DE19936612A1 - Low dose, soluble builder - Google Patents

Abstract

The invention relates to a soluble builder system for detergents and cleaning agents that is free of phosphates and aluminosilicates. The inventive detergents and cleaning agents contain a soluble builder system that substantially consists of a) one alkali silicate with a M2O:SiO2 modulus in the range of 1:1,9 to 1:3,3, wherein M represents an alkali metal ion, b) alkali carbonate, c) one oxidatively modified oligosaccharide, d) one complexing phosphonate and e) optionally one acidifying component. The soluble builder system accounts for less than 40 % by weight of the entire agent and the alkali product of the agent is in the range of 7.0 to 11.4.

Description

The invention is concerned with phosphate-free detergents and cleaning agents have soluble builder system without aluminosilicates.

The builders or builder systems fulfill a multitude of in detergents and cleaning agents Tasks that deal with the constant change in composition, the Offer form and the production of detergents in recent years and decades also change significantly. Modern detergents now contain approx. 30 to 60% by weight Builder substances. These are among the most important classes of substances for building 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, the strengthening of the washing effect, an inhibition of graying and the Dirt dispersion. Builders are said to have the alkalinity necessary for the washing process contribute to a high absorption capacity for surfactants show the effectiveness of the surfactants improve, positive contributions to the properties of solid products, for example in Deliver powder form, and thus structure-building or reduce the dust problem. These different requirements can usually be met with just one Builder component alone do not meet, so that usually a system of builders and Co-builders are 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. To a considerable extent, especially in the context of textile detergents, however, it is also used here So-called CoBuilder necessary, in particular to counter unwanted incrustations Act. To a large extent, polymers are now being used together with zeolite NaA Polycarboxylates, in particular copolymers based on acrylic acid and maleic acid  Molar masses in the range 20,000-100,000 g / mol, together with soda for this purpose used. These are synthetic polymers of unsaturated mono- and dicarboxylic acids however, it is difficult to biodegrade. It appears from an ecological point of view therefore, it is desirable to replace these polymers with other materials, the one have better biodegradability.

European patent application EP 0 874 890 describes oxidized oligosaccharides described, which have a carboxylic acid function at the originally reducing end. These oligosaccharides are very similar to the natural oligosaccharides. Hence the It is reasonable to assume that these compounds also degrade biologically in a comparable manner to let. The application shows that zeolite-containing agents modified such Oligosaccharides contain, in their washing performance are comparable to those agents that contain maleic acid-acrylic acid copolymers instead of the oligosaccharides.

Simultaneously with the development of the zeolite NaA as a builder, it was proposed selected water-soluble amorphous sodium silicate compounds as builder substances in Use detergents and cleaning agents. For example, reference is made to the US Patents 3,912,649, 3,956,467, 3,838,193 and 3,879,527. Are described here amorphous sodium silicate compounds as builder substances by spray drying aqueous water glass solutions, subsequent grinding and subsequent compression and Rounding can be made with additional dehydration of the regrind. According to the EP-A-0 444 415 detergents with 5 to 50 wt .-% of at least one surfactant, 0.5 to 60 wt .-% of a builder and conventional washing aids proposed, the Characteristic is that an amorphous, low-water sodium disilicate with a water content of 0.3 to 6 wt .-% is used.

German Offenlegungsschrift DE 22 40 309 describes a zeolite-free agent, which is 5 to 40% by weight of surfactant, 30 to 70% by weight of alkali carbonate, 1 to 30% by weight Complexing agents, preferably citrate, and 0.05 to 15% by weight of a deposition inhibitor for calcium carbonate contains. This deposit preventer is either a phosphate, a phosphonic acid or a polymeric carboxylate.

DE deals with detergents or cleaning agents with a reduced zeolite content - A-4442977. There are extruded detergents or cleaning agents with bulk weights produced above 600 g / l, which anionic and optionally nonionic surfactants as well as water-soluble builder substances such as sodium carbonate and amorphous sodium silicate  to the extent that zeolite can be partially or completely dispensed with without that there are procedural problems in the production of these during extrusion Means is coming. This was achieved by limiting the salary Zeolite (based on anhydrous active substance) on average less than 19 wt .-% of the content from the sum of sodium carbonate and amorphous sodium silicate (each based on anhydrous active substance) is 10 to 40 wt .-%, the weight ratio Sodium carbonate to sodium silicate is in the range from 5: 1 to 1:10 and the one used Sodium carbonate was at least partially in the form of granules.

International patent application WO 98/20105 describes a phosphate and aluminosilicate presented free agent, which in addition to surfactants and polyethylene glycol on a builder system Contains base of carbonate, sulfate, silicate and polycarboxylate. Advantages of this remedy consist in the price and the environmental behavior of the builder system. Preferred Embodiments have a sodium carbonate to sodium sulfate ratio of 1: 1 to 1: 3 on.

From the older German patent application DE 199 12 679 is a zeolite-free Buildersystem known that made of alkali silicate, alkali carbonate, polymeric polycarboxylate a molecular weight <10000 g / mol, phosphonate and an acidic component. This soluble builder system is dosed in low d. H. less than 40% by weight of the detergent are claimed by this builder system and the alkali product of this agent is in the range of 7.0 to 11.4. Compared to a zeolite-containing builder system this soluble builder system has advantages especially in residue behavior. Now it was found that such agents with a zeolite-free, soluble builder system also then advantages over comparable agents with zeolite-based builder system if the agents modified instead of the polymeric polycarboxylates Contain oligosaccharides.

Accordingly, a first subject of the invention are washing or cleaning agents containing at least one anionic surfactant and essentially no aluminosilicate, which are characterized in that they are a soluble builder system consisting essentially of a) an alkali silicate with a module M ₂ O: SiO ₂ , where M stands for an alkali metal ion, in the range from 1: 1.9 to 1: 3.3, b) an alkali carbonate, c) an oxidatively modified oligosaccharide, d) a phosphonate capable of complex formation and e) optionally an acidic one Component included, the soluble builder system is less than 40 wt .-% of the total agent and the alkali product of the agent is in the range of 7.0 to 11.4.

The alkali product is a size that allows statements about the alkalinity of detergents or cleaning agents. To determine the alkali product, a pH titration of a 10% by weight solution of the agent in water is carried out using a pH electrode and 1.0 molar hydrochloric acid. The alkali product is calculated as follows:

V: consumption of 1.0 molar HCl at pH = 10 (in ml)
E: weight in g
Initial pH: the 10% by weight solution

If the alkali product is over 10, it leaves statements about the initial pH and about that Buffering capacity of the solution; if it is at or below 10, it is identical to that Initial pH, then statements about the buffer behavior of the solution are not from the size possible.

