WO2005093034A1

WO2005093034A1 - Multi-phase tablets with an improved sensation of fragrance

Info

Publication number: WO2005093034A1
Application number: PCT/EP2005/000371
Authority: WO
Inventors: Maren Jekel; Rolf Bayersdörfer; Arnd Kessler
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2004-03-09
Filing date: 2005-01-15
Publication date: 2005-10-06
Also published as: DE102004011256A1; DE102004011256B4

Abstract

The aim of the invention is to improve the sensation of fragrance even after completion of the rinsing programme in an automatic dishwasher. To achieve this, the invention provides two- or multi-phase detergent or cleaning agent moulded bodies consisting of compressed particulate detergents or cleaning agents comprising one or more polymer(s), builder(s), perfume and optional additional detergent and cleaning agent constituents. According to the invention, one phase of the moulded body contains more perfume in relation to the weight of said body than the other phase(s) and the phase of the moulded body containing the higher perfume concentration in relation to weight contains more polymer(s) in relation to weight than the other phase(s).

Description

"Multi-phase tablets with improved fragrance perception"

The present invention relates to multi-phase detergent tablets. In particular, the invention relates to multi-phase RMFK, which are used for the mechanical cleaning of dishes in household dishwashers and are briefly referred to as detergent tablets for machine dishwashing or as tableted MGSM.

The automatic cleaning of dishes in household dishwashers usually comprises a pre-wash, a main wash and a rinse cycle, which are interrupted by intermediate wash cycles. In most machines, the pre-wash cycle for heavily soiled dishes can be activated, but is only selected by the consumer in exceptional cases, so that in most machines a main wash cycle, an intermediate rinse cycle with pure water and a rinse cycle are carried out. The temperature of the main wash cycle varies between 40 and 65 ° C depending on the machine type and program level selection. In the rinse cycle, rinse aids are added from a metering tank in the machine, which usually contain non-ionic surfactants as the main component. Such rinse aids are in liquid form and are widely described in the prior art. Your main task is to prevent limescale and deposits on the cleaned dishes. In addition to water and low-foaming non-surfactants, these rinse aids often also contain hydrotopes, pH-adjusting agents such as citric acid or deposit-inhibiting polymers and often perfume.

Machine dishwashing detergents themselves are also often perfumed. Here there is the additional problem that when the water is changed between the individual rinse cycles, the perfume is also pumped out, so that, although the product smells when it is bought, the consumer cannot perceive the scent impression after the cleaning process. In addition, the sometimes sensitive fragrances suffer from the drastic conditions in the rinse aid. As a result, the "unpleasant smell of lye", which the consumer perceives as unpleasant, is only inadequately masked when the dishwasher is opened. In addition, only a small proportion of the cost-intensive fragrances end up where it is supposed to have an effect.

As a solution to this problem, international patent application WO98 / 07812 (Procter SGamble) proposes incorporating fragrance release systems into automatic dishwashing detergents which contain β-keto esters of fragrance alcohols. These esters are slowly broken down and are intended to create a long-lasting fragrance. Here, too, the esters are partly broken down by the chemical and thermal stress in the main and rinse cycle, so that the sensitive fragrances are decomposed or pumped out with the rinse water before the rinse cycle. The proportion of fragrances that reaches the desired place of action is still low.

German patent application DE 199 48 667 (Henkel) suggests using detergent components which contain 0.1 to 20% by weight of one or more esters, ethers, acetals or ketals of fragrances, 20 to 99.9% by weight of meltable substance (s) with a melting point above 30 ° C and 0 to 60 wt .-% of other active ingredients and / or auxiliaries. By incorporating the fragrance precursors into meltable substances, the release of these sensitive substances can be controlled in a targeted manner, so that the exposure to the alkaline cleaning liquor and the ambient temperatures is avoided until the meltable substances release the fragrance precursors. As a result of the cleavage of the fragrance precursors, which is only now beginning, the released perfume is exposed to thermal or chemical loads for a significantly shorter period of time, so that less perfume is destroyed by environmental influences. Although the fragrance compounds disclosed in this document lead to significantly improved fragrance perception and largely prevent the perfume from being pumped out in the meantime, they are cost-intensive to produce, since the fragrances are first esterified, etherified, acetalized or ketlized and then in a melt matrix must be introduced.

There was therefore still the task of providing means which can be produced inexpensively and which release the perfume contained in them to a higher percentage or ideally completely where on the one hand it no longer decomposes and on the other hand can be perceived by the consumer. If possible, the perfume should be able to be used directly. The object of the present invention was to solve this problem.

It has now been found that an improved fragrance impression also results after the rinsing program has ended if the perfumes or perfume oils are packaged in multiphase tablets together with polymer (s), the remaining phase (s) having a reduced content Have perfume and polymer.

The present invention relates to two-phase or multi-phase detergent tablets made from compressed particulate detergent or detergent, comprising polymer (s), builder (s), perfume and, if appropriate, further detergent and cleaning agent components, one phase of the tablet based on its weight contains more perfume than the other phase (s) and the more perfume-rich phase of the shaped body contains more polymer (s) than the other phase (s) based on its weight. According to the invention, the detergent tablet consists of at least two phases, one phase being more rich in perfume and polymer than the other phase (s). According to the invention, in a three-phase tablet, one phase contains more perfume and more polymer than the other two phases. According to the invention, the perfume and polymer contents relate to the weight of the individual phase. A phase is "richer" in perfume or polymer when the value given in% by weight (based on the phase) for the ingredient in question is greater than the value of the other phase (s).

It is particularly preferred according to the invention if the content of the phases in perfume or polymer varies significantly. Here, detergent tablets according to the invention are preferred in which the perfume content of the individual phases of the tablet, based on the weight of the individual phase, by more than 0.1% by weight, preferably by more than 0.25% by weight and in particular by more than 0.5% by weight.

Analogous information can be given for the polymer content. Preferred detergent tablets according to the invention are characterized in that the polymer content of the individual phases of the tablet, based on the weight of the individual phase, by more than 0.05% by weight, preferably by more than 0.1% by weight, particularly preferably varies by more than 0.2% by weight and in particular by more than 0.5% by weight.

In the context of the present application, the variation by more than 0.1% by weight, based on the weight of the individual phases, means that the absolute values of the perfume content in the phases vary by more than 0.1% by weight. Thus, if one phase contains 2.0% by weight of perfume, the perfume content of the other phase (s) should be selected according to the invention such that the width of the variation around the value 2.0 is at least 0.1% by weight, that is is less than 1.9% by weight or more than 2.1% by weight, in each case based on the phase. In other words, the percentage numerical value of the perfume content of the poorest perfume phase is subtracted from the percentage numerical value of the perfume content of the perfume-richest phase, the result having to be> 0.1. The greatest possible difference in the perfume content in the individual phases can be achieved if at least one phase contains perfume, while at least one other phase is free of perfume. This is another preferred embodiment of the present invention.

In the context of the present invention, the individual phases of the shaped body can have different spatial shapes. The simplest possible implementation is in two- or multi-layer tablets, with each layer of the shaped body representing a phase. However, it is also possible, according to the invention, to produce multiphase molded articles in which individual phases have the form of inclusions in (another) other phase (s). In addition to so-called "ring core tablets", for example, coated tablets or combinations of the named th embodiments possible. Examples of multi-phase moldings can be found in the illustrations in EP-A-0 055 100 (Jeyes), which describes toilet cleaning blocks. The currently widespread spatial form of multi-phase tablets is the two- or multi-layer tablet. In the context of the present invention, it is therefore preferred that the phases of the shaped body have the form of layers. Three-phase molded articles are currently preferably offered by providing a two-phase tray tablet whose tray is filled with a "core" as the third phase. These products have high consumer acceptance and are preferred as three-phase tablets.

The differences in the perfume content of the individual phases can be realized, for example, in that each phase contains a different perfume, the perfume contents differing in the phases. In this way, different fragrance impressions can be realized for each individual phase or the composition of the perfumes can be adapted to the other ingredients of the phase in question. For reasons of production economy, however, it is preferred if the detergent tablets according to the invention have two phases which contain the same perfume in different amounts.

