DE19858887A1 - High density compacted washing and cleaning agent compositions based on codried mixture of amorphous sodium silicate and polymeric polycarboxylate - Google Patents

Abstract

A codried aqueous mixture of amorphous Na silicate and a polymeric polycarboxylate is used together with other ingredients in the preparation of compacted washing and cleaning agents with a powder density of over 700 g/l. A process for preparing a compacted washing and/or cleaning agent with a powder density of over 700 g/l comprises spraying an aqueous composition containing an amorphous silicate with a ratio Na2O:SiO2 of 1:2 to 1:3.3 (1:2 to 1:2.8) and a polymeric polycarboxylate with a molecular weight of 500-10,000 g/mol together with other washing- and/or cleaning agent ingredients into a drying unit in which granulation can take place simultaneously with the drying; if necessary mixing the resulting washing agent base composition with additional ingredients; and compacting the resulting composition.

Description

The invention relates to a method for producing washing and Detergent compact that contain a silicate builder.

The builders or builder systems fulfill a large number in detergents and cleaning agents of tasks that deal with the constant change in composition, the Offer form and the production of detergents in the late years and Decades also change significantly. Modern detergents now contain around 20 up to 50% by weight builder substances. These belong to the most important classes of substances for the construction of detergents and cleaning agents.

Because of the variety and evolution of detergent systems indicated here, they are Tasks of the builders varied and neither fully nor quantitatively defined. The However, the main requirements are well described. Above all, those are to be mentioned Water softening, washing enhancement, graying inhibition and the dirt dispersion. Builders are said to be necessary for the washing process Contribute alkalinity, show a high absorption capacity for surfactants, the effectiveness of Improve surfactants, positive contributions to the properties of solid products deliver in powder form, for example, and thus have a structure-forming effect or also Reduce dust problems. These different requirements can be usually not meet with only one builder component alone, so that usually a system of builders and co-builders is used.

For ecological reasons, builders containing phosphorus and / or nitrogen are considered Detergent components come under criticism. Has become large today especially in textile detergent formulations, the three-dimensionally cross-linked,  water-insoluble sodium aluminosilicate zeolite NaA prevailed. In considerable Extent, especially in the context of textile detergents, is however here The use of so-called cobuilders is necessary, especially to avoid unwanted ones Counteract incrustations. To a large extent, today together with Zeolite NaA polymeric polycarboxylates, in particular copolymers based on Acrylic acid and maleic acid with molecular weights in the range 20000-150000 g / mol, together used with soda for this purpose. In addition, complexing agents are often used also used.

Simultaneously with the development of the zeolite NaA as a builder, it was proposed to use selected water-soluble amorphous sodium silicate compounds as builders in washing and cleaning agents. Reference is made, for example, to US Pat. Nos. 3,912,649, 3,956,467, 3,838,193 and 3,879,527. Amorphous sodium silicate compounds are described here as builder substances, which are produced by spray drying aqueous water glass solutions, subsequent grinding and subsequent compression and rounding with additional removal of water from the ground material, cf. see, for example, FIG. 3 of US 3,912,649. The water content of the products used is approx. 18 to 20% by weight with bulk densities well above 500 g / l.

According to EP-A-0 444 415, detergents containing 5 to 50% by weight are at least one Surfactant, 0.5 to 60 wt .-% of a builder and usual washing aids proposed, the characteristic being that an amorphous as a builder low-water sodium disilicate with a water content of 0.3 to 6% by weight becomes. The amorphous sodium disilicate should preferably contain 0.5 to 2% by weight of water. The These highly dehydrated amorphous disilicates are produced in a multiple staged process that initially produces a powdery amorphous Provides sodium silicate with a water content of 15 to 23 wt .-%. This material is in a rotary kiln with flue gas at temperatures of 250 to 500 ° C in Countercurrent treated. The amorphous sodium disilicate emerging from the rotary kiln is crushed to a grain size of 0.1 to 12 mm using a mechanical crusher and then grind to a particle size of 2 to 400 µm with a mill.

EP-A-0 542 131 describes a process for producing alkali silicates in granular form Form known in a turbo dryer, wherein alkali silicate solutions with a defined  Solids content are introduced into a heated drum, one in the longitudinal axis Shaft with a plurality of arms ro reaching close to the inner surface of the drum animals. In this way, granular silicates with free water contents between 5 and 12 wt .-% and high bulk densities between 500 and 1200 g / l. Further granular alkali silicates with secondary washing ability are from the European Patent applications EP-A-0 561 656 and EP-A-0 488 868 are known. It is about this compounds of alkali silicates with certain Q distributions and alkali carbonates.

Patent application WO 96/20269 describes an amorphous alkali silicate with secondary washability and a molar ratio of M ₂ O: SiO ₂ between 1: 1.5 and 1: 3.3, which is impregnated with detergent ingredients and a bulk density of 300 g / l. The silicate carrier grain to be impregnated is preferably in granular form and / or as a compound with alkali carbonates and can be produced by spray drying, granulation and / or compacting, for example roller compaction. In a preferred embodiment, the silicate is impregnated with surfactants and in particular with nonionic surfactants. By absorbing the impregnating agent, the flowability of the silicate material is reduced, but this can be restored if the impregnated material is subsequently treated with an aqueous solution.

Granular amorphous alkali silicates with bulk densities of at least 700 g / l, the one have high absorbency, i.e. also after impregnation during processing liquid to flowable ingredients of washing or cleaning agents are sufficiently free-flowing, can be found in the patent application Produce the process described in WO 97134977, which starts from spray drying and includes densification of the spray dried bead. It will spray-dried bead and grind simultaneously or subsequently with the addition of a granulated liquid granulation aid, bulk densities of at least 700 g / l - up to above 1000 g / l - can be set. Such granules are suitable especially for use in compact and surfactant-rich washing or Detergents with bulk weights above 700 g / l, because they prevent gel formation Prevent the agent from dissolving in water or at least greatly reduce it.  

The production of spray-dried amorphous silicates, which is common in conventional Processing conditions with liquid to waxy ingredients of washing or Cleaning agents are impregnated, the free-flowing ability does not deteriorate significantly, is described in patent application WO 97/07194. It is done through a process at which is an aqueous batch containing essentially an amorphous active substance Alkali silicate, spray dried and then with an aqueous dispersion of Impregnated ingredients of detergents or cleaning agents, one ingredient of which Dispersion is an organic cobuilder, and is optionally dried.

All of these processes are suitable for producing silicates which can be used as builders in washing and / or cleaning agents. Common to these applications is that the silicates are produced as separate components that are only subsequently made with ingredients from Detergents and cleaning agents added or detergents or cleaning agents first can be added later. In addition, these applications show that it is important for the builders of the silicates to provide them in a form which is delayed release.

