EP3599274A1 - Multiphase cleaning agent pouch - Google Patents

Abstract

The invention relates to a detergent and / or cleaning agent portion, which comprises at least one chamber and a water-soluble envelope, characterized in that it comprises at least one particulate phase, the at least one particulate phase being brought into direct contact with at least one liquid composition, and corresponding manufacturing processes.

Description

The invention relates to a detergent and / or cleaning agent portion, which comprises at least one chamber and a water-soluble envelope, characterized in that it comprises at least one particulate phase, the at least one particulate phase being brought into direct contact with at least one liquid composition, and corresponding manufacturing processes.

Detergents or cleaning agents are usually in solid form (for example as tablets) or in liquid form (or also as a flowing gel). Liquid washing or cleaning agents in particular are enjoying increasing popularity among consumers.

Solid detergents or cleaning agents have the advantage that, unlike liquid detergents or cleaning agents, they do not require any preservatives. Liquid forms of offer are becoming increasingly popular on the market, in particular due to their rapid solubility and the associated rapid availability of the active ingredients they contain. This gives the consumer the opportunity to use time-reduced washing programs and still get good cleaning performance.

Furthermore, consumers have become accustomed to convenient dosing of pre-portioned machine washing or cleaning agents, such as dishwashing detergents, and use these products in the form of tablets (solid washing or cleaning agents) or in the form of sachets, which are usually washed with a liquid - or cleaning agents are filled. Disposable portions in water-soluble bags are becoming increasingly popular not only because consumers no longer come into contact with the chemical composition, but not least because of the attractive appearance of the bags. The appearance of the dosage form is becoming increasingly important. In addition to good cleaning performance and sufficient storage stability, good optics is one of the reasons for choosing a product.

Solid detergent formulations with a high surfactant content generally show high stickiness and poor pouring or flow behavior. This leads to poorer meterability during manufacture. In particular, only lower bulk densities are achieved, so that larger volumes have to be used for the same performance of the cleaning agent. Larger cavities must then be used, particularly in pre-proportioned detergent portions, but this is generally limited by the size of the metering chamber.

The object of the present invention is therefore to provide detergent or cleaning agent portions which are compact and at the same time have good, in particular even improved washing or cleaning performance.

A first object of the present invention relates to a detergent and / or cleaning agent portion, which comprises at least one chamber and a water-soluble envelope, characterized in that it comprises at least one particulate phase, the at least one particulate phase in direct contact with at least one liquid composition brought.

The detergent or cleaning agent portions according to the invention are more compact due to the direct contact of the particulate phase with a liquid composition. The particulate phase is so to speak impregnated with the liquid phase. The liquid phase preferably moves into the particulate phase or is absorbed in some other way by it, e.g. B. in that the liquid composition diffuses into the pores of the particulate phase.

A second subject of the present invention relates to a manufacturing process for detergent or cleaning agent portions, which leads to more compact detergent and / or cleaning agent portions with good or even improved cleaning. This manufacturing process is explained in more detail below.

The manufacturing process according to the invention also leads to a higher compactness of the cleaning agent in the case of the pouches, which are filled with formulations which can be poured well, by contacting compositions which would otherwise have a negative effect on the pourability.

Advantageously, product changes, e.g. to other surfactants or amounts of surfactants or perfumes.

In particular with surfactants, a higher surfactant content, in particular with liquid surfactants, can be achieved than with normal, particulate formulations, since these should be as free-flowing as possible for better processability.

With the separate dosing of perfume oils there is a further advantage in addition to the better processability and a higher product density that no intensive cleaning of the system is necessary if a new fragrance or a new perfume is to be changed over.

The detergent and / or cleaning agent portion can have one or more chambers. At least one particulate phase is brought into direct contact with at least one liquid phase in the at least one chamber.

A phase in the sense of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous. A phase differs from another phase by different features, for example ingredients, physical properties, external appearance or spatial separation or arrangement etc. Preferably different phases can be optically distinguished. For the consumer, the at least one particular phase must be clearly distinguished from other phases. If the washing or cleaning agent according to the invention has more than one particulate phase, these can likewise be distinguished from one another with the naked eye because they differ from one another, for example in terms of their coloring. The same applies if there are two or more phases. In this case, too, an optical differentiation of the phases is possible, for example on the basis of a color or transparency difference. Phases in the sense of the present invention are thus self-contained areas that can be visually distinguished from one another by the consumer with the naked eye. When used, the individual phases can have different properties, such as, for example, the rate at which the phase dissolves in water and thus the rate and the order in which the constituents contained in the respective phase are released.

In the context of the present invention, a particulate phase is to be understood as a granular mixture of a solid composition. The particulate phase is formed from a large number of loose, solid particles, which in turn comprise so-called grains. According to the invention, the term particulate phase comprises particles, grains, powders and / or granules.

A grain is a term for the particulate constituents of powders (grains are the loose, solid particles), dusts (grains are the loose solid particles), granules (loose, solid particles are agglomerates of several grains) and other granular mixtures.

A preferred embodiment of the granular mixture of the composition of the particulate phase is the powder and / or the granulate, if the term "powder" or "granulate" is used here, it is also encompassed that these are also mixtures of different powders or different granules , Accordingly, the term powder and granules means mixtures of different powders with different granules. Said solid-shaped particles of the granular mixture in turn preferably have a particle diameter X _50.3 (volume average) of 10 to 1500 μm, more preferably of 200 μm to 1200 µm, particularly preferably from 600 µm to 1100 µm. These particle sizes can be determined by sieving or by means of a particle size analyzer Camsizer from Retsch.

It is also advantageous that particulate phases can be changed more easily in their appearance or composition compared to a compressed tablet. In particular, texture differences, such as coarse and fine particles, as well as particles or areas with different colors, as a whole or as colored speckles, can thus be used to improve an optically appealing appearance. This also offers improved solubility compared to compressed tablets even without the addition of disintegrants.

These and other aspects, features and advantages of the invention will become apparent to those skilled in the art upon studying the following detailed description and claims. Each feature from one aspect of the invention can be used in any other aspect of the invention. Furthermore, it goes without saying that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular the invention is not restricted to these examples. Unless otherwise stated, all percentages are% by weight. Numerical ranges that are specified in the format "from x to y" include the values mentioned. If several preferred numerical ranges are specified in this format, it goes without saying that all ranges that result from the combination of the different endpoints are also covered.

"At least one" as used herein means 1 or more, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In relation to an ingredient, the information relates to the type of ingredient and not to the absolute number of molecules. "At least one bleaching catalyst" thus means, for example, at least one kind of bleaching catalyst, i.e. that one type of bleaching catalyst or a mixture of several different bleaching catalysts can be meant. Together with the weight information, the information relates to all compounds of the specified type which are contained in the composition / mixture, i.e. that the composition contains no further compounds of this type beyond the stated amount of the corresponding compounds.

If reference is made here to molecular weights, this information always relates to the number-average molecular weight M _n , unless explicitly stated otherwise. The number average molecular weight can be determined, for example, by means of gel permeation chromatography (GPC) according to DIN 55672-1: 2007-08 with THF as the eluent. The weight average molecular weight M _w can also be determined by means of GPC, as described for M _n .

Unless explicitly stated otherwise, all percentages given in connection with the compositions described herein relate to% by weight, in each case based on the mixture or phase in question.

According to a preferred embodiment, the detergent and / or cleaning agent portion is characterized in that the at least one particulate phase is free-flowing, preferably at the time of addition. This is important for the preparation of the detergent or cleaning agent portions, so that a uniform filling of such portion packs is possible both with regard to the same amount and the same composition.

The granular mixture serving as the particulate phase of the solid composition of the present invention is preferably in free-flowing form (particularly preferably as free-flowing powder and / or free-flowing granules). The agent of the portion according to the invention thus comprises at least one particulate phase (a phase of a free-flowing, granular mixture of a solid composition).

The flowability of a granular mixture, particularly the particulate phase, affects the ability to flow freely under its own weight. The pourability is determined by measuring the time for 1000 ml of detergent or cleaning agent powder to flow out of a standardized pouring test funnel with an outlet of 16.5 mm diameter, which is initially closed at its outlet direction, by measuring the time for the granular mixture to completely flow out, particularly the particulate phase measured after opening the outlet and compared with the outlet speed (in seconds) of a standard test object whose outlet speed is defined as 100%. The defined sand mixture for the calibration of the trickle equipment is dry sea sand. Sea sand with a particle diameter of 0.4 to 0.8 mm is used, available for example from Carl Roth, Germany CAS no. [14808-60-7]. For drying, the sea sand is dried for 24 hours at 60 ° C in a drying cabinet on a plate with a maximum layer height of 2 cm.

Preferred embodiments of the particulate phases according to the invention have an angle of repose / embankment of from 26 to 35, from 27 to 34, from 28 to 33, the angle of repose according to the method mentioned below after 24 h after the preparation of the granular mixture of the solid composition / the particulate phase , and storage at 20 ° C is determined. Such angles of repose have the advantage that the cavities can be filled with the at least one particulate phase comparatively quickly and precisely.

To determine the angle of repose (or also called the angle of repose) of the at least one particulate phase, a powder funnel with a content of 400 ml and a drain with a diameter of 25 mm is just hung on a tripod. The funnel is closed manually using a operating knurled wheel at a speed of 80 mm / min, so that the granular mixture, in particular the particulate phase, preferably the powder and / or granulate, for example the powder, trickles out. This creates a so-called pouring cone. The height of the cone and the diameter of the cone are determined for the individual particulate phases. The slope angle is calculated from the quotient of the cone height and the cone diameter * 100.

Such granular mixtures of a solid composition are particularly suitable, in particular those particulate phases, preferably the powders and / or granules, e.g. the powders which have a flowability in% of the standard test substance specified above of greater than 40%, preferably greater than 50, in particular greater than 55%, particularly preferably greater than 60%, particularly preferably between 63% and 80%, for example between 65% and 75 % exhibit. Particularly suitable are those granular mixtures of a solid composition, in particular those powders and / or granules which have a flowability in% of the standard test substance specified above of greater than 40%, preferably greater than 45%, particularly greater than 50%, particularly preferably greater than 55 %, particularly preferably greater than 60%, the measurement of the pourability being carried out 24 h after the preparation of the powder and storage at 20 ° C.

Lower values for the flowability are rather unsuitable, since from a process engineering point of view an exact dosage of the granular mixture, in particular the particulate phase, preferably the powder and / or granules, e.g. of the powder is necessary. In particular, the values greater than 50%, in particular greater than 55%, preferably greater than 60% (the free-flowing properties being measured 24 hours after the powder has been produced and stored at 20 ° C.) have proven to be advantageous, since the good meterability the granular mixture, in particular the particulate phases, preferably the powder and / or granules, for example Powder only show slight fluctuations in the metered amount or composition. The more precise dosing leads to a constant product performance, economic losses through overdosing are avoided. It is also advantageous that the granular mixture, in particular the particulate phase, preferably the powder and / or granules, e.g. the powder can be dosed well, so that the dosing process runs faster. Furthermore, it is better avoided by such good pourability that the granular mixture, in particular the particulate phase, preferably the powder and / or granules, e.g. the powder reaches the part of the water-soluble coating which is intended for the production of the sealed seam and should therefore remain as granule-free as possible, in particular powder-free.

According to a preferred embodiment, the at least one liquid composition comprises perfume preparations and / or surfactants, preferably nonionic surfactants.

The at least one liquid composition is preferably low in water, in particular essentially water-free. This has the advantage that the particulate phase, which as a rule contains washing or cleaning-active substances, partially can react with each other with water and / or in aqueous solutions, these reactions do not already occur during the preparation and / or during the storage of the portion. This improves product manufacture and shelf life, and thus generally product stability.

Surprisingly, it has been shown that particularly good storage stability is achieved if the at least one liquid composition is low in water.

Low water in the sense of the present invention means that small amounts of water can be used to produce a phase or composition. The proportion of water in this phase or composition is in particular 20% by weight or less, preferably 15% by weight or less, particularly 12% by weight or less, in particular between 10 and 5% by weight. The percentages by weight relate to the total weight of the respective phase or composition.