The alkali product of the agents according to the invention is in the range from 7.0 to 11.4. It is preferably in the range 8.5 to 11.2, with the agents in a particular one preferred embodiment of the invention have an alkali product of 10.7 ± 0.4.

The alkali product of the agents is the composition of the invention determined and can be targeted in particular with the help of the acidic component to be influenced. For this purpose, all are suitable for use in washing and Acid components suitable for cleaning agents. This can be both carboxylic acids also mineral acids or acid salts of mineral acids. Among the carboxylic acids are preference is given to those which are also suitable as cobuilders. Here are in particular polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and Mixtures of these. These acids can be anhydrous or in the form their hydrates are used. Among the mineral acids that can be used are in particular Sulfuric acid, phosphoric acid, carbonic acid and hydrochloric acid, as well as their acid salts call. Acid components are preferred in the agents according to the invention  Citric acid and / or sodium hydrogen sulfate used, the sole use of Citric acid represents a particularly advantageous embodiment. The content of the agent however, the acidic component is preferably not more than 10.0% by weight; in particularly preferred embodiments it is in the range 0.1 and 5% by weight. In principle, the acidic component can be used at any stage in the preparation of the agent be added. However, it is preferred if the acid component Detergent or cleaning agent is subsequently mixed in, the acidic Component either alone or in the form of compounds with others, preferably neutral reacting, detergent or cleaning agent ingredients are present.

The total content of builder substances is also essential for the alkali product. He is supposed to be in the agents according to the invention are not more than 40% by weight, with one being preferred Embodiments of the invention are in the range of 20 to 35% by weight. Especially Low levels of builder substances are possible if this is in the wash liquor active alkali carbonate predominantly not through the direct entry of alkali carbonate, For example, soda occurs, but if the alkali carbonate from precursors that first form alkali carbonate during the process. It should be mentioned here especially alkali percarbonate, which under the influence of moisture alkali carbonate releases. It provides, for example, the bleaching agent that is preferably used Sodium percarbonate in the wash liquor 68% of its weight as soda. Becomes Sodium percarbonate used as bleach, so it provides at least 30 wt .-% of total alkali carbonate active in the wash liquor, preferably even more than 50% by weight. Nevertheless, sodium percarbonate does not become the soluble builder system according to the invention counted because it is primarily a bleach. Accordingly, in means that Contain sodium percarbonate as bleach, particularly low levels of the soluble Buildersystem can be set in the washing properties without disadvantages. Such Agents preferably contain only 10 to 25% by weight of the soluble builder.

Because of the low, especially in relation to the possible surfactant content Builder content the agents can also be dosed low in the washing process. That's the way it is preferred if the agent is dosed so that during the wash in a Household washing machine maximum 45 g, preferably between 10 and 35 g, of the soluble Buildersystems are used. Thereby is contained in the wash liquor Builder quantities ensure that the builders have an adequate water softening function perceive. The builder system can preferably be largely independent of the Water hardness can be dosed. However, with high water hardness, it may be preferred  if builder amounts in the upper half of the specified range of 20 to 45 g, in particular from 25 to 35 g, can be dosed in the wash.

Accordingly, the invention further relates to a method for washing of textiles in which an agent according to the invention is used. This means it will preferably dosed so that during the washing cycle in a household washing machine a maximum of 45 g, preferably between 10 and 35 g, of the soluble builder system is used become. The builder system can preferably be largely independent of the Water hardness can be dosed. However, with high water hardness, it may be preferred if builder amounts in the upper half of the specified range of 20 to 45 g, in particular from 25 to 35 g, can be dosed in the wash.

The alkali carbonates used in the builder system are preferably Sodium and / or potassium carbonate, in particular the use of sodium carbonate is preferred. The content of these alkali carbonates is preferably chosen so that that the content of active alkali carbonate in the wash liquor 5 to 30 wt .-%, especially preferably 10 to 25% by weight and in particular at least 15% by weight of the total By means of.

The oxidatively modified oligosaccharide to be used according to the invention is is a compound that comes from the substance class of oxidized starches or Starch derivatives, especially thermally or enzymatically degraded starch derivatives, is selected. Starch, like glycogen or cellulose, belongs to the homoglycans. Starch consists of 3 different D-glucopyranose polymers, the amylose, the Amylopectin and a so-called intermediate fraction, which is also called an abnormal amylopectin as well as water (approx. 20%, depending on the variety and storage conditions), smaller amounts of protein, fats and phosphoric acid bound in ester form. The salary of the Starch on these ingredients varies depending on the variety. Higher plants contain 0-40% Amylose based on dry matter. The intermediate fraction is structurally between amylose and amylopectin. In the case of analytical determinations of strength, the Intermediate fraction mostly attributed to amylopectin.

Amylose consists of predominantly linear α-1,4-glycosidically linked D-glucose. As Diffusion amylose is the part of the amylose that occurs in water at temperatures <100 ° C is soluble. At temperatures of 60-70 ° C, diffusion amylose is obtained which is free of amylopectin. Starch with more than 70% amylose is called high amylose starch  designated, e.g. B. Pea starch (70% amylose) and Amylomais starch (<50% Amylose). The water and amylose content of starch is determined by NIR spectroscopy certainly. The chains form double helices.

In addition to the α-1,4 linkages described for amylose, amylopectin also contains 4-6% α-1,6 linkages

The average distance between the branches is about 12 to 17 glucose units. The molar mass (M _R = 107-108) corresponds to approx. 105 glucose units, making amylopectin one of the largest biopolymers. The branches are distributed over the molecule in such a way that a tuft structure with relatively short side chains develops. Two of these side chains each form a double helix. Due to the many branching points, amylopectin is relatively readily soluble in water and is better broken down enzymatically. As the amylopectin content increases, the crystallinity of a starch grain increases and the gelatinization energy increases. Starches that only contain amylopectin (from certain types of corn and potatoes) are called wax varieties. The appearance of the starch grains is typical of the respective parent plant. Amylose provides complexes in which organic or other molecules are embedded in the helical structure; with iodine it forms the blue-colored iodine-starch complex, whose absorption maximum depends on the chain length of the amylose. Amylopectin forms a reddish brown complex with iodine. Amylose can be separated from amylopectin by adding n-butanol to a hot starch dispersion: the amylose-n-butanol complex precipitates out on cooling.

Starch is a reserve carbohydrate that many plants in the form of 1-200 mm in size Starch grains are stored in different parts of plants, e.g. B. in tubers or Roots [Potatoes, Maranta (Arrowroot), Cassava (Tapioca), Batate], in cereal seeds (Wheat, corn, rye, rice, barley, millet, oats, sorghum), in fruits (chestnuts, Acorns, peas, beans and other legumes, bananas) and in the pulp (sago palm).

