EP1025198B1 - Method for producing scent intensifying washing and cleaning detergents - Google Patents

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

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

The scenting of solid washing and cleaning agents is a state of the art Knowledge. On the one hand, these products are perfumed for the reason of the consumer in addition to the structure and color impression, a recognizable and "unmistakable" To provide funds, on the other hand, the incorporation of fragrances cause the objects treated with the agents, in particular textiles, get a long-lasting fragrance that the consumer as a performance feature of the agent in question is assessed. Usually, the excipients that do not work directly in the washing or cleaning process, the washing and cleaning agents last added. This procedure particularly affects the "aesthetic" components like dyes and fragrances. The perfume is mostly incorporated in the way that the finished solid granules are sprayed with perfume, which if necessary is fixed with powdering components on the surface of the solid agent. This The procedure has the disadvantage that the fragrances are not homogeneous over the whole Means are distributed and additionally in any subsequent drying steps partially removed again. Also the fragrance impression of the agents or the treated ones Objects are often not intense enough with this type of perfuming and only through to make increased use of fragrance satisfactory.

The production of detergent and cleaning agent granules is state of the art broadly described, with extensive patent literature from each publication in trade journals up to the complete monograph an almost unmanageable There are numerous documents dealing with this topic.

Compacted detergents and cleaning agents and processes for their production 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.

In order 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 described in the prior art as highly fragrant and scented agents for use in detergents and cleaning agents, for example in patent applications and patents 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 being activated in the dryer: EP 376 385 (Procter & Gamble).

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

The present invention is based on the object of providing a method with which fragrance-reinforced detergents or cleaning agents or components therefor Can produce not only dry laundry, but also wet laundry give a stronger fragrance and as a medium itself more clearly perceptible smell as the traditionally scented means.

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

The invention relates to a method for producing fragrance-reinforced washing or Detergents or components therefor with bulk densities above 600 g / l, with a solid and essentially water-free premix of detergent or cleaning agent compounds and / or raw materials is produced which contains at least 0.1% by weight Perfume, based on the premix, and this premix contains a press agglomeration subjects, where the premix contains binders already at Temperatures up to a maximum of 150 ° C completely as a melt are present and the incorporation of the binder at temperatures takes place in which the binder is in the form of a melt is present.

In the context of this invention, a condition is "substantially water-free" understand, where the content of liquid, i.e. not in the form of water of hydration and / or Constitutional water 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 chemically and / or physically bound form or as part of the raw materials or compounds present as a solid, but not as a liquid, solution or dispersion in the manufacturing process of the Vorgemtsches are introduced. Advantageously, the premix as a whole a water content of not more than 15 wt .-%, so this water not in liquid free form, but chemically and / or physically bound, and it is particularly preferred that the content of not zeolite and / or silicates bound water in the solid premix not more than 10 wt .-% and in particular is not more than 7% by weight.

Detergents or cleaning agents are understood to mean such compositions that can be used for washing or cleaning, without usually more Ingredients must be added. A component for detergents or cleaning agents on the other hand consists of at least 2 usually in detergents or cleaning agents used components; Components or so-called compounds are usually but only in a mixture with other ingredients, preferably together with others Compounds used.

The ingredients used in the process according to the invention can - with the exception the possibly existing at temperatures below 45 ° C and a Pressure of 1 bar liquid non-ionic surfactants - separately manufactured compounds, however also be raw materials that are available in powder or particulate form (fine to coarse). Beads produced by spray drying, for example, can be used as particulate particles or (fluidized bed) granules etc. can be used. The composition of the compounds in itself is immaterial to the invention with the exception of the water content, which must be such that the premix is essentially anhydrous as defined above is and preferably not more than 10% by weight of water of hydration and / or water of constitution contains. In a preferred embodiment, they are over-dried Compounds used in the premix. Such compounds can, for example can be obtained by spray drying, the temperature control being regulated so that the tower outlet temperatures above 70 ° C, for example at 85 ° C or above lie. It is also possible that solid compounds are used in the premix as a carrier of liquids, for example liquid nonionic surfactants or silicone oil and / or paraffins. These compounds can contain water in the above Frame included, the compounds are free-flowing and even at higher Temperatures of at least 45 ° C remain free-flowing or at least conveyable. In particular it is preferred, however, that in the premix compound with a maximum of 10 wt .-% and with particular preference with a maximum of 7% by weight of water, based on the premix, be used. Free water, that is water that is not in any form a solid is bound and is therefore "in liquid form" is preferably done not included in the premix because very small amounts, e.g. around 0.2 or 0.5% by weight, based on the premix, are sufficient to be water-soluble per se To loosen components. This would have the consequence that the melting point or softening point reduced and the end product both in flowability and bulk density would lose.

Surprisingly, it has been shown that it is by no means indifferent on which solid raw material or in which solid compound the water is bound. That's how it is Water that builders like zeolite or silicates (description of the substances see below), especially if the water on zeolite A, zeolite P or MAP and / or Zeolite X is considered less critical. On the other hand, it is preferred that Water which is bound to other solid constituents than the builder substances mentioned is preferably contained in the premix in amounts of less than 3% by weight is. It is particularly advantageous if the premix contains no water at all is not bound to the builder substances. However, this is difficult to achieve technically, because, as a rule, at least always traces of the raw materials and compounds Water to be introduced.

