EP0888450B2 - Additive for a washing or cleaning agent and method for producing said additive - Google Patents

Abstract

The invention concerns additives with an apparent density of 500 g/l for use in granular washing or cleaning agents with apparent densities of at least 500 g/l, said additives containing one or several anion surfactants and at least one other ingredient that is usually subsequently added when producing washing or cleaning agents, provided that this other ingredient or ingredients is an ingredient chosen from the following; bleach activator, bleach catalyst and premanufactured foam inhibitor. By adding these solid additives to solid base granules, the additives having approximately the same apparent density, granular form and size as the base granules, washing or cleaning agents with greater apparent densities are produced which have a uniform appearance and are not inclined to separate.

Description

The invention relates to a detergent or cleaning agent additive, which in particular customary admixing components contains modern washing or cleaning agents, as well as a process for its preparation and the by adding detergents or cleaning agents available from these additives. In particular, under "modern Detergents or cleaning agents "are understood to mean those which have bulk densities of at least 500 g / l.

Granular detergents or cleaning agents with bulk densities above 500 g / l are now safe State of the art. The products available on the market usually consist of at least one Compound or several compounds, from one basic granulate or several basic granules and further admixing components, either because of their temperature sensitivity or their sensitivity to water or because of undesirable interactions with other ingredients are not used in the manufacturing process of the base granules can be. These are, in particular, solid ingredients such as bleach activators, so-called soil repellents, foam inhibitors, but also enzymes. Also anionic surfactants, which are not suitable, for example, To be used in higher quantities in a slurry for spray drying have already been described as compounds which have been subsequently mixed with other compounds or basic granules. These solids can be finely divided to granular. Usually they differ in their weight, their grain shape and / or in their particle size distribution both with respect to one another and with respect to the base granules or Base granules. As a rule, the individually blended components have a significantly lower bulk density as the base granules or the base granules as well as not only different grain sizes, but also different ones Grain shapes and other surface properties than the basic granules. The blended components for this reason generally lead to a reduction in the bulk density of the finished product with the bulk weight of the basic granules or the basic granules. This (and other properties) cause the known problem of segregation, so that - especially after transport and storage - an uneven Distribution of the ingredients in the finished washing or cleaning agent is obtained, which not only the finished product a disadvantage because it gives a visually uneven appearance, but also lead to disadvantages in use can, since it is no longer ensured that the distribution of the individual components is homogeneous on average. From one inhomogeneous distribution on average would also result in an inhomogeneous distribution of these ingredients in the individual package result in the consumer using different compositions when using the same package would result in significantly different washing results.

Another problem is the homogeneous distribution of the small solid components, i.e. those Ingredients that are only added to the basic granules in amounts of about 0.1 to 4% by weight. In the large-scale Manufacturing is precisely the admixture and homogeneous distribution of these small components in the mixture understandably with a relatively high error.

The invention was therefore based on the object of granular washing or cleaning agents with bulk weights of at least 500 g / l, which do not have the disadvantages mentioned above.

In a first embodiment, the invention therefore relates to a granular additive with a bulk density of at least 500 g / l, for use in granular washing or cleaning agents with bulk weights of at least 500 g / l is suitable, this additive one or more anionic surfactants and at least one further Contains ingredient that is usually added later in the manufacture of detergents or cleaning agents with the proviso that the additive 20 to 60 wt .-% anionic surfactant (s) and at least one component selected from bleach activator, bleach catalyst and pre-made foam inhibitor, the pre-made Foam inhibitor is preferred.

In a further embodiment of the invention, the subject of the invention is a method for the production a granular additive containing 20 to 60 wt .-% anionic surfactant (s) with a bulk density of at least 500 g / l, which is suitable for use in granular washing or Detergents with a bulk density of at least 500 g / l is suitable, a composition, Grain size and grain shape uniform additive is produced by granulating, compacting or extruding and one or more anionic surfactant (s) and at least one further constituent are used to prepare the additive, which is usually subsequently mixed in the manufacture of detergents or cleaning agents, with which Provided that in addition to the anionic surfactant (s) at least one component selected from bleach activator, Bleach catalyst and pre-assembled foam inhibitor is used, but at least one component is mandatory is introduced into the process in a pre-assembled form.

Another object of the invention is a granular washing or cleaning agent with a bulk density of at least 500 g / l, which usual ingredients including anionic surfactants and foam inhibitors as well optionally contains bleaching agents, bleach activators and / or bleaching catalysts, the agent consisting of at least 2 granular compounds and one compound is an additive which anionic surfactant (s) and at least contains another ingredient, which is usually retrofitted in the manufacture of detergents or cleaning agents is admixed, with the proviso that the additive 20 to 60 wt .-% anionic surfactant (s) and at least one Component selected from bleach activator, bleach catalyst and pre-assembled foam inhibitor.

In a preferred embodiment of the invention, the additive according to the invention has at least one further component usually contained in detergents or cleaning agents. In particular, there are additives preferred which anionic surfactant (s), pre-assembled foam inhibitor and bleach activator and / or bleach catalyst contain.

