DE102014218953A1 - Portion for textile treatment agent - Google Patents

Abstract

A portion for use in textile treatment, comprising at least two chambers with walls of water-soluble material, in which a) at least one of these chambers contains a liquid composition, each containing a total amount of from -25 to 60% by weight, based on the total weight of the liquid composition. % of at least one anionic surfactant and - 2 to 35 wt .-% of at least one nonionic surfactant, and b) at least one further of these chambers, a solid composition containing, in each case based on the total weight of the solid composition, a total amount of - 25 to 55 Wt .-% of at least one peroxide compound, - 2 to 25 wt .-% of at least one organic bleach activator, - 0 to 5 wt .-% surfactant contains, despite the high amount of solid peroxide compound and solid organic bleach activator at dosage in the washing drum to no local damage to the textile

Description

The present invention relates to the technical field of textile treatment, in particular textile cleaning or textile washing.

For the purification of textiles, the person skilled in the art knows various suitable active substances which, as an additive, for example in detergents, specifically effect the removal or the reduced perception of dirt. The skilled person will distinguish e.g. for this purpose, dirt removed predominantly by surfactants from dirt, e.g. can be removed with the help of enzymes or bleaches.

The quality of the removal of bleachable soils such as e.g. Colored fruit and vegetable stains is a central quality feature of a detergent. During bleaching, on the one hand, the bleachable dirt is to be bleached and / or removed. On the other hand, the textile should not be damaged by bleaching.

Conventional bleaches can be incorporated as an active ingredient storage stable in solid detergents, but not in liquid detergents. Liquid detergents are becoming increasingly popular with consumers and the market share of liquid detergents is growing. Due to the aforementioned stability problem of bleaches in liquid detergents, a solid bleach composition can be a useful supplement to the use of liquid detergents.

A solid bleach composition which can be used as an additive to a liquid detergent should contain little additional ingredients in addition to the bleach-active compound for gentle use of the resources. For the formulation of a solid bleach additive in a water-soluble casing as a metering unit, it is advantageous if said bleach additive occupies a small volume. The rationalization of additional ingredients and the reduction in the volume of the overall composition inevitably result in a high concentration of bleach-active compound in the solid component. This high concentration can lead to problems in the application, since at the beginning of the textile treatment, the addition of the said metering unit usually takes place via the washing drum of a washing machine and the metering unit thereby comes into direct contact with the textile. If water is now added during the textile treatment, the water-soluble coating dissolves and the bleach additive is released. In order to avoid damage to the textile due to local excess concentration of bleach, the bleach additive should dissolve quickly in the water. It has been found that the solubility behavior of the bleach additive decreases due to the presence of surfactant and a local over-concentration of surfactant during the textile treatment.

The skilled worker is aware of surfactant-containing portions as a one-time dosing aid for textile treatment compositions, which in addition to a solid composition additionally contain a liquid composition, which are enveloped by a water-soluble film.

The publication US 4,973,416 relates to a portion as a disposable dosing aid containing a liquid detergent and separately a bleach granules in the same portion, both compositions are covered by a water-soluble film.

The publication WO 01/83667 A1 relates to multi-compartment bags of a water-soluble film containing in a first chamber a liquid composition containing at least 50% by weight of surfactant; and in a second compartment contains a solid composition, which in turn may optionally contain a bleaching agent and, optionally, a bleach activator.

High performance bleach-active compounds are usually peroxide compounds in combination with bleach activators, with organic bleach activators being particularly effective. Bleach activators are understood by the person skilled in the art to mean chemical compounds which increase the bleaching action in the presence of peroxide compounds. In particular, less polar organic bleach activators require a certain amount of time to dissolve in water. If solid detergents containing solid bleach activators are added to the fabric in solid form in the wash basket, a local over-concentration of bleach activator may occur during the dissolution process (especially with a concomitant local over-concentration of surfactant). The latter can lead to punctiform damage to the textile, e.g. lead to local fading of the textile dye.

The patent EP 2 011 856 B1 relates to multi-chamber bags made of a water-soluble film containing a liquid composition in a first chamber; and in a second chamber, a solid composition containing from 60% to 95% by weight of a peroxide source. However, these multi-chamber bags are explicitly free of bleach activator.

The publication EP 2 014 756 A1 relates to multi-compartment bags of a water-soluble film containing in a first chamber a liquid composition having dissolved therein bleach activator; and in a second chamber, a solid composition containing from 60% to 95% by weight of a peroxide source.

It was therefore an object to provide a surfactant-containing portion for textile treatment which comprises a liquid composition and a solid bleach additive of peroxide compound and bleach activator in a solid composition, the bleach additive rapidly dissolving in water during the textile treatment. Local damage to the textile should be prevented.

In addition, when using said surfactant-containing portion of the textiles are to be spared and improve the washing performance of detergents, in particular liquid detergents in the context of a textile laundry. In particular, bleachable stains are effectively removed from the textile in a short time in a manner that protects the textile.

It has been found that by providing a high concentration of peroxide compound and bleach activator in the solid composition, a particular selection and formulation of the surfactants in the portion improves wash performance and protects the fabric.

• a) mindestens eine dieser Kammern eine flüssige Zusammensetzung, enthaltend jeweils bezogen auf das Gesamtgewicht der flüssigen Zusammensetzung jeweils eine Gesamtmenge von – 25 bis 60 Gew.-% mindestens eines anionischen Tensids und – 2 bis 35 Gew.-% mindestens eines nichtionischen Tensids, enthält, und

• b) mindestens eine weitere dieser Kammern eine festförmige Zusammensetzung, enthaltend jeweils bezogen auf das Gesamtgewicht der festförmigen Zusammensetzung jeweils eine Gesamtmenge von – 25 bis 55 Gew.-% mindestens einer Peroxidverbindung, – 2 bis 25 Gew.-% mindestens eines organischen Bleichaktivators, – 0 bis 5 Gew.-% Tensid,

enthält. A first subject of the invention is therefore a portion for use in textile treatment, comprising at least two chambers with walls of water-soluble material, characterized in that

• a) at least one of these chambers contains a liquid composition, in each case based on the total weight of the liquid composition contains a total amount of - 25 to 60 wt .-% of at least one anionic surfactant and - 2 to 35 wt .-% of at least one nonionic surfactant , and

• b) at least one further of these chambers has a solid composition, in each case based on the total weight of the solid composition, a total amount of from -25 to 55% by weight of at least one peroxide compound, from 2 to 25% by weight of at least one organic bleach activator, 0 to 5 wt.% Surfactant,

contains.

In said portion, said solid and liquid compositions are each in a chamber formed of water-soluble material. The water-soluble material forms walls of the chamber and thereby envelops the inventive composition of the first subject of the invention.

One portion is an independent dosing unit with at least one chamber, is contained in the metered Good. A chamber is a space bounded by walls (e.g., by a foil), which may exist even without the material to be dosed (possibly changing its shape). A layer of a surface coating thus does not explicitly fall under the definition of a wall.

The walls of the chamber are made of a water-soluble material. The water solubility of the material can be determined by means of a square film of the said material (film: 22 × 22 mm with a thickness of 76 μm) fixed in a square frame (edge length on the inside: 20 mm) according to the following measurement protocol. Said framed film is immersed in 800 mL of distilled water heated to 20 ° C in a 1 liter beaker with a circular bottom surface (Schott, Mainz, 1000 mL beaker, low mold) so that the surface of the clamped film is at right angles to the Bottom surface of the beaker is arranged, the upper edge of the frame is 1 cm below the water surface and the lower edge of the frame is aligned parallel to the bottom surface of the beaker such that the lower edge of the frame along the radius of the bottom surface of the beaker and the center of the lower edge of the frame is located above the center of the radius of the beaker bottom. The material should stir (stirring speed magnetic stirrer 300 rpm, stirring bar: 6.8 cm long, diameter 10 mm) within 600 seconds in such a way that no single solid-shaped film particles are more visible to the naked eye. The walls are preferably made of a water-soluble film. This film may according to the invention preferably have a thickness of at most 150 microns (more preferably of at most 120 microns). Accordingly, preferred walls are made of a water-soluble film and have a thickness of at most 150 μm (more preferably of at most 120 μm, very particularly preferably of at most 90 μm).

Such water-soluble portions may be prepared by either vertical fill-seal (VFFS) or thermoforming techniques.

The thermoforming process generally includes forming a first layer of water-soluble film material to form at least one protrusion for receiving at least one composition therein, filling the composition into the respective protrusion, covering the composition-filled protrusions with a second layer of water-soluble one Film material and sealing the first and second layers together at least around the protrusions.

The water-soluble material preferably contains at least one water-soluble polymer. In addition, the water-soluble material preferably contains a water-soluble film material selected from polymers or polymer blends. The wrapper may be formed of one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, may be the same or different.

It is preferable that the water-soluble material contains polyvinyl alcohol or a polyvinyl alcohol copolymer.

Suitable water-soluble films as water-soluble material are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in each case in the range from 10,000 to 1,000,000 gmol ^-1 , preferably from 20,000 to 500,000 gmol ^-1 , particularly preferably from 30,000 to 100,000 gmol ^-1 and in particular from 40,000 to 80,000 gmol ^-1 .

The production of polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble material comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

The film material suitable as water-soluble material may additionally be added polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyether polylactic acid, and / or mixtures of the above polymers.

Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.

Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.

Suitable water-soluble films for use as the water-soluble material of the water-soluble portion according to the invention are films sold under the name Monosol M8630 by MonoSol LLC. Other suitable films include films called Solublon ^® PT, Solublon ^® CA, Solublon ^® KC or Solublon ^® KL from the AICELLO Chemical Europe GmbH or films VF-HP by Kuraray, or HiSelon SH2312 Nippon Gohsei.

The solid and liquid compositions may contain, in addition to the mandatory ingredients, other optional ingredients. The said total quantities are selected from the predetermined weight ranges in such a way that, together with the quantities of optional ingredients for said composition based on their total weight of 100% by weight.

A fabric (e.g., a composition) is, as defined by the invention, solid when in the solid state at 25 ° C and 1013 mbar.

A substance (e.g., a composition), as defined by the invention, is liquid when in the liquid state at 25 ° C and 1013 mbar.

A chemical compound is an organic compound when the molecule of the chemical compound contains at least one covalent bond between carbon and hydrogen. This definition applies inter alia to "organic bleach activators" as a chemical compound mutatis mutandis.

A chemical compound is, inversely to the definition of the organic compound, an inorganic compound when the molecule of the chemical compound does not contain a covalent bond between carbon and hydrogen. This definition applies inter alia to inorganic peroxide compounds as a chemical compound mutatis mutandis.

A peroxide compound is a chemical compound containing, as a structural fragment, the peroxo atomic group -O-O-.

In the context of this application for polymeric ingredients specified average molecular weights are - unless otherwise indicated - always to weight average molecular weights Mw, which are basically determined by gel permeation chromatography using an RI detector, the measurement is advantageously carried out against an external standard ,

It has been found preferable if the solid-shaped composition of the portion is formed from a plurality of solid particles. Such an embodiment of the solid composition is preferably present as powder or granules. The said solid particles in turn preferably have a particle diameter X _50.3 (volume average) of 100 to 1500 microns. These particle sizes can be determined by sieving or by means of a particle size analyzer Camsizer from Retsch.

