EP1440141B2 - 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

The invention relates to a particulate, aluminosilicate-, silicate- and phosphate-free washing or cleaning agent whose aqueous dispersion has a mild pH and which can be dispersed substantially sediment-free in tap water. The invention also deals with the use of this detergent for washing textiles, especially delicate textiles.

The manufacturers of detergents and cleaners invest a great deal of time and effort in the further development and improvement of their products in order to better meet the consumer's wishes. Examples of fields where progress is currently being made include improved wash performance, ease of handling, solution and flushing behavior, and deposition behavior. The optimization of the detergent ingredients, in particular the builder or builder systems and the surfactants or surfactant systems, as well as the optimization of their formulations plays a crucial role.

Builders or builder systems perform a variety of tasks in detergents or cleaners that have changed significantly in recent years and decades with the constant changes in composition, formulation, and detergent manufacture. Modern detergents today contain about 30 to 60 wt .-% builders. These are among the most important substance classes for the construction of detergents and cleaners.

Because of the variety and evolution of detergent systems suggested here, the builders' tasks are varied and neither completely nor quantitatively defined. However, the main requirements are well described. Worth mentioning here are above all the water softening, the reinforcement of the washing effect, a grayness inhibition and the dirt dispersion. Builders should contribute to the necessary for the washing process alkalinity, 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 structure-forming or reduce the dust problem. These different requirements can not normally be met with just one builder component alone, so that as a rule a system of builders and co-builders has to be used.

For ecological reasons, builders containing phosphorus and / or nitrogen have come under criticism as detergent components. To a great extent, in particular in textile detergent formulations, the three-dimensionally crosslinked, water-insoluble sodium aluminosilicate zeolite NaA has become established today. To a considerable extent, in particular in the context of textile detergents, however, the co-use of so-called co-builder is required here, in particular to counteract undesirable incrustations. To a great extent, together with zeolite NaA, polymeric polycarboxylates, in particular copolymers based on acrylic acid and maleic acid with molar masses 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 major disadvantages of using aluminosilicates, such as zeolite NaA, in detergents or cleaners is their insolubility. This leads under unfavorable circumstances to the fact that the machine-washing with aluminosilicate-containing detergents or cleaners, the aluminosilicate is not completely rinsed in the wash cycle and deposited on the laundry in the form of white dots or stains, so-called residues. This problem has been compounded by the current trend towards washing machines, which for ecological reasons operate with less and less water per wash, and are getting more and more full.

Very early on there was a search for possible substitutes for the aluminosilicates. Concurrently with the development of the water-insoluble zeolite NaA as a builder, it has been proposed in this connection to use selected water-soluble amorphous sodium silicates as builders in detergents or cleaners. Reference is made, for example, to the 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.). Therein, amorphous sodium silicate compounds are described as builder substances which are prepared by spray-drying aqueous waterglass solutions, then grinding and subsequent compacting and rounding with additional removal of water from the mahogany. According to the EP-A-0 444 415 (Hoechst ) detergents containing from 5 to 50% by weight of at least one surfactant, from 0.5 to 60% by weight of a builder and customary laundry auxiliaries are proposed, the characteristic being that an amorphous, low-sodium disilicate having a water content of 0, 3 to 6 wt .-% is used.

In the German Offenlegungsschrift DE-A-22 40 309 (Unilever ) describes a zeolite-free composition which comprises 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 0.05 to 15% by weight of a deposit prevention agent for calcium carbonate. This anti-deposition agent is either a phosphate, a phosphonic acid or a polymeric carboxylate.

In the international application WO-A-96117045 (Henkel ) detergents or cleaning agents are described with bulk densities above 600 g / l, which contain a surfactant system and a builder system in which zeolite is replaced wholly or partly by sodium carbonate and amorphous silicate, without causing difficulties from the 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 an average of less than 19 wt .-% of the content of the sum of sodium carbonate and amorphous sodium silicate (each based on anhydrous active substance) 10 to 40 wt. % by weight, wherein the weight ratio of sodium carbonate to sodium silicate is in the range from 5: 1 to 1:10 and the sodium carbonate used is present at least partially in the form of a granulate.

In the 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. Advantages of this agent are the price and the environmental behavior of the builder system. Preferred embodiments have a ratio of sodium carbonate to sodium sulfate 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 having a molecular weight less than 10,000 g / mol, phosphonate and an acidic component. This soluble builder system is dosed low, ie less than 40% by weight of the detergent is claimed by this builder system and the alkali product of this agent is in the range of 7.0 to 11.4. In comparison to a zeolite-containing builder system, this soluble builder system has advantages, especially in the residue behavior.

However, it has now been found that even the complete omission of the insoluble aluminosilicates does not solve the problem of deposits. It has even been found that deposits can occur under unfavorable circumstances, even if the aluminosilicate-free detergents or cleaning agents release residue-free. As the cause of these deposits, the silicates used were considered. These have the unfavorable property, in the alkaline, aqueous medium, in particular at elevated temperatures, to partially hydrolyze and to precipitate in the form of silica. As a result of this discovery, work is underway to develop next-generation detergents or cleaners that are not only free of phosphate and aluminosilicate but also to limit the content of silicates or certain silicates.

In the international application WO-A-00/18859 (Procter & Gamble ), for example, the content of amorphous alkali silicate is limited. A phosphate-free detergent or cleaning agent is described which has improved solubility and 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 wholly water-soluble and constitutes 60 to 100% by weight of the builder system, preferably crystalline layer-structured alkali silicate. Another builder is water-insoluble and constitutes from 0 to 40% by weight of the builder system. Overall, less than 9% by weight of aluminosilicate, preferably no aluminosilicate at all, and less than 5% by weight of amorphous alkali silicate should be included in the composition. The surfactant system comprises one or more surfactants, preferably an anionic alkyl sulphate and an anionic sulphonate or mixtures thereof, wherein one of the surfactants is intimately mixed with one of the partially or wholly water-soluble builders as a particulate component. However, the detergents or cleaning agents disclosed in this application in the examples also contain large amounts of silicates, namely of crystalline layer silicates and / or builder amounts of more than 35% by weight and / or amounts of surfactant of more than 25% by weight and / or none Surfactant system comprising at least one anionic surfactant and at least one nonionic surfactant.

Now, the omission of certain ingredients from detergents or cleaners 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, making the industrial handling and processing of detergents or cleaners more difficult. Lubricating the surfactants also results in unsightly stains on the detergent or cleaning product package, making the product less attractive to the consumer. In addition, the particles of washing or cleaning agents having oiling problems tend to clump together, making their use more difficult and more uncomfortable for the consumer. These problems worsen at elevated temperatures and humidities as well as longer storage times. In addition, detergents or cleaners without silicates and aluminosilicates have poorer performance profiles because the particles can absorb less surfactant; Add to this the harmful effects of water hardness on the washing performance under the typical washing conditions in the private sector.

