DE102006015837A1 - Dirt-repellent particles for use as additives in detergents, care materials and cleaning materials, contain polyethylene glycol and an amphiphilic polyester, especially e.g. polyethylene glycol terephthalate - Google Patents

Abstract

u Dirt-repellent particles (I) suitable for use as additives in detergents, care materials and/or cleaning materials (II), comprise 1-70 wt% polyethylene glycol (PEG) and 30-99 wt% amphiphilic polymer(s) (AMPP) containing ester units derived from 2-4C alkylene glycol and/or poly-(2-4C alkylene)-glycol with aromatic dicarboxylic acids. u Independent claims are included for (1) finished products, especially (II) as above, containing 0.01-30 (preferably 3) wt% (I) (2) a method for the production of (I) by heating solid PEG and PEG terephthalate to form a sprayable material, spraying this material with water into a fluidised bed and then solidifying the material .

Description

The The present invention relates to particles having soil repellents Effect based on polyethylene glycol and amphiphilic polymer, in particular polyethylene glycol terephthalate, suitable as an additive in detergents and / or cleaners, comprising a finished product these particles as well as a process for producing the particles.

Soil release polymers have been the subject of intensive development work for many years and are also used today as so-called washing aids in detergents and cleaners for household linen. Common names for such Substances with a soil-repelling effect are "soil release polymers" or "soil repellents". They prevent For example, when washing textiles the redeposition of Dirt on the textile.

That's how it describes US 5,652,283 A. already a process for the preparation of finely divided mixtures of amphiphilic polymers and polycarboxylates and the use of the mixtures as an additive to detergents.

• (a) wäßrige Dispersionen oder kolloidale wäßrige Lösungen mindestens eines amphiphilen Polymers und
• (b) eine wäßrige Lösung eines Polycarboxylats im Gewichtsverhältnis (a) : (b) von 1 : 1 bis 1 : 20, jeweils bezogen auf die Feststoffe, gemischt und die so erhältlichen Dispersionen durch Sprühtrocknung zu einer feinteiligen Polymermischung verarbeitet.

After in the US 5,652,283 A. described method for the preparation of finely divided mixtures

• (A) aqueous dispersions or colloidal aqueous solutions of at least one amphiphilic polymer and
• (B) an aqueous solution of a polycarboxylate in the weight ratio (a): (b) from 1: 1 to 1: 20, in each case based on the solids, mixed and the dispersions thus obtainable by spray drying to form a finely divided polymer mixture.

finely divided However, polymer blends have the disadvantage that these as Blends in finished products no uniform distribution of finely divided mixtures of amphiphilic polymers and polycarboxylates guarantee. Due to mechanical influences, especially during transport, it can lead to a separation of finely divided mixtures from amphiphilic polymers and polycarboxylates in the finished product come.

After US 5,652,283 A. Amphiphilic polyesters are usually incorporated in the form of aqueous solutions or dispersions in the detergent formulations. However, this form of application is often impractical or even inappropriate. For example, most dispersions of such amphiphilic polyesters can not be processed in concentrations above 25% by weight at room temperature because the viscosity is too high.

For the production of free-flowing powders or granules from aqueous dispersions of amphiphilic polyester by spray drying, is in the US 5,652,283 A. proposed to choose a weight ratio of the amphiphilic polymers and polycarboxylates of 1: 1 to 1:20. The disadvantage is that the high Polycarboxylatanteil leads to very hard finely divided particles, which on the one hand promotes the tendency to segregation and on the other hand with larger particles, a poorer solubility of such particles in the aqueous application liquor by itself.

task It is the object of the present invention to repel particles with dirt Effect available too which, for example, has no or a marked reduction Tendency to segregate, for example in detergents and / or cleaning agents show, and / or at the same time a good solubility in the aqueous Have application fleet and / or a good homogeneous distribution have the components contained in the particles.

To achieve the above object according to the invention particles with dirt-repellent effect, suitable as an additive in detergents and / or cleaning products, provided, wherein the particles, based on the total weight of the particles, as components 1 wt .-% to 70 wt. -% polyethylene glycol and 30 wt .-% to 99 wt .-% of at least one amphiphilic polymer comprise, wherein the amphiphilic polymer ester units of C ₂ - to C ₄ -alkylene glycol and / or C ₂ - to C ₄ -polyalkylene glycol having aromatic dicarboxylic acids and wherein the components are chosen so that the total weight of the components does not exceed 100% by weight.

The term "amphiphilic polymer" in the meaning of the present invention in relation to the particles of the invention has the meaning and is used as a short name for "amphiphilic polymer, wherein the amphiphilic polymer ester units of C ₂ to C ₄ alkylene glycol and / or C ₂ to C ₄ -polyalkylene glycol with aromatic dicarboxylic acids ".

particle with dirt-repellent effect according to the present invention Prevent redeposition when washing textiles, for example of dirt on the textile material. Without being bound to a particular theory to be able to the particles with dirt repellent effect the treated surfaces dirt give repellent properties, for example by a dirt repellent equipment of surfaces like textiles. Alternatively or additionally, particles with dirt repellent Effect according to the present Invention in the aqueous Add to application fleet dirt, so as to reincorporate of contaminants to be cleaned soft or hard surface, in particular Textiles, to prevent.

The Particle with dirt-repellent effect according to the present invention can have a very high active content of amphiphilic polymer.

Especially It is advantageous that the particles according to the invention are homogeneous Distribution of the components contained in the particles, such as polyethylene glycol, amphiphilic polymer. This promotes for example, a good dispersibility of the amphiphilic polymer in the application fleet.

One Another advantage of the particles with dirt-repellent effect, that the combination of polyethylene glycol and amphiphilic polymer the particles have a high solubility gives. This is particularly advantageous for larger particles.

Yet An advantage is that the particles have a dirt repellent effect according to the present Invention in finished products based on particles, such as detergents, have no or only a slight tendency to segregation.

Around a good water solubility the particles of the invention to ensure It has been shown that the polyethylene glycol content of the particles important is. It has turned out to be advantageous to one good flowability To ensure the particle with dirt-repellent effect and yet the segregation of the particles according to the invention in a particulate finished product prevent or significantly reduce when the particles contain sufficient amounts of polyethylene glycol. It is preferred when the particles according to the invention, based on the total weight of the particles, polyethylene glycol with a proportion by weight of 5 wt .-% to 45 wt .-%, preferably from 10 wt .-% to 40 wt .-%, preferably from 15 wt .-% to 30 wt .-% and most preferably from 20% to 25% by weight.

A good processability and good sprayability of the components of the particles according to the invention In the preparation of the particles according to the invention, it is possible to obtain when the polyethylene glycol has a melting temperature of ≥ 40 ° C and ≤ 100 ° C, preferably of ≥ 45 ° C and ≤ 70 ° C, preferred of ≥ 50 ° C and ≤ 65 ° C and on most preferably ≥55 ° C and ≤60 ° C.

It has also been shown that the molecular weight of the used Polyethylene glycol may be important to particles of the invention with good solubility, sufficient bulk density and no or at most a small degree of segregation in Finished products available to deliver. It may therefore be provided according to the invention that the Polyethylene glycol has an average molecular weight of 400 to 20,000, preferably from 1000 to 10000, preferably from 2000 to 8000 and most preferably from 3,000 to 5,000.

Particulates according to the invention with good particle properties, i. Particles no or one only slight tendency to segregation and at the same time one high solubility in the aqueous Application liquor, can be obtained if the middle Polyethylene glycol molecular weight, for example, 3000 to 5000 and most preferably 3500 to 4500.

Suitable usable polyethylene glycols are known commercially under the names PEG; Carbowax ^®; polyglycol; wherein polyethylene glycol 3350, 4000 and 6000 are preferred. Particularly suitable is PEG 4000. The numbers in these terms indicate the average molecular weight.

Another essential ingredient of the particles, are amphiphilic polymers with dirt-repellent, the effect. According to the invention, suitable amphiphilic polymer has ester units of C ₂ - to C ₄ -alkylene glycol and / or C ₂ - to C ₄ -polyalkylene glycol with aromatic dicarboxylic acids. Such amphiphilic polymers can have very different properties in the solid state. You can be crystalline, in part as crystalline, glassy solidified or present in the rubbery state above the glass transition temperature. Amphiphilic polymers which can be used according to the invention can be prepared, for example, by condensation of terephthalic acid and / or dimethyl terephthalate with ethylene glycol and / or polyethylene glycol, cf. US Pat. No. 3,557,039 to which reference is made in full here.

• – aromatischen Dicarbonsäuren, ausgewählt aus der Gruppe umfassend Dimethylterephthalsäure und/oder Terephthalsäure; und
• – Glykol-Einheiten und/oder Polyglykol-Einheiten.

Preferably, the amphiphilic polymer has ester units formed from:

• - aromatic dicarboxylic acids selected from the group comprising dimethylterephthalic acid and / or terephthalic acid; and
• - Glycol units and / or polyglycol units.

Amphiphilic polymers preferred according to the invention consist of ester units formed from dimethyl terephthalic acid and / or terephthalic acid and glycol units and / or polyglycol units, with amphiphilic polymers formed from terephthalic acid and glycol units and / or polyglycol units being particularly preferred. Most preferred is the use of Repelotex ^® SRP6, commercially available from Rhodia.

Of the Weight fraction of the amphiphilic polymer, preferably polyethylene glycol terephthalate, makes 55% by weight, based on the total weight of the particles with preference to 85 wt.%, preferably 60 wt.% to 80 wt.%, preferably 65 Wt .-% to 78 wt .-% and most preferably 70 wt .-% to 75 wt .-% of. Leave by the manufacturing method described below according to the invention particles produce high active content of amphiphilic polymer, wherein the particles of the invention despite the high active ingredient content in the aqueous application liquor a good solubility have and in a finished detergent no or only one at most have a low tendency to segregation.

Further can the particles are low levels of a polymer such as polycarboxylate preferably polyacrylate, polymethacrylate, polycarboxylate formed from acrylate and methacrylate, from acrylic acid and maleic acid units and their salts. Preferably, the copolymer is a sodium salt a polyacrylate, polymethacrylate, acrylic acid / maleic acid copolymer, wherein the acrylic acid units in the copolymer in excess available.

The used polymer is different from the amphiphilic polymer. Suitable polymers are preferably sprayable polymers, preferably water-soluble polymers and especially polymers which are readily dispersible in water. Most preferably, the polymer is one from acrylic acid and maleic acid units formed polymer and / or salts thereof.

The molar ratio the acrylic acid units to the maleic acid units in the polycarboxylate may preferably be from 5: 1 to 1: 1, more preferably from 4: 1 to 2: 1 and especially 7: 3.

Invention is particularly suitable polycarboxylates that can be used include Sokalan ^®, commercially available from BASF AG, with the use of Sokalan ^® CP5 is particularly preferred.

It it can be provided that the particles according to the invention contain the polycarboxylate, preferably acrylic acid / maleic acid copolymer, with a weight fraction, based on the total weight of the particles, of ≥ 0.05% by weight to ≤ 10 Wt .-%, preferably from 0.1 wt .-% to 8 wt .-%, preferably from From 0.5% to 5% by weight and more preferably from 1% to 3% by weight Wt .-% included. However, a good solubility, in particular larger inventive particles to ensure, and at the same time no or at most only a small segregation To ensure the particles in a finished product has become less Weight fraction of acrylic acid / maleic acid copolymer in the particles of the invention proved to be advantageous.

Also It may be advantageous if the particles are amphiphilic the components Polymer, preferably polyethylene glycol terephthalate, and polycarboxylate in weight ratio from 125: 1 to 10: 1, preferably from 100: 1 to 12.5: 1, more preferably from 75: 1 to 15: 1, more preferably from 50: 1 to 17.6: 1 and in particular from 25: 1 to 20: 1.

Farther It has proved to be advantageous if the weight ratio of amphiphilic polymer, preferably polyethylene glycol terephthalate, too Polyethylene glycol from 99: 1 to 1: 2, preferably from 75: 1 to 1: 1.5, more preferably from 50: 1 to 1: 1, more preferably from 25: 1 to 1.5: 1 and in particular from 5: 1 to 2: 1.

In the context of the present invention, the terms "particle size" or "particle size", which are used interchangeably in the present text, mean the value commonly referred to as "d ₅₀ ", ie the value at which about 50% by weight. the particles have a smaller diameter and about 50% by weight of the particles have a larger diameter.