According to the invention, the essentially water-free premixes contain perfume, with 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 becomes a homogeneous distribution of the fragrances over the whole Detergent or cleaning agent or the component for this is achieved. Since with an im essential water-free premix is worked, later drying steps are omitted, in which perfume could evaporate in whole or in part. Through targeted training of the perfume in the means or components also occurs during transport or storage a significantly reduced loss of fragrance. Compared to conventionally scented Not only is the perfume distributed much more evenly, but also more intensely To achieve a fragrance impression of the product. In this way, products can do the same olfactory impression can be scented with less perfume or with the same Perfume quantity significantly improved fragrance impressions can be achieved. The improvement of Fragrance not only occurs on the scented product, but also on the treated one Objects, preferably textiles, are clearly visible. Both on damp as well on dry laundry, the agents leave a stronger fragrance impression in comparison to conventionally scented press agglomerates. Because the fragrances are homogeneous the entire press agglomerate are distributed, problems are avoided that the conventional Fragrance brings: Because the suction power of the agglomerates for sprayed Perfume is low and continues to decrease with increasing degree of compaction, most of it sticks of the perfume on the powder. That which is inevitably moved during transport is conventional Scented product loses part of the powdering agent which carries most of the perfume. These loose fines then fall with further movement through the coarser grain solid bed and collect on the bottom of the containers, so that a certain proportion of fragrance is hardly used for product scenting and no longer at all Fragrance of the treated objects contributes. These disadvantages are also overcome by the avoided inventive method.

As perfume oils or fragrances, individual fragrance compounds, e.g. synthetic products of the ester, ether, aldehyde type, Ketones, alcohols and hydrocarbons can be used. fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethyl acetate, Benzyl acetate, ethyl methylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, Benzyl salicylate, cyclohexyl salicylate, floramate, melusate and jasmine cyclate. To the ethers include, for example, benzyl ethyl ether and ambroxan, the aldehydes e.g. the linear alkanals with 8 - 18 C atoms, citral, citronellal, citronellyloxy-acetaldehyde, Cyclamenaldehyde, Lilial and Bourgeonal, to the ketones e.g. the Jonone, ∝-isomethylionon and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, belong to the hydrocarbons mainly the terpenes like limes and pinene. However, mixtures are preferred different fragrances, which together make an appealing Generate fragrance.

Such perfume oils can also contain natural fragrance mixtures such as those from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or Ylang-ylang oil. Also suitable are muscatel sage oil, chamomile oil, clove oil, lemon balm oil, Mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, Galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and Sandalwood oil.

The essentially water-free premix, which reaches the press agglomeration, has preferably no dust-like components and in particular no particles with particle sizes less than 200 µm. Such particle size distributions are particularly preferred, which at least 90 wt .-% 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 at least 70% by weight, advantageously at least 80% by weight and with particular preference up to 100% by weight of spherical or almost spherical (pearl-shaped) particles with a particle size distribution, which has at least 60 wt .-% particles between 0.8 and 2.0 mm.

The solid and essentially water-free premix contains conventional solid washing and Detergent ingredients such as builders, solid surfactants, bleach, Bleach activators, polymers and other common 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 are. Pre-mixtures are preferably used in the context of the present invention, the individual raw materials and / or compounds that are at room temperature and one Pressure of 1 bar as a solid and not a melting or softening point Have below 45 ° C and optionally up to 20 wt .-%, preferably up to 15 % By weight and in particular up to 10% by weight, based on the premix, at temperatures Contain liquid nonionic surfactants below 45 ° C and a pressure of 1 bar. This is the use of commonly used in detergents and cleaning agents alkoxylated alcohols such as fatty or oxo alcohols preferred, so that a preferred Process is designed such that the premix in addition to the solid components up to 20% by weight, preferably up to 15% by weight and in particular up to 10% by weight Liquid non-ionic at temperatures below 45 ° C and a pressure of 1 bar Surfactants, especially those commonly used in washing or cleaning agents alkoxylated alcohols 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 Contains alcohol, the addition of the liquid nonionic surfactants preferably in Mix with the perfume.

To facilitate the press agglomeration of the premix and the physical properties the fragrance-reinforced washing or cleaning agents obtained by press agglomeration or to improve components for this, the premix can be a raw material or contain a compound that as a binding and disintegration aid acts. These binding and disintegration aids serve as press agglomeration Lubricants and adhesives that glue the solid components of the premix together and the passage of the premix through the pressure zone of the press agglomeration apparatus facilitate. As water-soluble binders, they also facilitate redissolution the press agglomerates, since they act as disintegrants in aqueous liquors. In a preferred method within the scope of the present invention, this contains Premix at least one raw material or compound that at a pressure of 1 bar and temperatures below 45 ° C in solid form in the press agglomeration but is in the form of a melt, this melt being a polyfunctional, in Water soluble binder serves both function in the preparation of the agents a lubricant as well as an adhesive function for the solid detergent or cleaning agent compounds exercises or raw materials when redissolving the agent in aqueous Fleet has a disintegrating effect.

Binders suitable for use in the method according to the invention are available in one Pressure of 1 bar and temperatures below 45 ° C, but are within the process conditions the press agglomeration as a melt. Incorporation of the binders in the premix can be done in such a way that a melt of the binder or binder mixture sprayed onto the premix or the premix is added dropwise. The binder (mixture) can also as a fine solid in the Be premixed.

The type of suitable binder and the temperature in the compression step in press agglomeration are interdependent. Since it turned out to be beneficial if the binder in the compression step is as homogeneous as is possible distributed in the material to be compacted, the Compression temperatures are present, at which the binder at least softens, preferably but completely and not only partially in the molten form. Becomes So a binder with a high melting point or high softening point is selected, see above a temperature must be set in the compression step, which ensures the melting of the binder. In addition, depending on the desired composition of the end product also temperature-sensitive raw materials should be able to be processed. Here the upper temperature limit is determined by the decomposition temperature given the sensitive raw material, it being preferred, significant to work below the decomposition temperature of this raw material. In contrast, the lower one Limit for the melting point or softening point is therefore of such great importance as a rule at melting points or softening points below 45 ° C an end product is obtained that is already at room temperature and slightly elevated temperatures around 30 ° C, i.e. at summer temperatures and under storage or transport conditions tends to stick. It has proven to be particularly advantageous if a few degrees, for example 2 to 20 ° C, above the melting point or above the Softening point is worked

Without wishing to be limited to this theory, the applicant is of the opinion that due to the homogeneous distribution of the binder within the premix Process conditions of compression of the solid compounds and, if necessary existing individual raw materials in this way enclosed by the binder and then are glued together that the finished end products almost exactly from these many small individual particles that are built up by the binder that the Takes on the role of a preferably thin partition between these individual particles, be held together. In the idealized form it can be of a honeycomb-like Structure are assumed, these honeycombs with solids (compounds or individual raw materials) are filled. In contact with water, also with cold water, so for example at the beginning of a machine wash, loosen or disintegrate these thin partitions almost instantaneously; Surprisingly, this is also the case the case when the binder itself at room temperature, for example due to a Crystal structure, is not quickly soluble in water. However, such are preferred Binder used, which in a test procedure as described below in a Concentration of 8 g binder in 1 l water at 30 ° C almost within 90 seconds let it solve completely.

