DE4438850A1 - Solid recyclable preparations for multi-stage textile washing - Google Patents

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

The teaching according to the invention describes new proposals for implementation of the known working principle important improvements in the frame the textile laundry to ensure that the treatment of the too textile goods in several stages, for example in successive ones 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 particularly wants the principle in verbes Realize real, to be cleaned textile goods first a Be treatment under acidic to weakly basic pH conditions of the liquor subject to what is essentially a conventional textile wash under comparatively more alkaline washing conditions. in the Within the scope of this task, the invention particularly wants new textile washing Describe agents that are suitable for the household laundry sector and only one thing for the consumer in the offer form Mixed product can be made available. The invention However, teaching does not focus on such uniform mixed products limits. The working principle described below can also be used with a plurality of separate components of the total for Realize the coming mixture of recyclables. Practical importance can, for example, such embodiments in particular when used coming from household washing machines, which with separate Be charging devices, for example for a pre-wash and a follow-up main wash, are equipped.

The multi-stage Tex - based on the pH of the aqueous wash liquor tilwashing is known in the art. Which dates back to 1962 outgoing US 3,042,621 describes detergent mixtures for such a more step wash, the first stage under non-acidic conditions, especially in the basic area, takes place and a downstream Treatment stage of the textile goods takes place in the range of acidic pH values.  This sequence in the regulation of the liquor pH has changed in practice not enforced. Workwear pH workers worldwide are becoming textile laundry today te of the wash liquor in the alkaline range and in special cases in the neutral range to weakly alkaline range.

Summarizing representations of the more scientifically theore tables as well as practical knowledge and experience on the com complex processes of textile washing can be found in two in Publications published in book form, based on the Erfin Reference to the description of the specialist knowledge referred to several times becomes. This is G. Wildbrett et. al. "Technology of Household cleaning ", published by Eugen Ulmer, Stuttgart, 1981, and G. Ja kobi et. al. "Detergents and Textile Washing, Principles and Practice", VCH Verlagsgesellschaft mbH, Weinheim, 1987. This latter publication publication in book form is, according to her preface, the chapter "Detergents" in Ullmann’s Encyclopedia of Industrial Chemistry.

Natural knowledge is detailed in these two publications principles and practical conditions of textile washing described. Optimized washing results are also based on today's Er Preserve knowledge in the alkaline range. Find only in special cases instructions for washing textiles in the neutral area. Is referred here, for example, to U.S. 4,110,262, in which liquid detergent preparations with pH values in the range between 6.0 and 7.5 are described are.

Under the impression of the need for phosphate substitution in textiles detergent formulations is the concept in a number of proposals been taken up, the aqueous-acidic textile pretreatment with a to combine the following alkaline laundry. The goal here is ins special, the build-up of mineral incrustations on the washed To prevent textile from repeated washing, which on the what hardness of the aqueous washing and rinsing liquors can be attributed. Straight also the problem addressed here - improvement of the so-called "Secondary detergency" - was used in detergent formulations of the old It is known that this is caused by the use of polyphosphate salts, in particular  their STP, solved. The ecological pollution caused by this but then made the development of others, the water hardness and especially Calcium binding adjuvants required. There is a bigger one today Number of soluble or finely divided insoluble builder components for the subject mentioned here is available, the water hardness and ins especially calcium under the usual working conditions in practice of the particularly basic pH range.

DE 24 37 173 describes a two-stage washing process for textiles Material that set at least one pre-wash in an acidic combines aqueous solution with a separate main wash. The pH the waste liquor from the prewash cycle is in the acidic range, for example 1.6 to 3.5, the pH of the main wash is in the neutral to ba area. The goal of this process sequence is to build of water hardness and incrustations on the textile goods as part of a more to prevent specialist washing that in the acidic prewash cycle The incrustations formed in the last wash cycle are loosened and thus can be washed out at least predominantly. From the same goal the teaching is based on the teaching of US 3,761,415. It is supposed to be 2-stage but nevertheless be worked in one operation in such a way that phosphate-free detergent mixture based on synthetic surfactant compounds a combination of appropriate materials is used as alkalizing agent sodium or potassium carbonate or ent containing speaking bicarbonates or sesquicarbonates and at the same time water-soluble sodium or potassium salts of citric acid respectively contain the citric acid itself. When dissolving such a wash citrate ions go according to the information this document so quickly in the aqueous solution that it at sufficiently high dosage are capable of training from usual Inhibit incrustations based on calcium carbonate. Indeed comes to the present day the alkaline salts of citric acid a practical meaning as a builder or cobuilder component to. The examples of the US mentioned then consistently in the Try washing the aqueous phase as "hot water". With today Such a household procedure is standard household washing machines worldwide not possible. The induction process for the specified solid detergent  As is well known, the mixture is made with cold tap water. The in the Washing machine together with the water to be cleaned textile Ge fleet is then set to the specified level by heating elements in the machine Washing temperature warmed up.

US 4,210,550 takes up the suggestions of the two last cited prints write up and deal with it critically. The teaching of the DE 24 37 173 is rejected as disadvantageous because here two of each other ge separate wake-up operations are provided that separate the wash liquor of the first wash cycle before the second wash cycle is started is set. The teaching of US 3,761,415 has the disadvantage that a comparatively high percentage of citrate is needed to make up the Teaching to realize this publication. So it is pointed out that the detergent formulations used in the examples are lemons contain acid or its salts in amounts of 33 to 57 wt .-% although a wash liquor with a very low hardness value (6 degrees dH) is used. The teaching of US 4,210,550 wants this Working principle of the 2-step wash cycle - first acidic liquor, then alkaline liquor - by washing washes Telemixes are used, which - in addition to 5 to 30 wt .-% of surfactants Components and 5 to 80 wt .-% alkali carbonate - selected lower di carboxylic acids in the area of succinic acid, glutaric acid and adipic acid in Amounts of 5 to 30 wt .-% contain. In this context, special provided the rate of dissolution of the alkaline com component, but at the same time the dissolution rate of the not to hinder acidic components. So it can be done as part of a usual Agglomeration technology should be provided, the components of the alkaline To provide component with a solution-delaying coating, so that the Dissolution or dispersion of this alkaline component only in the period of at least 2 to at most 10 minutes after the addition takes place in the aqueous liquor. There will be a majority of such solutions retarding coating materials listed in an amount of 0.1 to 15 wt .-%, based on the total detergent mixture for use can come.  

The goal of this teaching is the clearly described Ab view, first incrustations from the textile to be cleaned and also from attack the washing machine under the influence of acidic components and dissolve, but then the calcium and Magnesium ions in the subsequent alkaline work step under the Influence of the alkali carbonate used, cf. in this Context, the statements of the publication column 2, 45 to 50 and column 3, 65 to column 4, 5.

The working examples of US 4,210,550 also show that considerable difficulties in realizing the principle storage-stable multi-component mixture based on the affected here To build textile detergents so that the previous training of the washing fleet with acidic pH is guaranteed for the required period and only then the conversion of the wash liquor to the usual basic ones pH conditions. All examples of this publication work with a 2-chamber portioning aid that contains the acidic component if necessary together with selected surfactant compounds, separately from the provides alkaline component and its other active ingredient components. This is through a suitable design of this 2-chamber auxiliary element tes a delayed opening of the chamber for the alkaline detergent part provided.

The object of the invention

Textile detergents are known to be mixtures of a large number of active ingredients components, each individually and in their synergisti where appropriate interactions optimally perform the complex task of textile washing len should. The diversity of the task given here is derived on the one hand from the different types of soiling and on the other hand, from the different types of textile materials that - for example as part of a household textile laundry - regularly are clean. Modern forms of supply of these multi-substance mixtures are Debris and free-flowing materials with increased bulk densities of for example 600 to 1100 g / l. Through forced homogenization and compression tion today - instead of the previously comparatively volumi  detergent powder - highly compressed multi-substance mixtures, for example in spherical form, are offered, for example, by means of extrusion and subsequent rounding of the cut extrudate strands can be obtained. Other ways of extracting appropriately compacted materials are, for example, wet agglomerations, roller compaction and ver comparable compression processes.

Detergent mixtures of the type required today are in their selection Active ingredients and their composition in the direction of that previously briefly stated spoken complex requirement profile optimized. The multifunctionality the requirement profile corresponds to the multifunctional selection and to Compilation of the valuable and auxiliary materials of modern textile detergents. Here are from the detergent manufacturer - mostly depending on the hardness of the available water - optimized quantities of each Detergent specified per wash. Taking this into account doses are then optimized with the detergent concerned Get washing results. A substantial increase in washing results nisses by further increasing the amount of detergent per wash is in usually not accessible.

The teaching of the invention is based on this matter in an important aspect behave out. She wants to modify the washing procedure driving towards a multi-stage wash with a certain Detergent amount adjustable washing result can improve for no reason legendary changes in the composition of the wash, optimized as such to have to make a mixture of mediums. Minor through the use Amounts of additional components, which at least partly also include washing main component can be removed and thereby - again at least in part - through an increased solution speed in the The wash liquor should also be distinguished at the cold wash-in temperatures Possibility of targeted multi-stage treatment of the soiled textile good can be created in a washing process.

The concept according to the invention uses what is known per se behave that the today 's preferred high - density forms of supply Detergent mixtures, for example the spherical extrudates mentioned,  a delayed release speed in the morning own phase of the washing process, especially in cold liquor. Which he Teaching according to the invention uses this initial phase, which correspond by a de Equipment of the multifunctional main detergent component also be can be extended for a previous treatment stage of the cleaning textile goods with a pre-fleet of selected active ingredients.

The teaching of the invention is based on an important embodiment the task, the now common worldwide textile wash in alkaline Modify the area so that you have a work level in the area acidic to neutral or only weakly alkaline pH values upstream becomes. On the one hand, the invention also wants to create the possibility in which pre-existing incrustations on the textiles to be treated and / or attack effectively in the washing machine. The Erfin dung also wants special, in the following descriptions ten, embodiments also use this stage of work to substan tial relief and improvements for the subsequent alkaline Washing stage and for the desired cleaning result in its entirety ensure. The teaching according to the invention is based on the goal exhibition, a formation and deposition of calcium carbonate and others Compounds of water hardness in the alkaline washing stage in the sense of exclude as much of today's knowledge as possible, in order to this way optimizations regarding the secondary washing power put. In particular, however, the teaching according to the invention wants to go further design the overall process so that through the use of time separated preliminary stage improvements also with regard to the so-called pri poor washing power become accessible.

The object of the teaching according to the invention is also concrete forms of offer for textile detergent mixtures of the type concerned here to describe the correspond to today's forms of such aids, especially special have at least partially grain shape and in the usual way in be favorite washing machine types by means of the dosage provided therein elements can be used without the particular use designed and separately loaded dosing elements is required. In this most important embodiment, the textile detergent mixture should accordingly  chend be formed as a multi-component mixture, the individual com components in an at least largely storage-stable homogeneous mixture contains. Nevertheless, the invention in its broad conception encompasses more component detergent mixtures in which at least two of each other separate recyclables or mixtures of recyclables in the wash cycle are set, then the objective of the invention in its entirety the improved primary and secondary washing power.

