EP1238054B2 - Washing agent, rinsing agent or cleaning agent portions with enzyme-controlled active ingredient release - Google Patents

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

The present invention relates to detergent, detergent or detergent controlled release portions. More particularly, the present invention relates to detergent, rinse or detergent portions having a system which permits controlled release of at least one active ingredient in the washing, rinsing, cleaning or aftertreatment process due to the targeted action of enzymes on the portion. The invention also relates to a process for the preparation of such detergent, detergent or cleaner portions with enzyme-controlled drug release. The invention also relates to washing methods, rinsing methods or cleaning methods using said detergent, rinse or detergent portions.

For a long time, it has been customary to provide the consumer with detergents, dishwashing detergents or cleaning agents in the form of bulk-packaged goods and to leave it to the consumer, in use, to dispense the detergent, dishwashing or cleaning agent according to the application requirements, that of the water hardness , the type, amount and / or the degree of contamination of the laundry, items or items to be cleaned, the amount of wash liquor, wash liquor or cleaning liquor and also other parameters depended.

In response to the desire of the consumer to obtain simpler and more conveniently metered detergents, dishwashing detergents or detergents, these have increasingly been provided in a form that eliminates the need for individual case-based dosing: detergents, dishwashing or cleaning agents were formulated in metered portions, all of them Contain components that are required for a wash, rinse or cleaning cycle. In the case of solid products, such portions have often been shaped into moldings (sometimes containing several phases) such as granules, beads, tablets ("tabs"), ashlars, briquettes, etc., which are dosed as a whole into the liquor. Liquid products were incorporated into water-soluble coatings which dissolve on contact with the aqueous liquor and release the contents into the liquor.

A disadvantage of these solutions is that all components that are needed in the course of a wash cycle, rinse or cleaning cycle, get into the aqueous liquor at the same time. Not only do problems of incompatibility of certain components of a detergent, dishwashing detergent or cleaning agent with other components occur, but it also becomes impossible to meter specifically targeted components into the liquor at a defined time.

The prior art has in the meantime described ways in which individual detergent, dishwashing or cleaning agent components can be metered in a targeted manner and at a defined time during use. Thus, for example, the temperature-controlled release of active substances is described which makes it possible to release active substances such as surfactants, bleaches, soil release polymers and the like either in the main washing, rinsing or cleaning cycle or even in the aftertreatment course, for example in the rinse cycle in automatic dishwashing.

The use of paraffins having a melting point above 50 ° C. has been described several times. A product on the market uses a paraffin core in a dishwashing tablet as a carrier or matrix in order to release a rinse aid surfactant incorporated therein not already in the cleaning cycle, but only in the final rinse cycle of a dishwashing machine. If released too early, for example during the cleaning cycle, the rinse-aid surfactant is largely pumped off during the intermediate rinse and can then develop no or only little 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 rinse-aid surfactant emulsified in the matrix or, ideally, dispersed with molecular dispersion remains trapped in the matrix during the cleaning cycle, which runs at temperatures up to 55 ° C. only in the rinse cycle, in which temperatures up to about 65 ° C can be achieved, is released after melting of the matrix material.

This solution for protecting the rinse aid surfactant has proven itself in practice. A disadvantage, however, is that the proportion of the matrix material to the consisting of paraffin and rinse aid surfactant core of the dishwashing tablet is between 30 and 95% of the total mass of the core, regularly about 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 in addition also impair the activity of the rinse aid surfactant contained therein when the paraffin is melted. One reason for this could be that the rinse aid surfactant remains bound at the interface between the lipophilic carrier material and the rinse liquor after melting the paraffin and thus does not exhibit the desired effect.

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

Approach to this fact can be accommodated by systems which, in contrast to a certain maximum achievable temperature, which is subject to the bandwidth described above, to the control parameter of the cooling and the targeted release of active ingredients or active ingredients from detergent, detergent or cleaning agent -Portions use. For example, in an earlier and not previously published German patent application, the Applicant describes detergents, dishwashing detergents or cleaning compositions which contain polymers which are called LCST polymers and have the special property that they are insoluble above a certain temperature (flocculation point) and only at lower temperatures. This principle can be used for all applications in which a release of certain components after falling below the flock point of the LCST polymers during the cooling phase in the washing, rinsing or cleaning process is to take place. Applications which fulfill these criteria include, for example, automatic 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 described principle 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 about 1/272. By means of a suitable administration form, for example a capsule with perforation, material from the environment can be sucked into the dosage form by 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 allow release of the desired ingredients.

Disadvantages of said controlled release of active ingredient by 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 detergent components in the liquor from a detergent, detergent or detergent portion available, which ensures that the component as possible without or with a minimum quantity of auxiliaries necessary for the preparation reaches the fleet at a defined time or during a period of time.

Another object of the invention was to provide a system for separating individual components of a detergent, rinse or cleaning agent from other components of the same agent to avoid incompatibilities of the individual components in preparation, storage and / or transport, and thus to ensure that the components are free from loss of activity enter the washing, rinsing or cleaning fleet at a defined 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, detergent or cleaning agent and those components of a use - or use with those of another state of aggregation - supply, which are not in solid form, for example in liquid, gelatinous 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 at different times of a washing, rinsing or cleaning process in the fleet, the comprising at least one release (physical) chemical switch which is not or not exclusively subject to temperature control but is activated by enzyme action.

The invention relates, in a preferred embodiment, to a detergent, rinse or detergent portion of the type referred to wherein the release (s) of at least one detergent active, rinse active or cleaning active component control one or two (physic) chemical switch (s) multiple component (s) is / are experiencing a change in physical and / or chemical properties upon the action of one or more enzymes from the wash, rinse or cleaning liquor.

The invention further relates to a process for the preparation of a detergent, dishwashing or cleaning agent portion with two or more washing, rinsing or cleaning-active components, of which at least two are released into the liquor at different times of a washing, rinsing or cleaning process to be in which one can be released at a later stage of the washing, rinsing or cleaning process in the fleet (s) washing active (n), rinse active (n) or cleaning active component (s) with a release due to enzyme action controlling (physico) chemical switch and the so-prepared washing active, rinse active or cleaning active component (s) with one or more other washing active, rinse active or cleaning active component (s) to a detergent , Detergent or detergent portion processed.

The invention further relates to a washing method, rinsing method or cleaning method using the detergent, detergent or detergent 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 quantity of a detergent, rinsing agent or cleaning agent which is sufficient 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, 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 washing cycle (performed, for example, in a hand basin or in a bowl) or a dishwashing process carried out by hand or another process of washing, rinsing or cleaning. According to the invention, the detergent, detergent or cleaner portions are preferably used in automatic washing, rinsing or cleaning operations.

In the context of the present invention, the term "detergent partial portion", "detergent partial portion" or "detergent partial portion" is understood to mean a subset of a detergent portion, detergent portion or detergent portion which is in one of other detergent, Detergent or detergent part-portions separate phase in spatial connection with other detergent portions, detergent partial portions or detergent partial portions of the same detergent portion, detergent portion or detergent portion is present and prepared by suitable measures or ready-made separated from other detergent portions, detergent partial portions or detergent partial portions of the same detergent portion, detergent portion or detergent portion added to the liquor and optionally dissolved or suspended in it. In this case, a partial detergent portion, partial detergent portion or partial detergent portion may contain the same ingredients as another portion of detergent, detergent or detergent portion of the same detergent, detergent or cleaning agent portion; However, two detergent partial portions, detergent partial portions or detergent partial portions of the same detergent, detergent or cleaner portion preferably contain different ingredients, in particular different detergent-active, rinse-active or detergent-active preparations or components.

According to the invention, the detergent, detergent or cleaner portions contain measured amounts of at least one wash-active, rinse-active or cleaning-active preparation, usually measured amounts of several washing-active, rinse-active or cleaning-active preparations. It is possible that the portions contain only detergent-active, rinse-active or cleaning-active preparations of a particular composition. According to the invention, however, it is preferred that several, usually at least two, washing active, rinse active or cleaning active preparations of different composition in the detergent, detergent or detergent portions are included. The composition may be (qualitatively) different with regard to the concentration of the individual components of the washing-active, rinsing-active or cleaning-active preparation (quantitatively) and / or with regard to the nature of the individual components of the washing-active, rinsing-active or cleaning-active preparation. It is particularly preferred that the components are adapted in terms of nature and concentration to the tasks that have to meet the detergent, detergent or detergent partial portions in the washing, rinsing or cleaning process.

In the context of the present invention, the term "detergent-active preparation / component", "detergent-active preparation / component" or "detergent-active preparation / component" is understood to mean preparations or components of all conceivable substances which are relevant in connection with a washing, rinsing or cleaning process Understood. These are primarily the actual detergents, dishwashing detergents or cleaning agents with their individual components explained in the further course of the description. These include active ingredients such as surfactants (anionic, nonionic, cationic and amphoteric surfactants), builders (inorganic and organic builders), bleaches (such as peroxy bleach and chlorine bleach), bleach activators, bleach stabilizers, bleach catalysts, enzymes, specialty polymers ( for example, those with cobuilder properties), grayness inhibitors, dyes and fragrances (perfumes), without the term being limited to these substance groups.