According to a further embodiment, the at least one liquid composition is essentially water-free. Anhydrous in the sense of the invention means that the respective phase or composition is preferably essentially free of water. “Essentially free” here means that small amounts of water can be present in the phase or composition. This water can, for example, be introduced into the phase by means of a solvent or as water of crystallization or due to reactions of components of the phase with one another. However, small amounts, in particular no water, are used as solvents for the preparation of the corresponding phase or composition. The proportion of water in the phase or composition in this embodiment is 4.9% by weight or less, 4% by weight or less, preferably 2% by weight or less, in particular 1% by weight or less, particularly 0.5% by weight or less, in particular 0.1% by weight or 0.05% by weight or less. The percentages by weight relate to the total weight of the respective phase or composition.

According to a preferred embodiment, the weight ratio of the total amount of the at least one liquid composition to the total amount of the at least one particulate phase is from 1: 800 to 5: 1, in particular from 1: 600 to 2: 1, preferably from 1: 500 to 2: 1, for example from 1: 450 to 1: 1.

The proportion by weight of the at least one liquid composition to the total weight of the composition is formed from the at least one liquid composition and the at least one particulate composition from 0.0001 to 25% by weight, in particular 0.005 to 20% by weight, preferably 0.1 to 18% by weight, very particularly preferably 0.2 to 15% by weight, is preferred.

It is particularly preferred that if the at least one liquid composition comprises at least one surfactant, preferably a nonionic surfactant, the total amount of the at least one liquid composition relative to the total amount of the at least one particulate phase is from 1: 200 to 5: 1, in particular from 1 : 100 to 1: 1, preferably from 1:50 to 1: 2, for example from 1:20 to 1: 5 and / or the proportion by weight of the at least one liquid composition to the total weight of the composition formed from the at least one liquid composition and the at least one particulate composition is 0.01 to 25% by weight, in particular 0.1 to 20% by weight, preferably 1 to 18% by weight, very particularly preferably 3 to 15% by weight.

The washing or cleaning agent according to the invention preferably comprises at least one surfactant. This surfactant is selected from the group of anionic, nonionic and cationic surfactants. The washing or cleaning agent according to the invention can also contain mixtures of several surfactants selected from the same group.

According to the invention, both the at least one particulate phase and the at least one liquid composition each comprise at least one surfactant. However, it is also possible that only the at least one particulate phase or only the at least one liquid composition comprise at least one surfactant. However, it is also possible for the phases or preparations to have different or the same surfactant or the same surfactants.

Particulate phases according to the invention and liquid compositions thus preferably comprise at least one surfactant, preferably at least one nonionic surfactant. All nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants. Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. These are specified in more detail below.

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

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

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

Other suitable surfactants are the polyhydroxy fatty acid amides known as PHFA. The washing or cleaning agents according to the invention, in particular cleaning agents for automatic dishwashing, particularly preferably contain nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 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 can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _8-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO.

Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

Preferred surfactants come from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

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

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

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

In addition to propylene oxide, butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit. However, other alkylene oxides in which R ² or R ³ are selected independently of one another from - CH ₂ CH ₂ -CH ₃ or -CH (CH ₃ ) ₂ are also suitable. Nonionic surfactants of the above formula are preferably used, in which R ² and R ³ for a radical —CH ₃ , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.

Further preferred nonionic surfactants are nonionic surfactants of the general formula R ¹ O (AlkO) _x M (OAlk) _y OR ¹ , where
R ¹ and R ² independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms; Alk represents a branched or unbranched alkyl radical having 2 to 4 carbon atoms; x and y independently represent values between 1 and 70; and M represents an alkyl radical from the group CH ₂ , CHR ³ , CR ³ R ⁴ , CH ₂ CHR ³ and CHR ³ CHR ⁴ , where R ³ and R ⁴ independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical with 1 are up to 18 carbon atoms.

Nonionic surfactants of the general formula are preferred

R ¹ -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y -CH ₂ CH (OH) -R ² ,

wherein R, R ¹ and R ² independently of one another are an alkyl radical or alkenyl radical having 6 to 22 carbon atoms; x and y independently represent values between 1 and 40.

Compounds of the general formula are particularly preferred

R ¹ -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y O-CH ₂ CH (OH) -R ² ,

in which R represents a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms and n and m independently of one another have values from 20 to 30. Corresponding compounds can be obtained, for example, by reacting HO-CHR-CH ₂ -OH alkyldiols with ethylene oxide, followed by a reaction with an alkyl epoxide to block the free OH functions to form a dihydroxy ether.

• R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• R² für Wasserstoff oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• A, A', A" und A'" unabhängig voneinander für einen Rest aus der Gruppe -CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-, -CH₂-CH(CH₂-CH₃) stehen,
• w, x, y und z für Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein können.

Durch den Zusatz der vorgenannten nichtionischen Tenside der allgemeinen Formel R¹-CH(OH)CH₂O-(AO)_w-(A'O)_x-(A"0)_y-(A"'O)_z-R², nachfolgend auch als "Hydroxymischether" bezeichnet, kann überraschenderweise die Reinigungsleistung erfindungsgemäßer Zubereitungen deutlich verbessert werden und zwar sowohl im Vergleich zu Tensid-freien System wie auch im Vergleich zu Systemen, die alternative nichtionischen Tenside, beispielsweise aus der Gruppe der polyalkoxylierten Fettalkohole enthalten.Preferred nonionic surfactants are those of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (AO) _x - (A "O) _y - (A" O) _z -R ² , in which

• R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 represents} hydrogen or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A, A ', A "and A'" independently of one another for a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ),
• w, x, y and z stand for values between 0.5 and 120, where x, y and / or z can also be 0.

By adding the aforementioned nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "0) _y - (A"'O) _z -R ² , hereinafter also referred to as "hydroxy mixed ether", surprisingly the cleaning performance of preparations according to the invention can be significantly improved, both in comparison to the surfactant-free system and in Comparison to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

By using these nonionic surfactants with one or more free hydroxyl groups on one or both terminal alkyl radicals, the stability of the enzymes contained in the cleaning agent preparations according to the invention can be significantly improved.

neben einem Rest R¹, welcher für lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 2 bis 30 Kohlenstoffatomen, vorzugsweise mit 4 bis 22 Kohlenstoffatomen steht, weiterhin einen linearen oder verzweigten, gesättigten oder ungesättigten, aliphatischen oder aromatischen Kohlenwasserstoffrest R² mit 1 bis 30 Kohlenstoffatomen aufweisen, wobei n für Werte zwischen 1 und 90, vorzugsweise für Werte zwischen 10 und 80 und insbesondere für Werte zwischen 20 und 60 steht. Insbesondere bevorzugt sind Tenside der vorstehenden Formel, in denen R¹ für C₇ bis C₁₃, n für eine ganze natürliche Zahl von 16 bis 28 und R² für C₈ bis C₁₂ steht.Those end group-capped poly (oxyalkylated) nonionic surfactants which, according to the following formula, are particularly preferred

in addition to a radical R ¹ , which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms, where n stands for values between 1 and 90, preferably for values between 10 and 80 and in particular for values between 20 and 60. Particularly preferred are surfactants of the above formula in which R ^{1 is} C ₇ to C ₁₃ , n is an integer from 16 to 28 and R ^{2 is} C ₈ to C ₁₂ .

Surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 up to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 1.5 and y stands for a value of at least 15. The group of these nonionic surfactants includes, for example, the C _2-26 fatty alcohol (PO) ₁ - (EO) _15-40 -2-hydroxyalkyl ethers, in particular also the C _8-10 fatty alcohol (PO) ₁ - (EO) ₂₂ -2 -hydroxydecylether.

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

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

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

• R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C 6-24-Alkyl- oder -Alkenylrest steht;
• R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• A für einen Rest aus der Gruppe CH₂CH₂, CH₂CH₂CH₂, CH₂CH(CH₃), vorzugsweise für CH₂CH₂ steht, und
• w für Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht.

Particularly preferred end group-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH ) CH ₂ OR ² simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 have} 9 to 14 carbon atoms, R ^{3 represents} H and x assumes values from 6 to 15. Finally, the nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ^{2 have} proven to be particularly effective in which

• R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical;
• R ^{2 represents} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A is a radical from the group CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH (CH ₃ ), preferably CH ₂ CH ₂ , and
• w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40.

The group of these nonionic surfactants includes, for example, the C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ethers, in particular also the C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ether and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ether.

The at least one particulate and / or the at least one gel phase and / or liquid preparation preferably contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, the weight fraction of the nonionic surfactant in the total weight of the gel phase preferably being 0.5% by weight .-% to 30 wt .-%, preferably 5 wt .-% to 25 wt .-% and in particular 10 wt .-% to 20 wt .-%.

In a further preferred embodiment, the nonionic surfactant of the particulate and / or gel phase and / or liquid preparation is selected from nonionic surfactants of the general formula R ¹ -O (CH ₂ CH ₂ O) _× CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which R ¹ and R ² independently of one another are an alkyl radical or alkenyl radical having 4 to 22 carbon atoms; R ³ and R ⁴ independently of one another represent H or an alkyl or alkenyl radical having 1 to 18 carbon atoms and x and y independently of one another values between 1 and 40.

Compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² in which R ³ and R ^{4 are} H and the indices x and y are preferred independently of one another assume values from 1 to 40, preferably from 1 to 15.
Particularly preferred are particularly compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which the radicals R ¹ and R ² independently of one another are saturated alkyl radicals with 4 to Represent 14 carbon atoms and the indices x and y independently assume values from 1 to 15 and in particular from 1 to 12.
Such compounds of the general formula are also preferred
R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which one of the radicals R ¹ and R ^{2 is} branched.
Compounds of the general formula are very particularly preferred
R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which the indices x and y independently assume values from 8 to 12.

The stated C chain lengths and degrees of ethoxylation or alkoxylation of the nonionic surfactants represent statistical mean values which can be an integer or a fraction for a specific product. Because of the manufacturing processes, commercial products of the formulas mentioned usually do not consist of an individual representative, but of mixtures, which can result in mean values and fractional numbers for the C chain lengths as well as for the degrees of ethoxylation or alkoxylation.

Of course, the aforementioned nonionic surfactants (nonionic surfactants) can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.

Particularly preferred in the at least one particulate phase or liquid composition are those nonionic surfactants which have a melting point above room temperature. Nonionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43.3 ° C. is / are particularly preferred ,

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa · s, preferably above 35 Pa · s and in particular above 40 Pa · s. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.

The nonionic surfactant, which is solid at room temperature, preferably has propylene oxide units (PO) in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants. Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight, of the total molecular weight of the nonionic Identify surfactants.

Further nonionic surfactants with melting points above room temperature which are particularly preferably to be used in the particulate phase or liquid composition contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which comprises 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

In a preferred embodiment, the weight fraction of the nonionic surfactant in the total weight of the particulate phase is from 0.1 to 20% by weight, particularly preferably from 0.5 to 15% by weight, in particular from 2.5 to 10% by weight ,

All anionic surface-active substances are suitable as anionic surfactants in dishwashing detergents. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 8 to 30 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Suitable anionic surfactants are preferably in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group, but also zinc, manganese (II), magnesium, calcium or Mixtures of these can serve as counterions.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

Instead of the surfactants mentioned or in conjunction with them, cationic and / or amphoteric surfactants such as betaines or quaternary ammonium compounds can also be used. However, it is preferred that no cationic and / or amphoteric surfactants are used.

It is particularly preferred if the total amount of the at least one liquid composition comprising at least one nonionic surfactant to the total amount of the at least one particulate phase has a weight ratio of 1: 200 to 5: 1, in particular 1: 100 to 1: 1, preferably of 1:50 to 1: 2, for example from 1:20 to 1: 5 and / or the proportion by weight of the at least one liquid composition to the total weight of the composition formed from the at least one liquid composition and the at least one particulate composition from 0.01 to 25% by weight. %, in particular 0.1 to 20% by weight, preferably 1 to 18% by weight, very particularly preferably 3 to 15% by weight.

