EP1440141A2 - Detergent or cleanser that can be dispersed in an essentially sediment-free manner - Google Patents

Abstract

The invention relates to a particulate detergent or cleanser that does not contain aluminosilicate, silicate and phosphate and whose aqueous dispersion (8 g, 1 l, 20 DEG C, 16 DEG d) has a pH value ranging from 6.5 to 9.5, and when dispersed in tap water (8 g, 1 l, 20 DEG C, 16 DEG d, agitated for 20 min. followed by a sedimentation time of 24 h), has a sedimentation volume of no greater than 0.5 ml. The inventive detergent or cleanser can be used for washing and cleaning, in particular, sensitive textiles.

Description

 "Detergent or cleaning agent that is essentially dispersible without sediment"

The invention is concerned with a particulate, aluminosilicate, silicate and phosphate-free washing or cleaning agent, the aqueous dispersion of which has a mild pH and which can be dispersed in tap water essentially without sediment. The invention is also concerned with the use of this agent for washing textiles, especially delicate textiles.

The manufacturers of detergents or cleaning agents invest a lot of time and work in the further development and improvement of their products in order to meet consumer wishes even better. Examples of fields in which progress is currently being worked are the improvement of the washing performance, the simplicity of use, the solution and flushing behavior, and the deposit behavior. The optimization of the detergent ingredients, especially the builders or builder systems and the surfactants or surfactant systems, as well as the optimization of their formulations play a crucial role.

Builders or builder systems perform a multitude of tasks in detergents or cleaning agents, which have also changed considerably in recent years and decades with the constant change in the composition, the form of supply and the production of detergents. Modern detergents today contain approx. 30 to 60% by weight builder substances. These are among the most important classes of substances for the construction of detergents and cleaning agents.

Because of the variety and evolution of detergent systems indicated here, the tasks of the builders are varied and neither fully nor quantitatively defined. However, the main requirements are well described. The water softening, the strengthening of the washing effect, a graying inhibition and the dirt dispersion are particularly worth mentioning here. Builders should contribute to the alkalinity required for the washing process, show a high absorption capacity for surfactants, improve the effectiveness of the surfactants, make positive contributions to the properties of the solid products, for example in powder form, and thus have a structure-forming effect or also reduce the dust problem. These different requirements can be normally not with just one builder component, so that a system of builders and co-builders usually has to be used.

For ecological reasons, phosphorus and / or nitrogen-containing builders have been criticized as detergent components. The three-dimensionally cross-linked, water-insoluble sodium aluminosilicate zeolite NaA has become widely accepted, particularly in textile detergent formulations. To a considerable extent, especially in the context of textile detergents, the use of so-called co-builders is required here, in particular in order to counteract undesirable incrustations. To a large extent, polymeric polycarboxylates, in particular copolymers based on acrylic acid and maleic acid with molecular weights in the range from 20,000 to 100,000 g / mol, are used together with soda for this purpose together with zeolite NaA.

One of the biggest disadvantages when using aluminosilicates such as zeolite NaA in detergents or cleaning agents is their insolubility. Under unfavorable circumstances, this leads to the fact that, when machine washing with aluminosilicate-containing detergents or cleaning agents, the aluminosilicate is not completely rinsed out in the rinse cycle and is deposited on the laundry in the form of white spots or stains, so-called residues. This problem has been exacerbated by the current trend towards washing machines which, for ecological reasons, operate with less and less water per wash and are loaded more and more.

Potential substitutes for the aluminosilicates were sought very early on. Simultaneously with the development of the water-insoluble zeolite NaA as a builder, it was proposed in this connection to use selected water-soluble amorphous sodium silicates as builders in detergents or cleaning agents. Reference is made, for example, to U.S. Patents 3,912,649 (JM Huber Corp.), 3,956,467 (OL Bertorelli), 3,971,727 (JM Huber Corp.), and 3,879,527 (JM Huber Corp.). It describes amorphous sodium silicate compounds as builder substances which are produced by spray drying aqueous water glass solutions, subsequent grinding and subsequent compression and rounding off with additional removal of water from the ground material. According to EP-A-0444415 (Hoechst), detergents containing 5 to 50% by weight of at least one surfactant, 0.5 to 60% by weight of one Builders and conventional washing aids are proposed, the characteristic being that an amorphous, low-water sodium disilicate with a water content of 0.3 to 6% by weight is used as the builder.

German Offenlegungsschrift DE-A-2240309 (Unilever) describes a zeolite-free agent which contains 5 to 40% by weight of surfactant, 30 to 70% by weight of alkali carbonate, 1 to 30% by weight of complexing agents, preferably citrate, and Contains 0.05 to 15 wt .-% of a deposit inhibitor for calcium carbonate. This deposition inhibitor is either a phosphate, a phosphonic acid or a polymeric carboxylate.

International application WO-A-96/17045 (Henkel) describes washing or cleaning agents with bulk densities above 600 g / l, which contain a surfactant system and a builder system in which zeolite is completely or partially replaced by sodium carbonate and amorphous silicate without causing difficulties from an application or process engineering point of view, even in the production of these agents by extrusion. This was achieved by limiting the content of zeolite (based on anhydrous active substance) to on average less than 19% by weight, the content of the sum of sodium carbonate and amorphous sodium silicate (each based on anhydrous active substance) 10 to 40% by weight. -%, the weight ratio of sodium carbonate to sodium silicate being in the range from 5: 1 to 1:10 and the sodium carbonate used being at least partially in the form of granules.

In international application WO-A-98/20105 (Procter & Gamble), a phosphate- and aluminosilicate-free agent is presented, which in addition to surfactants and polyethylene glycol contains a builder system based on carbonate, sulfate, silicate and polycarboxylate. The advantages of this product are the price and the environmental behavior of the builder system. Preferred embodiments have a sodium carbonate to sodium sulfate ratio of 1: 1 to 1: 3.

From the international application WO-A-00/39261 (Henkel) a zeolite-free builder system is known which consists of alkali silicate, alkali carbonate, polymeric polycarboxylate with a molar mass less than 10,000 g / mol, phosphonate and an acidic component consists. This soluble builder system is dosed low, ie less than 40% by weight of the detergent is used by this builder system and the alkali product of this agent is in the range from 7.0 to 11.4. Compared to a zeolite-containing builder system, this soluble builder system has advantages, particularly in terms of residue behavior.

However, it has now been shown that even completely eliminating the insoluble aluminosilicates does not solve the deposit problem. It has even been found that even with residues-free, aluminosilicate-free washing or cleaning agents, deposits can occur under unfavorable circumstances. The silicates used were considered to be the cause of these deposits. These have the unfavorable property of partially hydrolyzing in an alkaline, aqueous medium, in particular at elevated temperatures, and of separating out in the form of silica. As a result of this knowledge, work is currently underway on the development of next-generation detergents or cleaning agents which are not only free of phosphate and aluminosiiicate, but which also limit the content of silicates or certain silicates.