The binder or binders must therefore be of the type that the adhesive properties even at temperatures that are significantly above the melting point or the softening point lie, still remain. On the other hand, it is also essential for that Choice of the type and amount of the binder (s) used, that the binding Properties are not lost after re-cooling within the end product, the cohesion of the end product is thus assured, but the end product not glued even under normal storage and transport conditions.

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 in the form of a melt at temperatures up to a maximum of 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 specific 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 modified polyethylene glycols and polypropylene glycols. The modified polyalkylene glycols include in particular the sulfates and / or the disulfates of polyethylene glycols or polypropylene 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 have 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 ₃ -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 preferably used polyethylene glycols can be linear or branched Have structure, with linear polyethylene glycols being preferred in particular.

The particularly preferred polyethylene glycols include those with relative molecular weights between 2000 and 12000, advantageously around 4000, with polyethylene glycols with relative molecular weights below 3500 and above 5000 especially in Combination with polyethylene glycols with a molecular weight around 4000 used and such combinations advantageously to more than 50 wt .-%, based on the total amount of polyethylene glycols, polyethylene glycols with a have molecular weights between 3500 and 5000. However, as a binder also polyethylene glycols are used, which per se at room temperature and a pressure of 1 bar in the liquid state; here is mostly from polyethylene glycol with a relative molecular mass of 200, 400 and 600. Indeed These per se liquid polyethylene glycols should only be mixed with at least another binder can be used, this mixture again according to the invention Requirements must meet, i.e. a melting point or softening point must be 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 ₁₂ -alkyl chains which can be linear or branched. In particular, the end groups have the alkyl chains between C ₁ and C ₆ , especially between C ₁ and C ₄ , 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 in 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 content of binder in the premix, see below.

In a preferred embodiment of the method according to the invention, the Solids for the preparation of the solid and free-flowing premix initially at room temperature to slightly elevated temperatures, preferably below the melting temperature or the softening point of the binder and in particular at temperatures to 35 ° C mixed together in a conventional mixing and / or granulating.

The binders are preferably added as the last component. Your encore can, as already explained above, as a solid, that is at a processing temperature that is below its melting point or softening point, or as a melt respectively. However, the admixture is advantageous under such conditions carried out that a uniform, homogeneous distribution of the binder in the solid mixture is reached. With very finely divided binders, this can occur at temperatures below 40 ° C, for example at temperatures of the binder between 15 and 30 ° C. However, the binder advantageously has temperatures where it is already in the form of a melt, i.e. above the softening point, in particular in the form of a complete melt. Preferred temperatures the melt is at 60 to 150 ° C with particular preference for the temperature range from 80 to 120 ° C. During the mixing process, which takes up to room temperature slightly elevated temperature, but below the softening point or melting point of the binder occurs, the melt solidifies almost immediately, and the premix according to the invention is in solid, free-flowing form. The mixing process will in any case advantageously continued until the melt has solidified and that Premix is in solid, free-flowing form.

By incorporating the perfume into the premix, the proportion of binder (s) can be reduced. Since the fragrances act as lubricants and, due to 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-surfactant press agglomerates which cannot be prepared 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 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.

Incorporation of the perfume into the premix can be done in almost every stage of the premix respectively. So it is possible, for example, part or all of the amount the solids as described above at room temperature in a conventional mixing and / or Submit pelletizer and put the perfume on the moving solid bed or spray on. The perfume can also be combined with the binder as above described to be added to the solids. Here is both the mixing of Perfume with a solid binder as well as incorporating the perfume into a separately made one Melt the binder and add the pasty to liquid binder-perfume mixture possible to the solids. Of course, all of the above Incorporation methods can be combined with one another of the perfume is introduced into the premix in different ways. If in Non-ionic surfactants are used according to the invention, the addition is carried out of the perfume preferably as a mixture with the nonionic surfactants, where Mixtures of binder, nonionic surfactant and perfume can also be produced and used can.

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

By compressing the particle aggregate (premix), the agglomeration of the press on the one hand the porosity is reduced, on the other hand the plastic deformation of the Contact zones reinforce the particle adhesion, which is why materials that are largely plastic let deform, deliver compacts with high strength, while elastically deformable Particles with brittle behavior are more difficult to compress. By the addition The compressibility of binders can be improved. The press agglomeration process, to which the solid and essentially water-free premix is subjected, can be realized in different devices. Depending on the type of used A distinction is made between agglomerators and different press agglomeration processes. The four most common press agglomeration processes preferred in the context of the present invention are extrusion, roll pressing or compacting, the Hole pressing (pelleting) and tableting, so that in the context of the present invention preferred press agglomeration processes extrusion, roll compacting, pelletizing or tableting processes.