According to a further preferred embodiment of the present invention, the surfactant content of the at least one liquid composition is at least 50% by weight, in particular at least 70% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight, based on the total weight of the liquid composition. These can be both liquid surfactants themselves and mixtures of liquid and / or solid surfactants with solvents, preferably organic solvents, in order to improve the incorporation of the surfactants.

Alternatively, it is particularly preferred if the at least one liquid composition does not comprise a surfactant but a perfume preparation such that the total amount of the liquid composition relative to the total amount of the at least one particulate phase is from 1: 800 to 1:50, in particular from 1: 600 to 1: 100, preferably from 1: 500 to 1: 200, for example from 1: 400 to 1: 250 and / or the proportion by weight of the at least one liquid composition to the total weight of the composition formed from the at least one liquid composition and the at least one particulate composition 0.001 is up to 2% by weight, in particular 0.005 to 1.0% by weight, preferably 0.1 to 0.8% by weight, very particularly preferably 0.15 to 0.5% by weight.

According to a very particularly preferred embodiment, the washing or cleaning agent according to the invention comprises, in addition to the at least one particulate phase and the at least one liquid composition, at least one further gel phase.

According to the invention, a gel-like phase, hereinafter also referred to as gel phase, is to be understood as a composition / phase which has an internally structuring network. This internally structuring (spatial) network is formed by the dispersion of a solid but distributed substance with long or highly branched particles and / or gel-forming agent in at least one liquid (the at least one liquid is liquid at 20 ° C.). Such gel phases are thermoreversible.

This gel phase can be, for example, flowable or dimensionally stable. According to the invention, however, the gel phase is preferably dimensionally stable at room temperature. In the preparation, the gel former, preferably xanthan, gelatin or polyvinyl alcohol and / or its derivatives, is brought into contact with a solvent, preferably an organic solvent, preferably one or more polyhydric alcohol (s). This gives a flowable mixture which can be brought into a desired shape. After a certain period of time, a gel phase is obtained which remains in the specified form, i.e. is dimensionally stable. This period, the solidification time, is preferably 15 minutes or less, preferably 10 minutes or less, particularly preferably 5 minutes or less. The at least one gel phase yields under pressure, but does not deform as a result, but rather returns to the initial state after the pressure has dropped. The at least one gel phase is preferably elastic, in particular linear-elastic.

The at least one gel phase is preferably a shaped body. A molded body is a single body that stabilizes itself in its impressed shape. This dimensionally stable body is formed from a molding compound (for example a composition) by specifically bringing this molding compound into a predetermined shape, for example by pouring a liquid composition into it a casting mold and then curing the liquid composition, for example as part of a sol-gel process.

Certain minimum requirements are imposed on formulations of the at least one gel phase. As already stated, the gel phase must solidify within the shortest possible time. Long solidification times would lead to long production times and thus high costs. According to the invention, solidification time means the period of time during which the at least one gel phase changes from a flowable state to a dimensionally stable state which is not flowable at room temperature. Room temperature is understood to be a temperature of 20 ° C.

The at least one gel phase is preferably a solid gel phase. It is cut-resistant. For example, it can be cut with a knife after solidification without being further destroyed apart from the cut performed.

Furthermore, the gel phase must be stable in storage, and that under normal storage conditions. The gel phase according to the invention is part of a cleaning agent. Cleaning agents are usually stored in a household for a certain period of time. Storage is usually near the washing machine or dishwasher. The gel phase should be stable for such storage. Thus, the gel phase should in particular also be stable after a storage time of, for example, 4 to 12 weeks, in particular 10 to 12 weeks or longer at a temperature of up to 40 ° C., in particular at 30 ° C., in particular at 25 ° C. or at 20 ° C. be and do not deform or otherwise change their consistency during this time.

If the gel phase and a solid phase, in particular a powder phase, are in direct contact with one another, the gel phase penetrates into the interstices of the immediately underlying powder phase in the storage period of 4 weeks at 25 ° C., preferably at most 1 mm.

A disadvantage would be a change in volume or shrinkage during storage, as this would result in low consumer acceptance of the product. Leakage of liquid or exudation of components from the gel phase is also undesirable. Here, too, the visual impression is relevant. The stability of the gel phase can be influenced by the escape of liquid, such as, for example, solvents, so that the constituents are no longer contained in a stable manner and the washing or cleaning action can also be influenced thereby.

The at least one gel phase is preferably low in water. This has the advantage that the small amounts of water in combination with PVOH can have a structure or gel-forming effect. According to a preferred embodiment, the at least one gel phase is essentially water-free.

Particularly preferably, cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, contain at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate, in an amount of 0.05 to 3% by weight, in particular 0.1 to 2.4% .-%, very particularly preferably from 0.2 to 1.0 wt .-%, based on the total weight of the gel phase.

According to a preferred embodiment, the cleaning agents according to the invention, preferably dishwashing agents, in particular machine dishwashing agents, contain a gel former in the gel phase (gel phase), preferably selected from gelatin, xanthan and / or polyvinyl alcohol, in particular gelatin or polyvinyl alcohol, particularly preferably polyvinyl alcohol, in an amount of 4 up to 40, in particular from 6 to 30% by weight, particularly preferably in an amount of 7 to 24% by weight, very particularly preferably 8 to 22% by weight, in particular for example 14 to 20% by weight, in each case based on the total weight of the gel phase.

According to the invention, the at least one gel phase particularly preferably comprises PVOH (polyvinyl alcohol) and / or their derivatives. Polyvinyl alcohols are thermoplastic materials that are usually produced as white to yellowish powder by hydrolysis of polyvinyl acetate. Polyvinyl alcohol (PVOH) is resistant to almost all anhydrous organic solvents. Polyvinyl alcohols with a molecular weight of 30,000 to 60,000 g / mol are preferred. For the purposes of the invention, preferred PVOH derivatives are copolymers of polyvinyl alcohol with other monomers, in particular copolymers with anionic monomers. Suitable anionic monomers are preferably vinyl acetic acid, alkyl acrylates, maleic acid and their derivatives, in particular monoalkyl maleates (in particular monomethyl maleate), dialkyl maleates (in particular dimethyl maleate), maleic anhydride, fumaric acid and their derivatives, in particular monoalkyl fumarate (in particular monomethyl fumarate), dialkyl fumarate (especially fumarate), dialkyl fumarate itaconic acid and its derivatives, especially monomethyl itaconate, dialkyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid (methylmaleic acid) and derivatives thereof, Monoalkylcitraconsäure (especially Methylcitraconat) Dialkylcitraconsäure (Dimethylcitraconat), citraconic acid, mesaconic acid (methylfumaric) and their derivatives, Monoalkylmesaconat, Dialkylmesaconat, mesaconic, glutaconic and their derivatives, monoalkyl glutaconate, dialkyl glutaconate, glutaconic anhydride, vinyl sulfonic acid, alkyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido-1 -methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethylacrylate and their combinations as well as the alkali metal salts or esters of the above-mentioned monomers.

Particularly preferred derivatives of PVOH are those which are selected from copolymers of polyvinyl alcohol with a monomer, in particular selected from the group of the monoalkyl maleates (in particular monomethyl maleate), dialkyl maleates (in particular dimethyl maleate), maleic anhydride, and their combinations, and the alkali metal salts or esters of the above mentioned monomers. The values given for polyvinyl alcohols themselves apply to the suitable molar masses. In the context of the present invention, it is preferred that the at least one gel phase comprises a polyvinyl alcohol and / or its derivatives, preferably polyvinyl alcohol, the degree of hydrolysis of which is preferably 70 to 100 mol%, in particular 80 to 90 mol%, particularly preferably 81 to 89 Mol% and especially 82 to 88 mol%.

Particularly preferred are polyvinyl alcohols, which are white-yellowish powders or granules with degrees of polymerization in the range from about 100 to 2500 (molar masses from about 4000 to 100,000 g / mol) and degrees of hydrolysis from 80 to 99 mol%, preferably from 85 to 90 mol %, in particular from 87 to 89 mol%, for example 88 mol%, which accordingly still contain a residual content of acetyl groups.

PVOH powders with the properties mentioned above, which are suitable for use in the at least one gel phase, are marketed, for example, under the name Mowiol® or Poval® by Kuraray. Suitable is e.g. also Exceval® AQ4104 from Kuraray. Mowiol C30, the Poval® qualities, in particular the qualities 3-83, 3-88, 6-88, 4-85, and particularly preferably 4-88, very particularly preferably Poval 4-88 S2, and Mowiol® 4- are particularly suitable. 88 from Kuraray.

The water solubility of polyvinyl alcohol can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization). Polyvinyl alcohols which have been acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous because of their extremely good solubility in cold water. The reaction products of polyvinyl alcohol and starch are to be used extremely advantageously. Furthermore, the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus adjusted to the desired values.

Surprisingly, it has been shown that PVOH are particularly suitable for producing gel phases which meet the requirements shown above. At least one gel phase is therefore particularly preferred which, in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate, has PVOH and at least one polyhydric alcohol. The at least one gel phase particularly preferably has PVOH and at least one polyhydric alcohol.

According to the invention, the at least one gel phase comprises at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate, PVOH and / or its derivatives in a proportion of approximately 4% by weight to 40% by weight, in particular 6% by weight. % to 30% by weight, preferably from 7 to 24% by weight, particularly preferably between 8% by weight to 22% by weight. Significantly lower proportions of PVOH do not lead to the formation of a stable gel phase. The values are based on the total weight of the gel phase.

According to a very particularly preferred embodiment, the at least one gel phase comprises PVOH (polyvinyl alcohol). The gel phases thus produced are particularly high-melting, dimensionally stable (even at 40 ° C.) and do not change their shape, or only insignificantly, even during storage. In particular, they are also not very reactive with regard to a direct negative interaction with constituents of the granular mixture, in particular the powder phase. In particular, PVOH can also generate water-free or water-free gel phases without difficulty. When using PVOH as a polymer for the at least one gel phase, low-viscosity melts result at 110-120 ° C., which can be processed particularly easily as a result, in particular the gel phase can be poured into the water-soluble coating quickly and accurately without any Gluing takes place or the amount is metered inaccurately. Furthermore, these gel phases adhere particularly well to the water-soluble coating, especially if it is also made from PVOH. This is also visually advantageous. The rapid solidification of the at least one gel phase with PVOH means that the gel phases can be further processed particularly quickly. Furthermore, the good solubility of the gel phases produced is particularly favorable for the overall solubility of the cleaning agent. In addition, gel phases with such short solidification times are advantageous so that the at least one solid phase metered thereon, comprising granular mixtures, in particular powder, does not sink into the gel which has not yet solidified or is too soft. This leads to less appealing detergent portions.

In particular in the case of the multi-phase disposable portions according to the invention with at least one solid phase, it is important that the at least one gel phase is dimensionally stable so that as few interactions as possible can take place between the solid and the gel phase. If the at least one gel phase also includes gelatin in addition to PVOH, the toughness of the gel phase is increased during production.

The present invention furthermore relates to cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, which in the gel phase are at least one organic solvent, in particular selected from 1,2-propanediol, 1,3-propanediol, glycerol, 1,1,1 -Trimethylolpropane, triethylene glycol, dipropylene glycol, polyethylene glycols and / or mixtures thereof.

The at least one gel phase preferably comprises at least one polyhydric alcohol. In addition to the production of flowable gel phases, the at least one polyhydric alcohol also enables the production of a dimensionally stable, non-flowable gel phase within a short setting time, within 15 minutes or less, in particular 10 minutes or less. Polyhydric alcohols in the context of the present invention are hydrocarbons in which two, three or more hydrogen atoms have been replaced by OH groups. The OH groups are bound to different carbon atoms. A carbon atom does not have two OH groups. This is in contrast to (simple) alcohols, in which only one hydrogen atom in hydrocarbons is replaced by one OH group. Polyhydric alcohols with two OH groups are referred to as alkane diols, polyhydric alcohols with three OH groups as alkane triols. A polyhydric alcohol thus corresponds to the general formula [KW] (OH) _x , where KW is a hydrocarbon which is linear or branched, saturated or unsaturated, substituted or unsubstituted. Substitution can take place, for example, with SH or NH groups. KW is preferably a linear or branched, saturated or unsaturated, unsubstituted hydrocarbon. KW comprises at least two carbon atoms. The polyhydric alcohol comprises 2, 3 or more OH groups (x = 2, 3, 4 ...), only one OH group being bound to each C atom of the KW. KW particularly preferably comprises 2 to 10, that is to say 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. In particular, polyhydric alcohols with x = 2, 3 or 4 (for example, pentaerythritol with x = 4) can be used. X = 2 (alkanediol) and / or x = 3 (alkanetriol) is preferred.