• – die besagte feste Zusammensetzung in einer Gesamtmenge von 4,0 bis 10,0 g, insbesondere von 5,0 bis 9,0 g und/oder
• – die besagte flüssige Zusammensetzung in einer Gesamtmenge von 10,0 bis 20,0 g, insbesondere von 14,0 bis 18,0 g.

The portion preferably contains

• - The said solid composition in a total amount of 4.0 to 10.0 g, in particular from 5.0 to 9.0 g and / or
• - The said liquid composition in a total amount of 10.0 to 20.0 g, in particular from 14.0 to 18.0 g.

The solid composition of the portion according to the invention necessarily contains a defined amount of peroxide compound. It has proved to be preferred according to the invention if the solid-form composition according to the invention, based on the total weight of the composition, contains peroxide compounds in a total amount of from 30 to 50% by weight, in particular from 33 to 45% by weight.

It is preferred according to the invention if the peroxide compound is selected from at least one inorganic peroxide compound.

Suitable peroxide compounds are in particular percarbonate compounds, perborate compounds, peroxodisulfate compounds, hydrogen peroxide, addition compounds of hydrogen peroxide to inorganic compounds, organic peroxyacids or mixtures of at least two of these compounds. It is particularly preferred according to the invention if the peroxide compound is selected from sodium percarbonate, sodium perborate, sodium peroxodisulfate or mixtures thereof. Sodium percarbonate is a most preferred peroxide compound. Sodium percarbonate is an addition compound of hydrogen peroxide to sodium carbonate having the formula yNa ₂ CO ₃ .xH ₂ O ₂ , where x is the molar amount of hydrogen peroxide per mole of Na ₂ CO ₃ . Most preferably, the peroxide compound is Na ₂ CO _3. 1.5H ₂ O ₂ with the CAS number 15630-89-4 ,

According to the invention, the peroxide compound used according to the invention preferably has an active oxygen content of between 9.0% and 15.0%, in particular from 10.0% to 14.0% (measured in each case by titration with potassium permanganate).

It has proved to be preferable for the solution of the object according to the invention, when the peroxide compound is particulate, in particular as a powder or granules. In this case, it is again preferred if the particles containing the peroxide compound (for example the powder or granules) have a bulk density of from 0.70 to 1.30 kg / dm ³ , particularly preferably having a bulk density of from 0.85 to 1.20 kg / dm ³ (each measured after ISO 697 ), exhibit.

In addition, preference is given to those peroxide compounds whose particles have an average particle size (volume average) X _50.3 of 0.40 to 0.95 mm, in particular of 0.50 to 0.90 mm (eg measured by sieve analysis or by a Particle size analyzer Camsizer, Retsch) have.

A solid peroxide compound, in particular sodium percarbonate, can be provided with a coating for additional protection against decomposition on the surface. The coating should protect against decomposition of the percarbonate. Suitable coating agents are preferably water-soluble passivating agents, such as, for example, sodium bicarbonate, sodium carbonate, sodium sulfate or metaborate compounds. It may be preferred according to the invention if the solid peroxide compound, in particular sodium percarbonate, is coated on the surface with at least sodium sulfate. In this case, it is preferred according to the invention if the solid-form peroxide compound has an average particle size X _50.3 of 0.40 to 0.95 mm, in particular 0.40 to 0.90 mm (for example measured with sieve analysis or by means of a particle size analyzer Camsizer, Retsch company) and are coated with sodium sulfate.

In order to additionally increase the storage stability of the composition according to the invention, the phthalmatization (ie reduction or prevention of possible heat formation by exothermic decomposition of the solid peroxide compound) can be used with a phlegmatizer, in particular with a metaborate compound (advantageously the composition according to the invention contains based on the peroxide compound content is from 50 to 100% by weight of Metaborate coated peroxide compound). However, the phlegmatizing coating of the solid peroxide compound is not mandatory.

The solid composition of the portion according to the invention necessarily contains organic bleach activator in a total amount of 10 to 20 wt .-%, preferably from 11 to 18 wt .-%, particularly preferably from 12 to 16 wt .-%, again preferably from 10 to 15 wt .-%, most preferably from 11 to 14 wt .-%.

As organic bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give peroxycarboxylic acids (in particular aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms), and / or optionally substituted perbenzoic acid. The aforementioned total amounts apply mutatis mutandis for these special organic bleach activators.

Solid compositions which contain organic bleach activator from at least one compound of the group of compounds which form aliphatic peroxycarboxylic acids under perhydrolysis conditions are preferred according to the invention. It is particularly preferred if the organic bleach activator is selected from at least one compound of the poly-N-acylated organic amines. The aforementioned total amounts apply mutatis mutandis for these special organic bleach activators.

Perhydrolysis is known to the person skilled in the art as a reaction in which, in a protic solvent (eg water), an anion ^- OOH covalently binds to a reactant RX by nucleophilic substitution to give the compound ROOH and the cleavage of a leaving group X leads to lysis of the chemical bond between R and X causes.

Of all the bleach activators known to the person skilled in the art, multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT) , acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferably used. The aforementioned total amounts apply mutatis mutandis for these special organic bleach activators.

• – 25 bis 55 Gew.-% (insbesondere 30 bis 50 Gew.-%) mindestens einer anorganischen Peroxidverbindung, insbesondere Natriumpercarbonat, und
• – 10 bis 20 Gew.-% mindestens eines organischen Bleichaktivators, aus mindestens einer Verbindung der Gruppe von Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxycarbonsäuren bilden, insbesondere mindestens ein mehrfach N-acyliertes organisches Amin.

Most preferably, the solid composition contains the portion as a bleaching agent

• - 25 to 55 wt .-% (in particular 30 to 50 wt .-%) of at least one inorganic peroxide compound, in particular sodium percarbonate, and
• From 10 to 20% by weight of at least one organic bleach activator, of at least one compound of the group of compounds which form aliphatic peroxycarboxylic acids under perhydrolysis conditions, in particular at least one multiply N-acylated organic amine.

According to the invention, it is imperative that the solid composition of the present invention does not contain a surfactant up to a maximum of 5 wt% surfactant (i.e., 0 to 5 wt% surfactant) based on the weight of the solid composition. Preferably, the solid composition according to the invention of the portion contains a total amount of 0 to 3 wt .-% surfactant, most preferably the inventive solid-like composition of the portion is free of surfactant.

Suitable surfactants are all surfactants suitable for textile treatment.

If the solid-form composition additionally contains surfactant, it is preferred to use soap as the surfactant. Soaps are the water-soluble sodium or potassium salts of the saturated and unsaturated fatty acids having from 10 to 20 carbon atoms, the rosin acids of rosin (yellow rosin soaps) and naphthenic acids which are used as solid or semi-solid mixtures mainly for washing and cleaning purposes. Sodium or potassium salts of the saturated and unsaturated fatty acids having 10 to 20 carbon atoms, in particular having 12 to 18 carbon atoms, are preferred soaps according to the invention.

Preferably, the solid composition having the aforesaid total surfactant content based on the total weight of the solid composition contains a total amount of 0 to 1% by weight (preferably 0 to 0.5% by weight) of nonionic surfactant.

Preferably, the solid composition, with the proviso of the aforementioned total surfactant content based on the total weight of the solid composition, contains a total amount of 0 to 4% by weight (in particular 0 to 2.5% by weight) of anionic surfactant.

The solid-shaped composition of the portion according to the invention preferably additionally contains an amount of alkali metal silicate. Particularly suitable alkali metal silicates are sodium silicate and / or potassium silicate. Particularly preferred is sodium silicate. As sodium silicates, very particular preference is given to using sodium metasilicate or water glass, again preferably water glass, in the solid-form composition according to the invention.

When the solid composition of the present invention contains the portion of alkali silicate, it preferably contains from 5.0 to 20.0% by weight in a total amount based on the weight of the solid composition.

The amount of alkali metal silicate is calculated without the water content (hydrate) optionally contained in the alkali metal silicate.

It is inventively preferred if the alkali metal silicates contained in the form of particles, in particular as granules, are present. In addition, preference is given to those alkali metal silicates whose particles have an average particle size (volume average) X _50.3 of 0.20 to 1.00 mm, in particular of 0.30 to 0.90 mm, in particular of 0.50 to 0.80 mm, (eg measured by sieve analysis or by a particle size analyzer Camsizer, Retsch).

Of these, independently or in combination, a weight ratio of alkali silicate to peroxide compound in a range of 10 to 1 to 1 to 4 proved to be particularly favorable.

Independently of or in combination, alkali metal silicates of the formula (SiO ₂ ) _n (Na ₂ O) _m (K ₂ O) _{p are} particularly preferred according to the invention, where n is a positive rational number and m and p independently of one another represent a positive rational number with the provisos that at least one of the parameters m or p is different from 0 and the ratio between n and the sum of m and p is between 1: 4 and 4: 1, in particular in the ratio range from 2: 1 to 4: 1 ,

• (A) Festförmige Zusammensetzung der erfindungsgemäßen Portion, enthaltend jeweils bezogen auf das Gesamtgewicht der festförmigen Zusammensetzung jeweils eine Gesamtmenge von – 25 bis 55 Gew.-% mindestens einer Peroxidverbindung, insbesondere Natriumpercarbonat, – 10 bis 20 Gew.-% mindestens eines organischen Bleichaktivators, – 5 bis 20 Gew.-% Silikat der Formel (SiO₂)_n(Na₂O)_m, wobei n für eine positive rationale Zahl steht und m für eine positive rationale Zahl steht, mit der Maßgabe, dass das Verhältnis zwischen n und m zwischen 1:4 und 4:1, insbesondere zwischen 2:1 und 4:1, liegt, – 0 bis 5 Gew.-% Tensid.
• (B) Festförmige Zusammensetzung der erfindungsgemäßen Portion, enthaltend jeweils bezogen auf das Gesamtgewicht der festförmigen Zusammensetzung jeweils eine Gesamtmenge von – 25 bis 55 Gew.-% mindestens einer Peroxidverbindung, insbesondere Natriumpercarbonat, – 10 bis 20 Gew.-% mindestens eines organischen Bleichaktivators, – 5 bis 20 Gew.-% Granulat von Silikat mit der Formel (SiO₂)_n(Na₂O)_m mit einer mittleren Partikelgröße (Volumenmittel) X_50,3 von 0,20 bis 1,00 mm, insbesondere von 0,30 bis 0,90 mm, insbesondere von 0,50 bis 0,80 mm, wobei n für eine positive rationale Zahl und m für eine positive rationale Zahl steht, mit der Maßgabe, dass das Verhältnis zwischen n und m zwischen 1:4 und 4:1, insbesondere zwischen 2:1 und 4:1, liegt, – 0 bis 5 Gew.-% Tensid.