The international application WO-A-00/18859 (Procter & Gamble), for example, limits the content of amorphous alkali silicate. A phosphate-free washing or cleaning agent is described which has an improved solubility and an improved washing performance. The agent contains a special builder system and a special surfactant system. The builder system consists of at least two builders, one of which is partially or completely water-soluble and makes up 60 to 100% by weight of the builder system, preferably crystalline alkali silicate with a layer structure. Another builder is water-insoluble and makes up 0 to 40% by weight of the builder system. In total, less than 9% by weight of aluminosilicate, preferably no aluminosilicate at all, and less than 5% by weight of amorphous alkali silicate should be contained in the agent. The surfactant system comprises one or more surfactants, preferably an anionic alkyl sulfate and an anionic sulfonate or mixtures thereof, one of the surfactants being intimately mixed as a particulate component with one of the partially or completely water-soluble builders. However, the washing or cleaning agents disclosed in this application still contain relatively large amounts of silicates, namely crystalline layered silicates. Now the omission of certain ingredients from washing or cleaning agents is not without problems, especially when it comes to structuring ingredients such as silicates and aluminosilicates. Without the structural support of silicates and aluminosilicates, the surfactants tend to oil out of the chemical matrix, which complicates the industrial handling and processing of washing or cleaning agents. The oiling of the surfactants also leads to unsightly stains on the packaging of the detergent or cleaning agent, which makes the product less attractive to the consumer. In addition, the particles of detergents or cleaning agents with oiling problems tend to clump, making their use more difficult and uncomfortable for the consumer. These problems are exacerbated both at elevated temperatures and air humidity, and with longer storage times. In addition, detergents or cleaning agents without silicates and aluminosilicates have poorer performance profiles because the particles can absorb less surfactant; Added to this are the harmful effects of water hardness on washing performance under typical washing conditions in the private sector.

All of this shows that when new builders or a new builder system is introduced, in which proven builder components have been dispensed with, the surfactants or the surfactant system normally have to be adapted to the new builder system. The requirements placed on a suitable surfactant or surfactant system in a modern washing or cleaning agent are just as varied as those placed on the builder or the builder system. In addition to a favorable price / performance ratio, complete and rapid biodegradability and favorable ecotoxicological properties, modern surfactants or surfactant systems are expected to have a high potential for synergy with surfactants and other ingredients, a high wetting effect, good solubility, favorable cold behavior, electrolyte compatibility, chemical stability and a suitable foaming behavior.

With regard to the foaming behavior, there are conflicting requirements for modern washing or cleaning agents. On the one hand, a certain foam development with high foaming notes when washing sensitive textiles is quite desirable, for example because the foam acts like an air cushion ("foam cushion") and thus, in particular, sensitive textiles during machine washing before mechanical damage. damage protects. However, the foam levels must not be too high during washing, as otherwise the primary washing performance will drop sharply with regard to certain soiling. On the other hand, the foam should also be easy to rinse out, with low foam notes when rinsing, since otherwise the user will find foam residues on the laundry after the rinsing process has ended when he opens his washing machine to hang the laundry up to dry or put it in a machine dryer. Often, the foam is not only perceived visually, but also haptically, because the laundry feels sticky and greasy. These foam residues are found in particularly disadvantageous cases after drying in the form of visible deposits on the laundry.

In order to solve this contradiction between relatively high foam notes during washing and low foam notes during rinsing, foam regulators are mostly used in the prior art. International application WO-A-98/27189, for example, describes a weakly acidic laundry detergent which ensures improved protection of fine textiles and the improved removal of foam which arises during the rinsing out of hand washing. In addition to other ingredients, the detergent contains at least one rinse-active, pH-sensitive foam regulator which comprises a fatty acid. This fatty acid is inactive with regard to the foam during washing under weakly acidic conditions (pH 5.5 to 6.9), so that there is an acceptable foaming behavior, but is rinsed out with tap water (pH 7.5 to 8, 5), with the pH increasing, at least partially converted to soap. This reacts with the hardness ions of the rinsing water to form insoluble lime or heavy metal soaps, which are known to suppress foam.

The object of the present invention was to provide a washing or cleaning agent which has improved foaming behavior. In particular, the agent should develop a sufficient, advantageous foam height during the washing process, but the foam should be easy to rinse out in the course of the rinsing process.

Surprisingly, it has now been found that detergents or cleaning agents which form little sediment when dispersed show the required foaming behavior. Against- The present invention is therefore a particulate, aluminosilicate, silicate and phosphate-free washing or cleaning agent whose aqueous dispersion has a pH in the range of 6 under the conditions 8 g / l, 20 ° C., 16 ° d. 5 to 9.5 and which, when dispersed in tap water under the conditions 8 g / l, 20 ° C., 16 ° d, 20 min stirring, sedimentation time 24 h, has a sedimentation volume of at most 0.5 ml.

The scientific connection between freedom from aluminosilicate and the required foaming behavior is currently not fully understood. Without wishing to commit to this, however, it is assumed that the zeolite particles have a foam-stabilizing effect and thus lead to foam which is difficult to rinse out. The scientific connection between freedom from silicate and the required foaming behavior is also currently being investigated. not fully understood. A possible explanation is that the initially dissolved silicates from washing or cleaning agents of the prior art at least partially hydrolyze to silica, thereby forming silica particles, thereby - like the aluminosilicate particles - have a foam-stabilizing effect and thus lead to foam which is difficult to rinse out.

The agent also has several advantages:

^■ No special, expensive surfactants are required, but a proven surfactant system can be used.

^■ No additional foam regulators are required; the advantageous foam behavior sets itself automatically under the conditions mentioned.

^■ improved deposit behavior

^■ improved washability

The behavior of the agent according to the invention is underpinned by the foam test, the sedimentation test and the “black fabric test”, with which the deposition behavior is determined.

The agent according to the invention dissolves in a sediment-free or at least almost sediment-free manner, has an advantageous foam development during the wash cycle and a foam that can be easily washed out during the dilution and rinse cycles, and also exhibits good deposition behavior. Another advantage of The washing or cleaning agent according to the invention consists in the significantly improved washability of the agent during machine washing or cleaning. An additional advantage of the agent according to the invention is the relatively low pH of the agents according to the invention, which is in the range from 7 to 9 and which is particularly advantageous for washing or cleaning sensitive textiles. The details of these advantageous properties of the agent according to the invention and the description of the above-mentioned tests are explained further below (in the example part).

The invention also relates to the use of the washing or cleaning agent according to the invention for washing or cleaning textiles, in particular for machine washing or cleaning textiles, especially sensitive textiles. In the context of the present invention, sensitive textiles are understood to mean, in particular, those made from wool, cotton, silk, linen, viscose and / or blended fabrics made from the materials mentioned above, the focus being on textiles made from wool. Generally speaking, these sensitive textiles are those whose quality is due to deposits, e.g. Comfort, graying and shrinkage suffer particularly.

One embodiment of the invention relates to the use of the washing or cleaning agent according to the invention for reducing deposits when washing or cleaning textiles, in particular when washing or cleaning sensitive textiles.

The agents according to the invention can be used both mechanically and manually. In a preferred embodiment of the invention, the detergents are used in a machine wash, the use being particularly preferred, in particular with regard to the preferred textiles, in delicate washing programs or full washing programs. The application preferably takes place at temperatures from approximately 20 ° C. to approximately 60 ° C. and in particular at temperatures from approximately 30 ° C. to approximately 40 ° C.

In a further preferred embodiment of the invention, the agents are used in manual washing, especially in the hand wash basin, and at temperatures from about 15 ° C. to about 40 ° C., preferably from 20 to 35 ° C. The invention also relates to a method for washing or cleaning textiles, in particular sensitive textiles, while at the same time reducing deposits. The method according to the invention includes the following steps:

(a) dissolving the washing or cleaning agent according to the invention in water,

(b) contacting the textile or the textiles with the aqueous solution of the agent according to the invention,

(c) guiding the aqueous solution of the agent according to the invention past the textile or the textiles or vice versa, either manually (as in the case of a hand wash) or by machine,

(d) removing the aqueous solution of the agent according to the invention from the textile or the textiles, rinsing several times with fresh tap water, i.e. is rinsed out

(e) drying the textile or textiles.

