CA2315341A1 - Low-dosage soluble builder - Google Patents

Abstract

The invention relates to a soluble builder system for detergents which is free from phosphates and alumosilicates. Detergents according to the invention contain a soluble builder system which essentially consists of a) an alkali metal silicate with an M2O:SiO2 modulus, where M is an alkali metal ion, of 1:1.9 to 1:3.3, b) an alkali metal carbonate, c) an oxidatively modified oligosaccharide, d) a phosphonate capable of complexing and e) optionally an acidic component, the soluble builder system making up less than 40% by weight of the detergent as a whole and the alkali product of the detergent being in the range from 7.0 to 11.4.

Description

LOW-DOSAGE SOLUBLE BUILDER
Field of the Invention This invention relates to phosphate-free detergents containing a soluble builder system with no alumosilicates.
Background of the Invention Builders or builder systems in detergents perform a number of functions which have changed considerably in recent years and decades with the constant changes in the composition, supply form and production of detergents. Modern detergents now contain around 30 to 60% by weight of builders. Builders are among the most important classes of substances for the production of detergents.
On account of the diversity and evolution of detergent systems as indicated here, the tasks performed by builders are many-faceted and have not been completely or quantitatively defined. However, the main requirements they are expected to meet are easy to describe and include above all softening of water, boosting of the detersive effect, inhibition of redeposition and dispersion of soil. Builders are intended to contribute to the alkalinity required for the washing process, to show a high absorption capacity for surfactants, to improve the effectiveness of the surfactants, to make positive contributions to the properties of the solid products, for example in powder form, and hence to have a structure-forming effect or even to ease dust emission problems. These various requirements cannot normally be satisfied by one builder component alone so that it is generally necessary to use a system of builders and co-builders.
Phosphorus- and/or nitrogen-containing builders as detergent components have come in for criticism on ecological grounds. The three-dimensionally crosslinked water-insoluble sodium alumosilicate, zeolite NaA, is now widely used, especially in laundry detergent formulations.
However, so-called co-builders have to be used to a considerable extent with this builder, particularly in laundry detergents, in order above all to counteract unwanted incrustation. Polymeric polycarboxylates, especially copolymers based on acrylic acid and malefic acid with molecular weights of 20,000 to 100,000 g/mol, in conjunction with soda are now widely used together with zeolite NaA for this purpose. However, these synthetic polymers of unsaturated mono- and dicarboxylic acids are not readily biodegradable. From the ecological point of view, therefore, it appears desirable to replace these polymers by other materials with better biological degradability.
Oxidized oligosaccharides with a carboxylic acid function at the originally reducing end are described in European patent application EP 0 874 890. These oligosaccharides are very similar to the natural oligosaccharides. It would therefore be logical to assume that these compounds are just as readily biodegradable. It is shown in the patent application in question that zeolite-containing detergents incorporating such modified oligosaccharides are comparable in their washing performance with detergents which contain malefic acid/acrylic acid copolymers instead of the oligosaccharides.
At the same time as the development of zeolite NaA as a builder, it was proposed to use selected water-soluble amorphous sodium silicate compounds are builders in detergents, cf. for example US-PSS 3,912,649, 3,956,467, 3,838,193 and 3,879,527. These documents describe amorphous sodium silicate compounds - which have been produced by spray drying of aqueous waterglass solutions and grinding, compaction, spheronizing and additional drying of the ground material - as builders. EP-A-0 444 415 describes detergents containing 5 to 50% by weight of at least one surfactant, 0.5 to 60% by weight of a builder and typical washing aids, these detergents being characterized in that an amorphous low-water sodium disilicate containing from 0.3 to 6% by weight of water is used as the builder.
DE-OS 2240309 describes a zeolite-free detergent containing 5 to 40% by weight of surfactant, 30 to 70% by weight of alkali metal carbonate, 1 to 30% by weight of complexing agent, preferably citrate, and 0.05 to 15% by weight of a deposition inhibitor for calcium carbonate. This deposition inhibitor is either a phosphate, a phosphoric acid or a polymeric carboxylate.
DE-A-44 42 977 is concerned with detergents having a reduced zeolite content. The extruded detergents produced in accordance with this document, which have bulk densities above 600 g/I, contain anionic and optionally nonionic surfactants and water-soluble builders, such as sodium carbonate and amorphous sodium silicate, in such quantities that zeolite can be completely or partly replaced without any process-related problems in the production of these detergents by extrusion. To achieve this, the zeolite content (based on water-free active substance) is limited to an average of less than 19% by weight and the combined sodium carbonate and amorphous sodium silicate content (based on water-free active substance) is adjusted to a value of 10 to 40% by weight, the ratio by weight of sodium carbonate to sodium silicate being from 5:1 to 1:10 and the sodium carbonate used being at least partly granular.
International patent application WO 98120105 describes a phosphate- and alumosilicate-free detergent which, besides surfactants and polyethylene glycol, contains a builder system based on carbonate, sulfate, silicate and polycarboxylate. The advantages of this detergent include the price and environmental behavior of the builder system.
Preferred embodiments are characterized by a ratio of sodium carbonate to sodium silicate of 1:1 to 1:3.
Earlier German patent application DE 199 126 79 describes a zeolite-free builder system which consists of alkali metal silicate, alkali metal carbonate, polymeric polycarboxylate with a molecular weight of <
10,000 g/mol, phosphonate and an acidic component. This soluble builder system is used in a low dosage, i.e. less than 40% by weight of the detergent is made up by the builder system and the alkali product of the detergent is in the range from 7.0 to 11.4. This soluble builder system has advantages over a zeolite-containing builder system, particularly in regard to residue behavior.
Summary of the Invention It has now been found that detergents containing a zeolite-free soluble builder system have advantages over comparable detergents with a zeolite-based builder system providing the detergents contain modified oligosaccharides instead of the polymeric polycarboxylates.
In a first embodiment, therefore, the present invention relates to detergents containing at least one anionic surfactant and essentially no alumosilicate, characterized in that they contain a soluble builder system essentially consisting of a) an alkali metal silicate with a ratio of M20:Si02 (modulus), where M is an alkali metal ion, of 1:1.9 to 1:3.3, b) an alkali metal carbonate, c) an oxidatively modified oligosaccharide, d) a phosphonate capable of complexing and e) optionally an acidic component, in that the soluble builder system makes up less than 40% by weight of the detergent as a whole and in that the alkali product of the detergent is in the range from 7.0 to 11.4.
The alkali product is a quantity which is indicative of the alkalinity of detergents. The alkali product is determined by pH titration of a 10% by weight solution of the detergent in water using a pH electrode and 1.0 molar hydrochloric acid. The alkali product is calculated as follows:
10~0.4~ V
Alkali product = + initial pH
E~6 where V is the consumption of 1.0 molar HCI at pH 10 (in ml) E is the sample weight in g initial pH is the pH of the 10% by weight solution.

If the alkali product is above 10, it may be regarded as indicative of the initial pH and the buffer capacity of the solution. If it is below 10, it is identical with the initial pH and cannot be taken as an indication of the buffer behavior of the solution.
Detailed Description of the Invention The alkali product of the detergents according to the invention is in the range from 7.0 to 11.4 and preferably in the range from 8.5 to 11.2. In one particularly preferred embodiment of the invention, the detergent has an alkali product of 10.7 ~ 0.4.
The alkali product of the detergent is determined by the composition according to the invention and can be influenced as required in particular through the acidic component. Any acidic components suitable for use in detergents may be used for this purpose. These components may be both carboxylic acids and mineral acids or acidic salts of mineral acids.
Particularly preferred carboxylic acids are those which are also suitable as co-builders. These include in particular polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) - providing its use is not ecologically problematical - and mixtures thereof. These acids may be used either in water-free form or in the form of their hydrates. Suitable mineral acids include, in particular, sulfuric acid, phosphoric acid, carbonic acid and hydrochloric acid and acidic salts thereof. Preferred acidic components in the detergents according to the invention are citric acid and/or sodium hydrogen sulfate, the use of citric acid on its own representing a particularly advantageous embodiment. However, the content of the acidic component in the detergent is preferably no more than 10.0% by weight. In particularly preferred embodiments, it is in the range from 0.1 to 5% by weight. In principle, the acidic component may be added at any stage in the production of the detergent. In a preferred embodiment, however, the acidic component is subsequently added to the detergent, being used either on its own or in the form of compounds with other, preferably neutrally reacting, detergent ingredients.
The total builder content is also crucial to the alkali product. In the detergents according to the invention, it should not be any more than 40%
by weight and, in one preferred embodiment of the invention, is in the range from 20 to 35% by weight. Particularly low builder contents are possible when the alkali metal carbonate active in the wash liquor is not directly introduced, for example in the form of soda, but is made available for the most part by precursors which only form alkali metal carbonate during the process. Alkali metal percarbonate is mentioned in particular in this regard, releasing alkali metal carbonate under the influence of moisture. For example, the sodium percarbonate preferably used as bleaching agent provides 68% of its weight as soda in the wash liquor. If sodium percarbonate is used as bleaching agent, it provides at least 30%
by weight and, in a preferred embodiment, even more than 50% by weight of the total alkali metal carbonate active in the wash liquor. Nevertheless, sodium percarbonate does not count as part of the soluble builder system according to the invention because it is primarily a bleaching agent.
Accordingly, in detergents containing sodium percarbonate as bleaching agent, particularly low contents of the soluble builder system can be established without any adverse effect on the washing properties.
Corresponding detergents preferably contain only 10 to 25% by weight of the soluble builder.