The at least one gel phase particularly preferably comprises at least one alkanetriol and / or at least one alkanediol, in particular at least one C ₃ to C ₁₀ alkanetriol and / or at least one C ₃ to C ₁₀ alkanediol, preferably at least one C ₃ to C ₈ alkanetriol and / or at least one C ₃ to C ₈ alkanediol, especially at least one C ₃ to C ₆ alkanediol and / or at least one C _{3 to} C ₅ alkanediol as polyhydric alcohol. It preferably comprises an alkanetriol and an alkanediol as at least one polyhydric alcohol. In a preferred embodiment, the at least gel phase therefore comprises at least one polymer, in particular PVOH or PVOH with gelatin, and at least one alkanediol and at least one alkanetriol, in particular an alkanetriol and an alkanediol. Also preferred is a gel phase comprising at least one polymer, PVOH or PVOH with gelatin, as well as a C ₃ to C ₈ alkanediol and a C ₃ to C ₈ alkanetriol. A gel phase is further preferred which comprises at least one polymer, in particular PVOH or PVOH with gelatin, and also a C ₃ to C ₅ alkanediol and a C ₃ to C ₆ alkanetriol. According to the invention, the polyhydric alcohols do not include any derivatives such as ethers, esters, etc.

Surprisingly, it has been shown that when a corresponding triol (alkane triol) is combined with a corresponding diol (alkane diol), particularly short solidification times can be achieved. The gel phases obtained are also transparent and have a glossy surface, which gives an appealing visual impression of the invention Provide detergent. The terms diol and alkanediol are used synonymously here. The same applies to triol and alkanetriol.

According to a particularly preferred embodiment, in the cleaning agents according to the invention, preferably dishwashing agents, in particular machine dishwashing agents, the at least one organic solvent in the gel phase is present in amounts of 30 to 90% by weight, in particular 40 to 85% by weight, particularly preferably of 50 to 80 wt .-%, based on the total weight of the gel phase.

The amount of polyhydric alcohol or polyhydric alcohols used in gel phases according to the invention is preferably at least 45% by weight, in particular 55% by weight or more. Preferred quantitative ranges are from 45% by weight to 85% by weight, in particular from 50% by weight to 80% by weight, based on the total weight of the gel phase.

The C ₃ -C ₆ alkanetriol is preferably glycerol and / or 2-ethyl-2- (hydroxymethyl) -1,3-propanediol (also called 1,1,1-trimethylolpropane) and / or 2-amino-2- (hydroxymethyl) -1,3-propanediol (TRIS, trishydroxymethylaminoethane) and / or 1,3,5-pentanetriol.

The C ₃ - to C ₆ -alkanetriol glycerol and / or 2-ethyl-2- (hydroxymethyl) -1,3-propanediol (also called 1,1,1-trimethylolpropane) is particularly preferred. The C ₃ - to C ₅ -alkanediol is, for example, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-butanediol, 1,3-propanediol and / or 1,2-propanediol, preferably 1, 3-propanediol and / or 1,2-propanediol. Surprisingly, it has been shown that the chain length of the diol and in particular the position of the OH groups have an influence on the transparency of the gel phase. The OH groups of the diol are therefore preferably not arranged on immediately adjacent C atoms. In particular, there are three or four carbon atoms, in particular 3 carbon atoms, between the two OH groups of the diol. The diol 1,3-propanediol is particularly preferred. Surprisingly, it has been shown that particularly good results are achieved with mixtures which comprise glycerol and 1,3-propanediol and / or 1,2-propanediol.

According to the invention, polyethylene glycol (s) with an average molar mass of 200 to 600 g / mol are preferably additionally used in the at least one gel phase or the gel phases. In combination with polyvinyl alcohol, polyethylene glycols with an average molecular weight between about 200 and about 600 g / mol, preferably between 300 and 500 g / mol, particularly preferably between 350 and 450 g / mol, for example around 400 g / mol INCI: PEG400) used. Detergent portions according to the invention are thus characterized in that they have polyethylene glycol (s) with an average molecular weight of 300 to 500 g / mol, in particular of 350 to 450 g / mol.

It is particularly advantageous that the at least one gel phase or the gel phases, each based on the total weight of the gel phase, in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate, (preferably in amounts of 0.1 to 2 , 4 wt .-%, particularly preferably from 0.2 to 1.0 wt .-%), polyvinyl alcohol and at least one polyhydric alcohol, optionally additionally polyethylene glycols with an average molecular weight of about 200 to 600 g / mol in amounts of 5 to Contain 30% by weight, preferably from 8 to 26% by weight, in particular from 10 to 22% by weight, based on the total weight of the at least one gel phase.

Surprisingly, it has been shown that the addition of polyethylene glycols, in particular those with average molecular weights of 200 to 600 g / mol, to the at least one gel phase, in particular in the case of gel phases comprising polyvinyl alcohol, leads to an acceleration of the setting time of the gel phases. Values of a few minutes and even less than a minute can be achieved. This is of great advantage in particular for the production processes, since the gel phases can be further processed in the solidified state much more quickly and therefore generally more cost-effectively. Surprisingly, it was found that the presence of polyethylene glycol (s) with an average molecular weight of 200 to 600 g / mol in combination with polyvinyl alcohol and / or its derivatives makes a decisive contribution to reducing the setting times. Without being bound by theory, it is assumed that such polyethylene glycols, in particular those with a molecular weight of 350 to 450 g / mol, in particular by 400 g / mol, increase the sol-gel temperature.

In a particularly preferred embodiment, the amount of polyethylene glycol (s) with an average molecular weight of 350 to 450 g / mol, for example around 400 g / mol, is 10 to 22% by weight, based on the total weight of the gel phase.

A particularly preferred gel phase therefore comprises at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (for example zinc acetate anhydrate), PVOH, polyethylene glycol (s) with an average molecular weight of 200 to 600 g / mol and 1,3-propanediol and glycerol or 1,1,1-trimethylolpropane as polyhydric alcohols. Here, within a solidification time of 10 min or less, a non-flowable consistency that is stable at room temperature can be achieved, which remains dimensionally stable even after a long storage period. A corresponding phase is also transparent and has a glossy surface. A particularly preferred gel phase therefore comprises gelatin or PVOH as a polymer and 1,3-propanediol and glycerol or 1,1,1-trimethylolpropane as polyhydric alcohols.

In each case, based on the total weight of the gel phase, comprises the gel phase in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4% by weight, particularly preferably of 0.2 to 1.0% by weight) of an alkanetriol, in particular glycerol or 1,1,1-trimethylolpropane, the proportion of alkanetriol, in particular glycerol or 1,1,1-trimethylolpropane, based on the total weight of the gel phase , between 3 and 75% by weight, preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight, particularly 20% by weight to 40% by weight.

If the gel phase optionally comprises several alkanetriol (s), the total proportion of alkanetriol (s), based on the total weight of the gel phase, is between 3 and 75% by weight, preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight, particularly 20% by weight to 40% by weight.

If glycerol is present as alkanetriol in the gel phase, the proportion of glycerol based on the total weight of the gel phase is preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight, particularly 20 % By weight to 40% by weight.

If 1,1,1-trimethylolpropane is contained in the gel phase, the proportion of 1,1,1-trimethylolpropane, based on the total weight of the gel phase, is preferably 5% by weight to 70% by weight, in particular 10% by weight. % to 65% by weight, particularly preferably 18 to 45% by weight, particularly preferably 20% by weight to 40% by weight.

If 2-amino-2-hydroxymethyl-1,3-propanediol is present in the gel phase, the proportion of 2-amino-2-hydroxymethyl-1,3-propanediol, based on the total weight of the gel phase, is preferably 5% by weight. % to 70% by weight, in particular 10% by weight to 65% by weight, particularly 20% by weight to 40% by weight.

If there are possibly several alkanediols in the gel phase, the proportion of alkanediols, based on the total weight of the gel phase, is preferably 5% by weight to 70% by weight, in particular 7% by weight to 65% by weight, particularly 10 wt% to 40 wt%.

In each case, based on the total weight of the gel phase, comprises the gel phase in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4% by weight, particularly preferably of 0.2 up to 1.0% by weight) of at least one alkanediol, in particular 1,3-propanediol or 1,2-propanediol, the proportion of alkanediol, in particular 1,3-propanediol or 1,2-propanediol, based on the total weight the gel phase, preferably 5% by weight to 70% by weight, in particular 10% by weight to 65% by weight, particularly 20% by weight to 45% by weight. If 1,3-propanediol is contained in the gel phase, the proportion of 1,3-propanediol, based on the total weight of the gel phase, is in particular 10% by weight to 65% by weight, particularly 20% by weight to 45 wt .-%.

Preferred is a gel phase, each based on the total weight of the gel phase in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4% by weight, particularly preferably from 0.2 to 1.0% by weight) 20 to 45% by weight of 1,3-propanediol and / or 1, 2-propanediol and 10 wt .-% to 65 wt .-% 2-amino-2-hydroxymethyl-1,3-propanediol, each based on the total weight of the gel phase. Also preferred is a gel phase containing 20 to 45% by weight of 1,3 propanediol and / or 1,2-propanediol and 10% by weight to 65% by weight of 1,1,1-trimethylolpropane, based in each case on the Total weight of the gel phase. A gel phase which contains 20 to 45% by weight of 1,3 propanediol and / or 1,2-propanediol and 10% by weight to 65% by weight of glycerol, in each case based on the total weight of the gel phase, is particularly preferred. It has been shown that a rapid solidification at 20 ° C. of a gel phase is possible in these areas, the phases obtained are stable in storage and transparent. The proportion of glycerine in particular has an effect on the curing time.

If the at least one gel phase according to the invention, based on the total weight of the gel phase, has at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4% by weight, particularly preferably of 0 , 2 to 1.0% by weight) of a C ₃ to C ₆ alkanetriol and a C ₃ to C ₅ alkanediol, their weight ratio is preferably 3: 1 to 1: 2. In particular, the weight ratio is from 2: 1 to 1: 1.5, preferably from 1.5: 1 to 1: 1.2, preferably from 1.3 to 1: 1 if glycerol and 1,3-propanediol are polyhydric alcohols are included. Surprisingly, it has been shown that with these weight ratios, storage-stable, shiny, transparent gel phases can be obtained within 20 minutes or less at 20 ° C. In combination with polyethylene glycols with an average molecular weight of 200 to 600 g / mol, the preferred weight ratios, in particular weight ratios (C ₃ to C ₆ alkanetriol: C ₃ to C ₅ alkanediol) of 1.5: 1 to 1: 1.2, reduce to solidification times of 5 minutes and less.

According to a further preferred embodiment, in addition to the alkanols mentioned above, triethylene glycol can be present in the at least one gel phase, in particular the gel phases described above as preferred, in particular if this phase is PVOH and, if appropriate, polyethylene glycols with an average molecular weight of 200 to 600 g / mol contains. Triethylene glycol advantageously accelerates the solidification of the gel phase (s). It also results in the resulting gel phase, if at all, only slightly, unobservably, exchanging liquid with the environment. In particular, this improves the visual impression of the resulting detergent portions. It is particularly preferred if the at least one gel phase, based in each case on the total weight of the gel phase, in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.1 to 2.4% by weight , particularly preferably from 0.2 to 1.0% by weight) 1,3- and / or 1,2-propanediol, particularly preferably 1 to 3.5% by weight 1,3-propanediol, and glycerol between 0 , 1 and 20% by weight, preferably between 1 and 15 % By weight, in particular between 5 and 12% by weight, for example 8 to 11% by weight of triethylene glycol

Furthermore, the washing or cleaning agent according to the invention, in particular at least the at least one gel phase, preferably both the particulate phase and the gel phase, comprises a further anionic polymer, in particular polycarboxylates. These can either act as builders and / or as a thickening polymer. According to the invention, the at least one gel phase can further comprise anionic polymers or copolymers with builder properties. It is preferably a polycarboxylate. A copolymeric polyacrylate, preferably a sulfopolymer, preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate is preferably used as the polycarboxylate. The copolymers can have two, three, four or more different monomer units. In addition to monomer (s) containing sulfonic acid groups, preferred copolymeric polysulfonates contain at least one monomer from the group of unsaturated carboxylic acids.