All processes have in common that the premix compresses and plastifies under pressure and the individual particles are pressed together while reducing the porosity become and stick together. In all processes (with tableting with restrictions) the tools can be heated to higher temperatures or removed cool the heat generated by shear forces. The actual compression process takes place at processing temperatures that are at least in the compression step at least the temperature of the softening point, if not the temperature of the Correspond to 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 it is but preferred that the process temperature in the compression step be no more than 20 ° C above the melting temperature or the upper limit of the melting range of the binder lies. It is technically possible to set even higher temperatures; however, it has been shown that a temperature difference to the melting temperature or sufficient for the softening temperature of the binder of 20 ° C in general is and even higher temperatures have no additional advantages. Therefore it - particularly also for energy reasons - is particularly preferred, above however as close as possible to the melting point or the upper temperature limit of the Working range of the binder. Such a temperature control has the further advantage that thermally sensitive raw materials, for example peroxy bleach such as perborate and / or percarbonate, but also enzymes, increasingly without serious Active substance losses can be processed. The possibility of accurate Temperature control of the binder, especially in the crucial step of compaction, that is between the mixing / homogenization of the premix and the shaping, allows an energetically very cheap and for the temperature sensitive components of the premix extremely gentle process management, since the premix only is exposed to the higher temperatures for a short time. In preferred press agglomeration processes show the tools of the press agglomerator (the screw (s) of the Extruders, the roller (s) of the roller compactor and the press roller (s) of the pellet press) a temperature of a maximum of 150 ° C, preferably a maximum of 100 ° C and especially a maximum 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 effect is preferably in the compression range the press agglomerators a maximum of 2 minutes and is especially in a range between 30 seconds and 1 minute.

The compressed material preferably points directly after it leaves the production apparatus Temperatures not above 90 ° C, with temperatures between 35 and 85 ° C are particularly preferred. It has been found that outlet temperatures - before especially in the extrusion process - from 40 to 80 ° C, for example up to 70 ° C, particularly advantageous are.

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 extruded under pressure and the strand is cut to the predeterminable size of the granulate by means of a cutting device after it has emerged from the hole shape. 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, in the context of the present invention, with the exception of the nonionic surfactants mentioned above, are not introduced into the premix in liquid and in particular not in aqueous, but in solid form.

To explain the actual extrusion process, we hereby expressly refer to the referenced above patents and patent applications. In a preferred embodiment the invention, the premix is preferably continuously one Planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guide supplied, its housing and whose extruder pelletizing head must be heated to the predetermined extrusion temperature can. The premix is mixed in under the shear of the extruder screws Pressure, which is preferably at least 25 bar, depending on extremely high throughputs of the apparatus used but can also be below it, compressed, plasticized, in the form of fine strands through the perforated nozzle plate in the extruder head and finally, preferably the extrudate by means of a rotating knock-off knife reduced spherical to cylindrical granules. The hole diameter of the Perforated nozzle plate and the strand cut length are based on the selected granule dimension Voted. In this embodiment, the production of granules is successful an essentially uniformly predeterminable particle size, in particular the absolute particle sizes can be adapted to the intended application. In general, particle diameters up to at most 0.8 cm are preferred. Important Embodiments see 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 about 0.8 to 3 mm. The length / diameter ratio of the chipped primary In an important embodiment, granules are in the range from about 1: 1 to about 3: 1. Furthermore, it is preferred to add the still plastic primary granulate to another to supply shaping processing step; the raw extrudate is present Rounded edges so that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired, small amounts of can be added at this stage Dry powder, for example zeolite powder such as zeolite NaA powder, can also be used. This shape can be done in standard rounding machines. It is on it make sure that only small amounts of fine grain are produced in this stage. A Drying, which is preferred in the above-mentioned prior art documents Embodiment is described, but is unnecessary in the context of the present Invention, since the method according to the invention is essentially anhydrous, that is, without the Free, unbound water is added.

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

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

The low dwell times combined with the water-free process procedure enable it that peroxy bleaching agents may even be used together with bleach activators can also be extruded at higher temperatures without serious loss of activity to suffer.

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 to processing in continuously operating mixers / granulators or rollers, for example.

As in the extrusion process, it is also preferred in the other production processes the resulting primary granules / compactates a further shaping processing step supply, in particular a rounding, 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 much broader than that of the invention manufactured and end product according to the invention. The premix can be essential Larger fractions of fine grains, even dust, possibly also coarser grains Contain proportions, but it is preferred that a premix with relatively broad Particle size distribution and relatively high proportions of fine grain in an end product transferred relatively narrow particle size distribution and relatively small proportions of fine grain becomes.

Because the process of the invention is essentially anhydrous - i.e. with the exception water-free ("impurities") of the solid raw materials used - is carried out is not only the risk of gelling the surfactant raw materials already minimized to excluded in the manufacturing process, in addition also an ecologically valuable process is provided because by omitting a subsequent one Drying step not only saves energy but also emissions, such as they mainly occur with conventional types of drying, can be avoided. In addition, the omission of subsequent drying steps enables the Incorporation of the fragrances into the premix and thus the production of fragrance-reinforced Detergents or cleaning agents or components therefor.

In a further preferred embodiment of the present invention, the invention Process carried out by means of roller compaction. Here will the fragrance-containing solid and essentially water-free premix between metered in two smooth rollers or with recesses of a defined shape and between the two rollers under pressure to form a leaf-shaped compact, the so-called Schülpe, rolled out. The rollers exert a high line pressure on the premix and can be additionally heated or cooled as required. In the Using smooth rollers you get smooth, unstructured coulter bands while correspondingly structured slugs are produced by using structured rollers can be in which, for example, certain forms of the later detergent or cleaning agent particles can be specified. The cuff band is below broken down into smaller pieces by a knock-off and crushing process and can processed in this way to granules, which are known by others Surface treatment processes refined, especially in an approximately spherical shape can be brought.

The temperature of the pressing tools is also in the case of roller compacting the rollers, preferably at a maximum of 150 ° C, preferably at a maximum of 100 ° C and in particular at a maximum of 75 ° C. Particularly preferred manufacturing processes work for Roll compacting with process temperatures that 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 exposure in the compression area of the smooth or with depressions of defined Molded rollers is a maximum of 2 minutes and especially in one area is 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. 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 embodiments 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 also be conical in the plate devices, in the ring-shaped devices dies and press roll (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 interspersed with 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.

