WO1996014385A1

WO1996014385A1 - Solid useful material preparations for the multi-stage washing of textiles

Info

Publication number: WO1996014385A1
Application number: PCT/EP1995/004163
Authority: WO
Inventors: Wilfried Rähse; Johann Friedrich Fues; Beatrix Kottwitz; Jozsef Kozma; Horst Upadek
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1994-11-02
Filing date: 1995-10-24
Publication date: 1996-05-17
Also published as: DE4438850A1

Abstract

The invention concerns novel multi-component textile detergents in solid form which permit multi-stage washing of textiles even in only one wash. The main portion of the useful material mixture - surfactant compounds with a washing effect, alkalizing agents, builders which are soluble in the aqueous-alkali range and/or finely particulate and insoluble and which can bind with calcium and, if necessary, further conventional active and/or auxiliary components of textile detergents - is prepared to form a condensed, in particular granulated, mixing material with time-delayed solubility, at least in cold water. The invention is characterized in that at least one component which can also dissolve rapidly in cold water and is based on suitably soluble complexing agents for the polyvalent cations of the water hardness is provided additionally but separately, mixtures of these complexing agents with cold-soluble surfactant compounds in particular being present. When the components are jointly metered during the initial phase of the washing process the delayed dissolution of the main component is sufficient to ensure at least that the textile material is thoroughly wetted with the aqueous pre-liquor of the complexing agent. The invention further concerns a process for optimizing the washing and cleansing power of textile detergents in the area of alkali textile washing using the above-described multi-component textile detergent, and the use of the preparative forms of complexing agents for polyvalent metallic ions, which preparative forms can dissolve rapidly in cold water, in order to develop a multi-stage washing process and optimize the washing result on soiled textiles.

Description

O 96/14385 PCIYEP95 / 04163

- 1 -

'Solid recyclable preparations for multi-stage textile washing'

The teaching according to the invention describes new proposals for realizing the known working principle of important improvements in the context of textile washing by ensuring that the treatment of the textile goods to be cleaned is carried out in several stages, for example in successive stages at different pH values and / or at different temperatures ¬ temperatures of the wash liquor in these respective stages. The teaching according to the invention aims in particular to implement the principle in an improved manner of first subjecting the textile material to be cleaned to a treatment under acidic to weakly basic pH conditions of the liquor, which is followed by essentially conventional textile washing under comparatively more alkaline washing conditions. Within the scope of this task, the invention particularly wants to describe new textile detergents which are suitable for the household laundry sector and which can only be made available to the consumer in the form of a single mixed product. However, the teaching according to the invention is not restricted to such uniform mixed products. The working principle described below can also be achieved with a plurality of separate components of the mixture of recyclable materials used overall. Such embodiments can be of practical importance, for example, particularly when using household washing machines which are equipped with separate loading devices, for example for a prewash and a subsequent main wash.

Multi-stage textile washing, based on the pH of the aqueous washing liquor, is known in the art. US 3,042,621, which dates back to 1962, describes detergent mixtures for such multi-stage washing, the first working stage taking place under non-acidic conditions, in particular in the basic range, and a subsequent treatment stage of the textile material taking place in the range of acidic pH values. This sequence in the regulation of the liquor pH value has not become established in practice. Today, working pH values of the washing liquor in the alkaline range and in special cases in the neutral to weakly alkaline range are used for textile washing.

Summarizing representations of the more scientifically theoretical as well as the practical knowledge and experience on the complex processes of textile washing can be found, for example, in two publications which have been published in book form and to which reference is made several times in the description of the invention to represent the specialist knowledge. This is G. Wildbrett et. al. "Technology of cleaning in the household", Verlag Eugen Ulmer, Stuttgart, 1981, and G. Jakobi et. al. "Detergents and Textile Washing, Principles and Practice", VCH Verlagsgesellschaft mbH, Weinheim, 1987. According to its preface, this last-mentioned publication in book form is taken from the chapter "Detergents" in Ullmann's Encyclopedia of Industrial Chemistry.

The natural science principles and practicalities of textile washing are described in detail in these two publications. Optimized washing results are also obtained according to the current level of knowledge in the alkaline range. Instructions for textile washing in the neutral zone can only be found in special cases. Reference is made here, for example, to US Pat. No. 4,110,262, in which liquid detergent preparations with pH values in the range between 6.0 and 7.5 are described.

Under the impression of the need for phosphate substitution in textile detergent formulations, the concept has been taken up in a number of proposals to combine the aqueous-acidic textile pretreatment with a subsequent alkaline wash. The main objective here is to prevent the build-up of mineral incrustations on the washed textile during repeated washing, which is due to the hardness of the aqueous washing and rinsing liquors. In particular, the problem addressed here - improvement of the so-called "secondary washing power" - was known to be used in detergent formulations of the old type through the use of polyphosphate salts, in particular their STP, solved. The ecological pollution caused by this then made it necessary to develop other auxiliaries that bind water hardness and in particular calcium. A large number of soluble or finely insoluble builder components are available today for the subject area mentioned here, which bind water hardness and, in particular, calcium under the working conditions which are customary in practice, in particular the basic pH range.

DE 24 37 173 describes a 2-stage washing process of textile material which combines at least one pre-wash in an acidic aqueous solution with a separate main wash. The pH of the waste liquor from the prewash is in the acidic range, for example from 1.6 to 3.5, the pH of the main wash is in the neutral to basic range. The aim of this sequence of processes is to prevent the build-up of water hardness and incrustations on the textile material in the course of multiple washings in that the incrustations formed in the last wash cycle can be loosened regularly in the acidic pre-wash cycle and thus at least predominantly washed out. The teaching of US Pat. No. 3,761,415 is based on the same objective. It is to be carried out in two stages but nevertheless in one operation in such a way that a combination of appropriate recyclable materials is used as the phosphate-free detergent mixture based on synthetic surfactant compounds, which contain sodium or potassium carbonate or corresponding bicarbonates or sesquicarbonates as alkalizing agents and at the same time contain water-soluble sodium or potassium salts of citric acid or the citric acid itself. When such a detergent mixture is dissolved in hard water, the citrate ions pass into the aqueous solution so quickly, according to the information in this document, that they are capable of inhibiting the formation of conventional incrustations based on calcium carbonate with a sufficiently high dosage. In fact, the alkaline salts of citric acid are still of practical importance as a builder or cobuilder component. The examples in the US cited, however, consistently use the aqueous phase as "hot water" in the washing tests. Such a process control is not possible with the household washing machines customary worldwide today. The induction process for the specified fixed detergent As is well known, the mixture is made with cold tap water. The aqueous liquor in the washing machine together with the textile material to be cleaned is then heated to the predetermined washing temperature by heating elements in the machine.

US 4,210,550 takes up the suggestions of the last two publications cited and critically examines them. The teaching of DE 2437 173 is rejected as disadvantageous because here two separate washing processes are provided which make it necessary to separate the washing liquor from the first washing cycle before the second washing cycle is used. The teaching of US Pat. No. 3,761,415 suffers from the fact that a comparatively high percentage of citrate is required in order to implement the teaching of this publication. It is pointed out that the detergent formulations used in the examples must contain citric acid or its salts in amounts of 33 to 57% by weight, although a washing liquor with a very low hardness value (6 degrees dH) is used. The teaching of US Pat. No. 4,210,550 intends to implement the described working principle of the two-stage washing which takes place in one cycle - first acidic liquor, then basic liquor - by using detergent mixtures which - in addition to 5 to 30% by weight of surfactant components and 5 to 80% by weight of alkali carbonate - selected lower dicarboxylic acids in the range of succinic acid, glutaric acid and adipic acid in amounts of 5 to 30% by weight. In this context, it is particularly provided to delay the rate of dissolution of the alkaline component, but at the same time not to impede the rate of dissolution of the acidic components. It can be provided in the context of a conventional agglomeration technique to provide the constituents of the alkaline component with a solution-delaying coating, so that the dissolution or dispersion of this alkaline constituent only takes place in the period of at least 2 to at most 10 minutes after the addition to the aqueous liquor . A number of such solution-delaying coating materials are enumerated, which can be used in an amount of 0.1 to 15% by weight, based on the total detergent mixture. The objective of this teaching is the clearly described intention to attack and dissolve incrustations from the textile to be cleaned and also from the washing machine under the influence of the acidic components, but then the calcium and magnesium ions in the wash liquor in the subsequent alkaline working step precipitate under the influence of the alkali carbonate used, cf. in this context, the statements in the publication columns 2, 45 to 50 and columns 3, 65 to columns 4, 5.

The working examples of US Pat. No. 4,210,550 also show that there are considerable difficulties in realizing the principle of building up a storage-stable multicomponent mixture on the basis of the textile detergents concerned here in such a way that the previous formation of the washing liquor with an acidic pH is reliably ensured for the required period and only then is the washing liquor converted to the usual basic pH conditions. All examples of this publication work with a 2-chamber portioning aid which provides the acidic component, optionally together with selected surfactant compounds, separately from the alkaline component and its further active ingredient components. A suitable design of this 2-chamber auxiliary element provides a delayed opening of the chamber for the alkaline detergent component.

The object of the invention

Textile detergents are known to be mixtures of a large number of active components, each of which, individually and in their possibly synergistic interaction, should optimally fulfill the complex task of textile washing. The diversity of the task given here derives on the one hand from the different types of soiling and on the other hand from the different types of textile materials that are to be cleaned regularly, for example as part of a household textile wash. Modern forms of supply of these multi-substance mixtures are pourable and free-flowing materials with increased bulk densities of, for example, 600 to 1,100 g / l. Due to forced homogenization and compaction, today - instead of the previously usual comparatively volumetric detergent powder - highly compressed multi-material mixtures, for example in spherical form, which are obtained, for example, by extrusion and subsequent rounding of the cut extrudate strands. Other possibilities for obtaining appropriately compressed materials are, for example, wet agglomerations, roller compaction and comparable compression processes.

Detergent mixtures of the type required today are optimized in the selection of their active ingredients and their composition in the direction of the previously briefly discussed complex requirement profile. The multifunctionality of the requirement profile corresponds to the multifunctional selection and compilation of the valuable and auxiliary materials of modern textile detergents. The detergent manufacturer specifies optimized quantities of the respective detergent per wash cycle - usually depending on the degree of hardness of the water available. Taking these details into account, optimized washing results are then obtained with the detergent in question. A substantial increase in the washing result by further increasing the amount of detergent per wash cycle is generally not accessible.

The teaching of the invention is based on this fact in an important aspect. By modifying the course of the washing process in the direction of multi-stage washing, it wants to be able to improve the washing result that can be set with a certain amount of detergent without having to make fundamental changes in the composition of the detergent mixture, which is optimized per se. By using small amounts of additional components, which can at least partly also be taken from the main detergent component and which - again at least partly - are characterized by an increased dissolution rate in the wash liquor even at the cold washing-in temperatures, the possibility of targeted multi-stage treatment of the soiled textile is said to be possible ¬ good can be created as part of a washing process.

The concept according to the invention makes use of the fact that the known, preferred, highly compressed forms of supply of the detergent mixtures, for example the spherical extrudates mentioned, already have a time-delayed dissolution rate in the early phase of the washing process, in particular in a cold liquor. The teaching according to the invention uses this initial phase, which can also be extended as required by appropriate finishing of the multifunctional main detergent component, for a preliminary treatment stage of the textile material to be cleaned with a pre-liquor of selected active substances.

In an important embodiment, the teaching of the invention is based on the task of modifying the textile washing in the alkaline range which is customary worldwide today in such a way that it is preceded by a work step in the range of acidic to neutral or only weakly alkaline pH values. On the one hand, the invention also wants to make it possible to effectively attack existing incrustations on the textiles to be treated and / or in the washing machine in this preliminary stage. However, the invention also intends to use this working step in special embodiments described below to ensure substantial simplifications and improvements for the subsequent alkaline washing step and for the desired cleaning result in its entirety. The teaching according to the invention is based on the objective of excluding as far as possible the formation and deposition of calcium carbonate and other compounds of water hardness in the alkaline washing stage in the sense of today's specialist knowledge in order also to ensure optimizations with regard to the secondary washing power. In particular, however, the teaching according to the invention also wants to design the overall process in such a way that improvements in the so-called primary washing power are also accessible through the use of the temporally separated preliminary stage.

The object of the teaching according to the invention is furthermore to describe concrete forms of supply for textile detergent mixtures of the type concerned here, which correspond to the forms of supply of such auxiliaries today, in particular at least partly in the form of granules and in the usual manner in any washing machine types by means of the dosage elements provided therein can be used without the need to use specially designed and separately loaded dosing elements. In this most important embodiment, the textile washing agent mixture should accordingly be formed as a multi-component mixture containing the individual components in an at least largely storage-stable homogeneous mixture. Nonetheless, the broad concept of the invention encompasses multicomponent detergent compositions in which at least two separate recyclable materials or recyclable materials are to be used in the wash cycle in order to then fulfill the overall objective of the improved primary and secondary detergent according to the invention.