In a particularly preferred embodiment of the invention, the solid-form composition according to the invention comprises, as alkali metal silicate, silicate of the formula (SiO ₂ ) _n (Na ₂ O) _m , where n is a positive rational number and m stands for a positive rational number, with the proviso that the ratio between n and m is between 1: 4 and 4: 1, in particular in the ratio range of 2: 1 to 4: 1. The following embodiments (A) or (B) of the solid composition of the portion are therefore considered to be particularly preferred:

• (A) solid composition of the portion according to the invention, in each case based on the total weight of the solid composition, a total amount of from -25 to 55% by weight of at least one peroxide compound, in particular sodium percarbonate, from 10 to 20% by weight of at least one organic bleach activator, - 5 to 20 wt .-% silicate of the formula (SiO ₂ ) _n (Na ₂ O) _m , where n is a positive rational number and m is a positive rational number, with the proviso that the ratio between n and m is between 1: 4 and 4: 1, in particular between 2: 1 and 4: 1, - 0 to 5 wt .-% surfactant.
• (B) solid composition of the portion according to the invention, containing in each case based on the total weight of the solid composition in each case a total amount of from 25 to 55% by weight of at least one peroxide compound, in particular sodium percarbonate, from 10 to 20% by weight of at least one organic bleach activator, 5 to 20% by weight of granules of silicate with the formula (SiO ₂ ) _n (Na ₂ O) _m having an average particle size (volume average) X _50.3 of 0.20 to 1.00 mm, in particular of 0, 30 to 0.90 mm, in particular from 0.50 to 0.80 mm, where n stands for a positive rational number and m for a positive rational number, with the proviso that the ratio between n and m between 1: 4 and 4: 1, in particular between 2: 1 and 4: 1, - 0 to 5 wt .-% surfactant.

The solid composition of the portion may contain, in addition to thermal stabilization, bicarbonate, calculated as sodium bicarbonate. Hydrogen carbonate is to be understood according to the invention as meaning a chemical compound which contains at least one hydrogencarbonate ion (HCO ₃ ^- ) prior to the preparation of the composition according to the invention and which is different from peroxide compounds according to the invention. The amount by weight of bicarbonate in the composition of the present invention is expressed by the definition of the equivalent amount by weight of sodium bicarbonate.

Solid compositions of the portion preferably contain, based on the total weight of the composition, bicarbonate in a total amount of from 5 to 50% by weight, more preferably from 7.5 to 30% by weight, calculated as sodium bicarbonate.

It is also preferred according to the invention to select bicarbonate from sodium bicarbonate, potassium bicarbonate or mixtures thereof. Very particularly preferably, the bicarbonate of sodium bicarbonate is suitable.

It has also been found to be preferred when hydrogen carbonate is particulate, in particular as a powder or granules.

It is furthermore preferred if the bicarbonate-containing particles (for example the powder or granules) have a bulk density of 0.40 to 1.50 kg / dm ³ , particularly preferably with a bulk density of 0.90 to 1.10 kg / dm ³ ( each measured after ISO 697 ), exhibit. Within the scope of this preferred bulk density, it has proven to be advantageous and particularly preferred if the particles containing the peroxide compound (for example the powder or granules) have a bulk density of 0.70 to 1.30 kg / dm ³ , particularly preferably with a bulk density of 0, 85 to 1.20 kg / dm ³ (each measured after ISO 697 ), exhibit.

• (C) Festförmige Zusammensetzung der erfindungsgemäßen Portion, enthaltend jeweils bezogen auf das Gesamtgewicht der festförmigen Zusammensetzung jeweils eine Gesamtmenge von – 30 bis 50 Gew.-% mindestens einer Peroxidverbindung, insbesondere Natriumpercarbonat, – 10 bis 20 Gew.-% mindestens eines organischen Bleichaktivators, – 5 bis 20 Gew.-% Silikat der Formel (SiO₂)_n(Na₂O)_m, wobei n für eine positive rationale Zahl steht und m für eine positive rationale Zahl steht, mit der Maßgabe, dass das Verhältnis zwischen n und m zwischen 1:4 und 4:1, insbesondere zwischen 2:1 und 4:1, liegt, – 7,5 bis 30 Gew.-% Natriumhydrogencarbonat, – 0 bis 5 Gew.-% Tensid.
• (D) Festförmige Zusammensetzung der erfindungsgemäßen Portion, enthaltend jeweils bezogen auf das Gesamtgewicht der festförmigen Zusammensetzung jeweils eine Gesamtmenge von – 30 bis 50 Gew.-% mindestens einer Peroxidverbindung, insbesondere Natriumpercarbonat, – 10 bis 20 Gew.-% mindestens eines organischen Bleichaktivators, – 5 bis 20 Gew.-% Granulat von Silikat mit der Formel (SiO₂)_n(Na₂O)_m mit einer mittleren Partikelgröße (Volumenmittel) X_50,3 von 0,20 bis 1,00 mm, insbesondere von 0,30 bis 0,90 mm, insbesondere von 0,50 bis 0,80 mm, wobei n für eine positive rationale Zahl und m für eine positive rationale Zahl steht, mit der Maßgabe, dass das Verhältnis zwischen n und m zwischen 1:4 und 4:1, insbesondere zwischen 2:1 und 4:1, liegt, – 7,5 bis 30 Gew.-% Natriumhydrogencarbonat, – 0 bis 5 Gew.-% Tensid.

The following embodiments (C) and (D) of the solid-form composition are particularly preferred for the portion according to the invention:

• (C) solid composition of the portion according to the invention, each containing a total amount of each based on the total weight of the solid composition From 30 to 50% by weight of at least one peroxide compound, in particular sodium percarbonate, from 10 to 20% by weight of at least one organic bleach activator, from 5 to 20% by weight of silicate of the formula (SiO ₂ ) _n (Na ₂ O) _m where n stands for a positive rational number and m stands for a positive rational number, with the proviso that the ratio between n and m is between 1: 4 and 4: 1, in particular between 2: 1 and 4: 1, - 7.5 to 30 wt .-% sodium bicarbonate, - 0 to 5 wt .-% surfactant.
• (D) solid composition of the portion according to the invention, containing in each case based on the total weight of the solid composition in each case a total amount of from 30 to 50% by weight of at least one peroxide compound, in particular sodium percarbonate, from 10 to 20% by weight of at least one organic bleach activator, 5 to 20% by weight of granules of silicate with the formula (SiO ₂ ) _n (Na ₂ O) _m having an average particle size (volume average) X _50.3 of 0.20 to 1.00 mm, in particular of 0, 30 to 0.90 mm, in particular from 0.50 to 0.80 mm, where n stands for a positive rational number and m for a positive rational number, with the proviso that the ratio between n and m between 1: 4 and 4: 1, in particular between 2: 1 and 4: 1, is, - 7.5 to 30 wt .-% sodium bicarbonate, - 0 to 5 wt .-% surfactant.

As a further ingredient, the solid compositions of the portion based on their total weight may preferably contain a total amount of 1 to 15 wt .-% of at least one Polysacharids.

According to the invention, a polysaccharide is understood as meaning saccharides which contain at least 10 glyceride-linked sugar structural units.

Within the scope of a preferred embodiment, the polysaccharide is present in the form of particles (preferably as a powder or as granules, particularly preferably as granules). It is again preferred if these particles have an average particle size (volume average) X _50.3 from 200 to 1600 μm, in particular from 300 to 1400 μm, in particular from 400 to 1200 μm, very particularly preferably from 600 to 1100 μm ( eg measured with sieve analysis or by a particle size analyzer Camsizer, company Retsch).

Preferred polysaccharides are cellulose and its derivatives, starch and derivatives thereof, and mixtures thereof. As the polysaccharide, the solid composition of the present invention preferably contains methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylhydroxyethylcellulose, methylcarboxymethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose (CMC), an ether sulfonic acid salt, an ether sulfonic acid salt of cellulose, an acid sulfuric acid ester salt of cellulose, an acid sulfuric acid ester salt of starch or the like Mixture of at least two of these polysaccharides.

The effect according to the invention is particularly pronounced when the polysaccharide contains at least one polysaccharide with at least one anionic group in the solid-form composition according to the invention. The anionic group covalently bonded to the polysaccharide groups, which are in protic solvents capable of forming an anion with the formal release of an H ⁺ ion, in particular carboxyl groups (-COOH), sulfonic acid groups (-SO ₃ H), sulfate groups (-O-SO ₃ H), phosphonic acid groups (-PO ₃ H). Preference is given to the use of at least one polysaccharide containing at least one carboxyl group, more preferably at least one carboxyalkyl-derivatized polysaccharide. Carboxyl group is understood according to the invention as meaning both the acid form -COOH and the deprotonated salt form (carboxylate group) with a corresponding cation as counterion. Suitable cations are especially monovalent ions, such as sodium ions, potassium ions, ammonium ions. This applies mutatis mutandis for carboxyalkyl-derivatized polysaccharide.

In a preferred embodiment, the polysaccharide of the invention contains at least one anionic polysaccharide selected from anionic cellulose, anionic starch or mixtures thereof. Again, it is preferred that the polysaccharide is selected from carboxyalkyl-derivatized cellulose, carboxyalkyl-derivatized starch or mixtures thereof. Carboxyalkyl-derivatized cellulose is very particularly preferred according to the invention.

Very particular preference is given as the polysaccharide carboxymethylcellulose, in particular sodium carboxymethylcellulose, in the compositions according to the invention.

The preferred total amount of polysaccharide, in particular of preferred polysaccharide (vide supra) (particularly preferably of carboxymethylcellulose), is from 1.5 to 12.0% by weight, more preferably from 2.0 to 10.0% by weight, completely particularly preferably from 2.5 to 9.5 wt .-%, each based on the weight of said composition.

In a further preferred embodiment, the composition according to the invention additionally contains at least one soil-release agent. Soil release agents are often referred to as "soil release" agents or because of their property, the treated surface, for example, the fiber, to provide dirt repellent, referred to as "soil repellents". Because of their chemical similarity to polyester fibers particularly effective soil release agents, but can also show the desired effect in fabrics of other materials are copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Soil-releasing polyesters of the type mentioned as well as their use in detergents have been known for a long time.

