DE10153551A1 - Detergent or cleaning agent that is essentially dispersible without sediment - 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 is concerned with a particulate, aluminosilicate, silicate and Phosphate-free washing or cleaning agent, the aqueous dispersion of which is mild has a pH value and disperses it essentially without sediment in tap water can be. The invention is also concerned with the use of this agent for washing textiles, especially delicate textiles.

The manufacturers of washing or cleaning agents invest a lot of time and work in the further development and improvement of their products in order to To meet consumer needs even better. Examples of fields currently on Progress is being made to improve washing performance, the simplicity of the Handling, the solution and flushing behavior, as well as the deposit behavior. The optimization of the detergent ingredients, especially the builder or Builder systems and the surfactants or surfactant systems, as well as the optimization of their Formulations play a crucial role.

Builders or builder systems fulfill a multitude of in detergents or cleaning agents Tasks that deal with the constant change in composition, the Offer form and the production of detergents in recent years and decades also changed significantly. Modern detergents today contain approx. 30 to 60% by weight Builders. This makes them one of the most important classes of substances for construction of detergents and cleaning agents.

Because of the variety and evolution of detergent systems indicated here, they are Tasks of the builders varied and neither fully nor quantitatively defined. The However, the main requirements are well described. Above all, those are to be mentioned here Water softening, the strengthening of the washing effect, an inhibition of graying and the Soil dispersion. Builders are said to be at the alkalinity necessary for the washing process contribute to a high absorption capacity for surfactants show the effectiveness of Improve surfactants, positive contributions to the properties of solid products deliver in powder form, for example, and thus have a structure-forming effect or also Reduce dust problems. These different requirements cannot normally be met with only one builder component, so that usually a system from Builders and co-builders must be used.

For ecological reasons, builders containing phosphorus and / or nitrogen are considered Detergent components come under criticism. Has become large today especially in textile detergent formulations, the three-dimensionally cross-linked, water-insoluble sodium aluminosilicate zeolite NaA prevailed. To a considerable extent, especially in the context of textile detergents, however, it is also used here So-called co-builders necessary, especially for unwanted incrustations counteract. To a large extent, polymers are now being used together with zeolite NaA Polycarboxylates, in particular copolymers based on acrylic acid and maleic acid Molar masses in the range of 20000-100000 g / mol, together with soda for this purpose used.

One of the biggest disadvantages when using aluminosilicates like zeolite NaA in Detergents or cleaning agents are their insolubility. This leads under unfavorable Circumstances that machine washing with aluminosilicate washing or Detergents the aluminosilicate is not completely rinsed out in the rinse cycle and on the laundry in the form of white spots or stains, so-called residues, deposits. This issue has become related to the current trend towards washing machines operated with less and less water per washing process for ecological reasons always be loaded full, reinforced.

Potential substitutes for the aluminosilicates were sought very early on. Simultaneously with the development of the water-insoluble zeolite NaA as a builder in this Context suggested, selected water-soluble amorphous sodium silicate to use compounds as builder substances in detergents or cleaning agents. Reference is made, for example, to US Pat. Nos. 3,912,649 (J.M. Huber Corp.), 3,956,467 (O. L. Bertorelli), 3,971,727 (J.M. Huber Corp.), and 3,879,527 (J.M. Huber Corp.). It contains amorphous sodium silicate compounds as builder substances described by spray drying aqueous water glass solutions, subsequent Grinding and subsequent compacting and rounding with additional water removal of the regrind are produced. According to EP-A-0 444 415 (Höchst) Detergent with 5 to 50 wt .-% of at least one surfactant, 0.5 to 60 wt .-% of one Builders and usual washing aids are proposed, with the mark in it lies in the fact that an amorphous, low-water sodium disilicate with a Water content of 0.3 to 6 wt .-% is used.

In the German patent application DE-A-22 40 309 (Unilever) a zeolite-free Described agent, which 5 to 40 wt .-% surfactant, 30 to 70 wt .-% alkali carbonate, 1st up to 30% by weight of complexing agents, preferably citrate, and 0.05 to 15% by weight of one Depositor for calcium carbonate contains. With this deposit preventer it is either a phosphate, a phosphonic acid or a polymer Carboxylate.

In the international application WO-A-96/17045 (Henkel) washing or Detergent with bulk weights above 600 g / l, which a Contain surfactant system and a builder system, in which zeolite completely or partially Sodium carbonate and amorphous silicate is replaced without causing difficulties comes from an application or process technology perspective, even during production this means by extrusion. This was achieved by using a restriction the content of zeolite (based on anhydrous active substance) to on average less than 19% by weight the content of the sum of sodium carbonate and amorphous sodium silicate (in each case based on anhydrous active substance) is 10 to 40% by weight, 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 at least partially in the form of granules.

In international application WO-A-98120105 (Procter & Gamble) a phosphate and aluminosilicate-free agent presented that alongside surfactants and polyethylene glycol Contains buildersystem based on carbonate, sulfate, silicate and polycarboxylate. benefits this means the price and the environmental behavior of the builder system. preferred Embodiments have a sodium carbonate to sodium sulfate ratio of 1: 1 to 1: 3 on.

From the international application WO-A-00/39261 (Henkel) is a zeolite-free Buildersystem known, which consists of alkali silicate, alkali carbonate, polymeric polycarboxylate with a Molar mass <10000 g / mol, phosphonate and an acidic component. This soluble builder system is dosed in low d. H. less than 40% by weight of the detergent are claimed by this builder system and the alkali product of this agent lies in the range of 7.0 to 11.4. Compared to a zeolite builder system this soluble builder system has advantages especially in residue behavior.