In the sense of an economical procedure in the manufacture of washing and Cleaning agents, however, it is desirable to use the silicates used as builders directly can be processed together with the other ingredients without losses in the Having to put up with washing and cleaning properties. First try, Process silicates together with other ingredients in a spray drying step showed that when using detergents produced in this way, the residues on the laundry increase dramatically. So there was still a need for a process which allows silicates together with other detergents or cleaning agents Process ingredients, the resulting products have no disadvantages compared to the commercial, mostly zeolite-containing detergents or cleaning agents exhibit.

It has now surprisingly been found that amorphous sodium silicates coexist with other washing or cleaning agent ingredients for washing and / or cleaning medium-sized compacts with a bulk density above 700 g / l can be processed,  if certain polymeric polycarboxylates are used at the same time. Surprisingly, detergents resulting from the process are those agents which contain zeolite and the classic acrylic acid-maleic acid copolymers, in Secondary washing behavior, especially in the graying-inhibiting effect and in Residue behavior (ash), superior.

A first subject of the ending is accordingly a process for producing a detergent and / or cleaning agent compactate with a bulk density above 700 g / l, which is characterized in that aqueous preparations of an amorphous sodium silicate with a module Na ₂ O: SiO ₂ of 1: 2 to 1: 3, 3 and a polymeric polycarboxylate with M = 500-10,000 g / mol are sprayed together with other detergents and / or cleaning agent ingredients in a drying device, wherein granulation can take place simultaneously with the drying, and the resulting basic detergent subsequently , if necessary after adding other ingredients, is compacted.

The amorphous sodium silicates used with preference include those with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8, preferably of 1: 2 to 1: 2.6. The processing according to the invention results in a delay in dissolution and the silicates have secondary washing properties. In the context of the present invention, the delay in dissolution compared to conventional amorphous sodium silicates occurs on the one hand through the compaction / compression, but on the other hand can also be caused by overdrying, for example on drying water contents below 15% by weight. Amorphous is also understood to mean so-called X-ray amorphous silicates, which do not provide sharp X-ray reflections in the X-ray diffraction spectrum, 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, but on the other hand in electron diffraction experiments provide washed-out or even sharp diffraction maxima. X-ray amorphous silicates of this type have microcrystalline regions of the size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. X-ray amorphous silicates of this type are described, for example, in German patent application DE-A-44 00 024. It is believed that the release delay increases the secondary washing ability of amorphous silicates.

It is expressly pointed out that all amorphous sodium silicates of the specified module, also commercially available granular silicates or carbonate silicate Compounds are suitable starting materials for the purposes of this invention. These silicates can itself by spray drying, granulation and / or compacting, for example by roller compaction, if such Production of the silicate starting products is also not always sensible, since this Products must be dissolved in an aqueous batch.

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 10,000 g / mol. For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{W of} the respective acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document. In particular, polyacrylates, which preferably have a molecular weight of 2000 to 6000 and particularly preferably 3000 to 5000 g / mol, have proven to be particularly suitable according to the invention. Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic or methacrylic acid with maleic acid, copolymers of acrylic acid with maleic acid containing 50 to 90% by weight of 10 acrylic acid and 50 to 10% by weight of maleic acid being particularly suitable have proven suitable.

The drying device into which the aqueous preparation is sprayed may be trade any drying equipment.

In a preferred process, drying is spray drying in one Drying tower carried out. The aqueous preparations are in a known manner  exposed to a drying gas stream in finely divided form. The applicant describes this working principle of spray drying with superheated steam, in particular of materials and mixtures of materials from the field of wetting, washing and Detergents in a number of published publications and previous applications. The principle of work disclosed there is hereby expressly also the subject of present disclosure disclosure. Reference is made here in particular to the following publications: DE-A-40 30 688 and the further Publications according to DE-A-42 04 035; DE-A-42 04 090; DE-A-42 06 050; DE-A- 42 06 521; DE-A-42 06 495; DE-A-42 08 773; DE-A-42 09 432 and DE-A-42 34 376.

In another variant of the method preferred according to the invention, the drying is carried out simultaneously with a granulation in a fluidized bed granulation system. This can be a fluidized bed running batchwise or continuously. It is particularly preferred to carry out the process continuously in the fluidized bed, as described, for example, in EP-B-0 603 207. The liquid preparations are introduced into the fluidized bed via disposable or reusable nozzles or via several nozzles. Any solids present are either dusted pneumatically via blow lines, the addition either taking place before the atomization of the liquid components or simultaneously with them, or as a solution or suspension in a mixture with the liquids. The liquid components are mixed either before spraying or directly in the nozzle. Fluidized bed apparatuses which are preferably used have base plates with dimensions of at least 0.4 m. In particular, fluidized bed apparatuses are preferred which have a base plate with a diameter between 0.4 and 5 m, for example 1.2 m or 2.5 m. However, fluidized bed apparatuses are also suitable which have a base plate with a diameter greater than 5 m. A perforated base plate or a Conidur plate (commercial product from Hein & Lehmann, Federal Republic of Germany) is preferably used as the base plate. The process according to the invention is preferably carried out at fluidizing air speeds between 1 and 8 m / s and in particular between 1.5 and 5.5 m / s. The granules are discharged from the fluidized bed advantageously by means of a size classification of the granules. This classification can take place, for example, with a sieve device or by means of an opposed air flow (classifier air) which is regulated in such a way that only particles of a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed. In a preferred embodiment, the inflowing air is composed of the heated or unheated classifier air and the heated soil air. The soil air temperature is preferably between 80 and 400 ° C, in particular between 90 and 350 ° C. The fluidized air cools down due to heat losses and the heat of vaporization of the constituents of the solvent. In a particularly preferred embodiment, the temperature of the vortex air is about 5 cm above the base plate 60 to 120 ° C, preferably 70 to 100 ° C. The air outlet temperature is preferably between 60 and 120 ° C, in particular below 100 ° C. If the discharge from the fluidized bed takes place against a classifier air flow, as described in EP-B-0 603 207, dust-free granules are obtained by this classification, ie the particle sizes of the particles are above 0.2 mm. Granules preferred according to the invention have ad ₅₀ values between 0.4 and 2.0 mm. In a particularly preferred embodiment, the grain fraction that is greater than 2.0 mm is returned. This coarse grain fraction can either be added as a solid component after grinding the fluidized bed or it is dissolved again and sprayed into the fluidized bed.

The first basic detergent resulting from the drying step has one Water content from 3 to 30 wt .-%. If after the subsequent compaction no further drying should take place, the water content is preferably below 20% by weight, especially below 10% by weight.

Drying is followed by compaction of the dried basic detergent on, with further washing and Detergent ingredients, such as bleach or enzyme granules, and compacting aids agents, such as binders, can be added. Under compacting is in In the sense of the invention understood every process in which the bulk density of the Kompaktats is increased.