The additive according to the invention is preferably not of a certain grain size, grain shape and certain Surface properties and limited to a certain bulk density, but can be made so that there is a (admixture) in bulk density, grain size and grain shape adapted to the basic granules or the basic granules Represents granules. In order to prevent segregation in any case, it is advisable to also add the trickle behavior of the additive essentially to adapt to the flow behavior of the base granules or the base granules. A common test for measuring the flow behavior is that 1 liter of the sample to be measured in each case filled a powder funnel initially closed at its outlet direction and then the outlet time of the samples compared to dry sea sand. The expiry time of the dry sea sand after opening the outlet opening (13 seconds) is set to 100%. The flow behavior of the samples to be examined is expressed in%, based on 100% (measured on sea sand). In a preferred embodiment, the trickle behavior - determined according to the test described above - the additive adjusted so that it does not accumulate more than 20 percentage points, preferably not more than 10% points from the flow behavior of the base granules or the sum of the base granules different.

The additive according to the invention contains at least anionic surfactants, preferably alkyl sulfates (further description For possible surfactants, see below in the general description section), and preferably as usually in Detergent or cleaning agents contain foam inhibitors in pre-assembled solid form; Further In addition to the preferred bleach activators or bleach catalysts, possible constituents are also peroxy bleaching agents, but also, for example, enzymes and so-called soil repellents.

Suitable anionic surfactants which are used in the additive according to the invention are, in particular, alk (en) yl sulfates, including 2,3-alkyl sulfates and alkylbenzenesulfonates (for a more detailed description, see below). They too are preferably used in prefabricated, in particular in granular form, anionic surfactant compounds with active substance contents above 60% by weight being particularly preferred. Examples of these are alkyl sulfate compounds with 70 to 90% by weight (optionally also above) active substance which contain sodium sulfate and / or sodium carbonate, unsulfonated constituents and water as other constituents and were produced in particular in the fluidized bed. Of particular interest are C chain cuts with at least 90% by weight, preferably with at least 95% by weight, of C ₁₂ -C ₁₈ , which contain more than 50% by weight of C ₁₆ -C ₁₈ and at least 20% by weight. have less than C ₁₆ . The anionic surfactants in the additives according to the invention, in particular in pre-assembled form, are 20 to 60% by weight and in particular at least 30% by weight.

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. According to the invention, the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are used in pre-assembled and solid form, these preferably being bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred. The content of solid foam inhibitor compounds in the additives according to the invention is preferably 1 to 25% by weight and in particular 5 to 20% by weight.

The weight ratio of anionic surfactants to pre-assembled foam inhibitor can be in the inventive Additives vary widely. It is also possible that the weight ratio of anionic surfactants prefabricated foam inhibitor is less than 1. In an advantageous embodiment of the invention the additives, however, anionic surfactants and pre-assembled foam inhibitors in a weight ratio of 5: 1 to a maximum of 1: 1, preferably from 4: 1 to 1.5: 1 and in particular from 3.5: 1 to 2: 1. It is particularly preferred that the additives of the invention 30 to 70 wt .-% of a highly concentrated anionic surfactant compound and 10 to 30% by weight, advantageously 12 to 25% by weight of a pre-assembled foam inhibitor.

Instead of the foam inhibitors or in combination with these, the additives according to the invention can also Contain bleach activators or bleach catalysts.

Compounds which are aliphatic peroxocarboxylic acids under perhydrolysis conditions can be used as bleach activators with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted Perbenzoic acid result are used. Substances containing the O- and / or N-acyl groups of the abovementioned are suitable 0 atom number and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from the German patent applications DE19616 693 and DE19616 767 known enol esters and acetylated sorbitol and Mannitol or their mixtures described in European patent application EP 0 525 239 (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated Lactams, for example N-benzoylcaprolactam, which are known from international patent applications WO-A-94/27970, WO-A-94/28102, WO-A-94/28103, WO-A-95/00626, WO-A-95/14759 and WO-A-95/17498 are known. The hydrophilically substituted acylacetals known from German patent application DE 196 16 769 and those in German patent application DE 196 16 770 and international patent application WO 95/14075 Acyl lactams are also preferred. Also that from German patent application DE 44 43 177 known combinations of conventional bleach activators can be used. Such bleach activators are in the usual range of amounts, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight up to 8 wt .-%, based on the total average. The content of the additive according to the invention is Bleach activator, preferably on prefabricated bleach activator, advantageously 10 to 50% by weight, in particular at least 20% by weight.

In addition to or in place of the conventional bleach activators listed above, the sulfonimines and / or bleach-enhancing agents known from European patents EP 0 446 982 and EP 0 453 003 Transition metal salts or transition metal complexes as so-called bleaching catalysts be included. The transition metal compounds in question include in particular those from the German Patent application DE195 29 905 known manganese, iron, cobalt, ruthenium or molybdenum salt complexes and their N-analog compounds known from German patent application DE 196 20 267, which are known from the German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, described in German patent application DE 196 05 688, Molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, derived from the German Patent application DE 196 20 411 known cobalt, iron, copper and ruthenium-amine complexes, which in the 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 resulting from the European patent application EP 0 693 550 known manganese complexes known from the European patent EP 0 392 592 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, EP 0 544 490 and EP 0 544 519 described manganese complexes. 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 conventional amounts, preferably in an amount of 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, each based on the entire mean. Their content in the additives according to the invention can, for example 0.5 to 5% by weight, preferably less than 3% by weight.