Now, however, it has been shown that even the complete waiver of the insoluble ones Aluminosilicate does not solve the deposit problem. It was even found that even with residue-free, aluminosilicate-free washing or cleaning agents deposits can occur under unfavorable circumstances. As the cause of this The silicates used were viewed as deposits. These have the unfavorable property, in alkaline, aqueous medium, especially under elevated Temperatures to partially hydrolyze and separate in the form of silica. As The result of this knowledge is currently in the development of washing or Next generation detergents that are not only phosphate and are free of aluminosilicate, but also the content of silicates or certain Silicates.

In international application WO-A-00/18859 (Procter & Gamble), for example the content of amorphous alkali silicate limited. A phosphate-free washing or detergent which has improved solubility and improved Has washing performance. The agent contains a special builder system and a special one Surfactant system. The builder system consists of at least two builders, one of which is partially or completely water-soluble and 60 to 100 wt .-% of the builder system constitutes, preferably crystalline alkali silicate with a layer structure. Another builder is water-insoluble and makes up 0 to 40% by weight of the builder system. Overall should less than 9% by weight aluminosilicate, preferably no aluminosilicate at all, and less than 5% by weight of amorphous alkali silicate can be contained in the agent. The Surfactant system comprises one or more surfactants, preferably an anionic alkyl sulfate and one anionic sulfonate or mixtures thereof, one of the surfactants with one of the partially or entirely water-soluble builders intimately mixed as particulate Component is present. The washing or cleaning agents disclosed in this application however, still contain large amounts of silicates, namely crystalline ones Phyllosilicates.

Now the omission of certain ingredients from washing or cleaning agents is not unproblematic, especially when it comes to structuring ingredients such as silicates and aluminosilicates. Without the structural support of silicates and Aluminosilicates tend to lubricate the surfactants from the chemical matrix, which is what industrial handling and processing of detergents or cleaning agents difficult. Oiling the surfactants also leads to unsightly stains on the packaging of the detergent or cleaning product, making the product less for the consumer makes you attractive. The particles of detergents or cleaning agents also have Oiling problems tend to clump together, making their use for the consumer makes it more difficult and uncomfortable. These problems are exacerbated by both increased temperatures and humidity, as well as with longer storage times. In addition, detergents or cleaning agents have no silicates and aluminosilicates poorer performance profiles because the particles can absorb less surfactant; to the harmful effects of water hardness on washing performance are still undermined the typical washing conditions in the private sector.

All of this shows that with the introduction of new builders or a new builder system, in which proven builder components have been dispensed with, the tensides or that Surfactant system normally has to be adapted to the new builder system. The Requirements for a suitable surfactant or surfactant system in a modern laundry or cleaning agents are as varied as those to the builder or the builder system. In addition to a favorable price / performance ratio, one complete and rapid biodegradability and favorable ecotoxicological Properties become high from modern surfactants or surfactant systems Potential synergy with surfactants and other ingredients expected, high wetting effect, good Solubility, favorable cold behavior, electrolyte compatibility, chemical stability and a suitable foaming behavior.

With regard to the foaming behavior, there are conflicting requirements modern washing or cleaning agents. On the one hand, there is a certain one Foam development with high foaming notes when washing delicate textiles desired, e.g. B. because the foam acts like an air cushion ("foam cushion") and so especially delicate textiles when washing mechanically Protects damage. However, the foam levels must not increase during washing be high, otherwise the primary washing performance with regard to certain soiling drops sharply. On the other hand, the foam should also be easy to rinse out, with low Foam notes when rinsing, otherwise the user after the rinsing process Remains of foam on the laundry when he opens his washing machine hang the laundry to dry or in a machine dryer give. The foam is often not only perceived visually, but also haptically, by making the laundry feel sticky and greasy. These foam residues can be found in particularly disadvantageous cases after drying in the form of visible Deposits on the laundry again.

This contradiction between relatively high foam notes when washing and loosening low foam notes during rinsing are known in the art mostly used foam regulators. In international application WO-A-98/27189 For example, a weakly acidic laundry detergent is described improved protection of fine textiles and improved removal of foam guaranteed that arises during rinsing during hand washing. Among other Ingredients, the detergent contains at least one active, pH sensitive foam regulator comprising a fatty acid. This fatty acid is during the Wash under mildly acidic conditions (pH 5.5 to 6.9) with regard to the Foam inactive, so that there is an acceptable foam behavior, but will Rinse with tap water (pH 7.5 to 8.5), whereby 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 act to suppress foam.

The object of the present invention was to provide a washing or cleaning agent To provide that has an improved foaming behavior. In particular, that should Adequate, advantageous foam height during the washing process develop, but the foam can be easily rinsed out during the rinsing process should.

Surprisingly, it has now been found that detergents or cleaning agents used in Disperse form little sediment, show the required foaming behavior. The present invention therefore relates to a particulate, aluminosilicate, silicate and phosphate-free washing or cleaning agent, its aqueous dispersion (8 g, 1 l, 20 ° C, 16 ° d) has a pH in the range from 6.5 to 9.5 and that during dispersion in tap water (8 g, 1 l, 20 ° C, 16 ° d, 20 min stirring, sedimentation time 24 h) Sedimentation volume of at most 0.5 ml.

The scientific connection between freedom from aluminosilicate and required foam behavior is z. Not fully understood at the moment. However, it will assumed that the zeolite particles have a foam-stabilizing effect and are therefore too bad rinse out foam. The scientific connection between Silicate freedom and the required foaming behavior is such. Not fully understood at the moment. On conceivable explanatory approach is that the initially dissolved silicates from washing or Cleaning agents of the prior art at least partially to silica hydrolyze, thereby forming silica particles, thereby - analogous to the Aluminosilicate particles - have a foam-stabilizing effect and thus lead to foam that is difficult to rinse out.

