DE102004011256A1 - Multi-phase tablets with improved fragrance perception - Google Patents

Abstract

Improved fragrance impressions even after the dishwasher dishwashing cycle has been completed can be achieved if two- or multi-phase detergent tablets of compacted particulate detergent or cleaning agent comprising polymer (s), builder (s), perfume and optionally other detergent and cleaner ingredients , wherein one phase of the molded article, by weight, contains more perfume than the other (n) phase (s) and the perfume-rich phase of the molded article contains, by weight, more polymer (s) than the other ( n) phase (s).

Description

The The present invention relates to multiphase detergent tablets. Especially The invention relates to multi-phase RMFK used for machine cleaning used by dishes in household dishwashers and short as detergent tablets for automatic dishwashing or be referred to as tableted MGSM.

The Machine cleaning of dishes in household dishwashers usually includes a prewash, a main wash and a rinse, which are interrupted by intermediate rinses. For most machines, the pre-rinse cycle is for heavily soiled dishes switchable, but is chosen only in exceptional cases by the consumer, so that in Most machines have a main wash, an intermediate wash with pure water and a rinse carried out become. The temperature of the main rinse varies depending on Machine type and program level selection between 40 and 65 ° C. In the rinse cycle from a dosing tank in the machine added rinse aid, which is usually contain nonionic surfactants as the main ingredient. Such rinse aid are in liquid Form and are widely described in the art. Your task consists mainly in limescale and deposits on the cleaned dishes to prevent. In addition to water and low-foaming nonionic surfactants this rinse aid often also hydrotopes, pH adjusters such as citric acid or deposit-inhibiting Polymers as well as often perfume.

Also the automatic dishwashing detergents in itself are often perfumed. Here is the additional Problem that with the water changes between the individual rinses the perfume is pumped out, so that though that means when buying smells, the consumer but the fragrance impression not can perceive the cleaning process. In addition, some suffer sensitive fragrances under the drastic conditions in the rinse cycle. When The consequence of this is the consumer perceived as unpleasant "alkali odor" when opening the dishwasher only insufficiently covered. About that In addition, only a small proportion of the expensive fragrances to where it should be effective.

When solution for this Problem strikes International Patent Application WO98 / 07812 (Proter & Gamble), fragrance release systems in automatic dishwashing detergent to incorporate which β-ketoesters contained by fragrance alcohols. These esters are split slowly and should cause such a long-lasting fragrance impression. Also Here are the esters due to the chemical and thermal stress in the main and rinse cycle partly already split, so that the fragrances sensitive decomposes or with the rinse water before the rinse cycle be pumped out. The proportion of fragrances is still to the desired Place of effect gets low.

The German patent application DE 199 48 667 (Henkel) proposes to use detergent components which contain 0.1 to 20% by weight of one or more esters, ethers, acetates or ketals of perfumes, 20 to 99.9% by weight of fusible substances) having a melting point above 30 ° C and 0 to 60 wt .-% of other active ingredients and / or adjuvants include. By incorporating the perfume precursors into fusible substances, the release of these sensitive substances can be selectively controlled so that exposure to the alkaline cleaning liquor and ambient temperatures is avoided until the fusible substances release the perfume precursors. As a result of the cleavage of the perfume precursor only now beginning, the released perfume is subjected to a significantly shorter thermal or chemical load, so that less perfume is destroyed by environmental influences. Although the fragrance compounds disclosed in this document lead to significantly improved fragrance perception and prevent the intermediate pumping of the perfume largely, but they are expensive to manufacture, since the fragrances first esterified, etherified, acetalized or ketlisiert and then into a melt matrix must be introduced.

It Therefore, it was still the task to provide low-cost which contains the perfume contained in them to a higher one Percentage or ideally completely free where it on the one hand no longer decomposed and perceived by the consumer can be. It should as possible the perfume can be used directly. The solution This object was the object of the present invention.