In view of the low builder content, particularly in relation to the possible surfactant content, the detergents can also be used in low doses in the washing process. Thus, in one preferred embodiment, the dosage of detergent is such that at most 45 g and preferably between 10 and 35 g of the soluble builder system are used during the wash cycle in a domestic washing machine. The quantities of builder present in the wash liquor ensure that the builders perform an adequate water-softening function. In one preferred embodiment, the quantity or dose in which the builder system is used is largely independent of the hardness of the water. With high water hardness levels, however, the builder is preferably used in the wash cycle in a dose or quantity in the upper half of the above-mentioned range of 20 to 45 g and, more particularly, 25 to 35 g.
Accordingly, the present invention also relates to a process for washing textiles in which a detergent according to the invention is used. In the process according to the invention, the detergent is preferably used in such a quantity that at most 45 g and preferably between 10 and 35 g of the soluble builder system is used during the wash cycle in a domestic washing machine. In one preferred embodiment, the quantity or dose in which the builder system is used is largely independent of the water hardness value. However, with high water hardness levels, the builder is preferably used in the wash cycle in a quantity or dose in the upper half of the above-mentioned range of 20 to 45 g and, more particularly, 25 to 35 g.
The alkali metal carbonates used in the builder system are preferably sodium and/or potassium carbonate, sodium carbonate being particularly preferred. The content of these alkali metal carbonates is preferably selected so that the content of alkali metal carbonate active in the wash liquor makes up 5 to 30% by weight, preferably 10 to 25% by weight and more preferably at least 15% by weight of the detergent as a whole.

The oxidatively modified saccharide to be used in accordance with the invention is a compound selected from the class of oxidized starches or starch derivatives, more particularly thermally or enzyme-degraded starch derivatives. Like glycogen or cellulose, starch is a homoglycan. Starch consists of three different D-glucopyranose polymers, amylose, amylopectin and a so-called intermediate fraction, which is also known as anormal amylopectin, and water (ca. 20%, according to type and storage conditions), relatively small quantities of protein, fats and phosphoric acid in an ester-like linkage. The content of these various constituents in the starch varies according to type. Higher plants contain 0 to 40% of amylose, based on the dry matter. Structurally, the intermediate fraction stands between amylose and amylopectin. In starch analyses, the intermediate fraction is mostly assigned to amylopectin.
Amylose consists of predominantly linear a-1,4-glycosidic D
glucose. Diffusion amylose is the term used for that part of the amylose which is soluble in water at temperatures below 100°C. Diffusion amylose free from amylopectin is obtained at temperatures of 60 to 7°C. Starch containing more than 70% of amylose is known as high-amylose starch, for example pea pulp starch (70% amylose) and amylocorn starch (>50%
amylose). The water and amylose content of starch is determined by NIR
spectroscopy. The chains form double helices.
Besides the a-1,4 links described for amylose, amylopectin also contains 4 to 6% of a-1,6 links:
Amylo-pectin The average interval between the branch points is about 12 to 17 glucose units. The molecular weight (MR = 107-108) corresponds to around 105 glucose units, so that amylopectin belongs to the largest biopolymers. The branches are distributed over the molecule in such a way that a cluster structure with relatively short side chains is formed. Two of these side chains together form a double helix. By virtue of the numerous branch points, amylopectin dissolves relatively easily in water and is better degraded by enzymes. The crystallinity of a starch granule and the gelatinization energies increase with increasing amylopectin content.
Starches which contain only amylopectin (from certain corn and potato varieties) are known as waxty varieties. The appearance of the starch granules is typical of the particular source plant. Amylose provides complexes in which organic or other molecules are incorporated in the helix structure. With iodine, it forms the blue colored iodine/starch complex of which the absorption maximum is dependent 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 on cooling.
Starch is a reserve carbohydrate which many plants store in various parts in the form of 1-200 mm large starch grains, for example in tubers or roots [potatoes, arrowroot, cassava, (tapioca), sweet potatoes], in cereal seed (wheat, corn, rye, rice, barley, millet, oats, sorghum), in fruits (chestnuts, acorns, peas, beans and other pulses, bananas) and in pulp (sago palm).
Starch from vegetable raw materials is preferably obtained from flour of corn, potatoes, wheat, rice and cassava (tapioca), the starch granules being mechanically released from the cell structure by the wet method after removal of the gluten. World-wide, corn is the most important source crop for starch.

In principle, oxidation processes on starch or starch derivatives, more particularly starch pyrolyzates or enzymatic degradation products of starch, may be carried out with any suitable oxidizing agent. Terminal aldehyde groups may be oxidized to acid functions and/or alcohol functions 5 may be oxidized to aldehyde or acid functions. However, preferred oxidatively modified starch derivatives essentially contain only alcohol and acid functions. The presence of aldehyde functions is undesirable in the starch derivatives preferably used in accordance with the present invention.
In principle, however, oxidized starches also include dialdehyde starches 10 which accumulate in the treatment of starches with selective oxidizing agents, for example periodic acid. However, these polymers tend to crosslink and form water-insoluble films. Accordingly, their use in detergents according to the invention is not preferred and is only possible in combination with very specific ingredients. If these dialdehyde starches are further oxidized to dicarboxy starches, in which units of the following type:
H Q
v HO'OC COOIii ~
are present as a complexing group, such compounds may very well be present in the detergents according to the invention.
Broadly speaking, various oxidizing agents are commonly .used for oxidizing polysaccharides, more especially polyglucosans made up exclusively of glucose. These include, for example, (atmospheric) oxygen, hydrogen peroxide, sodium hypochlorite or bromite, periodic acid or periodates, lead(IV) acetate, nitrogen dioxide and cerium(IV) salts. These oxidizing agents react very differently with the anhydroglucose units. For example, periodates or lead(IV) acetate promote C-C cleavage of the anhydroglucose rings. So-called 2,3-dialdehyde cellulose is obtained from cellulose and dialdehyde starch is similarly obtained from starch. In addition, it is known that, where cellulose is exposed to the action of nitrogen dioxide, oxidation of the primary alcohol group to the carboxyl group is by far the dominant reaction. The oxidizing agent, which is generally present in equilibrium with dinitrogen tetroxide, may be used either in gaseous form or in the form of a solution in an inert organic solvent. Even where starch is the starting material, the primary alcohol groups of the anhydroglucose units can also be largely selectively oxidized to the carboxyl group. Thus, the oxidation of starch with gaseous nitrogen dioxide or with nitrogen dioxide dissolved in water or in various organic solvents is known from US patent 2,472,590.
Under these conditions, the substantially complete conversion of the primary alcohol groups or the polysaccharides into carboxyl groups is only achieved after very long reaction times which, in some cases, can amount to several days. In addition, large quantities of nitrogen dioxide, based on the polysaccharide to be oxidized, are required in the known processes. A
significant improvement in the production of such polysaccharide oxidation products is known from International patent application WO 93116110. The invention disclosed in that document is based on the discovery that poly-carboxylates can be obtained in high yields from polysaccharides by a simple process in which the oxidation reaction with nitrogen dioxide/
dinitrogen tetroxide is carried out in the presence of oxygen at elevated temperatures and preferably at elevated pressures. The words "nitrogen dioxide/dinitrogen tetroxide" stand for the equilibrium mixture of nitrogen dioxide and its dimer, dinitrogen tetroxide, which is present under the particular reaction conditions.

If the variant of suspension-medium-free and solvent-free oxidation described in this document is carried out with gaseous nitrogen dioxide/
dinitrogen tetroxide, a solid polysaccharide selectively oxidized at C6 is obtained. This sparingly water-soluble acid form is not preferred for direct use as a builder or builder component (co-builder) in detergents. In general, it is preferred to use the oxidized polysaccharide in the form of a water-soluble salt, i.e. the neutralization product of the polycarboxylic acid obtained in the oxidation process. This neutralization may be carried out with aqueous base. Where this procedure is adopted, aqueous solutions of the polycarboxylate are obtained so that an energy-intensive drying step has to be carried out to obtain the polycarboxylate as a solid. This may be acceptable in the production of solid detergents where an "aqueous"
working-up step is included for the removal of nitrate and nitrite immediately after the actual oxidation reaction and the further processing of the aqueous neutralized polycarboxylate solution in spray drying processes. The accumulation of aqueous polycarboxylate solutions is a disadvantage in the production of detergents by processes which involve the mixing of solid components because the removal of water from the polycarboxylate solution and the conversion of the dissolved polycarboxylate into a solid is unavoidable in their case.
In a preferred process variant described in German patent application DE-A-44 26 443, which eliminates the need both for the "aqueous" working-up of the reaction products of polysaccharides with nitrogen dioxide/dinitrogen tetroxide and for their vacuum treatment, but which still gives products having acceptably low nitrate and nitrite contents providing the supply of the oxidizing agent nitrogen dioxide/dinitrogen tetroxide is terminated before the end of the actual oxidation reaction and the temperature is increased to a value above the reaction temperature, the aqueous neutralization of the polycarboxylic acid thus produced and the subsequent drying of the aqueous polycarboxylate solution appear almost paradoxical.
Accordingly, a process for the production of solid polycarboxylic acid salts from polysaccharides by oxidation with gaseous nitrogen dioxide/
dinitrogen tetroxide, the primary alcohol groups of the polysaccharides being at least partly converted into carboxyl groups and the carboxylic acid groups formed being at least partly neutralized, characterized in that the solid polycarboxylic acid is mixed with a solid neutralizing agent, is particularly preferred. This process is described in German patent application DE-A-195 07 717.
In this process, the oxidation of the polysaccharide preceding the neutralization step is preferably carried out 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/dinitrogen tetroxide is only continued until only at most 90%, preferably 60% to 85% and more preferably 65% to 80% of the required degree of oxidation, i.e. the degree of conversion of the primary alcohol groups into carboxyl groups, has been achieved. The required degree of oxidation is only fully achieved in the post-oxidation phase, i.e. after the supply of nitrogen dioxide/dinitrogen tetroxide has been terminated and the temperature has been increased by at least 10°C, preferably by 15°C to 80°C and more preferably by 20°C to 50°C in relation to the oxidation phase. It is important in this connection to ensure that an upper temperature limit of 160°C is not exceeded by the increase in temperature because decomposition has increasingly been observed at higher temperatures.
The oxidation reaction, which has to be terminated before the conversion is complete, is preferably carried out at temperatures of 30°C to 70°C and more preferably at temperatures of 40°C to 60°C.
Oxygen may be present either on its own or in the form of a mixture with a gas which is inert under the reaction conditions and which may be added either all at once at the beginning of the reaction or several times, if desired continuously, during the reaction. Where the second of these two alternatives is adopted, the oxidation reaction may be controlled through the introduction of oxygen as a function of temperature or pressure. The addition of oxygen is preferably controlled in such a way that the reaction temperature stays in the range from 30°C to 70°C.
Suitable inert gases, i.e. gases which do not react under the particular process conditions applied, include noble gases, such as helium or argon, and carbon dioxide, but especially nitrogen, nitrogen monoxide and dinitrogen monoxide and mixtures thereof. The oxygen content in the gas mixture is preferably in the range from 1 % by volume to 30% by volume and more preferably in the range from 3% by volume to 10% by volume. In one preferred embodiment of the process according to the invention, the oxygen is introduced in the form of air under pressure.
Another preferred embodiment of the process is characterized in that a pressure of less than 10 bar and, more particularly, a pressure of 2 bar to 6 bar at the required reaction temperature is adjusted in the reaction system before the beginning of the oxidation reaction by introducing one of the above-mentioned inert gases under pressure and then adding oxygen or a mixture of oxygen with one of the inert gases mentioned, repeatedly, if desired continuously, under pressure. Nitrogen dioxide/dinitrogen tetroxide may be added before or after the oxygen or before or after the beginning of the addition of the oxygen. It may be necessary to heat the reaction vessel to the required reaction temperature after the initial introduction of the inert gas under pressure. During the oxidation reaction, which is preferably carried out with intensive mixing of the reactants, the reaction temperature may generally be maintained solely by the amount of oxygen added, i.e.
without any need for external heating.