For example, polymers of ethylene terephthalate and polyethylene terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, and their use in detergents in the German Patent DE 28 57 292 described. Polymers having a molecular weight of 15,000 to 50,000 of ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 1000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 2: 1 to 6: 1, can according to the German Offenlegungsschrift DE 33 24 258 be used in detergents. The European patent EP 066 944 relates to textile treatment compositions containing a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. From the European patent EP 185 427 For example, methyl or ethyl group-end capped polyesters having ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents containing such soil release polymer are known. The European patent EP 241 984 relates to a polyester which in addition to oxyethylene groups and terephthalic acid units also contains substituted ethylene units and glycerol units. From the European patent EP 241 985 are known polyester containing in addition to oxyethylene groups and terephthalic acid units 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene and glycerol units and endgruppenverschlossen with C ₁ - to C ₄ alkyl groups are. The European patent EP 253 567 relates to soil release polymers having a molecular weight of 900 to 9000 of ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 0.6 to 0.95. From the European patent application EP 272 033 are at least partially by C _1-4 alkyl or acyl radicals end-capped polyester with poly-propylene terephthalate and polyoxyethylene terephthalate units known. The European patent EP 274 907 describes sulfoethyl end-capped terephthalate-containing soil release polyesters. In the European patent application EP 357,280 are prepared by sulfonation of unsaturated end groups soil release polyester with terephthalate, alkylene glycol and poly-C _2-4 glycol units.

in denen
a, b und c unabhängig voneinander jeweils für eine Zahl von 1 bis 200 steht,
d, e und f unabhängig voneinander jeweils für eine Zahl von 1 bis 50 steht,
g für eine Zahl von 0 bis 5 steht,
Ph für einen 1,4-Phenylenrest steht,
sPh für einen in Position 5 mit einer Gruppe -SO₃M substituierten 1,3-Phenylenrest steht,
M für Li, Na, K, Mg/2, Ca/2, Al/3, Ammonium, Mono-, Di-, Tri- oder Tetraalkylammonium steht,
wobei es sich bei den Alkylresten der Ammoniumionen um C₁-C₂₂-Alkyl- oder C₂-C₁₀-Hydroxyalkylreste oder deren beliebige Mischungen handelt,
R¹, R², R³, R⁴, R⁵ und R⁶ unabhängig voneinander jeweils für Wasserstoff oder eine C₁-C₁₈- n- oder iso-Alkylgruppe steht,
R⁷ für eine lineare oder verzweigte C₁-C₃₀-Alkylgruppe oder für eine lineare oder verzweigte C₂-C₃₀-Alkenylgruppe, für eine Cycloalkylgruppe mit 5 bis 9 Kohlenstoffatomen, für eine C₆-C₃₀-Arylgruppe oder für eine C₆-C₃₀-Arylalkygruppe steht, und In a preferred embodiment of the invention, the composition according to the invention contains at least one soil release-capable polyester comprising the structural units I to III or I to IV,

in which
a, b and c independently of one another each represent a number from 1 to 200,
d, e and f independently of one another each represent a number from 1 to 50,
g is a number from 0 to 5,
Ph is a 1,4-phenylene radical,
sPh is a 1,3-phenylene radical substituted in position 5 by a group -SO ₃ M,
M is Li, Na, K, Mg / 2, Ca / 2, Al / 3, ammonium, mono-, di-, tri- or tetraalkylammonium,
wherein the alkyl radicals of the ammonium ions are C ₁ -C ₂₂ -alkyl or C ₂ -C ₁₀ -hydroxyalkyl radicals or any mixtures thereof,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another each represent hydrogen or a C ₁ -C ₁₈ -n- or iso-alkyl group,
R ^{7 is} a linear or branched C ₁ -C ₃₀ -alkyl group or a linear or branched C ₂ -C ₃₀ -alkenyl group, a cycloalkyl group having 5 to 9 carbon atoms, a C ₆ -C ₃₀ -aryl group or a C ₆ -C ₃₀ arylalkyl group, and

Polyfunctional unit for a unit having 3 to 6 functional groups capable of esterification reaction.

Preference is given to polyesters in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen or methyl, R ^{7 is} methyl, a, b and c are each independently a number from 1 to 200, in particular 1 to 20, particularly preferably 1 to 5, very preferably a and b = 1 and c can be a number from 2 to 10, d is a number between 1 and 25, in particular between 1 and 10, particularly preferably between 1 and 5, e is a number between 1 and 30, in particular between 2 and 15, particularly preferred between 3 and 10 and f a number between 0.05 and 15, in particular between 0.1 and 10 and particularly prefers between 0.25 and 3 means. Such polyesters can be obtained, for example, by polycondensation of terephthalic acid dialkyl ester, 5-sulfoisophthalic acid dialkyl ester, alkylene glycols, optionally polyalkylene glycols (at a, b and / or c> 1) and polyalkylene glycols end capped on one side (corresponding to unit III). It should be pointed out that for numbers a, b, c> 1 there is a polymeric skeleton and thus the coefficients as an average can assume any value in the given interval. This value reflects the number average molecular weight. As the unit (I) is an ester of terephthalic acid with one or more difunctional, aliphatic alcohols in question, preferably used here are ethylene glycol (R ¹ and R ^{2 are} each H) and / or 1,2-propylene glycol (R ¹ = H and R ² = -CH ₃ or vice versa) and / or shorter-chain polyethylene glycols and / or poly [ethylene glycol-co-propylene glycol] having number-average molecular weights of 100 to 2000 g / mol. In the structures, for example, from 1 to 50 units (I) can be contained per polymer chain. As the unit (II) is an ester of 5-sulfoisophthalic acid with one or more difunctional, aliphatic alcohols in question, preferably used are the aforementioned. In the structures, for example, 1 to 50 units (II) may be present. Poly (ethylene glycol-co-propylene glycol) monomethyl ethers with average molecular weights of 100 to 2000 g / mol and polyethylene glycol monomethyl ethers of the general formula CH ₃ -O- (C ₂ H ₄ O) are preferably used as nonionically unilaterally sealed polyalkylene glycol monoalkyl ethers according to unit (III) _n -H where n = 1 to 99, in particular 1 to 20 and particularly preferably 2 to 10. Since the theoretical maximum quantitative molecular weight of a polyester structure to be achieved in quantitative conversion is predetermined by using such unilaterally closed ethers, the preferred use quantity of the structural unit ( III) that necessary to achieve the mean molecular weights described below. Apart from linear polyesters which result from the structural units (I), (II) and (III), the use of crosslinked or branched polyester structures is also according to the invention. This is expressed by the presence of a crosslinking polyfunctional structural unit (IV) having at least three to a maximum of 6 functional groups capable of esterification reaction. For example, acid, alcohol, ester, anhydride or epoxy groups can be named as functional groups. Different functionalities in one molecule are also possible. As examples, citric acid, malic acid, tartaric acid and gallic acid, particularly preferably 2,2-dihydroxymethylpropionic acid, can be used for this purpose. Furthermore, polyhydric alcohols such as pentaerythrol, glycerol, sorbitol and / or trimethylolpropane can be used. These may also be polybasic aliphatic or aromatic carboxylic acids, such as benzene-1,2,3-tricarboxylic acid (hemimellitic acid), benzene-1,2,4-tricarboxylic acid (trimellitic acid), or benzene-1,3,5-tricarboxylic acid ( Trimesithsäure) act. The proportion by weight of crosslinking monomers, based on the total weight of the polyester, can be, for example, up to 10% by weight, in particular up to 5% by weight and more preferably up to 3% by weight. The polyesters containing the structural units (I), (II) and (III) and optionally (IV) generally have number average molecular weights in the range from 700 to 50,000 g / mol, wherein the number average molecular weight can be determined by size exclusion chromatography in aqueous solution using a calibration using narrowly distributed polyacrylic acid Na salt standards. The number-average molecular weights are preferably in the range from 800 to 25,000 g / mol, in particular from 1,000 to 15,000 g / mol, particularly preferably from 1,200 to 12,000 g / mol. According to the invention, solid polyesters which have softening points above 40 ° C. are preferably used as part of the particle of the second type; they preferably have a softening point between 50 and 200 ° C, more preferably between 80 ° C and 150 ° C, and most preferably between 100 ° C and 120 ° C. The synthesis of the polyesters can be carried out by known methods, for example by first heating the abovementioned components with addition of a catalyst at normal pressure and then building up the required molecular weights in vacuo by distilling off superstoichiometric amounts of the glycols used. Suitable for the reaction are the known transesterification and condensation catalysts, such as, for example, titanium tetraisopropylate, Dibutyltin oxide, alkali or alkaline earth metal alcoholates or antimony trioxide / calcium acetate. For more details be on EP 442 101 directed.

Preferred polyesters are of solid consistency and can be simply ground into powder or compacted or agglomerated into granules of defined particle sizes. The granulation can be carried out by solidifying the copolymers obtained as melt in the synthesis by cooling in a cool gas stream, for example air or nitrogen, or by application to a flaking roll or to a treadmill to form flakes or flakes. This coarse material can optionally be further ground, for example, in the roll mill or in the screen mill, which can be followed by a sieving and a rounding as described above. The granulation can also be carried out in such a way that the polyesters are ground to powder after solidification and then reacted by compaction or agglomeration and the above-described rounding into granules with defined particle sizes.

The solid composition and / or the liquid composition of the portion may additionally contain at least one enzyme. In principle, all enzymes established in the state of the art for textile treatment can be used in this regard. Preferably, it is one or more enzymes which can develop a catalytic activity in a detergent, in particular a protease, amylase, lipase, cellulase, hemicellulase, mannanase, pectin-cleaving enzyme, tannase, xylanase, xanthanase, β-glucosidase, carrageenase, perhydrolase , Oxidase, oxidoreductase and their mixtures. Preferred hydrolytic enzymes include in particular proteases, amylases, in particular α-amylases, cellulases, lipases, hemicellulases, in particular pectinases, mannanases, β-glucanases, and mixtures thereof. Proteases, amylases and / or lipases and mixtures thereof are particularly preferred, and proteases are particularly preferred. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.

Among the proteases, those of the subtilisin type are preferable. Examples of these are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg in a developed form under the trade names Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP ^® protease variants derived. Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym ^®, Natalase ^®, Kannase® ^® and Ovozyme ^® from Novozymes, the ^® under the trade names Purafect ^®, Purafect ^® OxP, Purafect Prime, Excellase ^® and Properase.RTM ^® from Genencor, that under the trade name Protosol® ^® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ^® and Protease ^P® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan. Particular preference is also given to using the proteases from Bacillus gibsonii and Bacillus pumilus.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus and their further developments improved for use in detergents or cleaners. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar® ^® ST. Development products of this α-amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ^®, and variants derived from the α-amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948). Likewise, fusion products of all the molecules mentioned can be used. In addition, the enhancements available under the trade names Fungamyl.RTM ^® by the company Novozymes of α-amylase from Aspergillus niger and A. oryzae, which are. Other advantageous commercial products are for example the Amylase-LT ^®, and Stainzyme® ^® or ultra Stainzyme® ^® or Stainzyme® plus ^®, the latter also from the company Novozymes. Also variants of these enzymes obtainable by point mutations can be used according to the invention.

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

Depending on the purpose, cellulases may be present as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement each other in terms of their various performance aspects. These performance aspects include in particular the contributions of the cellulase to the primary washing performance of the composition (cleaning performance), to the secondary washing performance of the composition (anti-redeposition effect or graying inhibition), to softening (fabric effect) or to the exercise of a "stone washed" effect. A useful fungal, Endoglucanase (EG) -rich cellulase preparation, or their developments is offered by the company Novozymes under the trade name Celluzyme ^® . The products Endolase® ^® and Carezyme ^®, likewise available from Novozymes, are based on the 50 kD EG and 43 kD EG from H. insolens DSM 1800. Further commercial products of this company are Cellusoft® ^{®, ®} and Renozyme Celluclean ^®. Also usable are for example the 20 kD EG Melanocarpus, which are available from AB Enzymes, Finland, under the trade names Ecostone ^® and Biotouch ^®. Further commercial products from AB Enzymes are Econase® ^® and ECOPULP ^®. Other suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, those derived from Bacillus sp. CBS 670.93 from the company Genencor under the trade name Puradax ^{® is} available. Further commercial products of the company Genencor are "Genencor detergent cellulase L" and lndiAge ^® Neutra. Also variants of these enzymes obtainable by point mutations can be used according to the invention. Particularly preferred cellulases are Thielavia terrestris cellulase variants, cellulases from melanocarpus, in particular melanocarpus albomyces, cellulases of the EGIII type from Trichoderma reesei or variants obtainable therefrom.