Starch is preferably obtained from vegetable raw materials from flour from Corn, potatoes, wheat, rice u. Cassava (tapioca), with the starch grains after Removal of the adhesive mechanically detached from the cell structure by wet means become; Corn is the most important starch plant worldwide.

Oxidation processes on starch or starch derivatives, in particular starch pyrolisates or enzymatic degradation products of starch, can in principle be carried out with any suitable oxidizing agent. Terminal aldehyde groups can be oxidized to acid functions and / or alcohol functions can be oxidized to aldehyde or acid functions. However, oxidatively modified starch derivatives used with preference essentially contain only alcohol and acid functions. The presence of aldehyde functions is undesirable in the starch derivatives preferred according to the invention. In principle, however, the oxidized starches also include the dialdehyde starches which are used in the treatment of starches with selectively acting oxidizing agents, such as. B. periodic acid. However, these polymers tend to crosslink to form water-insoluble films. Their use in agents according to the invention is therefore less preferred and only possible in combination with very specific ingredients. These dialdehyde starches are further oxidized to dicarboxy starches, in which units of the following type

As a complexing group, such compounds can very well in the detergents according to the invention may be included.

To summarize roughly: A large number of oxidizing agents is for the oxidation of Polysaccharides, especially those made exclusively from glucose  Polyglucosans in use. Examples include (air) oxygen, hydrogen Peroxide, sodium hypochlorite or bromite, periodic acid or Periodate, lead (IV) acetate, nitrogen dioxide and cerium (IV) salts. This oxidizing agent right act very differently with the anhydroglucose units. For example Periodates or lead (IV) acetate a C-C cleavage of the anhydroglucose rings; one gets out Cellulose is the so-called 2,3-dialdehyde cellulose and, analogously, starch dialdehyde starch. It is also known that when nitrogen dioxide acts on cellulose, the oxides tion of the primary alcohol group to the carboxyl group is the predominant reaction. The oxidizing agent, usually present in equilibrium with nitrous oxide, can be used in gaseous or dissolved form in an inert organic solvent. Largely selective oxidations can also be started accordingly from the starch the primary alcohol group of the anhydroglucose units to the carboxyl group accomplish. This is the oxidation from US Pat. No. 2,472,590 of starch with gaseous or in water or in various organic Solvents dissolved nitrogen dioxide known.

Under these conditions the almost complete conversion of the primary is obtained Alcohol groups of the polysaccharides in carboxyl groups only after a very long time Response times, which may be up to several days. Moreover high amounts of nitrogen dioxide, based on oxidizing polysaccharide, needed. From the international patent application WO 93/16110 is a significant improvement in the production of such Oxidation products of polysaccharides known. The invention disclosed there is based on the Recognition that polycarboxylates from polysaccharides in a simple process in High yields can be obtained if the oxidation reaction with nitrogen dioxide / Distick substance tetroxide in the presence of oxygen at elevated temperatures and preferably at elevated pressure is performed. The phrase "nitrogen dioxide / nitrous oxide" stands for what is present under the respective reaction conditions Equilibrium mixture of nitrogen dioxide and its dimer dinitrogen tetroxide.

If one carries out the variant of the suspension-free and solvent-free oxidation with gaseous nitrogen dioxide / nitrous oxide hydroxide described in this document, a polysaccharide selectively oxidized to C _{6 is obtained} in solid form. This sparingly water-soluble acid form is less preferred for direct use as a builder or builder component (cobuilder) in washing or cleaning agents; it is generally preferred to use the oxidized polysaccharide in the form of a water-soluble salt, that is to say the neutralization product of the polycarboxylic acid obtained in the oxidation. This neutralization can be carried out with aqueous base. This procedure leads to aqueous solutions of the polycarboxylate which, if the polycarboxylate is required as a solid, make an energy-consuming drying step necessary. This can be an additional factor in the manufacture of solid washing or cleaning agents if an aqueous work-up step for removing nitrate and nitrite is provided immediately after the actual oxidation reaction and the further processing of the aqueous neutralized polycarboxylate solution in the context of spray drying processes. The disadvantage here is the accumulation of aqueous polycarboxylate solutions in the context of manufacturing processes for detergents and cleaning agents which involve the mixing of solid components, since the removal of water from the polycarboxylate solution and the conversion of the dissolved polycarboxylate into a solid are inevitable.

In a preferred one described in German patent application DE-A-44 26 443 Process variant, according to both the aqueous workup of the Reaction products of polysaccharides with nitrogen dioxide / dinitrogen tetroxide as well you can do without their vacuum treatment and still use products acceptably low nitrate and nitrite levels, if one before the actual conclusion Chen oxidation reaction the supply of the oxidizing agent nitrogen dioxide / dinitrogen tetroxide ended and the temperature increased to a value above the reaction temperature, appears the aqueous neutralization of the polycarboxylic acid thus produced and the subsequent drying of the aqueous polycarboxylate solution is paradoxical.

Therefore, a process for producing solid polycarboxylic acid salts is made from Polysaccharides by oxidation with gaseous nitrogen dioxide / nitrous oxide under Conversion of at least a portion of the primary alcohol groups of the polysaccharides to Carboxyl groups and at least partial neutralization of the resulting carbon acid groups, which is characterized in that the solid polycarboxylic acid with mixed with a solid neutralizing agent, particularly preferred. This procedure is in patent application DE-A-195 07 717.

The oxidation of the polysaccharide preceding the neutralization is preferred performed as described in German patent application DE-A-44 26 443. This means that the reaction of the polysaccharide to be oxidized with nitrogen dioxide / Di nitrogen oxides only so long that the desired degree of oxidation, that is Degree of conversion of the primary alcohol groups into carboxyl groups, only at most 90%, preferably 60% to 85% and in particular 65% to 80% is achieved. The The desired degree of oxidation is only fully achieved in the aftermath oxidation phase, that is, when the nitrogen dioxide / nitrous oxide supply has ended and in  Compared to the oxidation phase by at least 10 ° C, preferably 15 ° C to 80 ° C and ins special 20 ° C to 50 ° C elevated temperature. It is important to ensure that the Increasing the temperature does not exceed an upper limit of 160 ° C, as possible decomposition was increasingly observed at higher temperatures.

The oxidation reaction to be stopped before full conversion is reached preferably at temperatures from 30 ° C to 70 ° C, in particular from 40 ° C to 60 ° C carried out. Oxygen, alone or in a mixture with the Reaction conditions inert gas, be present, the addition of which once Start of the reaction or several times, if desired continuously, during the reaction can be done. As is well known, the latter reaction can lead to the oxidation reaction can be controlled depending on the temperature or pressure via the oxygen metering. Preferential wise one regulates the addition of oxygen so that the reaction temperature in the range of 30 ° C to 70 ° C remains.