In particular, it is preferred to also include the bleach activator in the process in a pre-assembled form Manufacture of the additive to bring. The bleach activator can thus be coated with coating substances in a known manner or, optionally using auxiliaries, in particular methyl celluloses and / or carboxymethyl celluloses, have been granulated or extruded / pelletized before use and, if desired, other additives, for example dye. Such granules preferably contain more than 70% by weight, in particular of 90 to 99% by weight bleach activator. The additive according to the invention preferably contains a bleach activator, which is under Washing conditions forms peracetic acid.

In a further preferred embodiment of the invention, the weight ratio (based on Active substance contents) of anionic surfactants to bleach activators and optionally bleach catalysts 0.5: 1 to 2: 1 and in particular 0.9: 1 to 1.5: 1. In a further preferred embodiment of the invention, one according to the invention contains Additive 30 to 60 wt .-% of a highly concentrated anionic surfactant compound and 25 to 40 wt .-% of one also highly concentrated bleach activator compounds.

Soil is one of the other possible ingredients of the compounds according to the invention repellents, but also superplasticizers, known substances that contribute to solubility improvement, color and Fragrances, possibly also enzymes and parts of the builder system, which are usually present in amounts up to a maximum 10% by weight, preferably up to a maximum of 8% by weight and in particular in amounts below 5% by weight, based on the finished product.

As so-called soil repellents, components can be contained which have oil and fat washability made of textiles. This effect is particularly evident when a textile that is already soiled previously washed several times with a detergent according to the invention, which contains this oil and fat-dissolving component has been. The preferred oil- and fat-dissolving components include, for example, non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and 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, they are particularly preferred the sulfonated derivatives of phthalic acid and terephthalic acid polymers. Preferably contain the invention Additives of such soil repellents (optionally in pre-assembled form), which are usually produced Agents are used in amounts of 0.2 to less than 5 wt .-%, in amounts of 1 to 8 wt .-% and especially in amounts of 2 to 6 wt .-%.

Depending on the requirements, the known flow agents can be used in particular to improve the flow behavior Silicas, silicic acid derivatives, but also aluminosilicates such as zeolite A, X and / or P can be used. Their content in the additives is preferably not more than 3% by weight.

Organic builder substances, in particular, are further ingredients of the additives according to the invention, especially those that are not suitable for spray drying. The contain advantageously Additive dextrins, for example oligomers or polymers of carbohydrates, which are obtained by partial hydrolysis of Strengths can be obtained. The hydrolysis can be carried out by customary methods, for example acid-catalyzed or enzyme-catalyzed Procedures are carried out. It is preferably hydrolysis products with average molecular weights in Range from 400 to 500000. Here is a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, are preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins can be used 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. A preferred dextrin is in British patent application 94 19 091. The oxidized derivatives of such dextrins act are their reaction products with oxidizing agents which are capable of at least one alcohol function or to oxidize an aldehyde function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and Methods of their production are, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO-A-92/18542, WO-A-93/08251, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608 are known. One at C6 of the saccharide ring oxidized product can be particularly advantageous.

Other suitable builder substances are oxidation products of carboxyl-containing polyglucosans and / or their water-soluble salts, as described, for example, in international patent application WO-A-93/08251 are described or their production, for example, in international patent application WO-A-93/16110 is described. Oxidized oligosaccharides according to the older German are also suitable Patent application DE-A-19 600 018.

In addition to or instead of the (poly) saccharides mentioned, the additives can also be oxydisuccinates and others Derivatives of disuccinates, preferably ethylenediamine disuccinate, contain. Are particularly preferred in this Also related to glycerol disuccinates and glycerol trisuccinates, such as those found in the United States Patents US 4,524,009, US 4,639,325, in European patent application EP-A-0 150 930 and the Japanese patent application JP 93/339896. Suitable amounts are those containing zeolite and / or formulations containing silicate at 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 have at least 4 carbon atoms and contain at least one hydroxy group and a maximum of two acid groups. Such cobuilders are, for example described 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 molecular weight of 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 with maleic acid have proven particularly suitable proven to contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative molecular mass, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and especially 50,000 to 100,000.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, 20 to 55% by weight aqueous solutions are preferred; in the latter case they serve as granulation aids (see below).

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

Other preferred copolymers are those described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and as monomers preferably acrolein and acrylic acid / acrylic acid salts or Have acrolein and vinyl acetate.

The content of (co) polymeric polycarboxylates in the finished, optionally dried additive is preferably 1 to 5% by weight. If desired, the content of these organic cobuilders can also be higher. Amounts which exceed this 5% by weight are advantageously in solid form and not in excess of Granulating liquid introduced into the additive. Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Polyaspartic acids are particularly preferred or their salts and derivatives, of which disclosed in German patent application DE-A-195 40 086 is that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are obtained by reacting dialdehydes with polyolcarboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as in the European patent application EP-A-0 280 223 described can be obtained. Preferred polyacetals will be from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.