In a preferred embodiment of the ending, this compacting of the Basic detergent in a press agglomeration process instead. The press agglomeration process to which the solid premix (dried basic detergent) is subjected, can be realized in different devices. Depending on the type of  Agglomerator used are different press agglomeration processes distinguished. The four most common and within the scope of the present invention preferred press agglomeration processes are extrusion, roll pressing or compacting, perforating (pelleting) and tableting, so that in Preferred press agglomeration processes within the scope of the present invention Extrusion, roll compacting, pelletizing or tableting operations.

All processes have in common that the premix compresses under pressure and is plasticized and the individual particles while reducing the porosity are pressed together and stick together. With all procedures (with the Tableting with restrictions), the tools can be adjusted to higher ones Heat up temperatures or dissipate the heat generated by shear forces cool.

In all processes, a binder can be used as an aid to compaction. In the further course of the description of this invention, for the sake of simplicity, only of one or the binder. However, it should be made clear that at there is always the use of several different binders and mixtures from different binders is possible. In a preferred embodiment of the Ending a binder is used that at temperatures up to a maximum of 130 ° C, preferably up to a maximum of 100 ° C and in particular up to 90 ° C already completely Melt is present. The binder must therefore, depending on the process and Process conditions are selected or the process conditions, in particular the process temperature, if a certain binder is required is desired - to be adapted to the binder.

The actual compression process is preferably carried out at Processing temperatures that at least in the compression step at least Temperature of the reach point, if not the temperature of the melting point of the binder. In a preferred embodiment of the ending the process temperature significantly above the melting point or above the tem temperature at which the binder is in the form of a melt. In particular, however, it is preferred  that the process temperature in the compression step is not more than 20 ° C above the Melting temperature or the upper limit of the melting range of the binder. It is technically possible to set even higher temperatures; it but has been shown that a temperature difference to the melting temperature or Er softening temperature of the binder of 20 ° C is generally sufficient and even higher temperatures have no additional advantages. That's why it is - especially for energy reasons - particularly preferred, above however as close as possible to the melting point or the upper temperature limit of the Melting range of the binder to work. Such a temperature control has the further advantage that thermally sensitive raw materials, such as peroxy bleaching agents such as perborate and / or percarbonate, but also enzymes, increasingly without gra four loss of active substance can be processed. The possibility of exact Temperature control of the binder, especially in the crucial step of compacting tion, i.e. between the mixing / homogenization of the premix and the form giving, allows an energetically very favorable and for the temperature sensitive Be components of the premix extremely gentle process management, because the premix is only exposed to the higher temperatures for a short time. In preferred Press agglomeration processes show the working tools of the press agglomerator (the Screws) of the extruder, the rollers) of the roller compactor and the press rollers) the pellet press) a temperature of at most 150 ° C, preferably at most 100 ° C and in particular at a maximum of 75 ° C and the process temperature is 30 ° C and in particular a maximum of 20 ° C above the melting temperature or the upper one Temperature limit of the melting range of the binder. The is preferably Duration of the temperature influence in the compression area of the press agglomerators maximum 2 minutes and is in particular in a range between 30 seconds and 1 Minute.

Preferred binders that can be used alone or in a mixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and modified poly ethylene 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 are relative Have molecular weights between 600 and 6000, preferably between 1000 and 4000. For a more detailed description of the modified polyalkylene glycol ethers, reference is made to the disclosure of the international patent application WO-A-93/02176. In the context of this invention, polyethyleneglycols include those polymers which, in addition to ethylene glycol, also use C ₃ -C ₅ glycols and glycerol and mixtures thereof as starting molecules in the production thereof. Also included are ethoxylated derivatives such as trimethylol propane with 5 to 30 EO. The polyethylene glycols preferably used can have a linear or branched structure, linear polyethylene glycols being particularly preferred. The particularly preferred polyethylene glycols include those with relative molecular weights between 2000 and 12000, advantageously around 4000, polyethylene glycols with relative molecular weights below 3500 and above 5000 especially in combination with polyethylene glycols with a relative molecular weight around 4000 can be used and such combinations advantageously to more than 50% by weight, based on the total amount of the polyethylene glycols, have polyethylene glycols with a relative molecular weight between 3500 and 5000. However, polyethylene glycols can also be used as binders, which are per se in liquid state at room temperature and a pressure of 1 bar; Here we are mainly talking about polyethylene glycol with a relative molecular mass of 200, 400 and 600. However, these per se liquid polyethylene glycols should only be used in a mixture with at least one further binder, this mixture again having to meet the requirements according to the end, ie must have a melting point or softening point of at least above 45 ° C.

Low molecular weight polyvinylpyrrolidones and derivatives are also suitable as binders of these with relative molecular masses up to a maximum of 30,000. Relative are preferred here Molecular mass ranges between 3000 and 30,000, for example around 10,000. Polyvinylpyrrolidones are preferably not used as the sole binder, but in Combination with others, especially in combination with polyethylene glycols, used.  

Other suitable binders have been found to be raw materials which have wash- or cleaning-active properties, for example nonionic surfactants with melting points of at least 45 ° C. or mixtures of nonionic surfactants and other binders. The preferred nonionic surfactants include alkoxylated fatty or oxo alcohols, in particular C ₁₂ -C ₁₈ alcohols. Degrees of alkoxylation, in particular degrees of ethoxylation, of on average 18 to 80 AO, in particular EO per mole of alcohol and mixtures thereof have proven to be particularly advantageous. In particular, fatty alcohols with an average of 18 to 35 EO, in particular with an average of 20 to 25 EO, show advantageous binder properties in the sense of the present invention. Binder mixtures may also contain ethoxylated alcohols with an average of fewer EO units per mole of alcohol, for example tallow fatty alcohol with 14 EO. However, it is preferred to use these relatively low ethoxylated alcohols only in a mixture with higher ethoxylated alcohols. Advantageously, the content of these relatively low ethoxylated alcohols in the binders is less than 50% by weight, in particular less than 40% by weight, based on the total amount of binder used. In particular, nonionic surfactants such as C ₁₂ -C ₁₈ alcohols with an average of 3 to 7 EO, which are usually used in washing or cleaning agents and which are liquid per se at room temperature, are preferably only present in the binder mixtures in such an amount that less than 2 % By weight of these nonionic surfactants, based on the end product of the process, are provided. As already described above, however, it is less preferred to use nonionic surfactants which are liquid at room temperature in the binder mixtures. In a particularly advantageous embodiment, such nonionic surfactants are not a component of the binder mixture, since they not only lower the softening point of the mixture, but can also contribute to the stickiness of the end product and also, due to their tendency to cause gelling when they come into contact with water The requirement for rapid dissolution of the binder / partition in the end product is not sufficient to the desired extent. Likewise, it is not preferred that conventional anionic surfactants or their precursors, the anionic surfactant acids, used in washing or cleaning agents are contained in the binder mixture. Other nonionic surfactants which are suitable as binders are the fatty acid methyl ester ethoxylates which do not tend to gel, in particular those with an average of 10 to 25 EO (for a more detailed description of this group of substances, see below). Particularly preferred representatives of this group of substances are predominantly methyl esters based on C ₁₆ -C ₁₈ fatty acids, for example hardened beef tallow methyl esters with an average of 12 EO or with an average of 20 EO. In a preferred embodiment of the invention, a mixture is used as the binder which uses C ₁₂ -C ₁₈ fatty alcohol based on coconut or tallow with an average of 20 EO and polyethylene glycol with a relative molecular weight of 400 to 4000. In a further preferred embodiment of the invention, a mixture is used as the binder which is predominantly methyl ester-based C ₁₆ -C ₁₈ fatty acids with an average of 10 to 25 EO, in particular hardened beef tallow methyl ester with an average of 12 EO or an average of 20 EO, and a C ₁₂ -C ₁₈ contains fatty alcohol based on coconut or tallow with an average of 20 EO and / or polyethylene glycol with a relative molecular weight of 400 to 4000.

