in the compression step, temperatures must be present in the compression step at which the binder at least softens, but preferably completely and not only partially is in molten form. If a binder with a high melting point or high softening point is selected, then a temperature must be set in the compression process step, which ensures that the binder melts. In addition, depending on the desired composition of the end product, temperature-sensitive raw materials should also be able to be processed. Here the upper temperature limit is given by the decomposition temperature of the sensitive raw material, it being preferred to work significantly below the decomposition temperature of this raw material. On the other hand, the lower limit for the melting point or softening point is of such great importance, since at melting points or softening points below 45 ° C, an end product is usually obtained which is already at room temperature and slightly elevated temperatures of 30 ° C, tends to stick at summer temperatures and under storage or transport conditions. It has proven to be particularly advantageous if a few degrees, for example 2 to 20 ° C., are used above the melting point or above the softening point

Without wishing to be limited to this theory, the applicant is of the opinion that the homogeneous distribution of the binder within the premix under the process conditions of compression compresses the solid compounds and any individual raw materials that may be present in the binder and subsequently glues them together the finished end products are made almost exactly from these many small individual particles, which are held together by the binder, which takes over the function of a preferably thin partition between these individual particles. In the idealized form, a honeycomb Similar structure can be assumed, these honeycombs are filled with solids (compounds or individual raw materials). Upon contact with water, also with cold water, for example at the beginning of a machine wash, these thin partitions dissolve or disintegrate almost immediately; Surprisingly, this is also the case if the binder itself is not readily soluble in water at room temperature, for example due to a crystal structure. However, such binders are preferably used, which can be almost completely dissolved within 90 seconds in a test method as described below in a concentration of 8 g of binder in 1 liter of water at 30 ° C.

The binder or binders must therefore be such that the adhesive properties are retained even at temperatures which are significantly above the melting point or the softening point. On the other hand, it is also essential for the choice of the type and the amount of the binder (s) used that, although the binding properties are not lost after cooling again within the end product, the cohesion of the end product is thus ensured, but that the end product itself is below usual storage and transport conditions not glued.

In the further course of the description of this invention, only one or the binder will be mentioned for the sake of simplicity. However, it should be made clear that the use of several different binders and mixtures of different binders is always possible.

In a preferred embodiment of the invention, a binder is used which is already completely present as a melt at temperatures of up to 130 ° C., preferably up to 100 ° C. and in particular up to 90 ° C. The binder must therefore be selected depending on the process and process conditions, or the process conditions, in particular the process temperature, must - if a particular binder is desired - be adapted to the binder.

Preferred binders which can be used alone or in a mixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and also modified polyethylene glycols and polypropylene glycols. The modified polyalkylene glycols include in particular the sulfates and / or the disulfates of polyethylene glycols or poly- lypropylene glycols with a relative molecular weight between 600 and 12000 and in particular between 1000 and 4000. Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which in turn have relative molecular weights between 600 and 6000, preferably between 1000 and 4000. For a more detailed description of the modified polyalkylene glycol ethers, reference is made to the disclosure of the international patent application WO-A-93/02176. In the context of this invention, polyethylene glycols include those polymers which, in addition to ethylene glycol, also use C -C ₅ glycols and glycerol and mixtures of these as starting molecules. Also included are ethoxylated derivatives such as trimethylol propane with 5 to 30 EO.

The polyethylene glycols preferably used can have a linear or branched structure, linear polyethylene glycols being particularly preferred.

The particularly preferred polyethylene glycols include those with relative molecular weights between 2000 and 12000, advantageously around 4000, polyethylene glycols with relative molecular weights below 3500 and above 5000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4000, and such combinations advantageously to more than 50% by weight, based on the total amount of polyethylene glycols, have polyethylene glycols with a relative molecular weight between 3500 and 5000. However, polyethylene glycols which are in the liquid state at room temperature and a pressure of 1 bar can also be used as binders; Here we are mainly talking about polyethylene glycol with a relative molecular mass of 200, 400 and 600. However, these per se liquid polyethylene glycols should only be used in a mixture with at least one further binder, this mixture again having to meet the requirements according to the invention, that is to say having a melting point or softening point of at least above 45 ° C.

The modified polyethylene glycols also include polyethylene glycols which are end-group-capped on one or more sides, the end groups preferably being C 1 -C ₂ -alkyl chains which can be linear or branched. In particular, the End groups on the alkyl chains between Ci and C ₆ , especially between Ci and C, with isopropyl and isobutyl or tert-butyl also being possible alternatives.

Polyethylene glycol derivatives capped at one end may also satisfy the formula C _x (EO) y (PO) _z , where C _{x can be} an alkyl chain with a C chain length of 1 to 20, y 50 to 500 and z 0 to 20. For z = 0 there are overlaps with connections from the previous paragraph. EO-PO polymers (x = 0) can also serve as binders.

Further suitable binders which can be used in low-water or water-free press agglomeration processes are disclosed in the earlier German patent application 196.38.599.7 and can also be used in the context of the present invention.

According to the teaching of the earlier German patent application 196.38.599.7, the binder or binder content in the premix is preferably at least 2% by weight, but less than 15% by weight, in particular less than 10% by weight, with particular preference given to 3 up to 6 wt .-%, each based on the premix. In particular, the water-swollen polymers are used in amounts below 10% by weight, advantageously in amounts of 4 to 8% by weight, with preference of 5 to 6% by weight. In the context of the present invention, it is possible due to the use of perfume in the premix to further reduce the minimum amount of binder in the premix, see below.