In the oxidation step of the process according to the invention, the oxidizing agent acts directly from the gas phase on the solid, intensively mixed polysaccharide substrates. The oxidation is preferably carried out in a fluidized bed of polysaccharide where the fluidizing agent is a gas 5 containing nitrogen dioxide. One such oxidation process is described in German patent application DE-A-44 02 851. In the present context, a fluidized bed is understood to be the phenomenon observed when gases known as fluidizing agents flow from beneath through a layer of loose fine-particle material on horizontal perforated plates. However, the invention is 10 by no means limited to this particular method of generating the fluidized bed.
A particularly preferred class of oxidatively modified oligo-saccharides are oxidized dextrin derivatives. Dextrins are, for example, oligomers or polymers of carbohydrates which can be obtained by partial 15 hydrolysis of the starches. The hydrolysis may be carried out by standard processes, for example acid- or enzyme-catalyzed processes. The oligomers of polymers are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000 g/mol. A
polysaccharide having a dextrose equivalent (DE) in the range from 0.5 to 40 and more particularly in the range from 2 to 30 is preferably used, DE
being a standard measure of the reducing effect of a polysaccharide by comparison with dextrose which has a DE of 100. Both maltodextrins with a DE of 3 to 20 and dry glucose syrups with a DE of 20 to 37 and so-called yellow dextrins and white dextrins with relatively high molecular weights in the range from 2,000 to 30,000 g/mol may be used. A preferred dextrin is described in British patent application 94 19 091. The oxidized derivatives of such dextrins are reaction products thereof with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Corresponding oxidized dextrins and processes for their production are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and from International patent applications WO 92118542, WO 93108251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95112619 and WO 95/20608.
An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also preferred. The preferred monomer in this oligosaccharide, which is preferably used after oxidative modification for the purposes of the invention, is glucose. The average degree of oligomerization, which - as an analytically determined quantity - may even be a broken number, is preferably in the range from 2 to 20 and more preferably in the range from 2 to 10. The oligosaccharide preferably used as a builder or co-builder has been oxidatively modified at its originally reducing end with the loss of 1 carbon atoms. If the originally reducing end of the oligosaccharide had been an anhydroglucose unit, an arabinonic acid unit would be present after the modification: (glucose)"+~ ~ (glucose)"
arabinonic acid.
This oxidative modification may be carried out, for example, using Fe, Cu, Ag, Co or Ni catalysts as described in International patent application WO 92/18542, using Pd, Pt, Rh or Os catalysts as described in European patent EP 0 232 202 or using a quinone/hydroquinone system in the alkaline range in conjunction with oxygen, optionally followed by aftertreatment with hydrogen peroxide. The oligosaccharide starting material modifiable by oxidation processes such as these is preferably an oligosaccharide with a dextrose equivalent (DE) of 20 to 50. So-called glucose syrups (DE 20 - 37) and the above-mentioned dextrins, which can both be obtained by partial hydrolysis of starch by standard processes, for example acid- or enzyme-catalyzed processes, and which may be used either as such or in the form of higher polymers, for example as starch, in the oxidation processes mentioned above providing the polymer chain structure of the starch also undergoes corresponding degradation under the oxidation conditions, are particularly suitable. The oligosaccharides thus oxidatively modified preferably have a -COOH group instead of the -CH(OH)-CHO group at the originally reducing end.
The detergents according to the invention preferably contain 0.5%
by weight to 8% by weight and more preferably 2% by weight to 6% by weight of the oxidatively modified oligosaccharide which is normally used in the form of its alkali metal salt. Concentrations of oxidatively modified oligosaccharide in the wash liquor of 0.001 % by weight to 0.05% by weight are preferred for the purposes of the use according to the invention and the washing process according to the invention.
In preferred embodiments of the invention, the alkali metal silicates are amorphous sodium silicates with a modulus (Na20 : Si02 ratio) of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and more preferably 1:2 to 1:2.6 which dissolve with delay and exhibit multiple wash cycle properties. The delay in dissolution in relation to conventional amorphous sodium silicates can have been obtained in various ways, for example by surface treatment, compounding, compacting or by overdrying. In the context of the invention, the term "amorphous" is also understood to encompass "X-ray amorphous". In other words, the silicates do not product any of the sharp X-ray reflexes typical of crystalline substances in X-ray diffraction experiments, but at best one or more maxima of the scattered X-radiation which have a width of several degrees of the diffraction angle. Particularly good builder properties may even be achieved where the silicate particles produce crooked or even sharp diffraction maxima in electron diffraction experiments. This may be interpreted to mean that the products have microcrystalline regions between 10 and a few hundred nm in size, values of up to at most 50 nm and, more particularly, up to at most 20 nm being preferred. So-called X-ray amorphous silicates such as these, which also dissolve with delay in relation to conventional waterglasses, are described for example in German patent application DE-A-4400024. Compacted amorphous silicates, compounded amorphous silicates and overdried X-ray-amorphous silicates are particularly preferred. Granular amorphous silicates having bulk densities of at least 700 g/I can be produced, for example, by the process described in patent application WO 97/34977 which is based on spray drying and which includes compaction of the spray-dried beads. To this end, the spray-dried beads are ground and are simultaneously or subsequently granulated in the presence of a liquid granulation aid, bulk densities of at least 700 g/I up to more than 1,000 g/I
being established.
In one particular embodiment of the invention, the alkali metal silicates may also be used in the form of preparations in which they are present together with alkali metal carbonate.
Another preferred embodiment of the present invention is characterized by the use of crystalline layer-form sodium silicates with the general formula Na2SiX02X+~y H20, where x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x being 2, 3 or 4. Crystalline layer silicates such as these are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layer silicates corresponding to the above formula are those where N is sodium and x has a value of 2 or 3. Both Vii- and b-sodium disilicates Na2Si205yH20 are particularly preferred.
Irrespective of the alkali metal silicate used, the total alkali metal silicate content of the detergents is preferably between 0.5 and 20% by weight and more preferably between 3 and 10% by weight.
Another component of the builder system are phosphonates, more particularly hydroxyalkane and aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly important as a co-builder. It is preferably used in the form of a sodium salt, the disodium salt showing a neutral reaction and the tetrasodium salt an alkaline ration (pH 9). Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and higher homologs thereof. They are preferably used in the form of the neutrally reacting sodium salts, for example as the hexasodium salt of EDTMP and as the hepta- and octasodium salt of DTPMP. Within the class of phosphonates, HEDP is preferably used as builder. The aminoalkane phosphonates also show a pronounced heavy metal binding capacity.
Accordingly, it can be of advantage, particularly where the detergents also contain bleaching agents, to use aminoalkane phosphonates, more especially DTPMP, or mixtures of the phosphonates mentioned. Such phosphonates are normally present in the detergents in quantities of 0.05 to 2.0% by weight and preferably in quantities of 0.1 to 1 % by weight.
Alumosilicates are present in the detergents in only small quantities, if at all. If they are present, it is not for their water-softening effect or for their carrier function. They may be present only when they serve as a granulation aid, for example for "powdering". Accordingly, the crystalline alumosilicate content of the detergents is less than 5% by weight and, preferably, even less than 3% by weight. Zeolites A, P, X and Y are preferably used as the alumosilicates. However, mixtures of A, X, Y and/or P are also suitable. A particularly preferred zeolite P is, for example, the zeolite MAP~ (a commercial product of Crosfield). A co-crystallized sodium/potassium aluminium silicate of zeolite A and zeolite X, which is commercially available as VEGOBOND AX~ (a commercial product of Condea Augusta S.p.A.), is also of particular interest.
Besides the modified oligosaccharide, polymeric polycarboxylates may be present as further co-builders in the detergents according to the invention. The polymeric polycarboxylates are preferably homopolymers or copolymers containing acrylic acid and/or malefic acid units. A particularly preferred embodiment of the invention is characterized by the use of 5 polymers with molecular weights below 10,000 g/I, these polymers preferably being homopolymers of polyacrylic acid. Polyacrylates preferably having a molecular weight of 3,000 to 8,000 and, more preferably, in the range from 4,000 to 5,000 g/mol have proved to be particularly suitable for the purposes of the invention. The molecular 10 weights mentioned in this specification for polymeric polycarboxylates are weight-average molecular weights MW which, basically, were determined by gel permeation chromatography (GPC) using a UV detector. The measurement was carried out against an external polyacrylic acid standard which provides realistic molecular weight values by virtue of its structural 15 similarity to the polymers investigated. These values differ distinctly from the molecular weights measured against polystyrene sulfonic acids as standard. The molecular weights measured against polystyrene sulfonic acids are generally higher than the molecular weights mentioned in this specification. Besides these short-chain polyacrylates, the detergents may 20 also contain copolymeric polycarboxylates with a molecular weight of 20,000 to 70,000 g/mol. Acrylic acid/maleic acid copolymers containing 50 to 90% by weight of acrylic acid and 50 to 10% by weight of malefic acid have proved to be particularly suitable. In order to improve solubility in water, the polymers may also contain allyl sulfonic acids, such as allyloxybenzene sulfonic acid and methallyl sulfonic acid (cf. EP-B-727 448), as monomer. Other particularly preferred polymers are biodegradable polymers of more than two different monomer units, for example those which contain salts of acrylic acid and malefic acid and vinyl alcohol or vinyl alcohol derivatives as monomers according to DE-A 43 00 772 or those which contain salts of acrylic acid and 2-alkylallyl sulfonic acid and sugar derivatives as monomers according to DE-C-42 21 381. Other preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid/acrylic acid salts or acrolein and vinyl acetate as monomers. In another preferred variant, mixtures of the short-chain polyacrylates having molecular weights of <10,000 g/mol with the copolymeric polycarboxylates having molecular weights of 20,000 to 70,000 g/mol are used. Irrespective of which polymeric polycarboxylates are used, it is preferred in accordance with the invention - where polymeric polycarboxylates are used - for the ratio of the modified oligosaccharides to polymeric polycarboxylates to be in the range from 2:1 to 1:20 and more particularly in the range from 1:1 to 1:15. In another preferred embodiment of the invention, however, the detergents do not contain any polymeric polycarboxylate. In that case, the modified oligosaccharide is the sole co-builder.
Important ingredients of the detergents according to the invention are surfactants, more particularly anionic surfactants, which are present in the detergents according to the invention in quantities of at least 0.5% by weight. Such surfactants include in particular sulfonates and sulfates, but also soaps.
Preferred surfactants of the sulfonate type are C9_~3 alkyl benzenesulfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxy-alkane sulfonates, and the disulfonates obtained, for example, from C~2_~$
monoolefins with an internal or terminal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
Other suitable surfactants of the sulfonate type are the alkane sulfonates obtained from C~2-~$ alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization.
The esters of a-sulfofatty acids (ester sulfonates), for example the a-sulfonated methyl esters of hydrogenated coconut oil, palm kernel oil or tallow fatty acids, which are obtained by a-sulfonation of the methyl esters of fatty acids of vegetable and/or animal origin containing 8 to 20 carbon atoms in the fatty acid molecule and subsequent neutralization to water-soluble monosalts are also suitable. The esters in question are preferably the a-sulfonated esters of hydrogenated cocofatty acid, palm oil fatty acid, palm kernel oil fatty acid or tallow fatty acids, although sulfonation products of unsaturated fatty acids, for example oleic acid, may also be present in small quantities, preferably in quantities of not more than about 2 to 3% by weight. a-Sulfofatty acid alkyl esters with an alkyl chain of not more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters, are particularly preferred. The methyl esters of a-sulfofatty acids (MES) and saponified disalts thereof are used with particular advantage.
Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, i.e. the monoesters, diesters and triesters and mixtures thereof which are obtained where production is carried out by esterification by a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol.
Preferred alk(en)yl sulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric acid semiesters of C~2_~$ fatty alcohols, for example cocofatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or Coo-2o oxoalcohols and the corresponding semiesters of secondary alcohols with the same chain length. Other preferred alk(en)yl sulfates are those with the chain length mentioned which contain a synthetic, linear alkyl chain based on a petrochemical and which are similar in their degradation behavior to the corresponding compounds based on oleochemical raw materials. C~2-~s alkyl sulfates and C12-15 alkyl sulfates and also C~4-~5 alkyl sulfates alkyl sulfates are particularly preferred from the washing performance point of view. Other suitable anionic surfactants are 2,3-alkyl sulfates which may be produced, for example, in accordance with US 3,234,258 or US 5,075,041 and which are commercially obtainable as products of the Shell Oil Company under the name of DAN~.
The sulfuric acid monoesters of linear or branched C~_2~ alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C9_~~ alcohols containing on average 3.5 mol of ethylene oxide (EO) or C~2_~$ fatty alcohols containing 1 to 4 EO, are also suitable. In view of their high foaming capacity, they are normally used in only relatively small quantities, for example in quantities of 1 to 5% by weight, in detergents.
Other preferred anionic surfactants are the salts of alkyl sulfosuccinic acid which are also known as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and, more particularly, ethoxylated fatty alcohols. Preferred sulfosuccinates contain C8_~8 fatty alcohol molecules or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol molecule derived from ethoxylated fatty alcohols which, considered in isolation, represent nonionic surfactants (for a description, see below). Of these sulfosuccinates, those of which the fatty alcohol molecules are derived from narrow-range ethoxylated fatty alcohols are particularly preferred. Alk(en)yl succinic acid preferably containing 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof may also be used.
Other suitable anionic surfactants are fatty acid derivatives of amino acids, for example of N-methyl taurine (taurides) and/or of N-methyl glycine (sarcosides). The sarcosides or rather sarcosinates, above all sarcosinates of higher and optionally mono- or poly-unsaturated fatty acids, such as oleyl sarcosinate, are particularly preferred.
Other suitable anionic surfactants are, in particular, soaps which are preferably used in quantities of 0.2 to 5% by weight. Suitable soaps are, in particular, saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and soap mixtures derived in particular from natural fatty acids, for example coconut oil, palm kernel oil or tallow fatty acids. The known alkenyl succinic acid salts may also be used together with these soaps or as soap substitutes.
The anionic surfactants (and soaps) may be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts and, more preferably, in the form of their sodium salts.
Anionic surfactants are present in the detergents according to the invention or are used in the process according to the invention in quantities of preferably 1 % by weight to 30% by weight and more preferably in quantities of 5% by weight to 25% by weight.
Besides the anionic surfactants and the cationic, zwitterionic and amphoteric surfactants, nonionic surfactants above all are preferred.
Preferred nonionic surfactants are alkoxylated, advantageously ethoxylated, more particularly primary alcohols preferably containing 8 to 18 carbon atoms and an average of 1 to 12 mol of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical may be linear or, preferably, 2 methyl-branched or may contain linear and methyl-branched radicals in the form of the mixtures typically present in oxoalcohol radicals. However, alcohol ethoxylates containing linear radicals of alcohols of native origin with 12 to 18 carbon atoms, for example coconut oil fatty alcohol, palm oil fatty alcohol, tallow fatty alcohol or oleyl alcohol, and an average of 2 to 8 EO per mol of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, C~2_~4 alcohols containing 3 EO or 4 EO, C9_~~ alcohols containing 7 EO, C~3_~5 alcohols containing 3 EO, 5 EO, 7 5 EO or 8 EO, C~2_~$ alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C~2_~4 alcohol containing 3 EO and C~2_~s alcohol containing 7 EO. The degrees of ethoxylation mentioned are statistical mean values which, for a special product, may be either a whole number or a broken number. Preferred alcohol ethoxylates have a narrow 10 homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols containing more than 12 EO may also be used, as described above. Examples of such fatty alcohols are (tallow) fatty alcohols containing 14 EO, 16E0, 20E0, 25 EO, 30 EO or 40 EO.
The nonionic surfactants also include alkyl glycosides with the 15 general formula RO(G)x where R is a primary, linear or methyl-branched, more particularly 2-methyl-branched, aliphatic radical containing 8 to 22 and preferably 12 to 18 carbon atoms and G is a glycose unit containing 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is a 20 number - which as an analytically determined quantity may even be a broken number - of 1 to 10 and preferably a number of 1.2 to 1.4.
Other suitable surfactants are polyhydroxyfatty acid amides cor-responding to formula (I):