A value denoted by "d ₇₀ " is understood to mean a value at which about 70% by weight of the particles have a smaller diameter and about 30% by weight of the particles have a larger diameter.

A value denoted by "d ₉₀ " is understood to mean a value at which about 90% by weight of the particles have a smaller diameter and about 10% by weight of the particles have a larger diameter.

Usual methods for determining particle size microscopy, electron microscopy ,. Sieve analysis, sedimentation analysis, Determination of the density of the surface and the same.

Generally can the particles of the invention with a grain size in the range of 0.05 mm and 5 mm, preferably in the range of 0.1 mm and 3 mm, more preferably in the range of 0.2 mm and 2.5 mm, more preferably in the range of 0.4 mm and 2 mm, and more preferably in the range of 0.6 mm and 1.8 mm in diameter.

It may be preferred if the particles according to the invention have a particle size d ₅₀ of ≥ 0.1 mm and ≦ 3 mm, preferably a particle size d ₅₀ of ≥ 0.3 mm and ≦ 2 mm, preferably a particle size d ₅₀ of ≥ 0.5 mm and ≦ 1.8 mm, more preferably have a particle size d ₅₀ of ≥ 0.8 mm and ≤ 1.7 mm, and particularly preferably have a particle size d ₅₀ of ≥ 1.0 mm and ≤ 1.6 mm.

However, the particles according to the invention can also have a narrower particle size distribution with a particle size d ₇₀ of ≥ 0.1 mm and ≦ 3 mm, preferably a particle size d ₇₀ of ≥ 0.3 mm and ≦ 2 mm, preferably a particle size d ₇₀ of ≥ 0, 5 mm and ≦ 1.8 mm, more preferably have a particle size d ₇₀ of ≥ 0.8 mm and ≤ 1.7 mm, and particularly preferably have a particle size d ₇₀ of ≥ 1.0 mm and ≤ 1.6 mm ,

With a very narrow particle size distribution, the particles according to the invention can have a particle size d ₉₀ of ≥ 0.1 mm and ≦ 3 mm, preferably a particle size d ₉₀ of ≥ 0.3 mm and ≦ 2 mm, preferably a particle size d ₉₀ of ≥ 0.5 mm and ≤ 1.8 mm, more preferably a d ₉₀ particle size of> 0.8 mm and ≤ 1.7 mm have, and particularly preferably a particle size d ₉₀ of ≥ 1.0 mm and ≤ 1.6 mm have.

The Particle diameters of the particles of the invention were based on of Siebzahlen determined. This can be determined by the used Sieve sizes for each sieve residue determine the particle diameter.

• – ≥ 0 bis 1 Gew.-% der Partikel einen Partikeldurchmesser von > 2 mm,
• – 0,5 bis 1,5 Gew.-% der Partikel einen Partikeldurchmesser von > 1,8 mm bis 2 mm,
• – 5 bis 20 Gew.-% der Partikel einen Partikeldurchmesser von > 1,6 mm bis 1,8 mm,
• – 20 bis 40 Gew.-% der Partikel einen Partikeldurchmesser von > 1,4 mm bis 1,6 mm,
• – 20 bis 40 Gew.-% der Partikel einen Partikeldurchmesser von > 1,18 mm bis 1,4 mm,
• – 10 bis 25 Gew.-% der Partikel einen Partikeldurchmesser von > 1,0 mm bis 1,18 mm,
• – 1 bis 15 Gew.-% der Partikel einen Partikeldurchmesser von > 0,80 mm bis 1,0 mm,
• – ≥ 0 bis 1 Gew.-% der Partikel einen Partikeldurchmesser von > 0,6 mm bis 0,80 mm, bezogen auf das Gesamtgewicht der Partikel, wobei das Gesamtgewicht der jeweiligen Siebfraktionen der Par tikel so gewählt ist, dass es 100 Gew.-% ergibt.

According to a preferred embodiment, the following sieving numbers can be determined for the particles according to the invention:

• - ≥ 0 to 1 wt .-% of the particles have a particle diameter of> 2 mm,
• 0.5 to 1.5% by weight of the particles have a particle diameter of> 1.8 mm to 2 mm,
• 5 to 20% by weight of the particles have a particle diameter of> 1.6 mm to 1.8 mm,
• 20 to 40% by weight of the particles have a particle diameter of> 1.4 mm to 1.6 mm,
• 20 to 40% by weight of the particles have a particle diameter of> 1.18 mm to 1.4 mm,
• 10 to 25% by weight of the particles have a particle diameter of> 1.0 mm to 1.18 mm,
• From 1 to 15% by weight of the particles have a particle diameter of> 0.80 mm to 1.0 mm,
• - ≥ 0 to 1 wt .-% of the particles have a particle diameter of> 0.6 mm to 0.80 mm, based on the total weight of the particles, wherein the total weight of the respective sieve fractions of the particles is selected such that it is 100 wt. -% results.

• – ≥ 0 bis 0,5 Gew.-% der Partikel einen Partikeldurchmesser von > 2 mm,
• – 0,8 bis 1,4 Gew.-% der Partikel einen Partikeldurchmesser von > 1,8 mm bis 2 mm,
• – 10 bis 15 Gew.-% der Partikel einen Partikeldurchmesser von > 1,6 mm bis 1,8 mm,
• – 25 bis 35 Gew.-% der Partikel einen Partikeldurchmesser von > 1,4 mm bis 1,6 mm,
• – 25 bis 35 Gew.-% der Partikel einen Partikeldurchmesser von > 1,18 mm bis 1,4 mm,
• – 15 bis 22 Gew.-% der Partikel einen Partikeldurchmesser von > 1,0 mm bis 1,18 mm,
• – 5 bis 10 Gew.-% der Partikel einen Partikeldurchmesser von > 0,80 mm bis 1,0 mm,
• – ≥ 0 bis 0,5 Gew.-% der Partikel einen Partikeldurchmesser von > 0,6 mm bis 0,80 mm, bezo gen auf das Gesamtgewicht der Partikel, wobei das Gesamtgewicht der jeweiligen Siebfraktionen der Partikel so gewählt ist, dass es 100 Gew.-% ergibt.

According to a further preferred embodiment, the following sieving numbers can be determined for the particles according to the invention:

• - ≥ 0 to 0.5 wt .-% of the particles have a particle diameter of> 2 mm,
• 0.8 to 1.4% by weight of the particles have a particle diameter of> 1.8 mm to 2 mm,
• 10 to 15% by weight of the particles have a particle diameter of> 1.6 mm to 1.8 mm,
• 25 to 35% by weight of the particles have a particle diameter of> 1.4 mm to 1.6 mm,
• 25 to 35% by weight of the particles have a particle diameter of> 1.18 mm to 1.4 mm,
• 15 to 22% by weight of the particles have a particle diameter of> 1.0 mm to 1.18 mm,
• From 5 to 10% by weight of the particles have a particle diameter of> 0.80 mm to 1.0 mm,
• - ≥ 0 to 0.5 wt .-% of the particles have a particle diameter of> 0.6 mm to 0.80 mm, based on the total weight of the particles, wherein the total weight of the respective sieve fractions of the particles is selected so that it is 100 Wt .-% results.

For particles according to the invention with the aforementioned particle sizes and / or Sieving figures, it has been shown that the tendency to segregation with narrower particle size distribution decreases or even no segregation in finished detergent containing the particles of the invention occurs.

It is further preferred that the distribution of the components in Particles themselves as possible is homogeneous. The homogeneity of a particle For example, examine the particle by sections or targeted breaking is divided into smaller units and these Samples then by spectroscopic methods such as flame ionization spectroscopy or plasma induced spectroscopy or by on the diffraction radiation-based methods such as EDX analysis (energy-dispersive X-ray analysis), analyzed for their qualitative and quantitative composition become. A comparison of the compositions of the individual samples of a Particles allows it, the homogeneity of the investigated particle (before dividing). However, the individual samples are preferably in a suitable solvent solved and by means of chromatographic methods on their quantitative and qualitative composition examined. In the present case the content of the particles according to the invention of amphiphilic polymer, preferably determined by gas chromatography.

Statements about the homogeneity the investigated particle according to the invention are possible, by taking individual samples with identical masses in identical quantities on solvent solved and the content of the individual samples of amphiphilic polymer or other components contained in the particle, which by means of Gas chromatography can be determined quantitatively. It is also possible, the Content of individual samples of amphiphilic polymer with the content of amphiphilic polymer in an undivided particle according to the invention to compare. One more way is the ratio of to determine two components in each sample studied and these relationships of the individual samples and a sample of the undivided particle.

Prefers is the maximum deviation of the content of amphiphilic polymer from 5 to 10 individual samples, in particular 10 individual samples, from a inventive particles were obtained by breaking or cutting and each one after the complete one solution in a suitable solvent were examined by gas chromatography, less than 50 wt .-%, preferably less than 40% by weight, more preferably less than 30% by weight, preferably less than 20% by weight, more preferably less than 10 wt .-%, most preferably less than 5 wt .-% and in particular less than 2.5 wt .-% based on the content of the amphiphilic polymer in a sample, passing through the solution an undivided particle according to the invention in the same solvent was obtained. The above percentages by weight of the amphiphilic polymer are solved on each one Samples, that is on by breaking or cutting a particle according to the invention obtained individual samples or on the undivided particles according to the invention based.

through Of the methods mentioned, it is also possible to homogenize the ingredients in a sample of the particles of the invention to investigate. The deviation of the concentration of the amphiphilic polymer and / or the polyethylene glycol in two randomly selected particles of the invention is preferably less than 50% by weight, preferably less than 40% by weight, especially preferably less than 30% by weight, more preferably less than 20% by weight, more preferably less than 10% by weight, especially preferably less than 5% by weight and in particular less than 2.5 Wt .-%. Very particular preference is given to the composition of the particles according to the invention identical in the comparison of two particles according to the invention. This can by the inventive method explained in more detail below be achieved.

One Gluing the particles of the invention with each other or with other components, can be - despite a relatively high Polyethylene glycol weight fraction in the particles - in the finished product significantly reduce or even prevent when these particles become one preferably spherical Have shape. According to the present It may therefore be preferred for the invention to be as possible as possible spherical are, for example, in a finished product a simple homogeneous To enable distribution.

It may therefore be preferred that the particles of the invention have a form factor of at least 0.70, preferably at least 0.75, more preferably at least 0.80, more preferably at least 0.85 and more preferably of at least 0.90.

The form factor, also known as Shape Factor or Rounding Factor, can be precisely determined by modern particle measurement techniques with digital image processing. A typical suitable particle shape analysis, as it is feasible, for example, with the Camsizer ^® system from Retsch Technology or with the KeSizer ^® of the company Kemira, based on the fact that the particles and the bulk material are irradiated with a light source and detects the particle as projection , digitized and processed by computer technology. The determination of the surface curvature is made by an optical measuring method in which the "shadow cast" of the parts to be examined is determined and converted into a corresponding form factor.

The particles according to the invention can Contain water. It is preferred if the water content as possible is low. Based on the total weight of the particles, the particles according to the invention a water content of ≥ 0 Wt .-% to ≤ 10 Wt .-%, preferably from 0.1 wt .-% to 8 wt .-%, preferably from From 0.5% to 5% by weight and more preferably from 1% to 3% by weight Wt .-%, contained.

The particles according to the invention can preferably a low bulk density exhibit. The bulk density the particle may for example be from 350 g / l to <600 g / l or from 370 g / l to 580 g / l, being a bulk density between 400 g / l to 550 g / l is preferred.

The particles according to the invention can but also a higher one bulk weight exhibit. The bulk density The particle may then be, for example,> 600 g / l to 900 g / l or 700 g / l to 800 g / l, with a bulk density between 720 g / l to 790 g / l is preferred.

The Determination of solubility shall be determined in accordance with the determination of the residue value in accordance with the following solubility carried out, being up to the full resolution touched becomes.

to Determination of the residue behavior or the solubility behavior were in a 2 liter beaker 8 g of the particles of the invention to be tested in 1000 ml of water with stirring (800 rpm with laboratory stirrer / propeller stirring head 1.5 cm from the beaker bottom centered) and 1.5 minutes at Stirred at 30 ° C or alternatively 40 ° C. The test was carried out with water of a hardness of 16 ° d. Subsequently was the solution immediately poured through a sieve 0.2 mm mesh size. The beaker was rinsed with very little cold water over the sieve. It happened a 2-fold determination. The sieves were placed in a drying oven at 40 ° C ± 2 ° C until Constant weight dried and the detergent residue weighed. The residue is the mean of the two individual determinations in percent specified. For deviations of the individual results by more than 5% by weight from each other further experiments were carried out.