The object of the teaching according to the invention in its entirety is that of The conception of such a multi-level text already considered to the experts to implement til wash in a practical embodiment so that optimized Washing results can be obtained, but neither for the Storage and distribution of the detergent mixture still for its rule moderate precautions special precautions are necessary.

Subject of the invention

The invention accordingly relates to solid textile detergents in in the form of a mixture of active components and, if desired, auxiliary substances that at least partially with a compacted mix delayed solubility in cold water - afterwards following also as "slowly soluble main component" and usually the Named "HK" for simplicity. This HK mix contains in detergent surfactants, alkalizing agents, in the aqueous-alkaline range soluble and / or finely insoluble Builder or builders with the ability to calcium calcium dung, and, if desired, other usual active and / or auxiliary compo nent of textile detergents.

The teaching of the invention is now characterized in that it is too additionally - but as a separate component from the HK - at least one Fast-soluble component also in cold water - in the following the For the sake of simplicity referred to as "SL-K" - also based on cold Rapidly soluble complexing agents for the polyvalent cations of Water hardness included. In the preferred embodiment, the SL-K these complexing agents for multivalent cations mixed with ten  sid compounds and in particular also cold-soluble surfactant connections before. The teaching according to the invention preferably further sees before that the solution delay of the HK in the initial phase of Waschpro zesses is chosen sufficiently that at least the wetting of the textile good is guaranteed with the aqueous SL-K pre-liquor.

The component (s) used as or in the SL-K can be used to adjust the pH values of the pre-liquor in acid up to the alkaline range. The subsequent dissolution of the HK leads in the preferred embodiment of the invention to the ge today Desired alkaline pH of the wash liquor, which is preferred 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 Auf Release of the HK, if this element is not a mandatory component the teaching of the invention. In this embodiment there are pulled pH values of the pre-liquor resulting from the dissolution of the SL-K in sau ren to weakly basic range, especially in the weakly acidic to new central area. Details on this are given in the following Erfin description given.

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 laundry using a multi-stage wash. The inventive method Ren is characterized here that the main wash in alkaline Area using a multi-component main component (HK in the sense of previously given definition), a pretreatment of the soiled textile good with the pre-fleet of a quickly soluble component (SL-K according to the previously given definition) is assigned. Still preferred, however the SL-K and the HK together in the wash liquor are not mandatory added. The at least predominant part of the HK is as such time-delayed soluble multicomponent component that at least the penetrating wetting of the textile material with the previously formed aqueous SL-K pre-fleet is guaranteed.

Finally, in a further variant, the teaching of the invention relates the use of a preparation that is quick-soluble even in cold water  form of complexing agents for polyvalent metal ions, especially for the Cations of water hardness and / or corresponding cations from Schmutzin encrustations on soiled textiles - SL-K according to the previously given Definition - in admixture with a delayed soluble preparation form of a multi-component textile detergent for alkaline textile washing - HK according to the definition given above - to form a multi-level washing and optimization of the washing result.

The teaching according to the invention enables diverse variations of the spe Design of the multi-stage wash. This is how the preliminary stage of the Treatment of the textile goods - and the interior of the washing machine - with one sufficiently acidic pre-fleet not only a dissolution best and incrustations and the at least partial binding of the free set polyvalent metal ions, especially the corresponding ions the water hardness, by suitable use of calcium and, if necessary Magnesium-binding builder components also make it possible for the little The overwhelming majority of the disruptive hardness constituents dissolved in the over transition of the pH from the acidic precursor to the neutral and finally basic liquor of the subsequent work stage in the builder components the basic work area and thus the washing process revoke. An interim or final precipitation of this Hardening agents in again insoluble form are not required. The invention However, teaching also uses the possibilities of multi-stage washing method for realizing targeted other and / or additional rei Cleaning and conditioning steps on the textile goods.

Details of the teaching according to the invention

The teaching according to the invention is also based on the basic concept, a first and comparatively quick-dissolving SL-K component in the wash to use a mixture of agents that control with the fresh water supplied development of pH values, for example in acid to neutral, but possibly also in the alkaline range. This first compo nente can be formed by a selected resource, in however, the use of a multi-component is usually already used here  Mixture of recyclables preferred, which through the targeted pH training in aqueous solution identified with the use of surfactant components is.

In combination with this, the basic HK basic component is used brings, which initially at least for the most part their time-delayed resolvability differs from the SL-K component, but then, when they dissolve, the pH of the wash liquor ensures in the desired area. The HK is in such menus gene and / or used in such a configuration of their multi-component mixture, that not only the necessary neutralization of the SL-K takes place. In particular, it is a (partial) task of HK, in water Bath ultimately adjust the pH of the preferably basic range len, which is aimed for the main wash in the conventional sense.

In another important embodiment, the teaching of the invention realize the idea, at least in part in the SL-K component Use recyclable materials that also and especially under basic conditions well-known and useful components of a basic text can be detergent mixture.

Before the concrete description of the Ele The following brief information on the better understanding of individual variants of the action according to the invention given. Understandably, this can only be an incomplete one Act in brief.

The washing and cleaning process in aqueous liquors using the Auxiliaries common today are known to be a highly complex process of here interacting components, which by a variety of physi calic and physico-chemical parameters. The beginning Literature cited here provides brief help for understanding, see ins special G. Jakobi et. al. loc. cit., Chapter 2, "Theory of the Washing- Processes "(pages 7-39) and here in particular the subsection 2.2" Types of Soil "and 2.3" Physical Soil Removal ". From the previously cited Ver publication G. Wildbrett et. al. especially refer to "Part 1 -  Theoretical foundations ", page 13 ff, and here in particular on the Un Chapter 2. "Dirt", 4. "Chemical auxiliaries for cleaning" and 5. "Process of wet cleaning". In connection with the variant of the invent teaching according to the invention, the washing stage in the basic area a treatment of the textile goods to be cleaned in the acidic area particular importance of the chemical reaction of acidic An undoubtedly handles acidic components of the dirt as well as existing incrustations on Ba sis of water hardness too. The acid attack under the influence of the SL-K leads for dissolving acid-labile solids, releases from dirt incrustations acid-soluble, especially polyvalent cations, and thus leads to break from such dirt deposits and reduces their liability to tear nigen fiber surface. The separation of additional solids through interaction of the water hardness always introduced with the washing liquor and, for example, surfactant and / or alkalizing components can be in the sow not take place in their area.

However, the acidic pretreatment stage provided according to the invention has an effect obviously also in a completely different way on the overall events of the Washing process. This is where the teaching according to the invention comes in. You connect For the first time, today's knowledge of textile washing with the old ones cited Suggestions. The following only applies in this connection:

A key parameter for the effectiveness and the process the washing and cleaning processes on the soiled textile in the aqueous Fleet are the respective electrostatic charge on the Fiber surfaces and the deposited dirt particles, as well as valuable and auxiliaries of the detergent mixture. The decisive factor is in particular in particular the controllability of this so-called electrokinetic interface po tentials - also called zeta potential - by the in the washing process set working conditions and auxiliary materials. Important importance comes in this connection to the pH of the wash liquor. In conventional alkaline washing process will optimize the negative charge of the Particles of dirt and thus maximizing the repulsion between fibers surface and dirt reached around pH 10 to 11. The pH-related The washing effect can then no longer increase. When the pH value drops  the zeta potential also decreases. In aqueous solutions below pH 7 above weigh the hydrogen ions against the hydroxyl ions. It will increase mend Protons on the surface of dirt particles and substrate absorbed beer. The originally pronounced negative charging of the interfaces sinks. Experience has shown that the transfer point for laundry dirt is around pH 5; a positive charge predominates only below this limit the dirt surface. As the pH value drops further, the Zeta-Po increases potential in the range of positive values again, for more details see e.g. G. Wildbrett, loc. cit., pages 37 to 39 and 75 to 77.

Involved in this complex and influencing the washing effect electrochemical events are not only the fixed parts of the Wash liquor, especially dissolved ionic - and also nonionic - Be components of the complex system or their interaction others are subject to the pH-dependent influence.

Based on this basic knowledge, the invention strikes for the easy a bundle of measures for the intensification and intensification of the aqueous textile laundry, that can lead to improvements in a variety of ways. Especially applies here: Positive results are not only in terms of incrustati ons prevention and thus with regard to the so-called secondary washing result achieved, substantial improvements are also being made in terms of dirt removal and thus accessible to the primary washing result Lich. Based on this, modifications of both the conditions of the Washing process as well as in relation to the composition of the solid washing and detergents for textile washing possible. To optimize the desired washing result is revealed by the inventive Teach a new open space not previously accessible.

In the following, the elements of the nature and the Structure of the SL-K portion in the detergent mixture according to the invention described ben.

The first essential component of this SL-K component is connections with the ability to form complexes with polyvalent cations and ins especially the corresponding cations of water hardness. Under consideration  adjustment of the temperature / time sequence in the normal washing process and the fact thing that the SL-K or the fleet formed from it to the Main wash cycle with the delayed solution HK is brought forward, are characterized by the complexing agents particularly suitable according to the invention additionally from the fact that they are so fast even in cold water are soluble that their interaction with the textile to be cleaned out the solution state in the aqueous pre-liquor is possible. Basic components This proportion can relate to organic acids and / or their salts partial salts, but also selected inorganic acids and / or their salts, including the partial salts.

The concept of organic acids covers a particularly important one Embodiment polybasic carboxylic acids and / or their (partial) salts. This can be selected monomolecular compounds of the ge act as described, but there are also corresponding oligomer compounds endings and / or polymer compounds of higher molecular weight in Be traditional costume, especially from the field of builder components for Detergent mixtures are known. The following apply in detail here preferred information:

Particularly important representatives of the SL-K in the sense of the Han according to the invention delns are low molecular weight polybasic carboxylic acids with preferably up to 20 carbon atoms and in particular with up to 10 to 15 carbon atoms in the molecule. Of the The carboxyl group content is at least 2 and is preferably so the carbon number turned off that a solubility of the polybasic Carboxylic acid in cold or even moderately heated water - especially in particular in the range from about 10 to 30 ° C.