However, the term "detergent-active preparations / component", "detergent-active preparation / component" or "detergent-active preparation / component" is also understood to mean washing auxiliaries, rinse aids and cleaning auxiliaries. Examples of these are optical brighteners, UV protective substances, so-called soil repellents, ie polymers which counteract re-soiling of fibers or hard surfaces, and silver protectants. Laundry-treating agents, such as fabric softeners or dishwashing detergent additives, such as rinse aids, are also considered as washing-active, rinse-active or cleaning-active preparations or components according to the invention.

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, dyes and fragrances and - in the event that the detergents , Detergent or detergent portions at least partially present as a shaped body - binding and disintegration aid. These classes of substances are described below.

To develop the washing performance, the detergent, detergent and cleaner portions according to the invention, surfactants from the group of anionic, nonionic, zwitterionic or contain cationic surfactants, with anionic surfactants for economic reasons and because of their power spectrum are clearly preferred.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. Suitable surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as, for example, from C _12-18 -monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise suitable are the esters of 2-sulfofatty acids (ester sulfonates), for example the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated 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.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which, for example, according to the U.S. Patents 3,234,258 or 5,075,041 are manufactured and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

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

Further 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 in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) yl-succinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

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

The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present 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 cleaner portions are preferred which contain from 5 to 50% by weight, preferably from 7.5 to 40% by weight and in particular from 15 to 25% by weight, of one or more anionic Surfactant (s), in each case based on the detergent, detergent and cleaning agent portion.

When selecting the anionic surfactants which are used in the detergent, detergent or cleaner portions according to the invention, there are no restrictions to be kept in the way of formulation freedom. However, preferred detergent, detergent or cleaning agent portions according to the invention have a soap content which exceeds 0.2% by weight, based on the total weight of the detergent, detergent or cleaning agent portion. Preferred anionic surfactants to be used are the alkylbenzenesulfonates and fatty alcohol sulfates, with preferred detergent, detergent and cleaner portions containing 2 to 20 wt .-%, preferably 2.5 to 15 wt .-% and in particular 5 to 10 wt .-% fatty alcohol sulfate (E), in each case based on the weight of the detergent, detergent or cleaning agent portion

As nonionic surfactants 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 used in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, and mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferred nonionic surfactants 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 having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters as they are for example in the Japanese Patent Application JP 58/217598 are described or preferably according to the in the international patent application WO 90/13533 be prepared described methods.

Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG). Usable alkylpolyglycosides satisfy the general formula RO (G) _z , in which R is a linear or branched, in particular in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably 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.

Preference is given to using linear alkyl polyglucosides, that is to say alkyl polyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

The detergent, detergent or cleaner portions according to the invention may preferably contain alkylpolyglycosides, with contents of the detergent portions of APG being above 0.2% by weight, based on the total molding, being preferred. Particularly preferred detergent, detergent and cleaner portions contain APG in amounts of from 0.2 to 10% by weight, preferably in amounts of from 0.2 to 5% by weight and in particular in amounts of from 0.5 to 3% by weight .-%.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further suitable surfactants are polyhydroxy fatty acid amides of the formula (I)

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

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.

[Z] is preferably 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 the international application WO-A-95/07331 be converted by conversion with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired Polyhydroxyfettsäureamide.

Furthermore, it may be preferable to use not only anionic and nonionic surfactants but also cationic surfactants. Their use is preferably carried out as Waschleistungsbooster, with only small amounts of cationic surfactants are required. If cationic surfactants are used, they are preferably present in the compositions in amounts of from 0.01 to 10% by weight, in particular from 0.1 to 3.0% by weight.

In the cases in which the detergent, detergent or cleaner portions according to the invention are detergents, they usually comprise one or more surfactants in total amounts of from 5 to 50% by weight, preferably in amounts of 10 to 35 wt .-%, wherein in partial portions of the detergent portions of the invention surfactants may be contained in greater or smaller amount. In other words: the amount of surfactant is not the same in all partial portions; Rather, partial portions can be provided with relatively larger and partial portions with relatively smaller surfactant content.

In the cases in which the detergent, detergent or cleaner portions according to the invention are detergents, in particular dishwashing agents, more preferably dishwashing compositions, these usually contain one or more surfactants in total amounts of from 0.1 to 10 wt .-%, preferably in amounts of 0.5 to 5 wt .-%, wherein in partial portions of the detergent or detergent portions of the invention surfactants may be contained in greater or smaller amount. In other words, the amount of surfactant is not the same for cleaning or dishwashing detergents in all partial portions; Rather, partial portions can be provided with relatively larger and partial portions with relatively smaller surfactant content.

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

Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .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 are. Such crystalline layered silicates are described, for example, in US Pat European Patent Application EP-A-0 164 514 described. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in International Patent Application WO-A-91/08171 is described.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that in X-ray diffraction experiments, the silicates do not give sharp X-ray reflections typical of crystalline substances but at best one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties when the silicate particles are involved in electron diffraction experiments provide blurred or even sharp diffraction maxima. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which likewise have a dissolution delay compared to the conventional water glasses, are described, for example, in US Pat German patent application DE-A-44 00 024 described. Especially preferred are densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

A fine crystalline, synthetic and bound water-containing zeolite optionally used is preferably zeolite A and / or P. Zeolite MAP (eg, commercial product: Doucil A24 from Crosfield) is particularly preferred as the P-type zeolite. Also suitable, however, are zeolite X and mixtures of the zeolites A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, also a cocrystal of zeolite X and zeolite A (about 80% by weight). zeolite X) which is marketed by CONDEA Augusta SpA under the trade name AX VEGOBOND ^® and by the formula

nNa ₂ O • (1-n) K ₂ O • Al 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, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course, in detergents, a use of the well-known phosphates as builders possible, unless such use should not be avoided for environmental reasons. Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided 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 thereof. The acids themselves can also be used. In addition to their builder effect, the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of washing and cleaning agent portions according to the invention. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these are to be mentioned in this context.

As builder further polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70,000 g / mol.

In the context of the present invention, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against 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 which have molecular weights of from 2,000 to 10,000 g / mol, more preferably from 3,000 to 5,000 g / mol, may 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 from 2,000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 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 detergent, detergent or cleaning agent portions of (co) polymeric polycarboxylates according to the invention is preferably from 0.5 to 20% by weight, in particular from 3 to 10% by weight.

To improve the water solubility, the polymers may also allylsulfonic acids, such as in the EP-B C 727 448 , Allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

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

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

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

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

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30, is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which is a DE of 100 owns. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2,000 to 30,000 g / mol. A preferred dextrin is in the British Patent Application 94 19 091 described.

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 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 as well as from the international ones Patent Applications WO 92/18542 . WO 93/08251 . WO 93/16110 . WO 94/28030 . WO 95/07303 . WO 95/12619 and WO 95/20608 known. Also suitable is an oxidized oligosaccharide according to German patent application DE-A 196 00 018 , A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are also other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS), its synthesis, for example, in the document US-A 3,158,615 is described, 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 US Patents US-A 4,524,009 and US-A 4,639,325 , in the European Patent Application EP-A 0 150 930 and in the Japanese Patent Application JP-A 93 / 339,896 to be discribed. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

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

Another class of substances with co-builder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroalkane phosphonates, the 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 neutral and the tetrasodium salt alkaline (pH = 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral reacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octasodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The Aminoalkanphosphonate also have a pronounced heavy metal binding capacity. Accordingly, it may be preferred, especially when the detergent, detergent or cleaner portions according to the invention also contain bleach, to use Aminoalkanphosphonate, in particular DTPMP, or to use mixtures of said phosphonates.

In addition, all compounds capable of forming complexes with alkaline earth metal ions can be used as co-builders.

In addition to the constituents surfactant and builder, the detergents, dishwashing or cleaning agent portions according to the invention may contain further ingredients customary in detergents, dishwashing detergents or cleaning compositions from the group of bleaches, bleach activators, enzymes, fragrances, perfume carriers, fluorescers, dyes, foam inhibitors, Silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, color transfer inhibitors and corrosion inhibitors.

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. When cleaning or bleaching preparations for automatic dishwashing are prepared, it is also possible to use bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate; (b) the aliphatic or substituted aliphatic peroxyacids such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxy-caproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate; and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxy-brassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid).

As bleaching agents in automatic dishwashing compositions it is also possible to use chlorine or bromine-releasing substances. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

In order to achieve an improved bending effect during washing, rinsing or cleaning at temperatures of 60 ° C. and below, bleach activators can be incorporated into the detergent, dishwashing and cleaning agent portions according to the invention. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic 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 stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated 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), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5- diacetoxy-2,5-dihydrofuran.