In a preferred embodiment of the process according to the invention, the solids for the preparation of the solid and free-flowing premix are firstly at room temperature to slightly elevated temperatures, which are preferably below the melting temperature or the softening point of the binder and in particular at temperatures up to 35 ° C. in a customary mixture. and / or pelletizer mixed together.

The binders are preferably added as the last component. As already stated above, they can be added as a solid, ie at a processing temperature which is below their melting point or their softening point, or as a melt respectively. However, the admixture is advantageously carried out under conditions such that the most homogeneous possible distribution of the binder in the solid mixture is achieved. In the case of very finely divided binders, this can be accomplished at temperatures below 40 ° C., for example at temperatures of the binder between 15 and 30 ° C. However, the binder advantageously has temperatures at which it is already in the form of a melt, that is to say above the softening point, in particular in the form of a complete melt. Preferred temperatures of the melt are 60 to 150 ° C with particular preference for the temperature range of 80 to 120 ° C. During the mixing process, which takes place at room temperature to a slightly elevated temperature, but below the softening point or melting point of the binder, the melt solidifies almost instantaneously, and the premix is, according to the invention, in solid, free-flowing form. The mixing process is advantageously continued until the melt has solidified and the premix is in a solid, free-flowing form.

The proportion of binder (s) can be reduced by incorporating the perfume into the premix. Since the fragrances act as lubricants and, because of their homogeneous distribution in the finished press agglomerate, do not hinder redissolution despite their mostly hydrophobic character, it is possible to adjust the content of the premix of binders mentioned in the earlier German patent application 196.38.599.7 (over 2 to under 15 wt %, preferably less than 10% by weight and in particular from 3 to 6% by weight), so that binder contents of 1 to 5% by weight, preferably 2 to 4% by weight, are used can. In preferred processes, a premix is used, the content of binder or binders of which is at least 1% by weight, but less than 10% by weight, preferably less than 8% by weight and, with particular preference, 2 to 4% by weight. , each based on the premix. With a decreasing binder content, the incorporation of higher amounts of nonionic surfactants is in turn possible, so that the process according to the invention enables the production of fragrance-reinforced high-tenside-containing press agglomerates which cannot be produced by previous methods. The premix preferably contains significantly more than the minimum amount of 0.1% by weight of perfume. Methods according to the invention are preferred in which the mix contains more than 0.15% by weight, preferably more than 0.2% by weight and in particular more than 0.3% by weight of perfume.

The perfume can be incorporated into the premix in almost every stage of the premix production. It is thus possible, for example, to place some or all of the solids, as described above, at room temperature in a conventional mixing and / or granulating device and to apply or spray the perfume onto the moving bed of solids. However, the perfume can also be added to the solids together with the binder as described above. Here it is possible to mix perfume with solid binder as well as to incorporate the perfume into a separately produced melt of the binder and to add the paste-like to liquid binder-perfume mixture to the solids. Of course, all of the above-mentioned incorporation methods can also be combined with one another, with each part of the perfume being introduced into the premix in different ways. If nonionic surfactants are used in the process according to the invention, the perfume is preferably added as a mixture with the nonionic surfactants, it also being possible to prepare and use mixtures of binder, nonionic surfactant and perfume.

The essentially water-free procedure enables the perfume to be incorporated into the premix, since subsequent drying steps in which fragrance losses could occur are not necessary. In addition, this procedure has the advantage that peroxy bleaching agents can be processed without loss of activity, and it also makes it possible to process peroxy bleaching agents and bleach activators (see description below exactly) without having to fear serious loss of activity.

By compressing the particle aggregate (premix), the porosity is reduced during the press agglomeration, on the other hand, the particle adhesion is increased by the plastic deformation of the contact zones, which is why materials that can be largely plastically deformed, deliver compacts with high strengths, while elastically deformed malleable particles with brittle behavior are more difficult to compress. The compressibility can be improved by adding binders. The press agglomeration process to which the solid and essentially water-free premix is subjected can be carried out in various apparatuses. Different press agglomeration processes are distinguished depending on the type of agglomerator used. The four most common press agglomeration processes preferred in the context of the present invention are extrusion, roll pressing or compacting, hole pressing (pelletizing) and tableting, so that preferred press agglomeration processes within the scope of the present invention include extrusion, roll compacting. , Pelleting or tableting processes.

All processes have in common that the premix is compressed and plasticized under pressure and that the individual particles are pressed against one another while reducing the porosity and adhere to one another. With all processes (with tableting with restrictions), the tools can be heated to higher temperatures or cooled to dissipate the heat generated by shear forces. The actual compression process takes place at processing temperatures which, at least in the compression step, correspond at least to the temperature of the softening point, if not even the temperature of the melting point of the binder. In a preferred embodiment of the invention, the process temperature is significantly above the melting point or above the temperature at which the binder is in the form of a melt. In particular, however, it is preferred that the process temperature in the compression step is not more than 20 ° C. above the melting temperature or the upper limit of the melting range of the binder. It is technically possible to set even higher temperatures; however, it has been shown that a temperature difference of 20 ° C. from the melting temperature or softening temperature of the binder is generally sufficient and even higher temperatures do not bring any additional advantages. It is therefore particularly preferred - especially for energy reasons - to work above, but as close as possible to, the melting point or the upper temperature limit of the melting range of the binder. Such a temperature control has the further advantage that thermally sensitive raw materials, for example peroxy bleaching agents such as perborate and / or percarbonate, but also enzymes, increasingly without grave four loss of active substance can be processed. The possibility of precise temperature control of the binder, especially in the decisive step of compression, i.e. between the mixing / homogenization of the premix and the shaping, allows an energetically very economical and extremely gentle process control for the temperature-sensitive components of the premix, since the premix only lasts for a short time exposed to higher temperatures. In preferred press agglomeration processes, the working tools of the press agglomerator (the screw (s) of the extruder, the roller (s) of the roller compactor and the press roller (s) of the pellet press) have a temperature of at most 150 ° C., preferably at most 100 ° C., and in particular to a maximum of 75 ° C and the process temperature is 30 ° C and in particular a maximum of 20 ° C above the melting temperature or the upper temperature limit of the melting range of the binder. The duration of the temperature exposure in the compression range of the press agglomerators is preferably a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.