The task of the teaching according to the invention in its entirety is to implement the concept of such a multi-stage textile wash already considered by experts in a practical embodiment in such a way that optimized washing results can be obtained, but at the same time neither for the storage and distribution of the detergent mixture nor for whose regular use special precautions are necessary.

Subject of the invention

The invention accordingly relates to solid textile detergents in the form of a mixture of active components and, if desired, auxiliaries which are at least partially processed into a compacted mixture with time-delayed solubility in cold water - hereinafter also as a "slowly soluble main component" and in which Rule named "HK" for simplicity. This HK mix contains, in a manner known per se, wash-active surfactant compounds, alkalizing agents, builders or builders which are soluble and / or finely insoluble in the aqueous-alkaline range and have the ability to bind calcium, and, if desired, further customary active and / or auxiliary components of Textile detergents.

The teaching according to the invention is now characterized in that it additionally - however as a constituent separate from the HK - at least one component which is also rapidly soluble in cold water - hereinafter referred to simply as "SL-K" for the sake of simplicity - also based on cold Contains water-soluble complexing agents for the polyvalent cations of water hardness. In the preferred embodiment, these complexing agents for polyvalent cations in admixture with ten- sid compounds and in particular also cold-soluble surfactant compounds. The teaching according to the invention preferably further provides that the delay in dissolving the HK in the initial phase of the washing process is chosen sufficiently that at least the wetting of the textile material with the aqueous SL-K pre-liquor is ensured.

The component (s) used as or in the SL-K can be specifically selected to adjust the pH values of the pre-liquor in the acidic to alkaline range. In the preferred embodiment of the invention, the subsequent dissolution of the HK leads to the alkaline pH values of the wash liquor desired today, which are preferably in the range from about 8 to 11. In important embodiments of the invention, the pH of the pre-liquor deviates from the pH of the wash liquor after dissolution of the HK, even if this element is not a mandatory component of the teaching according to the invention. In this embodiment, preferred pH values of the pre-liquor resulting from the dissolution of the SL-K are in the acidic to weakly basic range, in particular in the weakly acidic to neutral range. Details of this are given in the following description of the invention.

The teaching according to the invention comprises a method for optimizing the washing and cleaning power of textile detergents for the area of alkaline textile washing by means of a multi-stage washing. The process according to the invention is characterized here in that the main wash in the alkaline range using a multicomponent main component (HK in the sense of the definition given above), a pretreatment of the soiled textile material with the pre-liquor of a quick-release component (SL-K according to the previously given definition). Further preferred, but not mandatory, the SL-K and the HK are added together to the wash liquor. The at least predominant part of the HK is formed as a multi-component component that is soluble with a time delay such that at least the penetrating wetting of the textile goods with the previously formed aqueous SL-K pre-liquor is ensured.

In a further variant, the teaching of the invention finally relates to the use of a preparation which is soluble in snow even in cold water. form of complexing agents for polyvalent metal ions, in particular for the cations of water hardness and / or corresponding cations of dirt incrustations on soiled textiles - SL-K according to the definition given above - in admixture with a time-delayed soluble preparation form of a multi-component textile detergent for the alkaline textile laundry - HK according to the definition given above - for the formation of a multi-stage wash and optimization of the washing result.

The teaching according to the invention enables many variations of the special design of the multi-stage wash. Thus, in the preliminary stage of the treatment of the textile goods - and the washing machine interior - with a sufficiently acidic pre-liquor, not only does incrustation of existing incrustations dissolve and the at least partial binding of the released polyvalent metal ions, in particular the corresponding ions of water hardness, by suitable use of calcium- and possibly also magnesium-binding builder components, it becomes possible to remove the at least predominant proportion of the disruptive hardness-forming agents during the transition of the pH value from the acid precursor to the neutral and finally basic liquor of the subsequent work step to the builder components of the exchange the basic work area and thus remove it from the washing process. There is no intermediate or final precipitation of these hardness formers, which in turn is insoluble. However, the teaching according to the invention also makes use of the possibilities of the multi-stage washing process for realizing specific other and / or additional cleaning and conditioning steps on the textile material.

Details of the teaching according to the invention

The teaching according to the invention is also based on the basic concept of using a first and comparatively rapidly soluble SL-K component in the detergent mixture, which, if appropriate, with the fresh water supplied for the controllable formation of pH values, for example in acid to neutral but also in the alkaline range. This first component can be formed by a selected resource, but the use of a multi-component is usually already used here A mixture of valuable substances is preferred which is identified by the targeted pH formation in aqueous solution with the use of surfactant components.

In combination with this, the basic main component HK is used, which, for the time being, is at least predominantly different from the. SL-K component differentiates, but then also ensures the pH of the wash liquor in the desired range when it is dissolved. The HK is used in such quantities and / or in such a configuration of its multicomponent mixture that not only the necessary neutralization of the SL-K takes place. In particular, it is a (partial) task of HK to ultimately set the pH of the preferably basic range in the aqueous bath, which is aimed for in the conventional sense for the main wash cycle.

In a further important embodiment, the teaching according to the invention intends to realize the idea of using at least a proportion of valuable substances in the SL-K component, which can also be known and useful basic components of a basic-based textile detergent mixture under basic conditions.

Before the concrete description of the elements used according to the invention is discussed in more detail, the following brief instructions are given for a better understanding of individual variants of the inventive action. Understandably, this can only be an incomplete short description.

The washing and cleaning process in aqueous liquors using the auxiliaries customary today is known to be a highly complex process of the components which interact here, which is characterized by a large number of physiological and physicochemical parameters. The literature cited at the beginning provides brief help for understanding, see in particular G. Jakobi et.al. aaO, Chapter 2, "Theory of the Washing Processes" (pages 7-39) and here in particular subchapters 2.2 "Types of Soil" and 2.3 "Physical Soil Removal". From the previously cited publication G. Wildbrett et.al. especially refer to "Part 1 - Theoretical principles ", page 13 ff, and here in particular to subchapters 2." Dirt ", 4." Chemical auxiliaries for cleaning "and 5." Process of wet cleaning ". In connection with the variant of the teaching according to the invention, Preceding the washing stage in the basic area with a treatment of the textile goods to be cleaned in the acidic area is undoubtedly of particular importance for the chemical reaction of the acidic attack on acid-sensitive constituents of the dirt as well as for incrustations based on water hardness or that arise in the conventional process The acid attack under the influence of the SL-K leads to the dissolution of acid-unstable solids, releases acid-soluble, in particular polyvalent cations from dirt incrustations, and thus leads to the break-up of such dirt deposits and reduces their adhesion to the fiber surface to be cleaned Separation of additional solids by interaction of the mi Water hardness always introduced in the washing liquor and, for example, surfactant and / or alkalizing components cannot take place in the acidic range.

The acidic pretreatment stage provided according to the invention obviously also has a completely different effect on the overall process of the washing process. This is where the teaching according to the invention comes in. For the first time, it combines today's knowledge of textile washing with the old proposals cited. The following only applies in this connection:

A key parameter for the effectiveness and the course of the washing and cleaning processes on the soiled textile in the aqueous liquor are the respective electrostatic charge conditions on the fiber surfaces and the deposited dirt particles, as well as on valuable and auxiliary substances of the detergent mixture. The decisive factor is, in particular, the controllability of this so-called electrokinetic interface potential - also called zeta potential - by the working conditions and auxiliaries used in the washing process. The pH value of the wash liquor is of great importance in this context. In the conventional alkaline washing process, the optimization of the negative charge of the dirt particles and thus the maximization of the repulsion between the fiber surface and dirt is achieved at about pH 10 to 11. The pH-related washing effect can then no longer increase. When the pH value drops the zeta potential also decreases. In aqueous solutions below pH 7, the hydrogen ions outweigh the hydroxyl ions. Protons are increasingly absorbed on the surface of dirt particles and the substrate. The originally pronounced negative charging of the interfaces decreases. Experience has shown that the transfer point for laundry soiling is around pH 5; only below this limit does a positive charge on the dirt surface predominate. If the pH value drops further, the zeta potential rises again in the range of positive values, for more details see. for example G. Wildbrett loc. cit., pages 37 to 39 and 75 to 77.

Integrated in this complex electrochemical process, which influences the washing action, are not only the fixed parts of the washing liquor, but also dissolved ionic - and also nonionic - components of the complex system or their interaction with one another are subject to the pH-dependent influence.

Based on this basic knowledge, the invention proposes a bundle of measures for facilitating and intensifying the aqueous textile laundry, which can lead to improvements in a variety of ways. In particular, the following applies here: positive results are achieved not only with regard to the prevention of incrustation and thus with regard to the so-called secondary washing result, substantial improvements are also accessible especially with regard to dirt removal and thus to the primary washing result. Based on this, modifications of both the conditions of the washing process and the composition of the solid detergents and cleaning agents for textile washing are possible. For the optimization of the desired washing result, the teaching according to the invention opens up a previously unavailable new space.

In the following, the elements relating to the nature and structure of the SL-K content in the detergent mixture according to the invention are first described.

The first essential component of this SL-K component are compounds capable of complex formation with polyvalent cations and in particular the corresponding cations of water hardness. Under consideration Compensation of the temperature / time sequence in the normal washing process and the fact that the SL-K or the pre-liquor formed therefrom is earlier than the main wash cycle with the solution-delayed HK, the complexing agents which are particularly suitable according to the invention are additionally distinguished by the fact that they are so quickly soluble in cold water that their interaction with the textile material to be cleaned is possible from the solution state in the aqueous pre-liquor. Basic components of this portion can be organic acids and / or their salts or partial salts, but also selected inorganic acids and / or their salts including the partial salts.

In a particularly important embodiment, the term organic acids encompasses polybasic carboxylic acids and / or their (partial) salts. These can be selected monomolecular compounds of the type described, but corresponding oligo compounds and / or polymer compounds of higher molecular weight are also suitable, as are known in particular from the field of builder components for detergent mixtures. The following preferred details apply here:

Particularly important representatives of the SL-K in the sense of the action according to the invention are low molecular weight polybasic carboxylic acids with preferably up to 20 C atoms and in particular with up to 10 to 15 C atoms in the molecule. The content of carboxyl groups is at least 2 and is preferably adjusted to the carbon number in such a way that the polybasic carboxylic acid is soluble even in cold or only moderately heated water - in particular in the range from about 10 to 30 ° C.

Descendants of such polycarboxylic acids, the molecules of which, in addition to C, H and O units, are free of further heteroatoms - in particular N and / or P - can be particularly important here. Typical examples of this are polybasic carboxylic acids, preferably with up to 4 or 5 carboxyl groups, in particular di- and / or tricarboxylic acids - and their derivatives of the type of corresponding hydroxycarboxylic acids, ether carboxylic acids and / or ketocarboxylic acids. Polyfunctional carboxylic acids of this type are sequestering agents known in detergent technology, especially for cal- Cium ions, which are used, for example, as cobuilder components in practice, are referred to the relevant prior art, for example, on the aforementioned publication G. Jakobi loc. cit., subchapter 3.2.2 "Complexing Agents", in particular Table 15, page 68. In addition to citric acid, 1,2,3,4-cyclopentantetracarboxylic acid, O-carboxymethyltartronic acid and O-carboxymethyloxysuccinic acid are mentioned here. These compounds are used in today's detergent formulations in the form of their basic salts. The invention encompasses this possibility, taking into account the further parameters for acting according to the invention. In addition, the teaching according to the invention also provides for its use in the SL-K as a free polyfunctional carboxylic acid and / or in the form of its partial salts with, for example, a neutral or aqueous acidic pH.

However, the teaching according to the invention is not restricted to heterofree polycarboxylic acids of the type described here with regard to the organic acids which can be used here for setting and regulating the pH range in the first process stage. In principle, organic and inorganic acids and / or their salts corresponding to the definition according to the invention, which in a preferred embodiment adequately correspond to the above-mentioned element, polyvalent metal ions and in particular the cations of the water hardness - if appropriate also in the acidic range - are partially without precipitation be able to bind and when the pH of the aqueous liquor changes from the acidic to the basic range they can either be exchanged for the builder components introduced via the HK or at least partly also form sufficiently stable soluble complexes in alkaline. Thus, for example, polyfunctional acids of the type of nitrilotriacetic acid (NTA), N- (2-hydroxyethyl) iminodiacetic acid, ethylenediaminetetraacetic acid (EDTA) are also suitable for the teaching of the invention for the formation of the SL-K. Here, too, reference is made to the information given in the cited literature reference G. Jakobi et.al., subsection 3.2.2.