Furthermore, in particular for the removal of certain problem soiling, further enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, xanthanases, xyloglucanases, xylanases, pullulanases, pectin-splitting enzymes and β-glucanases. The recovered from Bacillus subtilis beta-glucanase is available under the name Cereflo ^® from Novozymes. According to the invention particularly preferred hemicellulases are mannanases, which are marketed under the trade names man Away ^® by the company Novozymes or Purabrite ^® by the company Genencor. The pectin-destroying enzymes in the context of the present invention are also counted enzymes with the designations pectinase, pectate lyase, pectin esterase, pectin methoxylase, pectin methoxylase, pectin methyl esterase, pectase, pectin methyl esterase, pectin esterase, pectin-pectin hydrolase, pectin-polymerase, endopolygalacturonase, pectolase, pectin hydrolase, pectin-polygalacturonase, Endo-polygalacturonase, poly-α-1,4-galacturonide glycanohydrolase, endogalacturonase, endo-D-galacturonase, galacturan 1,4-α-galacturonidase, exopolygalacturonase, poly (galacturonate) hydrolase, exo-D-galacturonase, exo-D Galacturonanase, exopoly-D-galacturonase, exo-poly-α-galacturonosidase, exopolygalacturonosidase or exopolygalacturanosidase. Examples in this regard, suitable enzymes for example, under the name Gamanase ^®, Pektinex AR ^®, X-Pect ^® or Pectaway ^® by the company Novozymes, UF under the name Rohapect ^®, Rohapect TPL ^®, Rohapect PTE100 ^®, Rohapect MPE ^®, Rohapect MA available plus HC, Rohapect DA12L ^®, Rohapect 10L ^®, Rohapect B1L ^® by the company AB Enzymes and under the name Pyrolase® ^® by the company Diversa Corp., San Diego, CA, United States.

Of all these enzymes, particular preference is given to those which have been stabilized per se with respect to oxidation in a comparatively stable manner or, for example, via point mutagenesis. Among the above-mentioned commercial products Everlase ^® and Purafect ^® OxP as examples of such proteases and Duramyl ^® are particular to cite as an example of such an α-amylase.

The portion of the invention preferably contains enzymes in total amounts of 1 × 10 ^-8 to 5 percent by weight based on active protein. Preferably, the enzymes are present in a total amount of from 0.001 to 2 wt.%, More preferably from 0.01 to 1.5 wt.%, Even more preferably from 0.05 to 1.25 wt.%, And most preferably from 0.01 to 0.5 wt .-% in this portion.

Furthermore, builders, complexing agents, optical brightener, pH adjuster, perfume, dye, dye transfer inhibitor or mixtures thereof in the solid-form composition and / or the liquid composition of the portion can be contained as additional ingredients.

Builders which may be present in the composition according to the invention are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

As builders further polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 600 to 750,000 g / mol.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,000 to 5,000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. To improve the water solubility, the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

An optical brightener is preferably selected from the substance classes of distyrylbiphenyls, stilbenes, 4,4'-diamino-2,2'-stilbenedisulfonic acids, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole systems, benzisoxazole systems, benzimidazole systems, heterocyclic substituted pyrene derivatives, and mixtures thereof.

Particularly preferred optical brighteners disodium 4,4'-bis- (2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene disulphonate (for example, available as Tinopal ^® DMS by BASF SE), disodium 2,2 ' -bis- (phenyl-styryl) disulphonate (for example, available as Tinopal ^® CBS available from BASF SE), 4,4'-bis [(4-anilino-6- [bis (2-hydroxyethyl) amino] -1,3,5 triazin-2-yl) amino] stilbene-2,2'-disulfonic acid (for example, available as Tinopal UNPA ^® from BASF SE), hexasodium 2,2 '- [vinylenbis [(3-sulphonato-4,1-phenylene) imino [6- (diethylamino) -1,3,5-triazine-4,2-diyl] imino]] bis- (benzene-1,4-disulfonate) (e.g. available as Tinopal SFP ^® from BASF SE), 2, 2 '- (2,5-thiophenediyl) bis [5-1.1-dimethylethyl) benzoxazole (e.g., available as Tinopal SFP ^® from BASF SE) and / or 2,5-bis thiophene (benzoxazol-2-yl).

It is preferred that the dye transfer inhibitor is a polymer or copolymer of cyclic amines such as vinylpyrrolidone and / or vinylimidazole. Suitable color transfer inhibiting polymers include polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI), polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride, polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole, and blends it. Particular preference is given to using polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) as color transfer inhibitor. The polyvinylpyrrolidone (PVP) preferably have an average molecular weight of from 2,500 to 400,000, and are commercially available from ISP Chemicals as PVP K 15, PVP K 30, PVP K 60 or PVP K 90 or from BASF as Sokalan ^® HP 50 or Sokalan ^® HP 53 available. The copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) used preferably have a molecular weight in the range from 5,000 to 100,000. Available commercially a PVP / PVI copolymer is, for example, by BASF under the name Sokalan ^® HP 56. Another highly preferred suitable dye transfer inhibitor are polyethylene glycol-modified copolymers of vinylpyrrolidone and of vinylimidazole, which available for example under the name Sokalan ^® HP 66 by BASF are.

The solid composition of the portion according to the invention is prepared by mixing the raw materials. A batch process or a continuous mixing process can be used. It is inventively preferred to use those mixing methods in which the particles of the ingredients (eg of the powder or granules) are not mechanically destroyed. Suitable mixers are especially tumble mixers, paddle mixers (Forberg, Fa. Lödige, Fa. Gericke) or Helix mixers (Fa. Amixon, Fa. Gebrueder Ruberg). The ingredients of the solid composition according to the invention are mixed with low energy input, in particular mixing tools are used, which mix with 0.1 to 5 m / s peripheral speed.

The portion of the invention contains in its liquid composition mandatory total amounts of anionic surfactant and nonionic surfactant.

The anionic surfactant used may preferably be sulfonates and / or sulfates.

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 C _12-18 alkanesulfonates and 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.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C 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. 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. 2,3-alkyl sulfates are also suitable anionic surfactants.

Also, fatty alcohol ether sulfates, such as 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.

Other suitable anionic surfactants are soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.

The anionic surfactants and the soaps may be in the form of their sodium, potassium or magnesium or ammonium salts. Preferably, the anionic surfactants are in the form of their ammonium salts. Preferred counterions for the anionic surfactants are the protonated forms of choline, triethylamine, monoethanolamine or methylethylamine.

In a very particularly preferred embodiment, the liquid composition of the portion contains a monoethanolamine-neutralized alkylbenzenesulfonic acid, in particular C _9-13 -alkylbenzenesulfonic acid, and / or a monoethanolamine-neutralized fatty acid.

The content of the anionic surfactant content liquid composition is preferably from 30 to 40% by weight, based on the weight of the liquid composition.

Suitable nonionic surfactants include alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides, and mixtures thereof.

The nonionic surfactant used is preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 4 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 5 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 4 EO or 7 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 5 EO or 7 EO and mixtures of these. The degrees of ethoxylation given represent statistical means which, for a particular product, may be 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. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Also suitable are also a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol, such as a mixture of a C _16-18 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO. Most preferably, the first composition contains a C _12-18 fatty alcohol with 7 EO, a C _13-15 oxoalcohol with 7 EO, and / or a C _13-15 oxoalcohol with 8 EO as the nonionic surfactant.

The content of the liquid composition of the nonionic surfactant portion is preferably a total amount of 18 to 28% by weight based on the weight of the liquid composition.

• – 30 bis 40 Gew.-% mindestens eines anionischen Tensids und
• – 18 bis 28 Gew.-% mindestens eines nichtionischen Tensids.

Portions which are particularly preferred according to the invention each contain in the liquid composition in each case based on the total weight of the liquid composition a total amount of

• From 30 to 40% by weight of at least one anionic surfactant and
• 18 to 28% by weight of at least one nonionic surfactant.

• (E) Flüssige Zusammensetzung der erfindungsgemäßen Portion, enthaltend jeweils bezogen auf das Gesamtgewicht der flüssigen Zusammensetzung jeweils eine Gesamtmenge von – 25 bis 60 Gew.-% mindestens eines anionischen Tensids, wobei als anionisches Tensid mindestens ein C_9-13-Alkylbenzolsulfonat enthalten ist, und – 2 bis 35 Gew.-% mindestens eines nichtionischen Tensids, wobei als nichtionisches Tensid mindestens ein alkoxylierter Alkohol mit 8 bis 18 Kohlenstoffatomen und durchschnittlich 4 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol enthalten ist.
• (F) Flüssige Zusammensetzung der erfindungsgemäßen Portion, enthaltend jeweils bezogen auf das Gesamtgewicht der flüssigen Zusammensetzung jeweils eine Gesamtmenge von – 25 bis 60 Gew.-% mindestens eines anionischen Tensids, wobei als anionisches Tensid mindestens 25 bis 60 Gew.-% mindestens eines C_9-13-Alkylbenzolsulfonats enthalten ist, und – 2 bis 35 Gew.-% mindestens eines nichtionischen Tensids, wobei als nichtionisches Tensid mindestens 2 bis 35 Gew.-% mindestens eines alkoxylierten Alkohols mit 8 bis 18 Kohlenstoffatomen und durchschnittlich 4 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol enthalten ist.
• (G) Flüssige Zusammensetzung der erfindungsgemäßen Portion, enthaltend jeweils bezogen auf das Gesamtgewicht der flüssigen Zusammensetzung jeweils eine Gesamtmenge von – 30 bis 40 Gew.-% mindestens eines anionischen Tensids, wobei als anionisches Tensid mindestens ein C_9-13-Alkylbenzolsulfonat enthalten ist, und – 18 bis 28 Gew.-% mindestens eines nichtionischen Tensids, wobei als nichtionisches Tensid mindestens ein alkoxylierter Alkohol mit 8 bis 18 Kohlenstoffatomen und durchschnittlich 4 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol enthalten ist.
• (H) Flüssige Zusammensetzung der erfindungsgemäßen Portion, enthaltend jeweils bezogen auf das Gesamtgewicht der flüssigen Zusammensetzung jeweils eine Gesamtmenge von – 30 bis 40 Gew.-% mindestens eines anionischen Tensids, wobei als anionisches Tensid mindestens 30 bis 40 Gew.-% mindestens eines C_9-13-Alkylbenzolsulfonats enthalten ist, und – 18 bis 28 Gew.-% mindestens eines nichtionischen Tensids, wobei als nichtionisches Tensid mindestens 18 bis 28 Gew.-% mindestens eines alkoxylierten Alkohols mit 8 bis 18 Kohlenstoffatomen und durchschnittlich 4 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol enthalten ist.

