EP1238055A2

EP1238055A2 - Washing agent, rinsing agent or cleaning agent portions having redox-controlled active substance release

Info

Publication number: EP1238055A2
Application number: EP00993413A
Authority: EP
Inventors: Peter Schmiedel; Thomas Gassenmeier; Rolf Bayersdörfer; Christian Nitsch; Wolfgang Von Rybinski
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1999-12-13
Filing date: 2000-12-02
Publication date: 2002-09-11
Anticipated expiration: 2020-12-02
Also published as: EP1238054A1; WO2001044421A3; ES2281378T3; CA2328326A1; DE50013790D1; AU2839701A; ES2277865T5; DE10035781A1; EP1238055B1; EP1238054B1; ES2277865T3; AU1706901A; WO2001044421A2; DE50014097D1; ATE346134T1; AU2671301A; EP1238054B2; WO2001044435A1; WO2001044434A1; ATE354633T1

Abstract

The invention relates to a washing, rinsing or cleaning-agent portion comprising two or more washing, rinsing or cleaning-active components of which at least two are released into the liquor at at least two different moments in time during a washing, rinsing or cleaning procedure. Said agents comprise at least one (physico-)chemical switch which controls release and is not or is only partially subjected to temperature control.

Description

"Detergent, detergent or cleaning agent portions with redox-controlled release of active ingredient"

The present invention relates to detergent, detergent or cleaning agent portions with controlled release of active ingredient. In particular, the present invention relates to detergent, detergent or cleaning agent portions which have a system which allows a controlled release of at least one active ingredient in the washing process, rinsing process, cleaning process or post-treatment process due to the targeted action of redox systems on the portion. The invention also relates to a method for producing detergent, dishwashing or cleaning agent portions of this type with enzyme-controlled release of active ingredient. The invention also relates to washing processes, rinsing processes or cleaning processes using the detergent, rinsing agent or cleaning agent portions mentioned.

For a long time, it was customary to provide the consumer with detergent, dishwashing liquid or detergent in the form of bulk packaged goods and to leave it up to the consumer to use the detergent, dishwashing liquid or detergent in accordance with the application requirements, depending on the water hardness , the type, amount and / or the degree of soiling of the wash ware, wash ware or wash ware, the amount of wash liquor, wash liquor or cleaning liquor and also other parameters.

In view of the desire of the consumer to obtain detergents, dishwashing detergents or cleaning agents that are easier and more convenient to dispense, these have increasingly been made available in a form that makes dispensing dependent on individual cases superfluous: detergents, dishwashing detergents or cleaning agents have been formulated in measured portions, all of which Contain components that are required for a wash cycle, rinse cycle or cleaning cycle. In the case of solid products, such portions were often added to (sometimes several phases ) shaped bodies such as granules, pearls, tablets ("tabs"), cuboids, briquettes, etc., which are dosed as a whole into the liquor. Liquid products were placed in water-soluble casings, which dissolve on contact with the aqueous liquor and release the contents into the liquor.

A disadvantage of these solutions is that all of the components which are required in the course of a washing cycle, rinsing cycle or cleaning cycle simultaneously enter the aqueous liquor. Not only do problems arise in the incompatibility of certain components of a detergent, dishwashing detergent or cleaning agent with other components, but it also becomes impossible to meter specific components into the fleet at a defined point in time.

In the prior art, ways have been described in which individual detergent, dishwashing or cleaning agent components can be dosed in a targeted manner and at a defined point in time during use. For example, the temperature-controlled release of active ingredients is described, which makes it possible to release active ingredients such as surfactants, bleaching agents, soil-release polymers and the like either in the main wash, rinse or cleaning cycle or even in the aftertreatment cycle, for example in the rinse cycle in automatic dishwashing.

The use of paraffins which have a melting point above 50 ° C. has been described many times. A product on the market uses a paraffin core as a carrier or matrix in a dishwashing detergent tablet so that a rinse aid surfactant stored therein is not released in the cleaning cycle, but only in the rinse cycle of a dishwasher. If the release is too early, for example during the cleaning cycle, the rinse aid surfactant is largely pumped out during the intermediate rinse and can then have little or no effectiveness in the rinse cycle. If the matrix material has a melting point at the temperature of the rinse cycle, it is ensured that the emulsified or in the matrix Ideally, molecularly dispersed rinse aid surfactant remains enclosed in the matrix during the cleaning cycle, which takes place at temperatures up to 55 ° C, and is only released after the matrix material has melted in the rinse cycle, which reaches temperatures of up to about 65 ° C.

This solution for protecting the rinse aid has proven itself in practice. However, it is disadvantageous that the proportion of the matrix material in the core of the dishwashing detergent tablet consisting of paraffin and rinse aid surfactant makes up between 30 and 95% of the total mass of the core, regularly approximately 50% of the total mass. The matrix material, in particular in this amount, can leave residues on the items to be cleaned, for example on the dishes, and moreover also impair the activity of the rinse aid surfactant contained therein and released when the paraffin melted. One reason for this could be that after the paraffin has melted, the rinse aid surfactant remains bound at the interface between the lipophilic carrier material and the washing liquor and therefore does not have the desired effect.

Another disadvantage of the temperature-controlled release of active ingredients in detergents or dishwashing detergents is that there are a larger number of programs in washing machines and dishwashers typically used in households, which differ significantly, in particular in the course of temperature and time. For example, the programs most frequently used in dishwashers today have peak cleaning temperatures of 50 to 60 ° C or 60 to 70 ° C, although the exact temperature can vary depending on the manufacturer and machine type. As well as a temperature-controlled release of active ingredient works, the effect achieved is often still dependent on the type of machine used and consumer behavior.

Appropriately, this fact can be taken into account by systems which, in contrast to a specific maximum achievable temperature which is subject to the bandwidth described above, rely on the control parameters of the React cooling and use for the targeted release of active substances or active substances from detergent, detergent or cleaning agent portions. Thus, in an older and not previously published German patent application by the applicant, detergents, dishwashing detergents or cleaning agents were described which contain polymers which are called LCST polymers and which have the special property that they are insoluble above a certain temperature (flocculation point) and are only found at solve lower temperatures. This principle can be used for all applications in which certain components are to be released after the LCST polymers have fallen below the flocculation point during the cooling phase in the washing, rinsing or cleaning process. Applications that meet these criteria are, for example, machine dishwashing and machine washing, as long as the washing and cleaning liquor is pumped out in intermediate rinsing and cleaning cycles and replaced by colder to cold rinsing water.

Another principle described is based on the fact that a cooling of an air volume heated to a certain temperature per ° Kelvin leads to a volume decrease of approximately 1/272. Using a suitable dosage form, for example a capsule with perforation, material can be sucked into the dosage form from the environment due to the negative pressure arising as a result of the air volume contraction. This step can then trigger secondary processes such as corrosion, dissolution, heating or gas formation, which enable the desired ingredients to be released.

Disadvantages of the controlled release of active substance mentioned by means of a temperature switch consist in the existing dependence on certain temperature profiles or on the need for cooling during the washing, rinsing or cleaning process.

The object of the invention was to provide switch systems which do not have the disadvantages mentioned. The object of the invention was also to provide a system for the controlled release of detergent, detergent or cleaning agent components into the liquor from a detergent, detergent or cleaning agent portion, which ensures that the component with or without a minimal amount of auxiliary materials necessary for the assembly is placed in the fleet at a defined point in time or during a period.

A further object of the invention was to provide a system for separating individual components of a detergent, dishwashing detergent or cleaning agent from other components of the same agent in order to avoid incompatibilities of the individual components during production, storage and / or transport, and thus to ensure that the components without loss of activity reach the washing, rinsing or cleaning liquor at a defined point in time, possibly also together with precisely defined other components.

Another object of the invention was to provide the possibility, in addition to naturally solid components of a detergent, dishwashing detergent or cleaning agent, of also supplying those components which are present in non-solid form, for example in liquid form, for use - or use with another aggregate state. gel-like or pasty form.

The invention accordingly relates to a detergent, dishwashing or cleaning agent portion with two or more washing, rinsing or cleaning-active components, of which at least two are to be released into the fleet at different times of a washing, rinsing or cleaning operation at least one (physico) chemical switch controlling the release, which is not or not exclusively subject to temperature control, but is activated by the action of a redox system or several redox systems.

In a preferred embodiment, the invention relates to a detergent, dishwashing or cleaning agent portion of the type mentioned, in which the Release of at least one washing-active, rinsing-active or cleaning-active component (s) controlling (physico) -chemical switch (s) is one or more component (s) which, when exposed to the action of a redox system or several redox systems from the washing, Flushing or cleaning liquor experiences a change in the physical and / or chemical properties.

The invention further relates to a method for producing a detergent, dishwashing or cleaning agent portion with two or more components that are active in washing, washing or cleaning, at least two of which are released into the fleet at different times during a washing, washing or cleaning process in which the washing-active, washing-active or cleaning-active component (s) to be released into the liquor at a later point in time of the washing, rinsing or cleaning process, with a release due to the action of a or several redox systems (s) controlling (physico-) chemical switches and the so assembled ^) wash-active, rinse-active or cleaning-active component (s) with one or more other wash-active, rinse-active or cleaning-active components Component (s) processed into a detergent, detergent or cleaning agent portion.

The invention further relates to a washing process, rinsing process or cleaning process using the detergent, rinsing agent or cleaning agent portions described in detail below.

The invention primarily provides detergent portions, detergent portions or detergent portions. In the context of the present invention, the term “detergent portion” or “detergent portion” or “detergent portion” is understood to mean a sufficient amount of a detergent, detergent or cleaning agent for a washing, rinsing or cleaning process taking place in an aqueous phase This can be, for example, a machine washing, rinsing or cleaning process such as is carried out with commercially available washing machines or dishwashers. According to the invention, however, this term is also understood to mean a hand wash cycle (for example carried out in a hand wash basin or in a bowl) or a dishwashing cycle carried out by hand or another process of washing, rinsing or cleaning. According to the invention, the detergent, detergent or cleaning agent portions are preferably used in machine washing, rinsing or cleaning operations.