The particles of the invention have a good solubility which exceeds the solubility of the products described in the prior art. Particles having a particle size d ₉₀ in the range of 0,8 mm to 1,6 mm consisting exclusively of Repelotex SRP 6 or additionally containing polycarboxylate in excess, but otherwise prepared by a process similar to that described below, have a much lower solubility and a significantly lower residue value.

• – 5 Gew.-% bis 45 Gew.-%, vorzugsweise 10 Gew.-% bis 40 Gew.-%, bevorzugt 15 Gew.-% bis 30 Gew.-% und noch bevorzugter 20 Gew.-% bis 25 Gew.-% Polyethylenglykol;
• – 55 Gew.-% bis 85 Gew.-%, vorzugsweise 60 Gew.-% bis 80 Gew.-%, bevorzugt 65 Gew.-% bis 78 Gew.-% und noch bevorzugter 70 Gew.-% bis 75 Gew.-% amphiphiles Polymer;
• – ≥ 0 Gew.-% bis 10 Gew.-%, vorzugsweise 0,1 Gew.-% bis 8 Gew.-%, bevorzugt 0,5 Gew.-% bis 5 Gew.-% Polymer und besonders bevorzugt 1 Gew.-% bis 3 Gew.-% Polymer, welches sich vom amphiphilen Polymer unterscheidet, vorzugsweise Polycarboxylat;
• – ≥ 0 Gew.-% bis 25 Gew.-%, vorzugsweise 5 Gew.-% bis 20 Gew.-% und bevorzugt 10 Gew.-% bis 15 Gew.-% weitere Inhaltsstoffe; und
• – ≥ 0 Gew.-% bis ≤ 10 Gew.-%, vorzugsweise 0,01 Gew.-% bis 5 Gew.-%, bevorzugt von 0, 05 Gew.-% bis 5 Gew.-% und weiter bevorzugt 0,5 Gew.-% bis 3 Gew.-% Wasser; worin die Komponenten so gewählt sind, dass das Gesamtgewicht der Komponenten 100 Gew.-% nicht übersteigt.

According to a preferred embodiment, the particles according to the invention may have the following composition:

• From 5% to 45%, preferably from 10% to 40%, preferably from 15% to 30%, and more preferably from 20% to 25% by weight. -% polyethylene glycol;
• From 55% by weight to 85% by weight, preferably from 60% by weight to 80% by weight, preferably from 65% by weight to 78% by weight and even more preferably from 70% by weight to 75% by weight. % amphiphilic polymer;
• - ≥ 0 wt .-% to 10 wt .-%, preferably 0.1 wt .-% to 8 wt .-%, preferably 0.5 wt .-% to 5 wt .-% polymer and particularly preferably 1 wt. % to 3% by weight of polymer other than the amphiphilic polymer, preferably polycarboxylate;
• - ≥ 0 wt .-% to 25 wt .-%, preferably 5 wt .-% to 20 wt .-% and preferably 10 wt .-% to 15 wt .-% of other ingredients; and
• From ≥0% by weight to ≤10% by weight, preferably from 0.01% by weight to 5% by weight, preferably from 0.05 to 5% by weight and more preferably 0, From 5% to 3% by weight of water; wherein the components are chosen so that the total weight of the components does not exceed 100% by weight.

It However, it may be preferred that particles according to the invention in addition to polyethylene glycol and amphipihlen polymer a maximum of five, preferably have three and more preferably two further substances selected from the group comprising surfactants, alkylbenzenesulfonates, water and / or Polymer, such as polycarboxylate.

Especially can be beneficial for the particles of the invention the incorporation of surfactants and in particular the incorporation of linear alkylbenzenesulfonates.

The particles according to the invention can the ones listed below Ingredients in addition to the main components amphiphilic polymer and polyethylene glycol or amphiphilic polymer, polyethylene glycol and polycarboxylate. The particles can but also be free from other ingredients or at least have another ingredient.

finished products in the sense of this invention exclusively the particles of the invention contain. However, it is preferred that the finished products are the particles according to the invention and further constituents, with the other constituents the finished product, inter alia, at least one, preferably several may have the ingredients listed below.

The The ingredients listed below may thus form part of the Particles according to the invention and / or Be part of the finished product. To avoid repetition These ingredients are listed only once.

Prefers Ingredients of the particles of the invention and / or components associated with the particles of the invention are blended into a finished product, are preferably care and / or cleaning substances such as anionic surfactants, cationic surfactants, amphoteric surfactants, builders, bleach, Bleach activators, bleach stabilizers, bleach catalysts, enzymes, other polymers, cobuilders, alkalizing agents, acidifying agents, Anti redeposition agents, silver protectants, optical brighteners, UV protection substances, fabric softeners, Auxiliaries, fragrances, other dirt-repellent substances, anti-wrinkle substances, antibacterial substances, colorants, discoloration inhibitors, foam inhibitors, phyllosilicates, Odor-complexing substances and / or rinse aid.

These preferred ingredients will be described in more detail below.

To the builders counting in particular the zeolites, silicates, carbonates, organic cobuilders and where no ecological Prejudices against their use exist - even the phosphates.

Preference is given to using crystalline layer-form silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, in which M represents sodium or hydrogen, x a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values x is 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layer-form silicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O are for example sold by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .xH ₂ O, Makatite).

Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O, in which x is 2. In particular, both β- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ .yH ₂ O and furthermore especially Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O _5, natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3H ₂ O, kanemite), Na-SKS-11 (t- Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ).

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle , cause.

alternative or in combination with the aforementioned amorphous sodium silicates become X-ray amorphous Silicate used, the silicate particles in electron diffraction experiments provide blurred or even sharp diffraction maxima. This is to interpret that the products microcrystalline areas the size ten up to several hundred nm, with values up to max. 50 nm and especially up to max. 20 nm are preferred. Such X-ray amorphous Silicates also have a dissolution delay over the conventional ones water glasses on. Particularly preferred are compacted / compacted amorphous Silicates, compounded amorphous silicates and overdried X-ray amorphous Silicates.

Of course it is also a use of the well-known phosphates as builders possible, if such use is not avoided for environmental reasons should be. Among the variety of commercially available Phosphates have the alkali metal phosphates, with particular preference of Pentasodium or pentakalium triphosphate (sodium or potassium tripolyphosphate) in the washing and cleaning industry the greatest importance.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent calcification on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

Technically particularly important phosphates are the pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate). The sodium potassium tripolyphosphates are also preferably used according to the invention.

Become in the context of the present application phosphates as washing or cleaning active Substances used in detergents or cleaners, so included preferred agents are said phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).

Further builders are the alkali carriers. As alkali carrier For example, alkali metal hydroxides, alkali metal carbonates, Alkali metal bicarbonates, alkali metal sesquicarbonates, the mentioned alkali metal silicates, alkali metal silicates, and mixtures of aforementioned substances, wherein for the purposes of this invention preferably the Alkali carbonates, especially sodium carbonate, sodium bicarbonate or sodium sesquicarbonate. Especially preferred is a builder system containing a mixture of tripolyphosphate and Sodium.

Especially preference is given to the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate.

When Organic co-builders are in particular polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) as well as phosphonates. These classes of substances are hereafter described.

useful organic builders For example, they are in the form of the free acid and / or their sodium salts usable polycarboxylic acids, where among polycarboxylic acids such carboxylic acids be understood that 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), if such an application for ecological reasons not is objectionable, as well as mixtures of these. Own the free acids In addition to their builder effect typically also the property of a acidifying and thus serve to set a lower and milder one pH value of detergents or cleaning agents. In particular, here are citric acid, Succinic acid, glutaric, adipic acid, gluconic and to name any mixtures of these.

When builders are further polymeric polycarboxylates suitable, these are for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight from 500 to 70000 g / mol. It should be noted at this point that in addition to the polymer, which in addition to the amphiphilic polymer in the particles of the invention may be included, further polycarboxylates in the particles of the invention and / or the further constituents of the finished product could be.

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 mass of 2000 to 20,000 g / mol. Because of their superior solubility can from this group again the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and more preferably from 3000 to 5000 g / mol, may be preferred.

Suitable are furthermore copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and the acrylic acid or methacrylic acid with maleic acid. Particularly suitable are copolymers of acrylic acid with maleic which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid. Your molecular weight, based on free acids, is in general from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

to Improvement of water solubility can the polymers also include allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as Contain monomer.

Especially Biodegradable polymers of more than two are also preferred various monomer units, for example, those 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-alkylallyl sulfonic acid and sugar derivatives.

Further preferred copolymers are those which are used as monomers acrolein and Acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

As well are as further preferred builders polymeric aminodicarboxylic acids whose Salts or their precursors to call. Particular preference is given to polyaspartic acids or their salts.

Further Suitable builders are polyacetals, which by reaction of dialdehydes with polyol carboxylic acids containing 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained. preferred Polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic receive.

Further suitable organic builders are dextrins, for example Oligomers or polymers of carbohydrates by partial Hydrolysis of starches can be obtained. The hydrolysis can be carried out according to usual, for example acidic or enzyme-catalyzed processes. Preferably These are hydrolysis products with average molecular weights in the range from 400 to 500,000 g / mol. It is a polysaccharide with a Dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 preferred where DE is a common one Measure of the reducing Effect of a polysaccharide compared to dextrose, which DE of 100 is. Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrup with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher Molar masses in the range of 2000 to 30,000 g / mol.

at the oxidized derivatives of such dextrins are their reaction products with oxidants, which are able are at least one alcohol function of the saccharide ring to the carboxylic acid function to oxidize.

Also Oxydisuccinates and other derivatives of disuccinates, preferably Ethylenediamine disuccinate are other suitable cobuilders. there becomes ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates.

Further 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.

Furthermore can all compounds that are capable of complexes with alkaline earth ions train as builders be used.

to Group of surfactants are the nonionic, the anionic, the cationic and the amphoteric surfactants counted.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

A another class of preferred nonionic surfactants, the 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 1 to 4 carbon atoms in the alkyl chain.

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 alkanolamide 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 half from that.

in der R 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

wherein R is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical 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 zyklischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder zyklischen 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

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 by reductive amination of a reduced sugar obtained, for example, glucose, fructose, maltose, lactose, galactose, Mannose or xylose. The N-alkoxy or N-aryloxy-substituted compounds can by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxyfatty acid amides are transferred.

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, washing or cleaning agents, in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols. As nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with vorzugswei se 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used, in which the alcohol radical may linear or preferably methyl branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are 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 and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. 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 or 40 EO.

Particular preference is therefore given to ethoxylated nonionic surfactants consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide. Of these, the so-called "narrow range ethoxylates" are particularly preferred.

With Particular preference continues to be combinations of one or several tallow fatty alcohols with 20 to 30 EO and silicone defoamers used.

Especially preferred are nonionic surfactants which have a melting point above Have room temperature. Nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred.

suitable nonionic surfactants, the melting or softening points in said Temperature range, for example, low-foaming nonionic Surfactants which may be solid or highly viscous at room temperature. Become Used nonionic surfactants which are highly viscous at room temperature, so it is preferred that this has a viscosity above 20 Pa · s, preferably above 35 Pa · s and in particular above 40 Pa · s. Also nonionic surfactants, which have waxy consistency at room temperature are, depending preferred according to their intended use.

nonionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO-Niotenside, are also with special Preference used.

The nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule. Preferably, such PO units make up to 25% by weight, especially preferably up to 20% by weight and in particular up to 15 wt .-% of the total molecular weight of the nonionic Surfactants. Particularly preferred nonionic surfactants are ethoxylated Monohydroxyalkanols or alkylphenols which additionally contain polyoxyethylene-polyoxypropylene Have block copolymer units. The alcohol or alkylphenol content such nonionic surfactant molecules makes preferably more than 30 wt .-%, more preferably more than 50 wt .-% and in particular more than 70 wt .-% of the total Molar mass of such nonionic surfactants. Preferred means are thereby characterized in that they are ethoxylated and propoxylated nonionic surfactants contain, in which the propylene oxide in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 Make up wt .-% of the total molecular weight of the nonionic surfactant.

Prefers Surfactants to be used come from the groups of the alkoxylated Nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control out.