In the context of the present inventions, “deposits” are understood to mean all substances which remain on the dry laundry after washing, their retention on the laundry being undesirable and contributing to a deterioration in the quality of the laundry. This also includes “residues”. These are residues of undissolved detergent or cleaning agent that can be found on the dry laundry in the form of white dots or stains after washing.The cause of residues is a poor, in the sense of too slow, solution kinetics of the detergent or cleaning agent used The problem of residues is exacerbated, especially in the case of machine washing, by the current trend towards ever smaller amounts of water and ever larger wash loads per wash cycle.

"Deposits" also include "incrustations". These are poorly soluble deposits on textile surfaces and / or surfaces of the machines (especially heating elements), which arise in particular when washing textiles under high temperatures and alkaline conditions and lead to hardening and graying of the fabric ,

In the following, "sediments" are understood to mean deposits which are influenced by "sedimentation", ie the movement of disperse particles in water gravity due to its higher density. Another name for sediments is "settable substances". This is the collective name for suspended solids that settle on the bottom of the measuring container in a certain time in a water sample and that are usually given as the sedimentation volume per liter of water sample. The term sediments therefore does not include the usual and unavoidable cloudiness of aqueous detergent or cleaning agent solutions resulting from the surfactants, which do not sediment, ie settle.

In the following, “essentially dispersible without sediment” is understood to mean that 8 g of the agent, when dissolved or dispersed in tap water (1 l, 20 ° C., 16 ° d, 20 min stirring, sedimentation time 24 h), has a sedimentation volume per liter of at most Result in 2 ml / l. The procedure for determining the sedimentation volume is described in more detail in the example on page 32.

In a preferred embodiment of the invention, when dissolving or dispersing 8 g of the washing or cleaning agent according to the invention in tap water (1 l, 20 ° C., 16 ° d, 20 min stirring, sedimentation time 24 h), a sedimentation volume per liter of at most 0.5 ml / l, in particular of at most 0.2 ml / l and very particularly preferably of 0 ml / l.

The determination of the "foam notes" is described in more detail in the example on page 33. Although the characterization of the foam behavior by specifying foam heights in length dimensions such as cm is widespread in the prior art, the use of foam notes advantageously leads to data which are easier to compare, especially in series tests, but both dimensions are equivalent, since foam note and foam heights can be converted into one another if the washing machine dimensions, in particular the porthole dimensions, are known.

The washing or cleaning agent according to the invention contains a builder system as an essential component. In a preferred embodiment, this builder system contains

(a) one or more sources of alkalinity,

(b) one or more pH control agents, (c) one or more cobuilders and

(d) optionally one or more calcium carbonate scale inhibitors.

The builder system preferably makes up 15 to 35% by weight, particularly preferably 20 to 30% by weight, of the total composition.

Suitable sources of alkalinity are e.g. Alkali metal carbonate, alkali metal bicarbonate, alkali metal sesquicarbonate and / or mixtures thereof. However, sodium carbonate, sodium hydrogen carbonate and / or sodium sesquicarbonate are preferred, sodium carbonate, if appropriate also in combination with hydrogen carbonate, being particularly preferred. The source or sources of alkalinity make up about 10 to 30% by weight, preferably 15 to 25% by weight of the total composition according to the invention and about 35 to 75% by weight, preferably 50 to 60% by weight, of the builder system.

The pH control agents perform an important function as organic builders and for setting a pH value suitable for the invention. Suitable pH control agents are, above all, monomeric organic polycarboxylic acids, polycarbonic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as their use is not objectionable for ecological reasons, and mixtures of these. In this context, preference is given to citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these. Citric acid is particularly preferred. The polycarboxylic acids mentioned can also be used in the form of their sodium salts. Preferred salts are the salts of the polycarboxylic acids citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. The agents according to the invention advantageously contain these pH control agents in amounts of about 0.5 to about 25% by weight, preferably in amounts of about 5 to about 20% by weight, particularly preferably in amounts of about 7.5 to about 15 % By weight based on the total average. The pH control agents thus make up about 25 to about 65% by weight, preferably 35 to 45% by weight, of the preferred builder system. In a preferred embodiment of the invention, aqueous dispersions of 8 g of the compositions according to the invention in one liter of water at 20 ° C. and 16 ° d have a pH of 7.0 to 9.0, in particular 7.5 to 8.5.

Also suitable as builders are polymeric polycarboxylic acids and / or their partially or fully neutralized metal and / or ammonium salts; these are, for example, the alkali metal salts of (homopolymeric) polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1200 to 8000 g / mol, for example 4500 or 8000, can in turn be preferred from this group.

Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention. The copolymers containing sulfonic acid groups are described in detail below.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with malic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 2,000 to 100,000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 30,000 to 80,000 g / mol.

To improve water solubility, the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.

Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,

Further preferred copolymers preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred.

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

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. It is preferably Hydrolysis products with average molecular weights in the range of 400 to 500000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders. In this case, ethylenediamine-N, ^{N'-disuccinate} (EDDS) is preferably in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context.

Iminodisuccinates (IDS) and their derivatives, for example hydroxyiminodisuccinates (HDIS), are suitable as further cobuilders, which can be present in liquid and particulate compositions or moldings together with phosphonates, but also as a partial to complete replacement for phosphonates. It has been known for some years that these raw materials can be used as cobuilders in washing or cleaning agents. The use of HIDS in detergents or cleaning agents has already been described in patent applications WO 92/02489 and DE 43 11 440. European patent application EP 0757094 discloses the advantageous use of iminodisucinates in combination with polymers which have recurring succinyl units. It has recently been discovered that agents containing IDS or HIDS can contribute positively to the color retention of textiles. For example, reference is made here to international patent applications WO 01/94514, WO 01/92449, WO 01/88077, WO 01/46371 and WO 01/44423. Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

In addition, all compounds which are able to form complexes with alkaline earth metal ions can be present as cobuilders in the particulate agents.

The cobuilders are preferably present in the agent according to the invention in amounts such that they contain up to 5% by weight, preferably 1 to 2% by weight of the total agent or 0.5 to 12% by weight, preferably 3 to 7.5 Make up% by weight of the builder system.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned. However, the phosphonates in the agents according to the invention are, if at all, only in small amounts, between about 0.1 to 2% by weight, based on the total agent, or in amounts of 0 to about 3% by weight, preferably of 0 up to about 2% by weight, based on the builder system.

Another important component of the washing or cleaning agents according to the invention is the surfactant system. In a preferred embodiment, it contains one or more anionic surfactants and one or more nonionic surfactants. The surfactant system preferably makes up 5 to 25% by weight, in particular 10 to 20% by weight, of the total composition.