In the context of the present invention, the term “detergent portion portion”, “detergent portion portion” or “detergent portion portion” is understood to mean a portion of a detergent portion, detergent portion or detergent portion which is contained in another detergent, Detergent or detergent portions separate phase in spatial connection with other detergent portions, detergent portions or detergent portions of the same detergent portion, detergent portion or detergent portion is present and is prepared or prepared by suitable measures so that it separate from other portions of detergent, portions of detergent or portions of detergent of the same portion of detergent, portion of detergent or portion of detergent in the liquor and, if necessary, can be dissolved or suspended in it. Teilpor portion or detergent portion contain the same ingredients as another detergent, dishwashing or detergent portion of the same detergent, dishwashing or detergent portion; However, two portions of detergent, portions of detergent or portions of detergent of the same portion of detergent, dishwashing or cleaning agent preferably contain different ingredients, in particular different detergent-active, detergent-active or detergent-active preparations or components.

According to the invention, the detergent, dishwashing or cleaning agent portions contain measured amounts of at least one washing-active, washing-active or cleaning-active preparation, usually measured amounts of several washing-active, washing-active or cleaning-active preparations. It is possible that the portions contain only wash-active, rinse-active or cleaning-active preparations of a certain composition. According to the invention, however, it is preferred that several, usually at least two, wash-active, rinse-active or cleaning-active preparations of different compositions are contained in the detergent, detergent or cleaning agent portions. The composition can differ in terms of the concentration of the individual components of the wash-active, rinse-active or cleaning-active preparation (quantitative) and / or in terms of the type of individual components of the wash-active, rinse-active or cleaning-active preparation (qualitative). It is particularly preferred that the components are adapted in terms of type and concentration to the tasks which the detergent, dishwashing or cleaning agent portions have to perform in the washing, washing or cleaning process.

In the context of the present invention, the term “wash-active preparation / component”, “rinse-active preparation / component” or “cleaning-active preparation / component” includes preparations or components of all conceivable substances relevant in connection with a washing, rinsing or cleaning process These are primarily the actual detergents, dishwashing detergents or cleaning agents with their individual components, which will be explained in the further course of the description, including active substances such as surfactants (anionic, non-ionic, cationic and amphoteric surfactants), builder substances (inorganic and organic builder substances). , Bleaching agents (such as peroxo bleaching agents and chlorine bleaching agents), bleach activators, bleach stabilizers, bleaching catalysts, enzymes, special polymers (for example those with cobuilder properties), graying inhibitors, dyes and fragrances (perfumes), without the term referring to these su banzgruppen is limited.

The terms “wash-active preparations / component”, “rinse-active preparation / component” or “cleaning-active preparation / component”, however, also include washing aids, rinsing aids and cleaning aids. the. Examples of these are optical brighteners, UV protection substances, so-called soil repellents, that is to say polymers which counteract re-soiling of fibers or hard surfaces, and silver protection agents. Laundry treatment agents such as fabric softener or dishwashing detergent additives such as rinse aid are also considered according to the invention as detergent-active, detergent-active or cleaning-active preparations or components.

The detergent portions, detergent portions or detergent portions according to the invention contain one or more substances from the group of surfactants, surfactant compounds, builders, bleaching agents, bleach activators, enzymes, foam inhibitors, colorants and fragrances and - in the event that the detergent , Detergent or cleaning agent portions are at least partially in the form of molded articles - binding and disintegration aids. These classes of substances are described below.

To develop the washing performance, the detergent, detergent and cleaning agent portions according to the invention can contain surface-active substances from the group of anionic, nonionic, zwitterionic or cationic surfactants, anionic surfactants being clearly preferred for economic reasons and because of their performance spectrum.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are preferably C ₉ -i ₃ -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from C _2- i ₈ monoolefins with terminal or internal double bond is obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C ₁₂ ₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of 2-sulfofatty acids (ester sulfonates), for example the 2- sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

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

As alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₂ -C ₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁ -C ₂ o-oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -Ci ₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₄ -C ₅ alkyl sulfates are preferred for washing technology reasons. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

Also, the Schwefelsäuremonoester with 1 to 6 moles of ethylene ethoxylated straight-chain or branched C _7-2 i alcohols such as 2-methyl-branched _C9 - ₁₁ - alcohols containing on average 3.5 mol ethylene oxide (EO) or C ₂ -ιβ -Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents, dishwashing detergents or cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight. Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain Cβ-iβ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts. In a further embodiment of the invention, surfactants are used in the form of their magnesium salts.

In the context of the present invention, detergent, detergent and cleaning agent portions are preferred which contain 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 15 to 25% by weight, of one or more anionic Surfactant (s), each based on the detergent, detergent and cleaning agent portion. When choosing the anionic surfactants that are used in the detergent, detergent or cleaning agent portions according to the invention, there are no restrictions to be observed in the freedom of formulation. Preferred detergent, detergent or cleaning agent portions according to the invention, however, have a soap content which exceeds 0.2% by weight, based on the total weight of the detergent, detergent or cleaning agent portion. The preferred anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, preferred detergent, dishwashing detergent and cleaning agent portions being 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight. % Of fatty alcohol sulfate (s), based in each case on the weight of the detergent, detergent or cleaning agent portion

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 may 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 or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁ -C ₄ alcohols with 3 EO or 4 EO, C ₉ n alcohol with 7 EO, C ₁₃ -C ₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Cι ₂ -ιβ- alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, and mixtures of Cι _2- ι ₄ alcohol with 3 EO and Cι _2nd ₁₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, too Fatty alcohols with more than 12 EO can be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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, in particular fatty acid methyl ester, as described for example in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.

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

Linear alkylpolyglucos.de, ie alkylpolyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical, are preferably used.

The detergent, dishwashing or cleaning agent portions according to the invention can preferably contain alkyl polyglycosides, with contents of the washing and cleaning agent portions of APG of more than 0.2% by weight, based on the entire molded body, being preferred. Particularly preferred detergent, detergent and cleaning agent portions contain APG in amounts of 0.2 to 10% by weight, preferably in amounts of 0.2 to 5% by weight and in particular in amounts of 0.5 to 3% by weight .-%. 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 polyhydroxy fatty acid amides of the formula (I),

R

R-CO-N- [Z] (I)

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

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

R ¹ -0-R ²

I

R-CO-N- [Z] (II)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical with 1 to 8 carbon atoms, where or phenyl radicals are preferred and [Z] stands for a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated, derivatives of this radical.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

It may furthermore be preferred to use cationic surfactants in addition to anionic and nonionic surfactants. They are preferably used as washing performance boosters, whereby only small amounts of cationic surfactants are required. If cationic surfactants are used, they are preferably contained in the agents in amounts of 0.01 to 10% by weight, in particular 0.1 to 3.0% by weight.

In the cases in which the detergent, detergent or cleaning agent portions according to the invention are detergents, these usually contain one or more surfactant (s) in total amounts of 5 to 50% by weight, preferably in amounts of 10 up to 35% by weight, wherein partial portions of the detergent portions according to the invention can contain surfactants in larger or smaller amounts. In other words: the amount of surfactant is not the same in all portions; rather, partial portions with a relatively larger and partial portions with a relatively smaller surfactant content can be provided. In the cases in which the detergent, detergent or cleaning agent portions according to the invention are detergents, in particular detergents, more preferably dishwashing detergents, these usually contain one or more surfactants in total amounts from 0.1 to 10% by weight, preferably in amounts of 0.5 to 5% by weight, with partial or large portions of the detergent or dishwashing agent portions of the invention containing surfactants. In other words, the amount of surfactant is not the same in all partial portions even with cleaning or dishwashing detergents; rather, partial portions with a relatively larger and partial portions with a relatively smaller surfactant content can be provided.

In addition to the washing-active substances, builders are the most important ingredients in washing, rinsing and cleaning agents. The detergent, dishwashing or cleaning agent portions according to the invention can usually contain builders used in washing, dishwashing and cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x +} ι H ₂ O, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ θ5 'yH ₂ O are preferred, with β-sodium disilicate being able to be obtained, for example, by the method described in international patent application WO-A-91/08171.

Amorphous sodium silicates with a Na ₂ O: SiO ₂ module of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to can also be used 1: 2.6, which are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

An optionally used finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. Zeolite MAP (eg commercial product: Doucil A24 from Crosfield) is particularly preferred as the zeolite of the P type. However, zeolite X and mixtures of zeolites A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight Zeolite X), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ O ^• (1-n) K ₂ O ^■ AI ₂ O ₃ ^■ (2 - 2.5) SiO ₂ ^• (3.5 - 5.5) H ₂ O can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It is of course also possible to use the generally known phosphates as builders in detergents, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, amino carboxylic acids, nitrilotriacetic acid (NTA), provided that their use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to adjust a lower and milder pH value of detergent and cleaning agent portions according to the invention. In this context, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned in particular.

Polymeric polycarboxylates are also suitable as builders. These are, 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. In the context of the present invention, the molar masses given for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene acids are generally significantly higher than the molecular weights specified in the context of the present invention.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights of 2,000 to 10,000 g / mol, particularly preferably 3,000 to 5,000 g / mol, can in turn be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid or of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molar mass, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in the detergent, dishwashing or cleaning agent portions according to the invention is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight. To improve water solubility, the polymers can also contain allylsulfonic acids, such as, for example, in EP-B 0 727 448, allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

In particular, biodegradable polymers of more than two different monomer units are preferred, for example those which, according to DE-A 43 00 772, are monomers as salts of acrylic acid and maleic acid and also vinyl alcohol or vinyl alcohol derivatives or according to DE-C 42 21 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.