• - 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 von selbst ein.
• - verbessertes Ablagerungsverhalten
• - verbesserte Einspülbarkeit

The agent also has several advantages:

• - No special expensive surfactants are required, but a proven surfactant system can be used.
• - No additional foam regulators are required, the advantageous foam behavior sets itself.
• - Improved deposit behavior
• - Improved flushability

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

The agent according to the invention dissolves almost without sediment, has a advantageous foam development during the wash cycle and a washable Foam during the dilution and rinse cycles, and also has a good one Deposit behavior. Another advantage of the washing or Detergent consists in the significantly improved washability of the detergent machine washing or cleaning. An additional advantage of the agent according to the invention is the relatively low pH of the agents according to the invention, which is in the range from 7 to 9 lies, and which is particularly advantageous for washing or cleaning delicate Textiles. The details of these advantageous properties of the invention By means of the example on pages 31 ff.

The invention also relates to the use of the washing or Detergent for washing or cleaning textiles, especially for machine washing or cleaning textiles, especially delicate textiles. Under sensitive textiles are particularly within the scope of the present invention those made of wool, cotton, silk, linen and / or blended fabrics from the above understood materials mentioned, the focus being on textiles made of wool. Generally speaking, these delicate textiles are those whose Quality due to deposits with regard to e.g. B. Comfort, graying and Shrinkage suffers in particular.

Another object of the invention relates to the use of the invention Detergent or cleaning agent to reduce deposits when washing or Cleaning textiles, especially when washing or cleaning delicate ones Textiles.

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

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

• a) dissolving the washing or cleaning agent according to the invention in water,
• b) bringing the textiles into contact with the aqueous solution of the agent according to the invention,
• c) passing the aqueous solution of the agent according to the invention past the textiles or vice versa, either manually (as in the case of a hand wash) or by machine,
• d) removing the aqueous solution of the agent according to the invention from the textiles, rinsing several times with fresh tap water, ie rinsing,
• e) drying of the textiles.

In the context of the present inventions, “deposits” include all substances understood, which remain on the dry laundry after washing, the Remaining on the laundry is undesirable and deteriorates in quality of the laundry. This also includes so-called "residues". These are remnants of undissolved detergent or cleaning agent, which after washing on the dry laundry in the form of white spots or stains. root cause for residues is a bad, in the sense of too slow, solution kinetics of the detergent or cleaning agent used. The problem of residues is v. a. at the machine washing due to the current trend towards ever smaller amounts of water and sharpened to ever larger wash loads per wash.

"Incrustations" also fall under the "deposits". Under it sparingly soluble deposits on textile surfaces and / or surfaces of the machines (especially Heating rods) understood, especially when washing textiles under high Temperatures and alkaline conditions arise and harden and gray the Lead tissue.

In the following, "sediments" are understood to mean deposits that result as a result the "sedimentation", d. H. the movement of disperse particles in water under the influence gravity due to its higher density. Another name for Sediment is "removable substances". This is the collective name for suspended solids that are in a water sample at a certain time at the bottom of the Set down the measuring container and usually as a sedimentation volume per liter Water sample can be given. So they do not fall under the concept of sediments usual and unavoidable cloudiness of aqueous originating from the surfactants Detergent or cleaning agent solutions that do not sediment, d. H. drop.

In the following, "essentially dispersible without sediment" means that 8 g of the agent when dissolving or dispersing in tap water (1 L, 20 ° C, 16 ° dH, 20 min Stirring, sedimentation time 24 h) a sedimentation volume per liter of result in a maximum of 2 ml / L. The procedure for determining the sedimentation volume is described in more detail in the example on page 32.

In a preferred embodiment of the invention, the resolution or Disperse 8 g of the washing or cleaning agent according to the invention in Tap water (1 L, 20 ° C, 16 ° dH, 20 min stirring, sedimentation time 24 h) Sedimentation volume per liter of at most 0.2 ml / L and very particularly preferably of 0 ml / L.

The determination of the "foam notes" is described in more detail in the example on page 33. The Characterization of the foam behavior by specifying foam heights in Length dimensions such as B. cm is more common in the prior art, the use of However, foam notes advantageously lead to data that are easier to compare, especially in series tests. However, both dimensions are equivalent, since foam note and Foam levels increase with knowledge of the washing machine dimensions, especially the Bull's-eye dimensions, convert to each other.

• a) eine oder mehrere Alkalitätsquelle(n),
• b) ein oder mehrere pH-Kontrollmittel
• c) ein oder mehrere Cobuilder und
• d) gegebenenfalls ein oder mehrere Calciumcarbonat-Ablagerungsverhinderer.

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

• a) one or more sources of alkalinity,
• b) one or more pH control agents
• c) one or more cobuilders and
• d) optionally one or more calcium carbonate deposition inhibitors.

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

Suitable sources of alkalinity are e.g. B. alkali metal carbonate, alkali metal bicarbonate, Alkali metal sesquicarbonate and / or mixtures thereof. However, are preferred Sodium carbonate, sodium hydrogen carbonate and / or sodium sesquicarbonate, where Sodium carbonate is particularly preferred. That or the alkalinity sources make about 10 to 30% by weight, preferably 15 to 25% by weight, of the total agent according to the invention and about 35 to 75% by weight, preferably 50 to 60% by weight, of the builder system.

The pH control agents perform an important role as an organic builder and Setting a pH value suitable for the invention. Come as a pH control agent especially monomeric organic polycarboxylic acids in question, whereby under Polycarboxylic acids are understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, Malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided its use is not due to ecological reasons is objectionable, and mixtures of these. Are preferred in this context Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any Mixtures of these. Citric acid is particularly preferred. The above 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 contain these pH control agents in amounts of 0.5 to 25% by weight, preferably in amounts of 5 to 20% by weight, particularly preferably in amounts of 7.5 to 15% by weight based on the total mean. The pH control agents thus make up 25 to 65% by weight, preferably from 35 to 45% by weight of the builder system.