Suitable anionic surfactants are, for example, surfactants of the sulfonate type. Cumene sulfonate, C ₁₀ -ι ₃ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as are obtained, for example, from C ₁₂ .i8 monoolefins having an end or internal double bond by sulfonating with gaseous are suitable Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which are obtained from C ₁ -C ₈ -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of 2-sulfofatty acids (ester sulfonates), for example the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerin esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

The alkali and, in particular, the sodium salts of the sulfuric acid semiesters of C ₁₂ are used as alk (en) yl sulfates. ₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₁₀ . ₂ o-oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₂ -C ₁₆ alkyl sulfates and C ₁₂ - ₁₅ alkyl sulfates and C ₁ are of technical washing interest. ₁₅ alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^® are suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C ethoxylated with 1 to 6 mol of ethylene oxide. ₂ rAlkohole such as 2-methyl-branched C ₉ .n alcohols containing on average 3.5 mol ethylene oxide (EO) or C ₁₂ _ ₁₈ fatty alcohols with 1 to 4 EO, are also suitable.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ -ι ₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.

The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts. In a further embodiment of the invention, surfactants are used in the form of their magnesium salts. However, particularly preferred according to the invention are linear alkylbenzenesulfonates such as, for example, the linear C ₁₀ -ι ₃ -alkylbenzenesulfonates. The anionic surfactant content of the agents according to the invention is advantageously 5 to 30% by weight, preferably 7.5 to 25% by weight, particularly preferably 10 to 20% by weight, based on the total agent. The surfactant system thus preferably consists of 60 to 95% by weight, particularly preferably 70 to 90% by weight, of anionic surfactant.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated or propoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 80, preferably 3 to 12, moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or can preferably be methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. Examples of the fatty alcohols are, from the point of view of the availability of the compounds, lauryl alcohol (C ₁₂ ), myristyl alcohol (C ₁ ), cetyl alcohol (C ₁₆ ) etc. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 C atoms are used for Example from coconut, palm, tallow or oleyl alcohol, and an average of 1 to 80, preferably 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols, for example, Cι_ _M4 alcohols with 3 EO or 4 EO, C ₉ .n include alcohol containing 7 EO, C ₁₃ -ι ₅ alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ _ ₁₈ alcohols with 3 EO, 5 EO or 7 EO, Cι ₆ -i ₈ alcohols with 5 EO and mixtures of these, and mixtures of C ₁₂ -ι ₄ alcohol with 3 EO and C ₁₂ . ₁₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO, 40 EO or up to 80 EO.

However, C ₁₂ have been particularly suitable as nonionic surfactants for the present invention. ₁₈ alcohols with 7 EO and C ₁₆ -ι ₈ alcohols with 5 EO, and mixtures of these have been proven. Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 8 carbon atoms in the alkyl chain and 3 to 80, preferred up to 20 alkoxy groups, preferably ethoxy groups in the molecule, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process disclosed in international patent application WO-A-90/13533.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkyl polyglycosides which can be used satisfy the general formula RO (G) _z , in which R represents a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G is Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4. Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

R ¹

R-CO-N-.Z] (I) in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

R ¹ -OR ²

I

R-CO-N- [Z] (II) in the R for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ¹ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1 -C 6 -alkyl or phenyl radicals being preferred and [Z] standing for a linear polyhydroxyalkyl radical, the alkyl chain of which has at least two Hydroxyl groups is substituted, or alkoxylated, preferably ethoxylated or propylated derivatives of this radical.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

From a practical point of view, it will be advantageous to take into account the fact that those compounds from the above-mentioned groups are used which are still liquid to pasty even with longer chain lengths at the application temperatures. In the present invention, the nonionic surfactants are used alone or in a mixture, advantageously in such a way that the total nonionic surfactant content of the washing or cleaning agents according to the invention is advantageously 1 to 10% by weight, preferably 2 to 5% by weight, or the surfactant system 5 contains up to 25% by weight, preferably 10 to 20% by weight, of at least one nonionic surfactant.

It may furthermore be preferred to use cationic surfactants in addition to anionic and nonionic surfactants. They are preferably used as washing performance boosters, whereby only small amounts of cationic surfactants are required.

The washing or cleaning agents according to the invention preferably contain at least one foam regulator. These are preferably fatty acids or fatty acid soaps. The foam regulators are contained in amounts of 0.5 to 8% by weight, preferably 1 to 5% by weight, based on the total composition.

A certain foaming behavior of the washing or cleaning agents according to the invention is essential for the present invention. It has proven to be advantageous, for example, if the detergent has a foam grade of at least 5 in the wash cycle, and then, after a single dilution and three further rinse cycles, a foam grade of at most 1.

In a particular embodiment, the washing or cleaning agent according to the invention is present in particulate form, in particular in the form of powders, extrudates, granules and / or mixtures thereof.

The detergents or cleaning agents according to the invention can, in addition to the ingredients mentioned above, all known and customary ingredients in detergents and cleaning agents, such as, for example, enzymes, dyes, optical brighteners, UV protective substances, fragrances and perfumes, perfume carriers, anti-redeposition agents, graying inhibitors, color transfer inhibitors, Contain corrosion inhibitors, bleach, bleach activators, softeners and fabric softeners. However, the agents preferably contain no bleaching agents and bleach activators with regard to protecting delicate textiles. The other ingredients mentioned are preferably in amounts of 2 to 40% by weight, in particular in amounts of 10 to 30% by weight, based on the total weight of the agent according to the invention.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate; (b) the aliphatic or substituted aliphatic peroxyacids such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamido operadipic acid and N-nonenylamide; and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyl-diperoxybutane-1, 4-diacid, N, N-di-terephthaloyl -aminopercaproic acid) can be used.

In principle, chlorine or bromine-releasing substances can also be used as bleaching agents. However, these are of little importance for use in detergents. Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, such as trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

In addition, bleach activators can be incorporated into the agents according to the invention. Bleach activators which can be used are compounds which, under perhydrolysis conditions, aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 up to 4 carbon atoms and / or optionally substituted perbenzoic acid can be used. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy and 2,5-acetiacetyl, 2,5-ethylene glycol , 5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the high-sodium particles. These substances are bleach-enhancing transition metal salts or transition metal complexes, for example Mn, Fe, Co, Ru or Mo salt complexes or -Carbonylkomp.exe. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

With regard to the use of the washing or cleaning agents according to the invention in the washing or cleaning of sensitive textiles, however, it may be preferred that the agents contain none of the above-mentioned bleaching agents and none of the above-mentioned bleach activators.

Agents according to the invention can contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all the enzymes established in the prior art for these purposes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents, which are accordingly preferred. Agents according to the invention preferably contain enzymes in total amounts of 1 × 10 ⁶ to 5 percent by weight based on active protein Protein concentration can be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-bichinolyl-4,4'-dicarboxylic acid) or the biuret method (AG Gornall, CS Bardawill and MM David, J. Biol. Chem 177 (1948), pp. 751-766).

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and that which can no longer be assigned to the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. The protease from Bacillus lentus DSM 5483 (WO 91/02792) is derived from the variants known under the name BLAP ^® , which are described in particular in WO 92/21760, WO 95/23221 and in applications DE 10121463 and DE 10153792. Other usable proteases from various Bacillus sp. and B. gibsonii emerge from the patent applications DE 10162727, DE 10163883, DE 10163884 and DE 10162728.