It has now been found that an improved scent impression even after the wash program results when the perfumes or perfume oils in polyphase tablets are compounded together with polymer (s), wherein the remaining phase (s) have a reduced content of perfume and polymer.

object the present invention are two- or multi-phase washing or Cleaning tablets of compacted particulate Washing or cleaning preparations, comprising polymer (s), builder (s), Perfume and optionally other detergent and cleaner ingredients, wherein a phase of the shaped body based on its weight contains more perfume than the other phase (s) and the more perfumed Phase of the molding based on its weight contains more polymer (s) than the other phase (s).

According to the invention the washing or cleaning product molding of at least two phases, wherein a phase of perfumery and more polymer-rich than the other phase (s). For a three-phase tablet contains one phase according to the invention more perfume and more Polymer as the other two phases. The perfume and polymer contents relate here according to the invention on the Weight of each phase. "Rich" in perfume or on Polymer is a phase when in wt .-% (based on the Phase) value for the ingredient in question is larger as the value of the other phase (s).

Especially it is preferred according to the invention if the content of the phases of perfume or polymer varies significantly. Here are washing or detergent tablets preferred in which the perfume content the individual phases of the molding, based on the weight of each phase to more than 0.1 wt .-%, preferably more than 0.25% by weight and in particular more than 0.5 wt .-%, varies.

For the polymer content can be made analogous information. Preferred detergent or cleaner tablets according to the invention are characterized in that the Polymer content of the individual phases of the molding, based on the weight the individual phase by more than 0.05 wt .-%, preferably by more as 0.1 wt .-%, more preferably more than 0.2 wt .-% and in particular by more than 0.5% by weight.

in the In the context of the present application, the variation means more as 0.1% by weight, based on the weight of the individual phases, of the absolute values the perfume content in the phases vary by more than 0.1 wt .-%. So it contains a phase 2.0% by weight perfume, so should the perfume content the other phase (s) are selected according to the invention so that the width the variation around the value 2.0 is at least 0.1% by weight, that is below 1.9% by weight or above 2.1% by weight, based in each case on the phase. In other words the percentage value of the perfume content the most perfumed phase from the percentage value of the perfume content the most perfumed Phase subtracted, the result must be ≥ 0.1. The biggest possible difference in perfume content in the individual phases can be reach if at least one phase contains perfume, while at least one other Phase free of perfume is. This is another preferred embodiment of the present invention Invention.

The individual phases of the molding can in the context of the present invention, different spatial forms exhibit. The simplest realization option lies in two or multilayer tablets, wherein each layer of the shaped body a Phase represents. However, it is also possible according to the invention to produce multiphase shaped bodies, in which individual phases take the form of incorporation into (another) one Phase (s). In addition to so-called "ring-core tablets" are, for example, coated tablets or combinations of said embodiments possible. Examples for multiphase moldings can be found in the drawings of EP-A-0 055 100 (Jeyes) which describes toilet cleaning blocks. The technically widespread spatial form of multiphase moldings is the two- or multi-layered tablet. In the context of the present invention It is therefore preferred that the Phases of the molding have the form of layers. Become three-phase form body presently preferably offered by a two-phase mortar tablet is provided, the trough is filled with a "core" as the third phase. These products have high consumer acceptance and are preferred as a three-phase molded article.

The Differences in perfume content the individual phases can be realized, for example, by that each Phase a different perfume contains whereby the perfume contents differentiate in the phases. In this way, different fragrance impressions for each individual Phase realized or the composition of the perfumes to the remaining ingredients adapted to the phase in question become. It is preferred for reasons the manufacturing economy however, if the washing or detergent tablets have two phases, the same perfume in different amounts contain.

As already mentioned, let yourself the biggest difference in the perfume content by the combination of perfume-free with perfume Achieve phases. In a two-layer molded body means this, that washing and detergent tablets preferred are those having two layers, one of which is free of perfume is.