Polymeric polycarboxylates are suitable as cobuilders according to the invention. these are for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molar mass of 500 to 70,000 g / mol.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, can In this group, the short-chain polyacrylates, the molecular weights of 2000 to 10000 g / mol, particularly preferably from 3000 to 5000 g / mol.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid or acrylic acid or methacrylic acid with maleic acid. As Copolymers of acrylic acid with maleic acid, the 50th contain up to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative Molar mass, based on free acids, is generally from 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol. The (co-) polymeric polycarboxylates can be either as a powder or as an aqueous solution be used.

In the context of the present invention, mixtures of short-chain homopolymeric polyacrylates with molecular weights of 10,000 g / mol and below with long-chain copolymeric polycarboxylates with molar masses of 20,000 to 70,000 g / mol in the ratio 2: 1 to 1:20, particularly preferably in a ratio of 1: 1 to 1:15.

To improve water solubility, the polymers can also allylsulfonic acids, such as for example in EP-B-0 727 448, allyloxybenzenesulfonic acid and Contain methallylsulfonic acid as a monomer.

Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which according to DE-A-43 00 772 as Monomeric salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of Acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.

Further preferred copolymers are those described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 are described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate contain.

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Are particularly preferred Polyaspartic acids or their salts and derivatives, of which in the German Patent application DE-A-195 40 086 discloses that they are in addition Co-builder properties also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are produced by the implementation of Dialdehydes can be obtained with polyol carboxylic acids having 5 to 7 carbon atoms and have at least 3 hydroxy groups, for example as described in the European patent application EP-A-0 280 223. Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from Obtained polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates by partial hydrolysis of Strengths can be obtained. The hydrolysis can be carried out according to conventional, for example acid or enzyme-catalyzed processes are carried out. It is preferably are hydrolysis products with average molecular weights in the range from 400 to 500000 g / mol. Here is a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30, preferably, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose, which is a DE out of 100. Both maltodextrins with a DE between 3 and 20 can be used and dry glucose syrups with a DE between 20 and 37 as well as so-called Yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol. A preferred dextrin is described in British patent application 94 19 091.

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. Such oxidized dextrins and processes for their preparation are known in particular from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and from international patent applications WO-A-92/18542, WO-A-93108251, WO-A-93/16110, WO-A-94/28030, WO-A-95107303, WO-A-95112619 and WO-A-95/20608 are known , An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates are also preferred Ethylene diamine disuccinate are other suitable co-builders. Doing so Ethylene diamine N, N'-disuccinate (EDDS), the synthesis of which is described, for example, in US Pat. No. 3,158,615 is described, preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and are also preferred in this context Glycerol trisuccinates, as described, for example, in US Pat. Nos. 4,524,009 and US-A-4,639,325, in European patent application EP-A-0 150 930 and in Japanese patent application JP-A-93 / 339,896.

Other useful organic co-builders are, for example, acetylated Hydroxycarboxylic acids or their salts, which may also be in lactone form and which have at least 4 carbon atoms and at least one Contain hydroxy group and a maximum of two acid groups. Such will be co-builders described for example in the international patent application WO-A-20029.

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

In addition, all compounds that are able to complex with To form alkaline earth metal ions can be used as co-builders.

The detergents or cleaning agents according to the invention can optionally have one or contain several calcium carbonate deposit inhibitors, it being preferred to phosphonates, in particular to hydroxyalkane or Aminoalkanephosphonate is. This is among the hydroxyalkane phosphonates 1-Hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a co-builder. It is preferably called Sodium salt used, the disodium salt being neutral and the tetrasodium salt reacts alkaline (pH = 9). Preferred aminoalkane phosphonates are Ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral-reacting sodium salts, for example as the hexasodium salt of EDTMP or as the hepta and octasodium salt of DTPMP. As a builder HEDP is preferably used from the class of the phosphonates. The Aminoalkanephosphonates also have a strong ability to bind heavy metals. Accordingly, especially if the agents according to the invention also contain bleach, be preferred to use aminoalkanephosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned. The phosphonates are in however, the agents according to the invention only in small amounts, between 0.1 and 2% by weight, based on the total mean.

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 is preferably 5 up to 25% by weight, in particular 10 to 20% by weight, of the total composition.

Suitable anionic surfactants are e.g. B. Sulfonate type surfactants. Cumene sulfonate, C _10-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C _12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide are preferred and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of 2-sulfofatty acids (ester sulfonates), for example the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

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

The alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C _12-18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C _10-20 oxo alcohols and those Half-secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C _12-15 alkyl sulfates as well as C _14-15 alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol ethylene oxide, such as 2-methyl branched C _9-11 alcohols with an average of 3.5 mol ethylene oxide (EO) or C _12-18 - Fatty alcohols with 1 to 4 EO are suitable.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Are suitable 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 from natural Fatty acids, for example coconut, palm kernel or tallow fatty acids, derived Soap mixtures.

The anionic surfactants including the soaps can 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 in the form of their Sodium or potassium salts, especially in the form of the sodium salts. In another Embodiments of the invention are surfactants in the form of their magnesium salts used.

According to the invention, however, linear alkylbenzenesulfonates such as, for. B. the linear C _10-13 alkylbenzenesulfonates. The anionic surfactant content of the agents according to the invention is 5 to 30% by weight, preferably 7.5 to 25% by weight, particularly preferably 10 to 20% by weight, based on the total agent. The surfactant system thus preferably consists of 60 to 95% by weight, particularly preferably 70 to 90% by weight, of anionic surfactant.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated or propoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 80, preferably 3 to 12, moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferred can be methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. Examples of the fatty alcohols are, from the point of view of the availability of the compounds, lauryl alcohol (C ₁₂ ), myristyl alcohol (C ₁₄ ), cetyl alcohol (C ₁₆ ) etc. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 C atoms are used for Example from coconut, palm, tallow or oleyl alcohol, and an average of 1 to 80, preferably 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol 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 _16-18 alcohols with 5 EO and mixtures thereof, 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 averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO, 40 EO or up to 80 EO.