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

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A 195 40 086 that, in addition to co-builder properties, they also have a bleach-stabilizing effect.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A 0 280 223. Preferred polyacetals are derived from dialdehydes such as glyoxal, Glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which are obtained by partial hydrolysis of Strengths can be obtained. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose, which is a DE of 100 owns. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2,000 to 30,000 g / mol can be used. A preferred dextrin is described in British patent application 94 19 091.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known in particular from European patent applications EP-A 0 232 202, EP-A 0 427 349, EP-A 0 472 042 and EP-A 0 542 496 and from international patent applications WO 92/18542 , WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608. An oxidized oligosaccharide according to German patent application DE-A 196 00 018 is also suitable. A product oxidized at Cβ of the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable co-builders. Ethylene diamine N, N'-disuccinate (EDDS), the synthesis of which is described, for example, in US Pat. No. 3,158,615, is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat. Nos. 4,524,009 and 4,639,325, in European patent application EP-A 0 150 930 and in Japanese patent application JP-A 93 / 339,896. Suitable amounts for use in zeolite-containing and / or silicate-containing formulations are 3 to 15% by weight.

Further useful organic co-builders are, for example, acetylated hydroxycarboxylic acids or salts thereof, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such co-builders are described, for example, in international patent application WO 95/20029.

Another class of substances with co-builder properties are the phosphonates. These are in particular hydroxyalkane or aminoalkanephosphonates. Among the hydroalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt alkaline (pH = 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral reacting sodium salts, e.g. used as the hexasodium salt of EDTMP or as the hepta- and octasodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, especially if the detergent, detergent or cleaning agent portions according to the invention also contain bleach, it may be preferred to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as co-builders. In addition to the surfactant and builder constituents mentioned, the detergent, dishwashing or cleaning agent portions according to the invention can contain further ingredients from the group of bleaching agents, bleach activators, enzymes, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, which are common in detergents, dishwashing agents or cleaning agents. Contain silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -supplying acid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. If cleaning or bleaching preparations for machine dishwashing are produced, 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. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate; (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxy-caproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxyca-pronic acid, N-

Nonenylamide operadipic acid and N-nonenylamidopersuccinate; and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperocysebacic acid, diperoxy-brassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1, 4-diacid, N, N-tere - di (6-aminopercaproic acid). Chlorine or bromine-releasing substances can also be used as bleaching agents in compositions for machine dishwashing. Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

In order to achieve an improved bleaching effect when washing, rinsing or cleaning at temperatures of 60 ° C. and below, bleach activators can be incorporated into the detergent, detergent and cleaning agent portions according to the invention. 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. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexa-hydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU) are preferred ), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyl alcohols, especially triac 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the detergent, detergent and cleaning agent portions. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or -car- bonylkomplexe. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with tripod ligands containing N as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules in the compositions according to the invention can be, for example, approximately 0.1 to 5% by weight, preferably 0.1 to approximately 2% by weight.

According to the prior art, enzymes are primarily added to a cleaning agent preparation, in particular a dishwashing agent which is intended for the main wash cycle. The disadvantage here was that the optimum effect of the enzymes used restricted the choice of temperature and problems also occurred with the stability of the enzymes in a strongly alkaline environment. With the detergent, detergent or cleaning agent portions according to the invention, it is also possible to use enzymes in the pre-rinse cycle and thus use the pre-rinse cycle in addition to the main rinse cycle for enzyme action on soiling of the wash ware. It is therefore particularly preferred according to the invention to add enzymes to the rinse-active preparation or active cleaning preparation or partial portion of a detergent portion intended for the pre-rinse cycle, and then to include such a preparation — more preferably — with a material that is already water-soluble at low temperature, for example to pre-prepare the enzyme-containing preparation protect against loss of effectiveness due to environmental conditions. The enzymes are furthermore preferably optimized for use under the conditions of the pre-rinse cycle, for example in cold water.

The detergent or cleaning agent portions according to the invention can be advantageous if the enzyme preparations are in liquid form, as some are commercially available, because then a quick effect can be expected, which already occurs in the (relatively short and cold water) pre-rinse cycle entry. Even if - as usual - the enzymes are used in solid form and these are provided with a covering made of a water-soluble material that is already soluble in cold water, the enzymes can develop their effect before the main wash or main wash cycle. The advantage of using a casing made of water-soluble material, in particular of a material soluble in cold water, is that the enzyme (s) quickly comes into effect in cold water after the casing has been dissolved. This can extend their effectiveness, which benefits the washing or rinsing result.

According to a particularly preferred embodiment, the detergent, detergent or cleaning agent portions according to the invention also contain further additives as are known from the prior art as additives for detergent, detergent or cleaning agent preparations. These can either be added to one or more portions of the detergent, dishwashing or cleaning agent portions according to the invention, or, if necessary, all partial portions (washing-active or rinsing-active or cleaning-active preparations) or - as in the pending patent application No. 199 29 098.9 titled "Active ingredient portion pack" - in water-soluble, the materials comprising active detergent preparations, for example in water-soluble wrapping films, but also in the capsules or coatings according to the invention.

A preferred group of additives used according to the invention are optical brighteners. The optical brighteners customary in detergents can be used here. These are added as an aqueous solution or as a solution in an organic solvent to the polymer solution which is converted into the film, or are added to a portion (detergent-active preparation) of a detergent or cleaning agent in solid or liquid form. Examples of optical brighteners are derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Are suitable for. B. salts of 4, 4'-bis (2-anilino-4-morpholino1, 3,5-triazinyl-6-amino-) stilbene-2,2'-disulfonic acid or compounds of the same structure, which instead of the morpholino group a Diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the type of the substituted diphenylstyryl can be contained in the partial portions (wash-active or rinse-active or cleaning-active preparations) of the detergent, detergent or cleaning agent portions according to the invention, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl or 4- (4-chlorostyryl-) 4 '- (2nd -sulfostyryl-) biphenyl. Mixtures of the aforementioned brighteners can also be used.

Another group of additives preferred according to the invention are UV protection substances. These are substances which are released in the washing liquor during the washing process or during the subsequent fabric softening process and which accumulate on the fiber in order to then achieve a UV protection effect. Products from Ciba Specialty Chemicals that are commercially available under the name Tinosorb are suitable.

Other conceivable additives which are preferred in special embodiments are surfactants which in particular influence the solubility of the water-soluble film can, but can also control their wettability and foam formation when dissolved, and foam inhibitors, but also bitter substances that can prevent accidental swallowing of such packaging or parts of such packaging by children.

Another group of additives preferred according to the invention are dyes, in particular water-soluble or water-dispersible dyes. Dyes are preferred here, as are usually used to improve the optical product appearance in detergents, dishwashing detergents and cleaning agents. The choice of such dyes does not pose any difficulties for the person skilled in the art, in particular since such customary dyes have a high storage stability and insensitivity to the other ingredients of the wash-active, rinse-active or cleaning-active preparations and to light, and have no pronounced substantivity to textile fibers in order not to dye them. According to the invention, the dyes are present in the detergent, detergent or cleaning agent portions in amounts of less than 0.01% by weight.

Another class of additives that can be added to the detergent, detergent or cleaning agent portions according to the invention are polymers. Among these polymers are, on the one hand, polymers which show cobuilder properties during washing or cleaning or rinsing, for example polyacrylic acids, also modified polyacrylic acids or corresponding copolymers. Another group of polymers are polyvinylpyrrolidone and other graying inhibitors, such as copolymers of polyvinylpyrrolidone, cellulose ether and the like. According to a further embodiment of the invention, so-called soil repellents are also suitable as polymers, as are known to those skilled in the detergent, dishwashing detergent or cleaning agent and are described in detail below.

Another group of additives are bleaching catalysts, in particular bleaching catalysts for automatic dishwashing detergents or detergents. encryption Complexes of manganese and cobalt are used here, especially with nitrogen-containing ligands.

Another preferred group of additives in the sense of the invention are silver protection agents. These are a large number of mostly cyclic organic compounds which are likewise familiar to the person skilled in the art and which help to prevent tarnishing of silver-containing objects during the cleaning process. Specific examples can be triazoles, benzotriazoles and their complexes with metals such as Mn, Co, Zn, Fe, Mo, W or Cu.

As further additives according to the invention, the detergent, detergent or cleaning agent portions can also contain so-called soil repellents, i.e. polymers which build up on fibers or hard surfaces (for example on porcelain and glass), have a positive influence on the oil and fat washability from textiles and thus counteracting soiling in a targeted manner. This effect is particularly evident when a textile or a hard object (porcelain, glass) is soiled that has already been washed, rinsed or cleaned several times beforehand with a detergent, dishwashing detergent or cleaning agent according to the invention which contains this oil and fat-dissolving component has been. The preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups from 15 to 30% by weight and of hydroxypropoxy groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ethers, as well as the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these compounds, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred. All of these additives are added to the detergent, dishwashing or cleaning agent portions according to the invention in amounts of at most 30% by weight, preferably 2 to 20% by weight. As already mentioned, the addition can also be made to a material of a water-soluble enclosure, which comprises one or more of the wash-active, rinse-active or cleaning-active preparation (s). In order to maintain the balance of the recipe, it is therefore possible for the person skilled in the art to either increase the weight of the plastic material for the enclosure, in order to exploit the depot effect which is achieved according to the invention, or else to add at least some of the additives mentioned the rest of the wash-active, rinse-active or cleaning-active preparation. However, this is less preferred.

Fragrances are added to the detergent, detergent or cleaning agent portions according to the invention in order to improve the overall aesthetic impression of the products and, in addition to the technical performance (fabric softener result, rinse aid result), to provide the consumer with a typical and unmistakable product. Individual fragrance compounds can be used as perfume oils or fragrances, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-t-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexyl benzyl propylate, allyl cyclohexyl propyl pionate. The ethers include, for example, benzyl ethyl ether. The aldehydes include e.g. B. linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lileal and bourgeonal.

The ketones include the ionones, α-isomethyl ionone and methyl cedryl ketone. Alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons mainly include terpenes such as limonene and pinene. Mixtures of different are preferred Fragrances are used that are coordinated so that together they produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures, such as are obtainable from plant sources. Examples are pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are nutmeg oil, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrance content is usually in the range up to 2% by weight of the total detergent or cleaning agent portion.

The fragrances can be incorporated directly into the wash-active preparations; However, it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance for the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven themselves as such carrier materials. The cyclodextrin-perfume complexes can also be coated with other auxiliaries.