Further particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene lenoxid and 44 moles of propylene oxide and 25 wt .-% of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane contains.

bevorzugt in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder-Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.In the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula

preferably in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently stand for integers from 1 to 6.

The preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula may vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions, preference is given to nonionic surfactants in which R ¹ in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or CH (CH ₃ ) ₂ are suitable. Preference is given to using nonionic surfactants of the above formula in which R ² or R ^{3 is} a radical -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another are values of 1 or 2.

In summary, particularly preferred are nonionic surfactants having a C _9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

Surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x (A''O) _y (A '''O) _z -R ² in which R ¹ and R ² independently represent a straight-chain or branched, saturated or mono- or polyunsaturated C _2-40 alkyl or alkenyl radical; A, A ', A''andA''' are independently of one another a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH _{2 is} -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z represent values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which are of the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² in addition to a radical R ¹ which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having from 1 to 30 carbon atoms, where x is between 1 and 90, preferably between 40 and 80, and especially between 40 and 60.

Particularly preferred are surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 Koh or atoms and mixtures thereof and x for values between 0.5 and 1.5 and y for a value of at least 15 stands.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CN ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ , but preferably represents -CH ₃ , and x and y independently of one another are values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values for x of 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² , in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. When the value x ≥ 2, each R ³ in the above formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 may be} different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula zu R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

The specified C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned Nonionic surfactants represent statistical averages that are suitable for a specific Product can be a whole or a fractional number. by virtue of the manufacturing process consist of commercial products of the formulas mentioned mostly not from an individual representative, but from mixtures, which is responsible for both the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation averages and resulting in fractional numbers.

Of course, the aforementioned nonionic surfactants not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants be used. As surfactant mixtures are not mixtures nonionic surfactants referred to in their entirety one of the above general formulas, but rather such mixtures, the two, three, four or more nonionic Containing surfactants by different of the aforementioned general Formulas can be described.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example, the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids suitable.

Further Suitable anionic surfactants are sulfated fatty acid glycerol esters. Among fatty acid glycerol esters are to understand the mono-, di- and triesters and their mixtures, such as they are produced 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 to be obtained. Preferred sulfated fatty acid glycerol esters are included the sulphonated products of saturated fatty acids with 6 to 22 carbon atoms, for example the 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, in particular, the sodium salts of the sulfuric monoesters of C _12-18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of 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 -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which can be obtained as commercial products of Shell Oil Company under the name DAN ^® , are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 . Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are 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 by themselves are nonionic surfactants. 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) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

When other anionic surfactants are especially soaps into consideration. Suitable are saturated fatty acid soaps, like the salts of lauric acid, myristic, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow derived soap mixtures.

The including anionic surfactants the soaps can in the form of their sodium, potassium or ammonium salts and as soluble salts 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.

At Place of said surfactants or in conjunction with them may also cationic and / or amphoteric surfactants are used.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.As cationic active substances, for example, cationic compounds of the following formulas can be used:

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

In automatic dishwashing detergents, is the content of cationic and / or amphoteric surfactants preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. Automatic dishwashing detergents, which contain no cationic or amphoteric surfactants particularly preferred.

to Group of polymers count in particular the washing or cleaning-active polymers, for example the rinse aid polymers and / or as a softener effective polymers. In general, detergents and cleaners are non-ionic Polymers also cationic, anionic and amphoteric polymers can be used.

"Cationic Polymers "in the sense The present invention relates to polymers which are a positive charge in the polymer molecule wear. This can be present, for example, in the polymer chain (Alkyl) ammonium moieties or other positively charged groups will be realized. Particularly preferred cationic polymers are derived from the groups of the quaternized cellulose derivatives, the polysiloxanes with quaternary Groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives the dialkylamino acrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 indicated polymers.

"Amphoteric Polymers "in the sense of the present invention have besides a positively charged group in the polymer chain also negatively charged groups or On monomer units. These groups may be, for example to carboxylic acids, sulfonic acids or phosphonic acids act.

Preferred washing or cleaning agents, in particular preferred automatic dishwashing agents, are characterized in that they contain a polymer a) which has monomer units of the formula R ¹ R ² C =CR ³ R ⁴ in which each R ¹ , R ² , R ⁴ radical ³ , R ^{4 is} independently selected from hydrogen, derivatized hydroxy, C _1-30 linear or branched alkyl groups, aryl, aryl substituted C _1-30 linear or branched alkyl groups, polyalkoxylated alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen , at least one quaternized nitrogen atom or at least one amino group having a positive charge in the partial range of the pH range of 2 to 11, or salts thereof, with the proviso that at least one radical R ¹ , R ² , R ³ , R ^{4 is} a heteroatomic organic group having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one Aminogr uppe with a positive charge is.

bei der R¹ und R⁴ unabhängig voneinander für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen steht; R² und R³ unabhängig voneinander für eine Alkyl-, Hydroxyalkyl-, oder Aminoalkylgruppe stehen, in denen der Alkylrest linear oder verzweigt ist und zwischen 1 und 6 Kohlenstoffatomen aufweist, wobei es sich vorzugsweise um eine Methylgruppe handelt; x und y unabhängig voneinander für ganze Zahlen zwischen 1 und 3 stehen. X repräsentiert ein Gegenion, vorzugsweise ein Gegenion aus der Gruppe Chlorid, Bromid, Iodid, Sulfat, Hydrogensulfat, Methosulfat, Laurylsulfat, Dodecylbenzolsulfonat, p-Toluolsulfonat (Tosylat), Cumolsulfonat, Xylolsulfonat, Phosphat, Citrat, Formiat, Acetat oder deren Mischungen.In the context of the present application, particularly preferred cationic or amphoteric polyme As a monomer unit contained a compound of the general formula

in which R ¹ and R ⁴ are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ^{3 are} independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3. X represents a counterion, preferably a counterion from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R ¹ and R ⁴ in the above formula are selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH , -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _n H.

wird im Falle von X^–= Chlorid auch als DADMAC (Diallyldimethylammonium-Chlorid) bezeichnet.Very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ¹ and R ^{4 are} H, R ² and R ^{3 are} methyl and x and y are each 1. The corresponding monomer unit of the formula

in the case of X ^- = chloride is also referred to as DADMAC (diallyldimethylammonium chloride).

in der R¹, R², R³, R⁴ und R⁵ unabhängig voneinander für einen linearen oder verzweigten, gesättigten oder ungesättigen Alkyl-, oder Hydroxyalkylrest mit 1 bis 6 Kohlenstoffatomen, vorzugsweise für einen linearen oder verzweigten Alkylrest ausgewählt aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, und -(CH₂CH₂-O)_nH steht und x für eine ganze Zahl zwischen 1 und 6 steht.Further particularly preferred cationic or amphoteric polymers contain a monomer unit of the general formula

in which R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently of one another are a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _n H and x is an integer between 1 and 6.

werden im Falle von X^–= Chlorid auch als MAPTAC (Methyacrylamidopropyl-trimethylammonium-Chlorid) bezeichnet.For the purposes of the present application, very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ^{1 is} H and R ² , R ³ , R ⁴ and R ^{5 are} methyl and x is 3. The corresponding monomer units of the formula

in the case of X ^- = chloride, also referred to as MAPTAC (methylacrylamidopropyltrimethylammonium chloride).

According to the invention preferred Polymers are used which are diallyldimethylammonium salts as monomer units and / or acrylamidopropyltrimethylammonium salts.

The aforementioned amphoteric polymers have not only cationic groups but also anionic groups or monomer units. Such anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates. Preferred monomer units are the acrylic acid, the (meth) acrylic acid, the (dimethyl) acrylic acid, the (Ethyl) acrylic acid, cyanoacrylic acid, vinylic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or allylphosphonic acids.

preferred usable amphoteric polymers are from the group of alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers, and the copolymers of unsaturated Carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Prefers usable zwitterionic polymers are from the group of Acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their Alkali and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the Methacroylethylbetain / methacrylate copolymers.

Prefers are further amphoteric polymers, which in addition to one or more anionic monomers as cationic monomers Methacrylamidoalkyl-trialkylammonium chloride and dimethyl (diallyl) ammonium chloride.

Especially preferred amphoteric polymers are from the group of the Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers as well as their alkali and ammonium salts.

Especially preference is given to amphoteric polymers from the group of methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers as well as their alkali and ammonium salts.

• – die Verkapselung der Polymere mittels wasserlöslicher oder wasserdispergierbarer Beschichtungsmittel, vorzugsweise mittels wasserlöslicher oder wasserdispergierbarer natürlicher oder synthetischer Polymere;
• – die Verkapselung der Polymere mittels wasserunlöslicher, schmelzbarer Beschichtungsmittel, vorzugsweise mittels wasserunlöslicher Beschichtungsmittel aus der Gruppe der Wachse oder Paraffine mit einem Schmelzpunkt oberhalb 30°C;
• – die Cogranulation der Polymere mit inerten Trägermaterialien, vorzugsweise mit Trägermaterialien aus der Gruppe der wasch- oder reinigungsaktiven Substanzen, besonders bevorzugt aus der Gruppe der Builder(Gerüststoffe) oder Cobuilder.

In a particularly preferred embodiment of the present invention, the polymers are present in prefabricated form. For the preparation of the polymers is suitable inter alia

• The encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;
• - The encapsulation of the polymers by means of water-insoluble, fusible coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C;
• - The cogranulation of the polymers with inert support materials, preferably with support materials from the group of washing or cleaning-active substances, particularly preferably from the group of builders (builders) or cobuilders.

When softeners effective polymers are, for example, the sulfonic acid-containing Polymers which are used with particular preference.

Especially preferably as sulfonic acid-containing Polymers can be used are copolymers of unsaturated carboxylic acids containing sulfonic acid groups Monomers and optionally further ionic or nonionic Monomers.

In the context of the present invention are as unsaturated monomer carboxylic acids of the formula R ¹ (R ² ) C = C (R ³ ) COOH in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the above formula in particular acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H, R ³ = CH ₃ ) and / or maleic acid (R ¹ = COOH, R ² = R ³ = H) prefers.

In the sulfonic acid-containing monomers are those of the formula R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H in which R ⁵ to R ⁷ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas H ₂ C = CH-X-SO ₃ H H ₂ C = C (CN ₃ ) -X-SO ₃ H HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H, in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CN ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n with n = 0 to 4, -COO- (CH ₂ ) k- with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Especially preferred sulfonic acid group-containing Monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, Sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts the acids mentioned.

Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds. The content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer. Particularly preferred polymers to be used consist only of monomers of the formula R ¹ (R ² ) C = C (R ³ ) COOH and monomers of the formula R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H.

• i) einer oder mehreren ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln: H₂C=CH-X-SO₃H H₂C=C(CH₃)-X-SO₃H HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H, in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂) mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)
• iii) gegebenenfalls weiteren ionogenen oder nichtionogenen Monomeren.

Further particularly preferred copolymers consist of

• i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid
• ii) one or more sulfonic acid group-containing monomers of the formulas: H ₂ C = CH-X-SO ₃ H H ₂ C = C (CH ₃ ) -X-SO ₃ H HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H, in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C ( O) -NH-CH (CH ₂ CH ₃ )
• iii) optionally further ionogenic or nonionic monomers.

The Copolymers can the monomers from groups i) and ii) and optionally iii) contained in varying amounts, all representatives from the group i) with all Representatives from group ii) and all representatives from the group Group iii) can be combined. Particularly preferred polymers have certain structural units on, which are described below.

For example, copolymers which are structural units of the formula are preferred - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. When the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise preferred. The corresponding copolymers contain the structural units of the formula - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p , wherein m and p are each an integer between 1 and 2,000, and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein Spacer groups in which Y is -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred.

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, copolymers which are structural units of the formula - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, are particularly preferred, just as preferred as copolymers, the structural units of the formula [CH ₂ -C (CH ₃ ) COOH] _m [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred copolymers, the structural units of the formula - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) where n = 0 to 4, -O- (C ₆ H ₄ ) -, -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , are preferred. Also preferred according to the invention are copolymers which contain structural units of the formula - [HCOOCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ )- stands.

In the polymers can the sulfonic acid groups wholly or partly in neutralized form, i. that the acidic acid atom of the sulfonic acid group in some or all of them Sulfonic acid groups against Metal ions, preferably alkali metal ions and in particular against Sodium ions, can be replaced. The use of partial or fully neutralized sulfonic acid group-containing Copolymer is preferred according to the invention.