The pelleting temperature is also the temperature of the pressing tools Pressure rollers or press rolls, preferably at a maximum of 150 ° C, preferably at a maximum 100 ° C and especially at a maximum of 75 ° C. Particularly preferred manufacturing processes work in roller compacting with process temperatures that are 10 ° C, in particular maximum 5 ° C above the melting temperature or the upper temperature limit of the Melting range of the binder.

Another press agglomeration process which can be used according to the invention is the tableting. Due to the size of the molded body, it can be Tableting may be useful, in addition to the binder, customary disintegration aids, for example to add cellulose and its derivatives or cross-linked PVP, which the Ease disintegration of the compacts in the wash liquor.

In a preferred embodiment of the invention, a fragrance-reinforced extruded, roller-compacted or pelletized detergent, which is at least 80 % By weight of compounds and / or treated raw materials produced according to the invention consists. In particular, there is an extruded, roller-compacted or pelletized Detergent to at least 80 wt .-% from a base agglomerate produced according to the invention. The remaining ingredients can be made by any known method and have been mixed. However, it is preferred that these remaining constituents, which compounds and / or treated raw materials can be, according to the invention Processes were made. In particular, this enables Basic granules and remaining components 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 washing 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 arise means that have these so-called fine particles as an outer shell. In turn, this advantageously takes place 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 base 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, ie powdering and spraying with perfume, can also 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 introduced into the agents via the manufacturing method according to the invention, ie into Press agglomerates incorporated, while the remaining 70 wt .-%, preferably 60 wt .-% and in particular 50 wt .-% of the total perfume contained on the press agglomerates, which can optionally be surface-treated, sprayed or otherwise applied.

By dividing the total perfume content of the agent into perfume, which in the Press agglomerates are included and perfume that adheres to the press agglomerates can be realize a variety of product characteristics that only through the invention Procedures become possible. For example, it is conceivable and possible to determine the total perfume content to divide the agent into two portions x and y, the portion 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, mainly from adherent ones Fragrance is composed. In this way, strong odoriferous substances, which the treated items, especially textiles, should be scented in the product and their effect is mainly on the treated laundry. In contrast, the more volatile fragrances contribute to a more intensive fragrance the means itself. In this way it is also possible to use detergents and cleaning agents to produce, which have an odor as a means that differs from the smell of the treated Objects differs. The creativity of perfumers is hardly there Limits, because on the one hand on the choice of fragrance substances and on the choice of the incorporation method in 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 the more volatile fragrances are incorporated into the press agglomerates and the heavier ones volatile, sticky fragrances are sprayed onto the agent. That way the loss of the more volatile fragrances from the packaging during storage and Transport minimized, while the fragrance characteristics of the agent from the more adhesive perfumes is determined.

The general description of the perfumes that can be used (see above) generally provided the different substance classes of fragrances. To be perceptible, a fragrance should be volatile, in addition to the nature of the functional groups and the Structure of the chemical compound also the molecular weight plays an important role. So most fragrances have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Because of the different Volatility of fragrances changes the smell of one of several fragrances composite perfume or fragrance during evaporation, wherein the smell impressions in "top note" (top note), "heart or middle note" (middle note or body) and "base note" (end note or dry out). Because the smell perception The top note is largely based on the smell intensity of a perfume or fragrance not only from volatile compounds, while the Base note for the most part from less volatile, i.e. adherent refractories. In the composition of perfumes, for example, more volatile fragrances certain fixatives are bound, which prevents them from evaporating too quickly becomes. The above-described embodiment of the present invention in which the more volatile fragrances or fragrances are incorporated into the press agglomerate, is such a method for fragrance fixation. In the following classification of Fragrance in "more volatile" or "sticky" fragrance is so about the odor impression and whether the corresponding fragrance is perceived as a top or heart note nothing is said.

Adhesive fragrances 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, champaca flower oil, noble fir oil, noble pine cone oil, elemi oil, Eucalyptus oil, fennel oil, spruce oil, galbanum oil, geranium oil, ginger grass oil, Guaiac wood oil, gurjun balsam oil, helichrysum oil, ho oil, ginger oil, iris oil, kajeput oil, calamus oil, Chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil, copaiva balsam oil, Coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, Lime oil, mandarin oil, lemon balm oil, musk seed oil, myrrh oil, clove oil, Neroli oil, 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, thuja oil, thyme oil, verbena 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.

But also the higher-boiling or solid fragrances of natural or synthetic origin can be used in the context of the present invention as adhesive odoriferous substances or Fragrance mixtures, i.e. fragrances, are used. These connections include the compounds mentioned below and mixtures of these: ambrettolide, α-amylcinnamaldehyde, Anethole, anisaldehyde, anis alcohol, anisole, anthranilic acid methyl ester, Acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, Benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerianate, borneol, bornyl acetate, α-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, Eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, Heptincarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, Hydroxy cinnamon alcohol, indole, iron, isoeugenol, isoeugenol methyl ether, isosafrol, Jasmon, camphor, Karvakrol, Karvon, p-cresol methyl ether, coumarin, p-methoxyacetophenone, Methyl-n-amylketone, methylanthranilic acid methyl ester, p-methylacetophenone, Methylchavicol, p-methylquinoline, methyl-β-naphthyl ketone, methyln-nonylacetaldehyde, Methyl-n-nonyl ketone, muskon, β-naphthol ethyl ether, β-naphthol methyl ether, Nerol, nitrobenzene, n-nonylaldehyde, nony alcohol, n-octylaldehyde, p-oxy-acetophenone, pentadecanolide, β-phenylethyl alcohol, phenylacetaldehyde dimethyacetal, Phenylacetic acid, pulegon, safrole, salicylic acid isamyl ester, salicylic acid methyl ester, Hexyl salicylic acid, cyclohexyl salicylic acid, Santalol, Skatol, Terpineol, Thymen, thymol, γ-undelactone, vanilin, veratrum aldehyde, cinnamaldehyde, zimate alcohol, Cinnamic acid, cinnamic acid ethyl ester, cinnamic acid benzyl ester.