Descendants of such polycarboxylic acids ha can be particularly important here ben, whose molecules besides C, H and O building blocks free of further hetero atoms - especially N and / or P - are. 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 Keto carboxylic acids. Polyfunctional carboxylic acids of this type are in the Detergent technology known sequestrants for Cal in particular  cium ions used as cobuilder components in practice are set, reference is made to the relevant state of the art for example to the mentioned publication G. Jakobi op. cit., Unterka section 3.2.2 "Complexing Agents", in particular Table 15, page 68. Ge In addition to citric acid, 1,2,3,4-cyclo are mentioned here pentantetracarboxylic acid, the O-carboxymethyl tartronic acid and the O-carboxy methyloxysuccinic acid. These connections are common in today Detergent formulations used in the form of their basic salts. The Invention includes - taking into account the other parameters to he acting according to the invention - this possibility. Goes beyond that the teaching of the invention but also its use in the SL-K as free polyfunctional carboxylic acid and / or in the form of their partial salts with Example of neutral or aqueous acidic pH.

The teaching according to the invention is based on the organic that can be used here Acids for setting and regulating the pH range in the first Process stage, however, not on heterofree polycarboxylic acids of the here limited kind described. In principle, inventions are also suitable according to the definition corresponding organic and inorganic acids and / or their salts, which in a preferred embodiment are the same as before sufficiently mentioned element, polyvalent metal ions and especially the cations of water hardness - if necessary also in acid Area - without being able to partially bind the precipitate and this when over change in the pH of the aqueous liquor from the acidic to the basic Area either in the builder components introduced via the HK exchange or at least partially also in alkaline form stable soluble complexes. So come into consideration for teaching The invention for training the SL-K, for example, also polyfunk tional acids of the type of nitrilotriacetic acid (NTA), the N- (2-Hy droxyethyl) iminodiacetic acid, ethylenediaminetetraacetic acid (EDTA). Here too, reference is made to the information given in the cited reference by G. Jakobi et.al., subsection 3.2.2.

The training of the preliminary fleet with its content of complexing agents and ge if necessary, the setting of acidic pH values in the first stage Washing process in the sense of the invention is however not on the one  set of corresponding carboxylic acids or polycarboxylic acids limits. Important mixture components for the teaching according to the invention can also be other, especially polyfunctional acid generators, the the ability to form complexes with polyvalent cations and especially the calcium and / or magnesium of the water hardness. Known complexing agents based on, for example, come into consideration here of polyfunctional phosphonic acid compounds. As an example, be called the 1-hydroxyethane-1,1-diphosphonic acid or the nitrilotrimethylene phosphonic acid. These connections are only listed here by way of example can be used as free acids or in the form of their salts including the acidic ones Partial salts part of the SL-K in the sense of the teaching according to the invention his.

As previously stated, the basic component of the SL-K can be assigned the Be Ability to complex bind polyvalent metal ions and especially the water hardness with good solubility even in cold water also be formed by appropriate inorganic components. First Appropriate builder components of detergent technology come here logic. The salts of oligophosphoric acids are known here, in particular alkali di-phosphates and / or alkali tri-phosphates. The na Trium triphosphate (STP) is known to be the most important for decades Builder component of detergent technology. The invention Proposal to take up this component again at differs from the old technical action of the subject concerned here area as follows: As described in detail below, is the proportion of SL-K based on the main detergent component HK only a minor fraction. The one used in the SL-K The amount of complexing agent, based on the HK, is at most in the Range of a few% by weight. The inorganic complexing agent STP can do this in the SL-K also in mixtures with other, P-free complexes be used. The teaching of the invention thus opens up the Possibility to use the known ones for the working area of the aqueous pre-liquor Advantages of the builder components based on oligophosphoric acids their salts without using the old problem of to revive potential reutrophication.  

Another class of purely inorganic complexing agents for use in the SL-K are the well-known cold-soluble (partial) salts of oligo and / or polysilicic acids, here corresponding oligo- and / or poly silicates is of particular importance, which is at least partly due to a chain or ring-shaped or sheet-like structure of the poly Silica residues are labeled and in the technical language as Q₂- and / or Q₃ structures are called. On the relevant status of Technology is based on German patent applications P 44 06 591.4, P 44 06 592.2 and P 44 08 359.9 from the applicant and those referenced therein Reference to the written state of the art. For the purpose of invention Disclosure is the subject of the earlier applications named here expressly also on the subject of the present disclosure of the invention made. Various configurations are described here in particular of alkali metal silicates in the module range (molar ratio SiO₂: M₂O, where M is alkali metal) from 0.8 to 4 in homogeneous mixture with further inorganic and / or organic valuable and / or auxiliary substances, which in particular as an over-dried good with oligomer or Po there is a polymer structure of the silica residues. Preferably, at least the majority of these oligosilicic or polysilicic acids Q₂- and / or Q₃ structure. Over-dried ones are particularly important here Materials of this type with residual water content in the alkali silicate content below 18% by weight and in particular below 15% by weight. As easily soluble Builder components are particularly suitable for X-ray amorphous alkali silicates with module values in the range from about 1.5 to 3.0 and preferably in the range range from 1.7 to 2.7. Alkali oligosilicates of the type affected here can in particular homogeneously mixed in water-soluble inorganic salts for example carbonates, sulfates, halides, borates, but especially also Phosphates and / or polyphosphates.

Inorganic complexing agents of the type described here as the main stock part of the SL-K are particularly practical in such embodiments be meaningful in which the desired pH of the aqueous pre brisk in the weakly acidic to basic range. For example partial salts of triphosphoric acid at initial pH values of SL-K Pre-liquors in the range of about pH 6 and higher values are used. In particular, however, the use of this inorganic complex  formers for the embodiment have meaning, in which already Pre-liquor in the at least weakly basic range - for example pH 7.5 up to 8 as the initial value - is or even a prior pH value of the Be rich from about 8.5 to 10 are already sought in the previous fleet. A mixture of inorganic and organic complexing agents can Optimization of technical action in the sense of the teaching according to the invention respectively. This optimization is determined not only by that in the SL-K Components used, the quality is also important the multifunctional HK, the type of dirty Tex to be treated tilgutes and the primary consideration of textile pollution. This one affected specialist reveals itself through the teaching of the presented here Invention a wide variety of options for setting optimal Ar results in terms of the goal of an improved and in its performance optimized textile detergent mixture.

In addition to the previously mentioned examples for a targeted regulation of the pH Value of the pre-fleet through acidic complexing agents in particular within the scope of the The structure of the SL-K also includes other sufficiently soluble acid types into consideration. Sufficiently soluble sulfones are mentioned here as examples acids of aliphatic and / or aromatic base molecules. Com men about corresponding optionally substituted alkanesulfonic acids or aromatic sulfonic acids. Examples of compounds of this class are such as sulfosuccinic acid or benzene or toloulsulfonic acid re. In particular, the substance class mentioned last can be Men of the invention are of particular importance when compounds of type affected here with HLB values in the area of detergent surfactants bindings are used. The following will deal with this in more detail received.

A particularly important representative for the class of low molecular weight polybasic carboxylic acids for adjusting and regulating the pH in The stage of the aqueous acid detergent liquor is citric acid. These can as such for pH regulation in the acidic range, but also at least partly in the form of their (partial) salts. In one technical expertise applies here. Citric acid is in hydration Sized form with changing amounts of water, especially stable  But also the anhydrous citric acid is an important component in the Sense of the action according to the invention. It is characterized by an extreme rapid solubility even at water temperatures in the range of 10 to 15 ° C off, so that here when metering a correspondingly designed Multi-substance mixture through previous solution of citric acid and / or of their (partial) salts an almost immediate conditioning and on setting the pH of the aqueous liquor to predeterminable values in acidic, in the neutral or in the basic range is possible.

In addition to the citric acid most recently highlighted here as important active ingredient components for discontinuing the pre-liquor are one today Majority of other commercial products, especially for the compilation of Recyclable materials known from the field of textile detergents. Referred becomes, for example, lower dicarboxylic acids of the specified C number rich in the dicarboxylic acid mixtures of adipic acid, succinic acid and Glutaric acid, under the protected trade name "SOKALAN DCS" (BASF) are sold.

Particularly suitable as (co) polymeric oligo- and / or polycarboxylic acids the known polyacrylates, poly methacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those from 50% to 90% acrylic acid and 10% to 50% maleic acid re. Connections of this type are as a builder or cobuildercom components known in today's basic textile detergents fabrics. The molecular weight of the homopolymers is generally between between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably from 50,000 to 120,000, based on the free acid. A be particularly preferred acrylic acid-maleic acid copolymer has a molecular weight from 50,000 to 100,000. In today's usual detergents the polymer acids mentioned here in the form of their water-soluble sal ze, in particular the sodium salts used. According to the invention in an important embodiment provided at least a portion of the SL-K due to the corresponding free acids or their pH value apply partial salts. Here, too, is the one described above Principle implemented, at least in the quick-dissolving SL-K component  Proportionally use such components that ent standing basic-based detergent mixture are known recyclables.

The Ci previously named as an important part of the SL-K component tronic acid and / or its partial salts and also the latter Oligo- or polymer carboxylic acids are characterized by the Fä ability of the at least partial complex binding of polyvalent metal Ions of water hardness and especially calcium even in acidic to neutral range. In the sense of the basic concept described above tion of the invention, the annoying water hardness and the acidic level detached from the textile to be cleaned or the washing machine polyvalent metal ions, in particular by means of complex formation from the ver To separate the driving process becomes the importance of the basic elements of a Embodiment of the action according to the invention can be seen. Already in the The acid wash liquor precursor finds the at least partial solution of especially calcium ions in the multifunctional acidic compo instead of. As the pH value increases, ver the willingness to bind of the complexing agents effective here is strengthened compared to the multivalent cation. When the alkaline effect occurs Builder components in the wash liquor, on their nature in the following the calcium is transferred in detail by exchange reaction in the main builder of the alkaline washing stage instead of. The annoying hardening agents are effective in the washing process and removed from a possible speech position on the textiles. Minor Residual deposits that can occur especially in the rinse stages are not only extremely limited in quantity, in the next wash they immediately replaced in the acid precursor.

Especially in connection with citric acid as an important component for the formation of the acidic wash liquor in the first stage of the wash procedure results from conventional work in the washing machine the further following advantage: citrates have in the alkaline range comparatively low temperatures a high complex binding capacity versus calcium. This complex bond decreases with increasing temperature but are able to rapidly, so that the complex binding at temperatures above at 50 ° C in the basic wash liquor is unsatisfactory. In the invent  conception according to the invention takes place in a preferred embodiment acidic washing stage and the subsequent exchange of the calcium ion in the Main builder components of the basic washing process in the lower area Temperatures instead. The detergent is rinsed in as before usually thinks with cold tap water, only in the machine the washing liquor is heated by the heating device provided there. The time limitation of the first washing stage in the preferred according to the invention Sinn provides that the calcium exchange from the primary salt formed the citric acid in the main builders takes place in the temperature range, in which the calcium binding capacity of the citrates is still pronounced. Here will thus also multifunctional from the given natural sciences Chen facts by using the teaching of the invention made.