According to a particularly preferred embodiment, the low-water gel phase contains a polymer comprising at least one monomer containing sulfonic acid groups.

Unsaturated carboxylic acids of the formula R ¹ (R ² ) C = C (R ³ ) COOH are used as unsaturated carboxylic acid (s), in which R ¹ to R ³ independently of one another are —H, —CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH2, -OH or -COOH as defined above or for -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylene malonic acid, sorbic acid, cinnamic acid or mixtures thereof. Of course, the unsaturated dicarboxylic acids can also be used.

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

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

According to a particularly preferred embodiment, the gel phase contains a polymer comprising, as the monomer containing sulfonic acid groups, acrylamidopropanesulfonic acids, methacrylamidomethylpropanesulfonic acids or acrylamidomethylpropanesulfonic acid.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl sulfopropyl acrylate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts. The sulfonic acid groups in the polymers can be wholly or partly in neutralized form, that is to say that the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.

The monomer distribution of the copolymers preferably used according to the invention is preferably 5 to 95% by weight in each case in copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90% by weight. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are preferably selected from the aforementioned. The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use. Preferred cleaning agents are characterized in that the copolymers have molar masses from 2000 to 200,000 g-mol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

In a further preferred embodiment, in addition to the monomer containing carboxyl groups and monomer containing sulfonic acid groups, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer. By using these hydrophobically modified polymers, in particular the rinse aid of dishwashing detergents according to the invention could be improved.

1. i) Carbonsäuregruppen-haltige Monomere
2. ii) Sulfonsäuregruppen-haltige Monomere
3. iii) nichtionische Monomere, insbesondere hydrophobe Monomere

eingesetzt wird.The at least one gel phase particularly preferably further comprises an anionic copolymer, a copolymer comprising as the anionic copolymer

1. i) Monomers containing carboxylic acid groups
2. ii) Monomers containing sulfonic acid groups
3. iii) nonionic monomers, especially hydrophobic monomers

is used.

The nonionic monomers used are preferably monomers of the general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another represent -H, -CH ₃ or - C ₂ H ₅ , X represents an optionally present spacer group which is selected from -CH ₂ -, - C (O) O- and -C (O) -NH-, and R ^{4 represents} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or represents an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, α-olefins with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C ₂₂ -α-olefin, 2-styrene, α-methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid propyl ester, acrylic acid butyl ester, acrylate, acrylate, acrylate, acrylate N - (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N - (2-ethylhexyl) acrylamide, octyl acrylate lester, Methacrylsäureoctylester, N - acrylamide (lauryl), stearyl acrylate, stearyl methacrylate, N - - (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N (stearyl) acrylamide, behenyl acrylate, Methacrylsäurebehenylester and N- (Behenyl) acrylamide or mixtures thereof, in particular acrylic acid, Ethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and their mixtures.

Surprisingly, it has been found that PVOH and / or its derivatives, together with anionic polymers or copolymers, in particular with copolymers containing sulfonic acid groups, leads to the formation of gel phases with insensitive surfaces. Appropriate surfaces can be touched by the end user without material sticking to the hands. There is also no material removal in packaging. The gel phase therefore preferably comprises PVOH, polyethylene glycol (s) with an average molecular weight of 200 to 600 g / mol, at least one polyhydric alcohol and an anionic copolymer / polymer. The proportion of the anionic polymer is preferably 1% by weight to 35% by weight, in particular 3% by weight to 30% by weight, particularly 4% by weight to 25% by weight, preferably 5% by weight. % to 20 wt .-%, for example 10 wt .-% based on the total weight of the gel phase. Sulfopolymers, in particular the preferred copolymeric polysulfonates, which, in addition to monomer (s) containing sulfonic acid groups, contain at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, also ensure an excellent gloss on the surface. In addition, fingerprints are not retained. Therefore, the proportion of sulfopolymers, in particular the preferred copolymeric polysulfonates, which, in addition to monomer (s) containing sulfonic acid groups, contain at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, in particular in the sulfopolymers mentioned with AMPS as the monomer containing sulfonic acid groups, for example Acusol 590, Acusol 588 or Sokalan CP50, preferably 1% by weight to 25% by weight, in particular 3% by weight to 18% by weight, particularly 4% by weight to 15% by weight, preferably 5 wt .-% to 12 wt .-% based on the weight of the gel phase. In a particularly preferred embodiment, the at least one gel phase therefore comprises PVOH and a sulfopolymer, in particular the preferred copolymeric polysulfonates which, in addition to monomer (s) containing sulfonic acid groups, contain at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, and at least one polyvalent one Alcohol.

According to a further embodiment, in addition to the polyethylene glycols mentioned with an average molecular weight of 200 to 600 g / mol, further polyalkylene glycols, in particular further polyethylene glycols with an average molecular weight between about 800 and 8000, can be contained in the at least one gel phase. The above-mentioned polyethylene glycols are particularly preferably used in amounts of 1 to 40% by weight, preferably 5 to 35% by weight, in particular 10 to 30% by weight, for example 15 to 25, preferably in each case based on the total weight of the gel phase ,

Very particularly preferred embodiments of the present invention comprise as at least one gel phase, based in each case on the total weight of the gel phase, in addition to at least one water-soluble zinc salt, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (preferably in amounts of 0.2 to 1.0% by weight). %) 8 to 22% by weight of PVOH, 15 to 40% by weight of 1,3-propanediol, 20 to 40% by weight of glycerin, 5 to 15% by weight of polyacrylate copolymer containing sulfonic acid groups, and 8 to 22% by weight, in particular 10 to 20% by weight %, Polyethylene glycol with an average molecular weight of 200-600 g / mol, optionally 2 to 10% by weight of 1,2-propanediol, and optionally also 2-15% by weight of triethylene glycol, based in each case on the total weight of the gel phase. For a good incorporation ability of the zinc salts, in particular zinc sulfate and / or zinc acetate, especially zinc acetate (for example in the anhydrous form of the salt) into water-poor gel phases which contain polymers containing carboxylate and / or sulfonic acid groups, it is particularly preferred if the amount of Zinc salt in the anhydrous gel phase of 0.2 to 1.0 wt .-%, for example 0.5 wt .-% is selected.

According to a further particularly preferred embodiment, the washing or cleaning agents according to the invention, in particular the particulate phase, comprise at least one further ingredient selected from the group consisting of builders, polymers, bleaching agents, bleach activators, bleaching catalysts, enzymes, sequestering agents, electrolytes, corrosion inhibitors, glass corrosion inhibitors, foam inhibitors, Dyes, additives to improve drainage and drying behavior, disintegration aids, preservatives, pH regulators, fragrances and perfume carriers.

The use of builder substances (builders) such as silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builder substances, can be advantageous.

In an embodiment preferred according to the invention, the use of phosphates (also polyphosphates) is largely or completely dispensed with. In this embodiment, the agent preferably contains less than 5% by weight, particularly preferably less than 3% by weight, in particular less than 1% by weight of phosphate (s). In this embodiment, the agent is particularly preferably completely phosphate-free, i.e. the agents contain less than 0.1% by weight of phosphate (s).

The builders include, in particular, carbonates, citrates, phosphonates, organic builders and silicates. The weight fraction of the total builders in the total weight of agents according to the invention is preferably 15 to 80% by weight and in particular 20 to 70% by weight.

Organic builders suitable according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which have more than one, in particular two to eight, acid functions, preferably two to six, in particular two, three, four or five acid functions carry throughout the molecule. Preferred polycarboxylic acids are therefore dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, Tri- and tetracarboxylic acids. The polycarboxylic acids can also carry further functional groups, such as hydroxyl or amino groups. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids, for example galactaric acid and glucaric acid), aminocarboxylic acids, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids, such as nitrutinotronic acid, for example nitrontractic acids, such as nitrinotronic acid, for example (nitraminotriestric acid), such as, for example, nitraminotriestric acid, such as, for example, nitraminotriestric acid, such as, for example, nitraminotriestric acid, such as, for example, nitraminotriestric acid -diacetic acid (also referred to as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA), methylglycinediacetic acid (MGDA) and their derivatives and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures of these.

Also suitable as organic builders are polymeric polycarboxylates (organic polymers with a large number of (in particular greater than ten) carboxylate functions in the macromolecule), polyaspartates, polyacetals and dextrins.

In addition to their builder action, the free acids typically also have the property of an acidifying component. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Particularly preferred washing or cleaning agents according to the invention, in particular dishwashing agents, preferably machine dishwashing agents, contain one or more salts of citric acid, ie citrates, as one of their essential builders. These are preferably in a proportion of 2 to 40% by weight, in particular 5 to 30% by weight, particularly 7 to 28% by weight, particularly preferably 10 to 25% by weight, very particularly preferably 15 to Contain 20 wt .-%, each based on the total weight of the agent.

Also particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali carbonate (s), particularly preferably sodium carbonate (soda), in amounts of 2 to 50% by weight, preferably 4 to 40% by weight. -% and in particular from 10 to 30 wt .-%, very particularly preferably 10 to 24 wt .-%, each based on the weight of the agent.

Particularly preferred washing or cleaning agents according to the invention, in particular dishwashing agents, preferably machine dishwashing agents, are characterized in that they contain at least two builders from the group of silicates, phosphonates, carbonates, aminocarboxylic acids and citrates, the weight fraction of these builders based on the total weight of the cleaning agent according to the invention, preferably 5 to 70 wt .-%, preferably 15 to 60 wt .-% and in particular 20 to 50 wt .-%. The combination of two or more builders from the group mentioned above has been found to be particularly suitable for the cleaning and rinsing performance of detergents or cleaning agents according to the invention Dishwashing detergents, preferably automatic dishwashing detergents, have proven to be advantageous. In addition to the builders mentioned here, one or more other builders may also be included.

Preferred washing or cleaning agents, in particular dishwashing agents, preferably machine dishwashing agents, are characterized by a combination of builders of citrate and carbonate and / or hydrogen carbonate. In a particularly preferred embodiment according to the invention, a mixture of carbonate and citrate is used, the amount of carbonate preferably being from 5 to 40% by weight, in particular 10 to 35% by weight, very particularly preferably 15 to 30% by weight and the amount of citrate is preferably from 5 to 35% by weight, in particular 10 to 25% by weight, very particularly preferably 15 to 20% by weight, in each case based on the total amount of the cleaning agent, the total amount of these two Builders are preferably 20 to 65% by weight, in particular 25 to 60% by weight, preferably 30 to 50% by weight. In addition, one or more other builders can also be included.

The washing or cleaning agents according to the invention, in particular dishwashing agents, preferably machine dishwashing agents, can contain, in particular, phosphonates as further builders. A hydroxyalkane and / or aminoalkane phosphonate is preferably used as the phosphonate compound. Of the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonates in agents according to the invention are preferably in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 8% by weight, very particularly preferably 2.5 to 7.5% by weight, in each case based on the total weight of the agent.

The combined use of citrate, (hydrogen) carbonate and phosphonate is particularly preferred. These can be used in the amounts mentioned above. In particular, in this combination, amounts of 10 to 25% by weight citrate, 10 to 30% by weight carbonate (or bicarbonate), and 2.5 to 7.5% by weight, based in each case on the total weight of the composition. Phosphonate used.

Further particularly preferred washing or cleaning agents, in particular dishwashing agents, preferably machine dishwashing agents, are characterized in that, in addition to citrate and (hydrogen) carbonate and optionally phosphonate, they contain at least one further phosphorus-free builder. In particular, this is selected from the aminocarboxylic acids, the further phosphorus-free builder preferably being selected from methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic diacetate (ASDA), Hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), particularly preferably from MGDA or GLDA. A particularly preferred combination is, for example, citrate, (hydrogen) carbonate and MGDA and, if appropriate, phosphonate.