All this shows that with the introduction of new builders or a new builder system which dispenses with proven builder components, the surfactants or surfactant system must normally be adapted to the new builder system. The requirements placed on a suitable surfactant or surfactant system in a modern detergent or cleaner are as varied as those on the builder or builder system. In addition to a favorable price / performance ratio, a complete and rapid biodegradability and favorable ecotoxicological properties of modern surfactants or surfactant systems a high synergy potential with surfactants and other ingredients expected, a high wetting effect, good solubility, a favorable low-temperature behavior, electrolyte compatibility, chemical stability and a suitable foaming behavior.

With regard to the foaming behavior, conflicting requirements are placed on modern detergents or cleaners. On the one hand, a certain foam development with high foam scents when washing delicate textiles is quite desirable, for example because the foam acts as an air cushion ("foam pad") and protects especially sensitive textiles from mechanical damage during machine washing. However, the foam heights must not be too high during washing, as otherwise the primary washing performance with regard to certain soiling drops sharply. On the other hand, the foam should also be easy to rinse, with low foam scents when rinsing, otherwise the user finds foam residues on the laundry after finishing the rinse, when he opens his washing machine to hang the laundry to dry or to give in a machine dryer. The foam is often not only visually perceived, but also tactile, as 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 again.

In order to solve this contradiction between disproportionately high foam scores during washing and low scum scours during rinsing, foam regulators are usually used in the prior art. In the international application WO-A-98/27189 For example, a mildly acidic laundry detergent is described which provides improved protection of fabric textiles and the improved removal of foam that results from rinsing during hand washing. Among other ingredients, the detergent contains at least one rinse-active pH-sensitive foam regulator comprising a fatty acid. This fatty acid is inactive during the washing in weakly acidic conditions (pH 5.5 to 6.9) with respect to the foam, so that an acceptable foaming behavior is present, but when rinsing with tap water (pH 7.5 to 8, 5), where the pH increases, at least partially converted to soap. This reacts with the hardness ions of the rinsing water to 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 an improved foaming behavior. In particular, the agent should develop a sufficient, advantageous foam height during the washing process, but the foam should be well rinsable in the course of the rinsing process.

Surprisingly, it has now been found that washing or cleaning agents which form little sediment during dispersion show the required foaming behavior. The present invention therefore relates to a particulate, builder-containing, but aluminosilicate, silicate and phosphate-free surfactant system-containing washing or cleaning agent whose aqueous dispersion under the conditions 8 g / l, 20 ° C, 16 ° d a pH in the range of 7.0 to 9.0 and when dispersed in tap water under the conditions 8 g / l, 20 ° C, 16 ° d, 20 min stirring, sedimentation time 24 h, a sedimentation volume of at most 0.5 ml, wherein the agent comprises (a) 15 to 35 wt .-% of a builder system and (b) 5 to 25 wt .-% of a surfactant system containing at least one anionic surfactant and at least one nonionic surfactant.

The scientific connection between aluminosilicate freedom and the required foam behavior is z.Z. not fully understood. Without wishing to be bound by it, however, it is assumed that the zeolite particles have a foam-stabilizing effect and thus lead to poorly flushable foam. Also, the scientific connection between silicate freedom and the required foam behavior z.Z. not fully understood. A conceivable explanation approach is that the first dissolved silicates of detergents or cleaning agents of the prior art at least partially hydrolyzed to silica, thereby forming silica particles, thereby - act analogous to the aluminosilicate - in a foam-stabilizing and thus lead to poor flushing foam.

• ■ Es werden keine speziellen kostspieligen Tenside benötigt, sondern es kann auf ein bewährtes Tensidsystem zurückgegriffen werden.
• ■ Es werden keine zusätzlichen Schaumregulatoren benötigt, das vorteilhafte Schaumverhalten stellt sich unter den genannten Bedingungen von selbst ein.
• ■ verbessertes Ablagerungsverhalten
• ■ verbesserte Einspülbarkeit

The agent additionally has several advantages:

• ■ No special costly surfactants are needed, but a proven surfactant system can be used.
• ■ No additional foam regulators are required, the advantageous foam behavior is self-adjusting under the conditions mentioned.
• ■ improved deposition behavior
• ■ improved flushability

The behavior of the composition according to the invention is substantiated by the foam test, the sedimentation test and the "black fabric test", with which the deposition behavior is determined.

The agent of the invention dissolves sediment-free or at least almost sediment-free, has an advantageous foaming during the wash cycle and a good leachable foam during the dilution and rinses, and also has a good deposition behavior. Another advantage of the washing or cleaning agent according to the invention consists in the significantly improved flushability of the agent during machine washing or cleaning. An additional advantage of the composition according to the invention is the relatively low pH of the compositions of the invention, which is in the range of 7 to 9, and which is particularly advantageous for washing or cleaning delicate textiles. The details of these advantageous properties of the agent according to the invention and the description of the abovementioned tests are explained 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 of textiles, especially of delicate textiles. In the context of the present invention, sensitive textiles are understood in particular as meaning those made of wool, cotton, silk, linen, viscose and / or blended fabrics made of the abovementioned materials, the focus being on textiles made of wool. Generally speaking, these sensitive textiles are those whose quality suffers particularly as a result of deposits in terms of eg comfort, graying and shrinkage.

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 delicate textiles.

The compositions according to the invention can be used both mechanically and manually. In a preferred embodiment of the invention, the agents are used in a machine wash, wherein the application is particularly preferred, especially with regard to the preferred textiles in fine washing programs or Vollwaschprogrammen. Preferably, the use takes place at temperatures of about 20 ° C to about 60 ° C and especially at temperatures of about 30 ° C to about 40 ° C instead.

In a further preferred embodiment of the invention, the agents are used in manual washing, especially in hand basins, and at temperatures of about 15 ° C to about 40 ° C, preferably from 20 to 35 ° C.

1. (a) Auflösen des erfindungsgemäßen Wasch- oder Reinigungsmittels in Wasser,
2. (b) Inkontaktbringen des Textils oder der Textilien mit der wäßrigen Lösung des erfindungsgemäßen Mittels,
3. (c) Vorbeiführen der wäßrigen Lösung des erfindungsgemäßen Mittels an dem Textil oder den Textilien oder umgekehrt, entweder manuell (wie bei einer Handwäsche) oder maschinell,
4. (d) Entfernen der wäßrigen Lösung des erfindungsgemäßen Mittels von dem Textil oder den Textilien, wobei mehrfach mit frischem Leitungswasser nachgespült, d.h. ausgespült wird,
5. (e) Trocknung des Textils oder der Textilien.