In addition to or in place of the conventional bleach activators, so-called bleach catalysts can also be incorporated into the detergent, detergent, and detergent portions. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Particularly suitable are bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. Enzyme mixtures, for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but in particular cellulase-containing mixtures are of particular interest. Peroxidases or oxidases have also proved suitable in some cases. The enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation. The proportion of the enzymes, enzyme mixtures or enzyme granules in the compositions according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

Enzymes are added according to the prior art primarily to a detergent composition, in particular a dishwashing agent, which is intended for the main rinse. Disadvantage was that the optimum effect of enzymes used limited the choice of temperature and also encountered problems in the stability of the enzymes in a strongly alkaline medium. With the detergent, detergent or cleaner portions according to the invention, it is possible to use enzymes in the pre-wash and thus to use the pre-rinse cycle in addition to the main rinse for an enzyme action on contaminants of the dishes.

According to the invention, therefore, it is particularly preferable to add enzymes to the rinse-active preparation or cleaning-active preparation or partial portion of a detergent portion intended for the pre-rinse cycle, and then to further such a preparation with a material which is already water-soluble at low temperature to protect, for example, the enzyme-containing preparation from loss of effect due to environmental conditions. The enzymes are more preferably optimized for use under the conditions of the pre-wash cycle, that is, for example, in cold water.

Advantageously, the detergent or cleaner portions according to the invention can then be when the enzyme preparations are liquid, as they are sometimes available commercially, because then a rapid effect can be expected, already in (relatively short and carried out in cold water) pre-wash entry. Even if - as usual - the enzymes are used in solid form and they are provided with an enclosure of a water-soluble material that is already soluble in cold water, the enzymes can unfold their effect even before the main wash or main cleaning. Advantage of the use of an enclosure of water-soluble material, in particular of cold water-soluble material is that the enzyme / enzymes in cold water after dissolution of the enclosure comes to effect quickly / come. Thus, their duration of action can be extended, which benefits the washing or rinsing results.

According to a particularly preferred embodiment, the detergent, detergent or cleaner portions according to the invention also contain further additives known from the state of the art as additives for detergents, dishwashing detergent preparations or detergent compositions. These can be added to one or more, if necessary also all partial portions (wash-active or active-detergent formulations) of the inventive detergent, dishwashing or cleaning agent portions or, as described in copending patent application no. 199 29 098.9 with the title "active substance portion pack" - into water-soluble, the wash-active preparations comprehensive materials, thus for example in water-soluble Umfassungs foils, but also in the capsules or coatings according to invention are incorporated.

A preferred group of additives used in the invention are optical brighteners. Can be used here, the usual in detergents optical brightener. These are added as an aqueous solution or as a solution in an organic solvent of the polymer solution, which is converted into the film, or are added to a partial portion (detergent preparation) of a detergent or cleaning agent in solid or liquid form. Examples of optical brighteners are derivatives of diaminostilbene disulfonic acid or its alkali metal salts. Suitable z. B. salts of 4, 4'-bis (2-anilino-4-morpholinol, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed compounds which instead of the morpholino group a Diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the type of substituted diphenylstyrene may be present in the partial portions (wash-active or rinse-active or cleansing-active preparations) of the detergent, rinse or cleaning agent portions according to the invention, eg. For example, the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl or 4- (4-chlorostyryl) 4 '- (2 -sulfostyryl-) biphenyl. Mixtures of the aforementioned brightener can be used.

Another group of additives which is preferred according to the invention are UV protection substances. These are substances that are released during the washing process or in the subsequent fabric softening process in the wash liquor and that accumulate accumulatively on the fiber, in order then to achieve a UV protection effect. Suitable are the products marketed under the name Tinosorb Ciba Specialty Chemicals.

Further conceivable additives, which are preferred in specific embodiments, are surfactants which in particular can influence the solubility of the water-soluble film, but can also control its wettability and foaming on dissolution, as well as foam inhibitors, but also bitter substances, which may inadvertently swallow such packaging or parts of such packaging prevent from children.

Another group of additives which is preferred according to the invention are dyes, in particular water-soluble or water-dispersible dyes. Preference is given here to dyes, as they are usually used to improve the appearance of the optical product in detergents, detergents and cleaning agents. The choice of such dyes is not difficult for a person skilled in the art, especially since such conventional dyes have a high storage stability and insensitivity to the other ingredients of the washing active, rinse active or cleaning active preparations and light and no pronounced substantivity to textile fibers, so as not to stain them. The dyes according to the invention in the detergent, detergent or detergent portions in amounts of less than 0.01 wt .-% present.

Another class of additives which may be added to the detergent, rinse or detergent portions in accordance with the invention are polymers. Among these polymers are on the one hand polymers in question, which show washing or cleaning or rinsing Cobuilder properties, so for example polyacrylic acids, and modified polyacrylic acids or corresponding copolymers. Another group of polymers are polyvinylpyrrolidone and other grayness inhibitors, such as copolymers of polyvinylpyrrolidone, cellulose ethers, and the like. According to a further embodiment of the invention, so-called soil repellents are also suitable as polymers, as are known to the detergent, dishwashing or cleaning agent specialist and will be described in detail below.

Another group of additives are bleach catalysts, in particular bleach catalysts for automatic dishwashing detergents or detergents. Here are used complexes of manganese and cobalt, in particular with nitrogen-containing ligands.

Another preferred group of additives within the meaning of the invention are silver protectants. These are a variety of mostly cyclic organic compounds, which are also familiar to the person skilled in the art and contribute to prevent the tarnishing of silver-containing objects in the cleaning process. Specific examples may 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 may also contain so-called. Soil repellents, ie polymers which are based on fibers or hard surfaces (for example on porcelain and glass), positively influence the oil and Fettauswaschbarkeit from textiles and thus specifically counteract re-soiling. This effect becomes particularly evident when a textile or a hard object (porcelain, glass) is contaminated which has been washed, rinsed or cleaned several times in advance with a detergent, dishwashing or cleaning agent according to the invention containing this oil and fat-dissolving component has been. Examples of preferred oil and fat dissolving components include nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a methoxy group content of 15 to 30% by weight and of hydroxypropoxy groups of 1 to 15% by weight, based in each case on the nonionic Cellulose ethers, as well as known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these compounds are the sulfonated derivatives of the phthalic and terephthalic acid polymers.

All of these additives are added to the inventive detergent, detergent or cleaner portions in amounts of at most 30 wt .-%, preferably 2 to 20 wt .-%. As already stated, the addition can also be made to a material of a water-soluble enclosure comprising the or one of the wash-active, rinse-active or cleaning-active preparation (s). To obtain the balance of the recipe, it is therefore possible for the skilled person to increase the plastic material for the enclosure either in its weight so as to achieve the depot effect of the invention is achieved exploit, or in addition at least partially in additives the remaining detergent-active, rinse-active or cleaning active preparation to keep. However, this is less preferred.

Fragrances are added to the detergent, detergent or cleaner portions according to the invention in order to improve the aesthetic overall impression of the products and to provide the consumer in addition to the technical performance (fabric softening result, rinse aid result) a sensory typical and distinctive product. As perfume oils or perfumes, individual perfume compounds can be used, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-t-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. The ethers include, for example, benzyl ethyl ether. The aldehydes include, for. B. linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, purple and bourgeonal.

The ketones include the ionone, α-isomethylionone, and methyl cedryl ketone. The alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons mainly include terpenes such as limonene and pinene. Preference is given to using mixtures of different odoriferous substances which are adapted to one another in such a way that together they produce an attractive fragrance note. Such perfume oils may also contain natural fragrance mixtures as are available 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, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroliol, orange peel oil and sandalwood oil.

Typically, the content of fragrances in the range up to 2 wt .-% of the total detergent or cleaning agent portion.

The fragrances can be incorporated directly into the detergent preparations; but it may also be advantageous to apply the fragrances on carriers that enhance the adhesion of the perfume on the laundry and provide by a slower release of fragrance for long-lasting fragrance of the textiles. As such carrier materials, for example, cyclodextrins have been proven. The cyclodextrin-perfume complexes can additionally be coated with other auxiliaries.

The perfumes and fragrances can in principle be contained in each of the partial portions (wash-active, rinse-active or cleansing-active preparations) of the detergent, dishwashing or cleaning agent portions according to the invention. However, it is particularly preferred that they in a detergent in a provided for Nachwaschgang or rinse cycle or rinse cycle or rinse cycle part-detergent portion, partial detergent portion or partial detergent portion or in a detergent, especially in a dishwashing detergent, in a part-detergent portion or partial-detergent portion provided for the final rinse or rinse cycle. she must therefore according to the invention of a water-insoluble only in the conditions (especially at the temperature) of the Nachwaschgangs or Nachspülgangs, at the conditions (especially at the temperature) of the previous washes or rinses water-insoluble material, in particular of a corresponding film or capsule or a corresponding Coating to be wrapped. According to the invention this is feasible, for example, with a bag consisting of several chambers made of films of different water solubility.