The perfumes and fragrances can in principle be contained in each of the portions (washing-active, rinsing-active or cleaning-active preparations) of the detergent, detergent or cleaning agent portions according to the invention. However, it is particularly preferred that they are in a detergent in a part-detergent portion, part-detergent portion or part-detergent portion provided for the post-wash or softener or rinse cycle or in a detergent, especially in a dishwashing detergent a portion of detergent portion or portion of detergent portion provided for the rinse or rinse cycle. According to the invention, therefore, they must be one that is water-soluble only under the conditions (in particular at the temperature) of the post-wash or rinse cycle, and under the conditions (in particular at the temperature) of the preceding one Wash cycles or rinse cycles of water-insoluble material, in particular by a corresponding film or capsule or a corresponding coating. According to the invention, this can be done, for example, with a pouch consisting of a plurality of compartments made of foils of different water solubility.

To combat microorganisms, the detergent, detergent or cleaning agent portions according to the invention can contain antimicrobial active ingredients. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenol mercuric acetate. In the context of the teaching according to the invention, the terms antimicrobial activity and antimicrobial active substance have the customary meaning, as used, for example, by KH Wallhäusser in "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Industrial Hygiene" (5th ed. - Stuttgart; New York: Thieme, 1995 Suitable antimicrobial active substances are preferably selected from the groups of alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes , Urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1, 2-dibromo-2,4-dicyanobutane, iodo-2-propyl -butyl carbamate, lo d, iodophores, peroxo compounds, halogen compounds and any mixtures of the above compounds or connecting groups.

The antimicrobial active ingredient can be selected from the group of the compounds mentioned below, it being possible to use one or more of the compounds mentioned: ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, Glycerin, undecylenic acid, ben- zoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N-methylmorpholine-acetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-methylene-bis- (6-bromo-4-chlorophenol), 4, 4'-dichloro-2'-hydroxydiphenyl ether (dichlosan), 2,4,4'-trichloro-2'-hydroxydiphenyl ether (trichlosan), chlorhexidine, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) - urea, N, N '- (1, 10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octane anamine) dihydrochloride, N, N'-bis (4-chlorophenyl) - 3,12-diimino-2,4,11,13-tetra-azatetradecanediimidamide, glucoprotamines, antimicrobial surface-active quaternary compounds, guanidines including the bi- and polyguanidines, such as 1,6-bis- (2-ethylhexyl- biguanido-hexane) dihydrochloride, 1, 6-D .- (Nι, Nι'-phenyldiguanido-N ₅ , N ₅ '-) hexane-tetrahydochloride, 1, 6-di- (Ni.Ni'-phenyl- Ni.Ni-methyldiguanido-Ns.Ns'-jhexane-dihydrochloride, 1, 6-di-

(N _L Ni'-o-chlorophenyldiguanido-N ₅ , N ₅ '-) hexane dihydrochloride, 1,6-di- (Nι, Nι'-2,6-dichlorophenyldiguanido-N ₅ , N ₅ ' -) hexane dihydrochloride, 1, 6-di- [Nι, Nι'-beta- (p-methoxyphenyl-) diguanido-N ₅ , N ₅ '-] hexane-dihydrochloride, 1, 6-di- (Nι, Nι'-alpha- methyl-beta-phenyldiguanido-Ns.Ns'-jhexane-dihydrochloride, 1, 6-di- (Nι, Nι'-p-nitrophenyldiguanido-N ₅ , N ₅ '-) hexane-dihydrochloride, omega: omega-di- ( Nι, Nι'- phenyldiguanido-N5, N ₅ '-) di-n-propylether-dihydrochloride, omega: omega'-di-

(N _L Ni'-p-chlorophenyldiguanido-Ns.N _δ '-Jdi-n-propylether-tetrahydrochloride, 1, 6- Di- (Nι, N ₁ ' -2,4-dichlorophenyldiguanido-N ₅ , N ₅ '- ) hexane-tetrahydrochloride, 1, 6-di- (N _L N '-p-methylphenyldiguanido-N ₅ , N ₅ ' -) hexane-dihydrochloride, 1, 6-di- (Nι, Nι'- 2,4,5 -trichlorophenyldiguanido-N ₅ , N ₅ '-) hexane-tetrahydrochloride, 1,6-di- [Nι, Nι'- alpha- (p-chlorophenyl) ethyldiguanido-N ₅ , N ₅ ' -] hexane-dihydrochloride, omega: omega-di- (Nι, Nι'-p-chlorophenyldiguanido-N ₅ , N ₅ '-) m-xylene-dihydrochloride, 1, 12-di-

(Nι, Nι'-p-chlorophenyldiguanido-N ₅ , N ₅ '-) dodecane dihydrochloride, 1,10-di- (Nι, Nι'- phenyldiguanido-N ₅ , N ₅ ' -) decane-tetrahydrochloride, 1, 12-Di- (Nι, Nι'-phen- yldiguanido- Ns.Ns'-) dodecane-tetrahydrochloride, 1, 6-Di- (N ₁ , Nι'-o-chlorophenyl-diguanido- N ₅ , N ₅ '- ) hexane dihydrochloride, 1, 6-di- (Nι, Nι'-o-chlorophenyldigua-nido-N ₅ , N ₅ '-) hexane-tetrahydrochloride, ethylene bis- (l-tolylbiguanide), ethylene bis- (p-tolylbiguanide) , Ethylenebis (3,5-dimethylphenylbiguanid), ethylenebis (p-tert-amylphenyibiguanid), ethylenebis (nonylphenylbiguanid), ethylenebis (phenylbiguanide), ethylenebis (N-butylphenylbiguanid), ethylenebis (2,5-diethoxyphenyl - biguanide), ethylene bis (2,4-dimethylphenyl biguanide), ethylene bis (o-diphenyl-bi- guanide), ethylene bis (mixed amyl naphthyl biguanide), N-butyl ethylene bis (phenyl yl biguanide), trimethylene bis (o-tolyl biguanide), N-butyl trimethylene bis (phenyl bi guanide) and the corresponding salts such as acetates, gluconates, hydrochlorides , Hydrobromides, citrates, bisulfites, fluorides, polymaleates, N-cocoalkylsarcosinates, phosphites, hypophosphites, perfluorooctanoates, silicates, sorbates, salicylates, maleates, tartrates, fumarates, ethylenediaminetetraacetates, iminodiacetates, cinamomateates, thiocyanates, thiates , Tetracarboxybutyrates, benzoates, glutarates, monofluorophosphates, perfluoropropionates and any mixtures thereof. Halogenated xylene and cresol derivatives, such as p-chloro-meta-cresol or p-chloro-meta-xylene, as well as natural antimicrobial active ingredients of vegetable origin (for example from spices or herbs), animal and microbial origin are also suitable. Preferably antimicrobial surface-active quaternary compounds, a natural antimicrobial active ingredient of plant origin and / or a natural antimicrobial active ingredient of animal origin, most preferably at least one natural antimicrobial active ingredient of plant origin from the group comprising caffeine, theobromine and theophylline as well as essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial active ingredient of animal origin from the group comprising enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface-active quaternary compound with an ammonium, sulfonium, phosphonium, iodonium - Or arsonium group, peroxo compounds and chlorine compounds are used. Substances of microbial origin, so-called bacteriocins, can also be used.

The quaternary ammonium compounds (QAV) suitable as antimicrobial active substances have the general formula (R ¹ ) (R ² ) (R ³ ) (R ⁴ ) N ⁺ X ^" , in which R ¹ to R ^{4 are} identical or different C to C ₂₂ Alkyl radicals, C - to C ₂ β-aralk-yl radicals or heterocyclic radicals, where two or, in the case of an aromatic integration, as in pyridine, even three radicals together with the nitrogen atom form the heterocycle, for example a pyridinium or imidazolinium compound, and X ^" Halide ions, sulfate ions, hydroxide ions or similar anions are. For an optimal antimicrobial effect, at least one of the residues preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.

QAV are by reacting tertiary amines with alkylating agents such as Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethyl enoxide can be produced. The alkylation of tertiary amines with a long alkyl radical and two methyl groups is particularly easy. The quaternization of tertiary amines with two long residues and one methyl group can also be carried out with the aid of methyl chloride under mild conditions. Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are not very reactive and are preferably quaternized with dimethyl sulfate.

Suitable QAC are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkon B (m, p-dichlorobenzyldimethyl-C12-alkylammonium chloride, CAS No. 58390-78- 6), benzoxonium chloride (benzyl dodecyl bis (2-hydroxyethyl) ammonium chloride), cetrimoni- bromide (N-hexadecyl-N, N-trimethylammonium bromide, CAS No. 57-09-0), benzetonium chloride ( N, N-Dimethyl-N- [2- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy-] ethyl-] benzylammonium chloride, CAS No. 121-54-0 ), Dialkyldimethylammonium chlorides such as di-π-decyldimethylammonium chloride (CAS No. 7173- 51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyldimethylammonium chloride, 1-cetylpyridinium chloride (CAS No. 123-03 -5) and thiazoline iodide (CAS No. 15764-48-1) and their mixtures. Particularly preferred QAV are the Benzalkoniumchlor.de with Cβ- to Ciβ-alkyl radicals, in particular Cι ₂ - to Ci4-alkylbenzyldimethylammonium chloride.

Benzalkonium halides and / or substituted benzalkoniumhalogen.de are, for example, commercially available as Barquat ^® from Lonza, Marquat ^® from Mason, Variquat ^® from Witco / Sherex and Hyamine ^® from Lonza, and Bardac ^® from Lonza. Other commercially obtainable antimicrobial agents are N- (3-chloroallyl) hexaminium chloride such as Dowicide and Dowicil ^® ^® from Dow, benzethonium chloride such as Hyamine ^® 1622, the company Rohm & Haas, methylbenzethonium as Hyamine ^® 10X from Rohm & Haas and cetylpyridinium as Cepacol the company Merrell Labs.

The antimicrobial active ingredients are in detergent, dishwashing or cleaning agent portions according to the invention in amounts of 0.0001% by weight to 1% by weight, preferably from 0.001% by weight to 0.8% by weight, particularly preferably from 0.005% by weight to 0.3% by weight and in particular from 0.01 to 0.2% by weight.