Immediately after leaving the production apparatus, the compressed material preferably has temperatures not above 90 ° C., temperatures between 35 and 85 ° C. being particularly preferred. It has been found that exit temperatures - especially in the extrusion process - from 40 to 80 ° C, for example up to 70 ° C, are particularly advantageous.

In a preferred embodiment of the invention, the method according to the invention is carried out by means of an extrusion, as described, for example, in European patent EP-B-0 486 592 (Henkel KGaA) or international patent applications WO-A-93/02176 (Henkel KGaA) and WO -A-94/09111 (Henkel KGaA). In this case, a solid premix is pressed in the form of a strand under pressure and the strand is cut to the predeterminable size of the granulate after it has emerged from the hole shape by means of a cutting device. The homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work. Preferred plasticizers and / or lubricants are surfactants and / or polymers, which are now within the scope of present invention with the exception of the above-mentioned nonionic surfactants, however, not in liquid and in particular not in aqueous, but in solid form in the premix.

To explain the actual extrusion process, reference is hereby expressly made to the patents and patent applications mentioned above. In a preferred embodiment of the invention, the premix is preferably fed continuously to a planetary roller extruder or a 2-screw extruder or 2-screw extruder with co-rotating or counter-rotating screw guide, the housing and the extruder pelletizing head of which can be heated to the predetermined extrusion temperature. Under the shear action of the extruder screws, the premix is compressed, plastified and extruded in the form of fine strands through the perforated die plate in the extruder head under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used and finally the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knife. The hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension. In this embodiment, the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use. In general, particle diameters up to at most 0.8 cm are preferred. Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm. In an important embodiment, the length / diameter ratio of the chopped-off primary granules is in the range from about 1: 1 to about 3: 1. Furthermore, it is preferred to feed the still plastic primary granulate to a further shaping processing step; edges present on the raw extrudate are rounded off so that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired, small amounts of dry powder, for example zeolite powder such as zeolite NaA powder, can also be used in this step. This shape can be done in standard rounding machines. Care should be taken to ensure that only small amounts of fine grain are produced in this stage. A Drying, which is described as a preferred embodiment in the abovementioned documents of the prior art, is unnecessary in the context of the present invention, since the process according to the invention is essentially water-free, that is to say without the addition of free, non-bound water.

Alternatively, extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press (from Amandus Kahl) or in the Bepex extruder.

In a particularly preferred embodiment, the invention now provides that the temperature control in the transition region of the screw, the pre-distributor and the nozzle plate is designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but preferably exceeded. The duration of the temperature influence in the compression range of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.

The low residence times combined with the water-free process procedure make it possible for peroxy bleaching agents to be extruded, if appropriate even together with bleach activators, even at higher temperatures, without suffering serious loss of activity.

In a particularly advantageous embodiment of the invention, the binder used has a melting temperature or a melting range of up to 75 ° C .; Process temperatures which are at most 10 ° C. and in particular at most 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder have then proven to be particularly favorable.

Under these process conditions, in addition to the previously mentioned modes of action, the binder also functions as a lubricant and at least prevents or at least reduces sticking to apparatus walls and compaction tools. This applies not only to processing in the extruder, but also equally to processing, for example in continuously operating mixers / granulators or rollers. Just as in the extrusion process, it is also preferred in the other production processes to feed the resulting primary granules / compactates to a further shaping processing step, in particular to round them, so that ultimately spherical to approximately spherical (pearl-shaped) grains can be obtained. It is the essence of a preferred embodiment of the invention that the particle size distribution of the premix is designed to be substantially wider than that of the end product produced according to the invention and according to the invention. The premix can contain much larger fine-grained fractions, even dust, and possibly also coarser-grained fractions, although it is preferred that a premix with a relatively broad particle size distribution and relatively high fractions of fine-grained material in an end product with a relatively narrow particle size distribution and relatively small fractions of fine-grain is transferred.

Because the method of the invention is essentially anhydrous - i.e. with the exception of water contents ("impurities") of the solid raw materials used, water-free, not only is the risk of gelling of the surfactant raw materials minimized to ruled out in the manufacturing process, in addition, an ecologically valuable process is also provided, since by dispensing with one subsequent drying step not only saves energy but also emissions, as they occur predominantly with conventional drying methods, can be avoided. In addition, the omission of subsequent drying steps only allows the fragrances to be incorporated into the premix and thus the production of fragrance-enhanced detergents or cleaning agents or Components for this.

In a further preferred embodiment of the present invention, the method according to the invention is carried out by means of roller compaction. Here, the fragrance-containing solid and essentially water-free premix is metered in between two smooth rollers or with recesses of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe. The rollers practice a high linear pressure and can be additionally heated or cooled as required. When using smooth rollers, smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs can be produced in which, for example, certain shapes of the later detergent or cleaning agent particles can be specified. The sliver belt is subsequently broken up into smaller pieces by a knocking-off and comminution process and can be processed in this way into granules which can be refined, in particular in an approximately spherical shape, by further known surface treatment processes.