Of the Proportion of the individual phases on the whole tablet can be in broad Limits are varied. For the preferred according to the invention In the case of a two-layer tablet, detergent tablets are preferred. in which the two layers of the molding in the weight ratio of 5 to 95 to 50 to 50, preferably from 10 to 90 to 60 to 40 and in particular from 15 to 85 to 65 to 35, the perfume preferably in the proportionately lower Layer higher is concentrated.

phases with higher Perfume fraction can do not bind them so strongly, i. the fragrance is less strong in the molding sticking in front and can when opening the packaged tablet perceived by the consumer more intense become. Also, by the variation of the perfume content in layers of a tablet stability of both layers as well adjust their disintegration times or control them selectively. An additional one Effect occurs at higher perfume contents in a colored layer, as their color intensity is increased.

When Perfume can in the moldings of the invention a wide variety of substances are used.

Of the Term "perfume", a Germanized Word, which, like the French root word "parfum" from the Latin "per fumum" = by (sacrificial) smoke is derived in the German language with different Meanings used. So one understands under perfumes alcoholic solutions suitable fragrances (fragrances), but also the fragrance or the Perfume itself, occasionally also the terms perfumery and Perfume equated. In the context of the present application features the term "perfume" both individual Fragrances as well as perfume mixtures in concentrated or with suitable solvents diluted Shape. The term perfume oil "is next to the pure Fragrance mixture that is not diluted with solvents, used. The basic ingredients of the perfume oils are essential oils, Flower oils, extracts from plant and animal drugs, isolated from natural products, chemically altered (semi-synthetic) and purely synthetically derived fragrances. "Fragrances" is the colloquial Collective name for those Fragrances that give humans a pleasant smell trigger and therefore for perfuming of detergents and cleaners are suitable. In an expanded sense You can also count on essences and aromas to the fragrances.

When Perfume oils or Fragrances can according to the invention individual Fragrance compounds, e.g. the synthetic products of the type the esters, ethers, aldehydes, ketones, alcohols and hydrocarbons be used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethyl acetate, Benzyl acetate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate, benzyl salicylate, cyclohexyl salicylate, floramate, Melusat and Jasmecyclat. Ethers include, for example, benzyl ethyl ether and ambroxan, to the aldehydes e.g. the linear alkanals with 8-18 C atoms, Citral, citronellal, citronellyloxy-acetaldehyde, cyclamenaldehyde, Lilial and Bourgeonal, to the ketones e.g. the ionone, α-isomethylionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons belong mainly the terpenes like limonene and pinene. However, mixtures are preferred different fragrances used, which together create an appealing Create a fragrance.

Such Perfume oils can also natural Contain fragrance mixtures, as they are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are Muscat sage oil, Chamomile oil, Clove oil, Balm oil, mint oil, Cinnamon leaf oil, lime 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 Now cleaning agents are produced, in which the proportion of the perfume, the in the on perfume and polymer richer phase, mainly from adherent fragrances is composed. In this way, adherent fragrances be "held" in the product and their Effect thereby mainly in rinse unfold. In contrast, wear the more volatile ones Fragrances contribute to a more intensive scenting of the funds themselves. In this way it is also possible To produce cleansers that have a smell as an agent, the smell of the opening the dishwasher different. The creativity from perfumers There are hardly any limits.

The The principle described above can be Of course also reverse by adding the more volatile fragrances into the to perfume and polymer richer phase incorporated and the less volatile, adherent fragrances are sprayed on the agent. In this way will be the loss of the more volatile fragrances minimized from the packaging during storage and transportation while the Fragrance characteristic of the agents determined by the more adhesive perfumes becomes.