According to the invention, the detergent portions, detergent portions or detergent portions comprise at least two, but possibly also more than two, detergent-active, detergent-active or detergent-active components or preparations, for example those according to the detailed description above, which are released into the fleet at different times should be. For example, in the case of a detergent portion according to the invention, these can be wash-active preparations or components for the pre-wash cycle of a wash cycle on the one hand and for the main wash cycle of a wash cycle on the other hand or wash-active components or preparations for the main wash cycle of a wash cycle and on the other hand for the post-wash cycle of a wash cycle. It is preferred that the respective courses are courses of a washing process in a washing machine. In a detergent according to the invention - to name a further preferred example of the invention - the at least two components can be active components or preparations for the pre-wash and main wash or for the main wash and final wash of a wash, preferably in a dishwasher.

The detergent, detergent or cleaning agent portions according to the invention with two or more washing, rinsing or cleaning-active components, of which at least two are to be released into the fleet at different times of a washing, rinsing or cleaning process, comprise at least one of the Release-controlling (physico-chemical) Switch that is not or not exclusively subject to temperature control, but is activated by the action of one or more redox systems.

In the most general embodiment, the term “(physico-) chemical switch” in the context of the present invention is understood to mean that the detergent, detergent or cleaning agent portion by means of suitable components encompassed by it due to one or more changes. in the surrounding wash liquor, rinse liquor or cleaning liquor, which can / can be controlled by the user in accordance with the conditions or the desired results, for example can / can be controlled in accordance with the washing, rinsing or cleaning program of a machine, to release at least two washing-active, rinsing-active or cleaning-active components contained therein into the respective liquor at different times or during different periods of the washing, rinsing or cleaning process.

In preferred embodiments of the invention, such components can be structural components, for example. This is understood to mean that the structural structure of the detergent portion, detergent portion or detergent portion is designed such that a release of one or more washing-active, dishwashing or cleaning-active component (s) of the respective portion is independent of one or more others wash-active, rinse-active or cleaning-active component (s) of the respective portion into the wash liquor, rinse liquor or cleaning liquor can take place. In a preferred embodiment of the detergent, detergent or cleaning agent portions according to the invention, this structural structure can be a structure in layers or in slices, in which - just to name one of numerous conceivable and practical examples, without restricting the invention thereto - One or more wash-active, rinse-active or cleaning-active component (s) of a detergent, dishwashing or cleaning agent portion, which is later to be released into the liquor (s), in one or more layers in the form of a molded body present portion (s), which is only later exposed to the entry of an aqueous liquor / are as one or more other washing-active, dishwashing or cleaning-active component (s) of a detergent, dishwashing or cleaning agent portion, which already form one to be released into the fleet earlier in the washing, rinsing or cleaning process. The structural components can also include, for example, a structure in which particles of individual (or also several) wash-active, rinse-active or cleaning-active components or aggregates of such particles, which are released into the fleet at a late point in time of a washing, rinsing or cleaning process , are surrounded by one or more layers of one or more wash-active, rinse-active or cleaning-active components which can be released into the liquor at an early stage. In the same way, a structure can be counted among the structural components in which one or more components to be released later into the respective fleet are surrounded by a coating which is poorly or only water-soluble under certain conditions, one or more to be released earlier into the respective fleet However, component (s) not, or in which one or more component (s) to be released into the liquor at a later point in time of the washing process, rinsing process or cleaning process is stronger or denser to an agglomerate of particles or one or more layer (s) thereof or to a denser molded body or one / more layer (s) thereof are compressed than one or more other component (s) of a detergent, detergent or cleaning agent portion, which are to be released into the liquor at an earlier point in time. Of course, combinations of several such (or other) structural components are possible.

In another preferred embodiment of the detergent portion, detergent portion or detergent portion according to the invention, the (s) controlling the release of at least one detergent-active, detergent-active or detergent-active component (s) are one or several structural or substantial components of the detergent, or detergent serving. This means that the detergent portion, detergent portion or detergent portion contains at least one substance as a component which, in response to changes in the environment of the detergent, detergent or cleaning agent portion, for example changes in certain properties of the washing liquor, Rinsing liquor or cleaning liquor - this can include, for example, the electrolyte concentration or the H ⁺ ion concentration (i.e. the pH value) or the concentration on one or more other components such as the concentration of enzymes or the concentration of components of a redox system - prevents or delays the release of one or more wash-active, rinse-active or cleaning-active component (s) into the wash liquor, rinse liquor or cleaning liquor, while one or more other components ^) of the respective detergent, detergent or cleaning agent portion or part ortion was released into the fleet. The substantial component (s) which prevent or delay the release can themselves be non-wash-active, non-rinse-active or non-cleaning-active substances; however, it corresponds to a preferred embodiment of the detergent, dishwashing or cleaning agent portion according to the invention that one or more such substantial component (s) which prevent or delay the release is itself a washing-active, rinsing-active or cleaning-active component / are.

Of course, combinations of the aforementioned preferred embodiments of the invention are also possible. The (physico) chemical switch (s) controlling the release of at least one wash-active, rinse-active or cleaning-active component can have one or more structural components or one or more substantial components or a combination one or more structural component (s) with one or more substantial component (s) of the detergent, detergent or cleaning agent portion. In the context of the present invention, “redox system” is understood to mean one or more components of a combination of components which, in the context of a chemical reaction in the sense of the action of one or more oxidizing agents (s) on one or more oxidation-sensitive substances or in the sense the action of one or more reducing agents on a reduction-sensitive substance or substances, in the former case the oxidizing agent is reduced while the oxidation-sensitive substance is oxidized, while in the second case the reducing agent is oxidized while the reduction-sensitive substance is reduced. The terms “oxidation” or “reduction” are to be understood in their broadest meaning in this context. The invention is described below using the example of the action of an oxidizing agent on an oxidation-sensitive substance This is only to illustrate the invention by way of example and not to limit it. In the same way, the action of several oxidizing agents on one or more oxidation-sensitive substance (s) and the action of one or more reducing agents on one or more reducing-sensitive substance (s) for releasing one or more washing-active, rinsing-active or cleaning-active component (s) of a detergent- , Detergent or detergent portion of the invention.

In particularly preferred embodiments of the invention, suitable redox-sensitive materials are oxidation-sensitive or reduction-sensitive organic and inorganic substances and polymers. An example of an oxidation-sensitive redox-sensitive material is polyvinyl pyridine. For example, a percarbonate can be used as the oxidizing agent, the latter in particular in combination with a bleach activator such as. B. TAED. An example of a reduction-sensitive redox-sensitive material is ...? .... As a reducing agent for a redox reaction taking place with such a reduction-sensitive material in the detergent, dishwashing detergent or cleaning agent, for example ...? ... Also preferred according to the invention are detergent portions, detergent portions or detergent portions in which the (physico) chemical switch (s) controlling the release of at least one detergent-active, detergent-active or detergent-active component (s) ) is / are that undergoes a change in the physical and / or chemical properties when a redox system or several redox systems from the washing, rinsing or cleaning liquor act. In the context of the present invention, a (physico) chemical switch can therefore preferably be used which brings about a redox system-controlled release of active substance. In the case of, for example, detergents or dishwashing agents for use in washing machines or dishwashers, the difference in the liquor content, for example the cleaning cycle and the rinse cycle, of a component of a redox system, for example the content of an oxidizing agent, can be used. The oxidizing agent (s) mentioned by way of example can be one or more components contained in the detergent, dishwashing detergent or cleaning agent portion, which have a washing-active, washing-active or cleaning-active effect there, or the oxidizing agent (s) can be one or more component (s) that are added to the detergent, dishwashing detergent or cleaning agent portion or the respective application liquor at a point in time that provides for a targeted release of the component to be released at a desired point in time (n) allows, for example at a time which is so far before the desired time of release of the component (s) to be released later that the action of the oxidizing agent can bring about the release at the desired time. During assembly, the activity of the oxidizing agent (s) acting on the detergent, dishwashing detergent or cleaning agent (partial) portion as well as its / its optimal exposure temperature, the suitable pH value, the optimal electrolyte concentration the fleet, etc. must be taken into account. In an advantageously applicable and therefore preferred embodiment of the detergent, detergent or cleaning agent portions according to the invention, one or more redox-sensitive material (s), that is to say degradable by the action of one or more oxidizing agents, is either used as Carrier or used as a material (s) for a coating of particles of, moldings of or capsules for ingredients (s) of detergent, dishwashing or cleaning agent portions, which are used in one washing process, washing process or cleaning process at one time or for a period of time should be released, to or during which other components are already in the fleet or have already been used in a previous course of the washing process, rinsing process or cleaning process and / or have already been withdrawn after use with the application fleet. After a certain exposure time of the oxidizing agent (s), which depends on the activity of the oxidizing agent and other parameters (temperature, pH value, electrolyte concentration, etc.), the redox-sensitive carrier material (s) are degraded and thus accompanied by a release of the wash-active, rinse-active or cleaning-active component ^) which is / are embedded in the carrier material (s), is contained in the coated particle (s) or in the molded body (s) or is / are contained in the coated capsule (s).

In a particularly preferred embodiment of the invention, the detergent portions, detergent portions or detergent portions thus comprise those (physico-) chemical switches which, when exposed to one or more components of one (or more) redox systems (s) from the application liquor experience a change in physico-chemical properties. In particular, it is preferred that such substances are used as (physico-) chemical switches which experience a change in solubility due to the action of one or more components of one or more redox systems in the application liquor preferably have an increased solubility in water. As an alternative or in addition, such switch substances are preferred which, when exposed to a redox Systems from the application fleet experience a change, in particular a decrease, in the diffusion density and / or a change, particularly preferably an acceleration, in the solution kinetics and / or a change, particularly preferably a decrease, in the mechanical stability.