As particularly advantageous embodiments of the invention, binders have been found to be used either alone on polyethylene glycols with a relative molecular weight of around 4000 or on a mixture of C ₁₂ -C ₁₈ fatty alcohol based on coconut or tallow with an average of 20 EO and one of those described above Fatty acid methyl ester ethoxylates or on a mixture of C ₁₂ -C ₁₈ fatty alcohol based on coconut or tallow with an average of 20 EO, one of the fatty acid methyl ester ethoxylates described above and a polyethylene glycol, in particular with a molecular weight of around 4000.

In small quantities, in addition to the substances mentioned here, there may be others suitable substances can be contained in the binder.

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

In a preferred embodiment of the invention, the invention Process carried out by means of an extrusion, such as in the European patent EP-B-486592 or international patent applications WO 93/02176 and WO 94/09111 and WO 98/12299 are described. In doing so, a solid premixed under pressure in the form of a strand and the strand after exiting the Hole shape by means of a cutting device to the predeterminable granule dimension  tailored. The homogeneous and solid premix contains a plasticizer and / or Lubricant, which causes the premix under the pressure or under the entry specific work is plastically softened and becomes extrudable. Preferred plasticizing and / or lubricants are surfactants and / or polymers.

To explain the actual extrusion process, we hereby expressly refer to the referenced above patents and patent applications. In a preferred embodiment tion form of 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 fed, its housing and whose extruder pelletizing head must be heated to the predetermined extrusion temperature can. Under the shear of the extruder screws, the premix is under Pressure, which is preferably at least 25 bar, at extremely high throughputs in Depending on the apparatus used, however, it can also be less, condensed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally preferably the extrudate by means of a rotating knife reduced in size from spherical to cylindrical granules. The hole diameter the perforated nozzle plate and the strand cut length are selected Granulate dimension matched. In this embodiment, the production of Granules of a substantially uniformly predeterminable particle size, wherein in particular, the absolute particle sizes adapted to the intended application could be. In general, particle diameters up to a maximum of 0.8 cm prefers. Important embodiments see the production of uniform Granules in the millimeter range, for example in the range from 0.5 to 5 mm and ins especially in the range of about 0.8 to 3 mm. The length / diameter ratio of the In an important embodiment, chipped primary granules lie in Range from about 1: 1 to about 3: 1. It is further preferred that the still plastic primary to supply granulate to a further shaping processing step; thereby on Raw extrudate edges rounded off, so that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired you can use this Stage small amounts of dry powder, for example zeolite powder such as zeolite NaA Powder to be used. This shape can be found in standard rounding machines  respectively. It should be ensured that only small amounts of fine are used in this stage grain proportion arise. A drying process, which is described in the above documents of the State of the art as a preferred embodiment is described below possible, but not absolutely necessary according to the invention. It may just be preferred be no longer drying after the compacting step.

Alternatively, extrusions / pressings can also be carried out in low-pressure extruders, in the 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 nozzles plate is designed such that the melting temperature of the binder or the upper Limit of the melting range of the binder at least reached, but preferably is exceeded. The duration of the temperature influence is Compression range of the extrusion preferably less than 2 minutes and especially in a range between 30 seconds and 1 minute.

In a further preferred embodiment of the present invention, the The method according to the invention is carried out by means of roller compaction. Here the premix is targeted between two smooth or with wells of defined Formed rollers metered in and between the two rollers under pressure a leaf-shaped compact, the so-called Schülpe, rolled out. Practice the reels a high line pressure on the premix and can be added as required be heated or cooled. When using smooth rollers, you get smooth, unstructured wristbands, while using structured rollers accordingly structured Schülpen can be generated in which, for example certain forms of the later detergent or cleaning agent particles specified can be. The Schülpenband is followed by a tee and Crushing process broken into smaller pieces and can be done in this way Granules are processed by other known surfaces treatment process refined, in particular brought into an approximately spherical shape can be.  

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 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 Melting range of the binder. It is further preferred that the duration the temperature effect in the compression range of the smooth or with depressions of rollers in a defined form is a maximum of 2 minutes and in particular in is between 30 seconds and 1 minute.

In a further preferred embodiment of the present invention, the Process according to the invention carried out by means of pelleting. Here is the Premix applied to a perforated surface and by means of a pressure Body pressed through the holes with plasticization. In usual embodiments Pellet presses compress the premix under pressure, plasticize it using a rotating roller in the form of fine strands pressed through a perforated surface and finally crushed into granules with a knock-off device. Here are the Different configurations of the pressure roller and perforated die are conceivable. So flat perforated plates are used as well as concave or convex ring matrices through which the material by means of one or more pressure rollers is pressed through. The press rolls can also be conical in the plate machines in the ring-shaped devices, dies and press roller (s) can run in the same direction or have opposite sense of rotation. One for performing the invention Apparatus suitable for the process is described, for example, in the German patent application DE 38 16 842. The ring die press disclosed in this document exists from a rotating ring die penetrated by press channels and at least one with the inner surface of the press roller, which is the die space feeds material through the press channels into a material discharge. Here are Ring die and press roller can be driven in the same direction, resulting in a reduced Shear stress and thus lower temperature increase of the premix can be realized is. Of course, it can also be used for pelleting with heatable or coolable ones  Rollers are operated to a desired temperature of the premix adjust.

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 with roller compaction with process temperatures of 10 ° C, in particular a maximum of 5 ° C above the melting temperature or the upper one Temperature limit of the melting range of the binder.