As inert, that is to say unreactive under the respectively desired process conditions Gases can include noble gases such as helium or argon and carbon dioxide, but especially Nitrogen, nitrogen monoxide and nitrous oxide, but also any mixtures of the like gases are used. The oxygen content in the gas mixture lies there preferably in the range from 1% by volume to 30% by volume, in particular from 3% by volume to 10% by volume %. A preferred embodiment of the method according to the invention includes Supply of oxygen by injecting air.

Another preferred embodiment of the method is characterized in that a pressure of less than 10 bar in the reaction system before the start of the oxidation reaction, in particular from 2 bar to 6 bar, at the desired reaction temperature Pressing an inert gas mentioned is set and then oxygen or a mixture of oxygen with said inert gas, several times, if desired, con is being pressed on. The addition of nitrogen dioxide / nitrous oxide can before or after the addition of oxygen or the start of the addition of oxygen consequences. It may be necessary to remove the reaction vessel after the initial one Pressurizing the inert gas to the desired reaction temperature. While the course of the oxidation reaction, which is expedient with intensive mixing of the Re action partner, the reaction temperature can usually be achieved without external heating can be kept solely by the addition amount of oxygen.

The oxidizing agent arrives in the oxidation step of the method according to the invention from the gas phase directly onto the solid, thoroughly mixed poly  saccharide substrates for exposure. Oxidation in a fluidized bed is preferred from polysaccharide, the fluidizing agent of which is a gas containing nitrogen dioxide. Such one Oxidation process is described in German patent application DE-A-44 02 851. Under the fluidized bed, the - without being limited to this type of production Appearance to be understood that can be observed when on horizontal, perforated Fine-grained bulk goods stored in the bottom of gases, referred to as eddies, is flowed through.

A particularly preferred class of oxidatively modified oligosaccharides are oxidized Dextrin derivatives. Dextrins are, for example, oligomers or polymers of Carbohydrates that can be obtained by partial hydrolysis of starches. The Hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes be performed. They are preferably hydrolysis products with medium Molar masses in the range from 400 to 500,000 g / mol. There is a polysaccharide with one Dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 preferred, where DE is a common measure of the reducing effect of a polysaccharide in Compared to dextrose, which has a DE of 100. Both are usable 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 ones Molar masses in the range from 2000 to 30000 g / mol. A preferred dextrin is in the British patent application 94 19 091 described. Such in the oxidized derivatives Dextrins are their reaction products with oxidizing agents, which in the Are able to at least one alcohol function of the saccharide ring to the carboxylic acid function oxidize. Such oxidized dextrins and processes for 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 and the 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 are known.

An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also preferred. Glucose is the preferred monomer in this oligosaccharide to be used according to the invention after oxidative modification. The average degree of oligomerization, which can also take fractional numerical values as the quantity to be determined analytically, is preferably in the range from 2 to 20, in particular 2 to 10. The oligosaccharide which is preferably used as a builder or cobuilder is oxidative at its originally reducing end with the loss of a C- Atoms have been modified. If the originally reducing end of the oligosaccharide was an anhydroglucose unit, there is an arabinonic acid unit after modification:

(Glucose) _{n + 1} → (glucose) _n arabinonic acid.

This oxidative modification can, for example, with the aid of Fe, Cu, Ag, Co or Ni Catalysts as described in international patent application WO 92/18542 With the help of Pd, Pt, Rh or Os catalysts, as in the European patent specification EP 0 232 202 described, or by means of a quinone / hydroquinone system in alkaline with the addition of oxygen and optionally aftertreatment with hydrogen peroxide respectively. In the case of the oligosaccharide out which can be modified by means of such oxidation processes The starting material is preferably an oligosaccharide with a dextrose Equivalent (DE) in the range from 20 to 50. So-called glucos are particularly useful sesirupe (DE 20-37) and the above-mentioned dextrins, both by partial hydrolysis of starch by the usual, for example acid or enzyme catalyzed processes can be carried out, are accessible and which as such or in higher polymer form, can be used, for example, as starch in the oxidation processes mentioned above, if, under the conditions of the oxidation, a corresponding degradation of the polymer chain structure of strength takes place. Preferably, the so oxidatively modified Oligosaccharides at the original reducing end instead of the group -CH (OH) -CHO one Group -COOH on.

In detergents and cleaning agents according to the invention, 0.5% by weight is preferably up to 8% by weight, in particular 2% by weight to 6% by weight, of the oxidatively modified oligosaccharide, which is normally used in the form of its alkali salt. As part of the are use according to the invention and the washing method according to the invention Concentrations of oxidatively modified oligosaccharide in the wash liquor of 0.001% to 0.05% by weight is preferred.

In preferred embodiments according to the invention, the alkali silicates are amorphous sodium silicates with a module Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 up 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” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles 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 overdry x-ray amorphous silicates are particularly preferred. Granular amorphous alkali silicates with bulk densities of at least 700 g / l can be produced, for example, by a process described in patent application WO 97/34977, which starts from spray drying and includes the compression of the spray-dried beads. The spray-dried bead is ground and granulated simultaneously or subsequently with the addition of a liquid granulating aid, bulk densities of at least 700 g / l - up to above 1000 g / l - being set.

In particular, the alkali silicates according to the invention can also be used in preparation forms are used in which they are present together with alkali carbonate.

In a further embodiment of the invention, crystalline, layered sodium silicates of the general formula Na ₂ SixO _{2x + 1} .yH ₂ O, where 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. 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 α-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

Regardless of which alkali silicate is used, the total content is Alkali silicate in the agents preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%. Another component of the builder system are phosphonates. It is about especially about hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane  The 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance for phosphonates as a cobuilder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt reacts alkaline (pH 9). As aminoalkane phosphonates come preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. you will be preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt EDTMP or as the hepta and octa sodium salt of DTPMP. As a builder HEDP is preferably used from the class of the phosphonates. The Aminoalkanephosphonates also have a strong ability to bind heavy metals. Accordingly, it may be preferred, especially if the compositions also contain bleach be to use aminoalkanephosphonates, in particular DTPMP, or mixtures of to use the phosphonates mentioned. Such phosphonates are in the middle usually contained in amounts of 0.05 to 2.0% by weight, preferably in amounts of 0.1 to 1% by weight.

The agents do not contain aluminosilicates or contain them only in small amounts. If you are included, but not because of their water softening effect or Carrier function. They can only be contained if they are used as granulation aids, for example, for powdering. The content is accordingly crystalline aluminosilicates in the compositions at less than 5 wt .-%, preferably even at less than 3% by weight. Zeolites A, P, X are preferably used as aluminosilicates and Y used. However, mixtures of A, X, Y and / or P are also suitable. As zeolite P becomes special, for example, Zeolite MAP® (commercial product from Crosfield) prefers. Of particular interest is also a cocrystallized sodium / potassium Aluminum silicate from zeolite A and zeolite X, which as VEGOBOND AX® (commercial product from the company Condea Augusta S. p. A.) is commercially available.