Of course, the additives can also include, for example, the polycarboxylic acids which can be replaced in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons is, and mixtures of these contain. 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 have also the property of an acidifying component and thus also serve to set a lower one and milder pH of detergents or cleaning agents. In particular, citric acid, succinic acid, To name glutaric acid, adipic acid, gluconic acid and any mixtures of these.

The content of organic builder substances in the additives according to the invention is preferably 0.1 to 15% by weight.

Further ingredients are preferably phosphonates, which are usually present in finished compositions in amounts of 0.1 to normally not more than 2.5% by weight are used. Their content in the additives according to the invention however, is preferably more than 1 wt .-% and in particular 1.5 to 5 wt .-%.

If desired, the additives can also be equipped with colors and fragrances, but then usually applied in liquid form.

Enzymes in particular include those from the class of hydrolases, such as proteases, esterases, Lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases contribute to the removal of stains such as stains containing protein, fat or starch, and graying. Cellulases and other glycosyl hydrolases can remove pilling and microfibrils to maintain color and increase the softness of the skin Textiles contribute. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.

Bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens enzymatic active substances obtained. Proteases are preferred of the subtilisin type and in particular proteases which are obtained from Bacillus lentus. Are Enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytic Enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from Protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic Enzymes and cellulase, in particular, however, mixtures or mixtures containing protease and / or lipase lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the well-known cutinases. Peroxidases or oxidases have also 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, which are also called cellobiases are used, or mixtures of these. Since the different cellulase types are characterized by their CMCase and Avicelase activities can distinguish the desired activities by targeted mixtures of the cellulases can be set.

The enzymes can be adsorbed on carriers and / or embedded in coating substances to counter them to protect premature decomposition. If enzymes are used in the additives according to the invention, the is Proportion of the enzymes, enzyme mixtures or enzyme granules preferably 5 to 30% by weight, in particular 8 to 20% Wt .-%.

The bulk density of the additives according to the invention is preferably in a range between 550 and 1000 g / l. In particular, it is preferred that the bulk density of the additive according to the invention does not exceed ± 150 g / l, advantageously not more than 100 g / l from the bulk weight of the base granules or the base granules.

The additives are usually in granular form. The particle size distribution can - as with Granules common - cover a wide range. However, it has been shown and this is a particular advantage of the Invention that the particle size distribution depends on the type and amount of the pre-assembled raw materials. The coarser the pre-assembled raw materials used, the greater the particle size distribution be shifted to the higher range; the mostly undesirable proportion of fine grains is reduced accordingly. The spectrum of the particle size distribution can also be influenced by the use of pre-assembled ingredients become. As a result, not only the aesthetics of the finished agent can be significantly improved; if the spectrum the particle size of the additives is adapted to the spectrum of the particle size of the base granules also significantly reduce the tendency to segregate in the finished product.

Another particularly preferred embodiment is that the additives according to the invention deviate from the spherical shape by a maximum of 20 area%, in particular a maximum of 10 area%, the Deviation is measured with the method of silhouette projection. This measurement method can be used, for example carry out with the "particle size counter 3" from Zeiss. The deviation from the spherical shape is due to this determines what percentage of the area outside a circle with the same total area as that projected image of the granules lies.

In one embodiment of the invention, the additive contains anionic surfactant (s), pre-assembled foam inhibitor and bleach activator and / or bleach catalyst. It is particularly preferred that in addition to the foam inhibitors also the anionic surfactants and bleach activators or bleach catalysts in prefabricated, preferably granular form can be used.

In a preferred embodiment of the invention, the additives according to the invention accordingly contain Bleach activator and / or bleach catalyst, anionic surfactants, preferably alk (en) yl sulfates including the 2,3-alkyl sulfates and / or alkyl benzene sulfonates (for a more detailed description see below) and foam inhibitors, in particular each in a pre-assembled form.

In a further preferred embodiment of the invention, the additive according to the invention contains all of them usually in solid form to form a basic granulate or a plurality of basic granules, which in total up to 30% by weight, preferably up to 25% by weight and in particular at least 10% by weight of the make up finished detergent or cleaning agent.

In a particularly preferred embodiment of the invention, the additives according to the invention contain Bleach activators and optionally bleach catalysts, anionic surfactants and foam inhibitors in amounts of at least 50% by weight (based on active substance). In particular, it is preferred that 70 to 100 wt .-% of the invention Additives consist of pre-assembled forms of these raw materials. Can be used as "filling materials" the other usually mixed components of detergents or cleaning agents, in particular should repellents and builders (including alkali carbonates and alkali silicates) as well as enzymes, but also inorganic ones Salts such as sodium sulfate are used. The water content of the additives is preferably below 10% by weight and in particular below 8% by weight.

However, embodiments which have no enzymes have proven particularly advantageous contain.

Basic granules are understood to mean such compounds that are already used on their own Make up detergent and usually at least surfactants, builder substances and optionally peroxy bleach contain. These ingredients do not have to be contained in a single basic granulate, but can also available on different compounds. A detailed list of the preferred ones Ingredients in the basic granules are added later.