The invention also relates to a method for washing or cleaning textiles, in particular sensitive textiles, while reducing deposits. The method according to the invention comprises the following steps:

1. (a) dissolving the washing or cleaning agent according to the invention in water,
2. (b) contacting the textile or textiles with the aqueous solution of the agent according to the invention,
3. (c) passing the aqueous solution of the agent of the invention on the textile or textiles or vice versa, either manually (as in a hand wash) or by machine,
4. (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, ie rinsing,
5. (e) drying the textile or textiles.

"Deposits" are understood in the context of the present inventions, all substances that remain after washing on the dry laundry, the whereabouts of which is undesirable on the laundry and contributes to a deterioration of the quality of the laundry. These include so-called "residues". These are remnants of undissolved detergent or cleaning agent that can be found after washing on the dry laundry in the form of white spots or stains. The cause of residues is a poor, in the sense of too slow, solution kinetics of the washing or cleaning agent used. The problem of the residues is v. A. In the case of machine washing, the current trend is leading to ever smaller quantities of water and to ever-increasing washing loads per wash.

Also among the "deposits" are "incrustations". These are understood as meaning sparingly soluble deposits on textile surfaces and / or surfaces of the machines (in particular heating rods), which arise in particular during washing of textiles under high temperatures and alkaline conditions and lead to hardening and graying of the fabric.

By "sediments" is meant in the following deposits which are due to "sedimentation", i. the movement of disperse particles in water under the influence of gravity due to their higher density. Another name for sediments is "settleable matter". This is the collective term for suspended solids that settle in a water sample in a certain time at the bottom of the measuring container and are usually given as sedimentation volume per liter of water sample. Thus, the term "sediments" does not include the usual and unavoidable clouding of aqueous detergents or cleaning solutions resulting from the surfactants, which do not sediment, i. drop.

By "substantially sediment-free dispersible" is hereinafter understood that 8 g of the agent when dissolved or dispersed in tap water (1 l, 20 ° C, 16 ° d, stirring for 20 min, sedimentation time 24 h) a sedimentation volume per liter of at most 2 ml / l. The method for determining the sedimentation volume is described in more detail in the example in [0138].

In a preferred embodiment of the invention results in the dissolution or dispersion of 8 g of the detergent or cleaning agent according to the invention in tap water (1 1, 20 ° C, 16 ° d, stirring for 20 min, 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 most preferably of 0 ml / l.

The determination of the "foam notes" is described in detail in the example on page 19. The characterization of the foaming behavior by specifying foam heights in linear dimensions, such as cm, for example, is widely used in the prior art, but the use of foam scores advantageously leads to more readily comparable data, in particular in the case of series tests. However, both dimensions are equivalent, since foam note and foam heights can be converted into each other with knowledge of the washing machine dimensions, in particular the porthole dimensions.

1. (a) eine oder mehrere Alkalitätsquelle(n),
2. (b) ein oder mehrere pH-Kontrollmittel,
3. (c) ein oder mehrere Cobuilder und
4. (d) gegebenenfalls ein oder mehrere Calciumcarbonat-Ablagerungsverhinderer.
   Das Buildersystem macht vorzugsweise 20 bis 30 Gew.-%, des gesamten Mittels aus.

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

1. (a) one or more sources of alkalinity (s),
2. (b) one or more pH control agents,
3. (c) one or more cobuilders and
4. (d) optionally one or more calcium carbonate scale inhibitors.
   The builder system preferably accounts for 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 bicarbonate or / and sodium sesquicarbonate are preferred, with sodium carbonate, if appropriate also in combination with bicarbonate, being particularly preferred. The or the sources of alkalinity make up about 10 to 30 wt .-%, preferably 15 to 25 wt .-% of the total inventive agent and about 35 to 75 wt .-%, preferably 50 to 60 wt .-%, of the builder system.

The pH control agents fulfill an important task as organic builders and for adjusting a pH value suitable for the invention. Suitable pH control agents are, in particular, monomeric organic polycarboxylic acids, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided their use is not objectionable for ecological reasons, and mixtures of these. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these are preferred in this context. Particularly preferred is citric acid. The stated polycarboxylic acids 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, more preferably in amounts of about 7.5 to about 15 Wt .-% based on the total agent. Thus, the pH control agents 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 agents according to the invention in one liter of water at 20 ° C and 16 ° d have a pH of 7.5 to 8.5.

Other suitable builders are polymeric polycarboxylic acids and / or their partially or fully neutralized metal and / or ammonium salts, for example the alkali metal salts of (homopolymeric) polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1000 to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,200 to 8,000 g / mol, for example 4,500 or 8,000, may again be preferred from this group.

Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers are particularly preferably used in the compositions according to the invention. The sulfonic acid-containing copolymers will be 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 maleic acid.

Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their molecular weight relative to free acids is generally from 2000 to 100,000 g / mol, preferably from 20,000 to 90,000 g / mol and in particular from 30,000 to 80,000 g / mol.

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

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

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

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives.

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

Further 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, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, 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 common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.

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 to C _{6 of} the saccharide ring may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates.

Other co-builders which may be present together with phosphonates, but also as partial to complete replacement of phosphonates in liquid or particulate agents or moldings, include iminodisuccinates (IDS) and their derivatives, for example hydroxyiminodisuccinates (HDIS). It has been known for some years that these raw materials can be used in detergents or cleaners as co-builders. Thus, the use of HIDS in detergents or cleaning agents already in the patent applications WO 92/2489 and DE 43 11 440 described. From the European patent application EP 0 757 094 For example, the beneficial use of iminodisucinates in combination with polymers having recurring succinyl moieties is known. More recently it has been discovered that IDS- or HIDS-containing agents can positively contribute to the color retention of textiles. For example, let's look at the international patent applications WO 01/94514 . WO 01/92449 . WO 01/88077 . WO 01/46371 and WO 01/44423 directed.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present 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 capable of forming complexes with alkaline earth ions may be included as co-builders in the particulate agents.

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned. The phosphonates are in the inventive compositions - if at all - but only in small amounts, between about 0.1 to 2 wt .-%, drawn on the total mean or in amounts of 0 to about 3 wt .-%, preferably from 0 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 accounts for 10 to 20% by weight of the total composition.