R'-CO-N-[Z] (I ) in which R'CO is an aliphatic acyl radical containing 6 to 22 carbon atoms, R2 is hydrogen, an alkyl or hydroxyalkyl radical containing 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical containing 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxyfatty acid amides are preferably derived from reducing sugars containing 5 or 6 carbon atoms, more particularly from glucose. The group of polyhydroxy-fatty acid amides also includes compounds corresponding to formula (II):

(ll) R3-CO-N-[Z]
in which R3 is a linear or branched alkyl or alkenyl group containing 7 to 12 carbon atoms, R4 is a linear, branched or cyclic alkylene group or an arylene group containing 2 to 8 carbon atoms and R5 is a linear, branched or cyclic alkyl group or an aryl group or a hydroxyalkyl group containing 1 to 8 carbon atoms, C1_4 alkyl or phenyl groups being preferred, and [Z] is a linear polyhydroxyalkyl group, of which the alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of such a group. Again, [Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy-substituted compounds may then be converted into the required polyhydroxyfatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst, for example in accordance with the teaching of International patent application WO-A-95/07331.
Another class of preferred nonionic surfactants which are used either as sole nonionic surfactant or in combination with other nonionic surfactants, particularly together with alkoxylated fatty alcohols and/or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters preferably containing 1 to 4 carbon atoms in the alkyl chain, more particularly the fatty acid methyl esters which are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in International patent application WO-A-90113533. C~2_~$ fatty acid methyl esters containing on average 3 to 15 EO and, more particularly, 5 to 12 EO are preferred as nonionic surfactants whereas fatty acid methyl esters with a relatively high degree of ethoxylation above all are advantageous as binders, as described above. C~2_~8 fatty acid methyl esters containing 10 to 12 EO may be used both as surfactants and as binders.
Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethyl amine oxide, and the fatty acid alkanolamide type are also suitable. The quantity in which these nonionic surfactants are used is preferably no more, in particular no more than half, the quantity of ethoxylated fatty alcohols used.
Other suitable surfactants are so-called gemini surfactants. Gemini surfactants are generally understood to be compounds which contain two hydrophilic groups and two hydrophobic groups per molecule. These groups are generally separated from one another by a so-called spacer .
The spacer is generally a carbon chain which should be long enough for the hydrophilic groups to have a sufficient spacing to be able to act independently of one another. Gemini surfactants are generally distinguished by an unusually low critical micelle concentration and by an ability to reduce the surface tension of water to a considerable extent. In exceptional cases, however, gemini surfactants are not only understood to be dimeric surfactants, but also trimeric surfactants.
Suitable gemini surfactants are, for example, the sulfated hydroxy mixed ethers according to German patent application DE-A-43 21 022 and the dimer alcohol bis- and trimer alcohol tris-sulfates and -ether sulfates according to German patent application DE 195 03 061. The end-capped dimeric and trimeric mixed ethers according to German patent application DE 195 13 391 are distinguished in particular by their bifunctionality and multifunctionality. Thus, the end-capped surfactants mentioned exhibit good wetting properties and are low-foaming so that they are particularly suitable for use in machine washing or cleaning processes.
However, the gemini polyhydroxyfatty amides or poly-polyhydroxyfatty acid amides described in International patent applications WO-A-95119953, WO-A-95119954 and WO-A-95/19955 may also be used.
Among the compounds yielding H202 in water which serve as bleaching agents, sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate are particularly important. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H202-yielding peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. In one preferred embodiment, sodium percarbonate is used as the bleaching agent, as mentioned above.
The other detergent ingredients include redeposition inhibitors (soil suspending agents), foam inhibitors, bleach activators, optical brighteners, enzymes, fabric softeners, dyes and perfumes and neutral salts, such as sulfates and chlorides in the form of their sodium or potassium salts.
Suitable bleach activators are compounds which form aliphatic peroxocarboxylic acids containing preferably 1 to 10 carbon atoms and more preferably 2 to 4 carbon atoms and/or optionally substituted perbenzoic acid under perhydrolysis conditions. Substances bearing O-and/or N-acyl groups with the number of carbon atoms mentioned and/or optionally substituted benzoyl groups are suitable. Preferred bleach activators are polyacylated alkylenediamines, more particularly tetraacetyl ethylenediamine (TAED), acylated triazine derivatives, more particularly 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycol-urils, more particularly tetraacetyl glycoluril (TAGU), N-acylimides, more particularly N-nonanoyl succinimide (NOSI), acylated phenol sulfonates, more particularly n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, more particularly phthalic anhydride, acylated polyhydric alcohols, more particularly triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and the enol esters known from German patent applications DE-A-196 16 693 and DE-A-196 16 767, acetylated sorbitol and mannitol and the mixtures thereof (SORMAN) described in European patent application EP-A-0 525 239, acylated sugar derivatives, more particularly pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetyl xylose and octaacetyl lactose, and acetylated, optionally N-alkylated glucamine and gluconolactone, and/or N-acylated lactams, for example N-benzoyl caprolactam, which are known from International patent applications WO-A-94/27970, WO-A-94/28102, WO-A-94/28103, WO-A-95/00626, WO-A-95/14759 and WO-A-95/17498. The substituted hydrophilic acyl acetals known from German patent application DE-A-196 16 769 and the acyl lactams described in German patent application DE-A-196 16 770 and in International patent application WO-A-95114075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE-A-44 43 177 may also be used. Bleach activators such as these are present in the usual quantities, preferably in quantities of 1 % by weight to 10% by weight and more preferably in quantities of 2% by weight to 8% by weight, based on the detergent as a whole.
Where the detergents are used in washing machines, it can be of advantage to add typical foam inhibitors to them. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin which have a high percentage content of C~$_24 fatty acids. Suitable non-surface-active foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized, silica and also paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silica or bis-stearyl ethylenediamide. Mixtures of different foam inhibitors, for example mixtures of silicones, paraffins and waxes, may also be used with 5 advantage. The foam inhibitors, more particularly silicone- and/or paraffin-containing foam inhibitors, are preferably fixed to a granular water-soluble or water-dispersible support. Mixtures of paraffins and bis-stearyl ethylenediamides are particularly preferred.
Suitable enzymes are, in particular, enzymes from the class of 10 hydrolases, such as proteases, lipases or lipolytic enzymes, amylases, cellulases and mixtures thereof. Oxidoreductases are also suitable.
Enzymes obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type are preferably 15 used, proteases obtained from Bacillus lentus being particularly preferred.
Of particular interest in this regard are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or of cellulase and lipase or lipolytic enzymes or of protease, amylase and lipase or lipolytic enzymes or protease, lipase or 20 lipolytic enzymes and cellulase, but especially protease- and/or lipase-containing mixtures or mixtures with lipolytic enzymes. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved to be suitable in some cases. Suitable amylases include in particular a-amylases, isoamylases, pullulanases and pectinases.
25 Preferred cellulases are cellobiohydrolases, endoglucanases and ~-glucosidases, which are also known as cellobiases, and mixtures thereof.
Since the various cellulase types differ in their CMCase and avicelase activities, the desired activities can be established by mixing the cellulases in the appropriate ratios.