The Monomer distribution of the copolymers preferably used according to the invention is for copolymers containing only monomers from groups i) and ii), preferably in each case from 5 to 95% by weight of i) or ii), particularly preferably 50 to 90% by weight of monomer from group i) and 10 to 50% by weight Monomer from group ii), in each case based on the polymer.

at Terpolymers are particularly preferred which contain from 20 to 85% by weight. Monomer from group i), 10 to 60 wt .-% monomer from the group ii) and 5 to 30 wt .-% of monomer from group iii).

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred washing or cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

The bleaching agents are a particularly preferred washing or cleaning substance. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organi bleaching agents 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-phthalimidoperoxycaproic acid [phthaliminoperoxyhexanoic acid (PAP)] , o-Carboxybenzamidoperoxycaproic acid, N-Nonenylamidoperadipinsäure and N-Nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-Diperoxyazelainsäure, Diperocysebacinsäure, Diperoxybrassylsäure, the Diperoxyphthalsäuren, 2-Decyldiperoxybutan-1,4- diacid, N, N-terephthaloyl-di (6-aminopercapronate).

When Bleach can Chlorine or bromine releasing substances are used. Among the suitable chlorine or bromine releasing materials come for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Bleach activators are used in detergents or cleaning agents, for example, to improve cleaning at temperatures of 60 ° C and below To achieve bleaching effect. As bleach activators, compounds, which under perhydrolysis aliphatic peroxycarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, are used. Suitable substances are the O and / or N-acyl groups of said carbon atom number and / or optionally substituted Wear 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, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA) and acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated Sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, Tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example, N-benzoyl-caprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Also combinations Conventional bleach activators can be used.

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist.Further bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula

in which R ¹ is -H, -CH _3, a C _2-24 -alkyl or -alkenyl radical, a substituted C _2-24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C _1-24 -alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) - CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion.

in der R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt sind aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, wobei R⁴ zusätzlich auch -H sein kann und X ein Anion ist, wobei vorzugsweise R⁵ = R⁶ = -CH₃ und insbesondere R⁴ = R⁵ = R⁶ = -CH₃ gilt und Verbindungen der Formeln (CH₃)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH(CH₃))₃N⁽⁺⁾CH₂-CN X^–, oder (HO-CH₂-CH₂)₃N⁽⁺⁾CH₂-CN X^– besonders bevorzugt sind, wobei aus der Gruppe dieser Substanzen wiederum das kationische Nitril der Formel (CH₃)₃N⁽⁺⁾CN₂-CN X^–, in welcher X^– für ein Anion steht, das aus der Gruppe Chlorid, Bromid, Iodid, Hydrogensulfat, Methosulfat, p-Toluolsulfonat (Tosylat) oder Xylolsulfonat ausgewählt ist, besonders bevorzugt wird.Particularly preferred is a cationic nitrile of the formula

in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , wherein R ⁴ additionally also -H may be and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ( CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{- are} particularly preferred, wherein from the group of these substances turn the cationic nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CN ₂ -CN X ^- in which X ^{- is} an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is particularly preferred.

In addition to The conventional bleach activators or in their place may also so-called bleach catalysts are used. For these substances These are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline 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 ammine complexes are useful as bleach catalysts.

Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate in usual Quantities, preferably in an amount up to 5 wt .-%, in particular from 0.0025 wt.% to 1 wt.%, and more preferably from 0.01 Wt .-% to 0.25 wt .-%, each based on the total weight of inventive agent used. In special cases can However, more bleach activator can be used.

It is particularly preferred to use complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1,4,7-triazacyclononane (Me / TACN). Suitable manganese complexes are, for example, [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₂ (μ-OAc) ₁ (TACN ) ₂ ] (BPh ₄ ) ₂ , [Mn ^IV ₄ (μ-O) ₆ (TACN) ₄ ] (ClO ₄ ) ₄ , [Mn ^III ₂ (μ-O) ₂ (μ-OAc) ₂ (Me-TACN ) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₁ (μ-OAc) ₂ (Me-TACN) ₂ ] (ClO ₄ ) ₃ , [Mn ^IV ₂ (μ-O) ₃ ( Me-TACN) ₂ ] (PF ₆ ) ₂ and [Mn ^IV ₂ (μ-O) ₃ (Me / Me-TACN) ₂ ] (PF ₆ ) ₂ (OAc = OC (O) CH ₃ ).

To increase the washing or cleaning performance of detergents or cleaners enzymes can be used. 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. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 × 10 ^-6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Under Proteases are preferred to those of the subtilisin type. Examples therefor are the subtilisins BPN 'and Carlsberg and its advanced forms, the protease PB92, subtilisins 147 and 309, the Bacillus alkaline protease lentus, subtilisin DY and the subtilases, but not anymore the enzymes subtilisins in the strict sense, thermitase, Proteinase K and the proteases TW3 and TW7.

Examples for inventively usable Amylases are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as those for use in washing and Detergents improved developments of the aforementioned Amylases. Furthermore are for this purpose the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Usable according to the invention are still lipases or cutinases, especially because of their Triglyceride-splitting activities, but also to in situ peracids from suitable precursors produce. These include for example, the original one from Humicola lanuginosa (Thermomyces lanuginosus) available, respectively further developed lipases, in particular those with the amino acid exchange D96L. Furthermore, for example, the cutinases can be used, the original from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose starting enzymes originally from Pseudomonas mendocina and Fusarium solanii have been isolated.

Farther can Enzymes are used, which are summarized by the term hemicellulases. These include for example mannanases, xanthan lyases, pectin lyases (= pectinases), Pectinesterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

Especially Preference is given to using perhydrolases in the compositions according to the invention.

to increase the bleaching effect oxidoreductases according to the invention, for example, oxidases, oxygenases, catalases, peroxidases, such as Halo, chloro, bromo, lignin, glucose or manganese peroxidases, Dioxygenases or laccases (phenol oxidases, polyphenol oxidases) be used. Advantageously, in addition preferably organic, particularly preferably aromatic, interacting with the enzymes Compounds added to the activity of the respective oxidoreductases to reinforce (Enhancer) or at very different redox potentials between the oxidizing enzymes and the soiling the electron flow to ensure (Mediators).

The Enzymes can used in any form established in the prior art become. These include for example, by granulation, extrusion or lyophilization obtained solid preparations or, especially in liquid or gelatinous Means, solutions the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers.

alternative can the enzymes for both the solid as well for the liquid Dosage form can be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are as in enclosed in a solidified gel or in those of the core-shell type, in which a enzyme-containing core coated with a water, air and / or chemical impermeable protective layer is. In superimposed layers additional active ingredients, For example, stabilizers, emulsifiers, pigments, bleach or Dyes are applied. Such capsules are after known methods, for example by shaking or Roll granulation or applied in fluid-bed processes. Advantageously Such granules, for example by applying polymeric film-forming agents, low in dust and storage-stable due to the coating.

Farther Is it possible, to assemble two or more enzymes together, making one individual granules has several enzyme activities.

One Protein and / or enzyme may be particularly harmful during storage against damage such as inactivation, denaturation or decay, for example through physical influences, Oxidation or proteolytic cleavage are protected. In microbial Obtaining the proteins and / or enzymes is inhibiting the Proteolysis particularly preferred, especially if the means Contain proteases. Detergents or cleaners can contain stabilizers for this purpose; the provision of such funds represents a preferred embodiment of the present invention.

Glass corrosion inhibitors prevent the occurrence of cloudiness, Streaks and scratches but also iridescence of the glass surface of mechanically cleaned glasses. Preferred glass corrosion inhibitors come from the group of Magnesium and zinc salts as well as the magnesium and zinc complexes.

The Spectrum of the invention preferred Zinc salts, preferably organic acids, more preferably organic Carboxylic acids, ranges from salts that are heavy or insoluble in water; so a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 mg / L, to such salts dissolved in water a solubility above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubility at 20 ° C water temperature). The first group of zinc salts includes, for example, zinc citrate, the zinc oleate and the zinc stearate, to the group of soluble Zinc salts belong for example, zinc formate, zinc acetate, zinc lactate and the zinc gluconate.

With Particular preference is given as a glass corrosion inhibitor at least one Zinc salt of an organic carboxylic acid, more preferably one Zinc salt from the group of zinc stearate, zinc oleate, zinc gluconate, zinc acetate, Zinc lactate and zinc citrate used. Also zinc ricinoleate, zinc abietate and zinc oxalate are preferred.

Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, especially silver protectants can selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. According to the invention, preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts. Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid. Especially effective are 5-pentyl, 5-heptyl, 5-nonyl, 5-undecyl, 5-isononyl, 5-versatic-10-alkyl-3-amino-1,2,4-triazoles and mixtures of these substances.

you In addition, cleaning agent formulations often contain active chlorine Means that can significantly reduce the corrosion of the silver surface. In Chlorine-free cleaners are especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds used. Also salt- and complex-like inorganic compounds, such as salts of Metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Prefers here are the transition metal salts, the selected are from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Also can Zinc compounds used to prevent corrosion of items to be washed become.

Instead of from or in addition to the silver protectants described above, for example the Benzotriazoles, can redox-active substances are used. These substances are preferably inorganic redox-active substances from the group Manganese, Titanium, Zirconium, Hafnium, Vanadium, Cobalt and Cerium salts and / or complexes, the metals preferably in one of the oxidation states II, III, IV, V or VI.

The used metal salts or metal complexes should at least partially soluble in water be. The counterions suitable for salt formation include all common ones mono-, di- or tri-negatively charged inorganic anions, e.g. Oxide, sulphate, nitrate, fluoride, but also organic anions such as. Stearate.

Particularly preferred metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ , and mixtures thereof, such that the metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) _{3 are used} with particular preference ,

The inorganic redox-active substances, in particular metal salts or metal complexes are preferably coated, i. completely with a waterproof, but easily soluble at the cleaning temperatures Material coated, to their premature decomposition or oxidation during storage too prevent. Preferred coating materials which, according to known methods, such as Sandwik's melt coating process from the food industry, are applied are paraffins, microwaxes, waxes of natural origin like carnauba wax, candellila wax, beeswax, higher melting Alcohols such as hexadecanol, soaps or fatty acids.

In the case, that the particles according to the invention or the finished product in the form of compacted shaped bodies such as Tablets are made up, it is preferred that the respective Formulation disintegrating agent contains. To the disintegration of prefabricated moldings to facilitate, it is possible Disintegration aids, so-called disintegrants, in to incorporate these agents to reduce disintegration times. Under Tablet disintegrants or disintegrators are adjuvants understood that for the rapid disintegration of tablets in water or other media and for ensure the release of the active ingredients.

These Substances that are also referred to as "explosives" due to their effect increase when water enters their volume, on the one hand increasing the intrinsic volume (swelling), on the other hand also about the Release of gases can create a pressure on the tablet can disintegrate into smaller particles. Well-known Disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can be used. Swelling disintegration aids are for example synthetic Polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified Natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Preferred disintegrating agents are cellulosic disintegrating agents, so that preferred washing or cleaning agents comprise such cellulose-based disintegrants in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight. % contain. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.

The Cellulose used as disintegration aid is preferably not used in finely divided form, but before mixing transferred to the premixes to be compressed in a coarser form, for example, granulated or compacted. The particle sizes of such Disintegrating agents are usually above 200 microns, preferably at least 90 wt .-% between 300 and 1600 microns and in particular at least 90 wt .-% between 400 and 1200 microns.

When another disintegrating agent based on cellulose or as an ingredient This component can be used microcrystalline cellulose. This microcrystalline cellulose is made by partial hydrolysis of Celluloses obtained under such conditions, only the amorphous ones Areas (about 30% of the total cellulose mass) of the celluloses attack and completely dissolve, the crystalline areas (about 70%) but leave undamaged. A subsequent disaggregation of the resulting from the hydrolysis microfine celluloses provide the microcrystalline celluloses, the primary particle sizes of approx. 5 μm and compactable, for example, to granules having an average particle size of 200 microns are.

preferred Disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are in the disintegrants containing agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6 wt .-%, each based on the total weight of the disintegrant-containing agent.