In the case of roller compaction, too, the temperature of the pressing tools, that is to say the rollers, is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at a maximum of 75 ° C. Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder. It is further preferred that the duration of the temperature effect in the compression area of the smooth rollers or with depressions of a defined shape is a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.

In a further preferred embodiment of the present invention, the method according to the invention is carried out by means of pelleting. Here, the fragrance-containing, solid and essentially water-free premix is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization. In conventional designs of pellet presses, the premix is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted into granules using a knock-off device. The most varied configurations of the pressure roller and perforated die are conceivable here. For example, flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed using one or more pressure rollers. The press rolls can with the plate devices also be conical, in the ring-shaped devices the dies and press roller (s) can have the same or opposite direction of rotation. An apparatus suitable for carrying out the method according to the invention is described, for example, in German laid-open specification DE 38 16 842 (Schlüter GmbH). The ring die press disclosed in this document consists of a rotating ring die penetrated by press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge. Here, the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved. Of course, it is also possible to work with heatable or coolable rollers in the pelletizing in order to set a desired temperature of the premix.

In pelletizing, too, the temperature of the pressing tools, that is to say the pressure rollers or pressure rollers, is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at most 75 ° C. Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.

Another press agglomeration process that can be used according to the invention is tableting. Because of the size of the molded articles produced, it may be useful for tableting to add customary disintegration aids, for example cellulose and its derivatives or crosslinked PVP, in addition to the binder, which facilitate the disintegration of the compacts in the wash liquor.

In a preferred embodiment of the invention, a fragrance-reinforced extruded, roller-compacted or pelletized detergent is provided which consists of at least 80% by weight of compounds and / or treated raw materials produced according to the invention. In particular, an extruded, roller-compacted or pelletized detergent consists of at least 80% by weight of a base agent produced according to the invention. glomerate. The remaining ingredients can be prepared and admixed by any known method. However, it is preferred that these remaining constituents, which may be compounds and / or treated raw materials, were also produced by the process according to the invention. In particular, this enables basic granules and remaining constituents to be produced with approximately the same pourability, bulk density, size and particle size distribution.

The particulate press agglomerates obtained can either be used directly as detergents or cleaning agents or can be aftertreated and / or prepared beforehand by customary methods. The usual aftertreatments include, for example, powdering with finely divided ingredients from detergents or cleaning agents, which generally further increases the bulk density. However, a preferred aftertreatment is also the procedure according to German patent applications DE-A-195 24 287 and DE-A-195 47 457, dusty or at least finely divided ingredients (the so-called fine fractions) of the particulate end products of the process, which are the core serve, be glued and thus funds are created which have these so-called fines as an outer shell. This advantageously takes place in turn by melt agglomeration, the same binders as can be used in the process according to the invention. For melt agglomeration of the fine fractions of the basic granules according to the invention and produced according to the invention, reference is expressly made to the disclosure in German patent applications DE-A-195 24 287 and DE-A-195 47 457.

Both the fragrance-reinforced detergents, which consist of at least 80% by weight of press agglomerates produced according to the invention, and the press agglomerates themselves can additionally be subsequently sprayed with perfume. The conventional fragrance variant, i.e. powdering and spraying with perfume can be carried out with the press agglomerates according to the invention.

Advantageously, in the fragrance-reinforced washing or cleaning agents according to the invention, at least 30% by weight, preferably at least 40% by weight and in particular at least 50% by weight of the total perfume contained in the agent is Manufacturing processes according to the invention introduced into the agents, ie incorporated into the press agglomerates, while the remaining 70% by weight, preferably 60% by weight and in particular 50% by weight of the total perfume contained in the agent onto the press agglomerates, which can optionally be surface-treated , sprayed on or otherwise applied.

By dividing the total perfume content of the agents into perfume, which is contained in the press agglomerates and perfume, which adheres to the press agglomerates, a variety of product characteristics can be realized, which are only possible through the inventive method. For example, it is conceivable and possible to divide the total perfume content of the compositions into two portions x and y, the proportion x consisting of adherent, i.e. less volatile and the portion y consists of more volatile perfume oils.

It is now possible to produce detergents or cleaning agents in which the proportion of the perfume which is introduced into the agents via the press agglomerates is composed mainly of adhesive fragrances. In this way, adherent odoriferous substances, which are intended to scent the treated articles, in particular textiles, can be "held" in the product and thus have their effect mainly on the treated laundry. In contrast, the more volatile fragrance substances contribute to a more intensive fragrance of the agents themselves In this way it is also possible to produce detergents and cleaning agents which have an odor which differs from the smell of the treated articles, and there are hardly any limits to the creativity of perfumers, because of the choice of fragrances on the one hand and about the choice of the method of incorporation into the means, on the other hand, there are almost limitless possibilities to scent the means and, via the means, the objects treated with them.

The principle described above can of course also be reversed by incorporating the more volatile fragrances in the press agglomerates and spraying the less volatile, adherent fragrances onto the compositions. In this way, the loss of the more volatile fragrances from the packaging during storage and transport is minimized, while the fragrance characteristic of the agents is determined by the more adhesive perfumes. The general description of the perfumes that can be used (see above) generally represented the different substance classes of fragrances. In order to be perceptible, a fragrance must be volatile, with the molecular weight also playing an important role in addition to the nature of the functional groups and the structure of the chemical compound . Most odoriferous substances have molecular weights of up to about 200 daltons, while molecular weights of 300 daltons and more are an exception. Due to the different volatility of odoriferous substances, the smell of a perfume or fragrance composed of several odoriferous substances changes during evaporation, whereby the odor impressions are expressed in "top note", "heart or middle note" (middle note or body) and "base note" (end note or dry out). Since the smell is largely based on the intensity of the smell, the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note largely consists of less volatile In the composition of perfumes, more volatile fragrances can be bound, for example, to certain fixatives, which prevents them from evaporating too quickly.The embodiment of the present invention described above, in which the more volatile fragrances or fragrances are incorporated into the press agglomerate be incorporated, i is such a method for fragrance fixation. In the subsequent classification of the fragrances into “more volatile” or “adhesive” fragrances, nothing is said about the odor impression and whether the corresponding fragrance is perceived as a top or heart note.