However, the formation of the pre-liquor with its content of complexing agents and, if appropriate, the setting of acidic pH values in the first stage of a washing process in the sense of the invention is not based on the set of corresponding carboxylic acids or polycarboxylic acids. Important mixture components for the teaching according to the invention can also be other, in particular polyfunctional, acid generators which are distinguished by their ability to form complexes with polyvalent cations and in particular the calcium and / or magnesium of the water hardness. For example, known complexing agents based on polyfunctional phosphonic acid compounds come into consideration. The l-hydroxyethane-l, l-diphosphonic acid or the nitrilotrimethylene-phosphonic acid may be mentioned as an example. These compounds, which are listed here only by way of example, can form part of the SL-K as free acids or in the form of their salts, including the acid partial salts, in the sense of the teaching according to the invention.

As already stated above, the basic component of the SL-K with the ability to complexly bind polyvalent metal ions and in particular the water hardness with simultaneous good solubility, even in cold water, can also be formed by corresponding inorganic components. Corresponding builder components of detergent technology are primarily considered here. The salts of oligophosphoric acids are known here, in particular alkali metal phosphates and / or alkali metal phosphates. As is well known, sodium triphosphate (STP) has been the most important builder component of detergent technology for decades. The proposal according to the invention to pick up this component again differs from the old technical action of the subject area concerned as follows: As described in detail below, the proportion of SL-K in relation to the main detergent component HK is only a minor fraction. The amount of complexing agent used in the SL-K is at most in the range of a few% by weight, based on the HK. The inorganic complexing agent STP can also be used in the SL-K in mixtures with other P-free complexing agents. The teaching according to the invention thus opens up the possibility of using the known advantages of the builder components based on oligophosphoric acids or their salts for the working area of the aqueous pre-liquor without reviving the old problem of potential reutrophication of water. Another class of purely inorganic complexing agents for use in SL-K are the known cold-soluble (partial) salts of oligosilicon and / or polysilicic acids, with corresponding oligosilicate and / or polysilicates being of particular importance here, at least in part are characterized by a chain or ring-shaped or sheet-like structure of the polysilicic acid residues and are referred to in the technical language as Q2 and / or (^ structures. The relevant prior art is referred to in German patent applications P 4406591.4, P 4406592.2 and P 4408359.9 For the purpose of the disclosure of the invention, the subject matter of the earlier applications named here is expressly made the subject of the present disclosure of the invention. In particular, various configurations of alkali metal silicates of the module range (MolVerhalt.) are described here nis SiO 2: M2O, where M is alkali metal) from 0.8 to 4 in a homogeneous mixture with further inorganic and / or organic valuable substances and / or auxiliaries, which are present in particular as over-dried material with an oligomer or polymer structure of the silica residues. At least the majority of these oligosilicic or polysilicic acids preferably have a Q2 and / or (^ structure. Particularly important here are over-dried materials of this type with residual water contents in the alkali silicate fraction below 18% by weight and in particular below 15% by weight. Particularly suitable as easily soluble builder components are X-ray-like orphalous alkali silicates with modulus values in the range from about 1.5 to 3.0 and preferably in the range from 1.7 to 2.7, and in particular homogeneously mixed in water-soluble inorganic salts , for example carbonates, sulfates, halides, borates, but in particular also phosphates and / or polyphosphates.

Inorganic complexing agents of the type described here as the main constituent of the SL-K will be of practical importance in particular in those embodiments in which the desired pH of the aqueous preliminary liquor is in the weakly acidic to basic range. For example, partial salts of triphosphoric acid can be used at initial pH values of the SL-K pre-liquor in the range of approximately pH 6 and higher values. In particular, however, the use of these inorganic complex are important for the embodiment in which the pre-liquor is already in the at least weakly basic range - for example pH 7.5 to 8 as the initial value - or even pH values in the range of approximately 8.5 to 10 from the outset are already aimed at in the previous fleet. Mixing inorganic and organic complexing agents enables technical action to be optimized in the sense of the teaching according to the invention. This optimization is determined not only by the components used in the SL-K, but also the nature of the multifunctional HK, the type of soiled textile material to be treated and the textile soiling that is primarily to be taken into account. The person skilled in the art affected by the teaching of the invention presented here opens up a wide variety of options for setting optimal work results in the sense of the objective of an improved textile detergent mixture which is optimized in terms of its performance.

In addition to the previously mentioned examples for a targeted regulation of the pH value of the pre-liquor by means of acidic complexing agents in particular as part of the structure of the SL-K, other sufficiently soluble acid types can also be considered. Sufficiently soluble sulfonic acids of aliphatic and / or aromatic basic molecules may be mentioned here as examples. Appropriate, optionally substituted alkanesulfonic acids or aromatic sulfonic acids are suitable. Examples of compounds of this class are, for example, sulfosuccinic acid or benzene or toloulsulfonic acid. In particular, the substance class mentioned last here can be of particular importance in the context of the invention if compounds of the type concerned here with HLB values in the field of detergent active surfactants are used. This will be discussed in more detail below.

Citric acid is a particularly important representative of the class of low molecular weight polybasic carboxylic acids for setting and regulating the pH in the aqueous acid detergent liquor stage. This can be used as such for pH regulation in the acidic range, but also at least partly in the form of its (partial) salts. The technical expertise applies here in particular. Citric acid is particularly stable in hydrated form with changing amounts of water However, anhydrous citric acid is also an important component in the context of the inventive action. It is characterized by an extremely rapid solubility, even at water temperatures in the range from 10 to 15 ° C, so that when a suitably designed multicomponent mixture is metered in, previous dissolution of the citric acid and / or its (partial) salts results in almost immediate conditioning and Adjustment of the pH value of the aqueous liquor to predeterminable values in the acidic, in the neutral or in the basic range is possible.

In addition to citric acid, which was most recently highlighted here as an important active ingredient component for adjusting the pre-liquor, a large number of other commercial products are nowadays also known for the compilation of valuable substances from the field of textile detergents. Reference is made, for example, to the dicarboxylic acid mixtures of adipic acid, succinic acid and glutaric acid, which are sold under the protected trade name "SOKALAN DCS" (BASF), for lower dicarboxylic acids of the specified C number range.

Suitable as (co) polymeric oligo- and / or polycarboxylic acids are, in particular, the polyacrylates, polymethacrylates and, in particular, copolymers of acrylic acid with maleic acid, preferably those from 50% to 90% acrylic acid and 10% to 10%, which are known in the field concerned here 50% maleic acid. Compounds of this type are known as builders or cobuilder components in basic textile detergents customary today. The molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably from 50,000 to 120,000, based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000. The detergents customary today use the polymer acids mentioned here in the form of their water-soluble salts, in particular the sodium salts. According to the invention, an important embodiment provides for at least a portion of the SL-K to be formed by appropriate free acids or their partial salts which are pH-controlled. The principle described above is also implemented here, at least in the fast-dissolving SL-K component Proportionally use those constituents which are known materials of value in the subsequently formed basic-based detergent mixture.

The citric acid and / or its partial salts previously mentioned as an important component of the SL-K component and also the last-mentioned oligo- or polymer-carboxylic acids are distinguished by the ability of the at least partial complex binding of polyvalent metal ions the water hardness and especially calcium even in the acidic to neutral range. In the sense of the above-described basic concept of the invention, the disruptive water hardness and the polyvalent metal ions dissolved via the acidic stage from the textile to be cleaned or the washing machine, in particular by means of complex formation, being separated from the process sequence, the importance of the basic elements of an embodiment of the action according to the invention can be seen. The at least partial dissolution of, in particular, calcium ions in the multifunctional acid component takes place already in the preliminary stage of the acid wash liquor. With the increasing shift of the pH value upwards, the binding capacity of the complexing agents which are effective here increases in relation to the polyvalent cation. When the alkaline builder components enter the wash liquor, the nature of which will be discussed in more detail below, the calcium is transferred by an exchange reaction into the main builder of the alkaline wash stage. The annoying hardening agents are effectively removed from the washing process and possible redeposition on the textiles. Minor residual deposits, which can occur in particular in the rinse stages, are not only extremely limited in terms of quantity, in the next wash they are immediately removed in the acidic preliminary stage.

Especially in connection with citric acid as an important component for the formation of the acidic washing liquor in the first stage of the washing process, there are the following advantages in conventional work in the washing machine: citrates have a high level of complex binding capacity in the alkaline range at comparatively low temperatures Calcium. However, this complex binding capacity decreases rapidly with increasing temperature, so that the complex binding at temperatures above 50 ° C. in the basic washing liquor is unsatisfactory. In the invented Conception according to the invention takes place in a preferred embodiment, the acidic washing stage and the subsequent exchange of the calcium ion in the main builder components of the basic washing process in the range of low temperatures. As previously mentioned, the detergent is usually flushed in with cold tap water, and the washing liquor is only heated in the machine by the heating device provided there. The temporal limitation of the first washing stage in the sense preferred according to the invention provides that the calcium exchange from the primarily formed salt of citric acid into the main builder takes place in the temperature range in which the calcium binding capacity of the citrates is still pronounced. Here, too, multi-functions11 are made use of the given scientific facts by using the teaching according to the invention.

In order to implement the principle according to the invention of multi-stage textile washing - with regard to the liquor pH ¹ s - there are basically several forms of access. An immediately illuminating embodiment provides for the addition of the acidic component separately and at the same time before the addition of the basic component. In this way, the period of treatment of the textile goods in the acidic washing liquor can be freely determined. Technical action in this sense falls within the scope of the invention.

In the more important embodiments, however, the invention wants to enable the simultaneous addition of both the SL-K and the HK to the aqueous liquor. To implement the 2-stage washing principle, a sufficient delay in dissolving the alkalizing components of the HK and a sufficiently quick solubility of the SL-K are imperative. Basically, the neutralization reaction is a spontaneous reaction which, for example, occurs spontaneously between an acidic liquor and a basic component even when the basic component is still present as an undissolved solid. In fact, this principle of spontaneous neutralization is also proposed in the relevant prior art to improve the redispersion behavior of basic detergent mixtures, cf. see, for example, the international patent application WO-A-92/18596 or the European patent application EP-A-0534525. In contrast to this, the teaching according to the invention is based on the fact that a defined minimum period for the treatment of the textile goods with the preliminary liquor is also available in the range of reduced, in particular acidic to neutral pH values. If this period can be kept very short even in special cases - and can therefore also be less than 1 min - it is nevertheless preferred according to the invention that, in particular when the SL-K and HK are added to the aqueous liquor at the same time, the time period for working with the previous liquor is Example up to neutralization of the initially acidic liquor, at least 1 to 2 minutes, preferably at least 2 to 3 minutes. In general, periods of up to 20 minutes are not exceeded for the treatment with the preliminary liquor. A period of time for the treatment of the textile laundry with the pre-liquor can, for example, be in the range of approximately 2 to 5 minutes, a period of approximately 2.5 to 8 minutes and in particular approximately 3 to 6 minutes being expedient.

The dissolving speeds of the SL-K and the HK are matched for practical use, particularly in the field of household detergents, to the cold or only slightly warmed tap water customary in the field of household detergents and thus in particular to the range from approximately 10 to 30 ° C.

The acidic components to be used in the SL-K should be capable of developing initial pH values in the range from about pH 1.5 to 7 in the aqueous liquor. Taking into account the previously cited technical knowledge regarding the importance of the electrokinet, interfacial potential (zeta potential) on the washing processes can be divided into two limiting ranges within the specified range of acidic pH values: In a first embodiment of the invention, the SL-K is designed such that that initial pH values in the range below and up to about pH 5 are formed in the acidic liquor, for example pH values in the range from about 2 to 5. Here a positive charge predominates on the surfaces, in particular of dirt, but also on the surfaces of important representatives of the textile goods to be cleaned. For the improvement aimed at according to the invention, in particular also the secondary washing effect, a temporary treatment of the textile goods in this pH range with subsequent Reversal of the surface charge in the area of the wash-active negative charge may be important.

But just a pretreatment of the textile goods to be cleaned in the range of the zero value for surface charging or a weak negative charging with subsequent strong alkalization in the range of high negative charging values gives important help in the sense of the invention. In this embodiment, the pretreatment of the textile goods can therefore take place, for example, in the pH range from about 5 to about 7, in particular in the range from 5.5 to 6.8, before the subsequent alkalization is carried out in the basic and, in particular, strongly basic range or takes place.

In the possibilities of designing the acidic pretreatment shown here, the sensitivity of the textile material to be cleaned can also be taken into account in the sense of the invention, this term “sensitivity” being widely understood and relating on the one hand to the fiber or fiber structure and on the other but also affects the finishing of the textile goods, for example the applied dyeing. For example, in laundry detergents for fine textiles, it can be useful to adjust the pH of the acidic liquor in the range from 3.5 to 7 and in particular in the range from 5 to 6.8 by buffering the acid generators in the SL-K. If desired, it is possible, as indicated, to choose the composition of the SL-K such that at least the majority of the acidic pretreatment is at pH values of the liquor of pH 5.5 and above.