For controlling microorganisms, the detergent, detergent or cleaner portions according to the invention may contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate. The terms antimicrobial action and antimicrobial agent have the usual meaning in the context of the teaching of the invention, the example of KH Wallhäusser in "Practice of Sterilization, Disinfection - Conservation: Germ Identification - Plant Hygiene" (5th edition - Stuttgart, New York: Thieme, 1995 ), wherein all the substances described there can be used with antimicrobial activity. Suitable antimicrobial agents 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-butylcarbamate, iodine, iodophores, peroxo compounds, halogen compounds and any mixtures of the above compounds or connection groups.

The antimicrobial active ingredient may 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, Glycerine, undecylenic acid, benzoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N-methylmorpholineacetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-methylenebis (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-octanamine) dihydrochloride, N, N'-bis (4-chlorophenyl) -3, 12-diimino-2,4,11,13-tetra-azatetradecandiimidamide, glucoprotamines, antimicrobial surface-active quaternary compounds, guanidines including the bi- and polyguanidines such as 1,6-bis- (2-ethylhexyl-biguanido-hexane) -dihydrochl orid, 1,6-di- (N ₁ , N ₁ '-phenyldiguanido-N ₅ , N ₅ ' -) hexane-tetrahydrochloride, 1,6-di- (N ₁ , N ₁ '-phenyl-N ₁ , N _1- methyldiguanido-N ₅ , N ₅ '-) hexane-dihydrochloride, 1,6-di- (N ₁ , N ₁ ' -o-chlorophenyl-diguanido- N ₅ , N ₅ '-) hexane-dihydrochloride, 1,6- Di- (N ₁ , N ₁ '-2,6-dichlorophenyldiguanido-N ₅ , N ₅ ' -) hexane dihydrochloride, 1,6-di- [N ₁ , N ₁ '-beta (p-methoxyphenyl) diguanido-N ₅ , N ₅ '-] hexane dihydrochloride, 1,6-di- (N ₁ , N ₁ ' -alpha-methyl-beta-phenyldiguanido-N ₅ , N ₅ '-) hexane dihydrochloride, 1, 6-di- (N ₁ , N ₁ '-p-nitrophenyl-diguanido-N ₅ , N ₅ ' -) hexane-dihydrochloride, omega: omega-di- (N ₁ , N ₁ '-phenyl-diguanido-N ₅ , N ₅ ' -) di-n-propyl ether dihydrochloride, omega: omega'-di- (N ₁ , N ₁ '-p-chlorophenyldiguanido-N ₅ , N ₅ ' -) di-n-propyl ether tetrahydrochloride, 1,6-di - (N ₁ , N ₁ '-2,4-dichlorophenyldiguanido-N ₅ , N ₅ ' -) hexane-tetrahydrochloride, 1,6-di- (N ₁ , N ₁ '-p-methylphenyl-diguanido- N ₅ , N ₅ '-) hexane dihydrochloride, 1,6-di- (N ₁ , N ₁ ' -2,4,5-trichlorophenyldiguanido-N ₅ , N ₅ '-) hexane-tetrahydrochloro oride, 1,6-di- [N ₁ , N ₁ '-alpha (p-chlorophenyl) ethyldiguanido-N ₅ , N ₅ ' -] hexane dihydrochloride, omega: omega-di- (N ₁ , N ₁ ' -p-chlorophenyldiguanido-N ₅ , N ₅ '-) m-xylene dihydrochloride, 1,12-di- (N ₁ , N ₁ ' -p-chlorophenyldiguanido-N ₅ , N ₅ '-) dodecane dihydrochloride, 1 , 10-di- (N ₁ , N ₁ '-phenyl-diguanido- N ₅ , N ₅ ' -) decane-tetrahydro-chloride, 1,12-di- (N ₁ , N ₁ '-phenyl-diguanido- N ₅ , N ₅ ' - ) dodecane tetrahydrochloride, 1,6-di- (N ₁ , N ₁ '-o-chlorophenyl-diguanido- N ₅ , N ₅ ' -) hexane-dihydrochloride, 1,6-di- (N ₁ , N ₁ '-o -chlorophenyl-diguanido-Nido-N ₅ , N ₅ '-) hexane-tetrahydrochloride, ethylenebis- (1-tolylbiguanide), ethylenebis (p-tolylbiguanide), ethylenebis (3,5-dimethylphenylbiguanide), ethylenebis (p-tert-butyl) amylphenyl biguanide), ethylenebis (nonylphenyl biguanide), ethylenebis (phenylbiguanide), ethylenebis (N-butylphenyl biguanide), ethylenebis (2,5-diethoxyphenyl biguanide), ethylenebis (2,4-dimethylphenyl biguanide), ethylenebis (o-diphenyl biguanide) , Ethylenebis (mixed amyl naphthylbiguanide), N-butyl-ethylenebis (phenyl biguanide), trimethylenebis (o-tolylbiguanide), N-butyl-trimethylenebis (phenylbiguanide) and the corresponding salts such as acetates, gluconates, hydrochlorides, hydrobromides, citrates, bisulphites, fluorides, polymaleates, N-cocoalkyl sarcosinates, phosphites, hypophosphites, perfluorooctanoates, Silicates, sorbates, salicylates, maleates, tartrates, fumarates, ethylenediaminetetraacetates, iminodiacetates, cinnamates, thiocyanates, arginates, pyromellitates, tetracarboxybutyrates, benzoates, glutarates, monofluorophosphates, perfluoropropionates and any mixtures thereof. Also suitable are halogenated xyioi and cresol derivatives, such as p-chloromethacresol or p-chloro-meta-xylene, and natural antimicrobial active ingredients of plant origin (for example from spices or herbs), of animal and microbial origin. Preferably, antimicrobial surface-active quaternary compounds, a natural antimicrobial agent of plant origin and / or a natural antimicrobial agent of animal origin, most preferably at least one natural antimicrobial agent of plant origin from the group comprising caffeine, theobromine and theophylline and essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial agent 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 Arsoniumgruppe, peroxo compounds and chlorine compounds are used. Also substances of microbial Origin, so-called bacteriocins, can be used.

The suitable as antimicrobial agents quaternary ammonium compounds (QAV) have the general formula (R ¹ ) (R ² ) (R ³ ) (R ⁴ ) N ⁺ X-, in the R ¹ to R ⁴ identical or different C ₁ - to C ₂₂ -alkyl radicals, C ₇ - to C ₂₈ -aralkyl radicals or heterocyclic radicals, where two or, in the case of an aromatic incorporation as in pyridine, even three radicals together with the nitrogen atom form the heterocycle, for example a pyridinium or imidazolinium compound and X- are halide ions, sulfate ions, hydroxide ions or like anions. For optimum antimicrobial activity, at least one of the radicals preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.

QACs are prepared by reacting tertiary amines with alkylating agents, e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethyl enoxide 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 radicals and one methyl group can 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 less reactive and are preferably quaternized with dimethyl sulfate.

Suitable QAVs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B ( m, p -dichlorobenzyldimethyl-C 12 -alkylammonium chloride, CAS No. 58390-78-6), benzoxonium chloride (Benzyl-dodecyl-bis (2-hydroxyethyl) ammonium chloride), cetrimonium 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] benzyl ammonium chloride, CAS No. 121-54-0), dialkyl dimethyl such as di- n -decyldimethylammoniumchlorid ( CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyldimethylammonium chloride, 1-cetylpyridinium chloride (CAS No. 123-03-5) and thiazolinium iodide (CAS No. 15764-48-1 ) and their mixtures. Particularly preferred QACs are the benzalkonium chlorides having C ₈ - to C ₁₈ -alkyl radicals, in particular C ₁₂ - to C ₁₄ -alkylbenzyldimethylammonium chloride.

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

The antimicrobial agents are in detergent, detergent or detergent portions according to the invention in amounts of 0.0001 wt .-% to 1 wt .-%, preferably from 0.001 wt .-% to 0.8 wt .-%, 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 optionally also more than two, wash-active, rinse-active or cleaning-active components or preparations, for example those according to the above detailed description, which release into the liquor at different times should be. For example, in the case of a washing agent portion according to the invention, these may be washing-active preparations or components for the pre-wash of a washing process on the one hand and for the main wash of a washing process on the other hand or wash-active components or preparations for the main wash of a washing process on the one hand and for the post-wash cycle of a washing process on the other hand. It is preferred that the respective gears are aisles of a washing process in a washing machine. In a rinsing agent according to the invention - to give a further preferred example of the invention - the at least two components can be rinse-active components or preparations for the pre-rinse and main rinse or for the main rinse and rinsing a rinse, preferably in a dishwasher.