The additive according to the invention is preferably prepared by batchwise or continuous granulation of its ingredients, the latter in a mixer / granulator with the addition of a small amount of granulating liquid to a possibly moist granulate, this - if spherical or pearl shape are desired - can compact and round in a rounder and if necessary subsequently, in particular in a fluidized bed, dries.

Known apparatus, for example granulators from Gebrüder Lödige, Paderborn, can be used as the mixer / granulator. Apparatus suitable for compacting and rounding are also known. An example is the rounder known under the name "Marumerizer ^(R) ". The mode of operation and the construction of this apparatus are described in GB-PS 1 517 713. Known rounding plates or rounding discs can also be used for rounding. In a particularly preferred embodiment of the invention, a rotating fluidized bed granulator, as described for example in Pietsch, "Size Enlargement by Agglomeration", John Wiley & Sons, 1990, p. 451, is used.

A large number of compounds can be used as granulation aids. So connections can from the class of water-soluble cellulose ethers, starch and starch ethers can be used. Carboxymethyl cellulose is preferred here, especially sodium carboxymethyl cellulose. As a granulating aid can also Additives such as oxidation-stable complexing agents and stabilizers for per compounds and / or other components of detergents and cleaning agents are added or introduced via the aqueous granulating liquid. Examples of these are salts of polyphosphonic acids, such as 1-hydroxyethane-1,1-diphosphonate, ethylenediamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate, each in the form of the sodium salt. More known and suitable additives in the granulating liquid are tallow alcohol sulfates and ethoxylated tallow alcohol sulfates (with up to 100 EO), starch phosphates, soaps and well-known emulsifying agents.

In a preferred embodiment of the invention, an aqueous solution of (Co) polymeric polycarboxylates used, as already described above. In particular, copolymers have acrylic acid and maleic acid as well as biodegradable polymers made up of more than 2 monomer units proven suitable.

It is also possible to use aqueous solutions of, in particular, inorganic salts, advantageously aqueous alkali silicate solutions, preferably sodium silicate solutions, silicates having a Na ₂ O: SiO ₂ ratio of about 1: 2 to 1: 3, in particular up to 1: 2.6, being used. In fact, aqueous polymer solutions of the type described above and aqueous alkali silicate solutions have proven particularly useful as granulation aids.

The amount of water-containing granulation aid is advantageously such that it follows the granulation does not require drying. In these cases, water-containing granulation aids are particularly useful not used in amounts above 5 wt .-%, with amounts between 0.1 and 2.5 wt .-% particularly are preferred. The quantities are based on the total amount of moist and undried granules. If drying is added afterwards, the content of the aqueous granulating liquid can be reduced also more than 10 parts by weight, based on 100 parts by weight of the solid mixture to be granulated. It but then usually no more than 15 parts by weight of aqueous granulating liquid are used, with values between 8 and 12 parts by weight can be particularly advantageous.

In a further preferred embodiment of the invention, the granulation is anhydrous, that is to say anhydrous Granulation aids carried out. The liquids which are liquid at the processing temperature are particularly suitable nonionic surfactants (detailed list see below), especially ethoxylated (fatty) alcohols with a melting point below 40 ° C, but also polyethylene glycols with molecular weights between 200 and 100,000, where the latter can advantageously be used in combination with nonionic surfactants or in aqueous solution / dispersion.

To achieve advantageous surface effects, e.g. B. the formation of a particularly effective barrier layer against migrating water and / or an increase in whiteness, the additives mentioned above, in particular an aqueous solution of a granulation aid, or other ingredients of washing and cleaning agents when rounding the moist granules added simultaneously, e.g. B. are injected. In an advantageous Embodiment of the invention, however, no liquid is added in this process step. The surface of the Granules can also be treated with finely divided to dusty components, which reduces the flow behavior the granules can be further improved. Agents for the surface treatment are, for example, aluminosilicates such as amorphous and / or crystalline zeolite and / or calcium stearate and / or silicas.

Preferably, the fine and / or coarse fractions are sieved off and guided, if appropriate after drying after crushing the coarse fractions for granulation.

By mixing one or more basic granules as defined above with a detergent or cleaning agent is obtained in the additive according to the invention, in which the admixing components are evenly distributed and remain evenly distributed and which has a visually uniform appearance and also can also have an increased bulk density. An increased bulk density is understood here that the bulk density of the agent according to the invention is higher than that of an agent with the same composition and the same basic granulate (s), but in which the admixing components are not added in compounded form become.

The base granules contain, in particular, surfactants, especially anionic surfactants, nonionic surfactants, if appropriate also cationic surfactants, amphoteric surfactants and / or zwitterionic surfactants, also builder substances, peroxy bleaching agents.

In a preferred embodiment of the invention, 60 to 90% by weight of a basic granulate with 10 up to 40% by weight of an additive according to the invention, it being particularly preferred that these the two components not more than 10% by weight, advantageously less than 5% by weight of further constituents all enzymes. Embodiments have proven to be particularly advantageous in which the base granules are in extruded form and part of the anionic surfactants according to the teaching of the German application DE-A-195 19 139 can now be admixed with the additives according to the invention.