The enzymes may be adsorbed to supports and/or encapsulated in shell-forming substances to protect them against premature decomposition.
The percentage content of enzymes, enzyme mixtures or enzyme granules is preferably from about 0.1 to 5% by weight and more preferably from 0.1 to about 2% by weight.
In addition to phosphonates, the detergents may contain other enzyme stabilizers. For example, 0.5 to 1 % by weight of sodium formate may be used. Proteases stabilized with soluble calcium salts and having a calcium content of preferably about 1.2% by weight, based on the enzyme, may also be used. Apart from calcium salts, magnesium salts also serve as stabilizers. However, it is of particular advantage to use boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H3B03), metaboric acid (HB02) and pyroboric acid (tetraboric acid H2B40~).
The function of redeposition inhibitors is to keep the soil detached from the fibers suspended in the wash liquor and thus to prevent the soil from being re-absorbed by the washing. Suitable redeposition inhibitors are water-soluble, generally organic colloids, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatine, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and other starch products than those mentioned above, for example degraded starch, aldehyde starches, etc., may also be used.
Polyvinyl pyrrolidone is also suitable. However, cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose, and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone are also preferably used, for example in quantities of 0.1 to 5% by weight, based on the detergent.
The detergents may contain derivatives of diaminostilbene disulfonic acid or alkali metal salts thereof as optical brighteners. Suitable optical brighteners are, for example, salts of 4,4'-bis-(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)-stilbene-2,2'-disulfonic acid or compounds of similar structure which contain a diethanolamino group, a methylamino group and anilino group or a 2-methoxyethylamino group instead of the morpholino group. Brighteners of the substituted diphenyl styryl type, for example alkali metal salts of 4,4'-bis-(2-sulfostyryl)-diphenyl, 4,4'-bis-(4-chloro-3-sulfostyryl)-diphenyl or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)-diphenyl, may also be present. Mixtures of the brighteners mentioned may also be used.
The detergents according to the invention may have any bulk densities. The range of possible bulk densities extends from low values below 600 g/I, for example 300 g/I, through medium values of 600 to 750 g/I
to high values of at least 750 g/I. However, in one preferred variant of the detergents according to the invention with high bulk densities, the bulk density is even above 800 g/I, bulk densities above 850 g/I being particularly advantageous. With supercompactates such as these, the advantages of the soluble builder system assume particular relevance because detergents as compact as these impose particular demands on their ingredients if they are to be readily dispersible. In addition, irrespective of the bulk density, the low-dosage builder system affords additional advantages by saving on packaging volume and reducing the input of chemicals per wash cycle into the environment.
Detergents of the type in question may be produced by any of the methods known from the prior art. The only important requirements so far as the invention is concerned is that an acidic component is present in the detergent in such a quantity that the resulting detergent has an alkali product of 7.0 to 11.4. As described above, the alkali product is preferably in the range from 8.5 to 11.2.
The detergents are preferably produced by mixing together various particulate components which contain detergent ingredients and which together make up at least 60% by weight of the detergent as a whole.
In one particularly preferred embodiment, the acidic component is subsequently added to the detergent, the acidic component being added either on its own or in the form of a compound with other preferably neutrally reacting detergent ingredients.
The particulate components may be produced by spray drying, simple mixing or complex granulation processes, for example fluidized-bed granulation. In one particularly preferred embodiment, at least one surfactant-containing component is produced by fluidized-bed granulation.
In another particularly preferred embodiment, aqueous preparations of the alkali metal silicate and alkali metal carbonate are sprayed in a dryer together with other detergent ingredients, drying optionally being accompanied by granulation.
The dryer into which the aqueous preparation is sprayed can be any type of dryer.
In one preferred embodiment of the process, drying is carried out by spray drying in a drying tower. In this case, the aqueous preparations are exposed in known manner to a stream of drying gas in fine-particle form.
Applicants describe an embodiment of spray drying using superheated steam in a number of publications. The operating principle disclosed in those publications is hereby specifically included as part of the disclosure of the present invention. Reference is made in particular to the following publications: DE-A-40 30 688 and the further developments 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 preferred variant, particularly where detergents of high bulk density are to be obtained, the mixtures are subsequently subjected to a compacting step, other ingredients being added to the detergents after this compacting step.
In one preferred embodiment of the invention, the ingredients are compacted in a press agglomeration process. The press agglomeration process to which the solid premix (dried basic detergent) is subjected may be carried out in various agglomerators. Press agglomeration processes are classified according to the type of agglomerator used. The four most common press agglomeration processes - which are preferred to the purposes of the invention - are extrusion, roll compacting, pelleting and tabletting, so that preferred agglomeration processes for the purposes of the present invention are extrusion, roll compacting, pelleting and tabletting processes.
One feature common to all these processes is that the premix is compacted and plasticized under pressure and the individual particles are pressed against one another with a reduction in porosity and adhere to one another. In all the processes (but with certain limitations in the case of tabletting), the tools may be heated to relatively high temperatures or may be cooled to dissipate the heat generated by shear forces.
In all the processes, a binder may be used as a compacting auxiliary. In the interests of simplicity, the specification will hereinafter refer only to a binder or to the binder. However, it must be made clear at this juncture that, basically, several different binders and mixtures of various binders may also be used. A preferred embodiment of the invention is characterized by the use of a binder which is completely in the form of a melt at temperatures of only at most 130°C, preferably at most 100°C and more preferably up to 90°C. In other words, the binder will be selected according to the process and the process conditions or, alternatively, the process conditions and, in particular, the process temperature will have to be adapted to the binder if it is desired to use a particular binder.
The actual compacting process is preferably carried out at processing temperatures which, at least in the compacting step, at least 5 correspond to the temperature of the softening point if not to the temperature of the melting point of the binder. In one preferred embodiment of the invention, the process temperature is significantly above the melting point or above the temperature at which the binder is present as a melt. In a particularly preferred embodiment, however, the process 10 temperature in the compacting step is no more than 20°C above the melting temperature or the upper limit to the melting range of the binder.
Although, technically, it is quite possible to adjust even higher temperatures, it has been found that a temperature difference in relation to the melting temperature or to the softening temperature of the binder of 15 20°C is generally quite sufficient and even higher temperatures do not afford additional advantages. Accordingly it is particularly preferred, above all on energy grounds, to carry out the compacting step above, but as close as possible to, the melting point or rather to the upper temperature limit of the melting range of the binder. Controlling the temperature in this way has 20 the further advantage that even heat-sensitive raw materials, for example peroxy bleaching agents, such as perborate and/or percarbonate, and also enzymes, can be processed increasingly without serious losses of active substance. The possibility of carefully controlling the temperature of the binder, particularly in the crucial compacting step, i.e. between mixing/
25 homogenizing of the premix and shaping, enables the process to be carried out very favorably in terms of energy consumption and with no damaging effects on the heat-sensitive constituents of the premix because the premix is only briefly exposed to the relatively high temperatures. In preferred press agglomeration processes, the working tools of the press agglomerator (the screws) of the extruder, the rollers) of the roll compactor and the pressure rollers) the pellet press) have a temperature of at most 150°C, preferably of at most 100°C and, in a particularly preferred embodiment, at most 75°C, the process temperature being 30°C
and, in a particularly preferred embodiment, at most 20°C above the melting temperature or rather the upper temperature limit to the melting range of the binder. The heat exposure time in the compression zone of the press agglomerators is preferably at most 2 minutes and, more preferably, between 30 seconds and 1 minute.
Preferred binders which may be used either individually or in the form of mixtures with other binders are polyethylene glycols, 1,2-poly-propylene glycols and modified polyethylene glycols and polypropylene glycols. The modified polyalkylene glycols include, in particular, the sulfates and/or the disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight of 600 to 12,000 and, more particularly, in the range from 1,000 to 4,000. Another group consists of mono- and/or disuccinates of polyalkylene glycols which, in turn, have relative molecular weights of 600 to 6,000 and, preferably, in the range from 1,000 to 4,000. A more detailed description of the modified polyalkylene glycol ethers can be found in the disclosure of International patent application WO-A-93/02176. In the context of the invention, poly-ethylene glycols include polymers which have been produced using C3_5 glycols and also glycerol and mixtures thereof as starting molecules. In addition, they also include ethoxylated derivatives, such as trimethylol propane containing 5 to 30 EO. The polyethylene glycols preferably used may have a linear or branched structure, linear polyethylene glycols being particularly preferred. Particularly preferred polyethylene glycols include those having relative molecular weights in the range from 2,000 to 12,000 and, advantageously, around 4,000. Polyethylene glycols with relative molecular weights below 3,500 and above 5,000 in particular may be used in combination with polyethylene glycols having a relative molecular weight of around 4,000. More than 50% by weight of such combinations may advantageously contain polyethylene glycols with a relative molecular weight of 3,500 to 5,000, based on the total quantity of polyethylene glycols. However, polyethylene glycols which, basically, are present as liquids at room temperature/1 bar pressure, above all polyethylene glycol with a relative molecular weight of 200, 400 and 600, may also be used as binders. However, these basically liquid polyethylene glycols should only be used in the form of a mixture with at least one other binder, this mixture again having to satisfy the requirements according to the invention, i.e. it must have a melting point or softening point at least above 45°C.
Other suitable binders are low molecular weight polyvinyl pyr rolidones and derivatives thereof with relative molecular weights of up to at most 30,000. Relative molecular weight ranges of 3,000 to 30,000, for example around 10,000, are preferred. Polyvinyl pyrrolidones are preferably not used as sole binder, but in combination with other binders, more particularly in combination with polyethylene glycols.
Other suitable binders are raw materials which, as raw materials, basically exhibit washing- or cleaning-active properties, i.e. for example nonionic surfactants with melting points of at least 45°C or mixtures of nonionic surfactants and other binders. Preferred nonionic surfactants include alkoxylated fatty or oxoalcohols, more particularly C~2_~8 alcohols.
Degrees of alkoxylation, more particularly degrees of ethoxylation, of on average 18 to 80 AO, more particularly EO, per mol of alcohol and mixtures thereof have proved to be particularly advantageous. Above all, fatty alcohols containing on average 18 to 35 EO and, more particularly, an average of 20 to 25 EO show advantageous binder properties in the context of the present invention. Binder mixtures may also contain ethoxylated alcohols containing on average fewer EO units per mol of alcohol, for example tallow fatty alcohol containing 14 EO. However, these alcohols with a relatively low degree of ethoxylation are preferably used solely in admixture with alcohols having a relatively high degree of ethoxylation. The binders advantageously contain less than 50% by weight and, more particularly, less than 40% by weight, based on the total quantity of binder used, of alcohols with a relatively low degree of ethoxylation.