The detergents, dishwashing or cleaning agent portions according to the invention having two or more washing, rinsing or cleaning-active components, of which at least two are to be released into the liquor at different times of a washing, rinsing or cleaning process, comprise at least one Release controlling (physico) chemical switch, which is not or not exclusively subject to the temperature control, but is activated by the action of enzymes.

For the purposes of the present invention, in the most general embodiment, the term "(physico-) chemical switch" means that the detergent, detergent or cleaning agent portion is blocked by means of suitable components comprised by it, due to one or more changes. in the surrounding wash liquor, wash liquor or cleaning liquor, which can be controlled according to the circumstances or the desired results according to the user / can, for example, the washing, rinsing or cleaning program of a machine can be controlled accordingly, can be brought to to release at least two washing-active, rinse-active or cleaning-active components contained in it at different times or during different periods of the washing, rinsing or cleaning process into the respective liquor.

In preferred embodiments of the invention, such components may be structural, for example Be components. By this is meant that the structural configuration of the detergent portion, detergent portion or detergent portion is designed so that release of one or more detergent, rinse active or detergent active component (s) of the respective portion is independent of one or more others detergent-active, rinse-active or cleaning-active component (s) of the respective portion in the wash liquor, wash liquor or cleaning liquor can be done. In a preferred embodiment of the detergent, rinse or detergent portions of the invention, this structural design may be a layered or sliced construction, in which - just to name one of many conceivable and practically usable examples, without limiting the invention thereto - One or more detergent-active, rinse-active or cleaning-active component (s) of a detergent, detergent or cleaning agent portion to be released later into the liquor (s) is contained in one or more layers of a present in the form of a molded portion / are only later exposed to the entry of an aqueous liquor than one or more other wash-active, rinse-active or cleaning-active component (s) of a detergent, detergent or cleaner portion which is already at an earlier point in time of washing, Flushing or cleaning process to be released into the fleet (en ). To the structural components, for example, a structure can be counted in the particles of individual (or more) washing active, flushing or cleaning active components or aggregates of such particles that are released at a late time of a washing, rinsing or cleaning process in the fleet , 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 can be counted among the structural components of a structure in which one or more later released into the respective fleet component (s) are surrounded by a poorly or only under certain conditions water-soluble coating, one or more earlier released into the respective fleet Component (s), however, or in which one or more components to be released into the liquor at a later stage of the washing, rinsing or cleaning operation are more dense to an agglomerate of particles or one or more layers thereof are compressed into a denser body or layer (s) thereof as one or more other component (s) of a detergent, rinse or detergent portion to be released into the liquor at an earlier 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 one or more release (s) controlling the release of at least one detergent-active, rinse-active or cleaning-active component is / are a (physico-chemical) switch or a plurality of structural or substantial component (s) of the detergent, rinse or detergent portion. This is understood to mean that the detergent portion, detergent portion or detergent portion contains as component at least one substance which, in response to changes in the environment of the detergent, detergent or cleaning agent portion, for example, changes in certain properties of the wash liquor, Rinsing liquor or cleaning liquor - this may, for example, the electrolyte concentration or the H ⁺ ion concentration (ie the pH) or the concentration of one or more other components such as the concentration of enzymes fall - a release of one or more active washing, rinse or detergent-active component (s) in the wash liquor, wash liquor or cleaning liquor prevented or delayed while one or more other component (s) of the respective detergent, detergent or cleaning agent portion or partial portion was released into the liquor (s). The substantive component (s) preventing or delaying release may themselves be non-detergent, non-rinse or non-detergent active substances; however, it is in accordance with a preferred embodiment of the detergent, rinse or detergent portion of the invention that one or more of such substantive component (s) preventing or delaying release is itself a wash-active, rinse-active or cleaning-active component (s) are.

Of course, combinations of the aforementioned preferred embodiments of the invention are possible. Thus, the (s) (physic) chemical switch (s) controlling the release of at least one detergent-active, rinse-active or detergent-active component may comprise one or more structural component (s) or one or more substantive component (s) or even a combination one or more structural component (s) with one or more substantial component (s) of the detergent, rinse or detergent portion.

In the detergent portions, detergent portions or detergent portions of the invention, the release (s) of at least one detergent active, dishwashing or cleaning active component controlling (n) (physic) chemical switch (s) is / are one or more component (s) ) experiencing a change in the physical and / or chemical properties upon the action of one or more enzymes from the washing, rinsing or cleaning liquor. In the context of the present invention, therefore, a (physico-) chemical switch is used, which causes an enzyme-controlled drug release. In the case of, for example, detergents or dishwashing detergents for use in washing machines or dishwashers, the difference in the enzyme content of the liquor, for example, the cleaning cycle and the rinse cycle can be exploited. The enzyme (s) may contain one or more per se contained in the detergent, detergent or detergent portion (s) Enzyme (s) which develop / develop therein a washing active, rinse active or cleaning active effect, or the enzyme (s) can be one or more enzyme (s), the detergent, rinse or cleaning agent -Portion or the respective application liquor can be added at a time that allows a targeted release of the release at a desired time component (s), for example, at a time that is so far before the desired time of release of the later release component (s) in that the enzyme action can cause the release at the desired time. During the preparation, the activity of the enzyme (s) acting on the detergent, rinse or detergent (partial) portion as well as its optimum exposure temperature, the appropriate pH, the optimal electrolyte concentration in the Fleet and so on.

In an advantageously applicable and therefore preferred embodiment of the detergent, detergent or cleaner portions according to the invention, one or more enzyme-sensitive material (s), ie material (s) degradable by enzymes, will become either a carrier or a material (ien) for coating particles of, moldings or capsules for ingredients of detergent, rinse or detergent portions to be released in a washing, rinsing or cleaning process at a time or during a period of time, to or during which other components are already in the liquor or have already been used in a previous cycle of the washing process, rinsing process or cleaning process and / or have already been withdrawn after use with the application liquor. After a certain, depending on the enzyme activity and other parameters (temperature, pH, electrolyte concentration, etc.) exposure time of the / the enzyme (s) there is a degradation of the enzyme-sensitive carrier material / the enzyme-sensitive carrier materials and concomitantly a release of the wash-active, rinse-active or cleaning-active component (s) embedded in the support material (s), in which the coated particle (s) or in the molding (s) is / are contained or in the coated capsule (s) is / are included.

Suitable enzymes for the (physicochemical) chemical switches in the detergent, detergent or cleaner portions according to the invention are, in particularly preferred embodiments, proteases, amylases, cellulases and / or lipases, but without limiting 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 detergent portions according to the invention. Suitable enzyme-sensitive substances are celluloses and their derivatives, starches and their derivatives, partially oxidized starch derivatives, glycerides, proteins and mixtures thereof and are used with advantage.

Detergent detergent or cleaner portions are particularly preferred with one or more enzyme-sensitive switch (s) in which the action of cellulases on cellulose (derivatives), amylases on starch (derivatives) or proteinases on e.g. Gelatin (derivatives) causes the release of at least one washing, rinsing or cleaning active component.

In a particularly preferred embodiment of the invention, the detergent portions, detergent portions or detergent portions thus comprise those (physico-) chemical switches which undergo a change in the physico-chemical properties when one or more enzymes from the application liquor act. In particular, it is preferred that such substances be used as (physico-) chemical switches that experience a change in solubility due to an enzyme action occurring in the application liquor, even more preferably have an increased solubility in water. Alternatively or additionally, those switch substances are preferred which, as a result of an enzyme action occurring in the application liquor, undergo a change, in particular a decrease, the diffusion density and / or experience a change, particularly preferably an acceleration, the dissolution kinetics and / or a change, particularly preferably a decrease who experience mechanical stability.

The enzyme-sensitive switches according to the invention and used according to the invention can be used for all applications, in particular in the washing, rinsing or cleaning agent sector, in which an active substance is to be released in the presence of one or more enzymes. This may be the case both in the washing machine washing and in the automatic dishwashing. In particular, according to the invention, detergent portions are included in which components of a dishwashing detergent formulation for machine dishwashing (eg surfactants, perfume, soil repellant, acid, complexing agents, builders, etc., or preparations containing these active ingredients) with the polymer according to the invention be formulated so that these components are not released into the rinse liquor in the main rinse in the absence of suitable enzymes, but in the subsequent rinse in the presence (and after sufficiently long exposure) of enzymes in whose presence the polymer becomes water-soluble, are released.

The polymer which is soluble on exposure to one or more enzymes can be used both as coating material and as matrix material, binder or disintegrant for the component (s) to be released at a later time or over a later period. It is not necessary for the polymer to completely dissolve at the conditions inherent in the polymer (type of enzyme (s), pH, temperature, electrolyte concentration) to release the active ingredient. Rather, it is sufficient if, for example, the permeability of a Polymer film changes and, for example, the penetration of water into the drug formulation and a removal of the dissolved components is made possible through the holes or pores formed. As a result, in a further preferred embodiment of the detergent, detergent or cleaner portions according to the invention, a secondary effect, for example the activation of an effervescent system or the swelling of a water-swellable disintegrant, which are known in particular from pharmacy, for the complete release of the / wash-active, rinse-active or active cleaning agents (s) provide.