As already mentioned, the greatest possible difference in perfume content can be achieved by combining perfume-free with perfume-containing phases. In the case of a two-layer molded article, this means that detergent tablets are preferred which have two layers, one of which is free of perfume.

The proportion of the individual phases in the total tablet can be varied within wide limits. In the preferred case of a two-layer tablet according to the invention, detergent tablets are preferred in which the two layers of the tablet in a weight ratio of 5 to 95 to 50 to 50, preferably 10 to 90 to 60 to 40 and in particular 15 to 85 to 65 35 stand, the perfume is preferably concentrated in the proportionately lower layer.

Phases with a higher fragrance percentage cannot bind them as strongly, i.e. the fragrance is less adherent in the shaped body and can be perceived more intensively by the consumer when the packaged tablet is opened. The stability of both layers and their disintegration times can also be adjusted or specifically controlled by varying the perfume content in the layers of the tablet. An additional effect occurs with higher perfume contents in a colored layer, since the color intensity is increased.

A wide variety of substances can be used as perfume in the moldings according to the invention. The term "perfume", a Germanized word which, like the French root word "parfum", is derived from the Latin "per fumum" = through (victim) smoke, is used in German in different ways with different meanings. This is how alcoholic perfumes are understood Solutions of suitable fragrances (fragrances), but also the fragrance or the fragrance itself, sometimes the terms perfumery and perfume are also equated. In the context of the present application, the term "perfume" denotes both individual fragrances and fragrance mixtures in concentrated or with suitable solvents diluted form. The term "perfume oil" is also used for the pure fragrance mixture, which is not diluted with solvents. The basic ingredients of the perfume oils are essential oils, flower oils, extracts from plant and animal drugs, isolated from natural products, chemically modified (semi-synthetic) and purely synthetic "Fragrances" is the colloquial collective name for those fragrances that trigger a pleasant sensation of smell in humans and are therefore suitable for perfuming detergents and cleaning agents. In a broader sense, essences and aromas can also be added to the fragrances.

According to the invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropylate, melyllalpylate, melateylylalpylate, melateylalpylate, melateylalpylate, melateylalpylate, benzylatepylate, melateylalpylate, benzylateolate, melylalpylate, benzylate, pylate, The ethers include, for example, benzyl ethyl ether and ambroxan, the aldehydes e.g. the linear alkanals with 8 - 18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, lilial and bourgeonal, to the ketones e.g. the jonones, oc-isomethylionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance.

Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil. It is now possible to produce cleaning agents in which the proportion of the perfume which is present in the phase which is richer in perfume and polymer is composed mainly of adhesive odoriferous substances. In this way, adherent odoriferous substances can be "held" in the product and thus develop their effect mainly in the rinse cycle. In contrast, the more volatile odoriferous substances contribute to a more intensive fragrancing of the agents themselves. In this way it is also possible to produce cleaning agents which are used as Have a smell that differs from the smell when you open the dishwasher, and there are hardly any limits to the creativity of perfumers.

The principle described above can of course also be reversed by incorporating the more volatile fragrances into the phase which is richer in perfume and polymer and spraying the less volatile, adherent fragrances onto the compositions. In this way, the loss of the more volatile fragrances from the packaging during storage and transport is minimized, while the fragrance characteristic of the agents is determined by the more adhesive perfumes.

The general description of the perfumes that can be used (see above) generally represented the different substance classes of fragrances. In order to be perceptible, a fragrance must be volatile, the molecular weight also playing an important role in addition to the nature of the functional groups and the structure of the chemical compound , Most odoriferous substances have molecular weights of up to about 200 daltons, while molecular weights of 300 daltons and more are an exception. Due to the different volatility of odoriferous substances, the smell of a perfume or fragrance composed of several odoriferous substances changes during evaporation, whereby the odor impressions are described in "top note", "heart or middle note" (middle note or body) and "base note" (end note or dry out). Since the smell is largely based on the intensity of the smell, the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note largely consists of less volatile In the composition of perfumes, more volatile fragrances can be bound, for example, to certain fixatives, which prevents them from evaporating too quickly.The embodiment of the present invention described above, in which the more volatile fragrances or fragrances relate to the water-insoluble ones Trägermateriali Such a method for fragrance fixation is applied in low density. In the subsequent classification of the fragrances into “more volatile” or “adherent” fragrances, nothing is said about the odor impression and whether the corresponding fragrance is perceived as a top or heart note.

Adhesive odoriferous substances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, anise oil, amica flower oil, basil oil, bay oil and berry oil. gamott oil, champaca flower oil, noble fir oil, noble pine cone oil, elemi oil, eucalyptus oil, fennel oil, spruce oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, gurjun balsam oil, helichrysum oil, ho oil, ginger oil, camomile oil, kale oil, camava oil, camava oil Cardamom oil, cassia oil, pine needle oil, Kopaϊvabalsamöl, coriander oil, Krausem inzeöl, caraway oil, Kuminöl, lavender oil, lemongrass oil, lime oil, mandarin oil, lemon balm oil, musk kernel oil, myrrh oil, clove oil, neroli oil, oriban oil oil, orolan oil, Niaouli oil, oil oil, Niaouli oil, oil oil, Niaouli oil, oil oil , Peru balsam oil, petitgrain oil, pepper oil, peppermint oil, allspice oil, pine oil, rose oil, rosemary oil, sandalwood oil, celery oil, spik oil, star anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil, ylang oil, winter green oil , Hyssop oil, cinnamon oil, cinnamon leaf oil, lemon oil, lemon oil and cypress oil.

However, the higher-boiling or solid odorants of natural or synthetic origin can also be used in the context of the present invention as adherent odorants or odorant mixtures, that is to say fragrances. These compounds include the compounds listed below and mixtures thereof: ambrettolide, α-amyl cinnamic aldehyde, anethole, anisaldehyde, anisyl alcohol, anisole, methyl anthranilate, acetophenone, benzyl acetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, Benzylvalerianat, borneol , Bornyl acetate, α-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchylacetate, geranyl acetate, geranyl formate, heliotropine, heptincarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroquinone dimethyl ether , Isoeugenol, isoeugenol methyl ether, isosafrol, jasmon, camphor, karvakrol, karvon, p-cresol methyl ether, coumarin, p- methoxyacetophenone, methyl-n-amyl ketone, methyl anthranilic acid methyl ester, p-

Methylacetophenone, methylchavicol, p-methylquinoline, methyl-ß-naphthyl ketone, methyl-n-nonylacetaldehyde, methyl-n-nonyl ketone, muscon, ß-naphtholethyl ether, ß-naphthol methyl ether, nerol, nitrobenzene, n-nonylaldehyde, nonylakaldehyde, nonyla p-oxy-acetophenone, pentadanolide, ß-phenylethyl alcohol, phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegon, safrole, salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester, salicylic acid cyclohexyl ester, santalolpineolate, santalolpineolate, santalolpineolate, santalolpineol, skeletal olefin Veratrum aldehyde, cinnamaldehyde, cimate alcohol, cinnamic acid, ethyl cinnamate, benzyl cinnamate.

The more volatile fragrances include, in particular, the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures. Examples of more volatile fragrances are alkyisothiocyanates (alkyl mustards), butanedione, limonene, linalool, linaylacetate and propionate, menthol, menthone, methyl-n-heptenone, phellandren, phenylacetaldehyde, terpinylacetate, citral, citronellal. The content of the individual phases of the shaped bodies can be varied as described above, it being preferred to incorporate the perfume into one layer while the other layer (s) is / are free of perfume. Irrespective of the perfume content in the individual phase (s), detergent tablets are preferred in which the tablets have total perfume contents of 0.05 to 10% by weight, preferably 0.1 to 5% by weight. and in particular from 0.25 to 1.5% by weight, in each case based on the weight of the shaped body.

The detergent tablets according to the invention contain, in addition to perfume, one or more polymer (s).