According to the invention preferred can about that in addition, gas-evolving effervescent systems as tablet disintegration aids be used. The gas-developing effervescent system can from a consist of a single substance which releases a gas on contact with water. Among these compounds is in particular the magnesium peroxide to call, which releases oxygen on contact with water. Usually However, the gas-releasing effervescent system in turn from at least two components that are together under gas formation react. While here a variety of systems is thinkable and executable, for example Nitrogen, oxygen or hydrogen will release the both in the detergents and cleaners used effervescent system on the basis of economic as well as ecological Select points of view to let. Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifier, the is suitable to release carbon dioxide from the alkali metal salts in aqueous solution.

When Acidifying agent consisting of the alkali metal salts in aqueous solution carbon dioxide are, for example, boric acid and alkali metal hydrogen sulfates, Alkali metal dihydrogen phosphates and other inorganic salts. However, preference is given to using organic acidifiers, where the citric acid a particularly preferred acidifying agent. Preferred are Acidifier in effervescent system from the group of organic Di-, tri- and oligocarboxylic acids or mixtures.

As perfume oils or fragrances, individual fragrance compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons, can be used in the context of the present invention. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also have natural odor mixtures of substances obtainable from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.

Around To be perceptible, a perfume must be volatile, being next to the Nature of the functional groups and the structure of the chemical Compound also plays a role in the molecular weight. So own most fragrances have molecular weights up to about 200 daltons, while molar masses from 300 daltons and above constitute an exception. Due to the different volatility changed by fragrances the smell of a compound of several fragrances perfumes or perfume during Evaporation, whereby the odor impressions in "top note", "middle note" (middle note or body) and "base note" (end note or dry divided out). Because the smell perception to a large extent too on the smell intensity is based, the top note of a perfume or fragrance is not alone from volatile Connections while the base note for the most part from less volatile, i.e. adherent fragrances. When composing perfumes can be easier volatile For example, fragrances can be bound to specific fixatives. which prevents it from evaporating too quickly. At the following Classification of the fragrances in "lighter volatile or "adherent" fragrances So over the smell impression and about it, whether the corresponding perfume perceived as a head or middle note nothing is said.

The Fragrances can can be processed directly, but it can also be beneficial to the Fragrances on carrier The slow release of fragrance for long-lasting Provide scent. As such carrier materials For example, cyclodextrins have proven useful, with the cyclodextrin-perfume complexes additionally still can be coated with other excipients.

preferred Dyes whose selection does not present any difficulty to the skilled person have a high storage stability and insensitivity to the rest Ingredients of the agents and against light and no pronounced substantivity to the with the dye-containing agents to be treated substrates such as for example textiles, glass, ceramics or plastic dishes, so as not to stain them.

When choosing the colorant, it must be taken into account that the colorants have a high storage stability and insensitivity to light. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, colorant concentrations in the range of a few 10 ^-2 to 10 ^-3 % by weight are typically selected. By contrast, in the case of the particularly preferred, but less readily water-soluble, pigment dyes due to their brilliance, the suitable concentration of the colorant in detergents or cleaners is typically about 10 ^-3 to 10 ^-4 % by weight.

It become colorants preferably oxidative in the washing process destroyed can be and mixtures thereof with suitable blue dyes, so-called. Bluing agents. It has proved to be advantageous to use dyes which in water or at room temperature in liquid organic substances are soluble. Suitable are, for example, anionic colorants, e.g. anionic Nitroso.

In addition to so far in detail described components can the detergents and cleaners contain other ingredients, which the application and / or aesthetic properties of this Improve funds further. Preferred agents include one or several substances from the group of electrolytes, pH adjusters, fluorescers, Hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, Anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Antistatic agents, ironing aids, Phobic and impregnating agents, Swelling and anti-slip agents as well as UV absorbers.

As electrolytes from the group of inorganic salts, a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl ₂ in the washing or cleaning agents is preferred.

In order to bring the pH of detergents or cleaners into the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use for application or environmental reasons or for the sake of Consumer protection prohibits. Usually, the amount of these adjusting agents does not exceed 1% by weight of the total formulation.

Suitable foam inhibitors are, inter alia, soaps, oils, fats, paraffins or silicone oils, which may optionally be applied to support materials. Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the abovementioned materials. In the context of the present application preferred agents include paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are constructed according to the scheme (R ₂ SiO) x and are also referred to as silicone oils. These silicone oils usually are clear, colorless, neutral, odorless, hydrophobic liquids having a molecular weight between 1,000 and 150,000, and viscosities between 10 and 1,000,000 mPa · s.

Suitable anti-redeposition agents, which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether , According to the invention, amphiphilic polymer which comprises ester units of C ₂ to C ₄ -polyalkylene glycol with aromatic dicarboxylic acids is present in the particles according to the invention. In addition, the further constituents which are mixed with the particles according to the invention to form a finished product may comprise further polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof , Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.

optical Brighteners (so-called "whiteners") can Detergents or cleaners are added to graying and to eliminate yellowing of the treated textiles. These Substances attract to the fiber and cause a whitening and feigned Bleaching action by turning invisible ultraviolet radiation into visible length wavy Convert light, with the ultraviolet absorbed from sunlight Light as slightly bluish Fluorescence is emitted and with the yellow of the bated or yellowed laundry pure white results. Suitable compounds are derived, for example, from the substance classes 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyryl-biphenylene, Methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid, Benzoxazole, benzisoxazole and benzimidazole systems and the by Heterocycles substituted pyrene derivatives.

graying have the task of removing the dirt from the fiber in the fleet to keep it suspended, thus allowing the dirt to be recovered prevent. These are water-soluble Colloids mostly organic nature suitable, for example, the water-soluble Salts of polymeric carboxylic acids, glue, Gelatin, salts of ether sulfonic acids the strength or the cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water-soluble, Acidic group-containing polyamides are suitable for this purpose. Farther can be soluble Starch preparations and other than the aforesaid starch products use, e.g. degraded starch, aldehyde etc. Also, polyvinylpyrrolidone is useful. As grayness inhibitors Cellulose ethers such as carboxymethylcellulose (Na salt) can also be used, Methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, Methylhydroxypropylcellulose, methylcarboxymethylcellulose and their Mixtures.

There textile fabrics, in particular of rayon; Creel, cotton and their mixtures, for Can tend to wrinkles, because the individual fibers against bending, bending, pressing and squeezing are sensitive to the grain direction, synthetic crease inhibitors be used. These include, for example synthetic products based on fatty acids, fatty acid esters, fatty acid amides, Alkylolestern, -alkylolamiden or fatty alcohols, usually with Ethylene oxide reacted or products based on lecithin or modified phosphoric acid ester.

Phobic and impregnation processes are used to furnish textiles with substances that prevent the deposition of dirt or facilitate its leaching ability. Preferred repellents and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum u. Zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or with perfluorinated acyl or sulfonyl radical coupled, polymerizable compounds. Antistatic agents may also be included. The antisoiling equipment with lathering and impregnating agents is often classified as an easy-care finish. The penetration of the impregnating agent in the form of solutions or emulsions of the active substances in question can be facilitated by adding wetting agents which reduce the surface tension. Another field of application of repellents and impregnating agents is the water-repellent finish of textiles, Zel ten, tarpaulins, leather, etc., in which, in contrast to waterproofing, the fabric pores are not closed, so the fabric remains breathable (hydrophobing). The water repellents used for hydrophobizing coat textiles; Leather, paper, wood, etc. with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups. Suitable water repellents are, for example, paraffins, waxes, metal soaps, etc. with additions of aluminum or zirconium salts, quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, silicones, tin-organic compounds and glutaric dialdehyde and perfluorinated compounds. The hydrophobized materials do not feel greasy; nevertheless, similar to greasy substances, water droplets emit from them without moistening. For example, silicone-impregnated textiles have a soft feel and are water and dirt repellent; Stains from ink, wine, fruit juices and the like are easier to remove.

to fight of microorganisms can antimicrobial agents are used. This is different depending on the antimicrobial spectrum and mechanism of action between Bacteriostats and bactericides, fungistats and fungicides etc .. Important substances from these groups are, for example, benzalkonium chlorides, Alkylarlylsulfonates, halophenols and Phenolmercuriacetat, wherein also completely on these compounds can be dispensed with.

Around unwanted, caused by oxygen and other oxidative processes changes on the detergents and / or the treated textiles to prevent the agents contain antioxidants. To this class of connection belong for example substituted phenols, hydroquinones, catechols and aromatic amines and organic sulfides, polysulfides, dithiocarbamates, Phosphites and phosphonates.

One increased Comfort can come from the extra Use of antistatics will result. Antistatic agents increase the surface conductivity and allow thus an improved drainage formed charges. External antistatic agents are usually substances with at least one hydrophilic molecule ligand and give on the surfaces a more or less hygroscopic film. These mostly surface-active Antistatic agents can be converted into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid ester) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistatics for Textiles or as an additive to detergents, with an additional Avivageeffekt is achieved.

to Improvement of water absorbency, rewettability treated textiles and to facilitate ironing treated textiles can Silicone derivatives are used. These additionally improve that rinse behavior of detergents or cleaners by their foam-inhibiting Properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes where the alkyl groups one to five Have C atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes which may optionally be derivatized can and are then amino-functional or quaternized or Si-OH-, Si-H- and / or Si-Cl bonds exhibit. Further preferred silicones are the polyalkylene oxide-modified Polysiloxanes, ie polysiloxanes, which are, for example, polyethylene glycols and the polyalkylene oxide-modified dimethylpolysiloxanes.

Finally, according to the invention, UV absorbers which are applied to the treated textiles and the light resistance improve the fibers. Compounds that have these desired properties are, for example, by radiationless deactivation effective compounds and derivatives of benzophenone with substituents in 2- and / or 4-position. Furthermore, substituted benzotriazoles, in the 3-position phenyl-substituted Acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes as well Natural substances such as umbelliferone and the body's own urocanic acid are suitable.

Protein hydrolyzates are due to their fiber-care effect further in the context of the present invention preferred active substances from the field of detergents and cleaners. Protein hydrolysates are product mixtures obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins). According to the invention, protein hydrolysates of both vegetable and animal origin can be used. Animal protein hydrolysates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolysates, which may also be present in the form of salts. Preferred according to the invention is the use of protein hydrolysates of plant origin, for example soybean, almond, rice, pea, potato and wheat protein hydrolysates. Although the use of the protein hydrolysates is preferred as such, amino acid residues otherwise obtained in their place may optionally be used or individual amino acids such as arginine, lysine, histidine or pyrroglutamic acid. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products.

One Another object of the present invention relates to finished products, which particles of the invention containing dirt repellent properties, it being preferred is that these finished products in addition to the particles of the invention contain further ingredients.

finished products For the purposes of this invention, in particular washing, care and / or cleaning agents for hard and / or soft surfaces.

finished products in the sense of this invention for example, a laundry care product, a softener, Fabric conditioners, a dishwashing detergent and / or a precursor of the aforementioned finished products.

Next the said applications of the particles according to the invention in detergents and care products, such as softener / laundry aftertreatment agent, can the particles of the invention with dirt repellent effect in household cleaning products and technical cleaning agents are used to a good Soil release effect, i. Dirt-repellent effect against soiling to achieve.

Examples for household cleaning products are all-purpose cleaners, dishwashing granules, carpet cleaning and impregnating agents, Cleaning and care products for Floors and other hard surfaces, for example, made of plastic, ceramic or glass.

Examples for technical Cleaning agents are plastic cleaning and care products, such as for housing and Car fittings, as well as cleaning and care products for lacquered surfaces like car bodies.

at the finished products are preferably solid products. fixed-shaped Products can for example, as granules, such as powder or as a compressed moldings such as detergent tablets, dishwasher tablets and the like. But there are also gel finished products conceivable that the particles of the invention Contains dirt repellent effect.

The Finished products can the particles of the invention as separate, i. as discrete particles. Especially can the particles in the finished product may be contained as loose discrete particles and / or in a compressed form as a shaped body, For example, in a tableted form, wherein finished product or the moldings in addition to the particles according to the invention preferably may have further ingredients.

As already described, the particles of the invention show no or at most a very small tendency to segregate, so that the particles homogeneously stable distribution in finished products or intermediates to let. It has been shown that finished products or intermediates, the particles of the invention contained, storage and / or transport stable with respect to a segregation the particles of the invention could be. It is not only granular finished products in which the particles according to the invention are homogeneously distributed, but also finished products such as compressed moldings, For example, tabs and the like, since the mixtures of the particles according to the invention and the ingredients added during the manufacturing process maintain their homogeneous distribution. Another advantage is that the particles according to the invention containing finished products when used in wash liquor good solubility and / or dispersibility, especially for larger particles.