However, C _12-18 alcohols with 7 EO and C _16-18 alcohols with 5 EO, and mixtures of these, have proven particularly suitable as nonionic surfactants for the present invention.

Another class of preferably used nonionic surfactants, which either as sole nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 8 carbon atoms in the Alkyl chain and 3 to 80, preferably up to 20 alkoxy groups, preferably ethoxy groups in the Molecule, especially fatty acid methyl ester, such as that found in Japanese Patent application JP 58/217598 are described or which are preferred according to the in the international patent application WO-A-90113533.

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

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the Fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than that Half of it.

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


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

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


in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -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 propylated Derivatives of this rest.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy substituted compounds can then, for example according to the teaching of international application WO-A-95107331 by implementation with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

From a practical point of view, it will be advantageous to consider that such connections from the above groups can be used, even with larger ones Chain lengths at application temperatures are still liquid to pasty.

In the present invention, the nonionic surfactants are used alone or in a mixture, and advantageously so that the total nonionic surfactant content of the invention Detergent or cleaning agent is 1 to 10% by weight, preferably 2 to 5% by weight, or the surfactant system 5 to 25 wt .-%, preferably 10 to 20 wt .-%, at least one Contains nonionic surfactants.

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

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

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

In a particular embodiment, the washing or Detergent in particulate form, especially in the form of powders, extrudates, Granules and / or mixtures thereof.

The detergents or cleaning agents according to the invention can, in addition to the above mentioned ingredients still all known and usual in detergents and cleaning agents Ingredients such as enzymes, dyes, optical brighteners, UV protection substances, fragrances and perfumes, perfume carriers, anti-redeposition agents, Graying inhibitors, color transfer inhibitors, corrosion inhibitors, bleaching agents, bleach activators, Softening agents and fabric softeners included. The agents preferably contain however, with regard to the protection of sensitive textiles, no bleach and Bleach activators. The other ingredients mentioned are preferably in amounts of 2 to 40 wt .-%, in particular in amounts of 10 to 30 wt .-%, based on the Total weight of the agent according to the invention.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.

Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate; (b) the aliphatic or substituted aliphatic peroxyacids such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamido operadipic acid and N-nonenylamide; and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-diap (6 ) can be used.

In principle, chlorine or bromine-releasing substances can also be used as bleaching agents 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-chloramides, such as trichloroisocyanuric acid, Tribromo isocyanuric acid, dibromo isocyanuric 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.

Bleach activators can also be incorporated into the agents according to the invention his. As bleach activators can be compounds that are under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid used become. Substances containing O- and / or N-acyl groups of the C- Bear atomic number and / or optionally substituted benzoyl groups. Are preferred polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n- Nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

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

With regard to the use of the washing or cleaning agents according to the invention However, washing or cleaning delicate textiles may be preferred None of the bleaches mentioned above and none of the above Bleach activators included.

Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. Are particularly well suited Strains of bacteria or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus-derived enzymatic agents. Proteases are preferably from Subtilisin type and in particular proteases derived from Bacillus lentus, used. Enzyme mixtures, for example of protease and amylase or Protease and lipase or protease and cellulase or from cellulase and lipase or from Protease, amylase and lipase or protease, lipase and cellulase, but especially mixtures of cellulase of particular interest. Peroxidases or Oxidases have been found to be suitable in some cases. The enzymes can Carriers can be adsorbed and / or embedded in coating substances to protect them against premature To protect decomposition.

Further additives conceivable in washing or cleaning agents according to the invention are foam inhibitors such as, for example, foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane. Mixtures of these active ingredients are also possible. Additives which are solid at room temperature, in particular in the case of the foam-inhibiting active substances mentioned, paraffin waxes, silicas which can also be hydrophobicized in a known manner, and bisamides derived from C _2-7 diamines and C _12-22 carboxylic acids are suitable.

For use in the washing or cleaning agents according to the invention upcoming foam-inhibiting paraffin oils, which are mixed with paraffin waxes can be present, generally make complex mixtures without sharp Melting point. For characterization, the melting range is usually determined by Differential thermal analysis (DTA) as described in "The Analyst" 87 (1962), 420, and / or the freezing point. This is the temperature at which the Paraffin changes from the liquid to the solid state by slow cooling. Paraffins with less than 17 carbon atoms cannot be used according to the invention, their proportion in the paraffin oil mixture should therefore be as low as possible and is preferred below that with usual analytical methods, for example gas chromatography, significantly measurable limit. Paraffins are preferably used in the range solidify from 20 ° C to 70 ° C. It should be noted that even at room temperature appearing paraffin wax mixtures different proportions of liquid paraffin oils can contain. The paraffin waxes which can be used according to the invention are the Liquid content at 40 ° C as high as possible without already being 100% at this temperature. Preferred paraffin wax mixtures have a liquid content of at least 40 ° C 50% by weight, in particular from 55% by weight to 80% by weight, and one at 60 ° C. Liquid content of at least 90 wt .-%. As a result, the paraffins at Temperatures down to at least 70 ° C, preferably down to at least 60 ° C are flowable and pumpable. It is also important to ensure that the paraffins if possible contain no volatile components. Preferred paraffin waxes included less than 1% by weight, in particular less than 0.5% by weight at 110 ° C. and Parts that can be evaporated at normal pressure. Paraffins which can be used according to the invention can for example under the trade names Lunaflex® from Fuller and Deawax® from DEA Mineralöl AG.