Non-stick odoriferous substances that can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, bergamot oil, champagne flower oil, noble fir oil, noble pine cone oil, elem oil, eucalyptus oil, fennel oil, galbane oil, spruce oil. geranium oil, ginger grass oil, guaiac wood oil, gurjun balsam oil, Helichrysumöl, Ho oil, ginger oil, iris oil, cajeput oil, Kal musöl, camomile oil, camphor oil, Kanagaöl, cardamom oil, cassia oil, pine needle oil, co- päϊvabalsamöl, coriander oil, spearmint oil, caraway oil, Kuminöl, lavender oil, Lemon grass oil, lime oil, mandarin oil, lemon balm oil, musk grain oil, myrrh oil, clove oil, Neroliol, Niaouli oil, Olibanum oil, Orange oil, Origanum oil, Palmarosa oil, Patchouli oil, Peru balsam oil, Petitgrain oil, Pepper oil, Peppermint oil, Allspice oil, Pine oil, Rose oil, Rosemary oil, Sandalwood oil, Celery oil, Spik oil, Star anise oil, Turpentine oil, Thja oil, Thja oil, Thja oil, Thja oil Vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, lemon oil, lemon oil and cypress oil.

However, the higher-boiling or solid fragrances of natural or synthetic origin can also be used in the context of the present invention as adhesive fragrances or fragrance mixtures, that is to say fragrances. These compounds include the compounds mentioned below and mixtures of these: ambrettolide, α-amyl cinnamaldehyde, anethole, anisaldehyde, anis alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzylacetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate , borneol, Bornyla- acetate, α-bromostyrene, n-decyl, n-dodecyl aldehyde, eugenol, eugenol, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, Heptincarbonsäuremethylester, heptaldehyde, hydroquinone dimethyl ether, taldehyd Hydroxyzim-, Hydroxyzimtalkohol , Indole, Iron, Isoeugenol, Isoeugenolmethylether, Isosafrol, Jasmon, Camphor, Karvakrol, Karvon, p-Cresolmethylether, Coumarin, p- Methoxyacetophenon, Methyl-n-amylketone, Methylanthranilsäuremethylester, p- Methylacetophenon, Methylchavikinol, Methylchavikolin, p-Methylchavikolin, p-Methylchavikolin, p-Methylchavikol, p-Methylacetophenon, Methylchavikinol, p-Methylchavikol -naphthyl ketone, methyl-n-nonylacetaldehyde, methyl-n-nonyl ketone, mus con, ß-naphthol ethyl ether, ß-naphthol methyl ether, nerol, nitrobenzene, n-nonyl aldehyde, nony alcohol, n-octyl aldehyde, p-oxy-acetophenone, pentadecanolide, ß-phenyl ethyl alcohol, phenylacetaldehyde dimethyacetal, salicylic acid, phenyl acetic acid, phenyl acetic acid, phenyl acetic acid, methyl ester, salicylic acid hexyl ester, salicylic acid cyclohexyl ester, Santalol, Skatol, terpinol, thymen, thymol, γ-undelactone, vanilin, veratrum aldehyde, cinnamaldehyde, cimate alcohol, cinnamic acid, ethyl cinnamate, cinnamic acid benzyl ester.

The more volatile fragrances include, in particular, the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures. Examples of more volatile fragrances are alkyisothiocyanates (alkyl mustards), butanedione, limonene, linalool, Linaylacetate and propionate, menthol, Menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinylacetate, citral, citronellal.

There now follows a detailed description of the possible further ingredients of the agents according to the invention and the constituents used in the method according to the invention.

Important ingredients of the agents according to the invention and substances that are used in the method according to the invention are surfactants, in particular anionic surfactants, which should be present in the agents according to the invention or agents according to the invention at least in amounts of 0.5% by weight. These include in particular sulfonates and sulfates, but also soaps.

Preferred surfactants of the sulfonate type are C ₉ -C 8 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 1 -C ₂ monoolefins with an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.

Also suitable are alkanesulfonates, the ₂ -Cι ₈ alkanes or chlorination of C, for example by sulfo sulfoxidation be recovered and subsequent hydrolysis or neutralization.

Also suitable are the esters of sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which by α-sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts. These are preferably the α-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, with sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight. %, can be present. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters. The methyl esters of α-sulfofatty acids (MES), but also their saponified disalts, are used with particular advantage.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters as well as their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol be preserved.

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid semiesters of C 1 -C ₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁ -C ₂ o- Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. For reasons of washing technology, C ₂ -C ₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₄ -C ₅ alkyl sulfates are particularly preferred. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN ^(R) , are also suitable anitone surfactants.

The sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂ -alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl branched C ₉ -C ₂ -alcohols with an average of 3.5 mol of ethylene oxide (EO) or C] ₂ -Cι ₈ fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Preferred 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 represent in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ - to C ₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Fatty acid derivatives of amino acids, for example of N-methyl taurine (taurides) and / or of N-methyl glycine (sarcosides) are suitable as further anionic surfactants. The sarcosides or sarcosinates, and in particular sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate, are particularly preferred.