The general description of the perfumes used (see above) was general the different substance classes of fragrances dar. To perceptible to be must Perfume be volatile, besides the nature of the functional groups and the structure the molecular weight of the chemical compound also plays an important role plays. So most perfumes have molecular weights up to about 200 Dalton, while Molar masses of 300 daltons and above rather an exception. Due to the different volatility changed by fragrances the smell of a compound of several fragrances perfumes or perfume during vaporizing, whereby the odor impressions in "top note", "middle note" body) and "base note" (end note or dry divided out). Because the smell perception to a large extent also on the smell intensity is based, the top note of a perfume or fragrance is not alone from volatile Connections while the base note for the most part from less volatile, i.e. adherent Riehcstoffen. When composing perfumes can be easier volatile For example, fragrances can be bound to specific fixatives. which prevents it from evaporating too quickly. The one described above embodiment of the present invention, in which the more volatile Fragrances or fragrances on the water-insoluble carrier materials of low density is applied, is such a method for fragrance fixation. In the fol lowing classification of fragrances in "lighter volatile or "adherent" fragrances So over the smell impression and about it, whether the corresponding perfume perceived as a head or middle note nothing is said.

Tenacious Fragrances that can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica oil, basil oil, bay oil, bergamot oil, Champacablütenöl, Edeltannöl, Edeltannenzapfenapfen, Elemiöl, eucalyptus oil, fennel oil, spruce alder oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, Gurjunbalsamöl, Helichrysumöl, Ho oil, Ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine oil, copaia balsam, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, musk kernel oil, myrrh oil, clove oil, neroli oil, niaouli oil, Olibanum Oil, Orange Oil, Origanum Oil, Palmarosa Oil, Patchouli Oil, Peru Balsam Oil, Petitgrain Oil, Pepper Oil, Peppermint Oil, Pimento Oil, Pine Oil, Rose Oil, Rosemary Oil, Sandalwood Oil, Celery Oil, Spik Oil, Star Aniseed Oil, Turpentine Oil, Thuja Oil, Thyme Oil, Verbena Oil, Vetiver Oil, Juniper Berry Oil, Vermouth Oil, Wintergreen oil, Ylang-Yla ng oil, hyssop oil, cinnamon oil, cinnamon oil, lemon oil, lemon oil and cypress oil.

But also the higher-boiling ones or solid odoriferous natural or of synthetic origin in the context of the present invention as adherent fragrances or Fragrance mixtures, so fragrances are used. To this Counting connections the following compounds as well as mixtures of these: Ambrettolide, α-amylcinnamaldehyde, Anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, Acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, Benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, Borneol, bornyl acetate, α-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, Farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, Heliotropin, heptincarboxylic acid methyl ester, Heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, Indole, iron, isoeugenol, isoeugenol methyl ether, isosafrole, jasmon, Camphor, Karvakrol, Karvon, p-cresol methyl ether, coumarin, p-methoxyacetophenone, Methyl n-amyl ketone, methyl anthranilate, p-methyl acetophenone, Methylchavikol, p-methylquinoline, methyl-β-naphthylketone, methyl-n-nonylacetaldehyde, Methyl n-nonyl ketone, Muskon, β-naphthol ethyl ether, β-naphthol methyl ether, Nerol, nitrobenzene, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxy-acetophenone, Pentadecanolide, β-phenylethyl alcohol, Phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegone, safrole, salicylic acid isoamyl ester, methyl salicylate, Salicylsäurehexylester, Salicylsäurecyclohexylester, Santalol, skatole, terpineol, thymen, thymol, γ-undelactone, vaniline, veratrum aldehyde, Cinnamaldehyde, cinnamyl alcohol, cinnamic acid, cinnamate, Zimtsäurebenzylester.

To the more volatile Scents count especially the lower-boiling fragrances natural or synthetic origin, used alone or in mixtures can be. In games for easier volatile Fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, Linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, Phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.

Of the Content of the individual phases of the moldings can be as described above be varied, it being preferred that the perfume into a To incorporate layer while the other layer (s) is / are free of perfume. Independent of perfume content in the individual phase (s) washing and cleaning agent tablets are preferred, where the moldings Total Partümgehalte from 0.05 to 10 wt .-%, preferably from 0.1 to 5 wt .-% and in particular from 0.25 to 1.5% by weight, in each case based on the molding weight, exhibit.