The more volatile fragrances include in particular the lower-boiling fragrances natural or synthetic origin, used alone or in mixtures can be. 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 invention Agents and the components used in the process according to the invention.

Important ingredients of the agent and ingredients according to the invention Methods used are surfactants, especially anionic surfactants, at least in amounts of 0.5% by weight in the agents according to the invention or according to the invention manufactured means should be included. These include in particular sulfonates and sulfates, but also soaps.

Preferred surfactants of the sulfonate type are C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C ₁₂ -C ₁₈ 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 obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.

The esters of α-sulfo fatty acids (ester sulfonates), e.g. 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 plant and / or animal origin with 8 to 20 carbon atoms in the fatty acid molecule and subsequent neutralization to water-soluble Mono salts are made into consideration. This is preferably the case the α-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, also 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. With particular advantage the methyl esters of α-sulfofatty acids (MES), but also their saponified disalts.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures as they are produced by esterification by a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of Triglycerides with 0.3 to 2 moles of glycerol can be obtained.

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

The sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol of ethylene oxide (EO) or C ₁₂ -C ₁₈ -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 which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Other anionic surfactants are fatty acid derivatives of amino acids, for example of N-methyl taurine (tauride) and / or of N-methyl glycine (sarcoside). The sarcosides or sarcosinates are particularly preferred, and above all Sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate.

Other anionic surfactants include, in particular, soaps, preferably in quantities from 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. Along with these soaps or the known alkenyl succinic acid salts can also be used as a substitute for soaps be used.

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

The anionic surfactants are in the agents according to the invention or are in the agents according to the invention Process preferably in amounts of 1 to 30 wt .-% and in particular contained or used in amounts of 5 to 25 wt .-%.

In addition to the anionic surfactants and the cationic, zwitterionic and amphoteric Surfactants, especially nonionic surfactants are 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 residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues 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 ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohols with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used, 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. I

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

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

in der R³ für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R⁴ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R⁵ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C₁-C₄-Alkyl- oder Phenylreste bevorzugt sind, und [Z] für einen linearen Polyhydroxyalkylrest, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes steht. [Z] wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielsweise nach der Lehre der internationalen Patentanmeldung WO-A-95/07331 durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden. The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in which R ^{3 is} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 is} a linear, branched or cyclic alkyl radical or an aryl radical is 2 to 8 carbon atoms and R ^{5 is} a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C ₁ -C 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 radical. [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 . C ₁₂ -C ₁₈ fatty acid methyl esters with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO, are preferred as nonionic surfactants, while, as described above, especially higher ethoxylated fatty acid methyl esters are advantageous as binders. In particular C ₁₂ -C ₁₈ fatty acid methyl esters with 10 to 12 EO can be used both as surfactants and as binders.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanol amide can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.

So-called gemini surfactants can be considered as further surfactants. Below are generally understood such compounds, the two hydrophilic groups and two have hydrophobic groups per molecule. These groups are usually by one so-called "spacers" separated from each other. This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups have a sufficient Distance so that they can act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In In exceptional cases, however, the term Gemini surfactants does not only refer to dimeric, but also understood 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. End group-blocked dimeric and trimeric mixed ethers according to German patent application DE-A-195 13 391 is particularly characterized by its 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 the international patent applications WO-A-95/19953, WO-A-95/19954 and WO-A-95/19955 , can also be used.

In addition to the surfactants, the inorganic and organic builder substances belong above all on the most important ingredients of washing 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 can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 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 O ₅ .y H ₂ O are preferred.

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

It goes without saying that the generally known phosphates are also used as builder substances possible, provided that such use is not avoided for ecological reasons should be. The sodium salts of orthophosphates, pyrophosphates, are particularly suitable and especially the tripolyphosphates. Your salary in general is not more than 25 wt .-%, preferably not more than 20 wt .-%, each based on the finished funds. In some cases it has been shown that tripolyphosphates in particular even in small quantities up to a maximum of 10% by weight, based on the finished agent, in Combination with other builder substances to a synergistic improvement of the Secondary washing power.

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 sheet 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 from 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.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if 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 from these.

The acids themselves can also be used. The acids have a builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these. Preferably these acids, if they are used in the premix according to the invention and not are subsequently added, used anhydrous.

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 methods, for example acid or enzyme catalysis. 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 customary measure for is the reducing effect of a polysaccharide compared 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 and 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 are known. 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 are 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 . Suitable amounts used in formulations containing zeolite and / or silicate are from 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may 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 from 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid have been particularly suitable Maleic acid proved to be 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain. Their relative molecular weight, based on free acids, is in general 5000 to 200000, preferably 10000 to 120000 and in particular 50000 to 100000.

The content of (co) polymeric polycarboxylates in the compositions is in 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 which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Further 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 that make the oil and fat washable made of textiles. This effect is particularly evident if a textile is soiled, which has previously been repeatedly with an inventive Detergent containing this oil and fat-dissolving component has been washed. To The preferred oil- and fat-dissolving components include, for example, non-ionic ones Cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion on methoxyl groups from 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and that from the Polymers of phthalic acid and / or terephthalic acid known from the prior art or of their derivatives, 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 acid and the terephthalic acid polymers.

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 O: SiO ₂ of 1: 1 to 1: 4.5, preferably of 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, bleaches 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.

Acid can also be used to reduce the pH of detergents or cleaning agents Salts or slightly alkaline salts can be used. Are preferred as acidifying components Bisulfates and / or bicarbonates or the above-mentioned organic polycarboxylic acids, which can also be used as builder substances at the same time. In particular preference is given to the use of citric acid, which is either added subsequently (usual procedure) or - in anhydrous form - in a solid premix is used.