In addition to the modified oligosaccharide, polymeric polycarboxylates may also be present in the agents according to the invention as further cobuilders. These are preferably homo- or copolymers which contain acrylic acid and or maleic acid units. In a preferred embodiment, polymers with molar masses below 10000 g / l are used, these polymers preferably being homopolymers of polyacrylic acid. In particular, polyacrylates, which preferably have a molecular weight of 3000 to 8000 and particularly preferably 4000 to 5000 g / mol, have proven to be particularly suitable according to the invention. The molar masses given in this document for polymeric polycarboxylates are weight-average molar masses M _w which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was made 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 molar masses measured against polystyrene sulfonic acids are generally higher than the molar masses specified in this document. In addition to these short-chain polyacrylates, the compositions may also contain copolymeric polycarboxylates which have a molar mass between 20,000 and 70,000 g / mol. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. To improve water solubility, the polymers can also contain allylsulfonic acids, such as, for example, in EP-B-727448 allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer. Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which, according to DE-A-43 00 772, are salts of acrylic acid and maleic acid, as well as vinyl alcohol or vinyl alcohol derivatives, or according to DE-C-42 21 381 as monomers contain salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives. Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers. In a further preferred variant, mixtures of the short-chain polyacrylates with molecular weights <10,000 g / mol with the copolymeric polycarboxylates with molecular weights between 20,000 and 70,000 g / mol are used. Regardless of which polymeric polycarboxylates are used, it is preferred according to the invention that, when polymeric polycarboxylates are used, the ratio of the modified oligosaccharides to polymeric polycarboxylates in the range from 2: 1 to 1:20, in particular 1: 1 to 1:15, lies. In a likewise preferred embodiment of the invention, however, the agents contain no polymeric polycarboxylate. Only the modified oligosaccharide then functions as the cobuilder.

Important ingredients of the agents according to the invention are surfactants, in particular Anionic surfactants, at least in amounts of 0.5 wt .-% in the agents according to the invention are included. These include in particular sulfonates and sulfates, but also soaps.  

Preferred surfactants of the sulfonate type are C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as 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 by α-sulfonation the methyl ester of fatty acids of plant and / or animal origin with 8 to 20 C- Atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono- Salts are made into consideration. This is preferably the α-sul Formed esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, whereby also Sulfonation products of unsaturated fatty acids, for example oleic acid, in low Amounts, preferably in amounts not above about 2 to 3% by weight, are present can. In particular, α-sulfofatty acid alkyl esters are preferred which do not have an alkyl chain have more than 4 carbon atoms in the ester group, for example methyl ester, ethyl ester, Propyl ester and butyl ester. The methyl esters of the α- Sulphofatty acids (MES), but also their saponified salts.

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

As alk (en) yl sulfates, the alkali and in particular the sodium salts of sulfuric acid are 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. From the washing are C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ - C ₁₅ alkyl sulfates are particularly preferred. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, 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 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 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 amounts of 0.2 to 5% by weight. Saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, e.g. B. coconut, palm kernel or tallow fatty acids, derived soap mixtures. Together with these soaps or as The known alkenylsuccinic acid salts can also be used as substitutes for soaps become.  

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 triethanolamine,. available. The anionic surfactants are preferably in the form of their sodium = or Ka lium 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 in particular contained or used 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 linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols 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 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 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 is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:

The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, 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 R5 for 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, the alkyl chain of which 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 95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Another class of preferably used nonionic surfactants, which are used either as sole nonionic surfactant or in combination with other nonionic surfactants, in particular 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 special 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-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 preferably not more than that of the ethoxylated fatty alcohols, especially not more than half from that.

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 micelle concentration and the ability to greatly reduce the surface tension of the water. In out However, under the term Gemini surfactants, 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 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. For example, the end group-closed surfactants mentioned have good ones Network properties and are low-foaming, so that they are particularly suitable for use suitable 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-95/19954 and WO95-A- / 19955.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate, sodium perborate monohydrate 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. As already explained above, sodium percarbonate is used as bleaching agent in a preferred embodiment.

The other detergent ingredients include graying inhibitors (dirt carriers), Foam inhibitors, bleach activators, optical brighteners, enzymes, fabric softeners Substances, colors and fragrances as well as neutral salts such as sulfates and chlorides in the form of their Sodium or potassium salts.

Compounds which are aliphatic under perhydrolysis conditions can be used as bleach activators cal peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms Atoms, and / or optionally substituted perbenzoic acid can be used. Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups. Multiple are preferred acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated Glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N- Nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol koldiacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from the German patent applications DE-A-196 16 693 and DE-A-196 16 767 known enol esters and acetylated sorbitol and Mannitol or their in European patent application EP-A-0 525 239 described mixtures (SORMAN), acylated sugar derivatives, especially Pentaace tylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated Lactams, for example N-benzoylcaprolactam, which are from the international Pa Tent 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 from the German patent application DE-A-196 16 769 known hydrophilically substituted acylacetals and those in the German Patent application DE-A-196 16 770 and international patent application WO-A- 95/14075 described acyl lactams are also preferably used. That too the German patent application DE-A-44 43 177 known combinations of conventional Bleach activators can be used. Such bleach activators are common Quantity range, preferably in amounts from 1% by weight to 10% by weight, in particular 2 % By weight to 8% by weight, based on the total average.

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 bi-stearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for. 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. In particular, mixtures of paraffins and bistearylethylenediamides are preferred.

Enzymes in particular come from the hydrolase class, such as the protea sen, lipases or lipolytically active enzymes, amylases, cellulases or their mixtures questionable. Oxidoreductoses are also suitable.

From bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens obtained enzymati active ingredients. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. There are Enzymmi creations, for example from protease and amylase or protease and lipase or lipoly table-acting enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic acting enzymes or protease, lipase or lipolytically acting enzymes and Cellu lase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipoly  The well-known cutinases are enzymes with a table effect. Also peroxidases or oxidases have proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which also Cellobiases are called, or mixtures of these are used. Since the ver distinguish different cellulase types by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases become.

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

In addition to phosphonates, the agents can also contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. In addition to calcium salts, magnesium salts also serve as stabilizers. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous.