The redox-sensitive switches according to the invention and used according to the invention can be used for all applications, in particular in the detergent, dishwashing or cleaning agent sector, in which an active ingredient is released in the presence of one or more components of one (or more) redox systems shall be. This can be the case both in the area of washing in the washing machine and in machine dishwashing. In particular, detergent portions are included according to the invention in which components of a detergent formulation for automatic dishwashing (for example surfactants, perfume, soil repellant, acid, complexing agents, builder substances etc., or preparations which contain these active substances) with the polymer according to the invention are formulated so that these components are not released into the washing liquor in the main rinse cycle in the absence of suitable redox systems or their components (e.g. oxidizing agents or reducing agents), but in the subsequent rinse cycle in the presence (and after a sufficiently long exposure) of one or several component (s) of one (or more) redox systems (s), in the presence of which the polymer becomes water-soluble, are released.

The polymer which is soluble when exposed to one or more redox systems can be used both as coating material and as matrix material, binder or disintegrant for the component (s) to be released at a later point in time or over a later period. It is not necessary for the polymer to dissolve completely to release the active substance under the conditions inherent to the polymer (type of redox system / systems, pH value, temperature, electrolyte concentration). Rather, it is sufficient if, for example, the permeability of a polymer film changes and, for example, the penetration of water into the active substance formulation and the dissolved components can be carried out through the holes or pores formed becomes. As a result, in a further preferred embodiment of the detergent, dishwashing or cleaning agent portions according to the invention, a secondary effect, for example the activation of a shower system or the swelling of a water-swellable disintegrant, which is known in particular from pharmacy, for the complete release of the / the wash-active, rinse-active or cleaning-active substances.

In a further embodiment, the invention provides that the detergent, detergent or cleaning agent portion according to the invention contains at least two switches, one of which is advantageously subject to temperature control. The use of two or more switches makes it possible for at least two differently acting switches to improve or even refine the controlled release of a washing-active, rinsing-active or cleaning-active agent or a combination of such agents. On the other hand, it is also conceivable that two differently acting switches bring about the controlled release of two or more different different wash-active, rinse-active or active cleaning agents or combinations of different active agents at different times or in different periods of the washing, rinsing or cleaning process.

In particular, it is preferred within the scope of this embodiment of the invention that at least two switches, which are not or not solely subject to the temperature control, are contained in the detergent portion, detergent portion or detergent portion, for example in the case of a shaped body with a cavity or depression are included as cavity or trough filling. It can be an advantage if several (physico-) chemical switches, at least one of which is not or not solely subject to temperature control, are contained in the cavity or well filling.

In a very particularly preferred embodiment of the invention, one of the (physical) chemical switches mentioned above, for example a redox-sensitive switch, is combined with a switch which Control is subject. In this case, so-called inverse temperature switches, which can be implemented using so-called LCST substances, are particularly preferred. LCST substances are substances that have better solubility at low temperatures than at higher temperatures. They are also referred to as substances with a low lower critical separation temperature (low critical solubility temperature) or with a lower lower cloud point or flocculation point. Depending on the application conditions, the lower critical segregation temperature should be between room temperature and the temperature of the heat treatment in the respective washing, rinsing or cleaning process, for example between 20 ° C. and 120 ° C., preferably between 30 ° C. and 100 ° C. , especially between 30 ° C and 50 ° C. The LCST substances are preferably selected from alkylated and / or hydroxyalkylated polysaccharides, cellulose ethers, polyisopropyl acrylamide, copolymers of polyisopropylacrylamide and mixtures of one or more of these substances.

Examples of alkylated and / or hydroxyalkylated polysaccharides are hydroxypropylmethyl cellulose (HPMC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropyl cellulose (HPC), methyl cellulose (MC), ethyl cellulose (EC), carboxymethyl cellulose (CMC) , Carboxymethylmethylcellulose (CMMC), Hydroxybutylcellulose (HBC), Hydroxybutylmethylcellulose (HBMC), Hydroxyethylcellulose (HEC), Hydroxyethylcarboxymethylcellulose (HECMC), Hydroxyethylethylcellulose (HEEC), Hydroxypropylcellulose (HPC), Hydroxypropylcellulose (HPC), Hydroxypropylcellulose (HPC), Hydroxypropylcellulose (HPC), Hydroxypropylcellulose Methylhydroxyethyl cellulose (MHEC), methyl hydroxyethyl propyl cellulose (MHEPC) and propyl cellulose (PC).

Further examples of LCST substances are cellulose ethers and mixtures of cellulose ethers with carboxymethyl cellulose (CMC). Other polymers which show a lower critical separation temperature in water and which are also suitable are polymers of mono- or di-N-substituted acrylic amides with acrylates and / or acrylic acids or mixtures of interlinked networks of the above (co-) polymers. Po- ethylene oxide or copolymers thereof, such as ethylene oxide-propylene oxide copolymers, graft copolymers of alkylated acrylamides with polyethylene oxide, polymethacrylic acid, polyvinyl alcohol and copolymers thereof, polyvinyl methylene ether, certain proteins such as poly (VATGW), a repeating unit made from the natural protein elastin and certain alginates , Mixtures of these polymers with salts or surfactants can also be used as the LCST substance. Such additives or the degree of crosslinking of the polymers can be used to modify the lower critical demixing temperature (LCST)

In a further preferred embodiment of the detergent, detergent or cleaning agent portions according to the invention, a redox-sensitive switch is combined with an LCST substance.

According to another, likewise preferred embodiment of the invention, a detergent portion, detergent portion or detergent portion according to the present invention can also contain other switches. For example, switches are suitable which can bring about a release of active detergent, rinse-active or cleaning-active substances controlled by the electrolyte concentration, particularly preferably controlled by the pH in the application liquor, at at least two different times or during at least two different periods. Such switches for an electrolyte-controlled or an active ingredient release controlled by the pH in the application liquor are described in the parallel patent application entitled "Detergent, dishwashing or cleaning agent portion with controlled active ingredient release". Such electrolyte - or pH shift-controlled switches can be used in combination with the redox-sensitive switches of the detergent, detergent or cleaning agent portions of the present invention.

In a further preferred embodiment of the invention, in addition to the above-mentioned pH shift sensitive switches, so-called pH shift Booster used. This can at least largely prevent residues, which consist in particular of the polymer substance which is soluble in a pH-dependent manner, from being found in the application liquor after the rinse cycle.

Suitable pH shift boosters for the purposes of this invention are all substances and formulations which are able to determine the extent of the shift in the pH (the pH shift) either locally, i.e. in the immediate vicinity of the substance used, sensitive to a shift in the pH value, or also generalized, i.e. in the entire wash liquor. These include - to name a group of substances which are particularly suitable according to the invention as pH shift boosters - all organic and / or inorganic water-soluble acids or acid-reacting salts, in particular at least one substance from the group consisting of alkylbenzenesulfonic acids, alkylsulfuric acids and citric acid , Oxalic acid and / or alkali metal bisulfates. The substances mentioned can be used alone or in a combination of two or more of them.

The pH shift booster, which can also be used if necessary, can be incorporated into the washing, rinsing or cleaning agent. In a further embodiment of the invention, however, it is also possible to supply the pH shift booster from the outside either after the end of the main wash or main rinse cycle or at the start of the post-wash or rinse cycle, for example into the corresponding feed chute or the corresponding metering chamber Machine or to release by a special delivery system (by coating with a slowly dissolving coating agent) or by diffusion from a matrix material or wrapping material in connection with a molded body or its wrapping.

In a further preferred embodiment of the invention, a pH shift-sensitive switch, preferably in combination with a pH shift booster, is combined with a redox-sensitive switch. A pH shift-sensitive switch, preferably in combination with a pH shift booster, as well as a redox-sensitive switch and an LCST substance can be used with particular advantage.

In addition to electrolyte-sensitive or pH-shift-sensitive switches, enzyme-controlled switches can also be used as other switches, i.e. those switches with the help of which the release of detergent-active, rinse-active or cleaning-active substances at least at two different times or during at least two different periods can be effected under the action of one or more enzymes. Enzyme-sensitive switches of this type are described in the parallel patent application entitled “Detergent, dishwashing detergent or cleaning agent portion with enzyme-controlled active ingredient release”. In particularly preferred embodiments, the enzymes for the (physico-) chemical switches include proteases, amylases, Cellulases and / or lipases into consideration, but without restricting the invention thereto, such enzymes are commercially available as individual substances or substance mixtures and are used with particular advantage in the detergent, detergent or cleaning agent portions according to the invention as additional (physical ) chemical switches are used as enzyme-sensitive substances celluloses and their derivatives, starches and their derivatives, partially oxidized starch derivatives, glycerides, proteins and their mixtures and are used with advantage.

In a further advantageous embodiment of the invention, a redox-sensitive switch is used together with an LCST substance and / or an enzyme-sensitive switch and / or a pH-shift-sensitive switch, preferably in combination with a pH-shift booster. Furthermore, it is preferred that all three switches, ie a redox-sensitive switch, an enzyme-sensitive and / or pH-shift-sensitive switch and a switch subject to temperature control, such as an LCST substance, in particular in combination with a pH-shift Booster to use. Another preferred embodiment of the invention provides for combining a redox-sensitive switch with an enzyme-sensitive switch. In addition, this combination can again have an LCST substance and / or a pH shift-sensitive switch, in particular in combination with a pH shift booster.

In a further embodiment of the invention, the detergent, detergent or cleaning agent portion according to the invention contains a redox-sensitive switch and one or more of the aforementioned pH-shift-sensitive switches, optionally in combination with a pH-shift booster, one Electrolyte-sensitive switch, an enzyme-sensitive switch and an LCST substance.

The detergent, detergent or cleaning agent portions according to the invention are in a preferred embodiment of the invention in solid form, for example as powder, granules, agglomerate, pellet, roller compactate and / or extrudate. However, the embodiment of the shaped body representing a detergent, rinsing agent or cleaning agent portion is particularly preferred, it being possible for one or more shaped bodies to be used per application in a washing, rinsing or cleaning operation. The configuration as a tablet or as a capsule is particularly advantageous. It is also possible to use one or more tablets and / or one or more capsules, optionally together with powders, granules, agglomerates, pellets, roller compacts and / or extrudates. Advantageously, two or more molded articles or the mixtures mentioned of different configurations are offered in a wrapping such as in a bag or in a film, which is / are either opened before use, so that the detergent, detergent or cleaning agent portion is in the dosing chamber of the washing machine or dishwasher can be inserted or which is / are water-soluble so that he / she can be inserted into the machine together with the washing-active, rinsing-active or cleaning-active preparation without having to wash, rinsing or cleaning process remains of it remain. Dosing via the dosing chamber is possible, as is the washing, rinsing or cleaning agent chamber of the respective machine.