Very particularly preferred liquid compositions of the portion according to the invention are the compositions (E) to (H):

• (E) Liquid composition of the portion according to the invention, in each case based on the total weight of the liquid composition, a total amount of from -25 to 60% by weight of at least one anionic surfactant, wherein at least one C _9-13 -alkylbenzenesulfonate anionic surfactant is present, and 2 to 35% by weight of at least one nonionic surfactant, containing as nonionic surfactant at least one alkoxylated alcohol having 8 to 18 carbon atoms and on average 4 to 12 moles of ethylene oxide (EO) per mole of alcohol.
• (F) Liquid composition of the portion according to the invention, in each case based on the total weight of the liquid composition, a total amount of - 25 to 60 wt .-% of at least one anionic surfactant, wherein as anionic surfactant at least 25 to 60 wt .-% of at least one C _9-13- Alkylbenzolsulfonats, and - 2 to 35 wt .-% of at least one nonionic surfactant, wherein as nonionic surfactant at least 2 to 35 wt .-% of at least one alkoxylated alcohol having 8 to 18 carbon atoms and an average of 4 to 12 moles of ethylene oxide (EO) per mole of alcohol is included.
• (G) Liquid composition of the portion according to the invention, containing in each case based on the total weight of the liquid composition in each case a total amount of from -30 to 40% by weight of at least one anionic surfactant, wherein at least one C _9-13 -alkylbenzenesulfonate is contained as anionic surfactant, and - from 18 to 28% by weight of at least one nonionic surfactant, containing as nonionic surfactant at least one alkoxylated alcohol having from 8 to 18 carbon atoms and on average from 4 to 12 moles of ethylene oxide (EO) per mole of alcohol.
• (H) Liquid composition of the portion according to the invention, in each case based on the total weight of the liquid composition, a total amount of from -30 to 40 wt .-% of at least one anionic surfactant, wherein as anionic surfactant at least 30 to 40 wt .-% of at least one C _9-13 alkyl benzene sulfonate is included, and - from 18 to 28 wt .-% of at least one nonionic surfactant, wherein the nonionic surfactant is at least 18 to 28 wt .-% of at least one alkoxylated alcohol having 8 to 18 carbon atoms and an average of 4 to 12 moles of ethylene oxide (EO) per mole of alcohol is included.

It is particularly preferred according to the invention to combine at least one liquid composition of embodiments (E) to (H) with at least one of the preferred solid compositions (A) to (D) (vide supra) in the portion according to the invention.

It is preferred according to the invention if the liquid composition of the portion contains at least one polyalkoxylated polyamine in addition to the anionic and nonionic surfactant.

The polyalkoxylated polyamine in the context of the present invention and its individual aspects is a polymer having an N-atom-containing backbone attached to the N atoms Carries polyalkoxy groups. The polyamine has at the ends (terminus and / or side chains) primary amino functions and internally preferably both secondary and tertiary amino functions; if appropriate, it may also have only secondary amino functions on the inside, so that the result is not a branched-chain but a linear polyamine. The ratio of primary to secondary amino groups in the polyamine is preferably in the range from 1: 0.5 to 1: 1.5, in particular in the range from 1: 0.7 to 1: 1. The ratio of primary to tertiary amino groups in the polyamine is preferably in the range from 1: 0.2 to 1: 1, in particular in the range from 1: 0.5 to 1: 0.8. Preferably, the polyamine has an average molecular weight in the range of 500 g / mol to 50,000 g / mol, in particular from 550 g / mol to 5000 g / mol. The N atoms in the polyamine are separated from one another by alkylene groups, preferably by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, wherein not all alkylene groups must have the same C atom number. Particularly preferred are ethylene groups, 1,2-propylene groups, 1,3-propylene groups, and mixtures thereof. Polyamines bearing ethylene groups as said alkylene group are also referred to as polyethyleneimine or PEI. PEI is an inventively particularly preferred polymer with N-atom-containing backbone.

The primary amino functions in the polyamine can carry 1 or 2 polyalkoxy groups and the secondary amino functions 1 polyalkoxy group, although not every amino function must be alkoxy group-substituted. The average number of alkoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably from 1 to 100, in particular from 5 to 50. The alkoxy groups in the polyalkoxylated polyamine are preferably polypropoxy groups which are bonded directly to N atoms, and / or Polyethoxy groups which are attached to any existing propoxy and N atoms which do not carry propoxy groups.

Polyethoxylated polyamines are obtained by reacting polyamines with ethylene oxide (EO for short). The polyalkoxylated polyamines containing ethoxy and propoxy groups are preferably accessible by reaction of polyamines with propylene oxide (abbreviated to PO) and subsequent reaction with ethylene oxide.

The average number of propoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably 1 to 40, in particular 5 to 20,

The average number of ethoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably 10 to 60, especially 15 to 30.

If desired, the terminal OH function Polyalkoxysubstituenten in the polyalkoxylated polyamine partially or completely be etherified with a C ₁ -C ₁₀ , in particular C ₁ -C ₃ alkyl group.

Polyalkoxylated polyamines particularly preferred according to the invention may be selected from polyamine reacted with 45EO per primary and secondary amino function, PEI's reacted with 43EO per primary and secondary amino function, PEI's reacted with, 15EO + 5PO per primary and secondary amino function, PEI's reacted with 15PO + 30EO per primary and secondary amino function, PEI's reacted with 5PO + 39.5EO per primary and secondary amino function, PEI's reacted with 5PO + 15EO per primary and secondary amino function, PEI's reacted with 10PO + 35EO per primary and secondary amino function, PEI's reacted with 15PO + 30EO per primary and secondary amino function and PEI's reacted with 15PO + 5EO per primary and secondary amino function. A most preferred alkoxylated polyamine is PEI containing 10 to 20 nitrogen atoms reacted with 20 units of EO per primary or secondary amino function of the polyamine.

A further preferred subject of the invention is the use of polyalkoxylated polyamines which are obtainable by reacting polyamines with ethylene oxide and optionally additionally propylene oxide. If polyalkyoxylated polyamines are used with ethylene oxide and propylene oxide, the proportion of propylene oxide in the total amount of the alkylene oxide is preferably 2 mol% to 18 mol%, in particular 8 mol% to 15 mol%.

The liquid composition contains polyalkoxylated polyamines, based on their weight, preferably in a total amount of from 0.5 to 12% by weight, in particular from 5.0 to 9.0% by weight.

The liquid composition prepared in the water-soluble portion in the first chamber may contain water, wherein, especially for liquid first compositions, the content of water based on the entire first composition is at most 20 wt .-%, preferably at most 15 wt .-%, is. The water content is determined according to the invention by Karl Fischer titration.

The liquid composition of the portion may contain other ingredients which further improve the performance and / or aesthetic properties of the liquid composition. In the context of the present invention, the liquid composition preferably additionally contains one or more substances from the group of builders, enzymes, electrolytes, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition agents, graying inhibitors, anti-shrinkage agents, anti-crease agents , antimicrobial agents, non-aqueous solvents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing auxiliaries, repellents and impregnating agents, skin-care active ingredients, swelling and anti-slip agents, softening components and UV absorbers.

It has been found according to the invention as an additional advantage if the portion according to the invention is characterized in that upon contact of the portion with water from the portion of the solid-like composition is released before the liquid composition. It is again preferred if, upon contact of the portion with water, the portion releases the solid-like composition at least 60 seconds, in particular at least 100 seconds, before the liquid composition from the portion.

To modify the dissolution profile of the portion and to more rapidly release the solid composition from the portion, it is advantageous if the wall of the chamber having the solid composition is thinner than the walls of the chamber having the liquid composition. In this case, it is preferred if at least one contiguous area of 5% (particularly preferably at least 10%) of the total area of the walls of the chamber with the solid composition has a smaller wall thickness (eg thickness of the water-soluble material, for example thickness of the water-soluble film) than the smallest wall thickness of the wall of the chamber with the liquid composition. This configuration of the film is preferably achieved by means of a thermoforming process wherein the water-soluble film material of the first layer is drawn into a deeper valley of the mold body to form a recess for the chamber of the solid composition than for the formation of the recess for the chamber of the liquid composition. For this purpose, a trough molding having at least two troughs is used, wherein the trough for the recess of the chamber of the solid composition, measured perpendicularly from the bearing surface of the water-soluble foil material before the molding process to the lowest point of the topography of the trough, is deeper than the trough for the bulge of the liquid composition chamber.

It is inventively preferred that in the portion according to the invention the walls of the chamber of the liquid composition have no continuous surface with a wall thickness less than 40 microns and a size of more than 2% of the total area and the walls of the chamber of the solid composition at least one contiguous area of at least 5% of the total area (more preferably at least 10% of the total area) has a wall thickness of at most 35 μm, more preferably of at most 30 μm. The wall thickness and area can be determined experimentally, for example by means of computed tomography. The total area refers to the entire outer surface of the walls of the respective chamber.

A second subject of the invention is the use of a portion of the first subject of the invention for textile treatment.

A third subject of the invention is a textile treatment process comprising the steps of dosing a portion of the first subject of the invention to produce a hydrous wash liquor and contacting the resulting wash liquor with fabrics.

The preferred embodiment described for the first subject invention applies mutatis mutandis for the second and third subject of the invention.