However, the teaching of the invention also includes, as a variant, a multi-stage process of the type specified, in which the SL-K pre-liquor practically immediately has pH values in the more alkaline range, for example in the range from 8 to 11 and preferably of approximately 8.5 to 10.5. Even if no use is made here of the possibility of being able to carry out the two working stages of the washing process at different pH values, additional space is created for the modification of the complex washing process. The pre-liquor obtained in this embodiment in the alkaline range can, in particular, immediately spread the Ensure complexing agents on the entire textile surface before the complex multicomponent mixture of the HK goes into solution and then in turn leads to interactions with the textile surface and the contamination present there. It is known per se that such an advance loading of the textile goods and its soiling with complexing agents based on corresponding carboxylates, in particular sodium citrate, which is not impeded by the main amount of the detergent, can lead to improved primary washing effects, cf. in this connection the PCT publication WO 91/15566. It is described here that an improvement in the primary washing result can be achieved with conventional alkaline detergent formulations by separating the addition of the detergent mixture as follows: The majority of the multifunctional detergent mixture is washed into the machine using the washing device provided in the machine metered in a known manner. Separately, a component containing water-soluble complexing agents is to be introduced directly into the textile material to be washed by means of an addition container. The organic carboxylic acids cited above in connection with the teaching according to the invention, in particular corresponding polybasic carboxylic acids, are mentioned as complexing agents, water-soluble alkali metal citrates being of particular importance. In the initial phase of the washing process, the citrate in direct contact with the soiled textile laundry is immediately distributed. The content of free calcium ions given here is substantially reduced to very low values within the preferred period of 15 seconds, before the detergent introduced via the machine washing-in device has dissolved in the liquor and in turn comes into contact with the soiled textile.

It is obvious that the inventive design of the combination of a directly soluble SL-K with its content of complexing agents and the controllably delayed soluble main component enables comparable work results without a separate dosage of complexing agent on the one hand and the main detergent on the other hand to have to make. The metering of the detergent combination according to the invention enables separate pretreatment of the liquor and the soiled textile material with the complexing agent even if the two components SL-K and HK are added to the washing process at the same time and by means of the same addition device - for example, the induction device provided in the machine. It is thus understandable that important improvements in the washing result, in particular for improving the primary washing power, can also be made when working with an SL-K pre-liquor which has already been made alkaline.

Together with the organic and / or inorganic complexing agents of the type described so far, in preferred embodiments of the teaching according to the invention, the SL-K contains additional constituents which broaden the functionality of the SL-K, in particular in the process phase of the aqueous preliminary liquor, and thus the washing result increase as a whole. These additional SL-K mixture components are discussed below.

Primarily, surfactant compounds are of particular importance. Corresponding surface-active components are preferred here, which are capable of rapidly, at least partially, dissolving even in cold water and thus promote the wetting processes on the textile material in the first process stage. Even if the use of anionic surfactant compounds is not excluded, nonionic surfactant compounds are of particular importance according to the invention. The type of nonionic surfactant to be selected in the specific case is determined, among other things, by the pH value established in the SL-K pre-liquor. In particular, this applies to the case that comparatively acidic pH values - if only for a short time - are the result of the dissolution of the SL-K.

Suitable nonionic surfactants, in particular also for acidic pretreatment, are the known addition products of generally 2 to 20, preferably 3 to 15, moles of alkylene oxide, in particular ethylene oxide, to 1 mole of a compound having essentially 10 to 20 carbon atoms from the Group of alcohols and alkylphenols. Liquid ethoxylated, especially primary fatty alcohols with preferably 8 to 18 carbon atoms and an average of up to 12 moles of ethylene oxide (E0) per mole of alcohol, in which the alcohol radical can be linear or methyl-branched, can be particularly suitable. Corresponding fatty alcohols are known, for example, as oxo alcohols from synthetic chemistry. In particular, however, are alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms preferred, for example from coconut, palm, tallow or oleyl alcohol. The preferred content of EO groups can be in the range from 2 to 10 and in particular from 4 to 8. The preferred ethoxylated alcohols include, for example, Ci2-i4 alcohols with 3 E0 or 4 E0, Cg_n alcohol with up to 10 E0,

with 3 E0, 5 E0, 7 EO or 8 E0, C12-

18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these non-sensitive alkoxylates in the fatty alcohol range. The degrees of ethoxylation given represent statistical averages, those for a special

Product can be an integer or a fractional number. Alcohol ethoxylates preferably have a narrow homolog distribution (NRE). To be particularly suitable, for example, ^Ci2-l4-r f ettalkoholethoxylate have shown having 4 to 7 EO.

Nonionic surfactants based on these fatty alcohol EO compounds, which are particularly flowable at room temperature, are acid and base stable and are therefore also suitable auxiliary components, in particular also in connection with an SL-K pre-liquor with an acidic pH. However, other important nonionic surfactants are also suitable for working in the weakly acidic to neutral or even in the basic range. The alkyl glycosides of the general formula R0 (G) _x in which R is a primary straight-chain or branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G are to be mentioned here and G the symbol is for a glycose unit with 5 or 6 carbon atoms. G is preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably from 1.2 to 2. Non-ionic surfactants based on the APG compounds described here are known substances which can be obtained by the relevant processes in preparative organic chemistry. As representative of the extensive literature, reference is made here to EP-0301 298 and WO 90/39 77.

Another important class of the suitable surfactants as mixture components for the SL-K are fatty acid N-alkylpolyhydroxyalkylamides of the following formula (I) R3

I.

R ² C0-N- (Z) formula (I)

in the R- ^ CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ^ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and (Z) for a linear or branched polyhydroxyalkyl radical with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups.

The fatty acid N-alkylpolyhydroxyalkylamides are known substances which are usually obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanol and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride can be obtained. With regard to the processes for their preparation, reference is made to US Pat. Nos. 1,985,424; 2,016,962 and 2,703,798 and international patent application WO 92/06984.

The mixing ratios between organic and / or inorganic complexing agents on the one hand and the surfactant compounds, in particular the nonionic surfactants, on the other hand, in the SL-K can be varied within a wide range. Basically, the known knowledge applies here that surfactant components in particular can trigger effective effects even in very low concentrations. As a rule, the proportions of complexing agent on the one hand and surfactant compound on the other hand will be at most about 1: 1. In general, the weight of the nonionic surfactant component is used in a deficit compared to the complexing agent or mixture of complexing substances. Suitable amounts of the nonionic surfactant components can be in the range of, for example, 2 to 50% by weight, based on complexing agents, again corresponding amounts of niotene in the range of about 5 to 35% by weight being particularly important.

The sufficient cold solubility of the nonionic surfactant components when used in the SL-K precursor influences the specific selection of suitable components or component mixtures. Here you can additional professional knowledge is required. The nonionic surfactant compounds can be flowable at room temperature - especially in the case of fatty alcohol ethoxylates - but readily soluble nonionic surfactants or mixtures containing nonionic surfactants which are solid at room temperature are also suitable, provided that their solubility corresponds to the requirements of the teaching according to the invention. APG compounds of the type cited above are interesting components in solid form at room temperature, reference is made in this connection to the disclosure of the applicant's German patent application P 4340015.9, the details of which, for the purpose of the disclosure of the invention, hereby expressly also relate to the subject matter of the present disclosure be made.

In important embodiments of the invention, additional additional components are present in the SL-K. There are two basic options which can also be linked:

Third-party components of the SL-K mixture can at least predominantly have the task of controlling the ability to be assembled, the solubility in cold, the density and other physical or physico-chemical properties. In particular, known auxiliaries, such as water-soluble salts and the like, which have no inherent functionality in the course of the washing process, come into consideration here. The fact that their use can nevertheless be significant can be understood from the following consideration: In preferred embodiments, the HK and the SL-K are used as a material in the textile detergent of the trade. For example, the HK can be present in particularly important forms as granular granules, in particular in the form of a rounded sphere of a mixture of substances obtained by extrusion. In order to exclude segregation processes between HK and SL-K during storage and the practical handling of corresponding substance mixtures, the SL-K must also have a comparable design in terms of shape and density. It is obvious that the use of carrier salts without their own function in the washing process, for example, can play an important role here.

In further embodiments, however, the invention provides that the SL-K in addition to the two previously discussed recyclable materials nenten - the complexing agents and the tenside compounds - further mixture components with targeted intrinsic action in the course of the washing and cleaning process are added. The following may be mentioned as examples without claim to completeness: components which are suitable for oxidative textile bleaching, where both organic per compounds or components containing hydrogen peroxide and inorganic heel salts can be considered; Catalysts for intensifying the oxidative bleaching, as are known, inter alia, from the field of textile detergents under the name of the bleach activators; Enzymes, in particular from the classes of proteases, lipases, amylases and / or cellulases; Dirt dispersers and / or graying inhibitors. In addition to or instead of the further additives mentioned here for SL-K, other active substances from detergent technology and / or further auxiliaries can also be used, provided they do not have the functionality of SL-K shown to form the pre-liquor in the pH desired in each case - Collide area. Further details of a particularly important embodiment of the invention are given below.

Typical representatives of the additional auxiliaries mentioned here are named below without claiming to be complete. Suitable bleaching agent components that release H2O2 in water are sodium perborate / tetrahydrate (NaB02 ^• H2O2 ^• 3 H2O) and monohydrate (NaBÜ2 ^• H2O2). However, other borates which produce H2O2 can also be used, for example the Perborax Na β4θ7 ^• 4 H2O2. These compounds can be partially or completely by other active oxygen carriers, in particular by peroxyhydrates, such as peroxycarbonates (NaH2Cθ3 ^• 1.5 H2O2), peroxypyrophosphates, citrate perhydrates, urea-H2O2 or melamine-H2θ2- compounds as well as by peracid salts or peracids, such as perbenzoates, Peroxyphthalate, diperazelaic acid or diperdodecanedioic acid can be replaced. However, salts of other peracids, for example alkali salts of persulfuric acids - for example K2S2O8 - can also be important additional components in the sense of the action according to the invention.

In order to achieve an improved bleaching effect when washing at temperatures below 80 ° C. and in particular in the range from 40 to 60 ° C. Bleach activators have already been incorporated into the SL-K. Examples of these are N-acyl or 0-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, such as N, N, N ', N'-tetraacetyl-ethylenediamine (TAED), and also carboxylic anhydrides, such as Benzoic anhydride and phthalic anhydride and esters of polyols such as glucose pentaacetate. For the nature of completely different catalysts - for example representatives from the class of active substances for heterogeneous solid catalysis - see the corresponding information in the representation of a particularly important embodiment of the teaching according to the invention.

From the area of enzymes, the use of proteases in the SL-K is of particular importance when the SL-K pre-liquor leads to the setting of pH values in the acidic range. It has been shown that the pretreatment of soils containing proteins with a distinctly acidic SL-K pre-liquor can nevertheless lead to a noticeable protein degeneration, which has a negative effect in the subsequent washing process with HK. This can also apply to the case that washing-active proteases are used in the usual amounts in the HK. In the context of the teaching according to the invention, however, it was found here that even by using the proteases in the preliminary stage of the SL-K, this negative effect of protein degeneration can not only be eliminated, but more than made up for, especially when an acidic liquor is used . Even extremely small amounts of the proteases added to the SL-K are enough to ultimately ensure the desired washing effect even against protein-containing soiling. Enzymes obtained from bacterial strains or fungi such as Bacillus sub¬ tilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. The enzymes can be adsorbed on carriers and / or embedded in the coating substance in order to protect them against premature decomposition.

The customary components come into consideration as graying inhibitors or dirt dispersers which are possibly also used in the SL-K. Particularly suitable here are water-soluble colloids, mostly of an organic nature, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids, starch or cellulose or salts of acidic ren sulfuric acid esters of cellulose or starch. Polyamides containing water-soluble acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches and the like. Polyvinyl pyrrolidone can also be used. Preferred components can be cellulose ethers such as carboxyethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxyl propyl cellulose, methyl carboxymethyl cellulose and mixtures thereof and polyvinylpyrrole don.

For all other potential mixture components for the SL-K mentioned here, with regard to the amounts to be used in each case, it is generally the case that at most approximately equal proportions - based on the or the organic and / or inorganic complexing agents - are also used. The use of larger amounts of the additives will only make sense in special cases.

The previous presentation of the teaching according to the invention relates essentially to considerations regarding the interaction of the active substances or active substance mixtures of the SL-K with the textile material to be cleaned in the stage of the aqueous preliminary liquor. However, this only affects a portion of the effects which can be triggered if desired by teaching the action according to the invention. It must be taken into account here that the SL-K can also interact with the recyclable materials or mixtures of recyclable materials of the HK. Even if the HK as a whole is made available to the washing process as a time-delayed water-soluble component, the possibility of interaction between the active components of the active substance is nevertheless already in the early phases of the washing process - especially when water begins to enter the solid mixture of substances Given SL-K and HK.