Another press agglomeration process that can be used according to the invention can is the tableting. Due to the size of the molded body it can be the tableting may be useful, in addition to the usual binder described above Disintegration aids, for example cellulose and its derivatives, especially in coarser form, or to add cross-linked PVP, which disintegrates the Lighten compacts in the wash liquor.

The particulate press agglomerates obtained can either be used directly as washing or cleaning agents used or previously treated according to conventional methods and / or processed. The usual post-treatments include, for example Powdering with finely divided ingredients from washing or cleaning agents, thereby the bulk density is generally further increased. A preferred after treatment however also presents the procedure according to German patent applications DE-A- 195 24 287 and DE-A-195 47 457, dusty or at least finely divided In Contents (the so-called fines) in the particles produced according to the invention shaped process end products, which serve as the core, are glued and thus Means are created which have these so-called fines as an outer shell. Advantage in turn, this is done by melting agglomeration, the same Binders can be used as in the inventive method. For Melt agglomeration of the fines on the inventive and inventive Base granules produced are expressly based on the disclosure in the German Pa tent applications DE-A-195 24 287 and DE-A-195 47 457 referenced.  

Among the resulting detergent and / or cleaning agent compacts are in Within the scope of the invention preferably understood such washing and cleaning agents that have a bulk density above 700 g / l, preferably above 800 g / l. Can continue those agents are preferred which have no dust-like components and in particular none Have particle sizes below 200 microns. In particular, there are such parts preferred size distributions, which at least 90 wt .-% particles with a Have a diameter of at least 400 µm. In a particularly preferred embodiment Form of the invention, the washing or cleaning agents are made at least 70 wt .-%, advantageously at least 80 wt .-% and with particular Preferred up to 100% by weight of spherical (pearl-shaped) particles with a particle size distribution which contains at least 80% by weight of particles between 0.8 and has 2.0 mm.

The detergent and / or cleaning agent compacts preferably exist at least 50 wt .-%, in particular at least 60 wt .-%, from the Basic detergent that is produced by the method according to the invention. In however, preferred embodiments of the invention make the basic detergent less than 90% by weight of the finished product, the rest being 100% by weight blended components, such as thermally sensitive ingredients, consists. In a special embodiment of the invention, the basic detergent even make up less than 80% by weight of the finished product. Then it is preferred if the remaining constituents have approximately the same pourability, Have bulk density, size and particle size distribution as the basic detergent.

Regardless of the proportion of the basic detergent, a second subject of the invention are detergent and / or cleaning agent compactates with a bulk density above 700 g / l, which contain 10-50% by weight of surfactants and are characterized in that they contain 5-40% by weight. % amorphous sodium silicate with a module Na ₂ O: SiO ₂ from 1: 2 to 1: 3.3 and 0.05-10% by weight polymeric polycarboxylate with M = 500-10,000 g / mol, and 0-10% by weight. -% contains aluminosilicate and / or crystalline layered silicate and 0-5 wt .-% polymeric polycarboxylate with M <20,000 g / mol, the amorphous sodium silicate and the polymeric polycarboxylate being processed together with other detergents and / or cleaning agents.

The amorphous sodium silicates and the polymeric polycarboxylates with M = 500-10,000 g / mol are the substances already described above. It is particularly preferred if the compositions contain sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8, preferably 1: 2 to 1: 2.6. The agents preferably contain at least 10% by weight of amorphous sodium silicates, but in special embodiments up to a maximum of 30% by weight, and it may even be preferred if a maximum of 20% by weight of the sodium silicates are contained.

The polymeric polycarboxylate according to the invention is as above described, preferably a sodium salt of a homo- or copolymer of Acrylic acid with M = 2000-6000 g / mol. These polymers are preferably in quantities less than 7% by weight, but at least 0.5% by weight in the compositions. Agents which are particularly effective according to the invention contain between 2 and 5% by weight. of these polymers.

In addition to the essential polymeric polycarboxylates for processing with M = 500 10,000 g / mol, the agents can also contain such polymeric polycarboxylate that a Have a molecular weight greater than 20,000 g / mol (as already explained above) Molar masses measured by means of GPC against an external polyacrylic acid standard). Such suitable polymeric polycarboxylates are, for example, the sodium salts of Polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular mass from 20,000 to 120,000 g / mol. 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 with maleic acid, 50 to 90 wt .-% acrylic acid and 50 to 10 % By weight of maleic acid. Their relative molecular mass, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol (measured against the polyacrylic acid standard). In preferred embodiments of the invention, however, these polymers are only minor Amounts (about 1 wt .-%) or not at all.  

As an additional inorganic builder, finely crystalline, synthetic and bound water-containing zeolite, preferably zeolite A, X, Y and / or P, and crystalline layered silicates can be used, which are likewise preferably only present in small amounts. Suitable zeolites are also mixtures of A, X, Y and / or P. As zeolite P, for example, zeolite MAP® (commercial product from Crosfield) is particularly preferred. Of particular interest is also a cocrystallized sodium / potassium aluminum silicate from zeolite A and zeolite X, which is commercially available as VEGOBOND AX® (commercial product from Condea Augusta SpA). The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 10 to 22% by weight, in particular 15 to 22% by weight, of bound water.

In addition to the zeolites, crystalline, layered sodium silicates corresponding to 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 × 2, 3 or 4 are included in the means. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline phyllosilicates of the formula given are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

Both zeolites and crystalline layered silicates are in the agents according to the invention but only of minor importance. In preferred embodiments of the Invention of these substances contain less than 5% by weight in total. Here it can even be preferred if they are completely absent, especially zeolites often can also be used as a powdering agent on admixed granules, and so in  The funds may be included in a small proportion, although their use as a builder was not intended.

Furthermore, the agents according to the invention contain in preferred embodiments also alkali carbonates, especially sodium carbonate. It is for the execution of the Invention advantageous if the weight ratio of alkali carbonate to amorphous Sodium silicate is in the range 1: 100 to 10: 1, preferably 1:50 to 5: 1. In Embodiments according to the invention can be particularly advantageous if the weight ratio of alkali carbonate to amorphous sodium silicate is less than 1.

In addition to the polymeric polycarboxylates, further organic builder substances can be contained in the agents according to the invention. Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular. Further 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. Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. 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 of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 owns, is. 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 g / mol 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 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous. Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS), the synthesis of which is described, for example, in US Pat. No. 3,158,615, is preferably used in the form of its sodium or magnesium salts. Also preferred in this connection are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP-A-0 150 930 and Japanese Patent Application JP 93/339896 become. Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight. Further usable organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and at most two acid groups. Such cobuilders are described, for example, in international patent application WO 95/20029. Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned. In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as cobuilders. Such organic cobuilders can be contained in the agents according to the invention in total in a proportion of up to 10% by weight, but preferably not more than 5% by weight.