Further usable proteases are, for example, those under the trade names Durazym ^® , Relase ^® , Everlase ^® , Nafizym, Natalase ^® , Kannase ^® and Ovozymes ^® from Novozymes, those under the trade names Purafect ^® , Purafect ^® OxP and Properase ^® from the company Genencor, which is sold under the trade name Protosol ^® by Advanced Biochemicals Ltd., Thane, India, which is sold under the trade name Wuxi ^® by Wuxi Snyder Bioproducts Ltd., China, and in the trade name Proleather ^® and Protease P ^® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from β. amyloliquefaciens or from B. stearothermophilus as well as their further developments for use in detergents and cleaning agents. The enzyme from B. licheniformis is from Novozymes under the name Termamyl ^® and available from Genencor under the name Purastar ^® ST. Development products of this α-amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase from ß. Amyloliquefaciens is sold by Novozymes under the name BAN ^® , and derived variants of the α-amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^® , also from Novozymes.

Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) described in the application PCT / EP01 / 13278; furthermore those which belong to the sequence space of α-amylases, which is defined in the application DE 10131441. Fusion products of the molecules mentioned can also be used, for example those from the application DE 10138753.

In addition, the further developments of the α-amylase from Aspergillus niger and A. oryzae available under the trade names Fungamyl ^® from Novozymes are suitable. Another commercial product is the Amylase-LT ^® .

Agents according to the invention can contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or developed further, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ^® , Lipolase ^® Ultra, LipoPrime ^® , Lipozyme ^® and Lipex ^® . Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. Lipase ^® , Lipase AP ^® , Lipase M-AP ^® and Lipase AML ^® available. From Genencor, for example, the lipases or cutinases, their starting enzymes, can be used originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products, the preparations originally sold by Gist-Brocades M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention, also the product Lumafast ^® from Genencor.

Agents according to the invention, especially if they are intended for the treatment of textiles, can contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement one another with regard to their various performance aspects. These performance aspects include, in particular, contributions to the primary washing performance, to the secondary washing performance of the agent (anti-deposition effect or graying inhibition) and finish (tissue effect), through to the exertion of a “stone washed” effect.

A useful fungal, endoglucanase (EG) -rich cellulase preparation or its further developments are offered by the Novozymes company under the trade name Celluzyme ^® . The products Endolase ^® and Carezyme ^{®, which} are also available from Novozymes, are based on the 50 kD-EG and the 43 kD-EG from H. insolens DSM 1800. Other possible commercial products from this company are Cellusoft ^® and Renozyme ^® . The cellulases disclosed in application WO 97/14804 can also be used; For example, it revealed 20 kD EG Melanocarpus, available from AB Enzymes, Finland, under the trade names Ecostone® ^® and Biotouch ^®. Other commercial products from AB Enzymes are Econase ^® and Ecopulp ^® . Other suitable cellulases from Bacillus sp. CBS 670.93 and CBS 669.93 are disclosed in WO 96/34092, the ones from Bacillus sp. CBS is available from Genencor under the trade name Puradax® ^® 670.93. Other commercial products from Genencor are "Genencor detergent cellulase L" and IndiAge ^® Neutra.

Agents according to the invention can contain further enzymes, which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, Xyloglucanases (= xylanases), pullulanases and ß-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and PektinexAR ^® from Novozymes, under the name Rohapec ^® B1 from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, United States. A suitable β-glucanase from a B. alcalophilus can be found, for example, in application WO 99/06573. The .beta.-glucanase obtained from B. subtilis is available under the name Cereflo ^® from Novozymes.

To increase the bleaching effect, washing and cleaning agents according to the invention can use oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) contain. Suitable commercial products are Denilite ^® 1 and 2 from Novozymes. Advantageously, organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of very different redox potentials between the oxidizing enzymes and the soiling.

The enzymes used in the agents according to the invention either originate from microorganisms, for example the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological processes known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi.

The enzymes in question are advantageously purified by methods which are in themselves established, for example by means of precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.

Agents according to the invention can be added to the enzymes in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel form agents, solutions of the enzymes, advantageously concentrated, low in water and / or mixed with stabilizers.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural, polymer or in the form of capsules, for example those in which the enzymes are enclosed in a solidified gel are or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in layers. Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.

It is also possible to assemble two or more enzymes together, so that a single granulate has several enzyme activities.

A protein and / or enzyme contained in an agent according to the invention can be protected, particularly during storage, against damage such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage. When the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Agents according to the invention can contain stabilizers for this purpose; the provision of such agents is a preferred embodiment of the present invention.

A group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used, including above all derivatives with aromatic groups, for example ortho-substituted according to WO 95/12655, meta-substituted according to WO 92/19707 and para-substituted according to US 5972873 substituted phenylboronic acids, or their salts or Ester. For the same purpose, applications WO 98/13460 and EP 583534 disclose peptide aldehydes, ie oligopeptides with a reduced C-terminus. Ovomucoid O ^ O 93/00418) and leupeptin are to be mentioned as peptide protease inhibitors; an additional option is the formation of fusion proteins from proteases and peptide inhibitors.

Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and - propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , as is known, for example, from applications EP 378261 and WO 97/05227, such as succinic acid, other dicarboxylic acids or salts of mentioned acids. The application DE 19650537 discloses end group-capped fatty acid amide alkoxylates for this purpose. Certain organic acids used as builders, as disclosed in WO 97/18287, can additionally stabilize an enzyme contained.

Lower aliphatic alcohols, but above all polyols, such as, for example, glycerol, ethylene glycol, propylene glycol or sorbitol are further frequently used enzyme stabilizers. According to the application EP 965268, di-glycerol phosphate also protects against denaturation by physical influences. Calcium salts are also used, such as calcium acetate or the calcium formate disclosed for this purpose in patent EP 028865, and magnesium salts, for example according to European application EP 378262.

Polyamide oligomers (WO 99/43780) or polymeric compounds such as lignin (WO 97/00932), water-soluble vinyl copolymers (EP 828762) or, as disclosed in EP 702712, cellulose ethers, acrylic polymers and / or polyamides stabilize the Enzyme preparation, among other things against physical influences or pH fluctuations. Polymers containing polyamine N-oxide (EP 587550 and EP 581751) act simultaneously as enzyme stabilizers and as color transfer inhibitors. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes disclosed in WO 97/05227 in addition to other constituents. According to the applications WO 97/43377 and WO 98/45396, alkyl polyglycosides can stabilize the enzymatic components of the agent according to the invention and even increase their performance. networked N-containing compounds, as disclosed in WO 98/17764, fulfill a double function as soil release agents and as enzyme stabilizers.

Reducing agents and antioxidants, as disclosed inter alia in EP 780466, increase the stability of the enzymes against oxidative decomposition. Sulfur-containing reducing agents are known, for example, from the patents EP 080748 and EP 080223. Other examples are sodium sulfite (EP 533239) and reducing sugars (EP 656058).

Combinations of stabilizers are preferably used, for example made of polyols, boric acid and / or borax according to application WO 96/31589, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids according to application EP 126505 or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts, as disclosed in the application EP 080223. The effect of peptide-aldehyde stabilizers is increased according to WO 98/13462 by the combination with boric acid and / or boric acid derivatives and polyols and according to WO 98/13459 by the additional use of divalent cations, such as calcium ions.

Further additives conceivable in the washing or cleaning agent according to the invention are foam inhibitors such as, for example, foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane, the use of foam inhibitors as already explained above not being absolutely necessary, but can be carried out if desired. Mixtures of these active ingredients are also possible. At room temperature and solid additives, particularly in the above-mentioned foam-inhibiting agents, paraffin waxes, silicas, which may have been rendered hydrophobic in a known manner, and of C ₂ _ ₇ -diamines and C ^. ^ - carboxylic acid bisamides derived.