One of these interactions used according to the invention has already been shown several times: the HK with its content of pH-regulating alkaline components is coordinated with the SL-K in such a way that the main wash cycle with the HK mix of valuable substances takes place in the desired basic range. finds. The range of possible interactions mentioned here is not limited to this simple process of pH regulation.

A variation which is possible according to the invention with the use of an SL-K component, which is particularly suitable for the primary formation of pH values in the acidic to neutral range in the pre-liquor, is shown in more detail here: an important sub-step in the washing process is the oxidative one Bleaching of the soiling. The bleaching active components used in practice today are the aforementioned salts which are capable of binding hydrogen peroxide, in particular corresponding perborates and / or percarbonates. An important sub-step in the complex reaction sequence of this oxidative influence on the soiling is the intermediate formation of peracids, in particular percarboxylic acids or their salts, which takes place through a primary reaction of the bound HO with, for example, carboxyl groups or their derivatives. The explanation given here for the activation of the bleaching process is based, for example, on the theory of the catalytic action of bleach activators of the TAED type, which are known to be used to accelerate and in particular to lower the activation temperature for the bleaching process in combination with perborate compounds.

The formation of the percarboxylic acid groups or their derivatives is obviously linked to an interaction with the H2O2 molecule of the introduced per compound. This fact is the basis for the conflict of the conflicting requirements: sufficient storage stability of the peroxide supplier in the dry detergent mixture on the one hand and sufficient reactivity at the lowest possible washing temperatures in the washing liquor in the context of textile washing. In today's detergent formulations, this conflict becomes a factor to be considered in particular if the textile washing is to be carried out at reduced temperatures, for example at 40 ° C. or at most 50 ° C.

The sufficiently stable storage of the hydrogen peroxide in the mixture of valuable materials of the commercial product requires the strongest possible integration and stability. bilization of the H2O2 into its carrier substance, on the other hand, the H2O2 should be available to the multi-stage reaction sequence of the textile bleach as easily as possible by conventional methods in the basic washing liquor.

According to the invention, this conflict can be substantially alleviated. The basis here is the known fact that the stability of peroxide compounds in the aqueous acidic range - and thus in one possible embodiment of the SL-K pre-liquor according to the invention - can be significantly reduced. If suitable auxiliary components for the formation of the bleach-oxidative-active acids are now offered as reactants at the same time in the preliminary liquor, then a significant relief can be achieved here compared to washing processes customary today. In particular, it also applies that in this preliminary stage the formation of wash-active peracids or peracid compounds can be accelerated again by using suitable catalysts. Finally, peroxide compounds - for example purely inorganic peroxides of the persulfate type - can also be used in small quantities here in order to promote the process of bleaching acceleration aimed at here by means of the SL-K preliminary stage without fear of damage to the textile goods.

The preferably polybasic carboxylic acids used for pH regulation in the context of the invention in the SL-K are, in principle, suitable transmitters, especially for the active oxygen in the context of the transaction shown here. However, not only monomolecular, in particular polybasic carboxylic acids in the sense of citric acid can be of particular importance, it has been shown that oligomeric and / or polymeric polycarboxylic acids can be particularly valuable auxiliaries in this reaction mechanism.

When dissolving the time-delayed HK in an acidic pre-liquor, there are conditions for a limited time in which the area of interactions between valuable materials from SL-K and HK to promote bleaching can take place. In an important embodiment, however, this course of the reaction is specifically enhanced by the fact that particularly suitable auxiliaries for promoting this reaction tion sequence can already be used in the SL-K. In particular, here:

The overall desired oxidative bleaching process can be initiated and sensibly influenced by its control at the stage of the SL-K pre-liquor. In this particularly important embodiment, water-soluble bleaching agents, and in particular water-containing H2O 2 compounds, are also used as a constituent of the SL-K - and not only in the time-delayedly soluble H -. In particular, here are the previously known bleaching agent components from textile washing technology, which are now activated by the choice and adjustment of the pH value of the aqueous preliminary liquor - preferably to the weakly acidic to neutral range - in their course of the reaction. In particular, it can be expedient here to use carboxylic acid compounds suitable for the interim formation of peracid together with hydrogen peroxide suppliers as constituents of the mixture of valuable substances to form the SL-K pre-liquor. Citric acid and / or its (partial) salts are here suitable and preferred components for initiating such reaction sequences in the particularly weakly acidic to neutral pH range. However, the other organic acids mentioned in connection with SL-K, in particular polybasic carboxylic acids, which are known, for example, as water-soluble builders capable of complex binding with polyvalent metal ions, can be suitable auxiliaries for the intended activation of bleaching . Examples include tartaric acid, but also lactic acid.

Together with this, already soluble compounds and in particular bleaching components that supply H2O2 in water are also used in the SL-K component. Already in the preliminary stage of treating the textile goods with the SL-K, the reaction steps of the bleaching are initiated and promoted. Overall, this can trigger a substantial increase in the washing result.

In this context, use can advantageously be made of further elements of the teaching according to the invention. It has been shown that by using organic framework substances based on polymeric polymers, carboxylates or the corresponding free polymeric polycarboxylic acids and / or their partial salts a particularly safe and long-term control and adjustment of the pH of the SL-K pre-liquor is possible. Using limited amounts of these polymeric acids, the pH of the pre-liquor can be ensured, for example, for a period of several minutes to predetermined values in the desired weakly acidic to neutral range - if desired, but also in the weakly basic range - without it special reinforcement of the solution inhibition of HK needs. With the simultaneous entry of the HK as spherically rounded extrudate grains on the one hand and the SL-K as a quickly soluble component on the other hand, the preselected pH value of the previous liquor, for example between 6 and 7, can be ensured for a period in the last case described here of about 2 to 8 minutes, in particular 3 to 6 minutes, without simultaneously using additional measures for further delaying the solution of the HK. In connection with the form of activating the bleach already in the SL-K preliminary stage, important advantages can thus be obtained. The specifically adjustable pH range of a reduced stability of the H2O2 suppliers in the aqueous liquor is available for a predeterminable period of time before the pH value increases to the strongly alkaline area of the main washing process due to the HK dissolving in the previous liquor . It is obvious that the peroxidic sub-process of the washing step can be specifically promoted.

In this context, in a further preferred embodiment, the partial result sought here can be reinforced. For this purpose, activators or catalysts for peracid formation in the SL-K fleet are also used. Basically known catalysts come into consideration here, for example organic complex compounds of metals which can occur in several valence levels - for example iron and / or manganese. However, completely different auxiliaries of the type mentioned are also suitable here, which can be assigned, for example, to the class of finely divided, insoluble heterogeneous catalysts. Examples of these are oxidic compounds of metals such as titanium or tungsten, silicate compounds which are insoluble in the pH range mentioned, for example corresponding aluminum silicates, but also heterogeneous Catalysis of known active substances such as activated carbon, which can be incorporated into the washing process, for example in packaged but water-permeable form. Finally, it has been shown that the use of conventional bleach activators can also make sense in the preliminary stage of the SL-K pre-liquor. This is immediately understandable for the embodiments in which the SL-K pre-liquor already works in the basic area. Suitable mixture components for the SL-K in the embodiment concerned here are, in particular, the N-acyl or O-acyl compounds which form with H2O2 organic peracids, preferably N, N'-tetraacylated diamines, and also carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. All further developments shown here in the SL-K composition are characterized by an honor-functional concept, which is not provided in the prior art in this embodiment. The use of the snow-soluble complexing agents in the preliminary liquor primarily influences the water hardness and the conditioning of the textile or the dirt incrustation on the textile with the complexing agents. At the same time, this work stage is used to initiate the wash-active bleaching process, which can then be optimized with the HK in the subsequent main wash cycle.

Before going into the - in itself usual - composition of the main component HK, which is soluble in a delayed manner, the following should be briefly stated again regarding the concrete form of the SL-K in the textile / laundry detergent mixture preferred according to the invention: In addition to the previously discussed mixing in of the SL-K In a grain-shaped HK material as a separate mixture component which is adapted to the HK in terms of spatial shape and density - preferably also in grain form - there is a completely different possibility of combining HK and SL-K. Here, the SL-K can be applied to the outer surface of the HK material so preformed at least in part after the HK has been formed, for example in the form of spherically rounded extrudate grains, and solidified there. If necessary, an intermediate layer with, for example, a hydrophobizing effect between the core and the outer shell not only ensures the storage stability of the goods combined in this way for an unlimited period of time, but also in particular the adjustable variable time delay in the Dissolution of the HK and thus the determination of the time period for the treatment of the soiled textile goods with the SL-K fleet. In practical use, the rapidly soluble shell of the SL-K is first detached from the respective ball. In this way, the time-delayed separating layer, if any, is exposed, so that in the further dissolving process the dissolution of the HK and thus the main washing cycle are only initiated after it has been overcome.

The use of appropriate time-delayed separating layers on the outer surface of the HK can also be useful in the first case, in which SL-K and HK are used from the start as spatially separate elements of the detergent mixture. If necessary, in addition to or instead of these measures, the outer casing of the HK and / or the SL-K can be provided with a preferably approximately pH-neutral solid, water-soluble and / or -dispersible material layer, which has an adequate storage stability of the mixtures of HK and SL K guaranteed under normal practical conditions, for example in carton packs. Here too, the knowledge of general specialist knowledge applies, taking into account the specific elements of the teaching according to the invention discussed above.

The SL-K is generally used in minor amounts by weight - based on HK - in the detergent mixture. In general, the amounts of SL-K are in the range up to at most 50% by weight and normally up to about 30% by weight, with amounts of SL-K - again based on HK - in the range from about 1 to 20% by weight. % and preferably about 1 to 15% by weight are normally used. The following examples show that with very small amounts of SL-K, which are, for example, in the range from about 1 to 10% by weight and preferably in the range up to at most about 5% by weight, in each case based on HK, the effects of multi-stage washing desired according to the invention can be adjusted with improved washing performance. The following additional considerations apply:

The active components of the SL-K, in particular their content of complexing agents and / or surfactant compounds, can be provided in addition to the corresponding components of the HK in the detergent mixture according to the invention. It is also possible, however, to take the active components used as SL-K from the multifunctional recyclable mix at HK, to use the pre-stage of SL-K washing to react with one another (partially) and on the soiled textile goods, but then in to combine the following main wash with the HK. Ultimately, the teaching according to the invention thus includes an improved embodiment for the use of complex textile detergent formulations in the form of the highly compressed multicomponent mixture desired today with delayed solubility. By assigning a portion of the multicomponent mixture to the shape of the SL-K, a widening and improvement of both the secondary and the primary washing effect can be achieved.

Basically, the structure of the HK, according to the type and amount of its ingredients, is based on the information in the printed state of the art known to experts. In this connection, reference is made in particular to the following publications, which go back to the applicant: International patent applications WO-A-91/02047, WO-A-93/02176 and WO-A-94/01526 and the relevant literature cited therein.

In the following, the known knowledge about the composition of the wash-active HK for the formation of the alkaline main wash liquor is summarized in a shortened version. However, the fact that the components of the SL-K can at least partially be taken from the HK if desired and thus are used in the HK in question in the sense of the teaching according to the invention there is correspondingly reduced in quantity. However, the action according to the invention is not restricted to this. An important embodiment provides for the use of preparations of detergent mixtures with an SL-K which are known and are at least predominantly time-delayed, the component (s) of which are additionally introduced into the multistage washing process designed according to the invention.

The HK in the sense of the definition according to the invention is a solid, preferably granular, mixed material containing

5 to 40% by weight anionic surfactant

1 to 20% by weight of nonionic surfactant 10 to 65% by weight builder up to 35% by weight, preferably 5 to 15% by weight alkali component up to 15% by weight, preferably 3 to 7% by weight cobuilder up to 40% by weight, preferably 10 to 30% by weight bleaching agent up to 15% by weight, preferably 1 to 10% by weight bleach activator up to 20% by weight, preferably 2 to 10% by weight alkali silicate 0.1 to 10% by weight. % of at least one substance from the group of foam inhibitors, foam boosters, fabric softeners, graying inhibitors, optical brighteners, dyes, adjusting agents, fillers and 1 to 20% by weight of water.

Particularly preferred as HK can be, for example, granular solid mixtures of the following composition, produced, for example, by extrusion, wet agglomeration, roller compaction and the like:

5 to 35% by weight of anionic surfactant from the group of alkylbenzenesulfonates, fatty alcohol sulfates, fatty alcohol ether sulfates, olefin sulfonates and / or fatty acid alkyl ester sulfates 50% by weight of zeolite NaA, NaX and / or NaP up to 20% by weight, preferably 5 to 15% by weight of alkali carbonate up to 10% by weight, preferably 3 to 7% by weight of polycarboxylic acid 13 to 25 % By weight bleaching agent 1 to 10% by weight bleach activator up to 6% by weight, preferably 2 to 5% by weight alkali silicate 0.1 to 3.5% by weight foam inhibitor and 1 to 3% by weight one or more substances from the group of textile softeners, graying inhibitors, enzymes, optical brighteners, dyes, fragrances, formulation auxiliaries and / or adjusting agents.