Suitable anionic surfactants are, for example, sulfonate-type surfactants. Cumene sulfonate, C _10-13 alkyl benzene sulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, are preferred, as can be obtained, for example, from C _2-18 monoolefins having terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise suitable are the esters of 2-sulfo fatty acids (ester sulfonates), for example the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, 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. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids containing 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) ylsulfates are the alkali metal salts, and especially the sodium salts, of the sulfuric monoesters of C _12-18 fatty alcohols, for example of coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or of C _10-20 oxo alcohols and those Half-ester secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C _12-15 alkyl sulfates and C _14-15 alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which, for example, according to the U.S. Patents 3,234,258 or 5,075,041 are manufactured and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

Also, the Schwefelsäuremonoester with 1 to 6 moles of ethylene ethoxylated straight-chain or branched C _7-21 alcohols, such as C 2-methyl-branched _9-11 alcohols containing on average 3.5 moles of ethylene oxide (EO) or C _12-18 fatty alcohols with 1 to 4 EO, are suitable.

Further 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 in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) yl-succinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

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

The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, 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 _10-13 -alkylbenzenesulfonates. The content of anionic surfactants according to the invention is advantageously from 5 to 20% by weight, preferably from 7.5 to 20% by weight, particularly preferably from 10 to 20% by weight, based on the total agent. Thus, the surfactant system preferably consists of 60 to 95 wt .-%, particularly preferably 70 to 90 wt .-%, of anionic surfactant.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated or propoxylated, in particular primary, alcohols having preferably 8 to 18 C atoms and on average 1 to 80, preferably 3 to 12, moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical is linear or preferred may be methyl branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. Examples of the fatty alcohols are lauryl alcohol (C ₁₂ ), myristyl alcohol (C ₁₄ ), cetyl alcohol (C ₁₆ ) etc., from the point of view of the availability of the compounds. In particular, however, are alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for Example of coconut, palm, tallow or Oleyfalkohol, and on average 1 to 80, preferably 2 to 8 EO per mole of alcohol is preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO, C _{18-18 alcohols} with 5 EO and mixtures of these, and mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alkoxyethoxylates 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 _12-18 alcohols with 7 EO and C _16-18 alcohols with 5 EO, as well as mixtures of these have proven particularly suitable for the present invention as nonionic surfactants.

Another class of preferred nonionic surfactants 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 having from 1 to 8 carbon atoms in the alkyl chain and from 3 to 80 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 are described or preferred according to the in the international patent application WO 90/13533 disclosed methods are produced.

Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG). Usable alkylpolyglycosides satisfy the general formula RO (G) _z , in which R is a linear or branched, in particular in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably 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. Preference is given to using linear alkyl polyglucosides, that is to say alkyl polyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further suitable surfactants are polyhydroxy fatty acid amides of the formula (I)

wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 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.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.

[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 the international application WO-A-95/07331 be converted by conversion with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired Polyhydroxyfettsäureamide.

From a practical point of view, it will be advantageous to take into consideration that compounds of the abovementioned groups are used which are still liquid to pasty even at relatively long chain lengths at the temperatures of use.

The nonionic surfactants are used in the present invention, alone or in admixture, and advantageously so that the total niotenside content of the detergents or cleaners according to the invention is advantageously from 1 to 10% by weight, preferably from 2 to 5% by weight, or the surfactant system 5 to 25 wt .-%, preferably 10 to 20 wt .-%, of at least one nonionic surfactant.

Furthermore, it may be preferable to use not only anionic and nonionic surfactants but also cationic surfactants. Their use is preferably as a washing power booster, with 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 wt .-%, preferably 1 to 5 wt .-%, based on the total agent.

Essential to the present invention is a specific foaming behavior of the washing or cleaning agents according to the invention. It has proven to be advantageous, for example, if the agent has a foam grade of at least 5 in the wash cycle, 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 particulate, in particular in the form of powders, extrudates, granules and / or mixtures thereof.

The detergents or cleaners according to the invention may contain, in addition to the above-mentioned ingredients, all known ingredients customary in detergents and cleaners such as, for example, enzymes, dyes, optical brighteners, UV protectants, fragrances and perfumes, perfume carriers, anti-redeposition agents, grayness inhibitors, dye transfer inhibitors, Corrosion inhibitors, bleaches, bleach activators, softeners and fabric softeners. Preferably, however, the agents do not contain bleaching agents and bleach activators for the protection of delicate textiles. The other ingredients mentioned are preferably present in amounts of from 2 to 40% by weight, in particular in amounts of from 10 to 30% by weight, based on the total weight of the composition according to the invention.

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the 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-phthalimidoperoxy-caproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamidoperadipic acid and N-nonylamidoperoperuccinate; and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid ) can be used.

As a bleaching agent, in principle, chlorine or bromine releasing substances can be used. However, these are of little importance for use in detergents. Suitable chlorine or bromine-releasing materials include, for example, heterocyclic N-bromo and N-chloroamides 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 may be incorporated in the compositions of the invention. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated 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, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2 , 5-dihydrofuran.

In addition to or in place of the conventional bleach activators, so-called bleach catalysts can also be incorporated into the high soda-containing particles. These substances are bleach-enhancing transition metal salts or transition metal complexes, for example Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

However, with regard to the use of the washing or cleaning agents according to the invention in the washing or cleaning of sensitive textiles, it may be preferred that the compositions do not contain any of the abovementioned bleaches and none of the abovementioned bleach activators.

Agents according to the invention may contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all enzymes established for this purpose in the prior art. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Agents ^according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-6 to 5 percent by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method ( Gomall AG, CS Bardawill and MM David, J. Biol. Chem. 177 (1948), pp. 751-766 ).

Among the proteases, those of the subtilisin type are preferable. Examples thereof 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 the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg in a developed form under the trade names Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. From the protease from Bacillus lentus DSM 5483 ( WO 91/02792 ) derive from the name under the name BLAP ^® variants, which in particular in WO 92/21760 . WO 95/23221 and in the applications DE 10121463 and DE 10153792 to be discribed. Other useful proteases from various Bacillus sp. and B. gibsonii go out of the patent applications DE 10162727 . DE 10163883 . DE 10163884 and DE 10162728 out.

Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® by the company Genencor, that under the trade name Protosol® ^® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, under the trade names 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, B. amyloliquefaciens or B. stearothermophilus and also their further developments improved for use in detergents and cleaners. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ^® and 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 B. amyloliquefaciens is marketed by Novozymes under the name BAN ^®, and variants derived from the α-amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes.

Furthermore, for this purpose in the application WO 02/10356 disclosed α-amylase from Bacillus sp. A 7-7 (DSM 12368) and in the application PCT / EP01 / 13278 highlighted cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948); further, those belonging to the sequence space of α-amylases described in the application DE 10131441 is defined. Likewise, fusion products of said molecules can be used, for example those from the application DE 10138753 ,

In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae, which are. Another commercial product is, for example, the amylase ^LT® .