Foam-inhibiting paraffin oils which can be used in the washing or cleaning agents according to the invention and which can be present in a mixture with paraffin waxes are generally complex mixtures of substances without a sharp melting point. The melting range is usually determined for characterization Differential thermal analysis (DTA) as described in "The Analyst" 87 (1962), 420, and / or the freezing point. This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling. Paraffins with less than 17 carbon atoms cannot be used according to the invention, their proportion in the paraffin oil mixture should therefore be as low as possible and is preferably below the limit which is significantly measurable with customary analytical methods, for example gas chromatography. Paraffins which solidify in the range from 20 ° C. to 70 ° C. are preferably used. It should be noted that even paraffin wax mixtures that appear solid at room temperature can contain different proportions of liquid paraffin oils. In the paraffin waxes which can be used according to the invention, the liquid fraction is as high as possible at 40 ° C. without already being 100% at this temperature. Preferred paraffin wax mixtures have a liquid content of at least 50% by weight, in particular from 55% by weight to 80% by weight, at 40 ° C and a liquid content of at least 90% by weight at 60 ° C. The consequence of this is that the paraffins are flowable and pumpable at temperatures down to at least 70 ° C., preferably down to at least 60 ° C. It is also important to ensure that the paraffins do not contain any volatile components. Preferred paraffin waxes contain less than 1% by weight, in particular less than 0.5% by weight, of parts which can be evaporated at 110 ° C. and normal pressure. Paraffins which can be used according to the invention can be obtained, for example, under the trade names Lunaflex® from Füller and Deawax® from DEA Mineralöl AG.

The paraffin oils can contain bisamides which are solid at room temperature and which are derived from saturated fatty acids having 12 to 22, preferably 14 to 18 C atoms and also alkylenediamines having 2 to 7 C atoms. Suitable fatty acids are lauric acid, myristic acid, stearic acid, arachic acid and behenic acid and mixtures thereof, as can be obtained from natural fats or hydrogenated oils, such as tallow or hydrogenated palm oil. Suitable diamines are, for example, ethylenediamine 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine. Preferred diamines are ethylenediamine and hexamethylenediamine. Particularly preferred bisamides are bis-myristoyl-ethylenediamine, bis-palmitoyl-ethylenediamine, bis-stearoyl-ethylenediamine and mixtures thereof, and the corresponding derivatives of hexamethylenediamine. Dyes, in particular water-soluble or water-dispersible dyes, can also be incorporated. Dyes are preferred here, as are usually used to improve the visual appearance of products in detergents and cleaning agents. The choice of such dyes does not pose any difficulties for the person skilled in the art, in particular since such customary dyes have a high storage stability and insensitivity to the other ingredients of the detergent formulations and to light and have no pronounced substantivity towards textile fibers in order not to dye them.

Examples of optical brighteners are derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar compounds which, instead of the morpholino group, contain a diethanolamino Group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenyl styrene type may also be present in the washing or cleaning agents according to the invention, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl , Mixtures of the aforementioned brighteners can also be used.

Another group of additives preferred according to the invention are UV protective substances. These are substances which are released in the washing liquor during the washing process or during the subsequent fabric softening process and which accumulate on the fiber in order to then achieve a UV protection effect. Products from Ciba Specialty Chemicals that are commercially available under the name Tinosorb are suitable.

Another class of common detergent or cleaning agent ingredients that can be added according to the invention are polymers. Among these polymers are, on the one hand, polymers which show cobuilder properties during washing or cleaning or rinsing. These have already been described in detail above. Another group of polymers are graying inhibitors. These have the task of keeping the dirt detached from the hard surface and in particular of the textile fibers suspended in the fleet and thus to support the co-builder. For this purpose, water-soluble colloids of mostly organic nature are suitable, for example glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Starch products other than those mentioned above can also be used, for example aldehyde starches. Cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the total agent, are preferred used.

As further additives according to the invention, the washing or cleaning agents can also contain anti-deposition agents, so-called soil repellents. These are polymers that attach to fibers or hard surfaces and counteract re-soiling there. This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, in each case based on the nonionic Cellulose ethers, as well as the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

Other polymers that can be used in the detergents or cleaning agents according to the invention are color transfer inhibitors. These include in particular polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole. In addition, the washing or cleaning agents according to the invention can also contain fragrances and fragrance preparations (perfumes). Individual fragrance compounds can be used as perfume oils or fragrances, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, pt-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbynyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexylpropyl pentyl pentyl pentate, stally. The ethers include, for example, benzyl ethyl ether. The aldehydes include, for example, linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lileal and bourgeonal.

The ketones include the ionones, α-isomethyl ionone and methyl cedryl ketone. Alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons mainly include terpenes such as limonene and pinene. Mixtures of different fragrances are preferably used which are coordinated with one another in such a way that they together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures as are obtainable from plant sources. Examples are pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are nutmeg oil, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olivan oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

It may be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and provide a long-lasting fragrance for the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven themselves as such carrier materials. The cyclodextrin-perfume complexes can also be coated with other auxiliaries.

The detergents or cleaning agents according to the invention can contain corrosion inhibitors to protect the items to be washed or washed or the machine, silver protection agents being particularly useful in the area of automatic dishwashing Have meaning. In general, silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface. Chlorine-free cleaners contain especially oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, for example hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

Other ingredients that are possible in the washing or cleaning agents according to the invention can be softening agents and / or fabric softening agents. Suitable examples are quaternary ammonium compounds of the formulas (I) and (II),

where in (I) R and R ^{1 are} each an acyclic alkyl radical having 12 to 24 carbon atoms, R ^{2 is} a saturated CC alkyl or hydroxyalkyl radical, R ^{3 is} either R, R ¹ or R ² or is an aromatic radical , X ^" stands for either a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof. Examples of cationic compounds of the formula (I) are didecyldimethylammonium chloride, ditallow dimethylammonium chloride or

Dihexadecylammonium. Compounds of formula (II) are so-called ester quats. Esterquats are characterized by excellent biodegradability. Here R ^{4 represents} an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds; R ⁵ stands for H, OH or O (CO) R ⁷ , R ⁶ independently of R ^{5 stands} for H, OH or O (CO) R ⁸ , where R ⁷ and R ⁸ each independently represent an aliphatic alkyl radical with 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds, m, n and p can each independently have the value 1, 2 or 3. X ^~ can be either a halide, methosulfate, methophosphate or phosphate ion, as well as mixtures of these. Compounds are preferred which contain the group O (CO) R ⁷ for R ⁵ and alkyl radicals having 16 to 18 carbon atoms for R ⁴ and R ⁷ . Compounds in which R ^{6 is} also OH are particularly preferred. Examples of compounds of the formula (II) are methyl N- (2-hydroxyethyl) -N, N-di (tallow acyl oxyethyl) ammonium methosulfate, bis (palmitoyl) ethyl hydroxyethyl methyl ammonium methosulfate or methyl -N, N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate. If quaternized compounds of the formula (II) are used which have unsaturated alkyl chains, preference is given to the acyl groups whose corresponding fatty acids have an iodine number between 5 and 80, preferably between 10 and 60 and in particular between 15 and 45 and which have a cis / trans isomer ratio (in% by weight) of greater than 30:70, preferably greater than 50:50 and in particular greater than 70:30. Commercial examples are the methylhydroxyalkyldialkoyloxyalkylammonium methosulfates sold by Stepan under the trademark Stepantex ^® or the products from Cognis known under Dehyquart ^® or the products from Goldschmidt-Witco known under Rewoquat ^® . Further preferred compounds are the diesterquats of the formula (III), which are available under the name Rewoquat® W 222 LM or CR 3099 and, in addition to the softness, also ensure stability and color protection.