With regard to the individual components of the above-mentioned detergent preparations, the following applies in particular: Anionic surfactants are generally surfactants of the sulfonate type or of the sulfate type. The surfactants containing sulfate groups include, in particular, alkyl sulfates and the corresponding sulfation products of alkoxylated, in particular ethoxylated, alcohols. Surfactants containing sulfonate groups are in particular alkylbenzenesulfonates, alpha-sulfofatty acid ester salts and alpha-sulfofatty acid disalts. The anionic surfactants are usually in the form of their alkali metal salts, in particular their sodium salts.

Addition products of 2 to 20, preferably 3 to 15 moles of ethylene oxide and 1 mole of a compound having essentially 10 to 20 carbon atoms from the group of alcohols and alkylphenols can be used as nonionic surfactants. In particular, reference is made to the information previously given in connection with the SL-K.

In addition to these water-soluble nonionic surfactants, polyglycol ethers with 2 to 6 ethylene glycol ether residues in the molecule which are not or not completely water-soluble are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants. Further suitable nonionic surfactants are alkyl glycosides or alkyl polyglycosides, the alkyl group of which has 8 to 18, preferably 10 to 16, carbon atoms.

Main builder components for the HK, which are used to exchange the polyvalent metal ions, in particular calcium ions, bound in the SL-K, are in particular synthetic zeolites, polycarboxylic acids and crystalline and / or non-crystalline alkali silicate compounds suitable for calcium binding, in particular the have already mentioned Q2 and / or Q3 structure. Reference is hereby expressly made once again to the disclosure of the applicant's earlier industrial property rights cited in this context.

Zeolite NaA with a calcium binding capacity (according to the information in DE 2224837) in the range from 100 to 200 mg CaO / g is an important builder component in the sense of a finely insoluble ion exchanger when building up the HK. Polymeric polycarboxylates suitable as builder components are, for example, the sodium salts of polyacrylic acid or of polyacrylic acid. methacrylic acid, for example those with a molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. In particular, terpolymers which are described in German patent DE 4221 381 and DE-A 4300722 are also preferred as polymeric polycarboxylates. The acids mentioned are usually used in the form of their water-soluble salts, in particular the sodium salts.

However, biodegradable terpolymers are also suitable in this connection, for example those which are salts of acrylic acid and maleic acid as monomers and vinyl alcohol or vinyl alcohol derivatives (DE-A 4300772) or salts of acrylic acid and 2-A1-alkylallylsulfonic acid as monomers as well as sugar derivatives (DE-A 4221 381).

Other suitable builder substances from HK are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids having 5 to 7 carbon atoms and at least 3 hydroxyl groups - see EP-A-0280223. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Suitable alkali components are alkali silicates, in particular sodium silicates of the composition Na2θ: Siθ2 = 1: 1 to 1: 3.5, preferably 1: 2 to 1: 3.35. Alkali carbonates and hydroxides, in particular the sodium compounds, are also suitable as alkali components.

The HK components according to the invention may contain phosphonic acids, for example aminoalkanephosphonic acids, as cobuilders. Preferred here are ethylene diamine tetramethylene phosphonate (EDTMP), diethylene triamine pentaethylene phosphonate (DTPMP) and their higher homologues. They are preferably used in the HK in the form of neutral sodium salts, for game as hexasodium salts of EDTMP or as hepta and octa sodium salts of DTPMP. Their proportion in the agents, calculated on free acid, is preferably up to 1% by weight, in particular 0.1 to 0.5% by weight. Another suitable phosphonic acid is the HEDP or the sodium salt or the tetra-sodium salt of this acid.

As stated above, the HK contains in particular bleaches and bleach activators. Suitable bleaching agents are, in particular, water-providing compounds of H2O2 of the type mentioned above in connection with the SL-K. The chemical nature of the bleach activators has already been explained in connection with the SL-K. Reference is made to this. In addition, reference is made to the disclosure of the applicant's already mentioned WO 94/01526, the disclosure of which is hereby expressly made the subject of the present disclosure of the invention.

The detergents can contain, as optical brighteners for cotton, in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. For example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazin-6-yl-amino) -stilbene-2,2'-disulphonic acid or the like are suitable Compounds built up which carry a diethanolamino group, a methyl ino group or a 2-methoxyethyl ino group instead of the morpholino group. Possible brighteners for polyamide fibers are those of the 1,3-diaryl-2-pyrazoline type, for example l- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline. Brighteners of the substituted 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl type can also be used. Mixtures of the aforementioned brighteners can also be used.

The representatives already mentioned in connection with the SL-K can be considered as enzymes. The enzymes can be adsorbed on carriers and / or embedded in Hü11 substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight. Suitable foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Bis- ^{acylamides derived} from Ci2-20- ' ^{fatty acids uπ (} l C2-6-diamines or from Ci2-20 ~ ^A ^ l ^am ^ ^{nen and (} * C2_6-dicarboxylic acids are also useful. Mixtures of different foam inhibitors are also advantageously used, for example those made from silicones and paraffins or waxes, or from bis-acylamides and paraffins or waxes, The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.

Layered silicates from the classes of bentonites and sectites are suitable as textile softening additives, for example those according to DE 2334899 or EP 026 529. Also suitable are synthetic fine-particle layered silicates with a smectite-like crystal phase, as characterized in more detail in DE 3526405. The layered silicate content can be, for example, 5% by weight to 20% by weight.

B e i s p i e l e

The following examples show the washing results which have been obtained in standardized washing tests in a household washing machine under identical conditions in each case. The following details apply:

Washing machine:

Household washing machine Zanussi Z914E, fleet volume approx. 20 1 per main wash. The duration of the main wash was 40 minutes. The temperature setting on the machine input: 60 ° C, 2 rinse cycles.

Textile load per wash:

3.5 kg terry towels. One of these terry towels is equipped with 10 differently soiled standard fabric samples, cf. the subsequent identification of these test samples.

The detergent mixture used in each case was added to the wash cycle in all cases via the induction chamber provided in the machine. In all washing trials, municipal cold tap water (average hardness 16 ° dH) is used to rinse the detergent mixture and prepare the washing liquor, as well as for the subsequent multiple rinsing of the washed material samples.

The degree of soiling in the soiled test cloth used in the washing process on the one hand and the test cloth washed, rinsed and dried in the respective wash cycle on the other hand is determined by measuring the reflectance with the Micro-Color V 2.1 from Dr. Long, FRG.

In the washing tests given below, 10 differently soiled test laps were subjected to the washing process with the respective textile detergent mixture. The 10 test flaps provided with standard soiling were used as part of the illustration of the examples Numbered consecutively from 1 to 10 and identified as follows.

Running number of soiling and Test fabric reflectance value of the feed material (average of 5 measurements each)

1 MR-B

Milk / soot on cotton 48.2 2 BMR-B

Blood / milk / soot on cotton 41.8 3 K-PBV

Coffee on polyester / cotton

(refined) 69.9

SH-BV

Dust / skin fat on cotton

(refined) 57.9

5 R-BV

Red wine on cotton (refined) 69.2 6 T-BV

Tea on cotton (refined) 72.7 7 SH-BPV

Dust / skin fat on polyester /

Cotton (refined) 58.2

8 LS-PBV

Lipstick on polyester /

Cotton (refined) 48.4

SW-B

Dust / wool grease on cotton 68.3

10 SH-P

Dust / skin fat on polyester 62.9 Comparative provisions

In a first series of washing tests, the cleaning results on the test soils 1 to 10 were carried out under identical washing conditions, using a compressed universal detergent available as a spherical extrudate - commercial product of the applicant according to the disclosure of the international patent application W0-91 / 02047 - certainly.

In successive experiments, this universal detergent was used in amounts of 60 g, 80 g and 100 g - in each case per washing process. This product, which is used as the “main component” in the sense of the invention, is referred to below as “UWM-HK”.

The reflectance values were determined on the rinsed and dried test rags. The following results were obtained:

60 g UWM-HK / 60 ° C per wash oano

Test No. : 1 2 3 4 5 6 7 8 9 10

Remission value: 74.8 59.2 90.8 86.3 85.5 82.8 82.6 79.9 80.1 86.0

Sum of the measured remission values: 808.0

The lower and upper limit values of the pH of the wash liquor - pH min and pH max - determined in the course of the wash were here: pH min: 7.7 pH max: 9.3

80 g UWM-HK / 60 ° C per wash - average of 3 wash attempts

Test No. : 1 2 3 4 5 6 7 8 9 10

Remission value: 78.8 64.4 90.7 89.2 85.5 85.0 80.5 88.6 82.3 86.3 Sum of the measured remission values: 831.3

pH min: 7.6 pH max: 9.7

100 g UWM-HK / 60 ° C per wash

Test No. : 1 2 3 4 5 6 7 8 9 10

Remission value: 84.3 66, 7 91, 2 90.0 86.9 85.8 80.5 87.0 86.5 85.8

Sum of the measured remission values: 844.7

pH min: 7.7 pH max: 9.9

Examples of the invention

In the subsequent experiments, a total amount of detergent used of 80 g per batch was assumed. The previously defined UWM-HK from the applicant was used as the main component with delayed solubility.

Along with this, valuable substances or valuable substance mixtures in the sense of the snow-soluble component (SL-K in the sense of the definition according to the invention) were also used.

The amount of UWM-HK used specifically in the respective test was reduced by the total amount of SL-K (mixture) used in the test concerned, so that in all cases the amount of the valuable materials used was taken as a whole Was 80 g per wash.

The SL-K component (s) were placed together with the UWM-HK in the wash-in chamber of the washing machine and from there transferred to the machine room using the wash-in water. The heating of the wash liquor to the pregiven bene main wash temperature (60 C ^β) carried out by the Machine provided heating elements, the temperature of the cold detergent liquor was in the range around 20 ° C. The beginning of the temperature rise by heating the wash liquor began after about 6 to 8 minutes of the respective washing process.

The following examples first identify the SL-K used in each case by type and quantity and the resulting quantity of use of the UWM-HK. The remission values determined after rinsing and drying twice are summarized in tabular order for the test stains 1 to 10.

The values for pH min and pH max and the time until neutralization of the wash liquor (pH 7) are also given if SL-K is used with acidic pH values in the initial phase of the washing process.

example 1

SL-K: 3.7 g of mono-potassium citrate together with 0.3 g of a nonionic surfactant based on fatty alcohol ethoxylate (commercial product "Dehydol LT 7" ( ^R ) from the applicant - Ci2-18 " ^tretta l '^< ohol - 7 EO) hereinafter referred to as "LT-7".

HK: 76.0 g UWM-HK

The reflectance values determined on the washed test soils are summarized in the following table:

Test No. : 1 2 3 4 5 6 7 8 9 10

Remission value: 80.8 61, 0 90.9 89, 1 87, 3 84, 1 82.2 89, 1 83.2 87, 2

Sum of the measured reflectance values: 834.9 pH min: 6.0 pH max: 9.3

Time to neutralization: 3.9 min Example 2

SL-K: 2.0 citric acid, 0.3 LT 7 with the addition of 0.2 TiO 2 HK: 77.5 g UWM-HK

The reflectance values determined on the washed test soils are

Test No. : 1 2 3 4 5 6 7 8 9 10

Remission value: 76.2 61, 6 91, 2 89.2 89.8 86, 2 83.7 90.2 82, 1 87, 1

Sum of the total remission values determined: 837.3 pH min: 5.7 pH max: 9.1

Time to neutralization: 2.0 min

The individual comparison of the washing results obtained with the corresponding values of the comparative tests yields a number of interesting information:

The acidic initial values of the wash liquor apparently lead to a degeneration of the protein-containing soiling to the test laps according to (1) and (2). The washing results obtained with the use of the SL-K were worse here than when 80 g UWM-HK were used as the sole multifunctional detergent component. Nevertheless, the total value of the overall remission numbers determined is higher than the mean value of the comparative tests for washing with 80 g UWM-HK. The reason for this is the sometimes considerable increase in the washing result with other test soiling.

The individual comparison of the washing results with the comparative test 100 UWM-HK is also interesting in this context: The drop in the washing result for protein-containing soiling (1) and (2) was again significantly more pronounced here, but was more so for the test soiling 3 to 8 and 10 achieved the same or even significantly better washing results than the values of the comparative test. This fact can be seen against the background of the fact that the invented the formulation according to the invention according to Example 2 uses the HK portion leaned to 76 g UWM-HK, while in the comparison test concerned the almost 1/3 higher amount of the universal detergent mixture (100 UWM-HK) was used.