The percentage by weight of the further phosphorus-free builder, in particular the MGDA and / or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 25% by weight. The use of MGDA or GLDA, in particular MGDA, as granules is particularly preferred. MGDA granules that contain as little water as possible and / or have a lower hygroscopicity (water absorption at 25 ° C., normal pressure) compared to the non-granulated powder are advantageous. The combination of at least three, in particular at least four builders from the group mentioned above has proven to be advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing agents, preferably machine dishwashing agents. It can also contain other builders.

Polymeric polycarboxylates are also suitable as organic builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol. Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 1100 to 10000 g / mol, and particularly preferably from 1200 to 5000 g / mol, can in turn be preferred from this group.

The content of (homo) polymeric polycarboxylates in the washing or cleaning agents according to the invention, in particular dishwashing agents, preferably machine dishwashing agents, is preferably 0.5 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight. %.

Detergents or cleaning agents according to the invention, in particular dishwashing detergents, preferably machine dishwashing detergents, can also contain crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values for x being 2, 3 or 4, and y being a number from 0 to 33, preferably from 0 to 20. Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are preferably delayed release and have secondary washing properties.

In certain washing or cleaning agents according to the invention, in particular dishwashing agents, preferably machine dishwashing agents, the content of silicates, based on the total weight of the washing or cleaning agent, limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight.

In addition to the builders mentioned above, the washing or cleaning agents according to the invention can furthermore contain alkali metal hydroxides. These alkali carriers are particularly preferred in the washing or cleaning agents and in particular in the at least one gel phase only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight preferably between 0.1 and 5% by weight and in particular between 0.5 and 5% by weight, in each case based on the total weight of the washing or cleaning agent. Alternative washing or cleaning agents according to the invention are free of alkali metal hydroxides.

Cleaning agents according to the invention preferably contain enzyme (s) in the at least one particulate and / or the at least one gel phase. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in cleaning agents, which are accordingly preferred. Cleaning agents according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-6 % by weight to 5% by weight, based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae and the further developments of the aforementioned amylases which are improved for use in cleaning agents. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Lipases or cutinases can also be used according to the invention, in particular because of their triglyceride-cleaving activities, but also to generate peracids in situ from suitable precursors. These include, for example, those originally from Humicola lanuginosa (Thermomyces lanuginosus) available or further developed lipases, especially those with the amino acid exchange in positions D96LT213R and / or N233R, particularly preferably all of the exchanges D96L, T213R and N233R.

Furthermore, enzymes can be used, which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

To increase the bleaching effect, oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenoloxidases, polyphenol oxidases) can be used according to the invention. Advantageously, organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of very different redox potentials between the oxidizing enzymes and the soiling. A protein and / or enzyme can be protected against damage, such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage, especially during storage. When the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Detergents can contain stabilizers for this purpose; the provision of such agents is a preferred embodiment of the present invention.

Proteases and amylases that are active in cleaning are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations. These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel form agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers or other auxiliaries.

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

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

As can be seen from the previous explanations, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0.8 and 10% by weight of the enzyme protein. Particularly preferred are cleaning agents which, based on their total weight, 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight of the respective enzyme preparations contain.

In addition to the constituents mentioned so far, the at least one particulate and / or the at least one gel phase of the washing or cleaning agent according to the invention can contain further ingredients. These include, for example, anionic, cationic and / or amphoteric surfactants, bleaching agents, bleach activators, bleaching catalysts, other solvents, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protection agents, glass corrosion inhibitors, foam inhibitors, dyes, fragrances (in particular in the at least one particulate phase), additives to improve the runoff and drying behavior, to adjust the viscosity, to stabilize, UV stabilizers, pearlescent agents, preservatives, antimicrobial agents (disinfectants), pH adjusting agents in amounts of usually not more than 5% by weight.

Agents according to the invention preferably contain at least one alkanolamine as a further solvent. The alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof. The alkanolamine is preferably present in agents according to the invention in an amount of 0.5 to 10% by weight, in particular in an amount of 1 to 6% by weight. In a preferred washing or cleaning agent, the at least one gel phase is free from alkanolamine and the alkanolamine is only present in the at least one particulate phase.

In a preferred embodiment, detergents or cleaning agents according to the invention, in particular dishwashing detergents, contain at least one zinc salt as a glass corrosion inhibitor as a further constituent. The zinc salt can be an inorganic or organic zinc salt. The zinc salt to be used according to the invention preferably has a solubility in water above 100 mg / l, preferably above 500 mg / l, particularly preferably above 1 g / l and especially above 5 g / l (all solubilities at 20 ° C water temperature). The inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate. The organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group of zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate. In a particularly preferred embodiment according to the invention, zinc acetate is used as the zinc salt. The zinc salt in cleaning agents according to the invention is preferably in an amount of 0.01% by weight to 5% by weight, particularly preferably in an amount of 0.05% by weight to 3% by weight, in particular in an amount of 0.1 wt .-% to 2 wt .-%, based on the total weight of the detergent. In addition or as an alternative to the abovementioned salts (in particular the zinc salts), polyethyleneimines, as are available, for example, under the name Lupasol® (BASF), can preferably be used in an amount of 0 to 5% by weight, in particular 0.01 to 2% by weight. -%, are used as glass corrosion inhibitors.

Polymers suitable as additives are, in particular, maleic acid-acrylic acid copolymer Na salt (for example Sokalan® CP 5 from BASF, Ludwigshafen (Germany)), modified polyacrylic acid Na salt (for example Sokalan® CP 10 from BASF, Ludwigshafen (Germany )), modified polycarboxylate Na salt (for example Sokalan® HP 25 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example Silwet® L-77 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example Silwet® L-7608 from BASF, Ludwigshafen (Germany)) and polyether siloxanes (copolymers of polymethylsiloxanes with ethylene oxide / propylene oxide segments (polyether blocks)), preferably water-soluble linear polyether siloxanes with terminal polyether blocks such as Tegopren® 5840, Tegopren® 5843 5847, Tegopren® 5851, Tegopren® 5863 or Tegopren® 5878 from Evonik, Essen (De lish land). Builder substances suitable as additives are, in particular, polyaspartic acid sodium salt, ethylenediamine triacetate coconut alkylacetamide (for example Rewopol® CHT 12 from Evonik, Essen (Germany)), methylglycinediacetic acid tri-sodium salt and acetophosphonic acid. Mixtures with surfactant or polymeric additives show synergisms in the case of Tegopren® 5843 and Tegopren® 5863. The use of Tegoprene types 5843 and 5863 is, however, less preferred when used on hard surfaces made of glass, in particular glass dishes, since these can pull silicone surfactants onto glass. In a particular embodiment of the invention, the additives mentioned are dispensed with.

A preferred washing or cleaning agent, in particular dishwashing agent, preferably further comprises a bleaching agent, in particular an oxygen bleaching agent and optionally a bleach activator and / or bleaching catalyst. Where available, these are only contained in the at least one particulate phase.

As a preferred bleaching agent, cleaning agents according to the invention contain an oxygen bleaching agent from the group sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Sodium percarbonate is particularly preferred for its good bleaching performance. A particularly preferred oxygen bleach is sodium percarbonate.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances which carry 0- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable. Multi-acylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) having proven to be particularly suitable.

The bleaching catalysts are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe-Cu and Ru-amine complexes can also be used as bleaching catalysts. Complexes of manganese are used with particular preference in oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S. Ligands which have nitrogen donor functions are preferably used. It is particularly preferred to use bleaching catalyst (s) in the agents according to the invention which contain 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN) as macromolecular ligands ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN ) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN) contain. Suitable manganese complexes are, for example, [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₂ (μ-OAc) ₁ (TACN ) ₂ ] (BPh ₄ ) ₂ , [Mn ^IV ₄ (µ-O) ₆ (TACN) ₄ ] (ClO ₄ ) ₄ , [Mn ^III ₂ (µ-O) ₁ (µ-OAc) ₂ (Me-TACN ) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (µ-O) ₁ (µ-OAc) ₂ (Me-TACN) ₂ ] (ClO ₄ ) ₃ , [Mn ^IV ₂ (µ-O) ₃ ( Me-TACN) ₂ ] (PF ₆ ) ₂ and [Mn ^IV ₂ (µ-O) ₃ (Me / Me-TACN) ₂ ] (PF ₆ ) ₂ (with OAc = OC (O) CH ₃ ).

When using benzoic acid, salicylic acid or lactic acid as pH regulators and / or buffer substances, these compounds can support or enhance the antibacterial effect of the silver and / or the silver compound.

The washing or cleaning agent according to the invention comprises at least one particulate phase and at least one gel phase. The washing or cleaning agent can thus have one, two, three or more different particulate phases; it can also have one, two, three or more different gel-like phases. The washing or cleaning agent according to the invention preferably comprises a particulate phase and a gel phase. The washing or cleaning agent particularly preferably comprises two particulate phases and a gel phase. It preferably comprises two particulate phases and two gel-like phases. Also preferred is an embodiment in which the washing or cleaning agent comprises three particulate phases and one or two gel-like phases.

The weight ratio of the total of the at least one particulate phase to the total of the at least one gel phase is generally 40: 1 to 2: 1, in particular 20: 1 to 4: 1, preferably 12: 1 to 6: 1, for example 10: 1 to 8: 1. The total weight of all phases in a detergent portion can be between 8 and 30 g, in particular 10 to 25 g, preferably 12 to 21 g, for example 14 to 16 g per detergent or detergent portion. In this weight ratio there is a good concentration of the respective ingredients of the particulate or gel phase in one cleaning process.

According to the invention, the at least one particulate phase and the at least one gel-shaped phase adjoin one another over the full or partial area. It is preferred that the two phases directly adjoin one another.

If the at least one particulate phase and the at least one gel-like phase immediately adjoin one another over the whole or part of the surface, the stability is important in addition to the shortest possible solidification time of the at least one gel-like phase. Stability here means that constituents contained in the gel-like phase do not pass into the at least one particulate phase but, even after prolonged storage, the at least one particulate phase and the gel-like phase are optically separate from one another and do not interact with one another, such as, for example, liquid diffusion Components from one phase to the other or reaction of components from one phase with those in the other phase. Surprisingly, it has been shown that this can be made possible by a gel-like phase which has polyethylene glycols with an average molecular weight of 200 to 600 g / mol, glycerol, PVOH and at least one C ₃ to C ₅ alkanediol.

According to a particularly preferred embodiment, the washing or cleaning agents according to the invention are characterized in that the at least one gel phase is less than 1% by weight, in particular less than 0.5% by weight, in particular less than 0.1% by weight Anionic surfactant, each based on the total weight of the gel phase comprises phase. The at least one gel phase is preferably essentially free of anionic surfactants. Essentially free means that the at least one gel phase contains less than 0.05% by weight of anionic surfactant, based in each case on the total weight of the phase gel. In this context, it has been shown that the presence of 1% by weight of anionic surfactant in the at least one gel phase leads to poorer foaming behavior and poorer rinsing behavior of the overall composition. Furthermore, higher amounts of anionic surfactants adversely affect curing.

In addition to the surfactants, the agent according to the invention, in particular the at least one gel phase, can also have sugar. According to the invention, sugars include sugar alcohols, monosaccharides, disaccharides and oligosaccharides. In a preferred embodiment, the at least one gel phase comprises at least one sugar alcohol, preferably mannitol, isomalt, lactitol, sorbitol, threitol, erythritol, arabitol and xylitol. Xylitol is particularly preferred.

In a further embodiment, the agent according to the invention, in particular the at least one gel phase, may comprise disaccharides, in particular sucrose. The proportion of sucrose is 0% by weight to 30% by weight, in particular 5% by weight to 25% by weight, particularly preferably 10% by weight to 20% by weight, based on the weight of the gel Phase. In higher amounts, the sugar does not dissolve completely in the gel phase and leads to a clouding of the same. The use of sugar, in particular in a proportion of 10% by weight to 5 to 15% by weight, reduces the development of moisture and thus improves the adhesion to the at least one particulate phase.