There now follows a list of ingredients of the finished washing or cleaning agents, this list does not claim to be complete.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type.

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 ester of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters as well their mixtures represent how they are in the preparation by esterification by a monoglycerol with 1 to 3 mol Fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol can be obtained. The sulfonation products represent a complex mixture, the mono-, di- and triglyceride sulfonates with α-and / or internally Contains sulfonic acid grouping. As by-products, sulfonated fatty acid salts, glyceride sulfates, glycerol sulfates, Glycerin and soaps. One goes with the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures out, the proportion of α-sulfonated fatty acid disalts can, depending on the procedure, well up to about 60% 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.

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 ₁₆ -C ₁₈ alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C ₁₆ -C ₁₈ alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize. In a preferred embodiment of the invention, the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C ₁₂ -C ₁₄ fatty alkyl sulfates or C ₁₂ -C ₁₈ fatty alkyl sulfates with C ₁₆ -C ₁₈ fatty alkyl sulfates and in particular C ₁₂ -C ₁₆ -Fatty alkyl sulfates with C ₁₆ -C ₁₈ fatty alkyl sulfates. In a further preferred embodiment of the invention, however, not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C ₁₆ to C ₂₂ are used. Mixtures of saturated sulfated fatty alcohols consisting predominantly of C ₁₆ and unsaturated sulfated fatty alcohols consisting predominantly of C ₁₈ are particularly preferred, for example those derived from solid or liquid fatty alcohol mixtures of the HD-Ocenol ^{(R) type} (commercial product of the applicant) , Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred. Mixtures in which the proportion of the alkyl radicals are 15 to 40% by weight on C ₁₂ , 5 to 15% by weight on C ₁₄ , 15 to 25% by weight on C ₁₆ and 30 find a preferred use up to 60% by weight on C ₁₈ and less than 1% by weight on C ₁₀ .

The total alk (en) yl sulfate content of the detergents is preferably 15 to 25% by weight.

2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN ^(R) , are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ alcohols ethoxylated with 1 to 6 mol ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol 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.

Other anionic surfactants include, in particular, soaps, preferably in amounts of 0.2 to 5% by weight, into consideration. Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, Palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

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

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 can 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. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

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

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

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 alkanolamides may be suitable. The amount of this nonionic surfactants are preferably no more than that of the ethoxylated fatty alcohols, especially not more than half of it.

in der R²CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R³ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Vorzugsweise leiten sich die Polyhydroxyfettsäureamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

in the R ² CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ³ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands. The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular 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.

So-called gemini surfactants can be considered as further surfactants. These are generally such Compounds understood that have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated from one another by a so-called "spacer". This spacer is in the Usually a carbon chain that should be long enough that the hydrophilic groups are spaced sufficiently have so that they can act independently of each other. Such surfactants are generally characterized by a unusually low critical micelle concentration and the ability to keep the surface tension of water strong to reduce from. In exceptional cases, however, Gemini surfactants are not only dimeric, but also also understood 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 the older one German patent application P 195 03 061.3. End group capped dimeric and trimeric mixed ethers according to the Older German patent application P 195 13 391.9 are particularly characterized by their bi- and multifunctionality out. The end group-closed 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 can also be used. as described in international patent applications WO-A-95/19953, WO-A-95/19954 and W095-A- / 19955 become.

As builder substances, in particular of an inorganic nature, are preferred in the base granules Zeolites and / or silicates, but possibly also "and / or" conventional phosphates, especially tripolyphosphates. Latter lead to significant improvements, especially in amounts of up to 10% by weight, based on the total agent in the washing performance when used in combination with zeolite and / or silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP ^(R) (commercial product from Crosfield) and zeolite NaP (commercial product from Degussa) are particularly preferred. 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 .yH 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.

Of course, the organic builder substances already mentioned can - at least for Part - be included in the base granules.

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.

Possible bleach activators and bleach catalysts have already been described in detail above.

Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these; 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 normal sodium silicate (water glass) is generally up to 10% by weight and preferably between 2 and 8% by weight.

Graying inhibitors have the task of suspending the dirt detached from the fiber in the liquor to keep and thus prevent the dirt from re-opening. For this purpose, water-soluble colloids are usually more organic Naturally suitable, 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. Water-soluble polyamides containing acidic groups are also suitable for this purpose suitable. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, are preferred Cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and Polyvinylpyrrolidone, 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 its 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 compounds of the same structure which, instead of the morpholino group, have a diethanolamino group, carry a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners can also be used of the substituted diphenyl styrene type, 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.

The basic granules can be produced by any of the known processes, such as spray drying, granulation or compacting (Roller compaction, pelleting, extrusion). Is a spray-dried basic granulate is present, then this with another base granulate, which is produced in another way and which contains the peroxy bleach contains, mixed. However, the washing or cleaning agents according to the invention preferably contain no base granules, which were produced by spray drying. In a particularly preferred embodiment According to the invention, the washing or cleaning agent consists of a basic granulate and an admixed inventive Additive.