Compositions according to the invention may contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, 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® are} available. From the company Genencor, for example, the lipases, or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii . Other important commercial products are the originally marketed by Gist-Brocades preparations 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.

Detergents according to the invention, especially if they are intended for the treatment of textiles, may contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously supplement each other in terms of their various performance aspects. These performance aspects include, in particular, contributions to the primary washing performance, the secondary washing performance of the composition (anti-redeposition effect or graying inhibition) and softening (fabric effect), up to the exercise of a "stone washed" effect.

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

Compositions of the invention may contain other 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 β-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and Pektinex AR ^® 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 , for example, from the application WO 99/06573 out. The obtained from B. subtilis β-glucanase is available under the name Cereflo ^® from Novozymes.

To increase the bleaching effect, detergents and cleaners according to the invention may contain 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 Denilite® ^® 1 and 2 from Novozymes should be mentioned. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

The enzymes used in agents of the invention are either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, such as transgenic expression hosts of the genera Bacillus or filamentous fungi.

The purification of the relevant enzymes is conveniently carried out by conventional methods, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.

The agents of the invention may be added to the enzymes in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of caplets, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

Furthermore, it is possible to assemble two or more enzymes together so that a single granule has multiple enzyme activities.

A protein and / or enzyme contained in an agent according to the invention can be protected against damage, for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, in particular during storage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Compositions according to the invention may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.

One group of stabilizers are reversible protease inhibitors. Frequently, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are used, including in particular derivatives with aromatic groups, for example according to WO 95/12655 ortho-substituted, according to WO 92/19707 meta-substituted and according to US 5972873 para-substituted phenylboronic acids, or their salts or esters. In the applications WO 98/13460 and EP 583534 For the same purpose, peptide aldehydes, that is, oligopeptides with reduced C-terminus are disclosed. As peptidic protease inhibitors include ovomucoid ( WO 93/00418 ) and leupeptin; An additional option is the formation of fusion proteins from proteases and peptide inhibitors.

Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and - propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as from the applications EP 378261 and WO 97/05227 is known, such as succinic acid, other dicarboxylic acids or salts of said acids. With the Application DE 19650537 For this purpose, end-capped fatty acid amide alkoxylates are disclosed. Certain organic acids used as builders are capable of, as in WO 97/18287 discloses additionally stabilizing a contained enzyme.

Lower aliphatic alcohols, but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers. After registration EP 965268 also protects di-glycerol phosphate against denaturation by physical influences. Likewise, calcium salts are used, such as calcium acetate or in the patent EP 028865 calcium formate disclosed for this purpose, and magnesium salts, such as according to the 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 in EP 702712 Cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations. Polyamine N-Oxide-Containing Polymers ( EP 587550 and EP 581751 ) act simultaneously as enzyme stabilizers and as color transfer inhibitors. Other polymeric stabilizers are those in WO 97/05227 among other ingredients disclosed linear C ₈ -C ₁₈ polyoxyalkylenes. Alkylpolyglycosides can according to the applications WO 97/43377 and WO 98/45396 stabilize the enzymatic components of the agent according to the invention and even increase their performance. Crosslinked N-containing compounds, as in WO 98/17764 disclosed perform a dual function as soil release agents and as enzyme stabilizers.

Reducing reducing agents and antioxidants, such as in EP 780466 discloses the stability of the enzymes to oxidative degradation. Sulfur-containing reducing agents are known for example from the patents EP 080748 and EP 080223 known. Other examples are sodium sulfite ( EP 533239 ) and reducing sugars ( EP 656058 ).

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

Further additives which are 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 stated above not being absolutely necessary, but if desired being able to take place. The use of mixtures of these agents is possible. As additives which are solid at room temperature, paraffin waxes, silicic acids, which may also be hydrophobized in a known manner, and in particular bismuth derivatives which are derived from C _2-7 -diamines and C _12-22 -carboxylic acids are suitable.

Foaming-inhibiting paraffin oils suitable for use in the detergents according to the invention, which may be present in admixture with paraffin waxes, generally represent complex mixtures without a sharp melting point. The melting range is usually determined for characterization by differential thermal analysis (DTA) as described in "The Analyst" 87 (1962), 420, and / or the solidification point. This is the temperature at which the paraffin passes from the liquid to the solid state by slow cooling. Paraffins with less than 17 carbon atoms are not useful in the invention, their proportion in the paraffin oil mixture should therefore be as low as possible and is preferably below the limit significantly measurable by conventional analytical methods, for example gas chromatography. Preferably paraffins are used which solidify in the range of 20 ° C to 70 ° C. It should be noted that even at room temperature appearing paraffin wax mixtures may contain different proportions of liquid paraffin oils. In the case of the paraffin waxes which can be used according to the invention, the liquid fraction at 40 ° C. is as high as possible, without already being 100% at this temperature. Preferred paraffin wax mixtures have at 40 ° C a liquid content of at least 50 wt .-%, in particular from 55 wt .-% to 80 wt .-%, and at 60 ° C, a liquid content of at least 90 wt .-% to. This has the consequence that the paraffins are flowable and pumpable at temperatures down to at least 70 ° C, preferably down to at least 60 ° C. It should also be ensured that the paraffins contain as far as possible no volatile components. Preferred paraffin waxes contain less than 1 wt .-%, in particular less than 0.5 wt .-% at 110 ° C and atmospheric pressure vaporizable fractions. Paraffins which can be used according to the invention can be obtained, for example, under the trade names Lunaflex® from Fuller and Deawax® from DEA Mineralöl AG.

The paraffin oils may contain at room temperature solid bisamides derived from saturated fatty acids containing 12 to 22, preferably 14 to 18, carbon atoms and alkylenediamines having 2 to 7 carbon atoms. Suitable fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof, such as those obtainable from natural fats or hardened oils, such as tallow or hydrogenated palm oil. Examples of suitable diamines are 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-palmitoylethylenediamine, bis-stearoyl-ethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine.

Furthermore, dyes, in particular water-soluble or water-dispersible dyes may be incorporated. Preferred here are dyes, as they are usually used to improve the appearance of the optical product in detergents and cleaners. The choice of such dyes is not difficult for a person skilled in the art, especially since such conventional dyes have a high storage stability and insensitivity to the other ingredients of the detergent compositions and to light and no pronounced substantivity to textile fibers in order not to stain them.

Examples of optical brighteners are derivatives of diaminostilbene disulfonic acid or their 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 similarly constructed compounds which instead of the morpholino group a Diethanoiamino Group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present in the washing or cleaning compositions 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 brightener can be used.