The detergent or cleaning agent portion according to the invention preferably comprises a washing or cleaning agent according to the invention in a water-soluble envelope. The water-soluble covering is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures. The sheath can be formed from 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, can be the same or different.

It is preferred that the water-soluble envelope contain polyvinyl alcohol or a polyvinyl alcohol copolymer. Water soluble wrappings that are made of polyvinyl alcohol or a Containing polyvinyl alcohol copolymer have good stability with a sufficiently high water solubility, in particular cold water solubility.

Suitable water-soluble films for producing the water-soluble covering are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which is 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 is in particular from 40,000 to 80,000 gmol ^-1 .

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

In a preferred embodiment, the water-soluble packaging consists of at least 20% by weight, particularly preferably at least 40% by weight, very particularly preferably at least 60% by weight and in particular at least 80% by weight, of a polyvinyl alcohol, the Degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

A polymer material containing polyvinyl alcohol suitable for producing the water-soluble covering can additionally be a polymer selected from the group comprising (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above Polymers can be added. A preferred additional polymer is polylactic acid.

In addition to vinyl alcohol, preferred polyvinyl alcohol copolymers comprise dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, itaconic acid being preferred. Also preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester or mixtures thereof.

It may be preferred that the film material contains further additives. The film material can contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerin, sorbitol, mannitol or mixtures thereof. Further Additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-adhesive agents or mixtures thereof.

Suitable water-soluble films for use in the water-soluble wrappings of the water-soluble packaging according to the invention are films which are sold by MonoSol LLC, for example under the designation M8720, M8630, M8312, M8440, M7062, C8400 or M8900. Also suitable are films which are marketed by Nippon Gohsei under the names SH2601, SH2504, SH2707 or SH2701. Other suitable films include films with the designation Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.

The water-soluble coating preferably has at least partially a bitter substance with a bitter value between 1,000 and 200,000, in particular those selected from quinine sulfate (bitter value = 10,000), naringin (bitter value = 10,000), sucrose octaacetate (bitter value = 100,000), quinine hydrochloride and mixtures thereof. In particular, the outer surface of the water-soluble coating is at least partially coated with a bitter substance with a bitter value between 1,000 and 200,000. In this context, it is particularly preferred that the water-soluble coating is coated with at least 50%, preferably at least 75% and very particularly preferably at least 90% with the bitter substance with a bitter value between 1,000 and 200,000. The bitter substance with a bitter value between 1,000 and 200,000 can be applied, for example, by means of printing, spraying or brushing.

According to the invention, the water-soluble covering has at least one continuously rotating sealing seam, which lies essentially in one plane. This is favorable in terms of process technology, since only a single sealing step, if necessary using only a single sealing tool, is necessary for a circumferential sealing seam which lies essentially in one plane. The continuous circumferential sealing seam leads to a better seal compared to such wrappings with several sealing seams and an excellent tightness of the sealing seam and thus the wrapping itself. Product escaping from the wrapping, e.g. on the surface of the portion would be disadvantageous since the consumer would then come into contact with the product. This is exactly what should be avoided if possible with a portion of detergent or cleaning agent with a water-soluble coating.

The water-soluble envelope can preferably be produced from at least 2 packaging parts. The at least two packaging parts are preferably water-soluble, so that no packaging parts remain in the dishwasher, which can then lead to problems in the dishwasher. It is not necessary that the at least two packaging parts are different. They can preferably be made from the same material and on be made the same way. In a preferred embodiment, these are two parts of a water-soluble film, in particular two parts of a water-soluble film of the same composition.

In a further embodiment, the at least two packaging parts can be made of different materials, e.g. be made from different foils or from material with two different properties (e.g. warm and cold water soluble foil). In this embodiment, it is preferred that a water-soluble film and another packaging part, which was produced by injection molding, be combined.

According to a particularly preferred embodiment of the present invention, the water-soluble covering comprises at least one at least partially plastically deformed film. In particular, this plastic deformation of the film can be produced by methods known to the person skilled in the art, such as deep drawing (with and without applying a vacuum), blow molding or stamping. In particular, the water-soluble covering comprises at least one at least partially plastically deformed film, which was produced by deep drawing. The at least one particulate phase and the at least one gel phase can be arranged in any combination with one another within the water-soluble coating. A particulate phase can be arranged on or next to a gel phase. In this embodiment, the washing or cleaning agent according to the invention has a particulate phase and a gel phase. It is also conceivable that a particulate phase is surrounded by gel-like phases. Embedding one phase in another is also included according to the invention. In a further, particularly preferred arrangement, the gel-like phase is in cast form, for example in the form of a gel core, which is surrounded by the particulate phase. There may also be 2 or more cavities separated from one another which are filled with the at least one gel phase. In this embodiment, the washing or cleaning agent comprises two gel-like phases, wherein the two gel-like phases can have different compositions.

According to a preferred embodiment there are 3, 4, 5 or 6 or more cavities separated from one another which are filled with one or more of the gel-like phases. Such detergents or cleaning agents preferably comprise 3, 4, 5 or 6 or more gel-like phases, it being possible for these gel-like phases to have the same or different compositions.

According to a particularly preferred embodiment, the detergent or cleaning agent portion according to the invention is characterized in that it contains a dishwashing agent, in particular a dishwashing agent for the automatic cleaning of dishes.

1. a) Bereitstellen einer Form mit mindestens einer Formmulde; optional enthaltend mindestens einen Steg zur Unterteilung des Bodens der Formmulde;
2. b) Zuführen einer wasserlöslichen Folie auf die Formmulde;
3. c) Ausbilden mindestens einer offenen Kammer in der Formmulde, durch Verformung der wasserlöslichen Folie;
4. d) optional Befüllen der offenen Kammer mit wenigstens einer gelförmigen Phase;
5. e) Befüllen der offenen Kammer mit wenigstens einer partikulären Phase;
6. f) optional Befüllen der offenen Kammer mit mindestens einer weiteren Zusammensetzung;
7. g) Bereitstellung eines zweiten wasserlöslichen Films als Deckel;
8. h) Übereinander Bringen der offenen Kammer und des Deckels, zur Versiegelung der Portionspackung an einem Versiegelungsbereich;
9. i) Versiegeln des Deckels mit der offenen Kammer.

Another object of the present invention is a method for producing detergent and / or cleaning agent portions, which contains a product with at least one particulate phase, comprising:

1. a) providing a mold with at least one mold cavity; optionally containing at least one web for dividing the bottom of the mold cavity;
2. b) feeding a water-soluble film onto the mold cavity;
3. c) forming at least one open chamber in the mold cavity by deforming the water-soluble film;
4. d) optionally filling the open chamber with at least one gel phase;
5. e) filling the open chamber with at least one particulate phase;
6. f) optionally filling the open chamber with at least one further composition;
7. g) providing a second water-soluble film as a lid;
8. h) bringing the open chamber and the lid on top of one another to seal the portion pack at a sealing area;
9. i) sealing the lid with the open chamber.

The mold comprises at least one trough (mold trough). The shape can be provided, for example, as a single shape or as part of a series of shapes in the form of a treadmill, as is known from the treadmill method and from the drum method. The shape includes an area on which the film can be placed, e.g. a sealing area that is typically defined around the opening of a mold cavity. The mold trough can have different geometries, if edges are present, it is advantageous that they are rounded. Rounded edges and / or dome-shaped troughs ensure that when the film is pulled into the trough, the film is pulled somewhat more homogeneously, and the film thickness remains uniform in this respect, and that no breakage or tear points are produced, which in turn leads to a more stable one Portion pack leads.

Optionally, but preferably according to a particular embodiment, the mold contains at least one mold trough which has at least one web for dividing the bottom of the mold trough. This forms one or more, preferably 2, 3, 4, 5 or 6 bulges or pockets in the shaped chamber, which optically produce a positive appearance. In particular, if only the areas of these bulges are completely or partially, preferably almost completely, filled with the gel-like phase (s), this area is again clearly separated from the granular mixture, in particular the particulate phase, and produces a particularly good appearance ,

The water-soluble film can be fed from a roll and guided onto the mold cavity. The film is positioned and held on the mold. The holding can take place through suction holes on the mold surface, which is not part of the mold cavity. The film can also be held on the mold by mechanical means, such as clips. For example, the film can be held by a stamp that presses on the sealing area. In the continuous manufacturing processes, e.g. Drum method and treadmill method, it is preferred that the speed of the film is adapted to the speed of the treadmill formed from the molds, so that the film is not unnecessarily pulled thinner by holding onto a running mold.

After the film is held in one place, relative to the mold cavity, a chamber is formed in the mold cavity area by at least partially adapting the film to the mold cavity. The adaptation is generated by an elastic and / or plastic deformation. The film deformation preferably has a larger plastic than elastic component. The deformation of the water-soluble film is e.g. generated by deep drawing or by means of suitable stamps. A preferred variant is deep drawing, by the application of negative pressure (forming pressure) in the mold cavity, for this purpose the mold cavity preferably comprises small openings, preferably in the base area, which are connected to a vacuum pump in terms of air pressure by appropriate lines.

In further steps, the open chamber is now filled. In this context, filled means the filling of quantities of the particular particulate or gel phases or of the liquid compositions into the open chamber. It includes the fact that the open chamber is only partially filled by filling or filling with one of the compositions / phases. This leaves space in the open chamber for filling in further phases or compositions.

After the open chamber has been formed, step d) optionally, but preferably, fills this or parts thereof with the at least one gel phase of the product. As soon as the at least one gel-like phase has solidified, possibly after an additional period of time which is necessary for the solidification, further product components can then be filled into the chamber. After a first gel phase in step d), one or more further gel phases can be filled in.

Then step e) can be filled in at least one particulate phase, the specifications and compositions of which have already been described in detail above. The at least one particulate phase according to step e) is preferably a solid, comprising a granular mixture, in particular it is particulate, in particular particulate and free-flowing.

It is preferred in the above-mentioned production process that the open chamber, which contains at least one gel-like and at least one particulate phase, is not completely filled with the gel-like phase (s). The chamber can preferably be filled only partially, preferably only in the lower region or only in the region or just above the region of the bulges or pockets of the chamber formed by the optional web according to a) with the gel-like phase (s).

When filling with product, the deformed film is preferably kept in the trough during filling. For example, in the case of negative pressure, the negative pressure is only broken after the sealing. The negative pressure after the formation of the chamber in relation to the forming pressure can have a lower strength (higher pressure), which only fulfills the holding function.

It is important that the sealing area remains free of product. For example, if the chamber is at least partially elastically deformed, this elastic deformation must not subside after filling and before sealing such that the product flows over and out of the open chamber and thus contaminates the sealing area.

According to a particular embodiment, the lid is positioned on the open chamber, so that the lid can be applied to the sealing area in the next step. The position of the lid is generally determined relative to the position of the chamber. If the chamber moves with a movable shape in a treadmill, the lid must move equally so that the relative position to the chamber remains the same.

The lid is then placed on the open chamber, which is closed in this way. The contact between the lid and the film in the sealing area thus closes the chamber.

A preferred embodiment of the seal is a material fusion between the film and the lid, for example by loosening the film before the lid is applied, or by melting the film and / or lid in the sealing area. Alternatively, the sealing is done by gluing or welding.

The positioning, application, and sealing can take place either in separate steps or simultaneously.

The mold can also comprise at least one second mold cavity, so that at least two open chambers are produced by process steps a) to d). The at least two chambers are formed in the same plane. It is preferred that the lid in method step h) is positioned over the at least two open chambers and the lid in method step i) is applied to at least both chambers to seal the portion pack at a sealing area. Because the at least two chamber with the same Lid connected, the chamber remain in a certain position to each other, contrary to the prior art, where adjacent chambers are connected by the web, which is formed by the thin films of the packaging. It is easily possible to design three, four, five or more chambers side by side, which are filled with a corresponding number of gel-shaped phases (with the same or different composition).

It is particularly preferred that the lid is provided as part of a band by feeding / transferring a band comprising at least one lid. The lid can be separated before positioning, after positioning but before application, during application, or after application to the chamber.