Other suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.2 to 5% by weight. Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. The known alkenylsuccinic acid salts can also be used together with these soaps or as a substitute for soaps.

The anionic surfactants (and soaps) can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The anionic surfactants are contained or used in the agents according to the invention or in the method according to the invention preferably in amounts of 1 to 30% by weight and in particular in amounts of 5 to 25% by weight. In addition to the anionic surfactants and the cationic, zwitterionic and amphoteric surfactants, nonionic surfactants are particularly preferred.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, -C ₂ -C ₄ alcohols with 3 EO or 4 EO, C ₉ -C 1 -alcohols with 7 EO, d ₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci ₂ -C] ₈ - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₂ -C ₄ alcohol with 3 EO and C ₂ -C ₈ - alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used, as described above. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

The nonionic surfactants also include alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4. 1

Also suitable are polyhydroxy fatty acid amides of the formula (I) in which R * CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ² for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] represents a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.

R ^χ

R -CO-N- [Z] (I)

The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

R -OR ⁵

(II)

R -CO-N- [Z]

in which R ^{3 represents} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{5 represents} a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, dC ₄ - alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of this rest stands. [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533. As nonionic surfactants, C] ₂ -C ₈ fatty acid methyl esters with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO, are preferred, while, as described above, higher ethoxylated fatty acid methyl esters are particularly advantageous as binders. In particular Ci ₂ -C] ₈ fatty acid methyl esters with 10 to 12 EO can be used both as surfactants and as binders.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanol amides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

So-called gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are generally separated from one another by a so-called “spacer”. This spacer is generally a carbon chain which should be long enough that the hydrophilic groups are sufficiently far apart that they can act independently of one another. Such surfactants are distinguished generally due to an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water, but in exceptional cases the term gemini surfactants means not only dimeric but also trimeric surfactants. Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE-A-43 21 022 or dimer alcohol bis and trimeral alcohol tris-sulfates and ether sulfates according to German patent application DE-A-195 03 061. Dimer and trimer mixed ethers which are capped by end groups According to German patent application DE-A-195 13 391, they are distinguished in particular by their bi- and multifunctionality. The end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes.

Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides, as described in international patent applications WO-A-95/19953, WO-A-95/19954 and WO95-A- / 19955, can also be used.

In addition to the surfactants, the inorganic and organic builder substances are among the most important ingredients of detergents or cleaning agents.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, for example, zeolite MAP ^(R) (commercial product from Crosfield) is used. However, zeolite X and mixtures of A, X and / or P are also suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production. In the event that the zeolite is used as a suspension, it may contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₂ -C ₈ fatty alcohols with 2 to 5 ethylene oxide groups , -C ₂ -C-fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x θ _2X + ι'yH ₂ θ, where M is sodium or hydrogen, x is a number from 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. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ 0 ₅ ^' y H ₂ O are preferred.

The preferred builder substances also include amorphous sodium silicates with a Na2θ: Siθ2 modulus of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, which are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression 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 in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

Of course, it is also possible to use the generally known phosphates as builders, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. Their content is generally not more than 25% by weight, preferably not more than 20% by weight, in each case based on the finished funds. In some cases, it has been shown that tripolyphosphates in particular, even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing ability.

Suitable substitutes or partial substitutes for the zeolite are layer silicates of natural and synthetic origin. Layered silicates of this type are known, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here.

Suitable layered silicates, which belong to the group of water-swellable smectites, are, for example, montmorrilonite, hectorite or saponite. In addition, small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas. Furthermore, due to their ion-exchanging properties, the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na ⁺ and Ca ²⁺ . The amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing. Useful sheet silicates are known, for example, from US-A-3,966,629, EP-A-0 026 529 and EP-A-0 028 432. Layered silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.

Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

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 serve thus also for setting a lower and milder pH value of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular. If they are used in the premix according to the invention and are not subsequently added, these acids are preferably used in anhydrous form.

Other 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 processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000. 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 one Measure for the reducing effect of a polysaccharide in comparison to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 can be used. A preferred dextrin is described in British patent application 94 19 091. 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. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO- A-92/18542, WO-A-93/08251, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Also particularly preferred in this context are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP-A-0 150 930 and Japanese Patent Application JP 93/339896 - be written. Suitable amounts used are 3 to 15% by weight in formulations containing zeolite and / or silicate.

Further usable organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO-A-95/20029.

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, 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 relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.

The content of (co) polymeric polycarboxylates in the compositions is within the usual range and is preferably 1 to 10% by weight.

Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which, according to DE-A-43 00 772, are salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C -42 21 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.

Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers. Other suitable builder substances are oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts, as are described, for example, in international patent application WO-A-93/08251 or whose preparation is described, for example, in international patent application WO-A-93/16110 . Oxidized oligosaccharides according to German patent application DE-A-196 00 018 are also suitable.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223. 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.

In addition, the agents can also contain components which have a positive effect on the oil and fat washability from textiles. This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil and fat-dissolving components include, for example, non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Of these, the sulfonated derivatives of phthalic and terephthalic acid polymers are particularly preferred.

Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates such as the above-mentioned dissolving-delayed silicates or mixtures thereof; in particular, alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Na ₂ 0: SiO ₂ from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used. The sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight. The content of sodium silicate in the agents is - if it is not to be used as builder substance - generally up to 10% by weight and preferably between 2 and 8% by weight, otherwise more.

The other detergent ingredients include graying inhibitors (dirt carriers), foam inhibitors, bleaching agents and bleach activators, optical brighteners, enzymes, fabric softening agents, dyes and fragrances as well as neutral salts such as sulfates and chlorides in the form of their sodium or potassium salts.