Another group of additives which is preferred according to the invention are UV protective substances. These are substances that are released during the washing process or in the subsequent fabric softening process in the wash liquor and that accumulate accumulatively on the fiber, in order then to achieve a UV protection effect. Suitable are the products marketed under the name Tinosorb Ciba Specialty Chemicals.

Another class of common detergent or cleaning ingredients that can be added according to the invention are polymers. Among these polymers are on the one hand polymers in question, which show co-washing 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 suspended from the hard surface and in particular of the textile fiber suspended dirt in the fleet and so to support the co-builder. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatine, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, it is possible to use other than the abovementioned starch products, for example aldehyde starches. Preference is given to using cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the total agent.

As further additives according to the invention, the detergents or cleaning agents may also contain antiredeposition agents, so-called soil repellents. These are polymers that are absorbed by fibers or hard surfaces and counteract re-soiling. This effect is particularly evident when a textile is dirty, which has been previously washed several times 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 methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30 wt .-% and to hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic Cellulose ethers, as well as known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

Other suitable polymers in the detergents 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, detergents or cleaners according to the invention may also contain fragrances and perfume preparations (perfumes). As perfume oils or fragrances, individual perfume compounds can be used, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance type compounds of the ester type include, for example, benzyl acetate, phenoxyethyl isobutyrate, p-t-butylcyctohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. Ethers include, for example, benzyl ethyl ether. The aldehydes include e.g. linear alkanals of 8 to 18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lileal and bourgeonal.

The ketones include the ionone, α-isomethylionone, and methyl cedryl ketone. The alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons mainly include terpenes such as limonene and pinene. Preference is given to using mixtures of different fragrances which are adapted to one another in such a way that together they produce an attractive fragrance note. Such perfume oils may also contain natural fragrance mixtures as are available 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, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroliol, orange peel oil and sandalwood oil.

It may be advantageous to apply the fragrances to carriers which enhance the adhesion of the perfume to the laundry and provide a lingering fragrance release for long-lasting fragrance of the textiles. As such carrier materials, for example, cyclodextrins have been proven. The cyclodextrin-perfume complexes can additionally be coated with other auxiliaries.

The detergents or cleaners according to the invention may contain corrosion inhibitors for the protection of the laundry or ware or the machine, with silver protectants being of particular importance in the field of automatic dishwashing. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners are particularly 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. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

wobei in (I) R und R¹ jeweils für einen acyclischen Alkylrest mit 12 bis 24 Kohlenstoff atomen, R² für einen gesättigten C₁-C₄ Alkyl- oder Hydroxyalkylrest steht, R³ entweder gleich R, R¹ oder R² ist oder für einen aromatischen Rest steht. X^- steht entweder für ein Halogenid-, Methosulfat-, Methophosphat- oder Phosphation sowie Mischungen aus diesen. Beispiele für kationische Verbindungen der Formel (I) sind Didecyldimethylammoniumchlorid, Ditalgdimethylammoniumchlorid oder Dihexadecylammoniumchlorid.Further ingredients which are possible in the detergents or cleaners 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),

wherein in (I) R and R ^{1 are} each an acyclic alkyl radical having 12 to 24 carbon atoms, R ^{2 is} a saturated C ₁ -C ₄ alkyl or hydroxyalkyl radical, R ^{3 is} either R, R ¹ or R ² or represents an aromatic radical. X ^- is either a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof. Examples of cationic compounds of the formula (I) are didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.

Compounds of formula (II) are so-called ester quats. Esterquats are characterized by excellent biodegradability. Here, R ^{4 is} an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds; R ⁵ is H, OH or O (CO) R ⁷ , R ⁶ is independently of R ^{5 is} H, OH or O (CO) R ⁸ , wherein R ⁷ and R ⁸ are each independently an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. m, n and p can each independently be 1, 2 or 3. X ^- may be either a halide, methosulfate, methophosphate or phosphate ion, as well as mixtures of these. Preference is given to compounds which contain the group O (CO) R ⁷ for R ⁵ and to alkyl radicals having 16 to 18 carbon atoms for R ⁴ and R ⁷ . Particularly preferred are compounds in which R ^{6 is} also OH. Examples of compounds of formula (11) are methyl N- (2-hydroxyethyl) -N, N-di (tallow acyloxyethyl) ammonium methosulfate, bis (palmitoyl) ethyl hydroxyethyl methyl ammonium methosulfate or methyl N, N bis (acyloxyethyl) -N- (2-hydroxyethyl) methosulfate. If quaternized compounds of the formula (11) which have unsaturated alkyl chains are used, 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 / translum ratio (in Wt .-%) of greater than 30: 70, preferably greater than 50: 50 and in particular greater than 70: 30 have. Commercial examples are sold by Stepan under the tradename Stepantex ^® methylhydroxyalkyldialkoyloxyalkylammonium or those known under Dehyquart ^® Cognis products known under or Rewoquat ^® manufactured by Goldschmidt-Witco. Further preferred compounds are the diester quats of the formula (III) which are obtainable under the name Rewoquat® W 222 LM or CR 3099 and, in addition to the softness, also provide stability and color protection.

R ²¹ and R ²² are each independently an aliphatic radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.

wobei R⁹ für H oder einen gesättigten Alkylrest mit 1 bis 4 Kohlenstoffatomen, R¹⁰ und R¹¹ unabhängig voneinander jeweils für einen aliphatischen, gesättigten oder ungesättigten Alkylrest mit 12 bis 18 Kohlenstoffatomen, R¹⁰ alternativ auch für O(CO)R²⁰ stehen kann, wobei R²⁰ einen aliphatischen, gesättigten oder ungesättigten Alkylrest mit 12 bis 18 Kohlenstoffatomen bedeutet, und Z eine NH-Gruppe oder Sauerstoff bedeutet und X^- ein Anion ist. q kann ganzzahlige Werte zwischen 1 und 4 annehmen.In addition to the quaternary compounds described above, it is also possible to use other known compounds, for example quaternary imidazolinium compounds of the formula (IV),

where R ^{9 is} H or a saturated alkyl radical having 1 to 4 carbon atoms, R ¹⁰ and R ¹¹ are each independently an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, R ^{10 may} alternatively be O (CO) R ²⁰ wherein 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 take integer values between 1 and 4.

wobei R¹², R¹³ und R¹⁴ unabhängig voneinander für eine C_1-4-Alkyl-, Alkenyl- oder Hydroxyalkylgruppe steht, R¹⁵ und R¹⁶ jeweils unabhängig ausgewählt eine C_8-28-Alkylgruppe darstellt und r eine Zahl zwischen 0 und 5 ist.Further suitable quaternary compounds are described by formula (V),

wherein R ¹² , R ¹³ and R ¹⁴ independently represent a C _1-4 alkyl, alkenyl or hydroxyalkyl group, each of R ¹⁵ and R ¹⁶ independently represents a C _8-28 alkyl group and r is a number between 0 and 5 is.