The detergents and cleaning agents according to the invention can, in addition to those mentioned In principle, builder substances are all known and customary in such compositions Contain ingredients. In particular, the agents contain 10-50% by weight, preferably 15- 35% by weight, surfactants, these surfactants being selected from the following groups:

A first group is the anionic surfactants, which contain at least 0.5% by weight. in the agents according to the invention or agents produced according to the invention should be included. These include, in particular, sulfonates and sulfates Soap.

Preferred surfactants of the sulfonate type are C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C ₁₂ -C ₁₈ monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.

Also suitable are alkanesulfonates obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.

Also suitable are the esters of α-sulfo fatty acids (ester sulfonates), e.g. B. the α- sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids 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 water-soluble mono-salts are considered. It is preferably are the α-sulfonated esters of hydrogenated coconut, palm, palm kernel or Tallow fatty acids, including sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt .-%, may be present. In particular, α-sulfofatty acid alkyl esters preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl ester, ethyl ester, propyl ester and butyl ester. With a special advantage are the methyl esters of α-sulfofatty acids (MES), but also their saponified disalts used.

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 during the transesterification of triglycerides with 0.3 to 2 moles of glycerol can be obtained.

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid half-esters of the 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, straight-chain alkyl radical prepared on a petrochemical basis and 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 the Shell Oil Company under the name DAN®, 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 moles of ethylene oxide, such as 2-methyl branched C ₉ -C ₁₁ alcohols with an average of 3.5 moles 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 represent 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 whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Other anionic surfactants include fatty acid derivatives of amino acids, for example 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. B. coconut, Palm kernel or tallow fatty acids, derived soap mixtures. Along with these soaps or the known alkenylsuccinic 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 ammo nium salts and as soluble salts of organic bases, such as mono-, di- or triethanol amine. 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 invented in the Process according to the invention preferably in amounts of 1 to 30 wt .-% and contain or used in particular in amounts of 5 to 25 wt .-%.

In addition to the anionic surfactants and the cationic, zwitterionic and amphoteric 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 radical can be linearly or preferably 2-branched methyl or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol 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 C atoms and G is for one 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 an arbitrary number - which, as an analytically determinable variable, can also take fractional values - between 1 and 10; x is preferably 1.2 to 1.4.

Also suitable are polyhydroxy fatty acid amides of the formula (I) in which R ¹ CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ² for hydrogen is an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical 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, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in which R ³ for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ⁴ for a linear, branched or cyclic alkylene radical or an arylene radical with 2 to 8 carbon atoms and R ⁵ for a linear, branched or cyclic alkyl radical or is an aryl radical or an oxyalkyl 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 95107331, 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 are 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-90113533. 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-di methylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanol amides can be suitable. The amount of these nonionic surfactants is preferred  not more than that of the ethoxylated fatty alcohols, especially not more than that Half of it.

So-called gemini surfactants can be considered as further surfactants. Below are in generally understood such compounds that two hydrophilic groups and two hy have drophobic groups per molecule. These groups are usually characterized by one called "spacer" separated from each other. This spacer is usually a coal material chain that should be long enough that the hydrophilic groups have a sufficient Have a distance so that they can act independently of each other. Such surfactants are generally characterized by an unusually low critical Micell concentration and the ability to greatly increase the surface tension of water reduce, out. In exceptional cases, however, the term gemini surfactants understood not only dimeric but also trimeric surfactants.

Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE-A-43 21 022 or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates according to German patent application DE-A-195 03 061. End group capped dimeric and trimeric mixed ethers according to the German Patent application DE-A-195 13 391 are particularly characterized by their bi- and Multifunctionality. So the end-capped surfactants mentioned good network properties and are low-foaming, so that they are particularly suitable for Suitable for use in machine washing or cleaning processes.

Gemini polyhydroxy fatty acid amides or Poly-Po can also be used lyhydroxy fatty acid amides, as described in international patent applications WO-A- 95/19953, WO-A-95119954 and WO95-A-119955.

In addition to surfactants and builders, all of the detergents according to the invention can be or cleaning agents common ingredients.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate monohydrate or tetrahydrate and sodium percarbonate are of particular importance. Other useful bleaching agents are, for example, 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 0 to 30% by weight and in particular 5 to 25% by weight, advantageously using perborate monohydrate, tetrahydrate or percarbonate.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples of these are N-acyl or O-acyl compounds which form organic peracids with H ₂ O ₂ , preferably multiply acylated alkylenediamines such as N, N'-tetraacylated diamines, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles , Triazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid esters such as p- (alkanoyloxy) benzenesulfonate, in particular sodium isisononanoyloxybenzenesulfonate, and the p- (alkenoyloxy) benzenesulfonate, also caprolactam derivatives, carboxylic acid anhydrides such as glucosalphene anhydrides such as phthalates and phthalates. Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described for example in European patent application EP-A-0 525 239, and acetylated pentaerythritol. The bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN). The bleach activator can be coated with coating substances in a known manner or, if appropriate with the aid of auxiliaries, in particular methyl celluloses and / or carboxymethyl celluloses, granulated or extruded or pelletized and, if desired, contain further additives, for example dye. Such granules preferably contain more than 70% by weight, in particular 90 to 99% by weight, of bleach activator. A bleach activator is preferably used which forms peracetic acid under washing conditions.

In addition to the conventional bleach activators listed above or other The place from the European patents EP 0 446 982 and EP 0 453 003 known sulfonimines and / or bleach-enhancing transition metal salts or contain transition metal complexes as so-called bleaching catalysts his. The transition metal compounds in question include in particular known from the German patent application DE 195 29 905 manganese, iron, Cobalt, ruthenium or molybdenum salt complexes and those from the German Patent application DE 196 20 267 known N-analog compounds, which from the German Patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or Molybdenum-carbonyl complexes, which are described in German patent application DE 196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and Copper complexes with nitrogenous tripod ligands derived from the German Patent application DE 196 20 411 known cobalt, iron, copper and ruthenium Ammine complexes described in German patent application DE 44 16 438 Manganese, copper and cobalt complexes described in the European patent application EP 0 272 030 described cobalt complexes, which from the European Patentan Message EP 0 693 550 known manganese complexes, which from the European Patent EP 0 392 592 known manganese, iron, cobalt and copper complexes and / or those in European Patent EP 0 443 651 or European Patent applications EP 0 458 397, EP 0 458 398, EP 0 549 271, EP 0 549 272, Manganese complexes described in EP 0 544 490 and EP 0 544 519. Combinations of Bleach activators and transition metal bleach catalysts are for example from the German patent application DE 196 13 103 and the international patent application WO 95/27775 known. Bleach-enhancing transition metal complexes, especially with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru are used in usual amounts, preferably in an amount up to 1% by weight, in particular from 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on all means.