In a further embodiment, the invention provides that the detergent, detergent or cleaning agent portion according to the invention contains at least two switches, of which at most one is subject to temperature control. By using two or more switches, it is 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 active ingredient or a combination of such active ingredients. On the other hand, it is also conceivable that two differently acting switches cause the controlled release of two or more different different washing active, rinse active or cleaning active ingredients or combinations of different active ingredients at different times or in different periods of the washing, rinsing or cleaning process.

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

In a very particularly preferred embodiment of the invention, one of the abovementioned (physico-) chemical switches, for example an enzyme-sensitive switch, is combined with a switch which is subject to temperature control. In particular, so-called inverse temperature switches, which can be realized by so-called LCST substances, are preferred. LCST substances are substances that have better solubility at low temperatures than at higher temperatures. They are also referred to as low critical solubility temperature or low low turbidity or flocculation point substances. Depending on the conditions of use, the lower critical demixing 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, in particular between 30 ° C and 50 ° C. The LCST substances are preferably selected from alkylated and / or hydroxyalkylated polysaccharides, cellulose ethers, polyisopropylacrylamide, copolymers of polyisopropylacrylamide and mixtures of one or more of these substances.

Examples of alkylated and / or hydroxyalkylated polysaccharides are hydroxypropylmethylcellulose (HPMC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropylcellulose (HPC), methylcellulose (MC), ethylcellulose (EC), carboxymethylcellulose (CMC), carboxymethylmethylcellulose (CMMC), Hydroxybutylcellulose (HBC), hydroxybutylmethylcellulose (HBMC), hydroxyethylcellulose (HEC), hydroxyethylcarboxymethylcellulose (HECMC), hydroxyethylethylcellulose (HEEC), hydroxypropylcellulose (HPC), hydroxypropylcarboxymethylcellulose (HPCMC), hydroxyethylmethylcellulose (HEMC), methylhydroxyethylcellulose (MHEC), methylhydroxyethylpropylcellulose (MHEPC) and Propyl cellulose (PC).

Further examples of LCST substances are cellulose ethers and mixtures of cellulose ethers with carboxymethylcellulose (CMC). Other polymers which exhibit a lower critical demixing temperature in water and which are also suitable are polymers of mono- or di-N-substituted acrylamides with acrylates and / or acrylic acids or mixtures of intertwined networks of the above-mentioned (co-) polymers. Also suitable are polyethylene 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 methyl ether, certain proteins such as poly (VATGVV), a repeating unit of the natural protein elastin and certain alginates. Mixtures of these polymers with salts or surfactants can also be used as the LCST substance. By such additions or by the degree of crosslinking of the polymers, the lower critical separation temperature (LCST) can be modified

In a further preferred embodiment of the detergent, dishwashing or cleaning agent portions according to the invention, an enzyme-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 may also contain other switches. In question are, for example, switches which can control a controlled by the electrolyte concentration, particularly preferably controlled by the pH in the application fleet release washing-active, flushing or cleaning active ingredients at least two different times or during at least two different periods. Such switches for an electrolyte-controlled or by the pH in the application fleet controlled drug release are described in the co-pending patent application entitled "Detergent, Detergent or Detergent Portion with Controlled Drug Release". Such electrolyte-controlled switches may be used in combination with the enzyme-sensitive switches of the detergent, rinse or detergent portions of the present invention.

In a further preferred embodiment of the invention, so-called pH-shift boosters are used in addition to the abovementioned pH-shift-sensitive switches. This can be prevented, at least to a large extent, that after the rinse cycle residues, which in particular consist of the pH-dependent soluble polymer substance itself, are found in the application liquor.

For the purposes of this invention, suitable pH-shift boosters are all substances and formulations which are capable of controlling the extent of the shift in the pH (of the pH shift) either locally, i. in the immediate vicinity of the respectively used, for a shift of the pH-sensitive substance, or generalized, i. in the entire rinsing, to enlarge. 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 acidic salts, in particular at least one substance from the group of alkylbenzenesulfonic acids, alkylsulfuric acids, citric acid, oxalic acid and / or alkali metal hydrogen sulfates. The above-mentioned substances may be used alone or in a combination of two or more of them.

The optionally additionally usable pH-shift booster can be incorporated into the washing, rinsing or cleaning agent. In a further embodiment of the invention, it is also possible to supply the pH-shift booster either after the end of the main wash or main rinsing or at the beginning of Nachwasch- or rinse cycle from the outside, for example, in the corresponding hopper or the corresponding dosing of the Machine or by a special delivery system (by coating with a slowly dissolving coating agent) or by diffusion of a matrix material or wrapping material in connection with a molded body or its sheath release.

In a further preferred embodiment of the invention, a pH-shift-sensitive switch, preferably in combination with a pH-shift booster, is combined with an enzyme-sensitive switch.

With particular advantage, both a pH-shift-sensitive switch, preferably in combination with a pH-shift booster, as well as an enzyme-sensitive switch and an LCST substance can be used.

Other switches besides electrolyte-sensitive or pH-shift-sensitive switches and redox switch in question, ie those switches, with the help of the release of washing active, rinse active or cleaning active ingredients at least two different times or during at least two different periods in Under a redox reaction can be effected. Such redox-sensitive switches are described in the co-pending patent application entitled "Detergent, Detergent or Detergent Portion with Redox Controlled Drug Release". As redox-sensitive materials in particularly preferred embodiments of the invention are oxidation-sensitive organic and inorganic substances and polymers in question. An example of a redox-sensitive material is polyvinylpyridine. As the oxidizing agent can be used, for example, a percarbonate, the latter in particular in combination with a bleach activator such. TAED. Such redox-responsive switches may be used in combination with the enzyme-sensitive switches of the detergent, rinse, or detergent portions of the present invention.

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 to use all three switches, that is to say an enzyme-sensitive switch, a redox-sensitive and / or pH-shift-sensitive switch and a switch under temperature control, for example an LCST substance, in particular in combination with a pH shift. Booster, use.

A further preferred embodiment of the invention provides for combining a redox-sensitive switch with an enzyme-sensitive switch. In addition, this combination may again comprise 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, dishwashing or cleaning agent portion according to the invention contains an enzyme-sensitive switch and one or more of the aforementioned pH-shift-sensitive switches, optionally in combination with a pH-shift booster Electrolyte-sensitive switch, a redox-sensitive switch and an LCST substance.

In a preferred embodiment of the invention, the detergent, dishwashing or cleaning agent portions according to the invention are present in solid form, for example as powder, granulate, agglomerate, pellet, roll compact and / or extrudate. However, particularly preferred is the embodiment of a detergent, detergent or detergent portion representing shaped body, wherein one or more moldings can be used per application in a washing, rinsing or cleaning process / can. The embodiment is particularly advantageous as a tablet or as a capsule. It is possible that also one or more tablet (s) and / or one or more capsule (s), optionally together with powder, granules, agglomerates, pellets, Walzenkompaktaten and / or Extrudates are used. Advantageously, two or more moldings or the mentioned mixtures of different embodiments are offered in a wrapper such as a pouch or in a foil which is either opened prior to use so that the detergent, rinse or detergent portion in the dosing chamber of the washing machine or the dishwasher can be introduced, or which is / are water-soluble, so that he / she can be introduced together with the washing active, rinse-active or cleaning-active preparation into the machine without after washing, Rinsing or cleaning process remains of which remain. In this case, a metering via the metering chamber is also possible, as well as via 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 surface, which may have rounded corners and edges. These may be single-layered white or colored tablets which preferably have differently colored speckles, but may also be multi-layered, 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-layered or multi-layered shaped bodies and in particular tablets have at least one cavity. This cavity can be designed so that it extends from the upper surface to the lower base surface and thus the shaped body forms a ring around a cavity. In a further preferred embodiment of the invention, the cavity is designed so that it does not extend from the upper surface to the lower base, but merely forms a trough, which may be formed either only over a layer or over several layers of the tablet. In particular, such wells have a round, oval or rectangular to cuboid base.

In a particularly preferred embodiment of the invention, the cavity, and preferably the well, contains part of the total composition of the composition. In this case, this part of the overall composition can fill a part of the cavity or the trough or the entire cavity or trough. In a preferred embodiment of the invention, one or more elevated-temperature mixture (s), which may comprise washing-active, rinse-active or cleaning-active components in addition to carriers and excipients, for example in the form of a melt, placed in the cavity or trough. The melt solidifies on cooling.