The agents according to the invention contain polymers as an essential component. The molecular weight of these polymers can be 2000 gmol ^"1 or more.

In a first embodiment of the present invention, preference is given to those polymers which have at least one positive charge, with detergents or cleaning agents which contain 0.02 to 7.5% by weight, preferably 0.05 to 5% by weight, in particular preferably 0.07 to 2.5% by weight and in particular 0.1 to 1% by weight of at least one polymer with a molecular weight of 2000 gmol ^"1 or above, which has at least one positive charge, are particularly preferred.

The aforementioned polymers with a cationic charge can in principle be cationic or amphoteric polymers. Preferred washing or cleaning agents according to the invention are characterized in that the polymer which has cationic monomer units is a cationic polymer and / or an amphoteric polymer.

“Cationic polymers” in the sense of the present invention are polymers which carry a positive charge in the polymer molecule. This can be achieved, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain. Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate Methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27. “Amphorere polymers” in the sense of the present invention also have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups can be, for example, carboxylic acids, sulfonic acids or phosphonic acids.

Washing or cleaning agents, characterized in that they contain a polymer c) which has monomer units of the formula R ¹ R ² C = CR ³ R ⁴ , in which each radical R ¹ , R ² , R ³ , R ^{4 is} selected independently of one another is from hydrogen, derivatized hydroxy group, C1 to C30 linear or branched alkyl groups, aryl, aryl substituted C ^ o linear or branched alkyl groups, polyalkoxyxylated alkyl groups, heteroatomic organic groups with at least one positive charge without charged nitrogen, at least one quaternized N atom or at least an amino group with a positive charge in the partial range of the pH range from 2 to 11, or salts thereof, with the proviso that at least one radical R ¹ , R ² , R ³ , R ^{4 is} a heteroatomic organic group with at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group with a positive charge are within the scope of the present application particularly preferred.

Cationic or amphoteric polymers which are particularly preferred in the context of the present application contain a compound of the general formula (I) as monomer unit

R ¹ R ² R ⁴ IIIH ₂ C = C- (CH ₂ ) _x -N ⁺ - (CH ₂ ) _y -C = CH ₂ X ^" (I), IR ³ for R ¹ and R ⁴ independently of one another for H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ³ independently of one another represent an alkyl, hydroxyalkyl or aminoalkyl group in which the alkyl radical is linear or branched and has between 1 and 6 carbon atoms, where it is preferably a methyl group; x and y independently of one another represent integers between 1 and 3. X ^" represents a counter ion, preferably a counter ion from the group chloride, bromide, iodine, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate , p-toluenesulfonate (tosylate), cumene sulfonate, xylene sulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R ¹ and R ⁴ in the above formula (I) are selected from -CH ₃ , -CH ₂ - CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, - CH ₂ -CH (OH) -CH ₃ , -CH (OH ) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -0) nH. In the context of the present application, very particular preference is given to polymers which have a cationic monomer unit of the general formula (I) in which R ¹ and R ^{4 are} H, R ² and R ^{3 are} methyl and x and y are each 1. The corresponding monomer units of the formula

H ₂ C = CH- (CH ₂ ) -N ⁺ (CH ₃ ) ₂ - (CH ₂ ) -CH = CH ₂ X ^"

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

Further cationic or amphoteric polymers which are particularly preferred in the context of the present application contain a monomer unit of the general formula (II)

R ¹ HC = CR ² -C (0) -NH- (CH ₂ ) _x -N ⁺ R ³ RR ⁵ X ^" (II),

in which R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently of one another for a linear or branched, saturated or unsaturated alkyl, or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably for a linear or branched alkyl radical selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , - CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , - CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -0) nH and x represents an integer between 1 and 6.

In the context of the present application, very particular preference is given to polymers which have a cationic monomer unit of the general formula (II) in which R ^{1 is} H and R ² , R ³ , R ⁴ and R ^{5 are} methyl and x is 3. The corresponding monomer units of the formula

H ₂ C = C (CH ₃ ) -C (0) -NH- (CH ₂ ) χ-N ⁺ (CH ₃ ) ₃ X ^"

In the case of X ^" = chloride are also referred to as MAPTAC (methyacrylamidopropyl trimethylammonium chloride).

Washing or cleaning agents preferred according to the invention are characterized in that the polymer c) contains diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units. The aforementioned amphoteric polymers have not only cationic groups, but also anionic groups or monomer units. Such anionic monomer units originate, for example, from the group of the linear or branched, saturated or unsaturated carboxylates, the linear or branched, saturated or unsaturated phosphonates, the linear or branched, saturated or unsaturated sulfates or the linear or branched, saturated or unsaturated sulfonates. Preferred monomer units are acrylic acid, (meth) acrylic acids, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinyl essingic acid, allyl acetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and their Derivatives, the allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, or the allylphosphonic acids.

Preferred amphoteric polymers that can be used come from the group of the alkyl acrylamide / acrylic acid copolymers, the alkyl acrylamide / methacrylic acid copolymers, the alkyl acrylamide / methyl methacrylic acid copolymers, the alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylate - mid / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylate / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic monomers.

Zwitterionic polymers which can be used with preference come from the group of acrylamidoalkyl trialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts, acrylamidoalkyl trialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts and methacroylethylbetaine / methacrylate copolymers.

Also preferred are amphoteric polymers which, in addition to one or more anionic monomers, comprise methacrylamidoalkyl-trialkylammonium chloride and dimethyl (diallyl) ammonium chloride as cationic monomers.

Particularly preferred amphoteric polymers come from the group of methacrylamidoalkyl trialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, methacrylic amidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and methacrylamidoalkyltrialkyllammonium chloride (hd) dimethylammonium chloride / Alkyl (meth) acrylic acid copolymers and their alkali and ammonium salts.

Particularly preferred are amphoteric polymers from the group of methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid Copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers and their alkali and ammonium salts.

In a further preferred embodiment of the present application, polymers are used which contain sulfonic acid groups. Preferred compositions according to the invention are therefore characterized in that they comprise at least one copolymer of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionic monomers

In the context of the present invention, unsaturated carboxylic acids of the formula III are preferred as the monomer

R ¹ (R ² ) C = C (R ³ ) COOH (III),

in which R ¹ to R ³ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or - COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

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

In the case of the monomers containing sulfonic acid groups, preference is given to those of the formula IV

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (IV),

in which R ⁵ to R ⁷ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or - COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optionally present one Spacer group, which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (0) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas IVa, IVb and / or IVc,

H ₂ C = CH-X-S0 ₃ H (IVa), H ₂ C = C (CH ₃ ) -X-S0 ₃ H (IVb), H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) - X-S0 ₃ H (IVc),

in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and - C (0) -NH- CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenlsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate , Sulfomethacrylamide, sulfomethyl methacrylamide and water-soluble salts of the acids mentioned.

Other suitable ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds. The group iii) monomer content of the polymers used according to the invention is preferably less than 20% by weight, based on the polymer. Polymers to be used with particular preference consist only of monomers of groups i) and ii).

In summary, copolymers are made of

i) unsaturated carboxylic acids of formula III.

R ¹ (R ² ) C = C (R ³ ) COOH (III),

in which R ¹ to R ³ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH-substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,

ii) Monomers of the formula IV containing sulfonic acid groups

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (IV),

in which R ⁵ to R ⁷ independently of one another for -H -CH _{3> are} a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or - COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group , which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (0) -NH-CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers

particularly preferred.

Particularly preferred copolymers consist of i) one or more unsaturated carboxylic acids from the group consisting of acrylic acid, methacrylic acid and / or maleic acid ii) one or more monomers of the formulas IVa, IVb and / or IVc containing sulfonic acid groups:

H ₂ C = CH-X-S0 ₃ H (IVa), H ₂ C = C (CH ₃ ) -X-S0 ₃ H (IVb), H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) - X-SÖ ₃ H (IVc),

in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and - C (0) -NH- CH (CH ₂ CH ₃ ) - iii) optionally further ionic or nonionic monomers.