A particularly preferred embodiment is a tablet with a round, oval or rectangular to cuboid base, which can have rounded corners and edges. These may be single-layered white or colored tablets, which preferably have speckles of a different color, but may also be multilayered, at least two-layered tablets, which in particular contain at least two colors, one of which may be white.

In a further embodiment of the invention, the single-layer or multilayer molded articles and in particular tablets have at least one cavity. This cavity can be designed in such a way that it extends from the upper surface to the lower base surface and the molded body thus forms a ring around a cavity. In a further preferred embodiment of the invention, the cavity is designed in such a way that it does not extend from the upper surface to the lower base surface, but merely forms a depression which can be formed either only over one layer or over several layers of the tablet. In particular, such troughs have a round, oval or rectangular to square base.

In a particularly preferred embodiment of the invention, the cavity and preferably the trough contains part of the total composition of the agent. This part of the overall composition can fill part of the cavity or the trough or the entire cavity or trough. In a preferred embodiment of the invention, one or more mixture (s) which are liquid at elevated temperature and which can comprise wash-active, rinse-active or cleaning-active components in addition to carriers and auxiliaries, for example in the form of a melt, are brought into the cavity or trough. The melt solidifies on cooling. As an alternative to this, it is also possible to produce the cavity or trough filling separately and then to insert them into the cavity or trough. The cavity or trough filling can then be present firmly, for example by gluing, or loosely in the cavity or trough, for example in the form of a plug connection. The separately manufactured cavity or trough filling can be manufactured in different ways. Preferred methods include the production of a non-pressed molded body, in particular a solidified melt body, or a pressed body. In particular, the separately produced fillers can have a shape other than that specified by the cavity or trough. For example, it is possible for the trough to be a semicircular opening in a tablet and for the filling to be spherical, but the latter may have a smaller diameter than the semicircular trough. On the other hand, it is also conceivable that the trough has an oval base, but the filling has a spherical shape. In particular, however, it is preferred that the molded body, including the cavity or trough filling, has a flat or almost flat surface.

Another embodiment of the invention provides that the cavity is inside and its filling is not visible from the outside. The actual molded body and in particular the actual tablet thus represent a jacket which completely surrounds the cavity, in particular filled. The cavity filling can in turn be produced in the manner already described either separately as a melting body or a pressing body and then cast or pressed to form the final shaped body, or the cavity filling is brought in the form of a melt into a pre-compressed shaped body, which is then pressed to the final shaped body.

In a particularly preferred embodiment, the invention provides that the cavity or trough filling contains at least one switch for the controlled release of active ingredient, which is not or not solely subject to the temperature control. In a further embodiment of the invention, the shaped body is in the form of a capsule. If only parts of the total composition are encapsulated, it is possible that the switch systems mentioned are incorporated into the capsule shell. The same applies to bags.

In the context of the present invention, it is particularly preferred to release surfactants, fragrances, dyes, bleaching agents, preferably an active chlorine carrier, acids, preferably citric acid, amidosulfonic acid or hydrogen sulfate, phosphonates, complexing agents, surfactants with complexing properties, builders and co-builders. It is a particularly preferred embodiment of the invention in practice to provide automatic dishwashing detergents which at the same time contain a rinse aid which is released in a controlled manner in the rinse cycle. Particularly preferred active ingredients are nonionic surfactants which have a rinsing effect and a melting point above room temperature, ie above 20 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43.3 ° C.

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

Preferred nonionic surfactants to be used at room temperature originate 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. In a preferred embodiment of the present invention, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 C atoms with preferably at least 12 mol, particularly preferably at least 15 Mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol.

A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _{_6-2} alcohol), preferably a Ciβ-alcohol and at least 12 moles, preferably at least 15 mol and recovered in particular at least 20 moles of ethylene oxide , Among these, the so-called "narrow ranks ethoxylates" are particularly preferred.

C _6-2 o-Monohydroxyalkanole or Cβ- ₂ o-alkylphenols or C-ι ₆ - ₂ o-fatty alcohols with more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol are particularly preferred.

The nonionic surfactant, which is solid at room temperature, preferably has additional propylene oxide units 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 portion 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 molecular weight of such nonionic surfactants. Preferred processes are characterized in that the core molding contains as an ingredient ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably accounts for up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant.

Other nonionic surfactants with melting points above room temperature which are particularly preferably used 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 mol 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.

Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-18 from Olin Chemicals.

Furthermore, nonionic surfactants of the following formula are preferred

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 represents} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1, 5 and y stands for a value of at least 15.

Further preferred nonionic surfactants are the end group-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon Atoms are, R ^{3 is} H or a methyl radical, ethyl radical, n-propyl radical, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, 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 above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 6 to 22 carbon atoms, radicals with 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, when x is 3, R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units that 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 ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula can be used

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. If the latter statements are summarized, end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] χ [CH ₂ ] _k CH (OH) [CH ₂ ] jOR ²

preferably 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 or isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

in which x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

In a preferred embodiment of the invention, cavity or trough fillings are used which contain a nonionic surfactant or a surfactant mixture with a clear rinsing effect in amounts of 20 to 50% by weight, one or more (physico) chemical switches, optionally in Combination with a temperature-sensitive switch in quantities of 40 to 70% by weight and optionally a pH shift booster in quantities of 2 to 15% by weight, in particular in quantities of up to 10% by weight the percentages by weight refer to the fillings.

Otherwise, the particularly solid detergent, detergent or cleaning agent portions can contain conventional ingredients in conventional amounts. Here, reference is made to the relevant specialist literature and the detailed description above. In particular, it is preferred to wash the detergent, detergent or cleaning agent portions according to the invention with a conventional Chen shower system, for example made of carbonate and citric acid, it may be particularly preferred that the cavity or trough filling additionally has such a shower system. This shower system can be activated in that the water permeability of the coating with the material of the (physico) chemical switch changes as a result of the change in the relevant parameter during the washing, rinsing or cleaning cycle. As an alternative to an effervescent system, a disintegrant known for example from pharmacy or detergent technology can also be used.

For use in textile detergents with a release at a certain point in the washing process, e.g. in the rinse cycles, consider:

Anti-aging components, enzymes, alkalis, acids, fragrances, dyes, fluorescent agents, optical brighteners, anti-shrink agents, anti-crease agents, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids, phobing and impregnating agents, UV absorbers and any mixtures of the above components.

The present invention can be used in particular in the case of solid machine dishwashing detergents in order to transport active substances over the main wash cycle into the rinse cycle. A formulation containing, for example, rinse aid surfactant or other active ingredients listed above, is mixed with one or more redox-sensitive material (s) and / or one or more other switches suitable as (physico-) chemical switches Coated material (ien) described above or in a matrix of one or more redox-sensitive material (ien) and / or one or more other, as (physico-) chemical (r) switch suitable material described above in detail (ien) incorporated. This formulation is then formulated together with the usual rinse-active component (s), for example added to a powder cleaner or combined with a shaped body. It is about as with the redox-sensitive switch, it is not absolutely necessary for the redox-sensitive material to dissolve completely in the appropriate conditions in the rinse cycle to release the active ingredient that is to be rinsed. Rather, it is sufficient if the permeability of the redox-sensitive film or the corresponding matrix changes and, for example, the penetration of water into the active substance formulation is made possible. A secondary effect, for example the activation of a shower system, can thereby ensure the complete release of the active ingredient.

In a particularly preferred embodiment of the invention, detergent, dishwashing or cleaning agent preparations are provided with a plurality of washing-active, dishwashing-active or cleaning-active components in which, in a later stage of the washing process, rinsing process or cleaning process, components to be released into the particular liquor, such as rinse aid surfactants, acids, for example (such as citric acid), fragrances, soil repellents, enzymes, catalysts, bleach etc. in agents for automatic dishwashing - in bulk or filled into a capsule - provided with a redox-sensitive coating, using a redox-sensitive coating Binder to be made into a wash-active, rinse-active or cleaning-active preparation or be made into a wash-active, rinse-active or cleaning-active preparation using a redox-sensitive matrix material. The coated or made-up product obtained in this way also contains other customary wash-active, rinse-active or cleaning-active components of detergent, detergent or cleaning agent portions, as described in detail above.

The materials mentioned can be used not only as a coating (coating) for wash-active, rinse-active or cleaning-active preparations in capsules or in the form of shaped articles (granules, tablets, etc.), but also for fastening in cutouts in shaped articles (e.g. tray tabs) , Ringtabs etc.) or in bags made of water-soluble polymers with other components of wash-active, rinse-active or cleaning-active preparations.

The invention also relates to a process for the preparation of the detergent, dishwashing or cleaning agent portions described in detail above, preferably those with two or more components which are active in washing, washing or cleaning, at least two of which at different times or in two different periods a washing, rinsing or cleaning process should be released into the fleet. According to the invention, the wash-active, rinse-active or cleaning-active component (s) to be released into the liquor at a later point in time of the washing, rinsing or cleaning process are packaged with a release due to the action one or more redox systems (s) controlling (physico-) chemical switches, and processes the so-made wash-active, rinse-active or cleaning-active component (s) with one or several other detergent-active, detergent-active or detergent-active component (s) for a detergent, detergent or cleaning agent portion.

In a preferred procedure according to the invention, the (physico) chemical switch (s) controlling the release of at least one wash-active, rinse-active or cleaning-active component due to the action of one or more redox systems is selected structural or substantial component (s) of a detergent, dishwashing or cleaning agent portion. Suitable structural or substantial components of the detergent, detergent or cleaning agent portion are described in detail above.

In a procedure which can be used with particular advantage, one selects as (physical) chemical switch one or more substance (s) which, when one or more redox systems (s) act, from the washing liquor, rinsing liquor or cleaning liquor (a) undergoes a change in solubility in water; and or

(b) undergoes a change in diffusion density; and or

(c) undergoes a change in solution kinetics; and or

(d) undergoes a change in mechanical stability.