Alternatively, it is also possible to produce the Kavitäts- or depression filling separately and then insert into the cavity or trough. The cavity or trough filling can then be solid, for example by gluing, or loose in the cavity or trough, for example in the form of a plug connection. The separately produced cavity or trough filling can be produced in various ways. Preferred methods include the production of a non-pressed molding, in particular a solidified melt body, or a compressed body. In particular, the separately produced packing can assume a different form than by the cavity or trough predetermined form. Thus, for example, it is possible for the trough to be a semicircular opening in a tablet and the filling to be in spherical form, but the latter possibly having 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 shaped body including the cavity or trough filling has a plane or nearly planar surface.

A further embodiment of the invention provides that the cavity is internal and their filling is not visible from the outside. The actual molded body and in particular the actual tablet thus represent a jacket which completely encloses the particular filled cavity. The cavity filling can in turn be prepared in the manner already described either separately as a fused body or compact and then potted or pressed to the final molded body, or the cavity filling is brought in the form of a melt in a pre-compressed molded body, and this is then pressed to the final molded body.

In a particularly preferred embodiment, the invention provides that the cavity or well filling contains at least one switch for the controlled release of active ingredient, which is not or not alone subject to Temperatursteue- tion.

In a further embodiment of the invention, the shaped body is present as a capsule. If only parts of the total composition are encapsulated, then it is possible that said switch systems are incorporated into the capsule shell. For bags is analogous.

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

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

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

In a preferred embodiment of the present invention, the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.

A particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called "narrow range ethoxylates" are particularly preferred.

Particular preference is given to C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols having more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol of alcohol.

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more 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 Kemformkörper as an ingredient contains ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total Make up the molecular weight of the nonionic surfactant.

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

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 is} 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 represents values between 0.5 and 1.5 and y is a value of at least 15.

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

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

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl radical, ethyl radical, n-propyl radical, isopropyl, n X is butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x = 2, each R ³ in the above formula may be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

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

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

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

simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

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

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

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, 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 is 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 well fillings are used which comprise a nonionic surfactant or surfactant mixture having a clear rinse effect in amounts of from 20 to 50% by weight, one or more (physicochemical) chemical switches, optionally in combination with a Temperature-sensitive switch in amounts of 40 to 70 wt .-% and optionally a pH-shift booster in amounts of 2 to 15 wt .-%, in particular in amounts to 10 wt .-%, containing the wt. -% - refer to the fillings.

Otherwise, the particular solid detergent, detergent or detergent portions may contain conventional ingredients in conventional amounts. Reference is made to the relevant literature and the above detailed description. In particular, it is preferred to provide the detergent, detergent or cleaner portions according to the invention with a conventional effervescent system, for example of carbonate and citric acid, it being particularly preferred that the cavity or trough filling additionally has such an effervescent system. This effervescent system can be activated by changing the water permeability of the coating with the material of the (physico-) chemical switch as a result of the change of the respectively relevant parameter during the washing, rinsing or cleaning cycle. As an alternative to an effervescent system, it is also possible to use a disintegrating agent known, for example, from pharmacy or from detergent technology.

For use in laundry detergents with a release at a certain point in the washing process, e.g. in the rinse cycles, come into consideration:

Conditioning components, enzymes, alkalis, acids, fragrances, dyes, fluorescers, optical brighteners, anti-shrinkage agents, anti-wrinkling agents, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing auxiliaries, repellents and impregnating agents, UV absorbers and any mixtures of the abovementioned detergent components.

In particular, the present invention can be used with solid automatic dishwashing agents to transport active ingredients throughout the main rinse cycle into the rinse cycle. Here, a formulation which contains, for example, rinse aid surfactant or also other of the active ingredients listed above, with one or more enzyme-sensitive material (s) and / or one or more other than (physico) chemical (s) suitable switch, above in individual described material (s) coated or in a matrix of one or more enzyme-sensitive material (s) and / or from one or more, as (physical) chemical (s) suitable switch, in detail described above material (ien ) incorporated. This formulation is then formulated together with the customary rinse-active component (s), for example, added to a powder cleaner or combined with a molding. It is, as with the enzyme-sensitive switch, not essential that the enzyme-sensitive material at the appropriate conditions in the rinse cycle to release the active ingredient flushing completely dissolves. Rather, it is sufficient if the permeability of the enzyme-sensitive film or the corresponding matrix changes and, for example, the penetration of water into the active ingredient formulation is made possible. This can provide a secondary effect, eg the activation of a effervescent system for the complete release of the active ingredient.

In a particularly preferred embodiment of the invention, detergent, dishwashing detergent or detergent preparations having a plurality of wash-active, rinse-active or detergent-active components are provided, in which components to be liberated in the respective liquor, for example rinse aid surfactants, acids in a later stage of the washing process, rinsing process or cleaning process (such as citric acid), fragrances, soil repellents, enzymes, catalysts, bleach, etc. in automatic dishwashing compositions - in bulk or in a capsule - provided with an enzyme-sensitive coating, using an enzyme-sensitive Binder be formulated into a wash-active, rinse active or cleaning active preparation or formulated using an enzyme-sensitive matrix material to a washing active, rinse active or cleaning active preparation. The coated or preformed product thus obtained also contains other customary detergent-active, rinse-active or detergent-active components of detergent, detergent or cleaner portions, as described in detail above.

The said materials can be used not only as a coating for detergent-active, rinse-active or cleaning-active preparations in capsules or in the form of moldings (granules, tablets, etc.), but also for fixing in recesses of moldings (for example Muldentabs , Ring tabs etc.) or in bags of water-soluble polymers, together with other components of washing-active, dishwashing or cleaning-active preparations.

The invention also relates to a process for the preparation of the detergent, detergent or cleaning agent portions described above in detail, preferably those with two or more washing, rinsing or cleaning-active components, of which at least two at different times or in two different periods a washing, rinsing or cleaning process to be released into the fleet. According to the invention, the washing-active, rinse-active or cleaning-active component (s) to be liberated into the liquor at a later time of the washing, rinsing or cleaning process are packaged with a release which controls the release on the basis of enzyme action ( physico-) chemical switch, and processes the thus prepared wash-active, rinse-active or cleaning-active component (s) with one or more other washing-active, rinse-active or cleaning-active component (s) to form a detergent , Detergent or detergent portion.

In a preferred method according to the invention, the release of at least one detergent-active, rinse-active or detergent-active component by enzyme-controlling (physico-chemical) switch (s) is selected as one or more structural or substantial component (s) Detergent, detergent or detergent portion. Suitable structural or substantial components of the detergent, rinse or detergent portion are described in detail above.

1. (a) eine Änderung der Löslichkeit in Wasser erfährt/erfahren; und/oder
2. (b) eine Änderung der Diffusionsdichte erfährt/erfahren; und/oder
3. (c) eine Änderung der Lösungskinetik erfährt/erfahren; und/oder
4. (d) eine Änderung der mechanischen Stabilität erfährt/erfahren.

In a procedure that can be used with particular advantage, one or more substances are selected as the (physico-) chemical switch, which is the result of the action of one or more enzymes from the wash liquor, washing liquor or cleaning liquor

1. (a) undergoes a change in solubility in water; and or
2. (b) undergoes a change in diffusion density; and or
3. (c) undergoes a change in the rate of dissolution; and or
4. (d) experiences a change in mechanical stability.

1. (a) eine Erhöhung der Löslichkeit in Wasser erfährt/erfahren; und/oder
2. (b) eine Abnahme der Diffusionsdichte erfährt/erfahren; und/oder
3. (c) eine Beschleunigung der Lösungskinetik erfährt/erfahren; und/oder
4. (d) eine Abnahme der mechanischen Stabilität erfährt/erfahren.

In with particular advantage and therefore preferably usable procedures of the invention, an enzyme-controlled action on the release of one or more washing active, rinse active or cleaning active component (s) of detergent detergent or detergent portion in which the enzyme-sensitive component (n )

1. (a) experiences an increase in solubility in water; and or
2. (b) experiences a decrease in diffusion density; and or
3. (c) experiences an acceleration of the solution kinetics; and or
4. (d) experiences a decrease in mechanical stability.

As already described above, one or more substances from the group of celluloses and their derivatives, starches and their derivatives, partially oxidized starch derivatives, glyceride proteins and mixtures thereof in combination with one or more enzymes from the group are used as (physicochemical) switch Proteases, amylases, cellulases, lipases and mixtures thereof.

Finally, the invention also relates to a washing method, in particular washing method in a washing machine, wherein a detergent portion according to the above detailed description with laundry in contact brings, in particular in the Einspülkammer a commercial washing machine inserts and rinsed with water of the first wash cycle in the wash, performs the early steps of the washing process in a conventional manner and then sets conditions under which the release steuemde (n) (physiko-) chemical switch (s) which is not or not exclusively subject to temperature control, but is activated by enzyme action which releases / releases later into the wash liquor the component (s) to be liberated in the wash liquor.