The copolymers can contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii). Particularly preferred polymers have certain structural units, which are described below.

For example, compositions according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula V.

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (V),

contain, in which m and p each represent an integer between 1 and 2000 and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H) -, for -NH- C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is preferred.

These polymers are produced by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the sulfonic acid group-containing acrylic acid derivative is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the compositions according to the invention is also preferred and is characterized in that the compositions contain one or more copolymers which have structural units of the formula VI

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VI),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H ₄ ) -, for -NH- C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Completely analogously, acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule to be changed. Compositions according to the invention which contain one or more copolymers which have structural units of the formula VII

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (VII),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -Ö- (C ₆ H) -, for -NH- C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is preferred, is also a preferred embodiment of the present invention, just as compositions are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula VIII

[CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (VIII),

Instead of or in addition to acrylic acid and / or methacrylic acid, maleic acid can also be used as a particularly preferred monomer from group i). In this way, preferred compositions according to the invention are obtained which are characterized in that they contain one or more copolymers, the structural units of the formula VIII

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VIII),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H ₄ ) -, for -NH- C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is preferred, and for compositions which are characterized in that they contain one or more copolymers, the structural units of the formula IX

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) 0-Y-S0 ₃ H] _p - (IX), contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H ₄ ) -, for -NH- C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In summary, compositions according to the invention which contain one or more copolymers which have structural units of the formulas IV and / or V and / or VI and / or VII and / or VIII and / or IX are preferred

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (IV), - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC ( 0) -Y-S0 ₃ H] _p - (VI), - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (VI), - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-SO ₃ H] _p - (VII), - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VIII), - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) 0-Y-S0 ₃ H] _p - (IX),

contain, in which m and p each represent an integer between 1 and 2000 and Y for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H ₄ ) -, for -NH- C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

The sulfonic acid groups in the polymers may be wholly or partly in neutralized form, i.e. that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. Corresponding compositions which are characterized in that the sulfonic acid groups in the copolymer are partially or fully neutralized are preferred according to the invention.

The monomer distribution of the copolymers used in the compositions according to the invention is preferably 5 to 95% by weight of i) or ii), particularly preferably 50 to 90% by weight, of copolymers which contain only monomers from groups i) and ii). % Of monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer. In the case of terpolymers, those which contain 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) are particularly preferred ,

The molar mass of the sulfo copolymers described above used in the compositions according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use. Preferred compositions are characterized in that the copolymers have molar masses of 2,000 to 200,000 gmol ^"1 , preferably 4,000 to 25,000 gmol ^{" 1} and in particular 5,000 to 15,000 gmol ^"1 .

The abovementioned polymers are also outstandingly suitable as perfume carriers, provided that the perfume is not to be incorporated by spraying onto a particulate premix - more details can be found below in the description of the process according to the invention.

In a further preferred embodiment of the present application, the polymeric carboxylates described below as cobuilders are used as polymers.

In a particularly preferred embodiment of the present invention, the polymers contained in the agents according to the invention are in pre-assembled form. Among other things, the following is suitable for packaging the polymers: encapsulation of the polymers by means of water-soluble or water-dispersible coating agents, preferably by means of water-soluble or water-dispersible natural or synthetic polymers; - Encapsulation of the polymers by means of water-insoluble, meltable coating agents, preferably by means of water-insoluble coating agents from the group of waxes or paraffins with a melting point above 30 ° C; - The co-granulation of the polymers with inert carrier materials, preferably with carrier materials from the group of active washing or cleaning substances, particularly preferably from the group of builders (builders) or cobuilders.

In addition to perfume and polymer, the detergent tablets according to the invention can also contain one or more surfactant (s). These come from the groups of anionic, nonionic, cationic and / or amphoteric surfactants, with nonionic surfactants being clearly preferred in the context of automatic dishwashing and Surfactants from the other groups are used only in minor amounts or preferably not at all.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C ₉ . _13- Alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C ₁₂ . ₁₈ -monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates, from C ₂ - ₁₈ are obtained, for example, alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

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

As alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₈ fatty alcohols, for example from 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 this chain length are preferred. Also preferred are alk (en) ylsu! Fates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₅ alkyl sulfates are preferred from a washing-technical point of view. 2,3-alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 mol of ethylene oxide. ₂₁ alcohols, such as 2-methyl-branched C _{_9-1} alcohols containing on average 3.5 mol ethylene oxide (EO) or C _{_12-18} fatty alcohols with 1 to 4 EO, are also suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight. Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-0 ₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alkyl (en) yl chain or salts thereof.

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

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

Another group of washing-active substances are the non-ionic surfactants. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ . ₁₄ -alcohols with 3 EO or 4 EO, C ₉ . _ι alcohol with 7 EO, C ₁₃ . ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ . ₁₈ - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ . ₁₄ - alcohol with 3 EO and C ₁₂ - _.8 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols can also be used can be used with more than 12 EO. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

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

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

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

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

I

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

in the RCO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ^ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical 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.

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

R ¹ -0-R ²

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

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, Cu 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 propylated, derivatives of this radical ,

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

In the case of detergents and cleaning agents for automatic dishwashing, all surfactants are generally suitable as surfactants. However, the nonionic surfactants described above, and above all the low-foaming nonionic surfactants, are preferred for this purpose. The alkoxylated alcohols are particularly preferred, especially the ethoxylated and / or propoxylated alcohols. The person skilled in the art generally understands by alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the sense of the present invention the longer-chain alcohols (C ₁₀ to C ₈ , preferably between C ₁₂ and C ₁₆ , such as Cn- , C ₁₂ -, C ₁₃ -, C ₁₄ -, C ₁₅ -, C ₁₆ -, C ₁₇ - and C ₁₈ -alcohols). As a rule, n moles of ethylene oxide and one mole of alcohol form a complex mixture of addition products of different degrees of ethoxylation, depending on the reaction conditions. A further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. You can also if desired, a final etherification with short-chain alkyl groups, such as preferably the butyl group, leads to the substance class of the "closed" alcohol ethoxylates, which can also be used in the sense of the invention. For the purposes of the present invention, very particularly preferred are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.

In the context of the present invention, weakly foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants. Among these, surfactants with EO-AO-EO-AO blocks are preferred, one to ten EO or AO groups being bonded to one another before a block follows from the other groups. Here, washing or cleaning agents according to the invention are preferred which contain surfactants of the general formula III as nonionic surfactant (s)

R ¹ -0- (CH ₂ -CH ₂ -0) _w - (CH ₂ -CH-0) _x - (CH ₂ -CH ₂ -0) _y - (CH ₂ -CH-0) _z -H (III ) IIR ² R ³

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

The preferred nonionic surfactants of the formula III can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in formula I above can vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is generally not shown, the linear radicals being of alcohols of native origin with 12 to 18 carbon atoms, for example coconut, palm, tallow or Oleyl alcohol are preferred. Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or, in the mixture, methyl-branched or linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. Regardless of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, washing or cleaning compositions according to the invention are preferred in which R ¹ in formula I for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

In addition to propylene oxide, butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit. But also re alkylene oxides in which R ² or R ³ are selected independently of one another from -CH ₂ CH ₂ -

CH ₃ or -CH (CH ₃ ) ₂ are suitable. Preferred washing or cleaning agents are characterized in that R ² or R ³ for a radical -CH ₃ , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.

In summary, nonionic surfactants which have a C ₉ . ₁₅ - alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.

Low-foaming nonionic surfactants are used as preferred additional surfactants. The washing or cleaning agents according to the invention particularly preferably contain a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred agents are characterized in that they contain nonionic surfactant (s) with a melting point above 20 ° C, preferably above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43, 3 ° C.