Example 3

In the following, the results of two detergent batches are summarized in the sense of the teaching according to the invention, which in the SL-K also use a small amount of a bleach activator (TAED) in addition to setting an acidic pH in the SL-K. The following applies in particular:

Example 3 a:

SL-K: 3.0 g of citric acid together with 0.3 g of a nonionic surfactant based on fatty alcohol ethoxylate (commercial product "Dehydol LT 5" from the applicant) and 0.7 g of TAED

HK: 76 g UWM-HK

The following reflectance values were determined on the washed test soils:

Test No. : 1 2 3 4 5 6 7 8 9 10

Remission value: 78, 1 62.5 90.9 89.3 88.3 85.3 78, 1 90, 1 84.6 85.8

Sum of the total remission values determined: 832.9 pH min: 4.5 pH max: 9.3

Time to neutralization: 2.8 min

Example 3 b:

SL-K: 2.0 g citric acid together with 1.5 g sodium bicarbonate, 0.2 g LT 7 and 0.3 g TAED HK: 76 g UWM-HK

The following reflectance values were determined on the washed test soils:

Test No. : 1 2 3 4 5 6 7 8 9 10

Remission value: 77, 6 62, 7 91, 0 89.9 87, 5 85, 5 81, 4 90, 3 81, 8 86, 0

Sum of the total remission values determined: 833.7 pH min: 6.2 pH max: 9.3

Time to neutralization: 2.5 min

In both Example 3a and 3b, the sum of the overall reflectance values corresponds approximately to the comparative value when using 80 g UWM-HK, although, as expected, the washing results for protein-containing soiling (1) and (2) are reduced and also the amount of HK heavy-duty detergent components had been reduced from 80 g to 76 g.

Example 4

Here, too, two separate washing tests are summarized, which are characterized by a common determination element. In both cases, in addition to citric acid and the non-ionic surfactant compound, the SL-K also contained the usual form of preparation of a detergent protease (BLAP). The details here were:

Example 4 a:

SL-K: 2.0 g citric acid together with 0.3 g LT 7 and 0.7 g BLAP HK: 77 g UWM-HK

The reflectance values of the washed test materials 1 to 10 were as follows: Test No. : 1 2 3 4 5 6 7 8 9 10

Remission value: 80, 7 70.0 90.9 89, 5 86, 9 84.3 80, 2 90, 3 82, 9 85.9

Sum of the total remission values determined: 841.6 pH min: 5.6 pH max: 9.3

Time to neutralization: 2.0 min

Example 4 b:

SL-K: 3.0 g citric acid together with 0.3 g LT 7 and 0.7 g BLAP HK: 76 g UWM-HK

The following remission values were determined on the washed test soils:

Test No. : 1 2 3 4 5 6 7 8 9 10

Remission value: 82.6 68, 9 90, 9 89, 6 84.8 86.8 80.5 90.4 83.4 85.5

Sum of the total remission values determined: 843.4 pH min: 5.0 pH max: 9.4

Time to neutralize: 2.2 min

The evaluation of both washing tests shows that the use of small amounts of the washing-active protease component BLAP in the SL-K more than compensated for the loss of activity observed in the acidic prewash to the protein-containing soiling (1) and (2). In both cases, the total values of the overall reflectance values determined are clearly above the corresponding total value of the work in the absence of the SL-K according to the invention with 80 g UWM-HK.

The total remission value of both experiments is approximately in the order of magnitude of the corresponding value from the comparative wash with 100 g UWM-HK, although in these two experiments as well, according to the invention Teaching that the amount of UWM-HK used as HK was significantly reduced.

Example 5

In the following example 5, 3 washing tests are summarized, each of which contained the mixture of citric acid and the nonionic surfactant LT 7 as basic SL-K components. In addition, the following additional auxiliary components were used in the SL-K:

Potassium persulfate (K2S2O8) as an inorganic oxidatively active component (Example 5 a); a mixture of T1O2 and BLAP (Example 5 b) and the mixture of BLAP and K2S2O8 (Example 5 c). The details here were:

Example 5 a:

SL-K: 2.0 g citric acid together with 0.3 g LT 7 and 0.2 g K2S2O8 HK: 77.5 g UWM-HK

The determined remission values are:

Test No. : 1 2 3 4 5 6 7 8 9 10 Remission value: 79, 0 62.8 91, 0 89.4 87, 7 85.4 81, 7 90.6 82, 1 87, 1

Sum of the total remission values determined: 836.8 pH min: 5.7 pH max: 9.2

Time to neutralization: 2.4 min

Example 5 b:

SL-K: 1.7 g citric acid together with 0.3 g LT 7, 0.2 g TiO 2 and 0.7 g

BLAP

HK: 77.1 g UWM-HK The following reflectance values were determined on the test soiling:

Test No .: 1 2 3 4 5 6 7 8 9 10 Remission value: 78.5 65.0 90.8 87.6 86.4 84.9 85.3 88.6 82.987.2

Sum of the total remission values determined: 837.2 pH min: 5.7 pH max: 9.7

Time to neutralization: 2.0 min

Example 5 c:

SL-K: 1.7 g citric acid together with 0.3 g LT 7, 0.2 g K2S2O8 and 0.7 g

BLAP

HK: 77.1 g UWM-HK

The following remission values were determined:

Test No .: 1 2 3 4 5 6 7 8 9 10

Remission value: 85.7 63.5 91.1 88.8 87.5 86.3 84.1 90.7 82.8 86.7

Sum of the total remission values determined: 847.2 pH min: 6.2 pH max: 9.2

Time to neutralization: 2.9 min

The comparison of the values of the washing tests shown here with the comparative tests given at the beginning provides a number of interesting results: As expected, in example 5 a the washing results for the protein-containing test soils (1 and 2) were reduced compared to the comparison with 80 g UWM-HK. Nevertheless, the sum of the measured remission values lies clearly above the sum value from the comparison with 80 g UWM-HK. The reason for this was the almost better washing results of the further test stains in almost all cases. Example 5b achieved the washing results of the comparison test with 80 g UWM-HK using the wash-active protease in the test soils (1 and 2) despite a considerably acidic starting pH of the wash liquor (5,7). The cleaning results for the other test soils were obtained overall in such an improved form that the comparison of the total values shows a clear increase for the 2-stage wash according to the invention.

The increase in the washing result is most impressively demonstrated by the numerical material of the experiment 5 c. The total value clearly exceeds the corresponding value from conventional laundry with 100 g UWM-HK, although the amount of UWM-HK used in this experiment was only about 77 g.

Example 6

The following examples 6 a and 6 b show a reduction in the UWM-HK used as the main component HK by more than 10%, based on the amount of 80 g used in the comparative tests. The SL-K used in each case contained, in addition to the combination of citric acid and the nioteside component LT 7, the bleaching component sodium perborate monohydrate known from the field of textile detergents, hereinafter referred to as "P2". In particular:

Example 6 a

SL-K: 5.8 g citric acid together with 0.3 g LT 7 and 2.2 g P2 HK: 71.7 g UWM-HK

The reflectance values determined on the washed test soils resulted as follows:

Test No. : 1 2 3 4 5 6 7 8 9 10

Remission value: 74, 7 61, 9 91, 0 87, 7 87, 9 84, 9 82.4 89.5 81, 3 86.4 Sum of the total remission values determined: 827.7 pH min: 5.9 pH max: 9.0

Time to neutralization: 2.7 min

As already shown before, the washing result for the test soils (1) and (2) also dropped compared to the comparison test with the HK as the sole detergent component at the comparatively acidic starting pH of the pre-liquor.

Example 6 b

SL-K: 3 g citric acid together with 0.3 g LT 7 and 4 g P2 HK: 72.7 g UWM-HK

The following remission values were determined:

Test No. : 1 2 3 4 5 6 7 8 9 10

Remission value: 78.4 62.6 90.8 88.5 86.0 88, 3 80, 3 88.8 83, 7 85, 7

Sum of the total remission values determined: 828.1 pH min: 7.4 pH max: 9.4

In this approach, an initial pH range of the pre-liquor in the neutral to very weakly basic range was selected. The comparison of the reflectance values for the test soils (1) and (2) compared to example 6 a and compared to the comparison values with 80 g UWM-HK as detergent shows that there was a significantly lower reduction in the washing result with regard to the protein-containing soiling.

For both tests of this example it is true that although the total value of the comparison test with 80 g UWM-HK is not quite reached, the 2-stage wash liquors constructed according to the invention only lead to insignificantly reduced total values, although the proportion of the UWM -HK has been lowered very considerably. In this context, it should also be taken into account the fact evident from the comparative tests that the total value of the washing result with 60 g UWM-HK is only 808.0.

Example 7

The following example compiles two test batches and the results obtained, which in the SL-K based on citric acid / LT 7 are a combination of the sodium perborate monohydrate "P2" with the polycarboxylate known as a detergent builder or co-builder. Sokalan ( ^R ) CP5 "- manufacturer BASF - were used. Example 7a worked with an initial pH of the pre-liquor in the weakly acidic range, Example 7b matched the components of the SL-K used in such a way that the initial pH of the SL-K Pre-liquor was in the neutral range.

It was striking in the pH course of both batches that - apparently due to the use of the polycarboxylate component "CP5" - the primary pH of the pre-liquor remained constant over a comparatively long period and only then to the higher pH ranges of the HK -Washing fleet rising.

In particular:

Example 7 a

SL-K: 2.3 g citric acid together with 0.2 g LT 7, 1.0 g P2 and 1.5 g CP5 HK: 75 g UWM-HK

The following reflectance values were determined on the test samples washed under standard conditions:

Test No. : 1 2 3 4 5 6 7 8 9 10

Remission value: 84.3 65.0 91, 0 90.2 86, 5 83, 5 80.4 91, 2 83, 9 86.9

Sum of the total remission values determined: 842.9 pH min: 6.2 pH max: 9.6 Time to neutralization: 4 min

The comparatively good reflectance values for test samples (1) and (2) were striking, although the pH range of the pre-liquor was clearly in the acid range.

Example 7 b

SL-K: 2.6 g citric acid together with 0.2 g LT 7, 2.0 g P2 and 2.0 g CP5 HK: 73.8 g UWM-HK

The following reflectance values were determined on the washed test soils:

Test No. : 1 2 3 4 5 6 7 8 9 10

Remission value: 91.4 68.6 91.0 89.3 85.3 83.9 82.6 91.3 83.5 88.0

Sum of the total remission values determined: 854.9 pH min: 7.0 pH max: 9.1 Time period at pH 7: 4 min

In the sum of the determined reflectance values, but also in the majority of the individual reflectance values, the washing result of this example was significantly above the comparison test using 100 g UWM-HK as the sole detergent component. The same was true to an even greater extent than the comparative tests using 80 g UWM-HK as the sole detergent component.

Example 8

As SL-K, the approach described here used a mixture of valuable substances consisting of citric acid, alkyl glycoside "APG" as a surfactant compound, fatty alcohol sulfate (anionic surfactant) and water glass. In addition to the citric acid, the last 3 components mentioned were in the form of a Dried compounds APG / FAS / water glass 45/45/10 used. In particular:

SL-K: 2.5 g citric acid mixed with 1.5 g of the previously mentioned multi-component compound HK: 76 g UWM-HK

The washing results on the test soils used were the following:

Test No. : 1 2 3 4 5 6 7 8 9 10

Remission value: 79, 5 63.8 90.8 89, 1 86, 5 80, 5 84.3 90.2 83.2 86.2

Sum of the total remission values determined: 834.4 pH min: 4.8 pH max: 9.2

Time to neutralization: 2.3 min

The clear increase in washing power compared to the test stains (7) and (8) was striking.

Example 9

Example 9a below describes the application of the principle of multi-stage washing according to the invention with a basic SL-K pre-liquor. Here, trisodium citrate was used as a complexing agent in a mixture with the APG / FAS / water glass compound described in Example 8.

Example 9b modified the SL-K approach in such a way that trisodium citrate in combination with LT 7 was used as the surfactant component. Here, too, basic washing conditions are established in the pre-liquor of the SL-K component.

Example 9 c finally modified the approach of Example 9 a in such a way that a soda / 01igo sodium silicate compound was used instead of the trisodium citrate. To manufacture these builder components with the For calcium binding cf. the corresponding information in the general description section.