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

As an essential ingredient, the compositions of the invention contain polymers. The molecular weight of these polymers may 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, washing or cleaning agents which comprise 0.02 to 7.5% by weight, preferably 0.05 to 5% by weight, especially preferably 0.07 to 2.5 wt .-% and in particular 0.1 to 1 wt .-% of at least one polymer having a molecular weight of 2000 gmol ^-1 or more, which has at least one positive charge, contain, are particularly preferred.

at The aforementioned polymers with cationic charge may be principally cationic or amphoteric polymers. preferred Washing according to the invention or detergents are characterized in that they are in the polymer having cationic monomer units, a cationic polymer and / or an amphoteric polymer is.

"Cationic Polymers "in the sense The present invention relates to polymers which are a positive charge in the polymer molecule wear. This can be present, for example, in the polymer chain (Alkyl) ammonium moieties or other positively charged groups will be realized. Particularly preferred cationic polymers are derived from the groups of the 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 the dialkylamino acrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 indicated polymers.

"Amphorere Poylmere "in the sense of the present invention have besides a positively charged group in the polymer chain also negatively charged groups or On monomer units. These groups may be, for example to carboxylic acids, sulfonic acids or phosphonic acids act.

Detergents or cleaners, 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} independently selected is hydrogen, derivatized hydroxy, C1 to C30 linear or branched alkyl groups, aryl, aryl substituted C _1-30 linear or branched alkyl groups, polyalkoxylated alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group having a positive charge in the partial range of the pH range of 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 having at least one positive charge without charged nitrogen, at least one quaternized nitrogen atom or at least one amino group with a positive charge, are within the scope of the present invention nmeldung particularly preferred.

bei der R¹ und R⁴ unabhängig voneinander für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen steht; R² und R³ unabhängig voneinander für eine Alkyl-, Hydroxyalkyl-, oder Aminoalkylgruppe stehen, in denen der Alkylrest linear oder verzweigt ist und zwischen 1 und 6 Kohlenstoffatomen aufweist, wobei es sich vorzugsweise um eine Methylgruppe handelt; x und y unabhängig voneinander für ganze Zahlen zwischen 1 und 3 stehen. X^- repräsentiert ein Gegenion, vorzugsweise ein Gegenion aus der Gruppe Chlorid, Bromid, Iodid, Sulfat, Hydrogensulfat, Methosulfat, Laurylsulfat, Dodecylbenzolsulfonat, p-Toluolsulfonat (Tosylat), Cumolsulfonat, Xylolsulfonat, Phosphat, Citrat, Formiat, Acetat oder deren Mischungen.In the context of the present application, particularly preferred cationic or amphoteric polymers comprise, as the monomer unit, a compound of the general formula (I)

when R ¹ and R ^{4 are} independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ^{3 are} independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3. X ^- represents a counterion, preferably a counterion from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R ¹ and R ² 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 -O) _n H.

For the purposes 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 ¹ 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 ^- in the case of X ^- = chloride, they are also referred to as DADMAC (diallyldimethylammonium chloride).

Further cationic or amphoteric polymers which are particularly preferred for the purposes of the present application comprise a monomer unit of the general formula (II) R ¹ HC = CR ² -C (O) -NH- (CH ₂ ) _x -N ⁺ R ³ R ⁴ R ⁵ X ^- (II) in which R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently of one another are a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably 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 -O) _n H and x is an integer between 1 and 6.

For the purposes 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 (O) -NH- (CH ₂ ) _x N ⁺ (CH ₃ ) ₃ X ^-

In the case of X ^- = chloride also referred to as MAPTAC (Methyacrylamidopropyl-trimethylammonium chloride).

According to the invention preferred Detergents or cleaning agents are characterized in that the polymer c) as monomer units diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts contains.