To implement the principle of the invention - with respect to Fleet pH's - multi-stage textile laundry are basically several forms given access. An immediately obvious embodiment sees that Addition of the acidic component separately and at the same time before the addition the basic component. In this way, the period of loading action of the textile goods in the acidic wash 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 the same allow early addition of both the SL-K and the HK to the aqueous liquor. One is sufficient to achieve the 2-stage washing principle de Delayed solution of the alkaline components of the HK as well as a Sufficiently quick solubility of the SL-K is a mandatory requirement. Reason In addition, the neutralization reaction is a spontaneous reaction that occurs with for example between an acidic liquor and a basic component also occurs spontaneously when the basic component is still unused dissolved solid is present. In fact, this principle becomes spontaneous neutralization in the relevant state of the art also for improvement the redispersion behavior of basic detergent mixtures gen, cf. see for example the international patent application WO-A- 92/18 596 or European patent application EP-A-0 534 525.  

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 Pre-liquor also in the area of lowered, especially acid to neutral pH values are available. If this period even in special cases can be kept very short - and therefore less than 1 min - it is nevertheless preferred according to the invention that in particular simultaneous addition of the SL-K and HK to the aqueous fleet the time span working with the previous fleet, for example, until the neutralization of the preferably acidic liquor, at least 1 to 2 min at least 2 to 3 minutes. In general, for the Be action with the previous fleet Do not exceed periods of up to 20 minutes. A period of time for treating the textile laundry with the previous liquor can for example, be in the range of about 2 to 5 minutes, with a time span of about 2.5 to 8 min and in particular about 3 to 6 min, expedient can be ugly.

The release speeds of the SL-K and the HK are practical use especially in the field of household detergents on the Tem normal or weakly heated tap water and thus especially matched to the range of about 10 to 30 ° C.

The acidic components to be used in the SL-K should be capable of doing so be, in the aqueous liquor initial pH values in the range of about pH 1.5 to train up to 7. Taking into account the previously cited knowledge on the importance of the electrokinetic interface potential (Zeta-Poten tial) on the washing processes can be within the specified range Acidic pH values can be divided into two limit ranges: In a first Embodiment of the invention, the SL-K is designed so that in the acidic liquor initial pH values in the range below and up to about pH 5 are formed, for example pH values in the range from about 2 to 5. Here, a positive charge predominates on the surfaces in particular Dirt, but also on the surfaces of important representatives of the reini good textile. For the improvement sought according to the invention, here in particular also the secondary washing effect, can be temporal temporary treatment of the textile goods in this pH range with subsequent  gender Reversal of the surface charge in the area of the wash-active nega charging is important.

But just a pretreatment of the textile goods to be cleaned in the Be range from zero to surface charge or a weak negative Charging with subsequent strong alkalization in the high range Negative charging values are important aids in the sense of the invention. In this embodiment, the pretreatment of the textile goods can be done for example in the pH range from about 5 to about 7, especially in the range from 5.5 to 6.8 take place before the subsequent alkalization in the basic and especially strong basic area is made drawing takes place.

In the possibilities of the design of the acidic presented here Treatment can also in the sense of the invention, the sensitivity of the cleaning textile goods are taken into account, this term being the "Sensitivity" is to be understood broadly and on the one hand relates to the fiber fiber structure, but also the equipment of the textile good, for example the applied dye. So it can be particularly useful in detergents for fine textiles, by buffering the acid generators in the SL-K initial pH values of the acidic ones Fleet in the range from 3.5 to 7 and in particular in the range from 5 to 6.8 adjust. If desired, it is possible, as indicated, to get together the SL-K should be chosen in such a way that at least the majority Period of acidic pretreatment at pH values of the fleet of pH 5.5 and lies above.

However, the teaching of the invention also includes a variant as a variant Step procedure of the specified type, in which the SL-K pre-fleet is practical immediate pH values in the more alkaline range, for example in the Be range from 8 to 11 and preferably from about 8.5 to 10.5. Even if here no use is made of the possibility of working the two carry out stages of the washing process at different pH values can create additional scope for modifying the complex Washing process created. The alkaline in this embodiment Pre-fleet can accumulate in particular the immediate spreading of the  Ensure complexing agents on the entire textile surface before the complex multicomponent mixture of the HK goes into solution and then in turn Interactions with the textile surface and the ver dirt. It is known per se that such a preferred and by the main amount of detergent loading of the Textile goods and their soiling with complexing agents based on corresponding carboxylates, especially sodium citrate, to improve Primary washing effects, cf. in this context the PCT-Ver publication WO 91/15 566. Here it is described that an improvement the primary wash result with common alkaline detergent formu Lungen can be achieved in that a separation of the addition of Detergent mixture takes place as follows: The main part of the multifunk tional detergent mixture is pre-read in the machine hen dispenser dosed in a conventional manner. Separately there of a component containing water-soluble complexing agent an addition container entered directly into the textile to be washed will. As complexing agents, these are also previously related to organic carboxylic acids cited in accordance with the teaching of the invention, in particular called corresponding polybasic carboxylic acids, water-soluble alkali citrates are of particular importance. In the early stages of Washing process is distributed in direct contact with the ver dirty citrate immediately. The Ge given here free calcium ions are retained within the preferred period of 15 Substantially seconds to very low values before that Detergent entered in the machine via the automatic induction unit Fleet has released and in turn in contact with the soiled textile comes well.

It is obvious that the combination according to the invention nation of an immediately soluble SL-K with its complex image content nern and the controllable delayed soluble main component comparable Work results become possible without a separate dosage of com plexers on the one hand and the main detergent on the other have to. The dosage of the detergent combination according to the invention enables light the separate pretreatment of the fleet and the dirty Tex tilgutes with the complexing agent even if the two components  SL-K and HK at the same time using the same addition device - for example, the induction device provided in the machine - be added to the washing process. It is understandable that also for working with an SL-K pre-liquor that is already alkaline important improvements in the washing result, especially for improvement primary washing power, can be adjusted.

Together with the organic and / or inorganic complexing agents the type shown so far contains the SL-K in preferred embodiments the teaching of the invention additional components that the functional act of the SL-K especially in the process phase of the aqueous pre-liquor wider and thus increase the washing result as a whole. In the following these additional SL-K mixture components are discussed.

Primarily, surfactant compounds are of particular importance. Prefers here are corresponding surface-active components that are already in cold water to the quickest possible, at least partial solution and thus the network processes on the textile goods in the first stage of the process demand. If also the use of anionic surfactant compounds is not excluded, it is of particular importance according to the invention here non-ionic surfactant compounds. The one in the specific case The nonionic surfactant type to be selected is determined, inter alia, by the K-pre-liquor co-determined pH. This applies in particular to the case that comparatively acidic pH values - if only for short Time - are the result of the dissolution of the SL-K.

Suitable nonionic surfactants, in particular also for acid 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 C 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 (EO) per mole of alcohol, in which the alcohol radical can be linear or also methyl-branched, can be particularly suitable. Corresponding fatty alcohols are known, for example, as oxo alcohols from synthetic chemistry. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, are particularly preferred. The preferred content of EO groups can range from 2 to 10 and in particular from 4 to 8. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with up to 10 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO , C _12-18 - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these non-sensitive alkoxylates of the fatty alcohol range. The specified degrees of ethoxylation represent statistical mean values, which can be an integer or a fraction for a specific product. Alcohol holoxylates preferably have a narrow homolog distribution (NRE). C _12-14 fatty alcohol ethoxylates with 4 to 7 EO have been shown to be particularly suitable.

Nonionic surfactants based on these fatty alcohol EO compounds, which are particularly flowable at room temperature, are acid and base stable and are therefore particularly suitable auxiliary components in connection with an SL-K liquor with an acidic pH. However, other important non-ionic surfactants are also suitable for working in the weakly acidic to neutral or even in the basic range. First of all, the alkyl glycosides of the general formula RO (G) _x are to be named here, in which R is a primary ge wheel-chain or branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G is the The symbol is for a glycose unit with 5 or 6 carbon atoms. Before G stands for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably from 1.2 to 2. Nonionic 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-0 301 298 and WO 90/39 77.

Another important class of suitable surfactants as a mixture compo Nenten for the SL-K are fatty acid-N-alkylpolyhydroxyalkylamides according to following formula (I)

in the R²CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R³ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 Carbon atoms and (Z) for a linear or branched polyhydroxy alkyl radical with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands.

The fatty acid N-alkylpolyhydroxyalkylamides are known substances that usually reduce one by reductive amination the sugar with ammonia, an alkylamine or an alkanolamine and after following acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride can be obtained. Regarding the procedures for their manufacture, reference is made to US Pat. No. 1,985,424; 2,016,962 and 2 703 798 and international patent application WO 92/06 984.

The mixing ratios between organic and / or anor ganic complexing agents and on the other hand the surfactant compounds, esp especially the non-ionic surfactants in the SL-K can be varied within a wide range. Basically, the well-known knowledge applies here that surfactant com components in very low concentrations trigger effective effects can. As a rule, the quantitative ratios of Complexing agent on the one hand and surfactant compound on the other hand at most about 1: 1. In general, the nonionic surfactant component is used in weight deficit to the complexing agent or mixture of complexing substances used. Appropriate amounts of nonionic components can range, for example, from 2 to 50% by weight. based on complexing agents - lie, again corresponding niotes amounts in the range from about 5 to 35% by weight are of particular importance can.

The sufficient cold solubility of the nonionic surfactant components on their on sentence in the SL-K pre-stage influences the respective concrete selection neter components or component mixtures. Here can reason  additional professional knowledge is required. The nonionic surfactants bonds can flow at room temperature - especially in the case the fatty alcohol ethoxylates - but they are also easily soluble at room temperature temperature solid non-ionic surfactants or mixtures containing non-ionic surfactants suitable, provided that their solubility meets the requirements of teaching according to the invention. APG compounds of the previously cited Kind are interesting compos in a fixed form at room temperature In this context, reference is made to the disclosure of the German patent application P 43 40 015.9 of the applicant, the details of which hereby expressly also for the purpose of the disclosure of the invention stood the present disclosure of the invention made.

In important embodiments of the invention, the SL-K also includes other components. Two basic options are possible differentiate that can also be linked:

Third-party components of the SL-K mixture can at least predominantly be the up gift, the ready-to-use, the cold solubility, the density and other physical or physico-chemical properties control. Known auxiliaries are particularly suitable here substances such as water-soluble salts and the like, to which no egg per se functionality within the scope of the washing process. That their with Use, however meaningful, will result from the following Considerable understanding: In preferred embodiments, the HK and the SL-K is used as a mixture of fabrics in the commercial laundry detergent. The HK can be used in particularly important forms as granular granules tes, especially in a rounded spherical shape, won by extrusion a mixture of substances is available. To segregation processes between HK and SL-K suitable material for storage and practical handling To exclude mixtures, the SL-K must also have a ver receive similar design. It is obvious that here, for example as the use of carrier salts without their own function in the wash important process.