Graying inhibitors have the task of removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acid ren or ether sulfonic acids of starch or cellulose or salts of acid sulfur acid esters of cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose. Soluble starch preparations can also be used and use starch products other than the above, e.g. B. degraded starch, Aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, are preferred Cellulose ethers, such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyal alkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, Methylcarboxymethylcellulose and mixtures thereof, as well as 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 their Contain alkali metal salts. 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 is a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Can continue Brighteners of the substituted diphenylstyryl type may be present, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4- Chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

The agents according to the invention can have any bulk density. That is enough Range of possible bulk weights of low bulk weights below 600 g / l, for example 300 g / l, over the range of average bulk weights from 600 to 750 g / l, to for high bulk weights of at least 750 g / l. In a preferred variant However, the bulk density of the agents according to the invention with high bulk densities is even above 800 g / l, with bulk weights above 850 g / l being particularly advantageous can. With such supercompacts, the advantages of the soluble come Buildersystems especially to carry, because such compact means special Make demands on the ingredients in order to be well dispersible. That also leads low-dose builder system, regardless of bulk density, adds additional benefits saving packaging volume and reducing the chemical input per Wash into the environment.

Any means known from the prior art are available for producing such agents Method, suitable. It is only essential to the invention that an acid is present in the agent acting component is metered so that the alkali product of the resulting agent in is in the range of 7.0 to 11.4. As already described above, the alkali product lies preferably in the range 8.5 to 11.2.

The agents are preferably prepared in that different particulate Components that contain detergent and / or cleaning agent ingredients and together form at least 60 wt .-% of the total agent, are mixed together.

In particular, it can be preferred that the acidic component is added to the washing or detergent is subsequently mixed in, the acidic component  either alone or in the form of compounds with others, preferably neutral reacting, detergent or cleaning agent ingredients are added.

The particulate components can be spray dried, simply mixed or complex granulation processes, for example fluidized bed granulation become. It is particularly preferred that at least one surfactant-containing component is produced by fluidized bed granulation.

It can furthermore be particularly preferred if aqueous preparations of the alkali silicate and the alkali carbonate together with other washing and / or cleaning agents ingredients are sprayed in a drying device, at the same time with the Drying a granulation can take place.

The drying device into which the aqueous preparation is sprayed can 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 an embodiment of spray drying with superheated steam in a row published publications. The working principle disclosed there is hereby expressly stated also made the subject of the present disclosure of the invention. Is referred here in particular to the following publications: DE-A-40 30 688 and 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, especially if medium bulk densities are to be obtained, In a preferred variant, the mixtures are then subjected to a compacting step subject to further ingredients of the agents only after the compacting step be added.

In a preferred embodiment, the ingredients are compacted Invention in a press agglomeration process instead. The press agglomeration process, the solid premix (dried basic detergent) is subjected to various devices can be realized. Depending on the type of used  Agglomerators are differentiated different press agglomeration processes. The four most common and preferred in the context of the present invention Press agglomeration processes are extrusion, roll pressing or -compact, the hole pressing (pelletizing) and the tableting, so that within the present invention preferred press agglomeration processes extrusion, Roll compacting, pelletizing or tableting processes.

All processes have in common that the premix compresses and plastifies under pressure and the individual particles are pressed against each other while reducing the porosity and stick together. For all processes (with tableting with restrictions) the tools can be heated to higher temperatures or for removal cool the heat generated by shear forces.

In all processes, a binder can be used as an aid to compaction. in the the further course of the description of this invention is only for the sake of simplicity one or the binder. However, it should be made clear that in itself always the use of several different binders and mixtures different binders is possible. In a preferred embodiment of the invention 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 is already completely present as a melt. The Binder must therefore be selected depending on the process and process conditions or the process conditions, in particular the process temperature, must - if one certain binder is desired - 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 softening point, if not the temperature of the melting point of the binder. In a preferred embodiment of the invention, the Process temperature significantly above the melting point or above the temperature at which the binder is in the form of a melt. In particular, however, it is preferred that the Process temperature in the compression step not more than 20 ° C above 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 temperature control has the Another 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 compaction, that is between the mixing / homogenization of the premix and the shaping, allows an energetically very favorable and for the temperature sensitive components of the Premix extremely gentle process management, since the premix is only for a short time is exposed to the higher temperatures. In preferred press agglomeration processes show the working tools of the press agglomerator (the screw (s) of the extruder, the Roller (s) of the roller compactor and the press roller (s) of the pellet press) a temperature of a maximum of 150 ° C, preferably a maximum of 100 ° C and in particular a maximum of 75 ° C on and the process temperature is 30 ° C and in particular a maximum of 20 ° C above that Melting temperature or the upper temperature limit of the melting range of the Binder. The duration of the temperature effect is preferably in Compression range of the press agglomerators is a maximum of 2 minutes and is particularly 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 12,000 and in particular between 1,000 and 4,000. Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which in turn have relative molecular weights between 600 and 6000, preferably between 1000 and 4000. For a more detailed description of the modified polyalkylene glycol ethers, reference is made to the disclosure of the international patent application WO-A-93/02176. In the context of this invention, 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 which are preferably used can have a linear or branched structure, linear polyethylene glycols in particular being preferred. The particularly preferred polyethylene glycols include those with relative molecular weights between 2000 and 12,000, advantageously around 4000, polyethylene glycols with relative molecular weights below 3500 and above 5000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4000, and such combinations advantageously to more than 50% by weight, based on the total amount of 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 of the invention, ie must have a melting point or softening point of at least above 45 ° C.

Low molecular weight polyvinylpyrrolidones and derivatives of are also suitable as binders these with relative molecular weights up to a maximum of 30,000. Relative Mo are preferred here molecular mass ranges between 3000 and 30,000, for example around 10,000. Polyvinylpyrroli are preferably not done as sole binders, but in combination with others ren, especially in combination with polyethylene glycols.

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. Here, degrees of alkoxylation, in particular degrees of ethoxylation of on average 18 to 80 AO, in particular EO per mole of alcohol and mixtures of these 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. The binder content of these relatively low ethoxylated alcohols is advantageously less than 50% by weight, in particular less than 40% by weight, based on the total amount of binder used. Above all, usually used in detergents or cleaning agents, nonionic surfactants such as C ₁₂ -C ₁₈ alcohols with an average of 3 to 7 EO, which are liquid per se at room temperature, are preferably only present in the binder mixtures in amounts that are 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, moreover, due to their tendency to gel when in contact with water, also does not meet the required extent of the rapid dissolution of the binder / partition in the end product. Likewise, it is not preferred that conventional anionic surfactants or their precursors, the anionic surfactant acids, used in detergents 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 8 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 Contains ₁₂ -C ₁₈ 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, are based.

In addition to the substances mentioned here, other suitable substances can be used in small quantities Substances can be contained in the binder.