To produce the basic granules, it is also possible to carry out the granulation in so-called granulators, which can consist of mixers with mixing tools rotating in a housing, however other technical designs of granulators are also possible and conceivable. A method of this kind is used described for example in WO 93/23523 A1.

Finally, the basic granules can also be obtained by extrusion of a premix with subsequent shaping can be produced, as described in more detail for example in WO-A-91/02047.

In a preferred embodiment of the invention, therefore, almost spherical base granules, in particular extruded base granules with almost spherical, rounded or rounded additives to a heavy granular washing or cleaning agent with bulk densities of preferably above 700 g / l mixed.

Examples

Two detergents with the same composition were produced, with both agents used as base granules an extrudate prepared according to the teaching of European patent EP-B-0 486 592, containing anionic surfactants, small amounts of nonionic surfactants, inorganic and organic builder substances and perborate monohydrate, was used.

a) 10,6 Gew.-% Granulat aus 75 Gew.-% der Natriumsalze von Kokosfettalkoholsulfat und Talgfettalkoholsulfat im Gewichtsverhältnis 1:1, 17 Gew.-% Natriumsulfat, 3 Gew.-% Natriumcarbonat, Rest unsulfierte Anteile und Wasser; hergestellt durch Granulierung und gleichzeitige Trocknung in der Wirbelschicht,

b) 7,82 Gew.-% Bleichaktivator-Granulat (TAED) verrundet,

c) 4,26 Gew.-% Schauminhibitor-Granulat auf Basis Silikonöl und Paraffinöl,

d) 0,63 Gew.-% Sokalan CP5® (Copolymeres der Firma BASF) und

e) 1,13 Gew-% Repelotex® SRP 4 (Handelsprodukt der Firma Rhöne-Poulenc).

In (comparative) example 1, the following components were mixed in the preparation with 73.56% by weight of this base extrudate and 2% by weight of an enzyme granulate of protease, lipase and cellulase:

a) 10.6% by weight of granules of 75% by weight of the sodium salts of coconut fatty alcohol sulfate and tallow fatty alcohol sulfate in a weight ratio of 1: 1, 17% by weight of sodium sulfate, 3% by weight of sodium carbonate, the rest of unsulfated components and water; produced by granulation and simultaneous drying in the fluidized bed,

b) 7.82% by weight of bleach activator granules (TAED) are rounded,

c) 4.26% by weight of foam inhibitor granules based on silicone oil and paraffin oil,

d) 0.63% by weight of Sokalan CP5® (copolymers from BASF) and

e) 1.13% by weight of Repelotex® SRP 4 (commercial product from Rhönen-Poulenc).

The (comparative) agent 1 had a bulk density of about 750 g / l. The sieve analysis (sieves 0.8 mm and 0.4 mm) showed that 74% by weight were 0.8 mm on the sieve and 26% by weight were 0.4 mm on the sieve. Im used Base extrudate was only 10% by weight on the 0.4 mm sieve; by mixing these became finer Shares more than doubled!

a) 43,41 Gew.-% Granulat aus 75 Gew.-% der Natriumsalze von Kokosfettalkoholsulfat und Talgfettalkoholsulfat im Gewichtsverhältnis 1:1, 17 Gew.-% Natriumsulfat, 3 Gew.-% Natriumcarbonat, Rest unsulfierte Anteile und Wasser; hergestellt durch Granulierung und gleichzeitige Trocknung in der Wirbelschicht,

b) 32 Gew.-% Bleichaktivator-Granulat (TAED), verrundet,

c) 17,34 Gew.-% Schauminhibitor-Granulat auf Basis Silikonöl und Paraffinöl,

d) 2,6 Gew.-% Sokalan CP5® (Copolymeres der Firma BASF) und

e) 4,65 Gew-% Repelotex® SRP 4 (Handelsprodukt der Firma Rhöne-Poulenc

In Example 2 according to the invention, an additive was prepared from the admixed components a) to e) in a mixer / granulator, the polymer being used not as a solid but as a granulating liquid in the form of a 30% by weight solution of Sokalan CP5®. The additive was then dried and had the following components and properties after drying:

a) 43.41% by weight of granules of 75% by weight of the sodium salts of coconut fatty alcohol sulfate and tallow fatty alcohol sulfate in a weight ratio of 1: 1, 17% by weight of sodium sulfate, 3% by weight of sodium carbonate, the rest of unsulfated components and water; produced by granulation and simultaneous drying in the fluidized bed,

b) 32% by weight of bleach activator granules (TAED), rounded,

c) 17.34% by weight of foam inhibitor granules based on silicone oil and paraffin oil,

d) 2.6% by weight of Sokalan CP5® (copolymers from BASF) and

e) 4.65% by weight of Repelotex® SRP 4 (commercial product from Rhönen-Poulenc

As in Comparative Example 1, the additive was now mixed with the base granules.