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 surfactant compounds - others Mixture components with a targeted intrinsic effect in the context of washing and Cleaning process can be added. Examples are without The claim to completeness is named: components for the oxidative Tex bleach are suitable, both organic per compounds or components containing hydrogen peroxide as well as anor ganic persalts can be considered; Intensi catalysts vation of the oxidative bleach, such as that from the area of Textile detergents known as bleach activators are; 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 other additives mentioned here for SL-K but also other active substances from detergent technology and / or advanced auxiliaries are used, unless they are with the illustrated functionality of the SL-K for training the previous fleet collide in the desired pH range. More details on a particularly important embodiment of the invention are in given below.

In the following, typical ver named of the additional auxiliaries mentioned here. Suitable Bleaching agent components that release H₂O₂ in water are sodium perborate / tetrahydrate (NaBO₂ · H₂O₂ · 3 H₂O) and the monohydrate (NaBO₂ · H₂O₂). But there are also other H₂O₂ supplying borates useful for the game of Perborax Na₂B₄O₇ · 4 H₂O₂. These connections can be partial or completely by other active oxygen carriers, in particular by Peroxyhydrates, such as peroxycarbonates (NaH₂CO₃ · 1.5 H₂O₂), peroxypyrophos phate, citrate perhydrates, urea-H₂O₂ or melamine-H₂O₂ compounds as well as peracid salts or peracids, such as perbenzoates, peroxyphtha late, diperazelaic acid or diperdodecanedioic acid can be replaced. But also Salts of other peracids, for example alkali salts of persulfuric acids - for example K₂S₂O₈ - can important additional components in the sense of he act according to the invention.

In order to wash at temperatures below 80 ° C and especially in loading range from 40 to 60 ° C to achieve an improved bleaching effect  Bleach activators have already been incorporated into the SL-K. Examples of this are with H₂O₂ organic peracids forming N-acyl or O- Acyl compounds, preferably N, N'-tetraacylated diamines, such as N, N, N ', N'-tetraacetyl-ethylenediamine (TAED), also carboxylic anhydrides, such as Ben zoic anhydride and phthalic anhydride and esters of polyols such as Glu cosepenta acetate. The nature of completely different catalysts - for the game representatives from the class of active substances to heterogeneous solid catalysis - see the corresponding information in the representation of a be particularly important embodiment of the teaching according to the invention.

From the area of enzymes, the particular use of Proteases in the SL-K then increase when the SL-K pre-fleet to discontinue pH values in the acidic range. It has been shown that the pretreatment Soiling of protein-containing soils with a distinctly acidic SL-K pre-liquor can lead to a noticeable protein degeneration, which is noticeable in the subsequent washing process with the HK. This can also apply in the event that washing-active proteases in the HD usual amounts are used. Within the framework of the teaching according to the invention However, it was found here that the fact that Pro teaser In the preliminary stage of the SL-K, especially when using an acidic one Fleet this negative effect of protein degeneration not only canceled ben, but more than can be made up for. This is extremely enough small amounts of proteases added to the SL-K, the desired washing effect ultimately also to ensure against protein-containing soiling. Especially are suitable from bacterial strains or fungi, such as Bacillus sub tilis, Bacillus licheniformis and Streptomyces griseus active ingredients. The enzymes can be adsorbed on carriers and / or be embedded in the coating substance to prevent them from premature decomposition protect.

As a graying, possibly also used in the SL-K hibitors or dirt dispersers come with the usual com components into consideration. Water-soluble ones are particularly suitable here Colloids, mostly organic in nature, for example the water-soluble sal ze polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids, starch or cellulose or salts of sau  ren sulfuric acid esters of cellulose or starch. Also water soluble polyamides containing acidic groups are suitable for this purpose. Wei Furthermore, soluble starch preparations and other than those above can be used use named starch products, for example degraded starch, aldehyde strengthen and the like. Polyvinyl pyrrolidone can also be used. Preferred Components can be cellulose ethers such as carboxymethyl cellulose, Methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxy ethyl cellulose, methyl hydroxyl propyl cellulose, methyl carboxymethyl cellu loose and their mixtures and polyvinylpyrrolidone.

Also for all other potential mixture components mentioned here for the SL-K with regard to the quantities to be used in each case, that in the Usually at most roughly equal shares - based on the relationship as the organic and / or inorganic complexing agents - also used will. Only in special cases is the use of higher quantities of the Zu substitutes make sense.

The previous presentation of the teaching according to the invention refers in the we based on considerations on the interaction of the active ingredients respectively Active ingredient mixtures of the SL-K with the textile goods to be cleaned in one step of the aqueous preliminary liquor. However, this only affects a portion of the Ef effects, if desired, through the teaching of the inventive action can be triggered. Here it has to be taken into account that the SL-K also in interaction with the recyclable materials the HK can kick. If the HK in its entirety as time delayed water-soluble component made available to the washing process is, however, already in the early phases of the washing process - in particular when water begins to enter the solid mixture of substances - the Possibility of interaction between the active components of the SL-K and HK given.

One of these interactions used according to the invention is already multiple shown: The HK is with its content of pH-regulating alkaline Components matched to the SL-K so that ultimately the main wash cycle with the HK material mixture in the desired basic range  finds. The range of possible interactions addressed here is limited but does not rely on this simple process of pH regulation.

A variation possible according to the invention with the use of an SL-K Component that is particularly used for the primary formation of pH values in sau suitable to neutral range in the previous fleet is here shown: An important step in the washing process is the oxidative bleaching of the soiling. Which turned into practice today set bleach active components are the aforementioned salts with the Ability to bind hydrogen peroxide, especially corresponding ones Perborates and / or percarbonates. An important step in the context of the complex reaction sequence of this oxidative influence on the ver Soiling is the intermediate formation of peracids, especially per carboxylic acids or their salts caused by a primary abreak tion of the bound H₂O₂ with, for example, carboxyl groups or their Derivatives takes place. The explanation given here for the activation of the The bleaching process lies, for example, in the theory of the catalytic effect of bleach activators of the type of TAED, which are known to be used for acceleration and in particular to lower the activation temperature for the bleaching process in combination with perborate compounds men.

The formation of the percarboxylic acid groups or their derivatives is obviously an interaction with the H₂O₂ molecule brought by connection. This is the basis for the Conflict of conflicting requirements: Sufficient stock on the one hand, the peroxide supplier in the dry detergent mixture and sufficient willingness to react with the lowest possible washing temperature fittings in the wash liquor as part of the textile wash. In today's wash This conflict then becomes a form of remedy factor to be taken into account if the textile is washed with the tempera lowered structures, for example at 40 ° C or a maximum of 50 ° C should.

The sufficiently stable storage of the hydrogen peroxide in the recyclable material The mix of the commercial product requires the strongest possible integration and sta  bilization of the H₂O₂ in its carrier substance, on the other hand by conventional methods in the basic wash liquor, the H₂O₂ possible the multi-stage reaction process of textile bleaching without any problems To be available.

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 way Embodiment of the SL-K pre-fleet according to the invention - significantly reduced can be. Are now simultaneously at this stage of the previous fleet suitable auxiliary components for the formation of the bleach-oxidative-active Persäu offered as reactants, then can be used here compared to the usual ones Washing procedures can be set to provide significant relief. In particular This also applies to the fact that in this preliminary stage the formation of wash-active Peracids or peracid compounds can also be used Neter catalysts can be accelerated again. Finally, you can here also peroxide compounds - for example purely inorganic peroxides of the type of persulfates are used in small amounts to the process of bleaching acceleration by means of the SL-K-Vorstu to promote fe without fear of damage to the textile goods.

The pH control used in the invention in the SL-K, preferably polybasic carboxylic acids are in principle suitable carriers especially for the active oxygen within the scope of the here shown Transaction. However, it is not only monomolecular that can be particularly important ren, especially polybasic carboxylic acids in the sense of citric acid come, it has been shown that oligomeric and / or polymeric polycarbon acids are particularly valuable auxiliary substances in this reaction mechanism can.

When dissolving the delayed soluble HK in an acidic pre-liquor there are conditions for a limited period in which the area of interactions between recyclable materials discussed here SL-K and HK can expire to promote bleaching. In one gave way term embodiment, however, this reaction sequence is targeted reinforces that particularly suitable auxiliaries to promote this reak  tion sequence can already be used in the SL-K. The following applies in detail here:

The overall desired oxidative bleaching process can by its tax already initiated at the stage of the SL-K pre-fleet and meaningfully influenced to be flowed. In this particularly important embodiment are already as part of the SL-K - and not only in the time-delayed HK - Water-soluble bleaching agents, especially H₂O₂-lie in water remote connections also used. In particular, the Known previously known bleach components from textile washing medium technology, but now by choosing and adjusting the pH value tes of the aqueous preliminary liquor - preferably on the weakly acidic to new central area - are activated in their reaction sequence. Especially it may be appropriate here for the temporary formation of peracid suitable carboxylic acid compounds together with hydrogen peroxide supplier as components of the mixture of recyclables to form the SL-K pre-liquor to use. Citric acid and / or its (partial) salts are suitable here nete and preferred components for the initiation of such reaction fe in the particularly weakly acidic to neutral pH range. But also the other organic acids mentioned in connection with the SL-K, esp special polybasic carboxylic acids, for example as water-soluble Builders capable of complex binding compared to polyvalent ones Metal ions are known, suitable auxiliaries for the spac bleach activated activation. As an example here are the wine acid, but also called lactic acid.

Together with this, soluble compounds are already in the SL-K component gene and especially in water H₂O₂-supplying bleaching components turns. Even in the preliminary stage of treating the textile goods with the SL-K the bleaching reaction steps are initiated and promoted. Overall, this can substantially increase the washing result to be triggered.

In this context, further elements of the invention can advantageously be used teaching in accordance with the invention. It has been shown that through the use of organic builders based on polymer poly  carboxylates or the corresponding free polymeric polycar bonic acids and / or their partial salts a particularly safe and longer Timely regulation and adjustment of the pH value of the SL-K pre-liquor possible becomes. Using limited amounts of these polymer acids, for example have the pH of the previous liquor for a period of several minutes predetermined values in the desired weakly acidic to neutral range - if desired, but also in the weakly basic range - ensured be, without there being a special enhancement of the solution inhibition the HK needs. When entering the HK as spherical abge rounded extrudate grains on the one hand and the SL-K as a quick-dissolving com component, on the other hand, succeeds in the last case described here Ensuring the preselected pH of the pre-liquor, for example between 6 and 7 for a period of about 2 to 8 minutes, in particular 3 up to 6 minutes without additional measures for further deletion delay of the HK. In connection with the affected here open bleach activation in the SL-K pre-stage so that important advantages become accessible. The specifically adjustable pH-Be a reduced stability of the H₂O₂ suppliers in the aqueous Fleet is available for a predeterminable period of time before through the HK dissolving in the previous liquor the pH value on the strongly alkali area of the main washing process increases. It makes sense that with that the peroxidic sub-process of the washing step is specifically promoted can be.