It can but also liquid Finished products are used, the particles of the invention stable contained, i. the particles according to the invention dissolve in the liquid Finished product not on and retain essentially their shape. Such finished products are saturated solutions, so that the particles according to the invention contained therein remain stable. saturated Solutions, the for Such use is contemplated in the art known.

The finished product may contain the particles according to the invention having a soil-repelling effect with a weight fraction of at least 0.01% by weight and not more than 30% by weight, preferably from 0.1% by weight to 20% by weight, preferably from 0, 5 wt% to 15 wt%, more preferably from 1 wt% to 10 wt%, even more preferably from 2 wt% to 5 wt%, and most preferably 3 wt%. -%, based on the total amount weight of the finished product.

The Finished products can additionally to the particles of the invention in particular contain the following ingredients. suitable Ingredients include ingredients such as washing, care and / or cleaning active Substances, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, builders, bleaches, bleach activators, Bleach stabilizers, bleach catalysts, soil release and soil repellent compounds, Enzymes, enzyme stabilizers, polymers, cobuilders, alkalizers, Acidifiers, anti redeposition agents, silver protectants, dye, UV protection substances, UV absorbers, optical brighteners, neutral filler salts as well as dyes and fragrances, fabric softeners, foam inhibitors and / or rinse aid, and optionally further admixed ingredients.

These as well as other suitable ingredients have already been described in detail above Service.

According to a preferred embodiment, a compacted under mechanical pressure, in particular extruded detergents, care and / or cleaning agents, particles according to the invention and other customary washing, care and / or detergent ingredients are added or admixed. Washing the compacted under mechanical pressure washing or cleaning agent components are included available for example as Megaperls ^® of Henkel KGaA. The compacted under mechanical pressure, extruded detergent, care and / or detergent ingredients may be added to the finished product preferably in nachverrundeter form. Inventive finished products, such as detergents, care and / or cleaning agents, contain the particles according to the invention and further admixed constituents, wherein the admixed constituents may be identical, in part identical or different in comparison to the constituents of the particles according to the invention.

The the finished products in addition to the particles of the invention added ingredients can be used in the preparation of the Finished products simultaneously with the particles of the invention be added and / or subsequently be added. To produce a homogeneous distribution of the Finished product contained particles of the invention and other ingredients These are mixed, for example by means of a mixer and bottled in a further step or portioned.

According to one another preferred embodiment have the particles according to the invention as well as the additional supplied Components of the finished product as equal as possible particle size.

It is therefore preferred if the finished product contains at least 50% by weight, preferably at least 55% by weight, preferably at least 60% by weight, more preferably at least 65% by weight, even more preferably at least 70% by weight %, moreover preferably at least 75% by weight, more preferably at least 80% by weight, even more preferably at least 85% by weight, at least 90% by weight, at least 95% by weight and most preferably at least 99% by weight in the form of particles, the particles having a particle size d ₅₀ of ≥ 0.1 mm and ≤ 5 mm, preferably a particle size d ₅₀ of ≥ 0.2 mm and ≤ 3 mm, in particular a particle size d ₅₀ of ≥ 0.3 mm and ≦ 2 mm, preferably a particle size d ₅₀ of ≥ 0.5 mm and ≦ 1.8 mm, more preferably a particle size d ₅₀ of ≥ 0.8 mm and ≦ 1, 7 mm, and particularly preferably have a particle size d ₅₀ of ≥ 1.0 mm and ≤ 1.6 mm.

According to one preferred embodiment In the present invention, the particles are repellent with dirt Effect in the finished product substantially homogeneous, preferably homogeneous distributed. Preferably, the concentration deviates from that contained according to the invention amphiphilic polymer or other constituent of the finished product in a single sample of the finished product by less than 50% by weight, preferably less than 40% by weight, more preferably less than 30% by weight, more preferably less than 20% by weight, especially preferably less than 10% by weight, most preferably about less than 5% by weight and in particular less than 2.5% by weight from a homogeneous distribution of the particles according to the invention in the finished product from. The homogeneity of the finished product can, as above in the homogeneity of the particles according to the invention executed be determined.

One Another object of the present invention relates to a method for producing the particles according to the invention with soil repellent Effect.

Surprisingly, it has now been found that it is possible to produce particles with a high active content of amphiphilic polymer and homogeneous distribution in the particles if the components comprising polyethylene glycol, amphiphilic polymers, wherein the amphiphilic polymer ester units of C ₂ to C ₄ alkylene glycol and / or C ₂ to C ₄ having polyalkylene glycol with aromatic dicarboxylic acids, and Gege if appropriate, polycarboxylate, sprayed in a fluidized bed. Preference is given to spraying into a fluidized bed which already has particles of the abovementioned substances as a template in the vortex chamber.

The By means of fluidized bed processes so produced particles according to the invention can in particular a very homogeneous distribution of the components contained therein Polyethylene glycol and amphiphilic polymer.

The used fluidized bed process for the preparation of the particles according to the invention with dirt-repellent effect allows in addition to a homogeneous Distribution of components also high levels of active substances, one setting the particle size distribution the particle, and a regulation of the water content.

Walzenkompaktierverfahren, as is common in the art for the Processing of high-active-matter masses, on the other hand have the disadvantage that already due to the applied pressure and the resulting from the pressure liquefaction of some ingredients a homogeneous distribution can not be achieved practically.

The used according to the invention Process for the preparation of particles with dirt-repellent effect thus avoids the disadvantages known from the roll compacting process, that due to the pressure exerted during the rolling compacting process and the resulting from the pressure liquefaction of some ingredients a homogeneous distribution is not guaranteed. Also be in the Compared to Walzkompaktierverfahren substantially spherical Obtained particles.

According to the present Invention can the particles with dirt-repellent effect preferably by a Melt granulation be prepared in the fluidized bed. For this becomes a melt comprising polyethylene glycol and amphiphilic polymer into a fluidized bed in which solids are atomized. In addition, can a polymer, preferably polycarboxylate, can be used.

The Polycarboxylate is preferably of acrylic acid and maleic acid units and their salts formed. Preferably, the copolymer is a sodium salt an acrylic acid / maleic acid copolymer, the acrylic acid units in the copolymer in excess available.

The Polycarboxylate is preferably sprayed as an aqueous solution in the fluidized bed. To the spray or nozzles in the fluidized bed, for example, 20 wt .-% to 40 are suitable Wt .-% aqueous Polycarboxylatlösungen. Suitable polycarboxylates have already been described in detail above which is why in order to avoid repetition of this in full Scope is referred to.

to Production of the particles according to the invention For example, spray dryers can be used with a dirt-repelling effect use with integrated fluidized bed. By installing a fluidized bed at the bottom of the spray tower If necessary, the product can be dried and sifted there become. As a product are large, low-dust, readily dispersible agglomerates obtained which a low Have demixing tendency.

Especially can be fluidized bed spray granulators ("Agglomeration dryer"), for the production from granules in the range of 0.3 mm to several mm of atomizable Solutions, like melting, use. For atomization, in the description also as spraying or nozzles denotes two-fluid nozzles are preferably used. The finished one Particle product is usually compact and abrasion resistant and flexible adjustable bulk weight characterized.

There the substances polyethylene glycol and the amphiphilic polymer are substances that are solid at room temperature, these are first transferred into a melt and then the fluidized bed is sprayed. The produced melt can Contain portions of water, wherein it is preferred that the melt is anhydrous.

For example You can melt a polyethylene glycol (PEG) and amphiphilic Make polymer in a stirred tank. The melt is over a nozzle atomized into the cold fluidized bed, where a melt solidification, preferably on already contained in the fluidized bed solids takes place. The fed from below Cold air solidifies the melt so that the granules are free-flowing. As support can also a polymer in small amounts, preferably an acrylic acid / maleic acid copolymer, or other detergent raw materials are sprayed into the fluidized bed.

If the particles of the invention in the fluidized bed the desired Particle size reached these settle in the lower part of the vortex chamber and can be removed continuously or discontinuously and / or be supplied to further process steps. Fines can be recycled become.

Further can in the fluidized bed and / or in a post-treatment step the particles according to the invention additional ingredients are added, which have already been described in detail above and to which reference is made in full. Especially can be beneficial for the particles of the invention the incorporation of surfactants and in particular the incorporation of linear alkylbenzenesulfonates.

• – Erwärmen festförmiger Bestandteile umfassend Polyethylenglykol und amphiphiles Polymer, wie Polyethylenglykolterephthalat, zwecks Erzeugung einer versprühfähigen Masse, beispielsweise einer Schmelze;
• – Versprühen der versprühfähigen Masse in eine Wirbelschicht, wobei die versprühfähige Masse zusätzlich Wasser aufweisen kann;
• – Verfestigen und Agglomerieren, beispielsweise Schmelzgranulation, der in die Wirbelschicht eingesprühten Masse zu Partikeln.

In general, the method for producing the particles with dirt-repellent effect may comprise the steps of

• Heating solid constituents comprising polyethylene glycol and amphiphilic polymer, such as polyethylene glycol terephthalate, for the purpose of producing a sprayable mass, for example a melt;
• - Spraying the sprayable mass in a fluidized bed, wherein the sprayable mass may additionally comprise water;
• Solidification and agglomeration, for example melt granulation, of the mass sprayed into the fluidized bed into particles.

According to the method of the invention For example, the polyethylene glycol (PEG) may be added in an amount corresponding to Recipe at 80 ° C be melted. After the addition of the PEG is also the amphiphilic Polymer, preferably acrylic acid / maleic acid copolymer, melted in the amount of the recipe in the same storage container. For homogenization can by means of stirrer several times the melt / powder mixture are circulated. The melting process can be done several hours before granulation.

The Granulation in the fluidized bed may preferably be at a supply air temperature of 10 to 55 ° C, preferred from 10 to 40 ° C and in particular from 20 to 35 ° C, carried out become.

The Air for atomization can over a compressor are generated, the air for atomizing up an elevated one Pressure of ≥ 0.5 bar, preferably ≥ 1 bar, in particular ≥ 1 bar, preferably ≥ 2.5 bar and / or a temperature of ≥ 70 ° C, preferably ≥ 80 ° C set can be. The pressure data are as overpressure based on normal pressure specified.

The Melt can, for example, over at least one, preferably 2 to 3 nozzles conveyed into the fluidized bed or sprayed become. about another nozzle may optionally be an aqueous Polymer solution for example, an aqueous Polycarboxylate solution, different from the amphiphilic polymer, fed or sprayed.

The sprayed Mass may, based on the weight fraction of the components of polyethylene glycol and amphiphilic polymer of the composition, at least 1% by weight to maximum 70 wt .-% polyethylene glycol and at least 30 wt .-% to maximum 99% by weight of amphiphilic polymer, in particular polyethylene glycol terephthalate, where the components are chosen are that the total weight of the mass does not exceed 100% by weight and the sprayable mass Water with a proportion by weight based on the sprayable mass of ≥ 0% by weight to ≤ 15 Wt .-%, preferably ≤ 10 % By weight.

According to the method of the invention can additionally a polymer different from the amphiphilic polymer, for example Polycarboxylate, preferably a 10% to 50%, preferably 20%, by weight to 40% by weight, aqueous Polycarboxylate solution, sprayed into the fluidized bed wherein the polycarboxylate is preferably of acrylic acid and Maleic acid units and salts thereof, preferably, the copolymer is a Sodium salt of an acrylic acid / maleic acid copolymer, the acrylic acid units in the copolymer in excess available.

The Polymer which is different from the amphiphilic polymer was already described in the description of the particles, so that To avoid repetition, to the full extent on the previous ones versions reference is made to this.

According to the inventive method, it may be preferred that the particles are kept in the fluidized bed until it has a particle size d ₅₀ of ≥ 0.1 mm and ≤ 3 mm, preferably a particle size d ₅₀ of ≥ 0.3 mm and ≤ 2 mm, in particular a particle size d ₅₀ of ≥ 0.5 mm and ≤ 1.8 mm, more preferably a particle size d ₅₀ of ≥ 0.8 mm and ≤ 1.7 mm, and particularly preferably have a particle size d ₅₀ of ≥ 1.0 mm and ≤ 1.6 mm.

According to one preferred embodiment the present invention can be sprayed into a fluidized bed, the already particulate Material comprising polyethylene glycol and polyethylene glycol terephthalate; or polyethylene glycol, polyethylene glycol terephthalate and polycarboxylate; or even more Having ingredients, which is already present in the fluidized bed Material on which sprayed is obtained, preferably from one of the preceding process runs has been.