When separating before positioning, the cover is preferably punched out.

The lid and film can also be separated at the same time as sealing. The device that produces the sealing by melting consists of at least two parts, one is the shape itself and the other part is a counter-stamp which presses onto the shape from the cover side. It is preferred that in the sealing step the pressure exerted by the mold and further part during the sealing must be lower at the sealing area than the pressure exerted in the separating area. The separation area surrounds the sealing area.

In the case of a separation after sealing, the lid and film are alternatively separated from the band, preferably in the same step, and thus the portion packs are separated. According to a preferred embodiment there are 2, 3, 4, 5 or 6 or more cavities separated from one another which are correspondingly filled with one or more of the gel-like phases. Such detergents or cleaning agents preferably comprise 3, 4, 5 or 6 or more gel-like phases, it being possible for these gel-like phases to have the same or different compositions.

According to a particularly preferred embodiment of the process according to the invention for the production of detergent and / or cleaning agent portions, the chamber is filled with at least one liquid composition, preferably containing perfume preparations and / or surfactants, in particular nonionic surfactants, before or after step e).

This has advantages with regard to the more compact and easier production of the particulate phases brought into contact with the liquid composition. The at least one liquid composition can be filled into the open chamber, which may contain the already solidified at least one gel phase before the particulate phase is filled.

Preferred methods include that in step d) after filling the open chamber with the at least one gel phase, the gel phase solidifies or solidifies.

The liquid composition is preferably applied to the gel-like and already solidified phase filled in according to step c), so that the composition does not mix with the gel-phase which has not yet solidified. The at least one liquid composition, in particular comprising perfume preparation and / or at least one surfactant, in particular nonionic surfactant, is thus brought into direct contact with the latter by the subsequent filling of the at least one particulate phase. The composition can then impregnate or move into the particulate phase.

It is also preferred that the at least one particulate phase is applied before the liquid composition (preferably onto the gel-like and already solidified phase filled in according to step c). The at least one liquid phase is then at least partially applied to the surface of the particulate phase and is thus in direct contact with it. The liquid composition can thus impregnate the particulate composition or move into it. The result is an open chamber which contains more compact compositions of detergents or cleaning agents.

In both cases, the particulate phase in the open chamber can also be compacted by applying pressure.

According to a further preferred embodiment of the invention, the open chamber in step f) can be filled with at least one further composition.

The further composition according to step f) can be at least one further liquid composition for further impregnation, and can also relate to at least one further particulate phase and / or at least one further gel-like phase, as already described above. Preferably, a solidifying composition can also be introduced in step f) (alternatively or additionally, such a solidifying composition can also be added after step c)). Suitable solidifying compositions (in addition to the gel-like phases already mentioned) are, for example, compositions such as those in DE102015213938 A1 or DE102015213939 A1 are disclosed. Reference is hereby made in full to the disclosure contained therein.

Multi-chamber pouches which contain at least one chamber which comprises at least one particulate phase according to the invention and at least one liquid composition, in particular additionally at least one gel-like phase according to the invention, in direct contact with one another and moreover at least one further one can also be produced in accordance with the aforementioned production processes , for example, have two, three or more further separate chambers.

For the at least one particulate phase, comprising granular mixtures of a solid composition, in particular the at least one particulate phase, the same applies to the cleaning agents according to the invention described above. It is preferred that the at least one particulate phase is particulate and free-flowing, preferably as described above.

For the liquid compositions, gel-like phases and particulate phases to be used in the processes according to the invention, the same applies to the detergent or cleaning agent portion mentioned above, to which reference is hereby explicitly made. A particular suitability of the gel-like phases described above for the process mentioned is that the rapid solidification times of the gel-like phases, in particular the phases with PVOH, at least one polyhydric alcohol and polyethylene glycol with an average molar mass of 200 to 600 g / mol, the step of solidification Allow the gel-like phase (s) to be shortened considerably and possibly even made unnecessary, since such phases cool and solidify particularly quickly, without additional cooling, long production lines or longer standing or waiting times being necessary.

In this context, very particularly preferred embodiments of the present invention comprise, as at least one gel phase, 8 to 22% by weight of PVOH, 15 to 30% by weight of 1,3-propanediol, 30 to 40% by weight of glycerol, 5 to 15 % By weight sulfonic acid group-containing polyacrylate copolymer, 10-22% by weight polyethylene glycol (s) with an average molecular weight of 200-600 g / mol), and optionally zinc salts, data in% by weight based in each case on the total weight of the gel Phase.

Depending on the manufacturing process, the gel-like phase (s) can be clearly above or below the sealing seam level (first-mentioned method) or approximately at the level of the sealing seam level (last-mentioned method).

The present invention further relates to detergent or cleaning agent portions such as are obtainable by one of the processes described above.

The present application also relates to a method for cleaning hard surfaces, in particular dishes, in which the surface is processed in a manner known per se using a cleaning agent according to the invention. In particular, the surface is brought into contact with the washing or cleaning agent according to the invention. The cleaning is carried out in particular with a cleaning machine, preferably with a dishwasher.

Another object of the present invention is also the use of a cleaning agent for cleaning hard surfaces, especially dishes, especially in automatic dishwashers. Another object of the invention is the use of a detergent portion for the mechanical cleaning of laundry or textiles.

In a preferred embodiment, the present application relates to automatic dishwashing detergents. According to this application, machine dishwashing detergents are compositions which can be used to clean dirty dishes in an automatic dishwashing process. The machine dishwashing detergents according to the invention thus differ, for example, from the machine rinse aids which are always used in combination with machine dishwashing agents and do not have their own cleaning action.

Insofar as it is stated in the present application that the washing or cleaning agent according to the invention comprises something in whole or in the at least one particulate phase or in the at least one gel phase or in the at least one liquid composition, then the washing or cleaning agents or the each phase can consist of it. In the exemplary embodiment below, the washing or cleaning agent according to the invention is described in a non-limiting manner.

EXAMPLES

Cleaning agents according to the invention were produced which comprised a solid phase and a gel phase. Different geometries were realized. Cleaning agents were also produced which comprised two solid phases and one gel phase. Cleaning agents were also produced, which comprised a solid phase as well as 3, 4 and 5 gel phases (of the same or different composition). The following information relates to% by weight of active substance based on the total weight of the respective phase (unless stated otherwise). Table 1: The solid granular mixtures of a solid composition, in particular powdery and free-flowing phases, had the following preferred composition: Wt .-% Citrate, Na salt 15-20 Phosphonate (e.g. HEDP) 2.5-7.5 MGDA, Na salt 0-25 Disilicate, sodium salt 5-35 soda 10-25 Silver protection (e.g. cysteine) 0.0 - 1.0 Percarbonate, Na salt 10-15 Bleaching catalyst (preferably Mn-based) 0.02-0.5 Bleach activator (e.g. TAED) 1-3 Non-ionic surfactant (s), for example fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 2.5-10 polycarboxylate 4 - 10 Cationic copolymer 0 - 0.75 Disintegrant - (e.g. Crosslinked PVP) 0 - 1.5 Protease preparation (tq) 1.5-5 Amylase preparation (tq) 0.5-3 Perfume 0.05-0.25 dye solution 0.0 to 1 Zn salt (e.g. acetate) 0.1-0.3 sodium sulphate 0.0 - 10 water 0.0 to 1.5 pH adjusting agent (e.g. citric acid) 0-1.5 processing aids 0-5 Wt .-% Water-soluble zinc salt (preferably zinc acetate anhydrate) 0.1 to 2.4 glycerin 10-50 Propanediol (preferably 1,3-propanediol) 10-50 Polycarboxylate copolymer with sulfonic acid groups 0-30 Non-ionic surfactant (s), for example fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 0-40 Polyethylene glycol average Mr 200-600, (e.g. PEG 400 (INCI) 8-26 PVOH 8-22 processing aids 0-10 dye solution 0.0 - 1.5 Misc., Other active ingredients, organic solvents, perfume, Add 100

The solid and the gel phases could be combined with one another as desired. The spatial configuration of the gel phase, which was liquid after the ingredients had been mixed and had a stable shape within a solidification time of a maximum of 10 minutes, was determined by the spatial configuration of the solid phase and by commercially available or self-designed shapes. A water-soluble envelope in the form of an open pouch was produced by deep-drawing a PVOH-containing film. A liquid composition was poured into this open cavity, which gave the gel phase after curing, and then solid phases in the form of a free-flowing solid were poured into a pouch comprising polyvinyl alcohol. 1.0 g of the liquid nonionic surfactant Genapol EC 50 was metered onto the resulting particulate surface. The proportion of non-ionic surfactants could thus be increased significantly without changing other phases. The open pouch is then sealed by placing a second film and sealing with a heat seal. The detergent portions produced in this way were characterized by an attractive aesthetic.

Claims (13)

Detergent and / or cleaning agent portion, which comprises at least one chamber and a water-soluble envelope, characterized in that it comprises at least one particulate phase, the at least one particulate phase being brought into direct contact with at least one liquid composition. Detergent and / or cleaning agent portion according to claim 1, characterized in that the at least one particulate phase, preferably at the time of addition, is free-flowing. Detergent and / or detergent portion according to claim 1 or 2, characterized in that the at least one liquid composition comprises surfactants, preferably nonionic surfactants, and / or perfume preparations, the liquid composition preferably being low in water, in particular essentially water-free. Detergent and / or cleaning agent portion according to claim 3, characterized in that the weight ratio of the total amount of the at least one liquid composition to the total amount of the at least one particulate phase is preferably from 1: 800 to 5: 1, in particular from 1: 600 to 2: 1 from 1: 500 to 2: 1, for example from 1: 450 to: 1 and / or the proportion by weight of the at least one liquid composition to the total weight of the composition formed from the at least one liquid composition and the at least one particulate composition is 0.0001 to 25% by weight %, in particular 0.005 to 20% by weight, preferably 0.1 to 18% by weight, very particularly preferably 0.2 to 15% by weight. Detergent and / or cleaning agent portion according to one of claims 3 or 4, characterized in that the surfactant content of the at least one liquid composition is at least 50% by weight, in particular at least 70% by weight, preferably at least 80% by weight, particularly preferably is at least 90% by weight, based on the total weight of the liquid composition. Detergent and / or cleaning agent portion according to one of the preceding claims, characterized in that in addition to the at least one particulate phase and the at least one liquid composition, at least one further gel phase is contained. Detergent and / or cleaning agent portion according to one of the preceding claims, characterized in that the particulate phase at least one further ingredient selected from the group consisting of builders, polymers, bleaching agents, bleach activators, bleaching catalysts, enzymes, sequestering agents, electrolytes, corrosion inhibitors, glass corrosion inhibitors, foam inhibitors , Dyes, additives to improve drainage and drying behavior, disintegration aids, preservatives, pH adjusters, fragrances and perfume carriers. A method for producing detergent and / or cleaning agent portions, which contains a product with at least one particulate phase, comprising: a) providing a mold with at least one mold cavity; optionally containing at least one web for dividing the bottom of the mold cavity; b) feeding a water-soluble film onto the mold cavity; c) forming at least one open chamber in the mold cavity by deforming the water-soluble film; d) optionally filling the open chamber with at least one gel phase e) filling the open chamber with at least one particulate phase; f) optionally filling the open chamber with at least one further composition; g) providing a second water-soluble film as a lid; h) bringing the open chamber and the lid on top of one another to seal the portion pack at a sealing area; i) sealing the lid with the open chamber. A method for producing detergent and / or cleaning agent portions according to claim 8, characterized in that before or after step e) the chamber is filled with at least one liquid composition, preferably containing perfume preparations and / or surfactants, in particular nonionic surfactants. Method according to one of the preceding claims, characterized in that in step d) after filling the open chamber with the at least one gel-like phase, the gel-like phase solidifies or solidifies. Method according to one of the preceding claims, characterized in that in step f) the open chamber is filled with at least one further composition, preferably a solidifying composition. Serving of detergent or cleaning agent, obtainable by one of the processes according to one of Claims 8 to 11. Use of a detergent portion according to one of claims 1 to 7 or 12 for the mechanical cleaning of dishes.