R ²¹ and R ²² each independently represent an aliphatic radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. In addition to the quaternary compounds described above, other known compounds can also be used, such as quaternary compounds

Imidazolinium compounds of the formula (IV),

where R ^{9 is} H or a saturated alkyl radical with 1 to 4 carbon atoms, R ¹⁰ and R ¹¹ independently of one another each represent an aliphatic, saturated or unsaturated alkyl radical with 12 to 18 carbon atoms, R ¹⁰ alternatively also for O (CO) R ²⁰ , where R ^{20 is} an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, and Z is an NH _^ group or oxygen and X ^"is an anion. q can have integer values between 1 and 4.

Further suitable quaternary compounds are described by formula (V)

X ^" (V);

where R ¹² , R ¹³ and R ¹⁴ independently represent a Ct ^ alkyl, alkenyl or hydroxyalkyl group, R ¹⁵ and R ¹⁶ each independently represent a Cs_ ₂₈ alkyl group and r is a number between 0 and 5 ,

In addition to the compounds of the formulas (I) and (II), it is also possible to use short-chain, water-soluble, quaternary ammonium compounds, such as trihydroxyethylmethylammonium methosulfate or the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, for example cetyltrimethylammonium chloride Stearyltrimethylammonium chloride, distearyldimethylammonium chloride,

Lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and

Tricetylmethylammonium chloride.

Protonated alkylamine compounds which have a softening effect and the non-quaternized, protonated precursors of the cationic emulsifiers are also suitable.

The quaternized protein hydrolyzates are further cationic compounds which can be used according to the invention.

Suitable cationic polymers include the polyquaternium polymers as described in the CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997), in particular the polyquaternium-6, polyquaternium-7, also known as merquats. Polyquaternium 10 polymers (Ucare Polymer IR 400; Amerchol), polyquaternium 4 copolymers, such as graft copolymers with a cellulose skeleton and quaternary ammonium groups which are bonded via allyldimethylammonium chloride, cationic cellulose derivatives, such as cationic guar, such as guar hydroxypropyltriammonium Similar quaternized guar derivatives (eg Cosmedia Guar, manufacturer: Cognis GmbH), cationic quaternary sugar derivatives (cationic alkyl polyglucosides), eg the commercial product Glucquat ^® 100, according to CTFA nomenclature a "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride", copolymers from PVP and dimethylaminomethacrylate, copolymers of vinylimidazole and vinylpyrrolidone, aminosilicone polymers and copo mers.

Also employable are polyquatemierte polymers (for example Luviquat Care from BASF) and also cationic biopolymers based on chitin and derivatives thereof, for example, under the trade designation chitosan ^® (manufacturer: Cognis) polymer obtainable.

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM -2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) Abil ^® -Quat 3270 and 3272 (Manufacturer: Goldschmidt-Rewo; diquartary polydimethylsiloxanes, Quaternium-80), and Siliconquat Rewoquat ^® SQ 1 (Tegopren ^® 6922, manufacturer: Goldschmidt-Rewo).

Compounds of the formula (VI) which can also be used are

the alkylamidoamines can be in their non-quaternized or, as shown, their quaternized form. R ¹⁷ can be an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds, s can assume values between 0 and 5. R ¹⁸ and R ¹⁹ each independently represent H, C 1-4 alkyl or hydroxyalkyl. Preferred compounds are fatty acid amidoamines such as the stearylamidopropyldimethylamine available under the name Tego Amid ^® S 18 or the 3-tallowamidopropyl trimethylammonium methosulfate available under the name Stepantex ^® X 9124, which not only have a good conditioning effect but also their color transfer-inhibiting action and special are characterized by their good biodegradability. Of this class of compounds, the non-quaternized alkylamidoamines are preferred. These include, for example, fatty acid amidoamines such as Talgamid B from Cognis GmbH.

Examples

Agents with compositions according to Table 1 were produced. E is an agent according to the invention, V is a comparative agent.

Table 1: Composition of the agents produced.

FA: fatty alcohol EO: mole of attached ethylene oxide silicate: amorphous sodium silicate with Na ₂ O: SiO ₂ = 3.35 Polycarboxylate: acrylic acid / maleic acid copolymer (Sokalan CP5, BASF)

The two agents were examined with regard to their sedimentation behavior, their deposition behavior, their foam behavior and their flushability. The measurements carried out are described in more detail below.

1. Sedimentation behavior

8 g of agent E or V were dissolved or dispersed at 20 ° C. in 1 liter of tap water with a hardness of 16 ° d with stirring (20 minutes). The resulting solutions or dispersions were filled into funnel-shaped glass vessels which had a calibrated scale accurate to 0.01 ml. The solutions or dispersions were then left to stand for sedimentation. After 24 h, the sedimentation volume was read using the calibrated ml scale.

Agent E according to the invention gave a sediment volume per liter of 0.15 ml, that of comparative agent V a sediment volume per liter of 2.50 ml.

2. Deposition behavior

To determine the deposit behavior in the "Black Fabric Test", 8 g of the agent E or V at 20 ° C. in 1 liter of tap water with a hardness of 16 ° dH were stirred (1.5 minutes, 800 rpm using a laboratory stirrer / propeller stirrer head 1 , 5 cm from the bottom of the vessel) dissolved or dispersed The resulting solutions or dispersions were filtered through black tissue by clamping the tissue between a frit bottom and a vertically attached glass tube with a diameter of 5 cm so that a filter surface with a diameter of 5 cm. The filtration was carried out solely under the influence of gravity. The fabric was a 100% cotton ribbed knit with the edge dimensions

16 cm - 16 cm and a weight of 8.5 g. The filter residues were left on the fabric, dried and visually examined by 3 different people according to Table 2 and graded accordingly. The criterion for the rating was the degree of coverage of the filter surface with filter residue. The grades of the 3 different people were added and divided by 3. Table 2: Grading of the filter residue by visual inspection.

optical impression note

No backlog 0

Little residue 1

clearly visible residue 2

Clearly visible residue that covers more than 3 half of the filter surface

Almost complete coverage with 4

Residue

Complete, closed covering 5 with residue

Very heavy coverage with residue 6

The filter residue of the agent E according to the invention was assessed on average with a grade of 1, that of the comparative agent V with a grade of 6.

3. Foam behavior

The foam behavior was determined with a washing machine from Miele (type W 918, without fuzzy logic). For this purpose, 100 g of agent E or V were dosed and 22 l of water with a hardness of 16 ° dH were used. The washing machine was operated with 2.0 kg of clean, standardized laundry in the easy-care / fine program. The foam was assessed with grades according to the table below. Table 3: Rating of the foam after visual inspection.

The foam height was assessed with a foam note when the washing machine was at a standstill, namely during the wash cycle, when diluting (after the water supply), during the 1st, 2nd and 3rd rinsing (each after the water supply).

Table 4: Assessment of foam behavior in the form of foam notes.