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

In a preferred embodiment of the invention, the method according to the invention carried out by means of an extrusion, as described, for example, in the European patent EP B-486592 or international patent applications WO 93/02176 and WO 94/09111 and WO 98/12299 can be described. A solid pre-mix is under pressure extruded and the strand after exiting from the hole shape by means of a Cutting device tailored to the predeterminable granule dimension. The homo gene and solid premix contains a plasticizer and / or lubricant which causes the premix under the pressure or under the entry of specific work plastically softens and becomes extrudable. Preferred plasticizers 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 nozzle plate in the extruder head and finally, preferably the extrudate by means of a rotating knock-off knife reduced spherical to cylindrical granules. The hole diameter of the Perforated nozzle plate and the strand cut length are in this case selected Granulate dimension matched. In this embodiment, the production of Granules of a substantially uniformly predeterminable particle size, in which individual the absolute particle sizes to be adapted to the intended application  can. In general, particle diameters up to at most 0.8 cm are preferred. Important embodiments see the production of uniform granules in the Millimeter range, for example in the range of 0.5 to 5 mm and in particular in the range from about 0.8 to 3 mm. The length / diameter ratio of the chipped In an important embodiment, primary granules are in the range of approximately 1: 1 to about 3: 1. Furthermore, it is preferred to add the still plastic primary granulate to another to supply shaping processing step; the raw extrudate is present Rounded edges, so that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired, small amounts of can be added at this stage Dry powder, for example zeolite powder such as zeolite NaA powder, can also be used. This shape can be done in standard rounding machines. It is about make sure that only small amounts of fine grain are produced in this stage. A Drying, which in the aforementioned documents of the prior art as preferred embodiment is described, is then possible according to the invention but not absolutely necessary. It may just be preferred after Compaction step no longer drying.

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 over is taken. The duration of the temperature influence is in the compression range Extrusion preferably less than 2 minutes and in particular 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 will the premix between two smooth or with wells of a defined shape provided rollers and metered under pressure between the two rollers leaf-shaped compact, the so-called Schülpe, rolled out. The reels practice that Premix a high line pressure and can be additionally heated or be cooled. When using smooth rollers, you get smooth, unstructured Cuffs, while using structured rollers accordingly  structured slugs can be created, in which, for example, certain shapes the later detergent or cleaning agent particles can be specified. The Schülpenband is subsequently cut into smaller ones by a knock-off and crushing process Pieces broken and can be processed into granules that way refined by further known surface treatment processes, especially in can be brought into an approximately spherical shape.

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 with roller compacting with process temperatures of 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 of the Effect of temperature in the compression area of the smooth or with depressions of rollers defined in a defined form is a maximum of 2 minutes and in particular in one Range 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, for example, as are concave or convex plates Ring matrices through which the material is held 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. A method according to the invention 05895 00070 552 001000280000000200012000285910578400040 0002019936612 00004 05776ngs a suitable apparatus is described, for example, in German published patent application DE 38 16 842 described. The ring die press disclosed in this document consists of a rotating ring die penetrated by press channels and at least one with their The inner surface is in operative connection with the press roller that feeds the die space Presses material through the press channels into a material discharge. Here are ring matrix and Press roller can be driven in the same direction, which results in reduced shear stress and thus  lower temperature increase of the premix is feasible. Of course you can but also in the pelletizing with heatable or coolable rollers to work set the desired temperature of the premix.

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

Another press agglomeration process which can be used according to the invention is the tableting. Due to the size of the molded body it can be Tableting may be useful, in addition to the 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 be used either directly as washing or Detergents used or previously treated by conventional methods and / or be 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.

Examples

Agents E1 and E2 according to the invention were composed of individual components mixed, with citric acid being metered in such a way that the agents are an alkali product of Had 10.7 ± 0.4. The comparative examples were prepared analogously, but contain Common builder systems based on zeolite or soda and acrylic / maleic acid copolymer (see Table 1). All of the detergents produced contained 9.5% by weight of sodium alkyl benzenesulfonate, 4.1% by weight fatty alcohol ethoxylate, 1.0% by weight soap, 11.6% by weight % Sodium percarbonate (E1, V1, V3) or 16.7% perborate tetrahydrate (E2 / V2), 2.4% by weight TAED, 2.0% by weight of enzyme granules and other auxiliaries. In addition, the Detergent builder according to Table 1 and to 100 wt .-% water, salts and other in small amounts of detergent ingredients used (e.g. defoamers, dyes).

Table 1

Builder in the investigated detergents (in% by weight based on the total detergent and anhydrous active substance)

The detergents were tested under practical conditions in household washing machines seem. For this purpose, the machines with 3.0 kg of clean laundry and 0.5 kg Loaded test fabric, the test fabric for examining the Primary washing behavior was partially impregnated with usual test soiling and Secondary washing ability test consisted of white fabric. As white Test fabrics were strips of standardized cotton fabric (laundry research Krefeld Institute; WFK), nettle (BN), knitwear (cotton jersey; B) and terry fabric (FT) used. The graying was determined in the last 5 washes Streak areas with 3 g of dust I skin fat on cotton yarn (15 g) added. Washing conditions  gen: tap water of 23 ° d (equivalent to 230 mg CaO / l), amount of detergent used per medium and machine: 135 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.

According to the dosage of 135 g detergent per machine, the in the wash liquor Amounts of builder given in Table 2.

Table 2

With a dosage of 135 g, quantities of builder contained in the wash liquor.

In the primary washing behavior, none were found in the examples according to the invention significant differences from the comparison test. After 25 washing cycles the Ash content of the textile samples determined in duplicate.

Claims (30)

1. washing or cleaning agent containing at least one anionic surfactant and essentially no aluminosilicate, characterized in that it is a soluble builder system, consisting essentially of a) an alkali silicate with a module M ₂ O: SiO ₂ , where M stands for an alkali metal ion , from the range from 1: 1.9 to 1: 3.3, b) alkali carbonate, c) an oxidatively modified oligosaccharide, d) a phosphonate capable of complex formation and e) optionally an acid component, contains less of the soluble builder system than 40% by weight of the total agent and the alkali product of the agent is in the range of 7.0 to 11.4. 2. washing or cleaning agent according to claim 1, characterized in that during of the washing cycle in a household washing machine a maximum of 45 g, preferably between 10 and 35 g of the soluble builder system can be used. 3. washing or cleaning agent according to claim 1 or 2, characterized in that the components

• a) in the agent in amounts of 0.5 to 20 wt .-%, preferably in amounts of 3 to 10 wt .-%;
• b) in amounts such that the content of alkali metal carbonate active in the wash liquor is 5 to 30% by weight, preferably 10 to 25% by weight and in particular at least 15% by weight;
• c) in amounts of 0.5 to 8% by weight, preferably in amounts of 2 to 6.5% by weight
• d) in amounts of 0.05 to 2.0% by weight, preferably in amounts of 0.1 to 1% by weight,
• e) in amounts of 0 to 10.0% by weight, preferably in amounts of 0.1 to 5% by weight, are contained.