Suitable, in addition to the nonionic surfactants contained in the compositions according to the invention, which have melting or softening points in the temperature range mentioned, are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If highly viscous 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 that have a waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants to be used at room temperature originate from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more 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 with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted. A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms, (Cι. ₆ ₂₀ alcohol), preferably a C ₁₈ alcohol and at least 12 mole, preferably at least 15 mol and recovered in particular at least 20 moles of ethylene oxide , Among these, the so-called "narrow ranks of ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) which consist of C ₆ . ₂₀ monohydroxyalkanols or C ₆ . ₂₀ -alkylphenols or C _{_16-2} o-fatty alcohols and more than 12 mol, preferably more than 15 mol and was recovered in particular more than 20 moles of ethylene oxide per mole of alcohol (s).

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

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

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

A further preferred washing or cleaning agent according to the invention contains nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (CH ₃ ) 0] _x [CH ₂ CH ₂ 0] _y [CH ₂ CH (OH) R ² ], in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y stands for a value of at least 15.

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

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

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

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

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

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 represents} H and x assumes values from 6 to 15.

If the last statements are summarized, washing or cleaning agents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

contain, in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (OH) CH ₂ OR ²

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

Anionic, cationic and / or amphoteric surfactants can also be used in conjunction with the surfactants mentioned, these being of only minor importance because of their foaming behavior in automatic dishwashing detergents and mostly only in amounts below 10% by weight, mostly even below 5% by weight .-%, for example from 0.01 to 2.5 wt .-%, each based on the agent. The agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as the surfactant component.

In the context of the present invention, it is preferred that the detergent tablets according to the invention surfactant (s), preferably nonionic surfactant (s), in amounts of 0.5 to 10 wt .-%, preferably from 0.75 to 7, 5 wt .-% and in particular from 1, 0 to 5 wt .-%, each based on the total agent. The agents according to the invention particularly preferably contain exclusively nonionic surfactant (s) and are accordingly free from anionic surfactants, cationic and amphoteric surfactants. Particularly preferred detergent tablets according to the invention are characterized in that the tablets contain only nonionic surfactant (s) as surfactant (s), the nonionic surfactant (s) preferably being at least 40%, particularly preferably at least 60% and in particular at least 75% its weight is contained in the more perfume phase. Agents according to the invention are particularly preferred, characterized in that the moldings contain only nonionic surfactant (s) as surfactant (s), the nonionic surfactant (s) preferably being at least 80%, particularly preferably at least 90% and in particular at least 95% of its weight is contained in the more perfume phase.

In the context of the present application, preference is therefore given in particular to such two-phase or multiphase detergent tablets made from compressed particulate detergent or cleaning agent, comprising polymer (s), builder (s), perfume, surfactant (s) and, if appropriate, further detergent and cleaning agent components , wherein one phase of the shaped body contains more perfume based on its weight than the other phase (s), characterized in that the phase with more perfume of the shaped body contains more polymer (s) and more surfactant (s) based on its weight, than the other phase (s).

In addition to the absolute content of perfume and polymer in the individual phases, which each relates to the composition of the individual phase, the ratio of the amounts in the individual phases to one another can also be varied. In the context of the present invention, detergent tablets are preferred which consist of two phases and in which the quotient of the difference in the perfume contents and the difference in the polymer contents is less than 2, preferably less than 1 and in particular less than 0.5.

For clarification, use is made of the example of a two-layer tablet in which the content of one phase of perfume is p1% by weight and that of the other phase is p2% by weight, and the polymer content of the more perfume-rich phase is denoted by d1, that of the poorer perfume Phase with d2, in preferred embodiments of the present invention the mathematical relationship (p1-p2) / (d1-d2) <2, preferably <1 and in particular <0.5.

The detergent tablets according to the invention contain builders as a further constituent. Preferred detergent tablets according to the invention contain, in addition to the ingredients mentioned above, one or more substances from the group of cobuilders, bleaches, bleach activators, enzymes, dyes, corrosion inhibitors, or another conventional constituent of detergents and cleaning agents. These ingredients are described below. Builder

According to the present invention, all builders normally used in detergents and cleaning agents can be incorporated into the washing and cleaning agents, in particular silicates, carbonates, organic cobuilders and also the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x 0 _{2x + 1} Η ₂ 0, 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. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ 0 ₅ "yH ₂ 0 are preferred.

Amorphous sodium silicates with a module Na ₂ 0: Si0 ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

Both monoalkali metal salts and dialkali metal salts of carbonic acid as well as sesquicarbonates can be included in the compositions as carbonates. Preferred alkali metal ions are sodium and / or potassium ions. In one embodiment, it may be preferred to admix the carbonate and / or bicarbonate at least partially as a further component separately or subsequently. Compounds made of, for example, carbonate, silicate and optionally other auxiliaries such as anionic surfactants or other, in particular organic builder substances, can also be present as separate components in the finished compositions. It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HP0 ₃ ) _n and orthophosphoric acid H ₃ P0 _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and limescale deposits on the wash ware and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ P0, exists as a dihydrate (density 1.91, preferably ^"3 , melting point 60 °) and as a monohydrate (density 2.04, preferably ^{" 3} ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ 0 ₇ ) at 200 ° C, and at higher temperatures in sodium trimetaphosphate (Na ₃ P ₃ 0 ₉ ) and Maddrell's salt (see below). NaH ₂ P0 _{4 is} acidic; it arises when phosphoric acid is adjusted to a pH of 4.5 with a Naronauge and the mash is sprayed. Potassium hydrogen phosphate (primary or monobasic potassium phosphate, potassium biphoshate, KDP), KH ₂ P0 ₄ , is a white salt with a density of 2.33 ^"3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0 ₃ ) χ] and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HP0, is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly ^"3 , water loss at 95 °), 7 mol. (Density 1, 68 gladly ^{" 3} , melting point 48 ° with loss of 5 H ₂ 0) and 12 mol. Water ( Density 1, 52 like ^"3 , melting point 35 ° with loss of 5 H ₂ 0), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ 0 ₇ when heated. Disodium hydrogen phosphate is lost by neutralizing phosphoric acid with soda solution Using phenolphthalein as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HP0 ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ P0 ₄ , are colorless crystals which, as dodeca- hydrate, have a density of 1.62 ^"3 and a melting point of 73-76 ° C (decomposition), as deca- hydrate (corresponding to 19-20 % P ₂ 0 ₅₎ has a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ 0 ₅₎ a density of 2.536 like ^"3 aufeisen. Trisodium phosphate is in Water is readily soluble in an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or three-base potassium phosphate), K ₃ P0 ₄ , is a white, deliquescent, granular powder with a density of 2.56 ^"3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction Heating of Thomas slag with coal and potassium sulfate Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred to the corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ 0 ₇ , exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also given 880 °) and as decahydrate (density 1, 815-1, 836 like ^{" 3} , melting point 94 ° with water loss). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na P ₂ 0 ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ 0 ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 ^"3 , which is soluble in water, the pH value being 1 % solution at 25 ° is 10.4.

Condensation of the NaH ₂ P0 ₄ or the KH ₂ P0 ₄ produces higher moles. Sodium and potassium phosphates, in which a distinction can be made between cyclic representatives, the sodium and potassium metaphoshates, and chain-like types, the sodium and potassium polyphosphates. A large number of names are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (0) (ONa) -0] _n that crystallizes with 6 H ₂ 0 -Na with n = 3. About 17 g of the salt of water free of water of crystallization dissolve in 100 g of water at room temperature, about 20 g at 60 ° and around 32 g at 100 °; after heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (> 23% P ₂ 0 ₅ , 25% K ₂ 0). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. Sodium potash also exists umtripolyphosphates, which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaP0 ₃ ) ₃ + 2 KOH - »Na ₃ K ₂ P ₃ O ₁₀ + H ₂ 0

According to the invention, these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

Washing or cleaning agents preferred in the context of the present invention contain no sodium and / or potassium hydroxide. Dispensing with sodium and / or potassium hydroxide as the alkali source has proven to be particularly advantageous if zinc gluconate, zinc formate and zinc acetate are used as zinc salts. .

builders

Organic cobuilders which can be used in the cleaning agents in the context of the present invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. The polymers can also be part of the active substance-containing matrix, but they can also be contained in the agents according to the invention completely independently of this. The substance classes mentioned are described below.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such 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, methylglycinediacetic acid, sugar acids and mixtures of these.