Acidic salts or slightly alkaline salts can also be used to reduce the pH of detergents or cleaning agents. Preferred acidifying components are bisulfates and / or bicarbonates or the above-mentioned organic polycarboxylic acids, which can also be used as builder substances at the same time. Particular preference is given to the use of citric acid, which is either added subsequently (customary procedure) or - in anhydrous form - in the solid premix.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate.

Compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used as bleach activators. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, especially triacetin 5-diacetoxy-2,5-dihydrofuran and the enol esters known from German patent applications DE-A-196 16 693 and DE-A-196 16 767, as well as acetylated sorbitol and mannitol or those described in European patent application EP-A-0 525 239 mixtures described (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose and acetylated, if appropriate N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are known from international patent applications WO-A-94/27970, WO-A-94/28102, WO-A-94/28103, WO -A- 95/00626, WO-A-95/14759 and WO-A-95/17498 are known. The hydrophilically substituted acylacetals known from German patent application DE-A-196 16 769 and the acyl lactams described in German patent application DE-A-196 16 770 and international patent application WO-A-95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE-A-44 43 177 can also be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.

When used in machine washing processes, it can be an advantage before adding foam inhibitors. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₈ -C ₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes. The foam inhibitors, in particular silicone and / or paraffm-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylene diamides are particularly preferred.

The salts of polyphosphonic acids which are preferably used are the neutral sodium salts of, for example, l-hydroxyethane-l, l-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate in amounts of 0.1 to 1.5% by weight.

Particularly suitable enzymes are those from the class of hydrolases, such as proteases, lipases or lipolytically active enzymes, amylases, cellulases or mixtures thereof. Oxireductases are also suitable.

Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxi in some cases, these have proven to be suitable. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

In addition to phosphonates, the agents can also contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. In addition to calcium salts, magnesium salts also serve as stabilizers. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid HBO), is particularly advantageous.

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

As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-moφholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the Moφholino- Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, 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) diphenyl. Mixtures of the aforementioned brighteners can also be used.

Examples:

Spray drying produced granules with the composition given in Table 1, which were mixed with further components according to Table 2 and processed into a premix in a Lödige mixer.

Table 1: Composition of the spray-dried granules [% by weight]:

Table 2: Composition of the premix [% by weight]:

The perfume oil was in the liquid before adding to the mixer solved with 7 EO. The free-flowing premix had a bulk density of 450 g / l after leaving the mixer and was placed in a twin-screw extruder from Lihotzky and plasticized and extinguished under pressure. The plasticized premix left the extrader at a pressure of 85 bar through a perforated plate with exit holes of 1.4 mm in diameter. The extruded strands were chopped to a length / diameter ratio of approx. 1 with a rotating knife and rounded in a MarumerizeA. After the fine parts (<0.4 mm) and the coarse parts (> 2.0 mm) had been sieved, the extrudate had a bulk density of 810 g / l.

The extrudates E1 and E2 produced according to the invention, which differed in the perfume oils used, were now compared with extrudates VI and V2 with an analog composition, in which the perfume oils in question were sprayed onto the extruded and rounded particles, which had been powdered with finely divided zeolite, in a conventional manner has been.

In order to demonstrate the variant of the distribution of the fragrances according to the invention, an extrudate E3 was also produced which contained part of the perfume and was also sprayed with the rest of the perfume. This agent was compared with a comparative sex trudate V3, in which the total amount of the perfume was applied by spraying.

The composition of the perfume oils is given in Table 3. The fragrance of the product and treated textiles (cotton) was assessed as a subjective smell impression by perfumers. The numerical values in the evaluation table (Table 4) indicate the number of perfumers who rated the respective products or the textiles treated with the respective agent as “more fragrant”. Because a different number of perfumers was present in the different smell tests , the values in the "Perfumers" columns do not always add up to the same value. The first block of the first column (product) should therefore be read in such a way that 5 out of 7 perfumers rated the extrudates produced according to the invention as more fragrant. The results of the smell tests are summarized in Table 4. Table 3: Composition of the perfume oils [% by weight]:

Table 4: Fragrance enhancement (preference of intensity)

Claims

Claims:

1. A process for the production of fragrance-reinforced detergents or cleaning agents or components therefor with bulk densities above 600 g / 1, characterized in that a solid and essentially water-free premix is produced from detergent or cleaning agent compounds and / or raw materials which contains at least 0.1% by weight of perfume, based on the premix, and subjecting this premix to press agglomeration.

2. The method according spoke 1, characterized in that the premix has a total water content of not more than 15 wt .-%, which water is not in free form and preferably the content of water not bound to zeolite and / or silicates is not is more than 10% by weight and in particular not more than 7% by weight.

3. The method according to any one of claims 1 or 2, characterized in that a premix is used, the individual raw materials and / or compounds which are present as a solid at room temperature and a pressure of 1 bar and a melting or softening point not below 45 ° C, and optionally up to 20% by weight, preferably up to 15% by weight and in particular up to 10% by weight, based on the premix, at temperatures below 45 ° C. and a pressure of 1 bar liquid nonionic Contains surfactants.

4. The method according to any one of claims 1 to 3, characterized in that the premix in addition to the solid components up to 20 wt .-%, preferably up to 15 wt .-% and in particular up to 10 wt .-% at temperatures below of 45 ° C and a pressure of 1 bar liquid nonionic surfactants, in particular the alkoxylated alcohols usually used in detergents or cleaning agents, such as fatty alcohols or oxo alcohols with a C chain length between 8 and 20 and in particular 3 to 7 ethylene oxide units per mole of alcohol, the liquid nonionic surfactants preferably being added in a mixture with the perfume.