The invention further relates to a rinsing method, in particular rinsing method in a dishwasher, wherein bringing a detergent portion according to the above detailed description with items in contact, in particular in the dispensing compartment of a commercial dishwasher inserts and rinsed with water of the first rinse in the rinse, the Performs early steps of the rinsing process in a conventional manner and then sets conditions under which the release the controlling (s) (physico-) chemical (s) switch, which / not or not exclusively subject to the temperature control / subject, but by enzyme action is activated / liberate / release the later liberated in the rinsing (s) component (s) in the rinse.

Finally, the invention relates to a cleaning method in which a detergent portion according to the above detailed description is brought into contact with items to be cleaned, which performs the early steps of the cleaning operation in a conventional manner and then sets conditions under which the release controlling (s) ( physico-) chemical switch (s) which is not or not exclusively subject to temperature control, but is activated by enzyme action which releases / liberates later into the cleaning liquor release component (s).

The invention is further illustrated by the following examples, but without being limited to these examples, which represent preferred embodiments of the invention.

Examples Examples 1 and 2

It (500 mg Poly Tergent SLF 18B45 ^®) manufactured tablets or capsules with an effective amount of rinse surfactant. Then the product by means of film coating with aminoalkyl methacrylate copolymer (Eudragit E ^®) was coated (Example 1).

According to the above example 1 coated moldings or capsules were prepared containing an effective amount of rinse surfactant (500 mg Poly Tergent SLF 18B45 ^®). Subsequently, these products were coated by film coating with the same aminoalkyl methacrylate copolymer as in Example 1 except that the coating material was admixed with amylose in an amount of 10% by weight dispersed as a fine powdery solid based on the whole coating material (Example 2).

The tablets or capsules thus prepared were combined with a commercial tableted automatic dishwashing detergent (Somat Professional ^®, Henkel KGaA) subjected to 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 rinsing agent-containing tablets or capsules were almost undissolved. After rinsing, the tablets or capsules were mostly dissolved, with the detectable residues predominantly consisting of coating material. A clear rinse effect on dishes could be detected.

After the cleaning cycle, the coated tablets or capsules of Example 2 were undissolved. At the sites where amylose-containing domains were present in the coating material, small holes were seen.

After the rinse, the tablets or capsules were completely dissolved. This was obviously achieved by the combination of the two control mechanisms.

Example 3

The tablets used in the Examples 1 and 2 or capsules with rinse surfactant (500 mg Poly Tergent SLF 18 B 45 ^®) were coated with an aqueous coating for the next from (a) methylcellulose (MC); (b) hydroxypropyl cellulose (HPC); (c) hydroxypropylmethylcellulose (HPMC); and (d) Hydroxyethylcellulo-se (HEC) (Tylose ^® products from the series of the company or from the Clarian "Klucel ^® series of the company Hercules) coated.

In the same manner as in Examples 1 and 2, the coated tablets or capsules were subjected to a cleaning program at 50 ° C. with a commercially available dishwashing detergent (Somat: ^Profi® , Henkel KGaA). The clear rinse effect was clearly visible and residues of the coating could no longer be found.

Example 4

The procedure was as in Example 3, with the difference that on the tablets or capsules with a Formaldehyde moderately crosslinked gelatin was applied from hot water as a coating. The gelatin coating was disintegrated by proteases after the cleaning cycle even at low temperatures (≤ 35 ° C). The rinse effect was clearly detectable; Residues of the coating were no longer observed after the rinse cycle.

Example 5

In the same manner as in Example 4 Tablets or gelatin capsules with a coating of a blend of a conventional film-forming agents have been (for example, of PVAL having a solubility in water> 60 ° C;., For example MOWIOL ^® grades from Hoechst) and amylose in an amount of 10 to 30 wt .-%, preferably 20 wt .-%, coated.

The tablets or capsules thus prepared were combined with a commercial tableted automatic dishwashing detergent (Somat Professional ^®, Henkel KGaA) subjected to 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 tablets or capsules were undissolved. Where the amylose-containing domains were present in the coating material, more or less large holes were seen at the locations where amylose-containing domains were present. After the rinse, the tablets or capsules were completely dissolved. It was a good rinse effect can be detected.

Claims (11)

1. Laundry, dishwash or cleaning product detergent portion having two or more detersive components of which at least two are to be released into the liquor at different points in time in a laundering, dishwashing or cleaning process, said portion comprising at least one release-controlling (physico)chemical switch which is not subject or not exclusively subject to temperature control, but is activated by exposure to one or more enzymes, wherein the laundry, dishwash or cleaning product detergent portion comprises as (physico)chemical switch(es) one or more substances from the group of celluloses and their derivatives in combination with one or more enzymes from the group of cellulases.
2. Detergent portion according to Claim 1, wherein the (physico)chemical switch(es) controlling the release of at least one detersive component is (are) one or more structural or substantive components of the detergent portion.
3. Detergent portion according to Claim 1 or Claim 2, comprising as (physico)chemical switch one or more substances which, when exposed to one or more enzymes from the detergent liquor,

   (a) undergo a change in solubility in water; and/or

   (b) undergo a change in diffusion density; and/or

   (c) undergo a change in dissolution kinetics; and/or

   (d) undergo a change in mechanical stability;

   preferably

   (a) undergo an increase in solubility in water; and/or

   (b) undergo a decrease in diffusion density; and/or

   (c) undergo an acceleration in dissolution kinetics; and/or

   (d) undergo a decrease in mechanical stability.
4. Detergent portion according to one or more of Claims 1 to 3, comprising at least two switches of which preferably not more than one is subject to temperature control.
5. Detergent portion according to one or more of Claims 1 to 4, comprising an enzyme-sensitive switch in combination with a switch subject to temperature control or an enzyme-sensitive switch and a pH shift-sensitive switch in combination with a switch subject to temperature control or an enzyme-sensitive switch and a redox-sensitive switch in combination with a switch subject to temperature control.
6. Process for producing a laundry, dishwash or cleaning product detergent portion having two or more detersive components of which at least two are to be released into the liquor at different points in time in a laundering, dishwashing or cleaning process, wherein the detersive component(s) for release into the liquor at a later point in time in the laundering, dishwashing or cleaning process is (are) compounded with a (physico)chemical switch which controls the release on the basis of enzyme exposure, and the detersive component(s) thus compounded is (are) processed with one or more other detersive components to give a laundry, dishwash or cleaning product detergent portion, wherein as (physico)chemical switch(es) is (are) used one or more substances from the group of celluloses and their derivatives in combination with one or more enzymes from the group of cellulases.
7. Process according to Claim 6, wherein the (physico)chemical switch(es) controlling the release of at least one detersive component is (are) chosen to comprise one or more structural or substantive components of a laundry, dishwash or cleaning product detergent portion.
8. Process according to Claim 6 or Claim 7, wherein the (physico)chemical switch(es) chosen comprise(s) one or more substances which, as a result of exposure to one or more enzymes from the detergent liquor

   (a) undergo a change in solubility in water; and/or

   (b) undergo a change in diffusion density; and/or

   (c) undergo a change in dissolution kinetics; and/or

   (d) undergo a change in mechanical stability;

   preferably

   (a) undergo an increase in solubility in water; and/or

   (b) undergo a decrease in diffusion density; and/or

   (c) undergo an acceleration in dissolution kinetics; and/or

   (d) undergo a decrease in mechanical stability.
9. Washing process, especially a washing process in a washing machine, wherein a laundry detergent portion according to any one of Claims 1 to 5 is brought into contact with laundry, being inserted in particular into the detergent compartment of a commercially customary washing machine, and is rinsed into the wash liquor with water of the first wash cycle, the early steps of the wash operation are conducted as normal and then conditions are established under which the release-controlling (physico)chemical switch(es) which is (are) not subject or not exclusively subject to temperature control, but is (are) activated by exposure to one or more enzymes, release(s) into the wash liquor the component(s) intended for later release into the wash liquor.
10. Washing process, especially a washing process in a machine dishwasher, wherein a dishwash detergent portion according to any one of Claims 1 to 5 is brought into contact with ware, being inserted in particular into the detergent compartment of a commercially customary machine dishwasher, and is rinsed into the wash liquor with water of the first wash cycle, the early steps of the wash operation are conducted as normal and then conditions are established under which the release-controlling (physico)chemical switch(es) which is (are) not subject or not exclusively subject to temperature control, but is (are) activated by exposure to one or more enzymes, release(s) into the wash liquor the component(s) intended for later release into the wash liquor.
11. Cleaning process, in which a cleaning product detergent portion according to any one of Claims 1 to 5 is brought into contact with material to be cleaned, the early steps of the cleaning operation are conducted as normal and then conditions are established under which the release-controlling (physico)chemical switch(es) which is (are) not subject or not exclusively subject to temperature control, but is (are) activated by exposure to one or more enzymes, release(s) into the cleaning liquor the component(s) intended for later release into the cleaning liquor.