Above all, nonionic surfactants typically used in detergents, such as C~2_~$
alcohols containing on average 3 to 7 EO, which are basically liquid at room temperature, are preferably present in the binder mixtures in only such quantities that less than 2% by weight of these nonionic surfactants, based on the end product of the process, are available. As described above, however, it is by no means preferred to use nonionic surfactants liquid at room temperature in the binder mixtures. In one particularly advantageous embodiment, therefore, nonionic surfactants of the type in question do not form part of the binder mixture because not only do they reduce the softening point of the mixture, they can also contribute towards tackiness of the end product and, because of their tendency to gel on contact with water, often fail adequately to satisfy the requirement that the binder/partition in the end product should dissolve quickly. In addition, the binder mixture preferably does not contain the anionic surfactants typically encountered in detergents or their precursors, namely anionic surfactant acids. Other nonionic surfactants suitable as binders are the fatty acid methyl ester ethoxylates with no tendency to gel, more particularly those containing on average 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 methyl esters based predominantly on C~6_~$
fatty acids, for example hydrogenated beef tallow methyl ester containing on average 12 EO or 20 EO. One preferred embodiment of the invention is characterized by the use as binder of a mixture containing C~2_~8 cocofatty alcohol or tallow fatty alcohol with on average 20 EO and polyethylene glycol with a relative molecular weight of 400 to 4,000. Another preferred embodiment of the invention is characterized by the use as binder of a mixture containing predominantly C~6_~a-fatty-acid-based methyl ester with on average 10 to 25 EO, more particularly hydrogenated beef tallow methyl ester with on average 12 EO or 20 EO, and a C~2_~$ cocofatty alcohol or tallow fatty alcohol with on average 20 EO and/or polyethylene glycol with a relative molecular weight of 400 to 4,000.
Binders based either solely on polyethylene glycols with a relative molecular weight of around 4,000 or on a mixture of C~2_~$ cocofatty alcohol or tallow fatty alcohol with on average 20 EO and one of the above-described fatty acid methyl ester ethoxylates or on a mixture of C~2_~$
cocofatty alcohol or tallow fatty alcohol with on average 20 EO, one of the above-described fatty acid methyl ester ethoxylates and a polyethylene glycol, more particularly with a relative molecular weight of around 4,000, have proved to be particularly advantageous embodiments of the invention.
Besides the substances mentioned here, other suitable substances may be present in the binder in small quantities.
Immediately after leaving the production unit, the compacted material preferably has temperatures of not more than 90°C, temperatures of 35 to 85°C being particularly preferred. It has been found that exit temperatures - above all in the extrusion process - of 40 to 80°C, for example up to 70°C, are particularly advantageous.
In one preferred embodiment of the invention, the process according to the invention is carried out by extrusion as described, for example in European patent EP-B-0 486 592 or International patent applications WO
93102176 and WO 94109111 or WO 98/12299. In this extrusion process, a solid premix is extruded under pressure to form a strand and, after emerging from the multiple-bore extrusion die, the strands are cut into granules of predetermined size by means of a cutting unit. The solid, homogeneous premix contains a plasticizer and/or lubricant of which the effect is to soften the premix under the pressure applied or under the effect 5 of specific energy, so that it can be extruded. Preferred plasticizers and/or lubricants are surfactants and/or polymers.
Particulars of the actual extrusion process can be found in the above-cited patents and patent applications to which reference is hereby expressly made. In one preferred embodiment of the invention, the premix 10 is delivered, preferably continuously, to a planetary roll extruder or to a twin-screw extruder with co-rotating or contra-rotating screws, of which the barrel and the extrusion/granulation head can be heated to the prede-termined extrusion temperature. Under the shear effect of the extruder screws, the premix is compacted under a pressure of preferably at least 25 15 bar or - with extremely high throughputs - even lower, depending on the apparatus used, plasticized, extruded in the form of fine strands through the multiple-bore extrusion die in the extruder head and, finally, size-reduced by means of a rotating cutting blade, preferably into substantially spherical or cylindrical granules. The bore diameter of the multiple-bore 20 extrusion die and the length to which the strands are cut are adapted to the selected granule size. In this embodiment, granules are produced in a substantially uniformly predeterminable particle size, the absolute particle sizes being adaptable to the particular application envisaged. In general, particle diameters of up to at most 0.8 cm are preferred. Important 25 embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and more particularly in the range from about 0.8 to 3 mm. In one important embodiment, the length-to-diameter ratio of the primary granules is in the range from about 1:1 to about 3:1. In another preferred embodiment, the still plastic primary granules are subjected to another shaping process step in which edges present on the crude extrudate are rounded off so that, ultimately, spherical or substantially spherical extrudate granules can be obtained. If desired, small quantities of drying powder, for example zeolite powder, such as zeolite NaA powder, can be used in this step. This shaping step may be carried out in commercially available spheronizing machines. It is important in this regard to ensure that only small quantities of fines are formed in this stage. According to the present invention, drying - which is described as a preferred embodiment in the prior art documents cited above - may be carried out in a subsequent step but is not absolutely essential. It may even be preferred not to carry out drying after the compacting step.
Alternatively, extrusion/compression steps may also be carried out in low-pressure extruders, in a Kahl press (manufacturer: Amandus Kahl) or in a so-called Bextruder (manufacturer: Bepex).
In one particularly preferred embodiment of the invention, the temperature prevailing in the transition section of the screw, the pre-distributor and the extrusion die is controlled in such a way that the melting temperature of the binder or rather the upper limit to the melting range of the binder is at least reached and preferably exceeded. The temperature exposure time in the compression section of the extruder is preferably less than 2 minutes and, more particularly, between 30 seconds and 1 minute.
In another preferred embodiment of the present invention, the process according to the invention is carried out by roll compacting. In this variant, the premix is introduced between two rollers - either smooth or provided with depressions of defined shape - and rolled under pressure between the two rollers to form a sheet-like compactate. The rollers exert a high linear pressure on the compound and may be additionally heated or cooled as required. Where smooth rollers are used, smooth untextured compactate sheets are obtained. By contrast, where textured rollers are used, correspondingly textured compactates, in which for example certain shapes can be imposed in advance on the subsequent detergent particles, can be produced. The sheet-like compactate is then broken up into smaller pieces by a chopping and size-reducing process and can thus be processed to granules which can be further refined and, more particularly, converted into a substantially spherical shape by further surface treatment processes known per se.
In roll compacting, too, the temperature of the pressing tools, i.e. the rollers, is preferably at most 150°C, more preferably at most 100°C and most preferably at most 75°C. Particularly preferred production processes based on roll compacting are carried out at temperatures 10°C and, in particular, at most 5°C above the melting temperature of the binder or the upper temperature limit of the melting range of the binder. The temperature exposure time in the compression section of the rollers - either smooth or provided with depressions of defined shape - is preferably at most 2 minutes and, more particularly, between 30 seconds and 1 minute.
In another preferred embodiment of the present invention, the process according to the invention is carried out by pelleting. In this process, the premix is applied to a perforated surface and is forced through the perforations and at the same time plasticized by a pressure roller. In conventional pellet presses, the premix is compacted under pressure, plasticized, forced through a perforated surface in the form of fine strands by means of a rotating roller and, finally, is size-reduced to granules by a cutting unit. The pressure roller and the perforated die may assume many different forms. For example, flat perforated plates are used, as are concave or convex ring dies through which the material is pressed by one or more pressure rollers. In perforated-plate presses, the pressure rollers may also be conical in shape. In ring die presses, the dies and pressure rollers may rotate in the same direction or in opposite directions. A press suitable for carrying out the process according to the invention is described, for example, in DE-OS 38 16 842. The ring die press disclosed in this document consists of a rotating ring die permeated by pressure bores and at least one pressure roller operatively connected to the inner surface thereof which presses the material delivered to the die space through the pressure bores into a discharge unit. The ring die and pressure roller are designed to be driven in the same direction which reduces the shear load applied to the premix and hence the increase in temperature which it undergoes. However, the pelleting process may of course also be carried out with heatable or coolable rollers to enable the premix to be adjusted to a required temperature.
In pelleting, too, the temperature of the pressing tools, i.e. the pressure rollers, is preferably at most 150°C, more preferably at most 100°C and most preferably at most 75°C. Particularly preferred production processes based on pelleting are carried out at temperatures 10°C and, in particular, at most 5°C above the melting temperature of the binder or the upper temperature limit of the melting range of the binder.
Another press agglomeration process which may be used in accordance with the invention is tabletting. In view of the size of the tablets produced, it may be appropriate in the tabletting variant to add conventional disintegration aids, for example cellulose and cellulose derivatives, more particularly in a coarse form, or crosslinked PVP, in addition to the binder described above to facilitate the disintegration of the tablets in the wash liquor.
The particulate press agglomerates obtained may either be directly used as detergents or may be aftertreated and/or compounded beforehand by conventional methods. Conventional aftertreatments include, for exam-ple, powdering with fine-particle detergent ingredients which, in general, produces a further increase in bulk density. However, another preferred aftertreatment is the procedure according to German patent applications DE-A-195 24 287 and DE-A-195 47 457, according to which dust-like or at least fine-particle ingredients (so-called fine components) are bonded to the particulate end products produced by the process according to the invention which serve as core. This results in the formation of detergents which contain these so-called fine components as an outer shell.
Advantageously, this is again done by melt agglomeration using the same binders as in the process according to the invention. On the subject of the melt agglomeration of fine components onto the basic granules according to the invention and produced in accordance with the invention, reference is specifically made to the disclosure of German patent applications DE-A-195 24 287 and DE-A-195 47 457.
Examples Detergents E1 and E2 according to the invention were mixed together from individual ingredients, citric acid being added in such a quantity that the detergents had an alkali product of 10.7 ~ 0.4. The comparison detergents was similarly produced, but contained standard builder systems based on zeolite or soda and acrylic/maleic acid copolymer (see Table 1 ). All the detergents produced contained 9.5% by weight of sodium alkyl benzenesulfonate, 4.1 % by weight of fatty alcohol ethoxylate, 1.0% by weight of soap, 11.6% by weight of sodium percarbonate (E1, C1, V3) or 16.7% by weight of perborate tetrahydrate (E2/C2), 2.4% by weight of TAED, 2.0% by weight of enzyme granules and other auxiliaries. The detergents also contained builders according to Table 1 and - to 100% by weight - water, salts and other detergent ingredients (for example defoamers, dyes) used in small quantities.