In this context, in a further preferred embodiment the partial result sought here will be reinforced. For this, additional Lich activators or catalysts for peracid formation in the Rah of the SL-K fleet can also be used. Consider here additionally known catalysts, for example organic complex compounds of metals that can occur in several valence levels - for example iron and / or manganese. But are also quite suitable here other auxiliary substances of the type mentioned, for example the class which can be assigned to finely insoluble heterogeneous catalysts nen. Examples of these are oxidic compounds of metals such as titanium or tungsten, silicate compounds insoluble in the pH range mentioned, for example, corresponding aluminum silicates, but also in the heterogeneous  Catalysis known active substances such as activated carbon, which, for example, in ver packed but water-permeable form brought into the washing process can be. Finally, it has been shown that also the use usual bleach activators make sense in the preliminary stage of the SL-K pre-liquor can be full. This is immediately understandable for the embodiments in for whom the SL-K pre-fleet is already working in the basic sector. In consideration come as a mixture component for the SL-K in the affected here Embodiment especially the bil with H₂O₂ organic peracids end N-acyl or O-acyl compounds, preferably N, N'-te traacylated diamines, also carboxylic anhydrides and esters of polyols like glucose pentaacetate. All advanced outlines shown here Events in the SL-K composition are characterized by one more functional conception, which in this embodiment in the prior art Tech nik is not provided. By using the quickly soluble complexing agents in the pre-liquor, the primary influence is on the water hardness and on the conditioning of the textile or dirt incrustation on the textile with the complexing agents. At the same time this will work used but also the wash-active bleaching process which is then optimized in the subsequent main wash cycle with the HK can be.

Before solving the - in itself usual - composition of the time-delayed solution main component HK is briefly mentioned again concrete offer form of the SL-K in the textile preferred according to the invention detergent mixture performed the following: in addition to the one previously discussed Mixing the SL-K into a granular HK material as a separate but after Spatial form and density of the mixture component adapted to the HK - preferred also in grain form - there is a completely different possibility of association of HK and SL-K. Here, the SL-K can at least partially move out Formation of the HK, for example in the form of spherically rounded extrudate grains, applied to the outer surface of the HK goods so preformed and be solidified there. If necessary, by a layer with, for example, a hydrophobic effect between the Core and the outer shell not only the unlimited storage stability of the goods combined in this way can be ensured here in particular the adjustable variable time delay in the  Dissolution of the HK and thus the determination of the period for the treatment the soiled textile goods with the SL-K fleet. In practical terms First of all, the quick-release shell of the SL-K from jewei will be used broken ball. This will delay the time delay that may be submitted separating separators 36791 00070 552 001000280000000200012000285913668000040 0002004438850 00004 36672has not been exposed, so that in the further after overcoming the dissolution of the HK and thus the main wash cycle is initiated.

The use of appropriate, time-delayed separating layers on the outer surface of the HK can also in the first case be sensible, with the SL-K and HK from the outset as spatially separate Elements of the detergent mixture are used. If necessary In addition or instead of these measures, the outer shell of the HK and / or the SL-K with a preferably approximately pH-neutral solid water soluble and / or dispersible material layer, which Adequate shelf life of the blends of HK and SL-K un the usual practical conditions, for example in cardboard boxes, guaranteed. Knowledge of general specialist knowledge also applies here taking into account the specific elements of the teaching according to the invention.

The SL-K is usually in minor quantities - based on HK - used in the detergent mixture. Generally the amounts are the SL-K ranges 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 of about 1 to 20% by weight and preferably about 1 to 15% by weight in the normal case are used. The following examples show that with very ge wrestle amounts of SL-K, for example in the range of 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 the Multi-stage laundry with improved washing performance can be set. The following additional considerations apply:

The active components of the SL-K, especially their content of complexing agents and / or on surfactant compounds in addition to the corresponding com components of the HK be provided in the detergent mixture according to the invention.  However, it is also possible to use the active components used as SL-K multifunctional mixture of recyclables from the HK, via the preliminary stage the SL-K laundry with each other for (partial) reaction and for the soiled To bring textile goods into effect, but then in the following main to combine laundry with the HK again. Ultimately, the fiction includes according teaching an improved embodiment for the use of com complex textile detergent formulations in the form of today's high compressed multi-component mixtures with delayed solubility. By To arrangement of a portion of the multi-component mixture in the form of the SL-K can broaden and improve both the secondary and the primary washing effect can be achieved.

Basically apply to the structure of the HK according to the type and amount of its content substances the information of the printed version known to the experts of the technique. In this context, reference is made in particular to the following publications and going back to the applicant: In 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 is abbreviated for the composition of the wash-active HK for the formation of the alkaline Main wash fleet summarized. However, this applies several times before fact presented that the components of the SL-K if desired can be taken at least in part from the HK and thus in each case affected HK in the sense of the teaching according to the invention there men accordingly are used in an appropriately reduced manner. The action according to the invention is but not limited to that. An important embodiment sees the use of known, at least for the most part time Lich delayed preparations of detergent mixtures with a SL-K before, the component (s) additionally trained in the invention Multi-stage washing processes were introduced.

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 of alkali component
up to 15% by weight, preferably 3 to 7% by weight, of cobuilder
up to 40% by weight, preferably 10 to 30% by weight, of bleach
up to 15% by weight, preferably 1 to 10% by weight, of bleach activator
up to 20 wt .-%, preferably 2 to 10 wt .-% alkali silicate
0.1 to 10 wt .-% 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 by extrusion, wet agglomeration, roller compaction and the like, in particular:
5 to 35 wt .-% anionic surfactant from the group of alkylbenzenesulfonates, fatty alcohol sulfates, fatty alcohol ether sulfates, olefin sulfonates and / or fatty acid alkyl ester sulfates
1 to 15 wt .-% nonionic surfactant from the group of alkyl poly ethylene glycol ether, nonylphenol polyethylene glycol ether and / or alkyl polyglycosides
20 to 50 wt .-% 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 wt% bleach
1 to 10% by weight bleach activator
up to 6% by weight, preferably 2 to 5% by weight, of alkali silicate
0.1 to 3.5 wt .-% foam inhibitor and
1 to 3% by weight of one or more substances from the group of textile softeners, graying inhibitors, enzymes, optical brighteners, dyes, fragrances, formulation aids and / or adjusting agents.

Regarding the individual components of the above-mentioned washing active The following applies in particular to preparations:  

Anionic surfactants are generally sulfonate or sulfate surfactants typ. The surfactants containing sulfate groups include in particular Al alkyl sulfates and the corresponding sulfation products of alkoxylated, especially ethoxylated alcohols. Surfactants containing sulfonate groups are in particular alkylbenzenesulfonates, alpha-sulfofatty acid ester salts and alpha sulfo fatty acid disalts. The anionic surfactants are usually in the form of their alkali salts, especially their sodium salts.

Addition products from 2 to 20 are preferred as nonionic surfactants 3 to 15 moles of ethylene oxide to 1 mole of a compound with essentially Lichen 10 to 20 carbon atoms from the group of alcohols and alkyl phenols can be used. In detail, the previously related to of the information provided in the SL-K.

In addition to these water-soluble nonionic surfactants, there are also no or not completely water-soluble polyglycol ethers with 2 to 6 ethylene glycol ether residues in the molecule of interest, especially if them together with water-soluble nonionic or anionic surfactants be used. Other suitable nonionic surfactants are alkylgly kosides or alkyl polyglycosides, the alkyl group of 8 to 18, preferably has 10 to 16 carbon atoms.

Main builder components for the HK, which are to be exchanged for the SL-K from bound multivalent metal ions, especially calcium ions, to Are used, in particular synthetic zeolites, polycarboxylic acids and crystalline and / or non-crystalline suitable for calcium binding Alkali silicate compounds, which in particular the Q₂- and / or have Q₃ structure. At the revelation of the The applicant's earlier protective rights cited above are hereby incorporated by reference expressly referred again.

Zeolite NaA with a calcium binding capacity (according to the data of DE 22 24 837) in the range from 100 to 200 mg CaO / g is an important buil the component in the sense of a finely divided insoluble ion exchanger Structure of the HK. Polymeric polycarboxylates suitable as a builder component are, for example, the sodium salts of polyacrylic acid or poly  methacrylic acid, for example those with a molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Have been particularly suitable copolymers of acrylic acid with maleic acid, the 50 to 90 % By weight of acrylic acid and 50 to 10% by weight of maleic acid. Your rela tive molecular weight, based on free acids, is generally 5000 up to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. In particular, terpolymers are also polymeric polycarboxylates preferred in the German patent DE 42 21 381 and DE-A 43 00 722 are described. The acids mentioned are usually in the form of their water-soluble salts, especially the sodium salts.

In this context, however, biodegradable terpo are also suitable polymers, such as those as monomers salts of acrylic acid and of maleic acid and vinyl alcohol or vinyl alcohol derivatives (DE-A 43 00 772) or the salts of acrylic acid and 2-Al as monomers contain kylallylsulfonic acid and sugar derivatives (DE-A 42 21 381).

Other suitable builder substances from HK are polyacetals, which by Reaction of dialdehydes with polyol carboxylic acids with 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained - see EP-A-0 280 223. Preferred polyacetals are derived from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde, and mixtures thereof and from polyol carboxylic acids such as Get gluconic acid and / or glucoheptonic acid.

Suitable alkali components are alkali silicates, especially sodium silicate Likates of the composition Na₂O: SiO₂ = 1: 1 to 1: 3.5, preferably 1: 2 to 1: 3.35. Alkali carbonates also come as alkali components and hydroxides, especially the sodium compounds, in question.

The HK components according to the invention can be phosphonic acids as cobuilders contain, for example aminoalkanephosphonic acids. Are preferred here Ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine penta methylene phosphonate (DTPMP) and their higher homologues. You will be in the HK preferably in the form of neutral sodium salts, for the sake of  as hexasodium salts of EDTMP or as hepta- and octa- DTPMP sodium salt used. Your share in the funds, on free Calculated acid is preferably up to 1 wt .-%, in particular 0.1 up to 0.5% by weight. Another suitable phosphonic acid is the HEDP approximately the sodium salt or the tetra sodium salt of this acid.

In particular, as previously stated, the HK contains bleach and bleach activators. As a bleaching agent are in particular H₂O₂-supplying in water Connections of the type previously mentioned in connection with the SL-K are suitable net. The chemical nature of the bleach activators is also already specific in connection with the SL-K. It will referred to. In addition, reference is made to the disclosure of the mentioned WO 94/01526 of the applicant, the disclosure of which hereby expressly Lich also made the subject of the present disclosure of the invention becomes.