In addition to the compounds of formulas (I) and (II), short chain, water soluble, quaternary ammonium compounds, such as trihydroxyethylmethylammonium methosulfate or the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride.

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

Further cationic compounds which can be used according to the invention are the quaternized protein hydrolysates.

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, Polyquaternium, also referred to as Merquats. 10 polymers (Ucare Polymer IR 400; Amerchol), polyquaternium-4 copolymers such as graft copolymers having a cellulose backbone and quaternary ammonium groups bonded via allyldimethylammonium chloride, cationic cellulose derivatives such as cationic guar such as guar hydroxypropyltriammonium chloride, and similar quaternized guar gum. derivatives (eg Cosmedia, guar, manufacturer: Cognis GmbH), cationic quaternary sugar derivatives (cationic alkyl polyglucosides), for example the commercial product Glucquat ^® 100, according to CTFA nomenclature a "lauryl methyl Gluceth-10 hydroxypropyl Dimonium Chloride", copolymers of PVP and dimethylaminomethacrylate, Copolymers of vinylimidazole and vinylpyrrolidone, aminosilicone polymers and copolymer e.

Polyquaternized 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 in the present invention are cationic silicone oils such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) Abil ^® -Quat 3270 and 3272 (manufacturer: Goldschmidt-Rewo; diquaternary polydimethylsiloxanes, quaternium-80), and Silicone quat Rewoquat ^® SQ 1 (Tegopren ^® 6922, manufacturer: Goldschmidt-Rewo).

die Alkylamidoamine in ihrer nicht quaternierten oder, wie dargestellt, ihrer quaternierten Form, sein können. R¹⁷ kann ein aliphatischer Alkylrest mit 12 bis 22 Kohlenstoffatomen mit 0, 1, 2 oder 3 Doppelbindungen sein. s kann Werte zwischen 0 und 5 annehmen. R¹⁸ und R¹⁹ stehen unabhängig voneinander jeweils für H, C_1-4-Alkyl oder Hydroxyalkyl. Bevorzugte Verbindungen sind Fettsäureamidoamine wie das unter der Bezeichnung Tego Amid^®S 18 erhältliche Stearylamidopropyldimethylamin oder das unter der Bezeichnung Stepantex^® X 9124 erhältliche 3-Talgamidopropyl-trimethylammonium-methosulfat, die sich neben einer guten konditionierenden Wirkung auch durch ihre farbübertragungsinhibierende Wirkung sowie speziell durch ihre gute biologische Abbaubarkeit auszeichnen. Von dieser Verbindungsklasse sind v.a. die nicht quaternierten Alkylamidoamine bevorzugt. Dazu gehören z.B. Fettsäureamidoamine wie Talgamid B der Firma Cognis GmbH.Also usable are compounds of the formula (VI)

the alkylamidoamines may be in their quaternized or, as shown, their quaternized form. R ¹⁷ may be an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. s can take values between 0 and 5. R ¹⁸ and R ¹⁹ are each independently H, C _1-4 alkyl or hydroxyalkyl. Preferred compounds are fatty acid amidoamines such as Stearylamidopropyldimethylamin available under the name Tego Amid ^® S 18 or 3-Talgamidopropyl-trimethylammonium methosulfate available under the name Stepantex ^® X 9124, which in addition to a good conditioning effect also by their color transfer inhibiting effect and especially by their good biodegradability. Of this class of compounds, especially the non-quaternized alkylamidoamines are preferred. These include, for example, fatty acid amidoamines such as Talgamid B from Cognis GmbH.

Examples

Means having compositions according to Table 1 were prepared. E is an agent according to the invention and V is a comparison agent. <b> Table 1: </ b> Composition of Prepared Means. composition e V alkylbenzenesulfonate 11.8 12.0 C _12-18 -FA · 7 EO 2.0 2.0 fatty acid 3.0 3.0 zeolite - 16.1 silicate - 2.0 polycarboxylate 1.5 2.3 soda 14.7 0.2 Citric acid 1H ₂ O 11.0 2.5 alkylamidoamine 0.2 0.2 sodium sulphate 52.0 53.9 Water, perfume, salts of raw materials rest rest PH value 7.9 - 8.0 8.5 FA: fatty alcohol
EO: mol of ethylene oxide attached
Silicate: Amorphous sodium silicate with Na ₂ O: SiO ₂ = 3.35
Polycarboxylate: acrylic acid / maleic acid copolymer (Sokalan CP5, BASF)

The two remedies were investigated with regard to their sedimentation behavior, their deposition behavior, their foaming behavior and their flushability. The measurements made will be described in more detail below.

1. sedimentation behavior

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

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

2. Deposition behavior

To determine the deposition behavior in the "Black Fabric Test" were 8 g of agent E or V at 20 ° C in 1 l tap water hardness 16 ° dH with stirring (1.5 minutes, 800 rev / min with laboratory stirrer / propeller mixing head , Centered 5 cm from the bottom of the vessel) dissolved or dispersed. The resulting solutions or dispersions were filtered through black fabric. For this purpose, the fabric was clamped between a fritted bottom and a vertically mounted glass tube with 5 cm in diameter, so that a filter surface with a diameter of 5 cm was present. The filtration took place solely under the action of gravity. The fabric was cotton rib knit 100% cotton with 16cm edge dimensions. 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. Criterion of grading was the degree of coverage of the filter surface with filter residue. The grades of the 3 different persons were added and divided by 3. <b> Table 2: </ b> Rating of the filter residue by visual inspection. optical impression grade No residue 0 Little residue 1 good visible residue 2 highly visible residue that covers more than half of the filter surface 3 Almost complete covering with residue 4 Complete, closed cover with residue 5 Very strong covering with residue 6

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

3. Foaming behavior

The foaming behavior was determined using a Miele washing machine (type W 918, without fuzzy logic). For this purpose, 100 g of the means E or V were metered and 22 water hardness 16 ° dH used. The washing machine was operated with 2.0 kg of clean, standardized filling wash in the easy-care / fine program. The foam was scored according to the following chart. <b> Table 3: </ b> Grading of the foam after optical inspection. grade 0 No foam 1 Foam stand under the edge of the porthole 2 Foam level: half of the porthole 3 Foam level 2/3 of the porthole 4 Porthole full of foam 5 Washing machine full of foam, but still below Einspülkammer 6 Foam in the dispenser

The evaluation of the foam height with a foam note was carried out in each case when the washing machine, during the wash, when diluting (after the water supply), the 1st, 2nd and 3rd rinse (respectively after the water supply). <b> Table 4: </ b> Evaluation of foam behavior in the form of foam notes. wash Dilute 1. rinse 2. Rinse 3. Rinse e 6 2 1 1 0.5 V 6 5 5 5 2

It can be seen that the agent E according to the invention, as desired, had a high degree of foam during washing, whereby the laundry was spared, and a low level of foam after the last rinse, which equals good rinsability. Although the comparison agent V, on the other hand, likewise had a comparatively high degree of foam during washing, this was still unacceptably high after the last rinse, which equates to poor rinsability.