The acids themselves can also be used. In addition to their builder effect, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Polymeric polycarboxylates are also suitable as builders; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights 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 to the polymers investigated. This information deviates significantly from the molecular weight information, for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 1000 to 10000 g / mol, and particularly preferably from 1200 to 4000 g / mol, can in turn be preferred from this group.

Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention. The copolymers containing sulfonic acid groups are described in detail below.

In addition, the sulfonic acid group-containing polymers described above can of course also be present in the agents according to the invention, without necessarily having to be part of the active ingredient-containing matrix.

As already mentioned further above, it is particularly preferred to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionic or nonionic monomers in the agents according to the invention. The polyacrylates were described in detail above. Combinations of the above-described copolymers containing sulfonic acid groups with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons, are particularly preferred. Such polyacrylates are commercially available under the trade names Sokalan ^® PA15 or Sokalan ^® PA25 (BASF). Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and 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 molecular weight, based on free acids, is generally 2,000 to 100,000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 30,000 to 80,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve water solubility, the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.

Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,

Further preferred copolymers preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other 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. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose Equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.

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. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders. Ethylenediamine-N, ^{N'-disuccinate} (EDDS) is preferably in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned. In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as cobuilders.

Agents according to the invention are characterized in the context of the present application in that they contain builders, preferably from the group of silicates, carbonates, organic cobuilders and / or phosphates in amounts of 0.1 to 99.5% by weight, preferably of 1 to 95 % By weight, particularly preferably from 5 to 90% by weight and in particular from 10 to 80% by weight, in each case based on the composition.

bleach

Bleaching agents and bleach activators are important components of detergents and cleaning agents, and a detergent and cleaning agent can contain one or more substances from the groups mentioned within the scope of the present invention. Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and supply H ₂ 0 ₂ in water. Other useful bleaching agents are, for example, sodium perborate tetrahydrate and the sodium perborate monohydrate. Peroxypyrophosphates, citrate perhydrates and H ₂ 0 ₂ -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.

“Sodium percarbonate” is a non-specific term for sodium carbonate peroxohydrates, which strictly speaking are not “percarbonates” (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate. The merchandise has the average composition 2 Na ₂ C0 ₃ -3 H ₂ Ö ₂ and is therefore not peroxycarbonate. Sodium percarbonate often forms a white, water-soluble powder with a density of 2.14 ^"3 , which easily disintegrates into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first obtained in 1899 by ethanol precipitation from a solution of sodium carbonate in hydrogen peroxide, but was mistakenly regarded as peroxy carbonate. It was not until 1909 that the compound was recognized as a hydrogen peroxide addition compound, however the historical name "sodium percarbonate" has become established in practice.

The industrial production of sodium percarbonate is predominantly produced by precipitation from an aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg ²⁺ ions). The precipitated salt, which is still 5 to 12 Contains wt .-% mother liquor, is then centrifuged and dried in fluid bed dryers at 90 ° C. The bulk density of the finished product can vary between 800 and 1200 g / l depending on the manufacturing process. As a rule, the percarbonate is stabilized by an additional coating. Coating processes and materials used for coating are widely described in the patent literature. In principle, according to the invention, all commercially available percarbonate types can be used, such as those offered by the companies Solvay Interox, Degussa, Kemira or Akzo.

Detergents for automatic dishwashing can also contain bleaches from the group of organic bleaches. Typical organic bleaching agents that can be used as ingredients in the context of the present invention are the diacyl peroxides, such as e.g. Dibenzoyl. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε -Phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxyacid, diperoxyacidoxyacid, diperoxyacidoxyacid, Diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid) can be used.

According to the present invention, chlorine or bromine-releasing substances can also be used as bleaching agents for machine dishwashing. Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chlorioramides, for example trichloroisocyanuric acid, tbromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Advantageous agents in the context of the present invention contain one or more bleaching agents, preferably from the group of oxygen or halogen bleaching agents, in particular chlorine bleaching agents, with particular preference for sodium percarbonate and / or sodium perborate monohydrate, in amounts of 0.5 to 40% by weight, preferably from 1 to 30% by weight, particularly preferably from 2.5 to 25% by weight and in particular from 5 to 20% by weight, in each case based on the total composition. Bleach activators

In order to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C. and below, cleaning agents can contain bleach activators within the scope of the present invention. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, ethylene glycol, diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or instead of them, so-called bleach catalysts can also be incorporated into the cleaning agents according to the present invention. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

According to the invention, agents are preferred to use one or more substances from the group of bleach activators, in particular from the groups of polyacylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), of acylated phenolsulfonates, in particular n- Nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), in amounts of 0.1 to 20% by weight, preferably 0.5 to 15% by weight % and in particular from 1 to 10 wt .-%, each based on the total agent.

The bleach activators preferred in the context of the present invention also include the “nitrile quats”, cationic nitriles of the formula (IV), R ¹

R ² -N ⁽⁺⁾ - (CH ₂ ) -CN X (iv),

R ³ in which R ¹ for -H, -CH ₃ , a C ₂ . ₂₄ alkyl or alkenyl radical, a substituted C ₂ - ₂₄ alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a C ₂₄ alkyl group, or for a substituted alkyl or alkenylaryl radical having a C 1-4 alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) - CH ₃ , -CH ₂ -CH ₂ -CH ₂ - OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -0) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion.

General formula (XXI) includes a large number of cationic nitriles which can be used in the context of the present invention. The detergent tablets according to the invention particularly advantageously contain cationic nitriles in which R ^{1 is} methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n- Tetradecyl, n-hexadecyl or n-octadecyl radical. R ² and R ³ are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, where one or both radicals can advantageously also be a cyanomethylene radical.

For reasons of easier synthesis, compounds are preferred in which the radicals R ¹ to R ^{3 are} identical, for example (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH (CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , or (HO -CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , where X ^{" is} preferably an anion selected from the group consisting of chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate is selected.

Detergents and cleaning agents preferred in the context of the present invention are characterized in that they contain the cationic nitrile of the formula (XXI) in amounts of 0.1 to 20% by weight, preferably 0.25 to 15% by weight and in particular from 0.5 to 10% by weight, based in each case on the weight of the shaped body.

enzymes

Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases help to remove stains such as protein, grease or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. For bleaching or to inhibit the transfer of color oxidoreductases can also be used. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and from their genetically modified variants are particularly suitable. Proteases of the subiiisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes.

Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition. Preferred agents according to the invention contain enzymes, preferably in the form of liquid and / or solid enzyme preparations, in amounts from 0.1 to 10% by weight, preferably from 0.5 to 8% by weight and in particular from 1 to 5% by weight. , each based on the total mean.

dyes

In order to improve the aesthetic impression of the detergents and cleaning agents, they can be colored with suitable dyes. Dyes preferred in the context of the present invention, the selection of which does not pose any difficulty for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards textile fibers in order not to dye them.

Preferred for use in the washing and cleaning agents according to the invention are all colorants which can be oxidatively destroyed in the cleaning process, and also mixtures of these with suitable blue dyes, so-called blue tones. It has proven to be advantageous to use colorants which are soluble in water or in liquid organic substances at room temperature. For example, anionic colorants, for example anionic nitroso dyes, are suitable. One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020)., That is as a commercial product, for example as Basacid ^® Green 970 from BASF, Ludwigshafen available, as well as mixtures thereof with suitable blue dyes. Other colorants are Pigmosol ^® Blue 6900 (Cl 74160), Pigmosol ^® Green 8730 (Cl 74260), Basonyl ^® Red 545 FL (Cl 45170), Sandolan ^® Rhodamine EB400 (Cl 45100), Basacid ^® Yellow 094 (Cl 47005), Sicovit ^® Patentblau 85 E 131 (Cl 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acidblue 183), Pigment Blue 15 (Cl 74160), Supranol ^® Blau GLW (CAS 12219-32-8, Cl A- cidblue 221)), Nylosan ^® Yellow N-7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan ^® Blue (Cl Acid Blue 182, CAS 12219-26-0).