The detergents can be used as optical brighteners for cotton, in particular Derivatives of diaminostilbenedisulfonic acid or its alkali tall salts included. For example, salts of 4,4'-bis (2-ani lino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulphonic acid or similarly constructed connections, which instead of the Morpholinogrup pe a diethanolamino group, a methylamino group or a 2-methoxy wear ethylamino group. Such come as brighteners for polyamide fibers of the type of 1,3-diaryl-2-pyrazolines in question, for example 1- (p-Sul famoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline. Brighteners can also be used of the substituted 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl type be set. Mixtures of the aforementioned brighteners can also be used will.

The enzymes already mentioned in connection with the SL-K come as enzymes Representative into consideration. The enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition to protect settlement. The proportion of enzymes, enzyme mixtures or enzyme grains nulate can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to be 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 C _12-20 fatty acids and C _2-6 diamines or from C _12-20 alkyl amines and C _2-6 dicarboxylic acids can also be used. Mixtures of various 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 class are suitable as textile softening additives the bentonites and smectites, for example those according to DE 23 34 899 or EP 026 529. Synthetic, finely divided sheet silicates are also suitable with smectite-like crystal phase, as characterized in more detail in DE 35 26 405 net. The layered silicate content can be, for example, 5% by weight to 20% % By weight.  

Examples

The following examples show the washing results, which are in stan standardized washing attempts in a household washing machine under each identical framework conditions have been obtained. Apply in detail the following information:

Washing machine:
Household washing machine Zanussi Z914E, fleet volume approx. 20 l per main wash. The duration of the main wash was 40 minutes. The temperature setting on the machine specification: 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 addition of the detergent mixture used in each case to the wash cycle was carried out in all cases via the induction unit provided in the machine mer. Local cold tap water is used in all washing tests (average hardness 16 ° dH) for washing in the detergent mixture and Preparation of the wash liquor and for the subsequent multiple rinsing of the washed material samples used.

The determination of the degree of contamination in the washing process set soiled test rags on the one hand and in the respective wash washed, rinsed and dried test rags on the other hand follows by measuring the degree of remission with the Micro-Color V 2.1 Dr. Long, FRG.

In the washing tests given below, 10 under differently soiled test rags with the respective washing process Textile detergent mixture subjected. The 10 with standard contamination Test rags are used as part of the presentation of the examples  consecutively numbered in the same order from 1 to 10 and are identified as follows.

Comparative provisions

In a first series of washing trials, identical tests are carried out Washing conditions the cleaning results on the test stains 1 to 10 using a compacted, spherical extrudate the universal detergent of the commercial product of the applicant according to the disclosure of the international patent application WO-91/02047.

In successive tests, this universal detergent is used in quantities of 60 g, 80 g and 100 g - each per washing process - used. This used as the "main component" in the sense of the invention The product is referred to below as "UWM-HK".

The reflectance values are shown on the rinsed and dried test rags certainly. The following results are obtained:

60 g UWM-HK / 60 ° C per wash

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 during 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

Sum of the measured remission values: 831.3
pH min: 7.6 pH max: 9.7

100 g UWM-HK / 60 ° C per wash

Sum of the measured remission values: 844.7
pH min: 7.7 pH max: 9.9

Examples of the invention

In the following experiments, the amount of detergent used is a total of 80 g per batch. The main component is delayed solubility the previously defined UWM-HK of the applicant Commitment.

Together with this, valuable substances or mixtures of valuable substances are ne the quickly soluble component (SL-K in the sense of the invention Definition).

The specific amount of UWM-HK used in the respective experiment is used for the overall menu used in the experiment concerned proportion of the SL-K (mixture) reduced, so that in all cases the amount of the recyclables used in their entirety 80 g per wash operation is.

The SL-K component (s) are placed together with the UWM-HK in the induction bowl given the washing machine and from there by means of the induction water into the Engine room transferred. The heating of the wash liquor to the pre The main washing temperature (60 ° C) takes place in the washing machine  provided heating elements, the temperature of the cold detergent fleet is around 20 ° C. The beginning temperature rise through Heating of the wash liquor begins after about 6 to 8 minutes respective washing process.

The following examples first identify the one sentence coming SL-K by type and quantity and the resulting A set quantity of the UWM-HK. The testan Determine soiling 1 to 10 after rinsing and drying twice remission values are summarized.

The values for pH min and pH max and the time are also given time until the wash liquor is neutralized (pH 7) if used of SL-K 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" ® from the applicant - C _12-18 fatty alcohol - 7 EO) in the following with "LT -7 ".
HK: 76.0 g UWM-HK

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

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 TiO₂
HK: 77.5 g UWM-HK

The reflectance values determined on the washed test soils are

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 ent speaking values of the comparison tests results in a number of interesting Outcrops:

The acidic initial values of the wash liquor apparently lead to a degeneracy the protein-containing stains to the test rags according to (1) and (2). The washing results obtained using the SL-K are here worse than when using 80 g UWM-HK as the sole multifunctional le detergent component. Nevertheless, the total value of the total the remission numbers were higher than the average of the comparative tests for washing with 80 g UWM-HK. The reason for this is partly the be considerable increase in washing results with other test soils gene.

The individual comparison of the Washing results with the comparison test 100 UWM-HK: the waste of the wash the result for protein soiling (1) and (2) is here again much more pronounced, but the Testan soiling 3 to 8 and 10 compared to the values of the comparison test achieved the same or even significantly better washing results. This thing behavior can be seen against the background of the fact that the inventor  formulation according to the invention according to Example 2 from the HK portion to 76 g UWM-HK used lean, while in the comparison experiment concerned here the almost 1/3 higher amount of the universal detergent mixture (100 UWM-HK) is used.

Example 3

In the following, the results of 2 detergent batches in the sense summarized the teaching of the invention, which in addition to the SL-K Setting an acidic pH in the SL-K small amount of bleach use activators (TAED). The following applies in particular:

Example 3a

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

There are the following remissions on the washed test soils values determined:

Sum of the total remission values determined: 832.9
pH min: 4.5 pH max: 9.3
Time to neutralization: 2.8 min

Example 3b

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 are shown on the washed test stains certainly:

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 example 3b, the sum corresponds to the ins Total remission values determined approximately the comparison value when using 80 g UWM-HK, although as expected the washing results for the protein soiling (1) and (2) and the amount of HK Heavy detergent component has become emaciated from 80 g to 76 g.

Example 4

Here, too, 2 separate washing tests are combined, which are indicated by a common determining element are marked. In both cases in the SL-K in addition to citric acid and the non-ionic surfactant the practical form of preparation of a detergent protease (BLAP) added. The following applies in particular:

Example 4a

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 are the fol areas:

Sum of the total remission values determined: 841.6
pH min: 5.6 pH max: 9.3
Time to neutralization: 2.0 min

Example 4b

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

Here are the following remissi on the washed test stains determined values:

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 joint use small amounts of the wash-active protease component BLAP in the SL-K die in the case of acidic prewashing, losses of activity observed so far to the pro contaminated soils (1) and (2) more than can be made up for nen. The total values of the remission values determined in each case lie in both cases well above the corresponding total value of the Ar beit in the absence of the SL-K according to the invention with 80 g UWM-HK.

The total remission value of both experiments lies approximately in the sizes order the corresponding value from the comparative laundry with 100 g UWM-HK, although also in these two experiments according to the invention  Teach the amount of UWM-HK used as HK significantly reduced is.

Example 5

In the following example 5 3 washing tests are summarized each because the basic components of SL-K are the mixing of citric acid and contain non-ionic surfactant LT 7. In addition, the The following additional auxiliary components are used:

Potassium persulfate (K₂S₂O₈) as an inorganic oxidative component (Example 5a); a mixture of TiO₂ and BLAP (Example 5b) and the Mixing of BLAP and K₂S₂O₈ (Example 5c). The following applies in particular:

Example 5a

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:

Sum of the total remission values determined: 836.8
pH min: 5.7 pH max: 9.2
Time to neutralization: 2.4 min

Example 5b

SL-K: 1.7 g citric acid together with 0.3 g LT 7, 0.2 g TiO₂ and 0.7 g BLAP
HK: 77.1 g UWM-HK

The following reflectance values are applied to the test soiling Right:

Sum of the total remission values determined: 837.2
pH min: 5.7 pH max: 9.7
Time to neutralization: 2.0 min

Example 5c

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 are determined:

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 those at the beginning specified comparison experiments provide a number of interesting Er Results: As expected, in Example 5a the washing results for the protein-containing test stains (1 and 2) compared to the comparison with 80 g UWM-HK lowered. Nevertheless, the sum of the remissi measured lies ons values significantly above the total value from the comparison with 80 g UWM-HK. The reason for this is the almost better in almost all cases Washing results of the further test stains.  

Example 5b achieved using the wash-active protease test soils (1 and 2) despite a considerably acidic type initial pH of the wash liquor (5, 7) the washing results of the comparison try with 80 g UWM-HK. The cleaning results in the other test Overall, soiling occurs in such an improved form that the comparison of the total values a significant increase for the fiction appropriate 2-step wash shows.

The most impressive is the increase in the washing result through the Figures from experiment 5c are documented. The total value exceeds that corresponding value from conventional laundry with 100 g UWM-HK Lich, although the UWM-HK amount used in this experiment is only approx. Is 77 g.

Example 6

The following examples 6a and 6b show a reduction in the Main component used UWM-HK by more than 10%, based on the Use of 80 g from the comparison tests. Use each of them dete SL-K contains in addition to the combination of citric acid and the niotes sid component LT 7 the well-known from the field of textile detergents Bleaching component sodium perborate monohydrate, hereinafter referred to as "P2" draws. The following applies in particular:

Example 6a

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 give themselves as follows:

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, the comparatively acidic also falls here Initial pH of the pre-liquor the washing result for the test soiling (1) and (2) compared to the comparison test with HK as the sole wash middle component.

Example 6b

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 are determined:

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 is neutral range from very weak to basic. The comparison of remissions values for the test soiling (1) and (2) compared to example 6a and compared to the comparison values with 80 g UWM-HK as detergent shows that here a significantly lower reduction in the washing result with respect to proteinaceous soiling has occurred.

For both attempts of this example, the fact that the total value of Ver same attempt with 80 g UWM-HK is not quite achieved, the fiction according to the built-up 2-stage washing liquors, however, reduced only to an insignificant extent Total values lead, although the share of UWM-HK is very considerable has been lowered. In this context, it should also be taken into account  the fact evident from the comparative experiments that the total value the washing result with 60 g UWM-HK is only 808.0.

Example 7

The following example shows 2 experimental approaches and the ones obtained The results obtained in the SL-K based on citric acid / LT 7 a combination of the sodium perborate monohydrate "P2" with that as a wash medium builders or co-builders known polycarboxylate "Soka lan® CP5 "- manufacturer BASF - use. The example 7a ar works with an initial pH of the pre-liquor in the weakly acidic range, Example 7b shows the components of the SL-K used so that the initial pH of the SL-K pre-liquor is neutral Area.