• 1. Portion zur Anwendung in der Textilbehandlung, umfassend mindestens zwei Kammern mit Wandungen aus wasserlöslichem Material, dadurch gekennzeichnet, dass a) mindestens eine dieser Kammern eine flüssige Zusammensetzung, enthaltend jeweils bezogen auf das Gesamtgewicht der flüssigen Zusammensetzung jeweils eine Gesamtmenge von – 25 bis 60 Gew.-% mindestens eines anionischen Tensids und – 2 bis 35 Gew.-% mindestens eines nichtionischen Tensids, enthält, und b) mindestens eine weitere dieser Kammern eine festförmige Zusammensetzung, enthaltend jeweils bezogen auf das Gesamtgewicht der festförmigen Zusammensetzung jeweils eine Gesamtmenge von – 25 bis 55 Gew.-% mindestens einer Peroxidverbindung, – 2 bis 25 Gew.-% mindestens eines organischen Bleichaktivators, – 0 bis 5 Gew.-% Tensid, enthält.
• 2. Portion nach Punkt 1, dadurch gekennzeichnet, dass bezogen auf das Gesamtgewicht der festförmigen Zusammensetzung Peroxidverbindung in einer Gesamtmenge von 30 bis 50 Gew.-%, insbesondere von 33 bis 45 Gew.-%, enthalten sind.
• 3. Portion nach einem der Punkte 1 oder 2, dadurch gekennzeichnet, dass die Peroxidverbindung ausgewählt wird aus Natriumpercarbonat, Natriumperborat, Natriumperoxodisulfat oder Mischungen davon.
• 4. Portion nach einem der Punkte 1 bis 3, dadurch gekennzeichnet, dass die Peroxidverbindung als Pulver oder Granulat vorliegt, bevorzugt mit einer Schüttdichte von 0,70 bis 1,30 kg/dm³, besonders bevorzugt mit einer Schüttdichte von 0,85 bis 1,20 kg/dm³ (jeweils gemessen nach ISO 697 ).
• 5. Portion nach Punkt 4, dadurch gekennzeichnet, dass die Peroxidverbindung eine mittlere Korngröße (Volumenmittel) X_50,3 von 0,40 bis 0,95 mm, insbesondere von 0,40 bis 0,90 mm, aufweist (jeweils gemessen mit Siebanalyse).
• 6. Portion nach einem der Punkte 1 bis 5, dadurch gekennzeichnet, dass als organischer Bleichaktivator ein oder mehrere Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxycarbon¬säuren mit vorzugsweise 1 bis 10 C-Atomen (insbesondere 2 bis 4 C-Atomen) bilden, in der festförmigen Zusammensetzung enthalten sind.
• 7. Zusammensetzung nach einem der Punkte 1 bis 6, dadurch gekennzeichnet, dass bezogen auf das Gesamtgewicht der festförmigen Zusammensetzung organischer Bleichaktivator in einer Gesamtmenge von 10 bis 20 Gew.-%, insbesondere 12 bis 16 Gew.-%, in der festförmigen Zusammensetzung enthalten ist.
• 8. Portion nach einem der Punkte 1 bis 7, dadurch gekennzeichnet, dass die festförmige Zusammensetzung bezogen auf ihr Gesamtgewicht eine Gesamtmenge von 5 bis 20 Gew.-% Alkalimetallsilikat enthält.
• 9. Portion nach Punkt 8, dadurch gekennzeichnet, dass als Alkalimetallsilikat Natriumsilikat und/oder Kaliumsilikat, insbesondere Natriumsilikat, enthalten ist.
• 10. Portion nach einem der Punkte 8 oder 9, dadurch gekennzeichnet, dass die Alkalimetallsilikate aus der Formel (SiO₂)_n(Na₂O)_m(K₂O)_p ausgewählt werden, wobei n für eine positive rationale Zahl steht und m und p unabhängig voneinander für eine positive rationale Zahl stehen, mit den Maßgaben, dass mindestens einer der Parameter m oder p von 0 verschieden ist und das Verhältnis zwischen n und der Summe aus m und p zwischen 1:4 und 4:1, insbesondere im Verhältnisbereich von 2:1 bis 4:1 liegt.
• 11. Portion nach einem der Punkte 8 bis 10, dadurch gekennzeichnet, dass als die Alkalimetallsilikate aus der Formel (SiO₂)_n(Na₂O)_m ausgewählt werden, wobei n für eine positive rationale Zahl und m für eine positive rationale Zahl steht, mit der Maßgabe, dass das Verhältnis zwischen n und m zwischen 1:4 und 4:1, insbesondere im Verhältnisbereich von 2:1 bis 4:1 liegt.
• 12. Portion nach einem der Punkte 8 bis 11, dadurch gekennzeichnet, dass das Gewichtsverhältnis von Alkalisilikat zu Peroxidverbindung in einem Bereich von 10 zu 1 bis 1 zu 4 liegt.
• 13. Portion nach einem der Punkte 1 bis 12, dadurch gekennzeichnet, dass die festförmige Zusammensetzung bezogen auf ihr Gesamtgewicht eine Gesamtmenge von 1 bis 15 Gew.-% Polysaccharid enthält.
• 14. Zusammensetzung nach einem der Punkte 1 bis 13, dadurch gekennzeichnet, dass als Polysaccharid mindestens ein Polysaccharid enthaltend mindestens eine anionische Gruppe (bevorzugt mindestens ein Polysaccharids enthaltend mindestens eine Carboxylgruppe, ganz besonders bevorzugt Carboxymethylcellulose) enthalten ist.
• 15. Portion nach einem der Punkte 1 bis 14, dadurch gekennzeichnet, dass in der flüssigen Zusammensetzung jeweils bezogen auf das Gesamtgewicht der flüssigen Zusammensetzung jeweils eine Gesamtmenge von – 30 bis 40 Gew.-% mindestens eines anionischen Tensids und – 18 bis 28 Gew.-% mindestens eines nichtionischen Tensids, enthalten ist.
• 16. Portion nach einem der Punkte 1 bis 15, dadurch gekennzeichnet, dass in der festförmigen Zusammensetzung bezogen auf das Gesamtgewicht der festförmigen Zusammensetzung eine Gesamtmenge von 0 bis 1 Gew.-% nichtionisches Tensid enthalten ist.
• 17. Portion nach einem der Punkte 1 bis 16, dadurch gekennzeichnet, dass die flüssige Zusammensetzung bezogen auf ihr Gesamtgewicht höchstens 20 Gew.-%, insbesondere höchstens 15 Gew.-% Wasser enthält.
• 18. Portion nach einem der Punkte 1 bis 17, dadurch gekennzeichnet, dass das wasserlösliche Material mindestens ein wasserlösliches Polymer enthält.
• 19. Portion nach einem der Punkte 1 bis 18, dadurch gekennzeichnet, dass besagte flüssige Zusammensetzung in einer Menge von 10,0 bis 20,0 g, insbesondere von 14,0 bis 18,0 g, und besagte festförmige Zusammensetzung in einer Menge von 4,0 bis 10,0 g, insbesondere von 5,0 bis 9,0 g, enthalten ist.
• 20. Portion nach einem der Punkte 1 bis 19, dadurch gekennzeichnet, dass bei Kontakt mit Wasser die Portion die festförmige Zusammensetzung vor der flüssigen Zusammensetzung aus der Portion freisetzt.
• 21. Portion nach Punkt 19, dadurch gekennzeichnet, dass bei Kontakt mit Wasser die Portion die festförmige Zusammensetzung wenigstens 60 Sekunden, insbesondere wenigstens 100 Sekunden, vor der flüssigen Zusammensetzung aus der Portion freisetzt.
• 22. Portion nach einem der Punkte 1 bis 20, dadurch gekennzeichnet, dass eine Wandung der Kammer mit der festförmigen Zusammensetzung dünner ist, als die Wandungen der Kammer mit der flüssigen Zusammensetzung.
• 23. Portion nach einem der Punkte 1 bis 21, dadurch gekennzeichnet, dass zumindest eine zusammenhängende Fläche von 5 % (besonders bevorzugt zumindest 10 %) der Gesamtfläche der Wandungen der Kammer mit der festförmigen Zusammensetzung eine kleinere Wandstärke hat, als die kleinste Wandstärke der Wandung der Kammer mit der flüssigen Zusammensetzung.
• 24. Portion nach einem der Punkte 1 bis 23, dadurch gekennzeichnet, dass Wandungen der Kammer der flüssigen Zusammensetzung keine zusammenhängende Fläche mit einer Wandstärke kleiner 40 µm und einer Größe von mehr als 2 % der Gesamtfläche aufweisen und die Wandungen der Kammer der festen Zusammensetzung mindestens eine zusammenhängende Fläche von mindestens 5 % der Gesamtfläche (besonders bevorzugt mindestens 10 % der Gesamtfläche) eine Wandstärke von höchstens 35 µm, besonders bevorzugt von höchstens 30 µm, aufweisen.
• 25. Verwendung einer Portion nach einem der Punkte 1 bis 24 zur Textilbehandlung.
• 26. Verfahren zur Textilbehandlung, enthaltend die Schritte der Dosierung einer Portion nach einem der Punkte 1 bis 24 zur Herstellung einer wasserhaltigen Waschlauge und in Kontakt bringen der resultierenden Waschlauge mit Textilien.

Another embodiment of the invention is characterized by the following points:

• 1. Portion for use in textile treatment, comprising at least two chambers with walls of water-soluble material, characterized in that a) at least one of these chambers a liquid composition, each containing, based on the total weight of the liquid composition, a total amount of - 25 to 60 Wt .-% of at least one anionic surfactant and - 2 to 35 wt .-% of at least one nonionic surfactant, contains, and b) at least one further of these chambers a solid composition, each containing a total amount of - 25 to 55 wt .-% of at least one peroxide compound, - 2 to 25 wt .-% of at least one organic based on the total weight of the solid composition Bleach activator, - 0 to 5 wt .-% surfactant.
• 2. Portion according to item 1, characterized in that based on the total weight of the solid composition peroxide compound in a total amount of 30 to 50 wt .-%, in particular from 33 to 45 wt .-%, are included.
• 3. Portion according to one of the items 1 or 2, characterized in that the peroxide compound is selected from sodium percarbonate, sodium perborate, sodium peroxodisulfate or mixtures thereof.
• 4. Portion according to one of the items 1 to 3, characterized in that the peroxide compound is present as a powder or granules, preferably with a bulk density of 0.70 to 1.30 kg / dm ³ , particularly preferably with a bulk density of 0.85 to 1.20 kg / dm ³ (each measured after ISO 697 ).
• 5. portion according to item 4, characterized in that the peroxide compound has an average particle size (volume average) X _50.3 from 0.40 to 0.95 mm, in particular from 0.40 to 0.90 mm (each measured with sieve analysis ).
• 6. Portion according to one of the items 1 to 5, characterized in that as organic bleach activator one or more compounds which form under perhydrolysis aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms (in particular 2 to 4 carbon atoms), in the solid-form composition are contained.
• 7. Composition according to any one of items 1 to 6, characterized in that, based on the total weight of the solid composition, organic bleach activator in a total amount of 10 to 20 wt .-%, in particular 12 to 16 wt .-%, in the solid-form composition is.
• 8. Portion according to one of the items 1 to 7, characterized in that the solid-form composition based on their total weight contains a total amount of 5 to 20 wt .-% alkali metal silicate.
• 9. portion according to item 8, characterized in that as alkali metal silicate sodium silicate and / or potassium silicate, in particular sodium silicate, is included.
• 10. Portion according to one of the items 8 or 9, characterized in that the alkali metal silicates are selected from the formula (SiO ₂ ) _n (Na ₂ O) _m (K ₂ O) _p , where n is a positive rational number and m and p independently represent a positive rational number, with the provisos that at least one of the parameters m or p is different from 0 and the ratio between n and the sum of m and p is between 1: 4 and 4: 1, in particular Ratio of 2: 1 to 4: 1 is.
• 11. Portion according to one of the items 8 to 10, characterized in that as the alkali metal silicates from the formula (SiO ₂ ) _n (Na ₂ O) _{m are} selected, where n stands for a positive rational number and m for a positive rational number with the proviso that the ratio between n and m is between 1: 4 and 4: 1, in particular in the ratio range of 2: 1 to 4: 1.
• 12. Portion according to one of the items 8 to 11, characterized in that the weight ratio of alkali silicate to peroxide compound in a range of 10 to 1 to 1 to 4.
• 13. Portion according to one of the items 1 to 12, characterized in that the solid composition based on their total weight contains a total amount of 1 to 15 wt .-% polysaccharide.
• 14. The composition according to any one of items 1 to 13, characterized in that as polysaccharide at least one polysaccharide containing at least one anionic group (preferably at least one polysaccharide containing at least one carboxyl group, most preferably carboxymethylcellulose) is included.
• 15. Portion according to one of the items 1 to 14, characterized in that in the liquid composition in each case based on the total weight of the liquid composition in each case a total amount of - 30 to 40 wt .-% of at least one anionic surfactant and - 18 to 28 wt. % of at least one nonionic surfactant.
• 16. Portion according to any one of items 1 to 15, characterized in that in the solid composition based on the total weight of the solid composition, a total amount of 0 to 1 wt .-% nonionic surfactant is included.
• 17. Portion according to one of the items 1 to 16, characterized in that the liquid composition based on their total weight contains at most 20 wt .-%, in particular at most 15 wt .-% water.
• 18. Portion according to one of the items 1 to 17, characterized in that the water-soluble material contains at least one water-soluble polymer.
• 19. Portion according to any one of items 1 to 18, characterized in that said liquid composition in an amount of 10.0 to 20.0 g, in particular from 14.0 to 18.0 g, and said solid composition in an amount of 4.0 to 10.0 g, in particular from 5.0 to 9.0 g, is included.
• 20. Portion according to any one of items 1 to 19, characterized in that on contact with water, the portion releases the solid-like composition before the liquid composition from the portion.
• 21. Portion according to item 19, characterized in that on contact with water, the portion releases the solid-like composition at least 60 seconds, in particular at least 100 seconds, before the liquid composition from the portion.
• 22. Portion according to any one of items 1 to 20, characterized in that a wall of the chamber with the solid composition is thinner than the walls of the chamber with the liquid composition.
• 23. Portion according to one of the items 1 to 21, characterized in that at least a contiguous area of 5% (more preferably at least 10%) of the total area of the walls of the chamber having the solid composition has a smaller wall thickness than the smallest wall thickness of the wall the chamber with the liquid composition.
• Portion according to one of the items 1 to 23, characterized in that walls of the chamber of the liquid composition do not have a contiguous area with a wall thickness of less than 40 μm and a size greater than 2% of the total area and the walls of the chamber of the solid composition at least a contiguous area of at least 5% of the total area (more preferably at least 10% of the total area) has a wall thickness of at most 35 μm, more preferably of at most 30 μm.
• 25. Use of a portion according to any one of items 1 to 24 for textile treatment.
• A textile treatment process comprising the steps of dosing a portion of any one of items 1 to 24 to produce an aqueous wash liquor and contacting the resulting wash liquor with fabrics.