4. washing or cleaning agent according to one of claims 1 to 3, characterized characterized in that the alkali product of the agent is in the range of 8.5 to 11.2. 5. washing or cleaning agent according to one of claims 1 to 4, characterized characterized in that the oxidatively modified oligosaccharide is a oxidized dextrin derivative, especially a polysaccharide with a dextrose Equivalent (DE) in the range from 0.5 to 40, more preferably in particular from 2 to 30,  where DE is a common measure of the reducing effect of a polysaccharide in Compared to dextrose, which has a DE of 100. 6. washing or cleaning agent according to one of claims 1 to 5, characterized characterized in that the oxidatively modified oligosaccharide is a Maltodextrin with a DE between 3 and 20 or a dry gui syrup with a DE between 20 and 37 or a so-called yellow dextrin or a white dextrin with higher molar masses in the range from 2000 to 30,000 g / mol or mixtures of such Connections. 7. washing or cleaning agent according to one of claims 1 to 6, characterized characterized in that the oxidatively modified oligosaccharide is a Dextrin acts, in which at least one alcohol function of the saccharide ring for Carboxylic acid function is oxidized. 8. washing or cleaning agent according to one of claims 1 to 7, characterized characterized in that the oxidatively modified oligosaccharide is a Oligosaccharide acts, which at its original reducing end instead of Group -CH (OH) -CHO has a group -COOH. 9. washing or cleaning agent according to one of claims 1 to 8, characterized characterized in that the agent in addition to the modified oligosaccharide contains at least one polymeric polycarboxylate, where it is in the polymer Polycarboxylates around a polymeric polycarboxylate with a molecular weight smaller 10000 g / mol, in particular a homopolymeric polyacrylate, or a copolymeric polycarboxylate, which is preferably a copolymer of (meth) - is acrylic acid with maleic acid, and a molecular weight in the range of 20,000 to Has 70000 g / mol and the ratio of c) to the polymeric polycarboxylates preferably in the range from 2: 1 to 1:20, particularly preferably in the range from 1: 1 to 1:15. 10. washing or cleaning agent according to one of claims 1 to 8, characterized characterized in that the agent contains no polymeric polycarboxylate. 11. Detergent or cleaning agent according to one of claims 1 to 10, characterized characterized in that the acidic component e) the washing or  Detergent was added afterwards, the acid component either alone or in the form of compounds with others, preferably neutral reacting, detergent or cleaning agent ingredients is present. 12. Washing or cleaning agent according to one of claims 1 to 11, characterized in that component a) is an amorphous sodium silicate, which is preferably a module Na ₂ O: SiO ₂ in the range from 1: 2 to 1 : 2.8, and component c) is a modified oligosaccharide, the average degree of oligomerization of the modified oligosaccharide being in the range from 2 to 20, in particular 2 to 10, and component e) is citric acid. 13. Detergent and cleaning agent according to one of claims 1 to 12, characterized characterized in that originally in the modified oligosaccharide c) an arabionic acid unit is present in the reducing end of the oligosaccharide. 14. Washing or cleaning agent according to one of claims 1 to 13, characterized characterized in that the agent contains sodium percarbonate as the bleaching component, wherein the sodium percarbonate contains at least 30% by weight of the active in the wash liquor Alkali carbonate forms. 15. A process for the preparation of a detergent or cleaning agent which is essentially contains no aluminosilicate, characterized in that an acidic in the agent acting component is metered so that the alkali product of the resulting agent in is in the range of 7.0 to 11.4 and the agent is an oxidatively modified Contains oligosaccharide. 16. The method according to claim 15, characterized in that it is oxidative modified oligosaccharide around an oxidized dextrin derivative, especially a Polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40 preferably in particular from 2 to 30, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose, which a DE of 100 owns, acts. 17. The method according to any one of claims 15 or 16, characterized in that it is in the oxidatively modified oligosaccharide around a maltodextrin with a DE  between 3 and 20 or a dry glucose syrup with a DE between 20 and 37 or a so-called yellow dextrin or a white dextrin with higher molar masses in Range of 2000 to 30,000 g / mol or mixtures of such compounds. 18. The method according to any one of claims 15 to 17, characterized in that it is the oxidatively modified oligosaccharide is a dextrin in which at least one alcohol function of the saccharide ring is oxidized to the carboxylic acid function. 19. The method according to any one of claims 15 to 18, characterized in that the Oligosaccharide at its originally reducing end instead of the group -CH (OH) - CHO has a group -COOH 20. A method for producing a detergent or cleaning agent according to one of the Claims 15 to 19, characterized in that the alkali product of the resulting Lies in the range of 8, 5 to 11, 2. 21. A method for producing a detergent or cleaning agent according to one of the Claims 15 to 20, characterized in that different particulate Components that contain detergent and / or cleaning agent ingredients and together form at least 60% by weight of the total agent, mixed together become. 22. A method for producing a detergent or cleaning agent according to one of the Claims 15 to 21, characterized in that the acid component the detergent or cleaning agent is subsequently mixed, the acid component acting either alone or in the form of compounds with others, preferably neutral reacting detergent or cleaning agent ingredients is added. 23. A method for producing a detergent or cleaning agent according to one of the Claims 15 to 22, characterized in that aqueous preparations of the Alkali silicate and the alkali carbonate together with other washing and / or Detergent ingredients are sprayed in a drying facility.   24. A method for producing a washing or cleaning agent according to claim 23, characterized in that the drying device is a drying tower for spray drying. 25. A method for producing a detergent or cleaning agent according to one of the Claims 15 to 24, characterized in that the mixture is then a Compaction step are subjected, whereby further ingredients are the agents after the compacting step. 26. A method for producing a detergent or cleaning agent according to one of the Claims 15 to 25, characterized in that the compacting as Press agglomeration is carried out. 27. A method for producing a washing or cleaning agent according to claim 26, characterized in that the press agglomeration in a roller compactor is carried out. 28. A method for producing a washing or cleaning agent according to claim 26, characterized in that the press agglomeration is carried out as an extrusion. 29. A process for washing textiles, characterized in that a detergent containing a soluble builder system, consisting essentially of a) an alkali silicate with a module M ₂ O: SiO ₂ , where M stands for an alkali metal ion, in the range from 1: 1, 9 to 1: 3.3, b) an alkali carbonate, c) an oxidatively modified oligosaccharide, d) a phosphonate capable of complex formation and e) optionally an acid component, at least one anionic surfactant and essentially no aluminosilicate, is used . 30. The method according to claim 29, characterized in that the agent is dosed so that during the washing cycle in a household washing machine a maximum of 45 g, preferably between 10 and 35 g, of the soluble builder system are used.