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 which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid 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.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-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 phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy, 2,5-diacetyloxy, 2,5-ethylene glycol 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 their mixtures described in European patent application EP-A-0 525 239 (SORMAN ), acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-al 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 advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -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 different foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes. The foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.

The salts of polyphosphonic acids are preferably the neutral sodium salts for example, 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate in amounts of 0.1 to 1.5 wt .-% used.

In particular, enzymes from the hydrolase class, such as proteases, Lipases or lipolytically active enzymes, amylases, cellulases or mixtures thereof in question. Oxireductases are also suitable.

Bacterial strains or fungi such as Bacillus subtilis and Bacillus are particularly suitable licheniformis, Streptomyces griseus and Humicola insolens Agents. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic acting enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic acting enzymes or protease, lipase or lipolytically acting enzymes and cellulase, in particular, however, mixtures or mixtures containing protease and / or lipase with lipolytic enzymes of particular interest. Examples of such The well-known cutinases are lipolytic enzymes. Also peroxidases or oxidases have proven to be suitable in some cases. To the suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases that also called cellobiases, or mixtures of these are used. Because the different Distinguish cellulase types by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases become.

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

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 H ₂ B ₄ O ₇ ), is particularly advantageous.

Graying inhibitors have the task of removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose. Soluble starch preparations can also be used and use starch products other than the above, e.g. degraded starch, Aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, are preferred Cellulose ethers, such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, Methyl carboxymethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone for example in amounts of 0.1 to 5 wt .-%, based on the agent used.

As optical brighteners, the agents can be derivatives of diaminostilbenedisulfonic acid or whose alkali metal salts contain. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed Compounds which, instead of the morpholino group, have a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, e.g. 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 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. Composition of the spray-dried granules [% by weight]: C _9-13 alkyl benzene sulfonate 26.00 sodium 8.50 Zeolite 4 A. 41,33 optical brightener 0.42 1-hydroxyethane-1,1-diphosphonic acid 1.00 Acrylic acid-maleic acid copolymer, Na salt 9.50 sodium hydroxide 0.50 Salts from solution 0.75 water 12,00 Composition of the premix [% by weight]: spray-dried granules (Table 1) 59.0 Sodium perborate monohydrate 20.0 C _12-18 fatty alcohol with 7 EO 7.0 C _12-18 fatty alcohol sulfate 92% 7.5 Polyethylene glycol 4000 6.0 perfume oil 0.5

The perfume oil was dissolved in the liquid C _12-18 fatty alcohol with 7 EO before being added to the mixer. After leaving the mixer, the free-flowing premix had a bulk density of 450 g / l and was placed in a twin-screw extruder from Lihotzky and plasticized and extruded under pressure.

The plasticized premix left the extruder at a pressure of 85 bar Perforated plate with 1.4 mm diameter holes. The extruded strands were measured with a rotating knives to a length / diameter ratio of cut off approx. 1 and rounded in a Marumerizer®. After screening the Fine parts (<0.4 mm) and coarse parts (> 2.0 mm) the extrudate had a bulk density from 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 V1 and V2 of the same composition, in which the perfume oils in question were sprayed onto the extruded and rounded particles, which were powdered with finely divided zeolite, in a customary procedure 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 extrudate 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 as well as of 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". Since 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. Composition of the perfume oils [% by weight]: Perfume oil 1 Bergamot oil 15.0 dihydromyrcenol 20.0 Lemon oil messina 7.5 Mandarin oil 2.5 Orange oil sweet 5.0 allyl amyl 2.0 Cyclovertal 0.5 Lavender oil grosso 2.5 Muscatel sage oil 1.0 lilial 2.0 β-Damascone 0.1 Geranium oil bourbon 3.0 hedione 5.0 cyclohexyl 4.0 Vertofix Coeur 10.0 Iso E Super 5.0 AMBROXAN.RTM 1.6 Ethylene 10.0 Evernyl 1.0 Dipropylene glycol (DPG) 2.3 Perfume oil 2 Phenylethylakohol 52.0 dimethyl benzyl 2.5 Iraldein gamme 5.0 phenylacetic acid 0.5 Geranylacetat 2.0 benzyl 30 Rose oxide L 10% in DPG 2.5 romilat 20 irotyl 0.5 cyclohexyl 20.0 floramat 10.0 Fragrance enhancement (preference of intensity) Perfumers (preference of intensity) product damp laundry dry laundry E1 (0.5% perfume oil 1 in the extrudate) 5 5 4 V1 (0.5% perfume oil 1 sprayed on) 2 2 3 E2 (0.5% perfume oil 2 in the extrudate) 4 5 4 V2 (0.5% perfume oil 2 sprayed on) 2 1 2 E3 (0.3% perfume oil 2 in the extrudate, 5 6 5 0.2% sprayed on) V3 (0.5% perfume oil 2 sprayed on) 1 2 0

Claims (26)