Enzymes which may be present in agents according to the invention include Proteases, amylases, pullulanases, cellulases, cutinases and / or lipases, for example wise proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®,  Purafect® OxP, Esperase® and / or Savinase®, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl®, Purafect® OxAm, cellulases such as Celluzyme®, Carezyme®, KAC® and / or the international patent applications WO 96/34108 and WO 96/34092 known cellulases and / or lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®. The enzymes used can, as for example in the international patent applications WO 92/11347 or WO 94/23005 Carriers can be adsorbed and / or embedded in enveloping substances to prevent them to protect against inactivation. They are in washing and cleaning agents according to the invention teln preferably in amounts up to 10 wt .-%, in particular from 0.05 wt .-% to 5 wt .-%, contain, particularly preferably stabilized against oxidative degradation Enzymes, such as those from international patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350 are used become.

In addition, the agents can also contain components which contain the oil and fat Positive influence on washability from textiles. This effect is particularly evident if a textile is soiled that has already been washed several times with one detergent according to the invention, which contains this oil and fat-dissolving component, was washed. The preferred oil and fat dissolving components include for example nonionic cellulose ethers such as methyl cellulose and methyl hydroxy propyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and Hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic Cellulose ether, as well as the polymers known from the prior art Phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers from ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid Polymers.

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 various foam inhibitors are also used, e.g. B. from silicone, 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.

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 of cellulose or starch. Also water-soluble, acidic Group-containing polyamides are suitable for this purpose. Furthermore, use soluble starch preparations and starch products other than those mentioned above, e.g. B. degraded starch, aldehyde starches, etc. Is preferred in the invention Means the use of polyvinylpyrrolidone, especially in the form of PVP granules. Cellulose ethers, such as carboxymethyl cellulose (Na salt), are also preferred. Methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof. Graying inhibitors, such as PVP, are usually used in amounts of 0.1 to 5% by weight, based on the funds used.

As optical brighteners, the agents can be derivatives of diaminostilbenedisulfonic acid or whose alkali metal salts contain. Are suitable for. B. Salts of 4,4'-bis (2-anilino-4- morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or the like Compounds which instead of the morpholino group a diethanolamino group, a Carry a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present,  e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) - diphenyls, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can be used.

In addition to the ingredients mentioned, the agents can also use other known detergents, Detergents or cleaning agents commonly used additives, for example small amounts of neutral filling salts as well as colors and fragrances, opacifiers or Pearlescent agents included.

Another object of the invention is a builder system, as in the agent according to the invention is included.

Such a builder system for use in washing and / or cleaning agent compactates with a bulk density above 700 g / l is characterized in that it contains 20-90% by weight of amorphous sodium silicate with a module Na ₂ OSiO ₂ of 1: 2 to 1 : 3.3 and 5-30% by weight of a polymeric polycarboxylate with M = 500-10,000 g / mol, and 0-20% by weight of aluminosilicate and / or crystalline layered silicate and optionally further constituents, such as phosphorus rates, citrates or Contains citric acid and other polymers, and the builder system is contained in the washing and cleaning agent compactates in amounts of 10 to 90% by weight.

All of these ingredients have already been described above, being in the builder system preferably the same substances are used as they are preferred as builders in the detergent and cleaning agent compact described.  

Examples

For the preparation of the inventive agents E1-E5 and the comparative examples V1-V3 (Table 1), a basic detergent was produced by spray drying and from this basic detergent, C ₁₂ -C ₁₈ fatty alkyl sulfate, citrate, sodium perborate monohydrate and polyethylene glycol as a binder with a relative molecular weight of 4000 creates a homogeneous premix. C ₁₂ -C ₁₈ fatty alcohol with an average of 7 EO was sprayed into the powder stream. The premix was then extruded. After the extrusion, 7% by weight of TAED granules were added. The resulting detergents had bulk densities between 770 and 850 g / l.

The resulting detergents contained, in addition to those listed in Table 1 Ingredients enzyme granules and other washing aids as well as water and salts.  

Table 1

Composition of the detergent (in% by weight based on the total detergent and anhydrous substance)

Silicate: amorphous sodium silicate with Na ₂ : SiO ₂ = 2.4
Polycarboxylate (M = 30000-100000 g / mol):
Sokalan CP5®; Acrylic acid-maleic acid copolymer; M _w ≈ 35000 g / mol; Commercial product from BASF
Polycarboxylate (M = 1000-10000 g / mol):
Norasol LMW 45N®; Polyacrylic acid, sodium salt; M _w ≈ 4500 g / mol; Commercial product from Rohm + Haas
Citrate: was added as citrate or citric acid depending on the pH to be set.

The detergents were tested under practical conditions in Household washing machines. For this purpose, the machines were filled with 3.0 kg of clean laundry and 0.5 kg of test fabric, the test fabric partly with conventional Test soiling was impregnated and for testing the secondary washing ability consisted partly of white fabric. Strips were made as white test fabric standardized cotton fabric (Krefeld laundry research institute; WFK), nettle (BN), knitwear (cotton jersey; B) and terry cloth (FT) are used. Washing conditions gen: tap water of 23 ° d (equivalent to 230 mg CaO / l), amount of detergent used per medium and machine: 76 g, 90 ° C wash program (including heating phase), Fleet ratio (kg of laundry: liters of wash water in the main wash cycle) 1: 5.7, three times Rinse with tap water, spin off and dry.

The primary washing behavior was not found in the examples according to the invention significant differences from the comparison tests.

After 25 washing cycles, the ash content of the textile samples as well as the graying (expressed in reflectance compared to the original reflectance V of the untreated tissue) quantified in duplicate determinations (Tables 2 and 3).

Table 2

Ash formation (residue in g)

Table 3

Graying inhibition (remission in%)

The superiority of the agents according to the invention over the comparative examples was shown both in the residue behavior and in the graying-inhibiting Effect.

When determining the ashes by burning organic components usually get a lower value than the actual incrustation. For Control was therefore also determined for E3-5 and V3 the total incrustation (1st Weighing of the untreated tissue, 2.Weighing the tissue after 25 washing cycles, 3. Weighing of the tissue after extraction with EDTA, 4. Determination of the so-called "soluble ash" from the difference between the weighings 2nd and 3rd, 5th ashing of the extracted tissue to determine the residual ash, 6. determination of the Total incrustation (sum of soluble ash and residual ash)).

Table 4

Residual ash and total incrustation

These examples also show the superiority of the agents according to the invention consistently lower residue values on the laundry than the comparison example.