The paraffin oils can solid bisamides at room temperature, which differ from saturated Fatty acids with 12 to 22, preferably 14 to 18 C atoms and alkylene diamines with 2 derive up to 7 carbon atoms. Suitable fatty acids are lauric, myristic, stearic, Arachinic acid and behenic acid as well as their mixtures, as they come from natural fats or hardened oils, such as tallow or hydrogenated palm oil, are available. suitable Diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylene diamine, Pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine. Preferred diamines are ethylenediamine and hexamethylenediamine. Particularly preferred Bisamides are bis-myristoyl-ethylenediamine, bis-palmitoyl-ethylenediamine, Bis-stearoyl-ethylenediamine and their mixtures and the corresponding derivatives of Hexamethylenediamine.

Furthermore, dyes, in particular water-soluble or water-dispersible Dyes are incorporated. Dyes such as those used for improvement are preferred here the optical product appearance in detergents and cleaning agents is usually used become. The selection of such dyes presents no problem for the person skilled in the art especially since such conventional dyes have a long shelf life and Insensitivity to the other ingredients of the detergent preparations and to To have light as well as no pronounced substantivity towards textile fibers not to stain.

Examples of optical brighteners are derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Are suitable for. B. salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or a similar structure Compounds which instead of the morpholino group a diethanolamino group, a Methylamino group, an anilino group or a 2-methoxyethylamino group wear. In addition, brighteners of the substituted diphenylstyryl type can be used in the Washing or cleaning agents according to the invention may be included, for. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

Another preferred group of additives according to the invention are UV protection substances. These are substances that are involved in the washing process or in the subsequent fabric softening process are released in the wash liquor and which are on the Accumulate the fiber in order to achieve a UV protection effect. Are suitable the products of the company Ciba which are commercially available under the name Tinosorb Specialty Chemicals.

Another class of common detergent or cleaning agent ingredients that According to the invention, polymers can be added. Come under these polymers on the one hand polymers in question when washing or cleaning or rinsing Show cobuilder properties. These have already been described in detail above.

Another group of polymers are graying inhibitors. These have the Task, the detached from the hard surface and especially from the textile fiber Keep dirt in the fleet and support the co-builder. Water-soluble colloids of mostly organic nature are suitable for this, for example glue, Gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or Cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also Water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, starch products other than those mentioned above can be used for Example aldehyde starches. Cellulose ethers such as carboxymethyl cellulose are preferred (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as Methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their Mixtures, for example in amounts of 0.1 to 5% by weight, based on the total Means used.

The detergents or cleaning agents can also be used as further additives according to the invention Antiredeposition agents, so-called Soil Repellents, contain. These are polymers that on fibers or hard surfaces and there a re-soiling counteract. This effect is particularly evident when a textile is soiled, already several times with a detergent according to the invention that this oil and contains fat-dissolving component. Among the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as Methyl cellulose and methyl hydroxypropyl cellulose with a methoxy group content of 15 up to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic cellulose ether, as well as those known from the prior art Polymers of phthalic acid and / or terephthalic acid or of their Derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Of these, the sulfonated derivatives of phthalic and are particularly preferred Terephthalic acid polymers.

Further, in the washing or cleaning agents according to the invention in question Polymers are color transfer inhibitors. These include in particular Polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and Copolymers of vinyl pyrrolidone with vinyl imidazole.

In addition, the washing or cleaning agents according to the invention can also Contain fragrances and fragrance preparations (perfumes). As perfume oils or fragrances individual fragrance compounds can be used, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and type Hydrocarbons. Fragrance compounds of the ester type are, for example, benzyl acetate, Phenoxyethyl isobutyrate, p-t-butylcyclohexyl acetate, linalyl acetate, Dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Count among the ethers for example benzyl ethyl ether. The aldehydes include e.g. B. linear alkanals with 8 to 18 Carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lileal and Bourgeonal.

The ketones include the ionones, α-isomethyl ionone, and methyl cedryl ketone. To the Alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and Terpineol. The hydrocarbons mainly include terpenes such as limonene and Pinene. Mixtures of different odoriferous substances are preferably used are coordinated so that together they produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures such as those from vegetable sources are accessible. Examples are pine, citrus, jasmine, patchouli, Rose or ylang-ylang oil. Nutmeg oil, sage oil, chamomile oil, Clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, Olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, Orange peel oil and sandalwood oil.

It may be advantageous to apply the fragrances to carriers that detract from the adhesion of the Increase perfumes on the laundry and by a slower fragrance release for long-lasting fragrance of the textiles. As such carrier materials have become for example, cyclodextrins have proven successful. The cyclodextrin-perfume complexes can additionally can be coated with other auxiliaries.

The detergents or cleaning agents according to the invention can be used to protect the washing or wash items or machine corrosion inhibitors, where Silver protection agents have a special meaning in the field of automatic dishwashing. In general, silver protection agents selected from the group of triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the Transition metal salts or complexes are used. Particularly preferred to benzotriazole and / or alkylaminotriazole are used. One finds in In addition, detergent formulations often contain active chlorine agents that corrode the Can significantly reduce silver surface. In chlorine-free cleaners, especially oxygen and nitrogen-containing organic redox-active compounds, such as divalent and trivalent Phenols, for example hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, Phloroglucin, 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. The transition metal salts are preferred here, which are selected from the group of manganese and / or cobalt salts and / or - complex, particularly preferably the cobalt (ammin) complexes, the Cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and Manganese sulfate. Zinc compounds can also be used to prevent corrosion on Washware can be used.