1. Process for the production of perfume-enhanced detergents or cleaners or components thereof with bulk densities above 600 g/l, characterized in that a solid premix, in which the content of liquid water - i.e. water not in the form of water of hydration and/or water of constitution - is below 2% by weight, of detergent or cleaning compounds and/or raw materials is prepared which comprises at least 0.1% by weight of perfume, based on the premix, and this premix is subjected to press agglomeration, where the premix comprises binders which are present completely in the form of melts even at temperatures up to at most 130°C and the incorporation of the binder takes place at temperatures at which the binder is present in the form of a melt.
2. Process according to Claim 1, characterized in that the premix has a total water content of not more than 15% by weight, where this water is not present in free form and preferably the content of water not bound to zeolite and/or silicates is not more than 10% by weight and in particular not more than 7% by weight.
3. Process according to either Claim 1 or 2, characterized in that a premix is used which comprises individual raw materials and/or compounds which are in the form of a solid at room temperature and a pressure of 1 bar and have a melting point or softening point no lower than 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, of nonionic surfactants which are liquid at temperatures below 45°C and a pressure of 1 bar.
4. Process according to one of Claims 1 to 3, characterized in that, in addition to the solid constituents, the premix comprises up to 20% by weight, preferably up to 15% by weight and in particular up to 10% by weight, of nonionic surfactants which are liquid at temperatures below 45°C and a pressure of 1 bar, in particular the alkoxylated alcohols customarily used in detergents or cleaners, such as fatty alcohols or oxo alcohols with a carbon chain length between 8 and 20 and, in particular, on average 3 to 7 ethylene oxide units per mole of alcohol, the liquid nonionic surfactants preferably being added in the form of a mixture with the perfume.
5. Process according to one of Claims 1 to 4, characterized in that the premix comprises at least one raw material or one compound which is in solid form at a pressure of 1 bar and temperatures below 45°C, but which exists as a melt during press agglomeration, this melt acting as a polyfunctional water-soluble binder which, in the production of the compositions, acts both as a lubricant and also as an adhesive for the solid detergent or cleaner compounds or raw materials, but as a disintegrator during the redissolution of the composition in aqueous liquor.
6. Process according to one of Claims 1 to 5, characterized in that the premix comprises one or more binders which dissolve almost completely in 90 seconds in a concentration of 8 g of binder to 1 l of water at 30°C.
7. Process according to one of Claims 1 to 6, characterized in that the binders are added to the premix as the last component, their addition taking place under conditions such that the most uniformly possible homogeneous distribution of the binder - in the form of solidified melt or in the form of a powder - in the solid mixture is achieved.
8. Process according to one of Claims 1 to 7, characterized in that the binder is incorporated at temperatures at which the binder is in the form of a melt, where the temperatures of the melt are 60 to 150°C, in particular in the temperature range from 80 to 120°C.
9. Process according to one of Claims 1 to 8, characterized in that the mixing operation is continued until the melt has solidified and the premix is in a solid, free-flowing form.
10. Process according to one of Claims 1 to 9, characterized in that a premix is used whose content of binder or binders is at least 1% by weight, but less than 10% by weight, preferably less than 8% by weight and especially preferably 2 to 4% by weight, in each case based on the premix.
11. Process according to one of Claims 1 to 10, characterized in that, immediately after leaving the production unit, the press-agglomerated material has temperatures no higher than 90°C, preferably between 35 and 85°C and in particular between 40 to 80°C, for example up to 70°C.
12. Process according to one of Claims 1 to 11, characterized in that the premix comprises more than 0.15% by weight, preferably more than 0.2% by weight and in particular more than 0.3% by weight of perfume.
13. Process according to one of Claims 1 to 12, characterized in that one part or the total amount of the solids is introduced into a customary mixer and/or granulator at room temperature, and the perfume is added or sprayed onto the moving bed of solids.
14. Process according to one of Claims 1 to 12, characterized in that the perfume is added to the solids together with the binder.
15. Process according to one of Claims 1 to 14, characterized in that the press agglomeration operation is an extrusion, roll compaction, pelleting or tableting operation.
16. Process according to Claim 15, characterized in that the tools of the press agglomerator (the screw(s) of the extruder, the roller(s) of the roller compactor, and the compression roller(s) of the pelleting press) have a temperature of at most 150°C, preferably at most 100°C and in particular at most 75°C, and the processing temperature is at most 30°C and in particular at most 20°C above the melting temperature or the upper temperature limit of the melting range of the binder.
17. Process according to Claim 15, characterized in that the heat exposure time in the compression zone of the press agglomerators is at most 2 minutes, and in particular is in a range between 30 seconds and 1 minute.
18. Process according to one of Claims 1 to 17, characterized in that the preparation takes place by extrusion, where the premix is compacted under pressure, plasticized, extruded in the form of fine strands through the multiple-bore extrusion die in the extruder head and, finally, is size-reduced by a rotating blade, preferably to form approximately spherical (bead-like) to cylindrical granules, and the temperature in the transition zone of the extruder screw, of the predistributor and of the extrusion die being controlled in such a way that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but is preferably exceeded.
19. Process according to one of Claims 1 to 17, characterized in that the preparation takes place by roller compaction, where the premix is compacted under pressure, plasticized, forced through the roller gap in the form of a sheet-like compactate and finally is size-reduced to granules by means of a chopping and size-reducing unit.
20. Process according to one of Claims 1 to 17, characterized in that the preparation takes place by pelleting, where the premix is compacted under pressure, plasticized, forced through a perforated plate in the form of fine strands by means of a rotating roller, and finally is size-reduced to granules by means of a chopping unit.
21. Perfume-enhanced detergent or cleaner, characterized in that it consists of at least 80% by weight of components produced in accordance with the invention, it being particularly advantageous if the remaining constituents are also compounds or treated raw materials which have been produced in accordance with one of Claims 1 to 20.
22. Perfume-enhanced detergent or cleaner according to Claim 21, characterized in that it has, as outer shell, dust-like or at least finely divided ingredients (the "fines"), which are sticked on by melt agglomeration.
23. Perfume-enhanced detergent or cleaner according to Claim 21 or 22, characterized in that it has subsequently been sprayed with perfume.
24. Perfume-enhanced detergent or cleaner according to Claim 23, characterized in that at least 30% by weight, preferably at least 40% by weight and in particular at least 50% by weight of the total perfume present in the composition has been incorporated into the composition by means of the production process according to one of Claims 1 to 20.
25. Perfume-enhanced detergent or cleaner according to Claim 24, characterized in that the proportion of the perfume which has been introduced into the composition by means of a production process according to one of Claims 1 to 20 is composed primarily of firmly adhering odorants.
26. Perfume-enhanced detergent or cleaner according to Claim 24, characterized in that the proportion of the perfume which has been introduced into the composition by means of a production process according to one of Claims 1 to 20 is composed primarily of readily volatile odorants.