The dissolution behavior of the extrudates was determined for Examples E3-5 and Comparative example V3 was examined using various tests:  

L-test: To determine the residue behavior or the solubility behavior in a 2 liter beaker 8 g of the agent to be tested while stirring (800 rpm with La borrührer / propeller stirring head 1.5 cm from the beaker bottom centered) and stirred at 30 ° C for 1.5 minutes. The test was carried out with water with a hardness of 16 ° d carried out. The wash liquor was then poured off through a sieve (80 μm). The beaker was rinsed over the sieve with very little cold water. It he a double determination followed. The screens were in the drying cabinet at 40 ° C ± 2 ° C to dried to constant weight and the detergent residue weighed out. The back is given as the average of the two individual determinations in percent. At Deviations of the individual results by more than 20% from each other are common further tests carried out; however, this was not the case in the present investigations required. All examined examples showed within the scope of the errors with the Comparative example matching results.

Bowl test: 25 g of the test agent were sprinkled into 5 l of tap water (30 ° C.) in a wash bowl made of dark plastic (dark red). After 15 seconds, the agent was distributed in the bowl by hand. After a further 15 seconds, 1 blue terry towel was added to the wash liquor and moved as in a typical hand wash. After 30 seconds the wall of the bowl was wiped with the towel. Finally, after another 30 seconds, the towel was wrung out and visually graded. The wash liquor was decanted off and the residue was also visually graded after treatment with 5 to 10 ml of water. The overall grades given in Table 5 mean:

Grade 1: perfect, no discernible residues
Grade 2: tolerable, isolated, not yet disturbing residues
Grade 3: recognizable residues that are already annoying when critically assessed
Grade 4: clearly recognizable and disturbing residues in increasing number and quantity; gelling when water is added

R-Test: 30 l of water were first introduced into a tub washing machine (TYPE Arcelik), 76 g of the agent were added and dissolved by stirring. The laundry, consisting of various dark-colored, easy-care delicate items made of wool, cotton, polyamide and polyacrylonitrile, was then inserted and the machine heated to a temperature of 30 ° C. After this temperature had been reached, the laundry was washed for 10 minutes by actuating the agitator, then the washing liquor was drained off, rinsed three times with 30 l of water each time and the laundry was spun for 15 seconds. The laundry was dried with an infrared heater and graded by 5 trained people according to the following scheme (averaging):

Grade 1: perfect, no discernible residues
Grade 2: tolerable, isolated, not yet disturbing residues
Grade 3: recognizable residues that are already annoying when critically assessed
Grade 4: clearly recognizable and annoying residues in increasing number and quantity

E-test: To determine the flushing behavior of the extrudates, the extrudates in Household drum washing machines with induction drawer at a water pressure of 0.5 bar tested. Test machines were Miele W918 and Quelle Privileg 1100. There were in 5 determinations carried out on each machine. The 10 results then became the mean given below. For this, 80 g of the extrudates per Put the washing process in the dispenser. The tap water with which the Extrudates into the respective machine, which was loaded with 3.5 kg of dry laundry, was flushed in, had a water hardness of 16 ° d. After the flushing was finished the detergent residues from the induction drawer and the induction chamber separately placed on a watch glass with a rubber wiper and balanced. Of these damp Residues were subtracted 30% moisture. The "dry residue" from The drawer and chamber were added and the mean was calculated from the sum of the Table 5 is given.

Table 5

Results of tests on dissolution behavior

The examples according to the invention cut in all the tests listed in Table 5 comparable to the agent not according to the invention, especially in the R test they even showed clear advantages.

Claims (14)

1. A method for producing a detergent and / or cleaning agent compactate with a bulk density above 700 g / l, characterized in that aqueous preparations of an amorphous sodium silicate with a module Na ₂ O: SiO ₂ of 1: 2 to 1: 3, 3 and of a polymeric polycarboxylate with M = 500-10,000 g / mol are sprayed together with other washing and / or cleaning agent ingredients in a drying device, granulation being able to take place simultaneously with the drying, and the resulting basic washing agent is then compacted, optionally after admixing further ingredients becomes. 2. The method according to claim 1, characterized in that the compacting as Press agglomeration is carried out. 3. The method according to claim 2, characterized in that the press agglomeration in a roller compactor is carried out. 4. The method according to claim 2, characterized in that the press agglomeration as Extrusion is carried out. 5. The method according to any one of claims 1 to 4, characterized in that the Drying is carried out as spray drying in a drying tower. 6. The method according to any one of claims 1 to 5, characterized in that the Drying at the same time as granulation in a fluidized bed granulation system is carried out. 7. washing and / or cleaning agent compactates with a bulk density above 700 g / l containing 10-50% by weight surfactants, characterized in that they contain 5-40% by weight amorphous sodium silicate with a module Na ₂ O: SiO ₂ of 1 : 2 to 1: 3.3 and 0.05-10% by weight of a polymeric polycarboxylate with M = 500-10,000 g / mol, and 0-10% by weight of aluminosilicate and / or crystalline layered silicate and 0-5% by weight .-% contains polymeric polycarboxylate with M <20,000 glmol, the amorphous sodium silicate and the polymeric polycarboxylate being processed together with other detergents and / or cleaning agents. 8. washing and / or cleaning agent compact according to claim 6, characterized characterized in that it is a polymeric polycarboxylate, preferably a homo- or Copolymer of acrylic acid, with M = 2000-6000 g / mol contains. 9. washing and / or cleaning agent compactate according to one of claims 6 or 7, characterized in that it contains an amorphous sodium silicate with a module Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. 10. washing and / or cleaning agent compactates according to one of claims 6 to 8, characterized in that it is an alkali carbonate, preferably sodium carbonate, contains, the weight ratio of alkali carbonate to amorphous sodium silicate is in the range 1: 100 to 10: 1. 11. Builder system for use in washing and / or cleaning agent compactates with a bulk density above 700 g / l, characterized in that it contains 20-90% by weight amorphous sodium silicate with a module Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3 and 5-30% by weight of a polymeric polycarboxylate with M = 500-10,000 g / mol, and 0-20% by weight of aluminosilicate and / or crystalline layered silicate and, if appropriate, further constituents, such as phosphonates, citrates or citric acid and further polymers, and the builder system is contained in the washing and cleaning agent compactates in amounts of 10 to 90% by weight. 12. Builder system according to claim 10, characterized in that it is a polymer Polycarboxylate, preferably around a homo- or copolymer of acrylic acid M = 2000-6000 g / mol contains. 13. Builder system according to one of claims 10 or 11, characterized in that it contains an amorphous sodium silicate with a module Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8, preferably up to 1: 2.6. 14. Builder system according to one of claims 10 to 12, characterized in that it contains an alkali carbonate, preferably sodium carbonate, the weight ratio from alkali carbonate to amorphous sodium silicate is in the range 1: 100 to 10: 1.