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


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

Compounds of formula (II) are so-called ester quats. Esterquats are characterized by excellent biodegradability. Here R ^{4 represents} an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds; R ⁵ stands for H, OH or O (CO) R ⁷ , R ⁶ independently of R ^{5 stands} for H, OH or O (CO) R ⁸ , where R ⁷ and R ⁸ each independently represent an aliphatic alkyl radical with 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. m, n and p can each independently have the value 1, 2 or 3. X can be either a halide, methosulfate, methophosphate or phosphate ion, as well as mixtures thereof. Compounds are preferred which contain the group O (CO) R ⁷ for R ⁵ and alkyl radicals having 16 to 18 carbon atoms for R ⁴ and R ⁷ . Compounds in which R ^{6 is} also OH are particularly preferred. Examples of compounds of the formula (II) are methyl N- (2-hydroxyethyl) -N, N-di (tallow acyl oxyethyl) ammonium methosulfate, bis (palmitoyl) ethyl hydroxyethyl methyl ammonium methosulfate or methyl -N, N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate. If quaternized compounds of the formula (11) are used which have unsaturated alkyl chains, preference is given to the acyl groups whose corresponding fatty acids have an iodine number between 5 and 80, preferably between 10 and 60 and in particular between 15 and 45 and which have a cis / trans isomer ratio (in% by weight) of greater than 30:70, preferably greater than 50:50 and in particular greater than 70:30. Commercial examples are the methylhydroxyalkyldialkoyloxyalkylammonium methosulfates sold by Stepan under the trademark Stepantex® or the products from Cognis known under Dehyquart® or the products from Goldschmidt-Witco known under Rewoquat®. Further preferred compounds are the diesterquats of the formula (III), which are available under the names Rewoquat® W 222 LM or CR 3099 and, in addition to the softness, also ensure stability and color protection.

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

In addition to the quaternary compounds described above, other known compounds can also be used, such as quaternary imidazolinium compounds of the formula (IV),


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

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, R ¹⁵ and R ¹⁶ each independently represent a C _8-28 alkyl group and r is a number between 0 and 5 is.

In addition to the compounds of the formulas (I) and (II), short-chain, water-soluble, quaternary ammonium compounds are used, such as Trihydroxyethylmethylammonium methosulfate or the alkyltrimethylammonium chlorides, Dialkyldimethylammoniumchloride and Trialkylmethylammoniumchloride, e.g. B. cetyltrimethylammonium chloride, Stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and Tricetylmethylammonium chloride.

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

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

Suitable cationic polymers include the polyquaternium polymers as they are in the CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997), in particular the polyquaternium-6, also known as merquats, Polyquaternium 7, polyquaternium 10 polymers (Ucare Polymer IR 400; Amerchol), Polyquaternium-4 copolymers, such as graft copolymers with a cellulose skeleton and quaternary Ammonium groups bound via allyldimethylammonium chloride are cationic Cellulose derivatives, such as cationic guar, such as guar hydroxypropyltriammonium chloride, and similar quaternized guar derivatives (e.g. Cosmedia Guar, manufacturer: Cognis GmbH), cationic quaternary sugar derivatives (cationic alkyl polyglucosides), e.g. B. that 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 Copolymers.

Polyquaternized polymers (e.g. Luviquat Care from BASF) and also cationic chitin-based biopolymers and their derivatives, for example that Polymer available under the trade name Chitosan® (manufacturer: Cognis).

Also suitable according to the invention are cationic silicone oils such as those in the Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized Trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) Abil®-Quat 3270 and 3272 (manufacturer: Goldschmidt-Rewo; diquatary polydimethylsiloxanes, quaternium-80), and silicone quat Rewoquat® SQ 1 (Tegopren® 6922, manufacturer: Goldschmidt-Rewo).

Compounds of the formula (VI) can also be used,


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

Examples

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

The two agents were compared with regard to their sedimentation behavior, their deposition behavior, investigated their foaming behavior and their flushability. The carried out Measurements are described in more detail below.

1. Sedimentation behavior

8 g of agent E or V were at 20 ° C in 1 L tap water with a hardness of 16 ° dH Stirring (20 minutes) dissolved or dispersed. The resulting solutions or Dispersions were filled into funnel-shaped glass jars, which were calibrated to 0.01 ml had exact scaling. The solutions or dispersions then became Sedimentation left alone. After 24 h, the sedimentation volume was reduced Read off using the calibrated ml scale.

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

2. Deposition behavior

To determine the deposit behavior in the "Black Fabric Test", 8 g of the agent E or V at 20 ° C in 1 L tap water hardness 16 ° dH with stirring (1.5 minutes, 800 rpm with laboratory stirrer / propeller stirring head 1 Centered 5 cm from the bottom of the vessel) dissolved or dispersed. The resulting solutions or dispersions were filtered through black tissue. For this purpose, the tissue was clamped between a frit bottom and a vertically fastened glass tube with a diameter of 5 cm, so that a filter surface with a diameter of 5 cm was present. The filtration took place solely under the influence of gravity. The fabric was made of 100% cotton rib knit with the edge dimensions 16 cm. 16 cm and a weight of 8.5 g. The filter residues were left on the fabric, dried and visually examined by 3 different people according to Table 2 and graded accordingly. The criterion for the rating was the degree of coverage of the filter surface with filter residue. The grades of the 3 different people were added and divided by 3. Table 2 Rating of the filter residue by visual inspection optical impression grade No backlog 0 Little residue 1 clearly visible residue 2 Clearly visible residue that covers more than half of the filter surface 3 Almost complete coverage with residue 4 Complete, closed coverage with residue 5 Very heavy covering with residue 6

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

3. Foam behavior

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

The foam height was assessed with a foam note each time the washing machine was at a standstill, specifically during the wash cycle, when diluting (after the water supply), during the 1st, 2nd and 3rd rinsing (each after the water supply). Table 4 Assessment of foam behavior in the form of foam notes

It can be seen that the agent E according to the invention has a high level as desired Foam note during washing, which protects the laundry and one low foaming note after the last rinsing, which means good rinsability comes. The comparison means V, however, also has a favorable high Foam note when washing on, but this is still after the last rinse unacceptably high, which equates to poor flushability.