Table 1:
Builders in the detergents tested (in % by weight, based on the detergent as a whole and expressed as water-free active substance) Silicate 2.7 2.7 - - 1.2 Zeolite A - - - - 16.7 Soda 5.8 13.3 5.8 13.3 16.7 Polycarboxylate (M = 20,000-70,000- - 2.6 2.6 3.3 g/mol) Modified oligosaccharide 2.6 2.6 - - -Phosphonate (HEDP) 0.14 0.14 0.14 0.14 0.2 Citric acid, water-free 0.6 0.6 0.6 0.6 -Silicate: amorphous sodium silicate with Na20 : Si02 = 2.4 Polycarboxylate (M = 20,000-70,000 glmol): Sokalan CP5~; acrylic acid/maleic acid copolymer, M = 35,000 g/mol; a product of BASF
Modified oligosaccharide: an oxidatively modified oligosaccharide according to patent application EP-A-0 874 890 was used.
The detergents were tested under simulated practical conditions in domestic washing machines. To this end, the machines were loaded with 3.0 kg of clean ballast washing and 0.5 kg of test fabric, the test fabric being partly impregnated with typical test soils for testing single wash cycle performance and consisting of white fabric for testing multiple wash cycle performance. Strips of standardized cotton cloth (Wascherei-forschungsanstalt Krefeld; WFK), grey cotton cloth (BN), knitted fabric (cotton tricot; B) and terry (FT) were used as the test fabrics. To determine redeposition, skeins containing 3 g dust/sebum on cotton yarn (15 g) were added in the last 5 wash cycles. Washing conditions: tap water with a hardness of 23°d (equivalent to 230 mg Ca0/I), quantity of detergent used per detergent and machine: 135 g, 90°C wash program (including heating phase), liquor ratio (kg washing : liter of wash liquor in the main wash cycle) 1:5.7, three rinses with tap water, spinning and drying.
For a dose of 135 g of detergent per machine, the wash liquor contained the quantities of builder shown in Table 2.
Table 2:
Quantities of builder in the wash liquor for a detergent dose of 135 g Silicate [g] 3.6 3.6 3.6 3.6 1.6 Zeolite A [g] 0 0 0 0 22.4 Soda (g] 7.8 18.0 7.8 18.0 22.4 Polycarboxylate (M = 20,000-70,0000 0 3.5 3.5 4.5 g/mol) [g]