5. The method according to any one of claims 1 to 4, characterized in that the premix contains at least one raw material or a compound which is present in solid form at a pressure of 1 bar and temperatures below 45 ° C, in the press agglomeration but is in the form of a melt, this melt serving as a polyfunctional, water-soluble binder which, in the preparation of the compositions, functions both as a lubricant and as an adhesive function for the solid detergent or cleaning agent compounds or raw materials, in the redissolution of the By means of disintegrating in an aqueous liquor.

6. The method according to any one of claims 1 to 5, characterized in that the premix contains one or more binders which dissolve in a concentration of 8 g of binder to 1 1 water at 30 ° C almost completely within 90 seconds.

7. The method according to any one of claims 1 to 6, characterized in that the premix contains binders which are already completely present as a melt at temperatures up to a maximum of 130 ° C, preferably up to a maximum of 100 ° C and in particular up to 90 ° C.

8. The method according to any one of claims 1 to 7, characterized in that the binders are added as the last component in the premix, their admixture taking place under conditions such that the most uniform, homogeneous distribution of the binder is possible - as a solidified melt or as a powder - Is reached in the solid mixture.

9. The method according to any one of claims 1 to 8, characterized in that the incorporation of the binder takes place at temperatures at which the binder is in the form of a melt, preferred temperatures of the melt at 60 to 150 ° C, in particular in the temperature range from 80 up to 120 ° C.

10. The method according to any one of claims 1 to 9, characterized in that the mixing process is continued until the melt has solidified and the premix is in solid, free-flowing form.

11. The method according to any one of claims 1 to 10, characterized in that a premix is used, the content of binder or binders at least 1 wt .-%, but less than 10 wt .-%, preferably less than 8 wt .-% % and, with particular preference, 2 to 4% by weight, in each case based on the premix.

12. The method according to any one of claims 1 to 11, characterized in that the compacted material immediately after leaving the manufacturing apparatus temperatures not above 90 ° C, preferably between 35 and 85 ° C and in particular between 40 to 80 ° C, for example up to 70 ° C.

13. The method according to any one of claims 1 to 12, characterized in that the premix contains more than 0.15% by weight, preferably more than 0.2% by weight and in particular more than 0.3% by weight of perfume .

14. The method according to any one of claims 1 to 13, characterized in that a part or the total amount of the solids at room temperature in a conventional mixing and / or granulating device and the perfume is applied or sprayed onto the moving bed of solids.

15. The method according to any one of claims 1 to 13, characterized in that the perfume is added to the solids together with the binder.

16. The method according to any one of claims 1 to 15, characterized in that the pressing agglomeration process is an extrusion, roller compacting, pelleting or tableting process.

17. The method according spoke 16 characterized in that the working tools of the press agglomerator (the screw (s) of the extruder, the roller (s) of the roller compactor and the press roller (s) of the pellet press) have a temperature of at most 150 ° C, preferably at most 100 ° C and in particular a maximum of 75 ° C and the process temperature is a maximum of 30 ° C and in particular a maximum of 20 ° C above the melting temperature or the upper temperature limit of the melting range of the binder.

18. The method according spoke 16, characterized in that the duration of the temperature effect in the compression range of the press agglomerators is a maximum of 2 minutes and in particular is in a range between 30 seconds and 1 minute

19. The method according to any one of claims 1 to 18, characterized in that the production is carried out by extrusion, the premix being compressed under pressure, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally by means of a rotating knives, preferably is reduced to about spherical (pearl-shaped) to cylindrical granules and the temperature control in the transition area of the extruder screw, the pre-distributor and the nozzle plate is designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but preferably exceeded .

20. The method according to any one of claims 1 to 18, characterized in that the production is carried out by roller compaction, the premix compacted under pressure, plasticized, in the form of a sheet-like compact ("Schülpenband") pressed through the nip and finally by means of a knock-off and comminution device is comminuted to granules.

21. The method according to any one of claims 1 to 18, characterized in that the production is carried out by pelletizing, the premix compressed under pressure, plasticized, by means of a rotating roller in the form of fine strands through a perforated Surface pressed and finally crushed into granules by means of a knock-off device.

22. Fragrance-reinforced washing or cleaning agent, characterized in that it consists of at least 80% by weight of components produced according to the invention, it being particularly advantageous if the remaining constituents are also compounds or treated raw materials which according to one of claims 1 to 21 were manufactured.

23. Fragrance-enhanced washing or cleaning agent according to claim 22, characterized in that it has dust-like or at least finely divided ingredients (the so-called fine particles) as the outer shell, which were adhered by melting agglomeration.

24. Fragrance-enhanced washing or cleaning agent according to spoke 22 or 23, characterized in that it has been subsequently sprayed with perfume.

25. Fragrance-enhanced washing or cleaning agent according to spoke 24, characterized in that at least 30 wt .-%, preferably at least 40 wt .-% and in particular at least 50 wt .-% of the total perfume contained in the preparation process according to one of the claims 1 to 21 has been introduced into the agent.

26. Fragrance-enhanced washing or cleaning agent according to claim 25, characterized in that the proportion of the perfume which has been introduced into the agent via a manufacturing process according to one of claims 1 to 25 is composed mainly of adhesive fragrances.

27. Fragrance-enhanced washing or cleaning agent according to spoke 25, characterized in that the proportion of the perfume which was introduced into the agent via a manufacturing process according to one of claims 1 to 25 is composed mainly of volatile fragrances.