When choosing the colorant, it must be ensured that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the washing or cleaning agents varies. For highly soluble dyes, for example, the above-mentioned Basacid ^® Green or the above-mentioned Sandolan Blue ^®, are typically selected dye concentrations in the range of some 10 ^"2 to ^{10" 3} wt .-%. In the due to their brilliance, particularly preferred, but are less readily water-soluble pigment dyes, for example the above-mentioned Pigmosol ^® ATTO-dyes, the appropriate concentration of the colorant is in washing or cleaning agents, however, typically a few 10 ^"3 to ^{10" 4} wt .-% ,

Corrosion inhibitors

Detergents for machine dishwashing can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents in particular being particularly important in the area of machine dishwashing. The known substances of the prior art can be used. In general, silver protective agents selected from the group consisting of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkyl laminotriazoles and the transition metal salts or complexes can be used. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, active chlorine-containing agents that corrode the silver surface are often found in cleaner formulations can significantly reduce. In chlorine-free cleaners, especially oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) -Complexes, the chlorides of cobalt or manganese and manganese sulfate as well as the manganese complexes

[Me-TACN) Mn ^IV (m-0) ₃ Mn ^IV (Me-TACN)] ²⁺ (PF ₆ ^_ ) 2.

[Me-MeTACN) Mn ^IV (m-0) ₃ Mn ^lv (Me-MeTACN)] ²⁺ (PF ₆ ^" ) ₂ ,

[Me-TACN) Mn ^III (m-0) (m-0AC) ₂ Mn ^{ll l} (Me-TACN)] ²⁺ (PF ₆ ^_) ₂ and

[Me-MeTACN) Mn ^III (m-0) (m-0AC) ₂ Mn ^{ll l} (Me-MeTACN)] ²⁺ (PF ₆ ^') ₂ - wherein MeTACN for 1, 4,7-trimethyl-1 , 4,7-triazacyclononan and Me-MeTACN stands for 1, 2,4,7-tetramethyl-1, 4,7-triazacyclononane, and zinc compounds can also be used to prevent corrosion on the wash ware.

A preferred agent for providing corrosion protection for glassware during cleaning and / or rinsing operations of a dishwasher is zinc in oxidized form, i.e. Zinc compounds in which zinc is cationic. Analogously, magnesium salts are also preferred. Here, both soluble and poorly or insoluble zinc or magnesium compounds can be used. Preferred compositions according to the invention contain one or more magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid.

The acids in question preferably originate from the group of the unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the Amino acids and / or the polymeric carboxylic acids, the unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acids with at least 8 carbon atoms and / or resin acids.

Although according to the invention all magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids can be present, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the groups of the unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, saturated and unsaturated dicarboxylic acids, aromatic mono-, di- and tricarboxylic acids, sugar acids, hydroxy acids, oxo acids, amino acids and / or polymeric carboxylic acids are preferred. Within the scope of the present invention, the acids mentioned below are again preferred within these groups:

From the group of unbranched saturated or unsaturated monocarboxylic acids: methanoic acid (formic acid), ethanoic acid (acetic acid), propanoic acid (propionic acid), pentanoic acid (valeric acid), hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid) ), Decanoic acid (capric acid), undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearic acid), eicosanoic acid (aricosanoic acid) ), Tetracosanoic acid (lignoceric acid), hexacosanoic acid (cerotinic acid), triacotanoic acid (melissic acid), 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid, 9c-octadecenoic acid (Elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (linol Aidic acid) and 9c, 12c, 15c-octadecatreic acid (linolenic acid).

From the group of the branched saturated or unsaturated monocarboxylic acids: 2-methylpentanoic acid, 2-ethylhexanoic acid, 2-propylheptanoic acid, 2-butyloctanoic acid, 2-pentylnonanoic acid, 2-hexyldecanoic acid, 2-heptylundecanoic acid, 2-octyldodecanoic acid, 2-nonyltridecanoic acid, 2 2- undecylpentadecanoic acid, 2-

Contains dodecylhexadecanoic acid, 2-tridecylheptadecanoic acid, 2-tetradecyloctadecanoic acid, 2-pentadecylnonadecanoic acid, 2-hexadecyleicosanoic acid, 2-heptadecylheneicosanoic acid.

From the group of unbranched saturated or unsaturated di- or tricarboxylic acids: propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonandioic acid (azelaic acid) ), Decanedioic acid (sebacic acid), 2c-butenedioic acid (maleic acid), 2t-butenedioic acid (fumaric acid), 2-butynedicarboxylic acid (acetylenedicarboxylic acid).

From the group of aromatic mono-, di- and tricarboxylic acids: benzoic acid, 2-carboxybenzoic acid (phthalic acid), 3-carboxybenzoic acid (isophthalic acid), 4-carboxybenzoic acid (terephthalic acid), 3,4-dicarboxybenzoic acid (trimellitic acid), 3,5-dicarboxybenzoic acid (Trimesionsäure).

From the group of the sugar acids: galactonic acid, mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid, 2-deoxy-ribonic acid, alginic acid. From the group of hydroxy acids: hydroxyphenylacetic acid (mandelic acid), 2-hydroxypropionic acid (lactic acid), hydroxysuccinic acid (malic acid), 2,3-

Dihydorxybutanedioic acid (tartaric acid), 2-hydroxy-1, 2,3-propanetricarboxylic acid (citric acid), ascorbic acid, 2-hydroxybenzoic acid (salicylic acid), 3,4,5-trihydroxybenzoic acid (gallic acid).

From the group of oxo acids: 2-oxopropionic acid (pyruvic acid), 4-oxopentanoic acid (levulinic acid).

From the group of amino acids: alanine, valine, leucine, isoleucine, proline, tryptophan, phenylalanine, methionine, glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine, aspartic acid, glutamic acid, lysine, arginine, histidine.

From the group of polymeric carboxylic acids: polyacrylic acid, polymethacrylic acid, alkyl acrylamide / acrylic acid copolymers, alkyl acrylamide / methacrylic acid copolymers, alkyl acrylate / methyl methacrylic acid copolymers, copolymers of unsaturated carboxylic acids, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl pyrrolidone / vinyl acrylate copolymers.

The spectrum of the zinc salts of organic acids, preferably organic carboxylic acids preferred according to the invention, extends from salts which are sparingly or not soluble in water, ie have a solubility below 100 mg / L, preferably below 10 mg / L, in particular no solubility, up to such salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, particularly preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C. water temperature). The first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate, the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate:

In a further preferred embodiment of the present invention, the compositions according to the invention contain at least one zinc salt, but no magnesium salt of an organic acid, it preferably being at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group consisting of zinc stearate, zinc oleate, zinc gluconate and zinc acetate , Zinc lactate and / or zinc citrate. Zinc ricinoleate, zinc abietate and zinc oxalate can also be used with preference

Another object of the present invention is a method for producing multiphase detergent tablets by compression molding known per se. Particulate premixes which contain different amounts of perfume, characterized in that the more perfume-based premix contains more polymer (s) than the other premix (s), based on its weight.

The perfume can be introduced into the moldings according to the invention in different ways. The simplest way is that the perfume is sprayed onto the premix (s) and introduced into the perfume-containing phase (s). Since the premixes to be pressed into the respective phases are usually mixtures of different particulate and, if appropriate, liquid or pasty substances, the perfume can simply be metered in in the mixing step. A fine distribution, for example spraying, is preferable to simple pouring.

The perfume can - especially if nonionic surfactants are used as surfactants - also mixed with the surfactant and applied to the premixes in a mixture with the latter.

However, it is also possible to apply the fragrances to carrier substances before adding them to the respective premix, or to increase their adhesion in a suitable manner. Cyclodextrin-perfume complexes or encapsulated perfumes are suitable for this. Methods in which the perfume is introduced into the perfume-containing phase (s) by adding such solid fragrance preparation forms to the premix (s) are also preferred.