In particular:

Example 9 a

SL-K: 3.0 g trisodium citrate mixed with 1.0 g APG / FAS / water glass

Compound

HK: 76.0 g UWM-HK

The following washing results were obtained:

Test No .: 1 2 3 4 5 6 7 8 9 10

Remission value: 82.4 62.5 90.2 90.5 86.6 84.8 83.2 88.9 81.9 86.5

Sum of the total remission values determined: 837.5 pH min: 7.4 pH max: 9.3

Example 9 b

SL-K: 3.75 g trisodium citrate together with 0.25 g LT 7 HK: 76.0 g UWM-HK

The following washing results were obtained:

Test No .: 1 2 3 4 5 6 7 8 9 10

Remission value: 82.9 64.7 90.7 89.5 85.4 83.1 79.0 87.6 82.6 86.3

Sum of the total remission values determined: 831.8 pH 9.6 after 1 min Example 9 c

SL-K: 3.0 g soda / natriu oligosilicate compound together with 1.0 g APG co-pound (according to Example 8)

HK: 76.0 g UWM-HK

The following washing results were obtained:

Test No. : 1 2 3 4 5 6 7 8 9 10

Remission value: 80.6 64.3 90.7 89.0 86.0 84.2 80.7 88.7 84.6 86.7

Sum of the total remission values determined: 835.5 pH min: 7.6 pH max: 10.0

Example 10

This example shows that the partial replacement of UWM-HK with SL-K can also significantly improve secondary washing capacity such as ash formation, overall incrustation and graying inhibition, although very good values can already be achieved by UWM-HK alone.

The test was carried out under practical conditions in household washing machines. For this purpose, the machines were loaded with 3.0 kg of clean laundry and 0.5 kg of test fabric, the test fabric consisting of white fabric. Strips of standardized cotton fabric (Krefeld laundry research institute; WFK), nettle (BN), knitwear (cotton jersey; B) and terry toweling fabric (FT) were used as the white test fabric. Washing conditions: tap water of 23 ° d (equivalent to 230 mg Ca0 / 1), amount of detergent used per detergent (UWM-HK alone or UWM-HK and SL-K) and machine (80 g), 90 ° C washing program ( including heating up phase), liquor ratio (kg of laundry: liters of wash liquor in the main wash cycle) 1: 5.7, rinsing three times with tap water, spinning off and drying. After every 25 washing cycles, both the graying inhibition and the ash content of the textile samples were determined quantitatively.

Example 10a

HK: 77.5 g UWM-HK, as defined above

SL-K: 2.5 g citric acid

Example 10b

HK: 75 g UWM-HK, as defined above

SL-K: 5 g citric acid

Example 10c

HK: 77.5 g UWM-HK, as defined above

SL-K: 2.5 g sodium citrate

Example lOd:

HK: 75 g UWM-HK, as defined above

SL-K: 5 g sodium citrate

Wt% ash FT BN B WFK

Initial value 0.78 0.15 0.68 0.23 0.46

UWM-HK (80 g) 2.53 1.93 2.97 2.32 2.44

Example 10a 2.41 1.71 2.21

Example 10b 2.38 2.20

Example 10c 1.72 2.31

Example 10 2.22 1.61 2.70 2.22 2.19

The total incrustation (from incrustation and residual ash) was also reduced by more than 10% overall over all determinations. Graying inhibition (remission in%)

FT BN WFK

Initial value 84.1 84.1 83.9 86.2 84.6

UWM-HK (80g) 70.9 73.8 70.1 72.7 71.9

Example 10b 72.4 75.1 71.3 73.5 73.1

Example IOD 73.0 74.2 72.2 72.5 73.0

Claims

Expectations

Solid textile detergent in the form of a mixture of detergent active substances and, if desired, auxiliaries - detergent surfactant compounds, alkalizing agents, builders soluble and / or finely insoluble in water-alkaline loading, or builders with the ability to bind calcium, and, if desired, further conventional active and / or auxiliary components vo textile detergents - which are at least partially prepared for a compacted mix with time-delayed solubility in cold water (slowly soluble main component "HK"), characterized in that they additionally - but as a separate component from the HK - at least one also quickly soluble in cold water Component ("SL-K") based on cold-soluble complexing agents for the polyvalent cations of water hardness and their mixtures with cold-soluble surfactant compounds.

Textile detergent according to claim 1, characterized in that the delay in dissolving the HK in the initial phase of the washing process is sufficient to ensure at least the penetrating wetting of the textile goods with the aqueous SL-K pre-liquor.

Textile detergent according to Claims 1 and 2, characterized in that the dissolution of the SL-K to adjust the pH values of the pre-liquor in the acid to alkaline range and the subsequent dissolution of the HK to alkaline pH values of the wash liquor, preferably in the range of about 8 to 11, leads.

Textile detergent according to claims 1 to 3, characterized in that the HK contains and / or finely soluble insoluble builders with the ability to bind calcium in the alkaline range and this in such quantities that the alkaline liquor counteracts at least during the washing process even at elevated washing temperatures the formation and precipitation of poorly soluble calcium compounds is at least largely stabilized. O 96/14385 PCΪYEP95 / 04163

- 65 -

5. Textile detergent according to claims 1 to 4, characterized in that (a) the dissolution of the SL-K to pH values of the pre-liquor equal to / less than 8, preferably in the pH range from about 2 to 8, in particular of least approximately 4.5, leads, whereby initial pH values of the pre-liquor in the range from about 5.0 to 7.5 can be particularly preferred, or (b) the dissolution of the SL-K directly to the pH range above 8, especially from 8 to 11, leads.

6. Textile laundry detergent according to claims 1 to 5, characterized in that the HK at least for the most part in the form of compressed and / or coated multi-material mixture, for example as corresponding granules, extrudates, agglomerates and / or compactates with bulk densities of at least 500 g / 1 is formed, but in particular is present at least predominantly as a multicomponent extrudate with preferred bulk densities in the range from 600 to 1,100 g / 1.

7. Textile detergent according to claims 1 to 6, characterized in that the SL-K contains organic acids, in particular polybasic carboxylic acids, and / or their (partial) salts and / or polybasic inorganic acids and / or their (partial) salts, Components which are preferred here are those which are valuable and / or auxiliary substances of the textile detergent even after neutralization in an alkaline bath.

8. Textile detergent according to claims 1 to 7, characterized in that the SL-K water-soluble builders with the ability to complex complex binding to polyvalent metal ions and preferably such auxiliaries based on polyvalent carboxylic acids and their derivatives, such as 1- and / or polybasic Hydroxycarboxylic acids, ether carboxylic acids and / or their (partial) salts with preferably up to 12 carbon atoms in the molecule, builders based on preferably cold-soluble oligomeric or polymeric polycarboxylic acids or mixtures of such builders, but optionally also nitrogen and / or phosphorus Containing complexing agents from textile detergent technology. 9. Textile detergent according to claims 1 to 8, characterized in that to form the SL-K pre-liquor water-soluble organic dicarboxylic acids, in particular in the range C4_8 and / or their (partial) salts, but preferably higher-functional polycarboxylic acids and / or their (partial) salts are used which are capable of at least partial binding of alkaline earth metals and in particular calcium in the dissolved phase, even in the acidic to neutral range.

10. Textile detergent according to claims 1 to 9, characterized in that the SL-K contains at least a proportion of citric acid and / or its cold-soluble salts, in particular alkali salts, preferably in admixture with oligo- and / or polymer carboxylic acids and / or their salts, in particular ¬ in particular from the area of builder substances for laundry detergents.

11. Textile detergent according to claims 1 to 10, characterized in that the SL-K - in particular for setting a pre-float with pH values in the weakly acidic to alkaline range - at least partially inorganic complexing agents and in particular cold-soluble (partial ) Contains salts of oligoacids of phosphorus and / or oligo- or poly-silicas.

12. Textile detergent according to claims 1 to 11, characterized in that as cold-soluble inorganic complexing agent oligo-phosphates, in particular alkali di- and / or tri-phosphate salts and / or alkali oligo- and / or polysilicates - preferably with at least partially Q2- and / or (^ structure - are present.

13. Textile detergent according to claims 1 to 12, characterized in that the HK contains alkaline soluble and / or finely insoluble Buil¬ der components which lead in particular to a calcium exchange in the neutral to basic range for fixing the calcium ions in the builder molecule even at elevated washing temperatures .

14. Textile detergent according to claims 1 to 13, characterized in that as water-insoluble fine particles and calcium ions exchanging Builders or builder components ion exchangers for polyvalent metal ions, in particular calcium, are used, the use or concomitant use of water-insoluble, finely divided alkali metal zeolites, in particular zeolite NaA, NaX and / or zeolite P, being particularly preferred.

15. Textile detergent according to claims 1 to 14, characterized in that in addition to or instead of the water-insoluble builders in HK soluble silicate compounds with builder action, in particular crystalline phyllosilicates and / or amorphous and / or crystalline alkali oligosilicates with at least partially Q2- and / or Qß structure are present.

16. Textile detergent according to claims 1 to 15, characterized in that the soluble and / or finely insoluble builders are present in the HK in such excess that in addition to the calcium exchange, the neutralization and alkalization of an acidic liquor is carried out by these builders.

17. Textile detergent according to claims 1 to 16, characterized in that the HK additionally contains alkalizing components without the ability to exchange calcium, and in particular water glass, soda and / or sodium bicarbonate.

18. Textile detergent according to claims 1 to 17, characterized in that the SL-K contains nonionic surfactants as compounds with a surfactant structure.

19. Textile detergent according to claims 1 to 18, characterized in that in the SL-K nonionic surfactants of the type of fatty alcohol alkoxylates and / or the alkylglycoside compounds (APG) are used at least in part.

20. Textile detergent according to claims 1 to 18, characterized in that even the SL-K - preferably in combination with nonionic surfactants - contain wash-active anionic surfactant compounds and / or the corresponding acids in the alkaline medium. 21. Textile detergent according to claims 1 to 19, characterized in that the delay in dissolving the HK is set so that with simultaneous addition of the SL-K and the HK to the aqueous liquor, the time span of the treatment of the textile goods with the SL-K pre-liquor is at least 0 , up to 1 min, preferably at least 2 min and preferably not more than 20 min, a period of pretreatment and in particular until the wash liquor is neutralized in the range from about 2 to 5 min may be particularly preferred.

22. Textile detergent according to claims 1 to 21, characterized in that the respective dissolution rates of the SL-K and the HK au the temperature range usual cold or only slightly heated Lei line water and thus in particular to the range of about 10 bi 30 ° C are matched.

23. Textile detergent according to claims 1 to 21, characterized in that the HK is present at least predominantly as granulated, roll-compacted, but in particular extruded Mehrstoffgem in grain form with preferred average particle sizes in the mm range, rounded extrudate grains for spherical shape are a preferred form of supply.

24. Textile detergent according to claims 1 to 23, characterized in that the HK material - in particular in the outer grain area - is provided with solution-delaying auxiliaries and is preferably coated with a bowl.

25. Textile detergent according to claims 1 to 24, characterized in that (a) either the SL-K material is finely powdered, but preferably also grain-shaped, in particular grain shape and density can be adapted to the HK material in such a way that in mixtures HK and SL-K have no significant segregation processes and / or that (b) the SL-K is applied to the HK as an outer shell.

26. Textile detergent according to claims 1 to 25, characterized in that the outer shell of the HK and / or the SL-K with a preferably about pH-neutral solid, water-soluble and / or -dispersible material layer is provided, the storage stability of the mixtures of HK and SL-K is guaranteed under normal practical conditions, for example in carton packs.

27. Textile detergent according to claims 1 to 26, characterized in that the SL-K is used in minor amounts by weight - based on HK -, amounts in the range up to 30% by weight, preferably 1 to 15% by weight and in particular 1 up to 10 wt .-% SL-K - based on HK - may be preferred.

28. Textile detergent according to claims 1 to 27, characterized in that the SL-K additionally wash-active components or auxiliary components are added, here the addition of perver¬ compounds, in particular H2O2-containing bleaching components; Catalysts for intensifying oxidative bleaching, such as TAED; the addition of wash-active enzymes, especially proteases; of dirt dispersers and / or graying inhibitors.

29. Textile detergent according to claims 1 to 28, characterized in that when the SL-K dissolves to pH values of the pre-liquor in the acidic to neutral range, wash-active enzymes, in particular wash-active proteases, are also used together with the SL-K.

30. A method for optimizing the washing and cleaning power of Textil¬ detergents for the area of alkaline textile laundry by a multi-stage wash, characterized in that the main wash in the alkaline area using a multi-component main component (HK according to claims 1 to 29) a pretreatment of soiled textile goods with the pre-liquor is assigned a snow-soluble component (SL-K according to claims 1 to 29).

31. The method according to claim 30, characterized in that the SL-K is separated in time and is added to the wash liquor before the HK, but preferably SL-K and HK are added together to the wash liquor and the HK as such a time-delayed soluble component - 70 -

is designed so that at least the penetrating wetting of the textile material with the aqueous SL-K pre-liquor is ensured.

32. Use of a preparation form of complexing agents for polyvalent metal ions which is also rapidly soluble in cold water, in particular for the cations from the water hardness and / or from incrustations of dirt on soiled textiles (SL-K according to claims 1 to 29) in admixture with a time delay soluble preparation form of a Mehr¬ textile detergent for alkaline textile washing (HK according to claims 1 to 29), for the formation of a multi-stage washing and optimization of the washing result on soiled textiles.