In summary, it can be said that the agent according to the invention is a had less sediment volume than the comparative, i.e. H. it contained less poorly soluble components. Both the deposition behavior and the foaming behavior especially when rinsing were rated better with the agent according to the invention than with Comparison means. So while there is enough foam during the actual washing process is available to gently clean even delicate textiles ensure that the foam note after the rinses is very low, so the foam can be rinse well; at the same time, they form only to a much lesser extent than with Comparative means of undesirable deposits on the laundry. By using the Buildersystems according to the invention is consequently both the foam and the Deposition behavior positively influenced.

Claims (17)

1. Particulate, aluminosilicate, silicate and phosphate-free washing or cleaning agent, the aqueous dispersion (8 g, 1 l, 20 ° C, 16 ° d) has a pH in the range from 6.5 to 9.5 , characterized in that when dispersed in tap water (8 g, 1 l, 20 ° C, 16 ° d, 20 min stirring, sedimentation time 24 h) it has a sedimentation volume of at most 0.5 ml. 2. Detergent or cleaning agent according to claim 1, characterized in that it when dispersing in tap water (8 g, 1 l, 20 ° C, 16 ° d, 20 min stirring, Sedimentation time 24 h) a sedimentation volume of at most 0.2 ml and preferably 0 ml having. 3. washing or cleaning agent according to claim 1 or 2, characterized in that whose aqueous dispersion (8 g, 1 l, 20 ° C, 16 ° d) has a pH in the range of 7.0 to 9.0, preferably from 7.5 to 8.5. 4. washing or cleaning agent according to one of claims 1 to 3, characterized in that it a) 15 to 35% by weight, preferably 20 to 30% by weight, of a builder system and b) 5 to 25 wt .-%, preferably 10 to 20 wt .-%, of a surfactant system. 5. washing or cleaning agent according to claim 4, characterized in that the builder system a) 35 to 75% by weight, preferably 50 to 60% by weight, of at least one source of alkalinity, b) 25 to 65% by weight, preferably 35 to 45% by weight, of at least one pH control agent, c) 0.5 to 12% by weight, preferably 3 to 7.5% by weight, of at least one organic co-builder, d) 0 to 3% by weight, preferably 0 to 2% by weight, of at least one complexing agent and e) contains no phosphate, no aluminosilicate and no silicate, in each case based on the entire builder system. 6. washing or cleaning agent according to claim 5, characterized in that it is the source of alkalinity is alkali metal carbonate, alkali metal hydrogen carbonate and / or alkali metal sesquicarbonate, preferably sodium bicarbonate and / or sodium sesquicarbonate, particularly preferably sodium carbonate. 7. washing or cleaning agent according to claim 5 or 6, characterized in that the pH control agent is at least one monomeric organic Polycarboxylic acid. 8. washing or cleaning agent according to claim 7, characterized in that the monomeric organic polycarboxylic acid is selected from the group citric acid, Adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids and / or nitrilotriacetic acid and / or their salts, preferably from the group citric acid, succinic acid, glutaric acid, Adipic acid and / or gluconic acid and / or their salts, citric acid and / or their salts are particularly preferred. 9. washing or cleaning agent according to one of claims 1 to 8, characterized characterized in that the organic co-builder is at least one polymeric Polycarboxylic acid and / or its partially or completely neutralized metal and / or ammonium salt (s), preferably their alkali metal salt (s), particularly preferred the sodium salt (s) and / or mixtures thereof. 10. washing or cleaning agent according to claim 9, characterized in that it is in the case of the polymeric polycarboxylic acid and / or its partially or completely neutralized metal and / or ammonium salt (s) with homopolymeric polyacrylic acids Molar masses ≤ 10000 g / mol, preferably with molar masses ≤ 5000 g / mol, and / or around copolymeric polycarboxylic acids with molecular weights of 20,000 to 70,000 g / mol, preferred from 20,000 to 50,000 g / mol, particularly preferably from 30,000 to 40,000 g / mol, in each case measured against polyacrylate as a standard, and / or mixtures thereof. 11. Detergent or cleaning agent according to one of claims 1 to 10, characterized characterized in that the complexing agent is at least one phosphonate is. 12. Detergent or cleaning agent according to one of claims 1 to 11, characterized in that the surfactant system a) 60 to 95% by weight, preferably 70 to 90% by weight, of at least one anionic surfactant, b) 5 to 25% by weight, preferably 10 to 20% by weight, of at least one nonionic surfactant, in each case based on the entire surfactant system. 13. washing or cleaning agent according to claim 12, characterized in that the anionic surfactants are selected from the group linear C _10-13 alkylbenzenesulfonates, C _12-18 disulfonates, C _12-16 alkanesulfonates, C _8-20 -α Sulfo fatty acid esters, sulfonated C _6-22 fatty acid glycerol esters, C _12-18 alk (en) yl sulfates, C _10-20 oxoalk (en) yl sulfates, 2,3-alkyl sulfates, C _7-21 fatty alcohol (glycol ether) _{3, 5} sulfates, C _8-18 alkyl sulfosuccinic esters, sarcosides, sarcosinates, C _12-22 fatty acid soaps, preferably from the group linear C _10-13 alkyl benzene sulfonates, C _12-22 fatty acid soaps. 14. Detergent or cleaning agent according to claim 12 or 13, characterized in that the nonionic surfactants are selected from the group C _8-18 fatty alcohols 1-12 EO, alkyl glycosides of the formula RO (G) _1-10 , C _12-18 - 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 agent according to one of claims 1 to 14, characterized characterized in that it is in particulate form, preferably in the form of powders, extrudates, Granules and / or mixtures thereof, particularly preferably in the form of powders. 16. Use of the washing or cleaning agent according to one of claims 1 to 15 for washing or cleaning textiles, preferably delicate textiles. 17. Use according to claim 16, characterized in that it is in the delicate textiles around textiles made of wool, cotton, silk, linen, viscose and / or blended fabrics of these, preferably wool.