Suitable carrier materials are, for example, the builder substances mentioned above, but also polymers from the group of the above-mentioned cobuilders. A particularly suitable perfume carrier is the above-described polymer containing sulfonic acid groups.

In preferred processes, a carrier material containing perfume and optionally surfactant or polymer is introduced into the particulate premix. This preferably has perfume contents of 1 to 60% by weight, particularly preferably 10 to 50% by weight and in particular 12 to 40% by weight, in each case based on its weight. If the perfume-containing material additionally contains surfactant, preferably nonionic surfactant, the surfactant content is preferably from 20 to 60% by weight, particularly preferably from 25 to 55% by weight and in particular from 30 to 45% by weight, in each case based on the Weight of the carrier material. In the latter cases, the perfume content is accordingly at the lower end of the above range.

If loaded carrier materials are used as perfume or surfactant carriers, the bulk density of the loaded materials is preferably at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l. In preferred methods according to the invention, the loaded carrier material has particle sizes between 100 and 2000 μm, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 μm.

The other ingredients of the detergent tablets according to the invention can also be incorporated into the method according to the invention, for which reference is made to the above statements. Preferred processes are characterized in that the particulate premix additionally contains one or more substances from the group of bleaching agents, bleach activators, disintegration aids, enzymes, pH regulators, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, Contains color transfer inhibitors and corrosion inhibitors.

The moldings according to the invention are first produced by dry mixing the constituents of the individual phases, which can be wholly or partially pregranulated, and then informing them, in particular pressing them into tablets, in which case conventional methods for producing multiphase moldings can be used. To produce the multiphase molded articles according to the invention, the premixes are compacted in a so-called die between two punches to form a solid compressed product. This process, which is briefly referred to below as tableting, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.

Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down. For small production quantities, eccentric tablet presses are preferably used, in which the punch or stamps are attached to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine. The pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disk, the number of die holes being correspondingly increased. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected in which a larger number of matrices are arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available. Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps. The die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation. At locations where a particularly serious lifting or lowering of the punches is required (filling, compacting, ejecting), these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks. The die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix. The pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers.

Rotary presses can also be equipped with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet. For the production of two- and multi-layer molded articles, several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling. With suitable process control, jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or the core layers not being covered in the case of the dot tablets and thus remaining visible. Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing. The throughputs of modern rotary tablet presses are over one million tablets per hour.

When tableting with rotary presses, it has proven to be advantageous to carry out the tabletting with the lowest possible fluctuations in the hardness of the tablet. This is achieved by tableting with constant pressing forces. The press forces are readjusted via the filling quantity or the tablet height. Small fluctuations in weight can be achieved in the following ways:

- Use of plastic inserts with small thickness tolerances

- Working without deposits with minimal tool tolerances and rotating punches

- Low number of revolutions of the rotor

- Big filling shoes

- Matching the filler paddle speed to the speed of the rotor

- Filling shoe with constant powder height

- Decoupling of filling shoe and powder feed To reduce stamp caking, all non-stick coatings known from the art are available. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotating punches have also proven to be advantageous, with the upper and lower punches being designed to be rotatable if possible. In the case of rotating punches, a plastic insert can generally be dispensed with. The stamp surfaces should be electropolished here.

It was also shown that long pressing times are advantageous. These can be set with pressure rails, several pressure rollers or low rotor speeds. Since the fluctuations in the hardness of the tablet are caused by the fluctuations in the pressing forces, systems should be used which limit the pressing force. Here elastic stamps, pneumatic compensators or spring elements can be used in the force path. The pressure roller can also be designed to be resilient.

Tableting machines suitable in the context of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Hörn & Noack Pharmatechnik GmbH, Worms, IMA Verpackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Ro-maco GmbH, Worms. Other providers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (Sl ). For example, the hydraulic double pressure press HPF 630 from LAEIS, D. Tablettierwerkzeuge are, for example, from the companies Adams Tablettierwerkzeuge, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Hörn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers are e.g. Senss AG, Reinach (CH) and Medicopharm, Kamnik (Sl).

The moldings can be manufactured in a predetermined spatial shape and size, whereby they always consist of several phases, ie layers, inclusions or cores and rings. Practically all practical configurations can be considered as the spatial form, for example, the design as a board, the shape of bars or bars, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross-section. This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1. The portioned compacts can each be designed as separate individual elements which correspond to the predetermined dosage of the detergents and / or cleaning agents. However, it is also possible to form compacts which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points. For the use of textile detergents in machines of the type customary in Europe with horizontally arranged mechanics, the portioned compacts can be designed as tablets, in cylindrical or cuboid form, with a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such compacts.

The spatial shape of another embodiment of the shaped bodies is adapted in its dimensions to the induction chamber of commercial household washing machines, so that the shaped bodies can be metered directly into the induction chamber without metering aid, where they dissolve during the induction process. Of course, the detergent tablets can also be used without problems using a metering aid.

Another preferred multi-phase molded body that can be produced has a plate-like or plate-like structure with alternating thick long and thin short segments, so that individual segments of this "multi-phase bar" at the predetermined breaking points, which represent the short thin segments, broken off and can be entered into the machine. This principle of the "bar-shaped" shaped body detergent can also be implemented in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side. For optical reasons, it makes sense to design the triangular base that connects the individual segments as one phase, while the triangle tip forms the second phase. Different coloring of both phases is particularly attractive in this embodiment.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to

2P σ = πDt

Herein σ stands for diametral fracture stress (DFS) in Pa, P is the force in N that leads to the pressure exerted on the molded body that causes the molded body to break, D is the molded body diameter in meters and t the height of the moldings.

Claims

claims:

1. Two-phase or multi-phase detergent tablets made of compressed particulate detergent or detergent, comprising polymer (s), builders (e), perfume and optionally further detergent and cleaning agent components, one phase of the tablet containing more perfume based on its weight than the other phase (s), characterized in that the more perfume-rich phase of the shaped body contains more polymer (s) than the other phase (s), based on its weight.

2. Detergent tablets according to claim 1, characterized in that the perfume content of the individual phases of the molding, based on the weight of the individual phase, by more than 0.1 wt .-%, preferably by more than 0.25 wt. -%, and in particular by more than 0.5% by weight.

3. Detergent or cleaning product tablets according to one of claims 1 or 2, characterized in that the polymer content of the individual phases of the molding, based on the weight of the individual phase, by more than 0.05% by weight, preferably by more than 0 , 1% by weight, particularly preferably by more than 0.2% by weight and in particular by more than 0.5% by weight.

4. Detergent tablets according to one of claims 1 to 3, characterized in that the tablets have two phases which contain the same perfume in different amounts.

5. Detergent or cleaning product tablets according to claim 4, characterized in that the tablets have two layers, one of which is free of perfume.

6. Detergent tablets according to one of claims 1 to 5, characterized in that the tablets total perfume contents from 0.05 to 10 wt .-%, preferably from 0.1 to 5 wt .-% and in particular from 0, 25 to 1.5% by weight, based in each case on the weight of the shaped body.

7. Detergent tablets according to one of claims 1 to 6, characterized in that the tablets further contain surfactant (s), preferably only nonionic surfactant (s), the surfactant (s) preferably at least 40%, particularly preferably at least 60% and in particular at least 75% of its weight is contained in the more perfume phase.

8. Detergent tablets according to one of claims 1 to 7, characterized in that the molded article consists of two phases and the quotient of the difference in the perfume contents and the difference in the polymer contents is less than 2, preferably less than 1 and in particular less than 0 , 5 is.

9. A process for the production of multi-phase detergent tablets by pressing different particulate premixes known per se, which contain different amounts of perfume, characterized in that the more perfume-containing premix contains more polymer (s) than the other (s) based on its weight ) Premixed (e).

10. The method according to claim 9, characterized in that the perfume is introduced by spraying onto the premix (s) in the perfume-containing phase (s).

11. The method according to any one of claims 9 or 10, characterized in that the perfume is introduced into the perfume-containing phase (s) by adding solid fragrance preparation forms to the premix (s).