In methods of the invention which can be used with particular advantage and therefore preferably, there is a redox-controlled action on the release of one or more wash-active, rinse-active or cleaning-active component (s) of a detergent, detergent or cleaning agent portion in which the redox-sensitive component (s )

(a) experiencing an increase in solubility in water; and or

(b) experiencing a decrease in diffusion density; and or

(c) experiencing an acceleration in solution kinetics; and or

(d) experiencing a decrease in mechanical stability.

As already described above, one or more substances from the group of oxidation-sensitive or reduction-sensitive organic and inorganic substances and polymers are used as (physico) chemical switches. An example of an oxidation-sensitive redox-sensitive material is polyvinyl pyridine. For example, a percarbonate can be used as the oxidizing agent, the latter in particular in combination with a bleach activator such as. B. TAED. An example of a reduction-sensitive redox-sensitive material is ...? .... As a reducing agent for a redox reaction taking place with such a reduction-sensitive material in the detergent, dishwashing detergent or cleaning agent, for example ...? ...

Finally, the invention also relates to a washing method, in particular a washing method in a washing machine, in which a detergent portion is brought into contact with laundry according to the above detailed description, in particular is placed in the washing-up chamber of a commercially available washing machine and is washed into the washing liquor with water from the first wash cycle, the early Performs washing steps in the usual manner and then sets conditions under which the (physico-) chemical ^) switch controlling the release, which is / are not or not exclusively subject to temperature control, but by the action of an or several redox systems ^) is / are activated, the component (s) to be released later into the wash liquor is released into the wash liquor.

The invention further relates to a rinsing process, in particular a rinsing process in a dishwasher, in which a detergent portion according to the detailed description above is brought into contact with items to be washed, in particular placed in the rinsing chamber of a commercially available dishwasher and rinsed into the washing liquor with water from the first rinse cycle carries out early steps of the rinsing process in the usual manner and then sets conditions under which the (physico) chemical switch (s) controlling the release, which is / are not or not exclusively subject to temperature control, but are subject to action one or more redox systems (s) is / are activated, the component (s) to be released later into the washing liquor is released into the washing liquor.

Finally, the invention relates to a cleaning method in which a detergent portion is brought into contact with the items to be cleaned as described above, the early steps of the cleaning process are carried out in a customary manner and then conditions are set under which the release-controlling person (s) physico-) chemical switch (s) that are not or not exclusively subject to temperature control, but are activated by the action of one or more redox systems, the component (s) to be released later into the cleaning solution ( n) releases into the cleaning liquor.

The invention is explained in more detail by the following examples, but without being restricted to these examples, which represent preferred embodiments of the invention. Examples

Examples 1 and 2

...? ...

Tablets or capsules were produced with an effective amount of rinse aid surfactant (500 mg Poly Tergent SLF ^® 18B45). The product was then coated by means of film coating with aminoalkyl methacrylate copolymer (Eudragit E ^® ) (Example 1).

According to Example 1 above were coated moldings or capsules prepared which (500 mg Poly Tergent SLF 18B45 ^®) an effective amount of rinse surfactant contained. These products were then coated by film coating with the same aminoalkyl methacrylate copolymer as in Example 1, with the difference that the coating material was admixed with polyvinylpyridine in an amount of 10% by weight, based on the total coating material (Example 2).

The tablets or capsules so prepared were subjected together with a commercial tableted automatic dishwashing detergent (Somat Professional ^®, Henkel KGaA) a 65 ° C-cleaning program, wherein the shaped bodies have been introduced with the capsules over the dosing chamber.

After the cleaning cycle, the coated and rinse aid-containing tablets or capsules from Example 1 were almost undissolved. After the rinse cycle, the tablets or capsules were largely dissolved, the visible residues consisting mainly of coating material. A clear rinse effect on dishes could be demonstrated. After the cleaning cycle, the coated tablets or capsules from Example 2 were undissolved. Small holes were visible at the locations where polyvinylpyridine-containing domains were present in the coating material.

After the rinse cycle, the tablets or capsules were completely dissolved. Obviously, this was achieved by combining the two control mechanisms.

example

Claims

claims

1. Detergent, dishwashing or cleaning agent portion with two or more washing, washing or cleaning-active components, of which at least two are to be released into the fleet at different times of a washing, washing or cleaning process, comprising at least one Release-controlling (physico-) chemical switch, which is not or not exclusively subject to temperature control, but is activated by the action of one or more redox systems.

2. Detergent, dishwashing or cleaning agent portion according to claim 1, wherein the release (s) controlling the release of at least one washing-active, washing-active or cleaning-active component (s) (physico) chemical (s) one or more structural or substantial components ( n) the detergent, detergent or cleaning agent portion is / are.

3. Detergent, dishwashing or cleaning agent portion according to claim 1 or claim 2, wherein the (s) controlling the release of at least one washing-active, washing-active or cleaning-active component (s) (physioco) chemical (s) one or more Component (s) is / are undergoing a change in the physical and / or chemical properties due to the action of one or more redox systems (s) from the washing, rinsing or cleaning liquor.

4. detergent, detergent or cleaning agent portion according to one or more of claims 1 to 3, containing as (physico-) chemical switch one or more substance (s), which when exposed to one or more redox systems ^) from the Wash liquor, rinse liquor or cleaning liquor

(a) undergoes a change in solubility in water; and or (b) undergoes a change in diffusion density; and or

(c) undergoes a change in solution kinetics; and or

(d) undergoes a change in mechanical stability;

preferably

(a) experiencing an increase in solubility in water; and or

(b) experiencing a decrease in diffusion density; and or

(c) experiencing an acceleration in solution kinetics; and or

(d) experiencing a decrease in mechanical stability.

5. detergent, detergent or cleaning agent portion according to one or more of claims 1 to 4, containing as (physico) chemical switch one or more substances from the group sensitive to oxidation or reduction sensitive organic and inorganic substances and polymers, preferably polyvinylpyridine or. ..? ..., in combination with an oxidizing agent from the group of percarbonate, especially together with a bleach activator like TAED, or ...? ... in combination with a reducing agent from the group ...? ....

6. detergent, detergent or cleaning agent portion according to one or more of claims 1 to 5, containing at least two switches, of which preferably at most one is subject to temperature control.

7. detergent, detergent or cleaning agent portion according to one or more of claims 1 to 6, containing a redox-sensitive switch in combination with a temperature-controlled switch or a redox-sensitive switch and a pH shift-sensitive switch in Combination with a switch subject to temperature control or a redox-sensitive switch and an enzyme-sensitive switch in combination with a switch subject to temperature control.

8. A process for the preparation of a detergent, dishwashing or cleaning agent portion with two or more washing, washing or cleaning-active components, of which at least two are to be released into the fleet at different times of a washing, washing or cleaning operation, wherein the wash-active, rinse-active or cleaning-active component (s) to be released into the liquor at a later point in time of the washing, rinsing or cleaning process with a release due to the action of a or several redox systems (s) controlling (physico-) chemical switches, and the so-assembled washing-active, rinsing-active or cleaning-active component (s) with one or more other washing-active, rinsing-active or detergent-active component (s) processed into a detergent, dish soap or detergent portion.

9. The method according to claim 8, wherein the (s) controlling the release of at least one washing-active, rinsing-active or cleaning-active component (s) (physico-) chemical switch (s) is one or more structural or substantial component (s) of a detergent, Detergent or detergent portion chooses.

10. The method according to claim 8 or claim 9, wherein one or more components are selected as the (physico-) chemical switch (s) controlling the release of at least one wash-active, rinse-active or cleaning-active component Exposure to one or more redox systems ^) experiences a change in the physical and / or chemical properties from the washing, rinsing or cleaning liquor.

11. The method according to any one of claims 8 to 10, wherein one selects as (physical) chemical switch one or more substance (s) which, as a result of the action of one or more redox systems (s) from the washing liquor, rinsing liquor or cleaning liquor (a) undergoes a change in solubility in water; and or

(b) undergoes a change in diffusion density; and or

(c) undergoes a change in solution kinetics; and or

(d) undergoes a change in mechanical stability;

preferably

(a) experiencing an increase in solubility in water; and or

(b) experiencing a decrease in diffusion density; and or

(c) experiencing an acceleration in solution kinetics; and or

(d) experiencing a decrease in mechanical stability.

12. The method according to any one of claims 12 to 17, wherein one or more substances from the group oxidation-sensitive or reduction-sensitive organic and inorganic substances and polymers, preferably polyvinylpyridine or ...? ..., in combination as a (physico-) chemical switch with an oxidizing agent from the percarbonate group, in particular together with a bleach activator such as TAED, or ...? ... in combination with a reducing agent from the group ...? ....

13. Washing process, in particular washing process in a washing machine, in which a detergent portion according to one of claims 1 to 7 is brought into contact with laundry, in particular placed in the washing-up chamber of a commercial washing machine and washed into the washing liquor with water from the first wash cycle, the early ones Performs washing steps in the usual manner and then sets conditions under which the (physico) chemical switch (s) controlling the release, which is / are not or not exclusively subject to temperature control, are subject to Action of one or more redox systems is activated, the component (s) to be released later into the wash liquor is released into the wash liquor.

14. rinsing process, in particular rinsing process in a dishwasher, in which a detergent portion according to one of claims 1 to 7 is brought into contact with items to be washed, in particular placed in the washing-up chamber of a commercially available dishwasher and washed into the washing liquor with water from the first wash cycle, the early ones Performs rinsing steps in the usual manner and then sets conditions under which the (physico) chemical switch (s) controlling the release, which is / are not or not exclusively subject to temperature control, are subject to Action of one or more redox systems is activated, the component (s) to be released later into the washing liquor is released into the washing liquor.

15. A cleaning method, wherein a detergent portion according to one of claims 1 to 7 is brought into contact with the items to be cleaned, the early steps of the cleaning process are carried out in a customary manner and then conditions are set under which the release-controlling (s) (physico -) Chemical switch (s) that are not or not exclusively subject to temperature control, but are activated by the action of one or more redox systems that later release components into the cleaning liquor releases the cleaning liquor.