Modified oligosaccharide 3.5 3.5 0 0 0 Phosphonate [g] 0.19 0.19 0.19 0.19 0.27 Total quantity [g] 15.1 25.3 15.1 15.1 51.2 There was no significant difference between the detergents according to the invention and the comparison detergents in regard to single wash cycle performance. After 25 wash cycles, the ash content of the fabric samples was measured in double determinations.
The invention may be varied in any number of ways as would be apparent to a person skilled in the art and all obvious equivalents and the like are meant to fall within the scope of this description and claims. The description is meant to serve as a guide to interpret the claims and not to limit them unnecessarily.

Claims (41)

1. A detergent composition containing at least one anionic surfactant and substantially no alumosilicate, a soluble builder system comprising a) an alkali metal silicate with a ratio of M2O:SiO2 (modulus), where M is an alkali metal ion, of 1:1.9 to 1:3.3, b) an alkali metal carbonate, c) an oxidatively modified oligosaccharide, d) a phosphonate capable of complexing and e) optionally an acidic component, and the soluble builder system makes up less than 40% by weight of the detergent as a whole and the alkali product of the detergent is in the range of from 7.0 to 11.4.

2. A detergent composition as claimed in claim 1, wherein at most 45 g of the soluble builder system is used during the wash cycle of a domestic washing machine.

3. A detergent composition as claimed in claim 2, wherein from 10 to 35 g of the soluble builder system is used.

4. A detergent composition as claimed in any of claims 1, 2 or 3, wherein the components are present as follows:
component a) in quantities of 0.5 to 20% by weight, component b) in such quantities that the content of alkali metal carbonate active in the wash liquor is from 5 to 30% by weight, component c) in quantities of 0.5 to 8% by weight, component d) in quantities of 0.05 to 2.0% by weight, component d) in quantities of 0 to 10.0% by weight.

5. A detergent composition as claimed in any of claims 1, 2, 3 or 4, wherein the components are present as follows:
component a) in quantities of 3 to 10% by weight component b) in quantities of from 10 to 25% by weight, component c) in quantities of 2 to 6.5% by weight, component d) in quantities of 0.1 to 1% by weight, component e) in quantities of 0.1 to 5% by weight

6. A detergent composition as claimed in claim 5, wherein component b) is present in quantities of at least 15% by weight.

7. A detergent composition as claimed in any of claims 1 to 6, wherein the alkali product of the detergent is present in the range of from 8.5 to 11.2.

8. A detergent composition as claimed in any of claims 1 to 7, wherein the oxidatively modified oligosaccharide is an oxidized dextrin derivative, more particularly a polysaccharide with a dextrose equivalent (DE) of 0.5 to 40 and preferably in the range from 2 to 30, DE being a standard measure of the reducing effect of a polysaccharide by comparison with dextrose which has a DE of 100.

9. A detergent composition as claimed in any of claims 1 to 8, wherein the oxidatively modified oligosaccharide is a maltodextrin with a DE of 3 to 20 or a dry glucose syrup with a DE of 20 to 37 or a so-called yellow dextrin or a white dextrin with relatively high molecular weights of 2,000 to 30,000 g/mol or mixtures of such compounds.

10. A detergent composition as claimed in any of claims 1 to 10, wherein 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.

11. A detergent composition as claimed in any of claims 1 to 10, wherein the oxidatively modified oligosaccharide is an oligosaccharide which has a -COOH group instead of the -CH(OH)-CHO group at its originally reducing end.

12. A detergent composition as claimed in any of claims 1 to 11, wherein in addition to the modified oligosaccharide, the composition also contains at least one polymeric polycarboxylate, the polymeric polycarboxylate being a polymeric polycarboxylate with a molecular weight below 10,000 g/mol, and the ratio of component c) to the polymeric polycarboxylates is from 2:1 to 1:20.

13. A detergent composition as claimed in claim 12, a homopolymeric polycarboxylate, or a copolymeric polycarboxylate is present.

14. A detergent composition as claimed in claim 12, wherein a copolymer of (meth)acrylic acid with malefic acid is present having a molecular weight of 20,000 to 70,000 g/mol and the ratio of component c) to the copolymer is 1:1 to 1:15.

15. A detergent composition as claimed in any of claims 1 to 11, wherein no polymeric polycarboxylate is present.

16. A detergent composition as claimed in any of claims 1 to 15, wherein the acidic component e) is subsequently added to the composition, the acidic component being present either on its own or in the form of compounds with other detergent ingredients.

17. A detergent composition as claimed in claim 16, wherein the acidic component is in the form of compounds with other neutrally reacting detergent ingredients.

18. A detergent composition as claimed in any of claims 1 to 17, wherein component a) is an amorphous sodium silicate, component c) is a modified oligosaccharide, the average degree of oligomerization of the oligosaccharide being in the range from 2 to 20 and composition component e) is citric acid.

19. A detergent composition as claimed in claim 18, wherein the silicate has an Na2O : SiO2 ratio (modulus) of 1:2 to 1:2.8, and the average degree of oligomerization is from 2 to 10.

20. A detergent composition as claimed in any of claims 1 to 19, wherein an arabinonic acid unit is present at the originally reducing end of the modified oligosaccharide.

21. A detergent composition as claimed in any of claims 1 to 20, wherein the composition contains sodium percarbonate as its bleaching component, the sodium percarbonate forming at least 30% by weight of the alkali metal carbonate active in the wash liquor.

22. A process for the production of a detergent containing substantially no alumosilicate, wherein an acidic component is added to the detergent in such a quantity that the resulting detergent has an alkali product of 7.0 to 11.4 and contains an oxidatively modified oligosaccharide.

23. A process as claimed in claim 21, wherein the oxidatively modified oligosaccharide is an oxidized dextrin derivative, DE being a standard measure of the reducing effect of a polysaccharide by comparison with dextrose which has a DE of 100.

24. A process as claimed in claim 23, wherein the derivative is a polysaccharide with a dextrose equivalent (DE) of 0.5 to 40.

25. A process as claimed in claims 23, wherein the DE is in the range from 2 to 30.

26. A process as claimed in any of claims 22 to 25, wherein the oxidatively modified oligosaccharide is a maltodextrin with a DE of 3 to 20 or a dry glucose syrup with a DE of 20 to 37 or a so-called yellow dextrin or a white dextrin with relatively high molecular weights of 2,000 to 30,000 g/mol or mixtures of such compounds.

27. A process as claimed in any of claims 22 to 26, wherein 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.

28. A process as claimed in any of claims 22 to 27, wherein the oligosaccharide has a -COOH group instead of the -CH(OH)-CHO group at its originally reducing end.

29. A process as claimed in any of claims 22 to 28, wherein the resulting detergent has an alkali product of 8.5 to 11.2.

30. A process as claimed in any of claims 22 to 29, wherein various particulate components which contain detergent ingredients and which together form at least 60% by weight of the detergent as a whole are mixed together.

31. A process as claimed in any of claims 22 to 30, wherein the acidic component is subsequently added to the detergent, the acidic component being added either on its own or in the form of compounds with other detergent ingredients.

32. A process as claimed in claim 31, wherein the other detergent ingredients are neutrally reacting.

33. A process as claimed in any of claims 22 to 32, wherein aqueous preparations of the alkali metal silicate and alkali metal carbonate are sprayed together with other detergent ingredients in a dryer.

34. A process as claimed in claim 33, wherein the dryer is a drying tower for spray drying.

35. A process as claimed in any of claims 22 to 34, wherein the mixture is subsequently subjected to a compacting step, other ingredients being added to the detergents after the compacting step.

36. A process as claimed in any of claims 22 to 35, wherein compacting is carried out by press agglomeration.

37. A process as claimed in claim 36, wherein the press agglomeration is carried out in a roll compactor.

38. A process as claimed in claim 36, wherein the press agglomeration is carried out by extrusion.

39. A process for washing textiles, wherein a detergent containing a soluble builder system essentially comprising a) an alkali metal silicate with an M2O:SiO2 modulus, where M is an alkali metal ion, of 1:1.9 to 1:3.3, b) an alkali metal carbonate, c) an oxidatively modified oligosaccharide, d) a phosphonate capable of complexing and e) optionally an acidic component, at least one anionic surfactant and essentially no alumosilicate is used.

40. A process as claimed in claim 39, wherein the detergent is added in such a quantity that at most 45 g of the soluble builder system is used in the wash cycle of a domestic washing machine.

41. A process as claimed in claim 40, wherein from 10 to 35 g of the soluble builder is used.