It can be seen that the agent E according to the invention had, as desired, a high foaming note during washing, thereby protecting the laundry, and a low foaming note after the last rinsing, which is equivalent to good rinsability. The comparative agent V, on the other hand, also had a favorable high foam note when washing, but it was still unacceptably high after the last rinse, which is equivalent to poor rinsability.

In summary, it can be stated that the agent according to the invention had a lower sediment volume than the comparative agent, ie it contained fewer poorly soluble components. Both the deposition behavior and the foaming behavior, especially when rinsing, were rated better with the inventive agent than with the comparative agent. So during the actual washing process sufficient foam is available to ensure gentle cleaning of even delicate textiles, the foam note after the rinse cycle is very low, so the foam can be easily rinsed out; at the same time, undesirable deposits are formed on the laundry only to a much lesser extent than in the comparative agent. The use of the builder system according to the invention consequently has a positive influence on both the foam and the deposition behavior.

Claims

claims

1. Particulate, builder-containing, but aluminosilicate, silicate and phosphate-free detergent or cleaning agent, the aqueous dispersion under the conditions 8 g / l, 20 ° C, 16 ° d a pH in the range of 6, 5 to 9.5, characterized in that it has a sedimentation volume of at most 0.5 ml when dispersed in tap water under the conditions 8 g / l, 20 ° C., 16 ° d, 20 min stirring, sedimentation time 24 h.

2. Detergent or cleaning agent according to claim 1, characterized in that when dispersed in tap water (8 g / l, 20 ° C, 16 ° d, 20 min stirring, sedimentation time 24 h) a sedimentation volume of at most 0.2 ml and preferably has 0 ml.

3. Detergent or cleaning agent according to claim 1 or 2, characterized in that its aqueous dispersion (8 g / l, 20 ° C, 16 ° d) has a pH in the range from 7.0 to 9.0, preferably from 7.5 to 8.5.

4. washing or cleaning agent according to one of claims 1 to 3, characterized in that it

(a) 15 to 35% by weight, preferably 20 to 30% by weight, of a builder system and

(b) contains 5 to 25% by weight, preferably 10 to 20% by weight, of a surfactant system.

5. washing or cleaning agent according to claim 4, characterized in that the builder system

(a) 35 to 75% by weight, preferably 50 to 60% by weight, of at least one source of alkalinity,

(b) 25 to 65% by weight, preferably 35 to 45% by weight, of at least one pH control agent,

(c) 0.5 to 12% by weight, preferably 3 to 7.5% by weight, of at least one organic co-builder,

(d) 0 to 3% by weight, preferably 0 to 2% by weight, of at least one complexing agent, in each case based on the entire builder system.

6. Detergent or cleaning agent according to claim 5, characterized in that the source of alkalinity is alkali metal carbonate, alkali metal bicarbonate and / or alkali metal sesquicarbonate, preferably sodium bicarbonate and / or sodium carbonate and / or sodium sesquicarbonate, particularly preferably sodium carbonate and optionally bicarbonate.

7. washing or cleaning agent according to claim 5 or 6, characterized in that the pH control agent is at least one monomeric organic polycarboxylic acid.

8. washing or cleaning agent according to claim 7, characterized in that the monomeric organic polycarboxylic acid is selected from the group citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids and / or nitrilotriacetic acid and / or their Salts, preferably from the group citric acid, succinic acid, glutaric acid, adipic acid and / or gluconic acid and / or their salts, citric acid and / or its salts being particularly preferred.

9. washing or cleaning agent according to one of claims 1 to 8, characterized in that it is in the organic co-builder at least one polymeric polycarboxylic acid and / or its partially or completely neutralized metal and / or ammonium salt (s), preferred the alkali metal salt (s), particularly preferably the sodium salt (s) and / or mixtures thereof.

10. washing or cleaning agent according to claim 9, characterized in that it is in the polymeric polycarboxylic acid and / or its partially or completely neutralized metal and / or ammonium salt (s) polyacrylates with a molecular weight of 1000 to 20,000 g / mol, preferably from 1000 to 10000 g / mol and particularly preferably from 1200 to 8000 g / mol, and / or copolymeric polycarboxylic acids with molecular weights from 20,000 to 90,000 g / mol, in particular from 30,000 to 80,000 g / mol.

11. Detergent or cleaning agent according to one of claims 1 to 10, characterized in that at least one phosphonate is contained as complexing agent.

12. Detergent or cleaning agent according to one of claims 1 to 11, characterized in that the surfactant system

(a) 60 to 95% by weight, preferably 70 to 90% by weight, of at least one anionic surfactant,

(b) 5 to 25% by weight, preferably 10 to 20% by weight, of at least one nonionic surfactant, based in each case on the entire surfactant system.

13. Washing or cleaning agent according to claim 12, characterized in that the anionic surfactants are selected from the group linear C ₁₀ .ι ₃ alkylbenzenesulfonates, Ci ₂ -ιs disulfonates, C ₁₂ -i ₈ alkanesulfonates, C ₈ . _20- u-sulfo fatty acid ester, sulfonated C ₆ . ₂₂ - fatty acid glycerol esters, C ₁₂ _ ₁₈ -A! K (en) yl sulfates, C ₁₀ . ₂ o-Oxoalk (en) yl, 2,3-alkyl sulfates, C ₇ _ ₂₁ fatty alcohol (glycol ether) _3ι5 sulfates, C _{8 8} -ι - Alkylsulfobernsteinsäureester, sarcosides, sarcosinates, C _12-22 fatty acid soaps, preferably from the group linear C ₁₀ -ι ₃ alkylbenzenesulfonates, C ₁₂ _ ₂₂ fatty acid soaps.

14. Washing or cleaning agent according to claim 12 or 13, characterized in that the nonionic surfactants are selected from the group C ₈ . ₁₈ fatty alcohols 1-12 EO, alkyl glycosides of the formula RO (G) ₁ . ₁₀ , C ₁₂ -i ₈ fatty acid-C _Jr alkyl (glycol ether) ₅ . ₁₂ esters, amine oxides, polyhydroxy fatty acid amides, preferred nonionic surfactants, however, are C ₈ -ββ fatty alcohols 1-12 EO.

15. Washing or cleaning agent according to one of claims 1 to 14, characterized in that it is in particulate form, preferably in the form of powders, extrudates, granules and / or mixtures thereof, particularly preferably in the form of powders.

16. Use of the washing or cleaning agent according to one of claims 1 to 15 for washing or cleaning textiles, preferably sensitive textiles.

17. Use according to claim 16, characterized in that the sensitive textiles are textiles made of wool, cotton, silk, linen, viscose and / or blended fabrics made of these, preferably wool.

18. Use according to claim 16 or 17 for reducing deposits when washing or cleaning textiles, in particular when washing or cleaning sensitive textiles.

19. Use according to one of claims 16 to 18 in a machine wash at temperatures from 20 to 60 ° C, preferably from 30 to 40 ° C, or in manual washing at temperatures from 15 to 40 ° C, preferably from 20 to 35 ° C.

20. Process for washing or cleaning textiles, in particular sensitive textiles, characterized in that

(a) a washing or cleaning agent according to one of claims 1 to 16 is dissolved in water,

(b) the textile (s) are brought into contact with the aqueous solution of the agent,

(c) the aqueous solution of the washing or cleaning agent is guided past the textile or the textiles or vice versa,

(d) the aqueous solution of the washing or cleaning agent is removed from the textile or the textiles, rinsing several times with fresh tap water, that is to say rinsing, and

(e) the textile is dried or the textiles are dried.