Examples

1.0 Preparation of the test compositions

The following compositions of Tables 1 and 2 were provided: TABLE 1 Solid compositions (% by weight): E1 V1 Sodium percarbonate (granules) 35.0 35.0 TAED 13.0 13.0 carboxymethylcellulose 4.0 4.0 sodium 9.0 9.0 Sodium silicate (SiO ₂ ) _2.5 (Na ₂ O) 11.0 11.0 C18 fatty acid soap 2.6 2.6 Enzymes (protease, lipase, amylase, mannanase) in granules of sodium sulfate 10.7 10.7 sodium sulphate ad 100 - C _11-13 alkyl benzene sulfonic acid - ad 100

The sodium percarbonate granules were treated with 6 g of sodium sulfate according to a known method ( WO 2008/012181 A1 ) homogeneously coated and presented in a tumble mixer. Instead of this coated sodium percarbonate, 53.3% by weight of sodium percarbonate Q35 (containing 88.18% by weight of sodium percarbonate, Evonik) can be initially charged. The remaining components were added to the tumble mixer and the compositions prepared by dry blending the components for 3 minutes at 10 revolutions / minute. Table 2: Liquid composition L1 [% by weight] C _11-13 alkyl benzene sulfonic acid 23.0 C _13-15 alkyl alcohol ethoxylated with 8 moles of ethylene oxide 24.0 glycerin 9.0 2-aminoethanol 6.8 ethoxylated polyethyleneimine 4.0 C _12-18 fatty acid 7.5 Diethylenetriamine-N, N, N ', N', N "-penta (methylenephosphonic acid), heptasodium salt (sodium DTPMP) 3.5 1,2-propylene glycol 4.5 ethanol 4.0 Soil-release polymer of ethylene terephthalate and polyethylene terephthalate 1.0 Perfume, dye 1.7 water ad 100

In a stirred tank, the components of the liquid composition were mixed with stirring in order.

The following portions were prepared: Table 3: Portions P1 P2 Festiform composition 8.5 g E1 8.5 g V1 Liquid composition 16.5 g L1 16.5 g L1

For this purpose, a film M8613 Fa. Monosol (88 microns) was clamped on a mold with Doppelkavität. The stretched film was heated by contact heating for a period of 2400 ms at 105 ° C and then pulled into the cavity by a vacuum. Subsequently, an appropriate amount of the solid composition of Table 1 was pre-weighed into the first cavity and then the amount of liquid composition L1 of Table 2 was added by syringe into the second cavity. Thereafter, a top film (M8630, 90 microns) is placed to seal the cavities and heat-sealed (150 ° C, 1000 ms) with the first film. After breaking the vacuum, the portion of the cavity was removed. A wall of the portion's powder chamber was subsequently perforated with a needle. As a result, excess air escaped from the powder chamber of the portion and the film of the wall relaxed.

2.0 bleaching test

equipment:

• - 1000ml beaker high shape
• - Magnetic stirrer
• Magnetic stirring bars 6.8 cm long, diameter 10 mm
• - 50ml beaker
• - City water 800ml (14-16 ° dH)
• - Beetroot juice 30ml (Commercially available quality)
• - Stopwatch

Test Protocol:

• - Add room temperature water (21.5 ° C) to the 1000ml beaker.
• - Adjust the stirring speed of the water so that the tip of the hyperbolic cone reaches the right point 600ml brand of beaker is enough.
• - Add 30ml of beetroot juice
• - Add test composition, from this point on the stopwatch is started, if necessary after a given time T in seconds add further test composition (see Table 4).
• - The color change is recorded in time

Table 4: Test sequence: T1 T2 T3 T4 T5 T6 T7 E1 8.5 g E1 addition at T = 0 8.5 g E1 - - - - - V1 - - - - - 8.5 g V1 - L1 16.5 g L1 addition at T = 120 - - - 16.5 g L1 - - portion - - - P1 - - P2 Mixture of E1 & L1 - - 8.5 g E1 & 16.5 g L1 - - - -

Results:

The formulas of the invention (E1 alone (T2) or E1 with a 120 second delayed addition of liquid L1 (T1)) showed a first clear color change already after 3 minutes, whereas powder E1, which was mixed with liquid L1 before addition (20 Homogenize sec with a rubber spatula - powder suspended in liquid, wait 180 seconds (T3)) until after 4.5 minutes the same shade of color is achieved.

The addition of the non-inventive formula (V1 alone (T6) resulted in a later color change compared to the addition of the inventive formula E1 (E1 alone (T2)).

When the portions P1 (T4) and P2 (T7) were added, the color change was first observed in portion P1 according to the invention.

The addition of only L1 according to T5 resulted in no significant color change.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 4973416 [0007]
• WO 01/83667 A1 [0008]
• EP 2011856 B1 [0010]
• EP 2014756 A1 [0011]
• DE 2857292 [0079]
• DE 3324258 A [0079]
• EP 066944 [0079]
• EP 185427 [0079]
• EP 241984 [0079]
• EP 241985 [0079]
• EP 253567 [0079]
• EP 272033 [0079]
• EP 274907 [0079]
• EP 357280 [0079]
• EP 442101 [0082]
• WO 2008012181 A1 [0136]

Cited non-patent literature

• CAS number 15630-89-4 [0040]
• ISO 697 [0042]
• ISO 697 [0068]
• ISO 697 [0068]
• ISO 697 [0134]

Claims (17)

Portion for use in textile treatment, comprising at least two chambers with walls of water-soluble material, characterized in that a) at least one of these chambers a liquid composition, each containing, based on the total weight of the liquid composition, a total amount of - 25 to 60 wt. -% of at least one anionic surfactant and - 2 to 35 wt .-% of at least one nonionic surfactant, and b) at least one further of these chambers a solid composition containing, based in each case based on the total weight of the solid composition in each case a total amount of - 55 wt .-% of at least one peroxide compound, - 2 to 25 wt .-% of at least one organic bleach activator, - 0 to 5 wt .-% surfactant. Portion according to claim 1, characterized in that based on the total weight of the solid composition peroxide compound in a total amount of 30 to 50 wt .-%, in particular from 33 to 45 wt .-%, are included. Portion according to one of claims 1 or 2, characterized in that the peroxide compound is selected from sodium percarbonate, sodium perborate, sodium peroxodisulfate or mixtures thereof. Portion according to one of claims 1 to 3, characterized in that the peroxide compound is present as powder or granules, preferably with a bulk density of 0.70 to 1.30 kg / dm ³ , particularly preferably with a bulk density of 0.85 to 1, 20 kg / dm ³ (each measured according to ISO 697). Portion according to Claim 4, characterized in that the peroxide compound has a mean particle size (volume average) X _50.3 of 0.40 to 0.95 mm, in particular from 0.40 to 0.90 mm (measured in each case with sieve analysis). Portion according to one of claims 1 to 5, characterized in that as organic bleach activator one or more compounds which form under perhydrolysis aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms (in particular 2 to 4 carbon atoms) in the solid-form Composition are included. Composition according to any one of Claims 1 to 6, characterized in that, based on the total weight of the solid composition, organic bleach activator is present in a total amount of from 10 to 20% by weight, in particular 12 to 16% by weight, in the solid composition. Portion according to one of claims 1 to 7, characterized in that in the liquid composition, in each case based on the total weight of the liquid composition, a total amount of - 30 to 40 wt .-% of at least one anionic surfactant and - 18 to 28 wt .-% at least one nonionic surfactant is included. Portion according to one of claims 1 to 8, characterized in that in the solid composition based on the total weight of the solid composition, a total amount of 0 to 1 wt .-% nonionic surfactant is included. Portion according to one of claims 1 to 9, characterized in that the liquid composition based on their total weight contains at most 20 wt .-%, in particular at most 15 wt .-% water. Portion according to one of claims 1 to 10, characterized in that the water-soluble material contains at least one water-soluble polymer. A portion according to any one of claims 1 to 11, characterized in that said liquid composition is in an amount of from 10.0 to 20.0 g, especially from 14.0 to 18.0 g, and said solid composition is in an amount of 4, 0 to 10.0 g, in particular from 5.0 to 9.0 g, is included. A portion according to any one of claims 1 to 12, characterized in that, upon contact with water, the portion releases the solid composition from the portion prior to the liquid composition. Portion according to Claim 13, characterized in that, upon contact with water, the portion releases the solid composition from the portion for at least 60 seconds, in particular at least 100 seconds, before the liquid composition. Portion according to one of claims 1 to 14, characterized in that a wall of the chamber with the solid composition is thinner than the walls of the chamber with the liquid composition. Portion according to one of claims 1 to 15, characterized in that at least a contiguous area of 5% (more preferably at least 10%) of the total area of the walls of the chamber having the solid composition has a smaller wall thickness than the smallest wall thickness of the wall of the chamber with the liquid composition. Portion according to one of claims 1 to 17, characterized in that the walls of the chamber of the liquid composition have no continuous surface with a wall thickness less than 40 microns and a size of more than 2% of the total area and the walls of the chamber of the solid composition at least one contiguous area of at least 5% of the total area (more preferably at least 10% of the total area) have a wall thickness of at most 35 .mu.m, more preferably of at most 30 .mu.m.