In summary, it can thus be stated that the agent according to the invention had a lower sediment volume than the comparison agent, ie it contained less sparingly soluble constituents. Both that Deposition behavior as well as the foaming behavior, especially during rinsing, were rated better in the composition according to the invention than in the comparison agent. Thus, while the actual washing process sufficient foam is present to ensure a gentle cleaning even delicate textiles, the foam after the rinse is very low, so the foam can be rinsed well; At the same time, unwanted deposits on the laundry are formed only to a much lesser extent than in the comparison agent. Consequently, the use of the builder system according to the invention positively influences both the foam behavior and the deposition behavior.

Claims (20)

1. Particulate, builder-containing, but aluminosilicate-, silicate- and phosphate-free, surfactant-containing washing or cleaning composition whose aqueous dispersion, under the conditions of 8 g/l, 20°C, 16°d, has a pH in the range of 7.9 to 9.0, the composition comprising

   (a) 15 up to 35% by weight of a builder system and

   (b) 5 up to 25% by weight of a surfactant system which comprises at least one anionic surfactant and a least one nonionic surfactant,

   characterized in that it has a sedimentation volume of at most 0.5 ml when dispersed in tap water under the conditions of 8 g/l, 20°C, 16°d, stirring for 20 min, sedimentation time 24 h.
2. Washing or cleaning composition according to Claim 1, characterized in that it has a sedimentation volume of at most 0.2 ml and preferably 0 ml when dispersed in tap water (8 g/l, 20°C, 16°d, stirring for 20 min, sedimentation time 24 h).
3. Washing or cleaning composition 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 of 7.5 to 8.5.
4. Washing or cleaning composition according to one of Claims 1 to 3, characterized in that it comprises

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

   (b) 10 to 20% by weight, of a surfactant system.
5. Washing or cleaning composition according to Claim 4, characterized in that the builder system comprises

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

   (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 cobuilder,

   (d) 0 to 3% by weight, preferably 0 to 2% by weight, of at least one complexing agent, based in each case on the overall builder system.
6. Washing or cleaning composition according to Claim 5, characterized in that the alkalinity source is alkali metal carbonate, alkali metal hydrogencarbonate and/or alkali metal sesquicarbonate, preferably sodium hydrogencarbonate and/or sodium carbonate and/or sodium sesquicarbonate, more preferably sodium carbonate and optionally hydrogencarbonate.
7. Washing or cleaning composition 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 composition according to Claim 7, characterized in that the monomeric organic polycarboxylic acid is selected from the group of 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 salts thereof, preferably from the group of citric acid, succinic acid, glutaric acid, adipic acid and/or gluconic acid and/or salts thereof, particular preference being given to citric acid and/or salts thereof.
9. Washing or cleaning composition according to one of Claims 1 to 8, characterized in that the organic cobuilder is at least one polymeric polycarboxylic acid and/or its partly or completely neutralized metal and/or ammonium salt(s), preferably its alkali metal salt(s), more preferably its sodium salt(s) and/or mixtures thereof.
10. Washing or cleaning composition according to Claim 9, characterized in that the polymeric polycarboxylic acid and/or its partly or completely neutralized metal and/or ammonium salt(s) are polyacrylates having a molar mass of 1000 to 20 000 g/mol, preferably of 1000 to 10 000 g/mol and more preferably of 1200 to 8000 g/mol, and/or copolymeric polycarboxylic acids with molar masses of 20 000 to 90 000 g/mol, in particular of 30 000 to 80 000 g/mol.
11. Washing or cleaning composition according to one of Claims 1 to 10, characterized in that at least one phosphonate is present as a complexing agent.
12. Washing or cleaning composition according to one of Claims 1 to 11, characterized in that the surfactant system comprises

    (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 overall surfactant system.
13. Washing or cleaning composition according to Claim 12, characterized in that the anionic surfactants are selected from the group of linear C_10-13-alkylbenzenesulphonates, C_12-18-disulphonates, C_12-18-alkanesulphonates, C_8-20-α-sulpho fatty acid esters, sulphated C_6-22 fatty acid glyceryl esters, C_12-18-alk(en)yl sulphates, C_10-20-oxoalk(en)yl sulphates, 2,3-alkyl sulphates, C_7-21 fatty alcohol (glycol ether)_3.5 sulphates, C_8-18-alkylsulphosuccinic esters, sarcosides, sarcosinates, C_12-22 fatty acid soaps, preferably from the group of linear C_10-13-alkylbenzenesulphonates, C_12-22 fatty acid soaps.
14. Washing or cleaning composition according to Claim 12 or 13, characterized in that the nonionic surfactants are selected from the group of C_8-18 fatty alcohols 1-12 EO, alkylglycosides of the formula RO(G)_1-10, C_12-18 fatty acid C_1-4-alkyl (glycol ether)_5-12 esters, amine oxides, polyhydroxy fatty acid amides, but preferred nonionic surfactants are C_8-18 fatty alcohols 1-12 EO.
15. Washing or cleaning composition according to one of Claims 1 to 14, characterized in that it is present in particulate form, preferably in the form of powders, extrudates, granules and/or mixtures thereof, more preferably in the form of powders.
16. Use of the washing or cleaning composition 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 blend fabrics thereof, preferably wool.
18. Use according to Claim 16 or 17 for reducing deposits in the washing or cleaning of textiles, especially in the washing or cleaning of sensitive textiles.
19. Use according to one of Claims 16 to 18 in a machine wash at temperatures of 20 to 60°C, preferably of 30 to 40°C, or in a manual wash at temperatures of 15 to 40°C, preferably of 20 to 35°C.
20. Process for washing or cleaning textiles, especially sensitive textiles, characterized in that

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

    (b) the textile(s) is or are contacted with the aqueous solution of the composition,

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

    (d) the aqueous solution of the washing or cleaning composition is removed from the textile or the textiles, and is rinsed, i.e. rinsed out, repeatedly with fresh tap water, and

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