Further may enter the fluidized bed or in a subsequent process step the particles with dirt repellent effect at least one ingredient with washing, care and / or cleaning activity, preferably anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic Surfactants, builders, bleaches, bleach activators, bleach stabilizers, Bleach catalysts, enzymes, polymers, cobuilders, alkalizers, Acidifiers, anti redeposition agents, silver protectants, Dyeing, optical Brighteners, UV protectants, fabric softeners, perfume, foam inhibitors and / or rinse aid be added.

Claims (26)

Particles having a dirt-repellent effect, suitable as an additive in detergents, care preparations and / or cleaners, characterized in that the particles, based on the total weight of the particles, as components 1 wt .-% to 70 wt .-% polyethylene glycol and 30 Wt .-% to 99 wt .-% of at least one amphiphilic polymer, wherein the amphiphilic polymer ester units of C ₂ to C ₄ alkylene glycol and / or C ₂ to C ₄ polyalkylene glycol having aromatic dicarboxylic acids, and wherein the components are so selected are that the total weight of the components does not exceed 100% by weight. Particle according to Claim 1, characterized that the particles, based on the total weight of the particles, polyethylene glycol with a weight fraction of 5 wt .-% to 45 wt .-%, preferably from 10% by weight to 40% by weight, preferably from 15% by weight to 30% by weight and most preferably from 20% to 25% by weight and / or amphiphilic Polymer in a weight fraction of 55 wt .-% to 85 wt .-%, preferably from 60% by weight to 80% by weight, preferably from 65% by weight to 78% by weight and most preferably from 70% to 75% by weight. Particles according to claim 1 or 2, characterized that the polyethylene glycol has a melting temperature of ≥ 40 ° C and ≤ 100 ° C, preferably of ≥ 45 ° C and ≤ 70 ° C, preferred of ≥ 50 ° C and ≤ 65 ° C and on most preferably ≥55 ° C and ≤60 ° C. Particles according to one of the preceding claims, characterized characterized in that the polyethylene glycol has a molecular weight from 400 to 20,000, preferably from 1,000 to 10,000, preferably from 2000 to 8000 and most preferably from 3000 to 5000. Particles according to one of the preceding claims, characterized characterized in that the amphiphilic polymer comprises ester units, made up from: - aromatic dicarboxylic acids, selected from the group comprising dimethyl terephthalic acid and / or terephthalic acid; and - Glycol units and / or polyglycol units. Particles according to one of the preceding claims, characterized in that the particles have a particle size d ₅₀ of ≥ 0.1 mm and ≤ 3 mm, preferably a particle size d ₅₀ of ≥ 0.3 mm and ≤ 2 mm, preferably a particle size d ₅₀ of ≥ 0.5 mm and ≤ 1.8 mm, still preferably has a particle size d ₅₀ of ≥ 0.8 mm and ≤ 1.7 mm, and particularly preferably has a particle size d ₅₀ of ≥ 1.0 mm and ≤ 1.6 mm, have. Particles according to one of the preceding claims, characterized characterized in that the particles having a particle size in the range of 0.05 mm and 5 mm, preferably in the range of 0.1 mm and 3 mm, more preferably in the range of 0.2 mm and 2.5 mm, more preferably in the range of 0.4 mm and 2 mm, and more preferably in the range of 0.6 mm and 1.8 mm in diameter. Particles according to one of the preceding claims, characterized in that the particles have a shape factor of at least 0.70, preferably of at least 0.75, preferably of at least 0.80, more preferably of at least 0.85 and most preferably of at least 0.90. Particles according to one of the preceding claims, characterized characterized in that the particles comprise a polymer which is different to the amphiphilic polymer, preferably polycarboxylate, is preferred formed from acrylic acid and maleic acid units and their salts, and preferably the copolymer is a sodium salt an acrylic acid / maleic acid copolymer, the acrylic acid units in the copolymer in excess available. Particles according to one of the preceding claims, characterized in that the particles prefer the polycarboxylate Acrylic acid / maleic acid copolymer, with a proportion by weight, based on the total weight of the particles, of ≥ 0.05 Wt .-% to ≤ 10 Wt .-%, preferably from 0.1 wt .-% to 8 wt .-%, preferably from From 0.5% to 5% by weight and more preferably from 1% to 3% by weight Wt .-%, contained. Particles according to one of the preceding claims, characterized in that the particles are water, based on the total weight of particles, of ≥ 0 Wt .-% to ≤ 10 Wt .-%, preferably from 0.1 wt .-% to 8 wt .-%, preferably from From 0.5% to 5% by weight and more preferably from 1% to 3% by weight Wt .-%, contained. Particles according to one of the preceding claims, characterized characterized in that the particles are the components amphiphilic polymer, preferably polyethylene glycol terephthalate and polycarboxylate in the weight ratio of 125: 1 to 10: 1, preferably from 100: 1 to 12.5: 1, more preferably from 75: 1 to 15: 1, more preferably from 50: 1 to 17.6: 1 and in particular from 25: 1 to 20: 1. Particles according to one of the preceding claims, characterized characterized in that the particles are the components amphiphilic polymer, preferably polyethylene glycol terephthalate, and polyethylene glycol in the weight ratio from 99: 1 to 1: 2, preferably from 75: 1 to 1: 1.5, more preferably from 50: 1 to 1: 1, more preferably from 25: 1 to 1.5: 1, and in particular from 5: 1 to 2: 1. Particles according to one of the preceding claims, characterized characterized in that the bulk density of the particles 350 g / l to <600 g / l and preferably 400 g / l to 550 g / l or> 600 g / l to 900 g / l and preferably 700 g / l to 800 g / l. Particles according to one of the preceding claims, characterized marked that - ≥ 0 to 1% by weight the particle has a particle diameter of> 2 mm, - 0.5 to 1.5 wt .-% of the particles a particle diameter of> 1.8 mm to 2 mm, - 5 up to 20% by weight of the particles have a particle diameter of> 1.6 mm to 1.8 mm, - 20 to 40% by weight of the particles have a particle diameter of> 1.4 mm to 1.6 mm, - 20 to 40% by weight of the particles have a particle diameter of> 1.18 mm to 1.4 mm, - 10 to 25% by weight of the particles have a particle diameter of> 1.0 mm to 1.18 mm, - 1 to 15% by weight of the particles have a particle diameter of> 0.80 mm to 1.0 mm, - ≥ 0 to 1% by weight the particle has a particle diameter of> 0.6 mm to 0.80 mm, based on the total weight of the particles, wherein the total weight of the respective Sieve fractions of the particles is chosen to be 100% by weight results. Particles according to one of the preceding claims, characterized marked that - ≥ 0 to 0.5 % By weight of the particles has a particle diameter of> 2 mm, - 0.8 to 1.4% by weight of the particles have a particle diameter of> 1.8 mm to 2 mm, - 10 to 15% by weight of the particles have a particle diameter of> 1.6 mm to 1.8 mm, - 25 to 35% by weight of the particles have a particle diameter of> 1.4 mm to 1.6 mm, - 25 to 35% by weight of the particles have a particle diameter of> 1.18 mm to 1.4 mm, - 15 to 22 wt .-% of the particles have a particle diameter of> 1.0 mm to 1.18 mm, - 5 to 10% by weight of the particles have a particle diameter of> 0.80 mm to 1.0 mm, - ≥ 0 to 0.5 % By weight of the particles has a particle diameter of> 0.6 mm to 0.80 mm, based on the total weight of the particles, wherein the Total weight of the respective sieve fractions of the particles is selected that it gives 100 wt .-%. Finished product, in particular washing, care and / or cleaning agent, characterized in that the finished product at least 0.01 wt .-% and at most 30 wt .-%, preferably 0.1 wt .-% to 20 wt .-%, preferably 0.5 wt% to 15 wt%, more preferably 1 wt% to 10 wt%, even further before 2 wt .-% to 5 wt .-% and most preferably 3 wt .-% of the particles according to one of claims 1 to 16, based on the total weight of the finished product having. Finished product according to claim 17, characterized that the finished product in addition has at least one, preferably more additives to the particles, selected from the group, comprising as washing, care and / or cleaning active Substances anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, builders, bleaches, bleach activators, Bleach stabilizers, bleach catalysts, enzymes, polymers, cobuilders, Alkalizing agent, acidifying agent, anti redeposition agent, Silver protectants, colorants, optical brighteners, UV protectants, softeners, perfume, foam inhibitors and / or rinse aid, and optionally further admixed ingredients. Finished product according to claim 17 or 18, characterized in that at least 50 wt .-%, preferably at least 60 wt .-%, preferably at least 70 wt .-%, more preferably at least 80 wt .-%, still preferably at least 90 wt. % and most preferably at least 99% by weight of the finished product is in the form of particles, the particles having a particle size d ₅₀ of ≥ 0.1 mm and ≤ 5 mm, preferably a particle size d ₅₀ of ≥ 0.3 mm and ≤ 2 mm, preferably has a particle size d ₅₀ of ≥ 0.5 mm and ≦ 1.8 mm, more preferably a particle size d ₅₀ of ≥ 0.8 mm and ≦ 1.7 mm, and particularly preferably has a particle size d ₅₀ of ≥ 1.0 mm and ≤ 1.6 mm. Process for producing the particles with dirt Repellent effect according to one of claims 1 to 16, characterized in that that the method comprises the steps of - Heating solid constituents comprising Polyethylene glycol and polyethylene glycol terephthalate for the purpose of production a sprayable mass; - Spraying the sprayable mass in a fluidized bed, wherein the sprayable mass additionally water having; - solidify the mass sprayed into the fluidized bed into particles. Process for the preparation of the particles according to claim 20, characterized in that the sprayed mass, based on the Weight fraction of the components polyethylene glycol and amphiphilic Polymer of the mass, at least 1 wt .-% to a maximum of 70 wt .-% polyethylene glycol and at least 30% by weight to at most 99% by weight of amphiphilic polymer, preferably polyethylene glycol terephthalate, wherein the Components chosen are that the total weight of the mass does not exceed 100% by weight and the sprayable mass Water with a proportion by weight based on the sprayable mass of ≥ 0% by weight to ≤ 15 % By weight. Process for the preparation of the particles according to claim 20 or 21, characterized in that additionally a polymer which is different to the amphiphilic polymer, preferably polycarboxylate, is preferred a 10 wt% to 50 wt%, more preferably 20 wt% to 40 Wt .-% aqueous Polycarboxylate solution, sprayed into the fluidized bed wherein the polycarboxylate is preferably selected from acrylic acid and Maleic acid units and salts thereof, preferably, the copolymer is a Sodium salt of an acrylic acid / Maleic acid copolymer, the acrylic acid units in the copolymer in excess available. Process for the preparation of the particles after a the claims 20 to 22, characterized in that is sprayed into a fluidized bed, the already particulate Material comprising polyethylene glycol and polyethylene glycol terephthalate; or polyethylene glycol, polyethylene glycol terephthalate and polycarboxylate; or the additional one Having ingredients, which is already present in the fluidized bed Material on which sprayed is obtained, preferably from one of the preceding process runs is. Process for producing the particles according to one of Claims 20 to 23, characterized in that the particles are kept in the fluidized bed until they have a particle size d ₅₀ of ≥ 0.1 mm and ≤ 3 mm, preferably a particle size d ₅₀ of ≥ 0 , 3 mm and ≦ 2 mm, preferably has a particle size d ₅₀ of ≥ 0.5 mm and ≦ 1.8 mm, more preferably a particle size d ₅₀ of ≥ 0.8 mm and ≦ 1.7 mm, and particularly preferably a particle size d ₅₀ of ≥ 1.0 mm and ≤ 1.6 mm. A process for the production of the particles according to any one of claims 20 to 24, characterized in that in the fluidized bed or in a subsequent process step the particles with dirt repellent effect at least one ingredient with washing, care and / or cleaning active, preferably anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, builders, bleach agents, bleach activators, bleach stabilizers, bleach catalysts, enzymes, polymers, cobuilders, alkalizers, acidifiers, anti-redeposition agents, silver protectants, colorants, optical brighteners, UV protectants, fabric softeners, perfume, foam inhibitors and / or rinse aid. Use of the method according to one of claims 20 to 25 for the production of particles with dirt-repellent effect according to one of the claims 1 to 16.