It is striking in the pH course of both approaches that - apparently due to the Use of the polycarboxylate component "CP5" - which is primarily a pH value of the previous liquor over a comparatively long period remains constant and only then to the higher pH ranges of the HK wash fleet increases.

The following applies in particular:

Example 7a

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

On the test samples washed under standard conditions, the fol the following reflectance values:

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

What is striking here are the comparatively good remission values for the Test samples (1) and (2), although the pH range of the pre-liquor clearly in the acidic area.

Example 7b

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 are shown on the washed test stains certainly:

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

In the sum of the determined remission values, but also in the majority the washing result of this example lies in the individual remission values les clearly above the comparison test using 100 g UWM-HK as sole detergent component. The same applies to even stronger ones Dimensions compared to the comparison tests using 80 g UWM-HK as sole detergent component.

Example 8

The approach described here uses as a SL-K a mixture 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 three components mentioned are used in the form of an APG / FAS / water glass 45/45/10 compound produced by superheated steam drying. The following applies in particular:
SL-K: 2.5 g of citric acid mixed with 1.5 g of the aforementioned multi-component compound
HK: 76 g UWM-HK

The washing results on the test soils used are the fol areas:

Sum of the total remission values determined: 834.4
pH min: 4.8 pH max: 9.2
Time to neutralization: 2.3 min

What is striking is the clear increase in washing power compared to the Testan dirt (7) and (8).

Example 9

The following example 9a describes the application of the fiction principle of multi-stage washing with a basic SL-K pre-liquor. Here, trisodium citrate is used as a complexing agent in admixture with the in Example 8 APG / FAS / water glass compound used.

Example 9b modifies the SL-K approach in such a way that here trisodium citrate is used in combination with LT 7 as a surfactant component. Also here already in the pre-fleet of the SL-K components are basic Washing conditions.

Example 9c finally modifies the approach of Example 9a in such a way that instead of trisodium citrate a soda / oligo sodium silicate compound is used. To manufacture these builder components with the Befä  For calcium binding cf. the corresponding information of the general Description part.

The following applies in particular:

Example 9a

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 are obtained:

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

Example 9b

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

The following washing results are obtained:

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

Example 9c

SL-K: 3.0 g soda / sodium oligosilicate compound together with 1.0 g APG compound (according to example 8)
HK: 76.0 g UWM-HK

The following washing results are obtained:

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

Claims (32)

1. Solid textile detergent in the form of a mixture of detergent active substances and, if desired, auxiliary substances - detergent active surfactant compounds, alkalizing agents, soluble and / or finely insoluble builders and / or finely insoluble builders with the ability to bind calcium, and, if desired, other conventional active substances and builders / or auxiliary components of textile detergents - which are at least partially processed into 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 contain quick-soluble components in cold water ("SL-K") based on cold-soluble complexing agents for the polyvalent cations of water hardness and their mixtures with cold-soluble surfactant compounds. 2. Textile detergent according to claim 1, characterized in that the Delayed solution of the HK in the initial phase of the washing process enough, at least the penetrating wetting of the textile with the to ensure aqueous SL-K pre-liquor. 3. Textile detergent according to claims 1 and 2, characterized in that the dissolution of the SL-K to adjust the pH values of the previous liquor in the acidic 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. 4. Textile detergent according to claims 1 to 3, characterized in that the HK soluble and / or finely insoluble in the alkaline range Builders with the ability to bind calcium and this in contains such amounts that the alkaline liquor at least during the washing process even at elevated washing temperatures against the bil at least formation and precipitation of poorly soluble calcium compounds is largely stabilized.   5. Textile detergent according to claims 1 to 4, characterized in that (a) the resolution of the SL-K to pH values of the previous liquor equal / less 8, preferably in the pH range from about 2 to 8, in particular of little at least about 4.5, with initial pH values of the pre-liquor in Range of about 5.0 to 7.5 may be particularly preferred, or but (b) the dissolution of the SL-K immediately to the pH range above 8, especially from 8 to 11, leads. 6. Textile detergent according to claims 1 to 5, characterized in that the HK at least for the most part in the form of condensed and / or coated multi-substance mixtures, for example as corresponding ones Granules, extrudates, agglomerates and / or compactates with bulk ten of at least 500 g / l is formed, but especially for white at least predominant as a multi-component extrudate with preferred Bulk densities range from 600 to 1100 g / l. 7. Textile detergent according to claims 1 to 6, characterized in that the SL-K organic acids, especially polybasic carboxylic acids, and / or their (partial) salts and / or polybasic inorganic acid ren and / or their (partial) salts, here such compo are preferred, even after neutralization in an alkaline bath Are valuable and / or auxiliary substances of the textile detergent. 8. Textile detergent according to claims 1 to 7, characterized in that the SL-K water-soluble builders with the ability to complex bond to polyvalent metal ions and preferably those Excipients based in particular on polyvalent carboxylic acids and their Derivatives, such as 1- and / or polybasic hydroxycarboxylic acids, ethers carboxylic acids and / or their (partial) salts with preferably up to 12 C atoms in the molecule, builders based on preferably cold soluble oligomeric or polymeric polycarboxylic acids or mixtures of such Ge builders, but optionally also nitrogen and / or phosphorus ent holding complexing agents from the textile detergent technology, ent holds.   9. Textile detergent according to claims 1 to 8, characterized in that water-soluble organic dicarboxylic acids, in particular in the range C _4-8 and / or their (partial) salts, but preferably higher-functional polycarboxylic acids and / to form the SL-K liquor. or their (partial) salts are used which are capable of at least partially binding alkaline earth metals and in particular calcium in dissolved phase even in the acidic to neutral range. 10. Textile detergent according to claims 1 to 9, characterized in that the SL-K at least partially citric acid and / or its cold-soluble Contains salts, especially alkali salts, preferably in a mixture with oligo- and / or polymer carboxylic acids and / or their salts, in particular especially from the field of builder substances for textile detergents, available. 11. Textile detergent according to claims 1 to 10, characterized in that the SL-K - especially for setting a pre-liquor with pH Values in the slightly acidic to alkaline range - at least in part wise inorganic complexing agents and in particular cold soluble ones (Partial) salts of oligoacids of phosphorus and / or oligo-reference contains 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 a proportion of Q₂- and / or Q₃ structure - are present. 13. Textile detergent according to claims 1 to 12, characterized in that the HK alkaline soluble and / or finely divided insoluble build contains the components, in particular via a calcium exchange in the neutral to basic range for fixing the calcium ions in the Builder molecule lead 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  Builder or builder components ion exchangers for more valuable metal ions, especially calcium, are used, whereby the use or co-use of water-insoluble fine-particle Al Kalizeolithe, in particular zeolite NaA, NaX and / or zeolite P, be can be 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 Liche silicate compounds with builder effect, especially crystalline Layered silicates and / or amorphous and / or crystalline alkali oligosi Likates with at least partially Q₂ and / or Q₃ structure are present. 16. Textile detergent according to claims 1 to 15, characterized in that the soluble and / or finely divided insoluble builders in the HK in such excess is present in addition to the calcium exchange the neutralization and alkalization of an acidic liquor by the se builder is done. 17. Textile detergent according to claims 1 to 16, characterized in that the HK additionally alkalizing components without the qualification for calcium exchange, 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 at least some nonionic surfactants of the fatty alcohol type holalkoxylate and / or the alkylglycoside compounds (APG) for Ein sentence come. 20. Textile detergent according to claims 1 to 18, characterized in that even the SL-K - preferably in combination with nonionic surfactants - in the alkaline medium wash-active anionic surfactant compounds and / or the contain corresponding acids.   21. Textile detergent according to claims 1 to 19, characterized in that the solution delay of the HK is set so that at equal timely addition of the SL-K and the HK to the aqueous fleet the time span treatment of the textile goods with the SL-K pre-liquor at least 0.5 to 1 min, preferably at least 2 min and preferably not is more than 20 min, with a period of pretreatment and in particular up to the neutralization of the wash liquor in the range of about 2 to 5 minutes may be particularly preferred. 22. Textile detergent according to claims 1 to 21, characterized in that the respective solution speeds of the SL-K and the HK on the temperature range usual cold or only slightly warmed lei tion water and thus in particular in the range from about 10 to 30 ° C are adjusted. 23. Textile detergent according to claims 1 to 21, characterized in that the HK at least predominantly as a granulated, wal zen compacted, but in particular extruded multicomponent mixture in Grain shape with preferred average particle sizes in the mm range lies, with rounded extrudate grains a preferred one Form of supply are. 24. Textile detergent according to claims 1 to 23, characterized in that the HK good - especially in the grain outside area - with solution ver hesitant auxiliaries and thus prefer bowl-shaped around is enveloped. 25. Textile detergent according to claims 1 to 24, characterized in that (a) either the SL-K material is finely powdered, but also preferred is grain-shaped, in particular grain shape and density can be adapted to the HK material in such a way that in mixtures of HK and SL-K no significant segregation processes occur, and / or that (b) the SL-K is applied as an outer shell to the HK. 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 mate rial layer is provided, the shelf life of the blends of HK and SL-K under normal practical conditions, for example in cardboard packs guaranteed. 27. Textile detergent according to claims 1 to 26, characterized in that the SL-K in minor quantities - based on HK - a is set, amounts in the range up to 30 wt .-%, preferably 1 up to 15% by weight and in particular 1 to 10% by weight 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 per compounds, in particular bleaching components containing H₂O₂; Catalysts for Intensification of oxidative bleaching, such as TAED; the addition of wash active enzymes, especially proteases; of dirt dispersers and / or graying inhibitors, may be preferred. 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 acid to neutral area also together with the SL-K wash-active enzymes, in particular wash-active proteases. 30. Process for optimizing the washing and cleaning power of textiles detergents for the area of alkaline textile washing by Multi-stage wash, characterized in that the main wash in alkaline range using a multi-component main component (HK according to claims 1 to 29) a pretreatment of the soiled Tex tilgutes with the pre-fleet of a quickly soluble component (SL-K ge according to claims 1 to 29). 31. The method according to claim 30, characterized in that the SL-K time Lich separated and added to the wash liquor before the HK, however, SL-K and HK are preferably added to the wash liquor the and the HK as such a time-delayed soluble component  is formed that at least the penetrating wetting of the textile good is guaranteed with the aqueous SL-K pre-liquor. 32. Use of a preparation that is quickly soluble even in cold water form of complexing agents for polyvalent metal ions, especially for the cations from water hardness and / or from dirt incrustations on soiled textiles (SL-K according to claims 1 to 29) in Abmi with a delayed, soluble form of preparation for more Fabric and textile detergent for alkaline textile washing (HK acc Claims 1 to 29) to form a multi-stage wash and opti the washing result on soiled textiles.