Agent 2 according to the invention had only a negligible reduction in bulk density 740 g / l to about 750 g / l. The sieve analysis (sieves 0.8 mm and 0.4 mm) showed that 85% by weight on the sieve 0.8 mm and only 15% by weight were on the sieve 0.4 mm. In the basic extrudate used, the fraction was on the 0.4 mm sieve again 10% by weight; the granulation reduced the finer fractions compared to agent 1, Accordingly, the aesthetics of the product are significantly improved. Agent 2 according to the invention also pointed a higher degree of whiteness (measured according to Berger and Ganz) than the (comparative) mean 1. Surprisingly the agent 2 according to the invention also had an improved dissolution rate after 1.5 minutes in comparison with the dissolving speed of the (comparative) agent 1.

Agent 2 according to the invention also showed significantly less segregation than (comparative) agent 1. This was investigated as follows: 3 filled 1.5 kg packets each were emptied with measuring spoons, each sample being 100 g. Of the 15 samples in each package, every third sample was analyzed for anionic surfactant content (AT), perborate monohydrate content (PBMH) and bleach activator content (TAED). The values obtained (in each case in% by weight) clearly show that the use of the additive according to the invention made it possible to achieve a substantially better homogeneity in the package. (Comparative) means 1 Medium 2 AT PBMH TAED AT PBMH TAED Average of the packets 14.5 to 15.2 10.0 to 11.7 7.1-7.8 14.5 to 15.1 10.4 to 11.2 7.1-7.6 minimal value 11.4 7.3 5.4 14.1 10.1 6.8 maximum value 16.9 13.0 8.9 15.9 10.8 8.0

Claims (13)

1. A granular additive with a bulk density of at least 500 g/l for use in granular detergents or cleaners with bulk densities of at least 500 g/l, characterized in that it contains one or more anionic surfactants and at least one other ingredient which is normally added in a subsequent step in the production of detergents or cleaners, with the proviso that, the additive contains 20 to 60% by weight of anionic surfactant(s) and at least one ingredient selected from bleach activator, bleach catalyst and precompounded foam inhibitor.
2. An additive as claimed in claim 1, characterized in that it contains anionic surfactant(s) and precompounded foam inhibitor and preferably bleach activator.
3. An additive as claimed in claim 1 or 2, characterized in that it is in the form of granules (granular additive) adapted to the basic granules in their bulk density, granule size and granule shape.
4. An additive as claimed in any of claims 1 to 3, characterized in that it contains both the foam inhibitor and the anionic surfactants and the bleach activators also present in the preferred embodiment in precompounded form.
5. An additive as claimed in any of claims 1 to 4, characterized in that 70 to 100% by weight of the additive consists of precompounded forms of the ingredients bleach activator and/or bleach catalyst, anionic surfactants and foam inhibitors.
6. An additive as claimed in any of claims 1 to 5, characterized in that it has a bulk density which differs by no more than ∀ 150 g/l and advantageously by no more than ∀ 100 g/l from the bulk density of the basic granules.
7. An additive as claimed in claim 6, characterized In that at most 20% and, more particularly, at most 10% of its surface area is non-spherical.
8. A granular detergent or cleaner with a bulk density of at least 500 g/l which contains typical ingredients, including anionic surfactants and foam inhibitors and optionally bleaching agents, bleach activators and/or bleach catalysts, characterized in that the detergent/cleaner consists of at least two granular compounds, one compound being an additive which contains 20 to 60% by weight of anionic surfactant(s) and at least one ingredient which is normally added in a subsequent step in the production of detergents or cleaners, with the proviso that, besides the anionic surfactant (s), the additive contains at least one ingredient selected from bleach activator, bleach catalyst and precompounded foam inhibitor.
9. A detergent/cleaner as claimed in claim 8, characterized in that it does not contain any spray-dried basic granules.
10. A detergent/cleaner as claimed in claim 8 or 9, characterized in that 60 to 90% by weight of basic granules are blended with 10 to 40% by weight of the additive claimed in any of claims 1 to 7, preferably no more than 10% by weight and, in particular, no more than 5% by weight of other ingredients, above all enzymes, having been added to these two components.
11. A process for the production of the granular additive with a bulk density of at least 500 g/l which contains 20 to 60% by weight of anionic surfactant(s) claimed in any of claims 1 to 7 which is suitable for use in granular detergents with a bulk density of at least 500 g/l, characterized in that an additive of uniform composition, granule size and granule shape is produced by granulation, compacting or extrusion and in that the additive is produced using one or more anionic surfactant(s) and at least one another ingredient which is normally added in a subsequent step in the production of detergents or cleaners, with the proviso that at least one ingredient selected from bleach activator, bleach catalyst and precompounded foam inhibitor is used in addition to the anionic surfactant(s), at least one ingredient having to be introduced into the process in precompounded form.
12. A process as claimed in claim 11, characterized in that the additive is produced by discontinuous or continuous granulation of its ingredients, these ingredients being processed in a mixer/granulator in the presence of a small quantity of granulation liquid to form optionally moist granules which, if spheres or beads are required, may be compacted and spheronized in a spheronizer and then optionally dried, more particularly in a fluidized bed.
13. A process for the production of the granular detergent or cleaner claimed in any of claims 8 to 10, characterized in that substantially spherical basic granules, more particularly extruded basic granules, are blended with substantially spherical, spheronized additives to form a heavy granular detergent or cleaner with bulk densities of preferably above 700 g/l.