The previously mentioned Amphoteric polymers have not only cationic groups, but also anionic groups or monomer units. Such anionic For example, monomer units come from the linear group or branched, saturated or unsaturated Carboxylates, linear or branched, saturated or unsaturated Phosphonates, which are linear or branched, saturated or unsaturated Sulfates or the linear or branched, saturated or unsaturated Sulfonates. Preferred monomer units are the acrylic acid, the (Meth) acrylic acids, the (dimethyl) acrylic acid, the (ethyl) acrylic acid, the cyanoacrylic acid, the vinylessing acid, the allylacetic acid, the crotonic acid, the maleic acid, the fumaric acid, the cinnamic acid and their derivatives, the allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallyl or the allylphosphonic acids.

Preferred employable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth ) -acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic mo nomeren.

Prefers usable zwitterionic polymers are from the group of Acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their Alkali and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the Methacroylethylbetain / methacrylate copolymers.

Prefers are further amphoteric polymers, which in addition to one or more anionic monomers as cationic monomers Methacrylamidoalkyl-trialkylammonium chloride and dimethyl (diallyl) ammonium chloride.

Especially preferred amphoteric polymers are from the group of the Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers as well as their alkali and ammonium salts.

Especially preference is given to amphoteric polymers from the group of methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the 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 The present application uses polymers which contain sulfonic acid groups contain. Preferred compositions according to the invention are therefore characterized in that at least one copolymer of unsaturated carboxylic acids containing sulfonic acid groups Monomers 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 the 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 is -COOH or -COOR ⁴ , wherein 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 the 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) is preferred.

In the sulfonic acid-containing monomers, those of the formula IV are preferred, R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (IV), in the 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 is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n with n = 0 to 4, -COO- (CN ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -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-SO ₃ H (IVa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (IVb), HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (IVc), in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₃ ) ₂ with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Especially preferred sulfonic acid group-containing Monomers 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-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, Sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts the acids mentioned.

When other ionic or nonionic monomers are used in particular ethylenically unsaturated compounds into consideration. Preferably the content of the invention used Polymers to monomers of group iii) less than 20 wt .-%, based on the polymer. Particularly preferred polymers to use only from monomers of groups i) and ii).

• i) ungesättigten Carbonsäuren der Formel III. R¹(R²)C=C(R³)COOH (III),in der R¹ bis R³ unabhängig voneinander für -H -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit-NH₂, -OH oder- COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,
• ii) Sulfonsäuregruppen-haltigen Monomeren der Formel IV R⁵(R⁶)C=C(R⁷)-X-SO₃H (IV),in der R⁵ bis R⁷ unabhängig voneinander für -H -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)
• iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren besonders bevorzugt.

In summary, copolymers are made of

• i) unsaturated carboxylic acids of the formula III. R ¹ (R ² ) C = C (R ³ ) COOH (III), in the 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 , -O-OH or -COOH-substituted alkyl or alkenyl radicals as defined above or -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) sulfonic acid group-containing monomers of the formula IV R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (IV), in the 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 is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ )
• iii) optionally further ionic or nonionic monomers particularly preferred.

• i) einer oder mehrerer ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln IVa, IVb und/oder IVc: H₂C=CH-X-SO₃H (IVa), H₂C=C(CH₃)-X-SO₃H (IVb), HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H (IVc),in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)₂ mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
• iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren.

Particularly preferred copolymers consist of

• i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid
• ii) one or more sulfonic acid group-containing monomers of the formulas IVa, IVb and / or IVc: H ₂ C = CH-X-SO ₃ H (IVa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (IVb), HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (IVc), in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) ₂ with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -
• iii) optionally further ionic or nonionic monomers.

The Copolymers can the monomers from groups i) and ii) and optionally iii) contained in varying amounts, all representatives from the group i) with all Representatives from group ii) and all representatives from the group Group iii) can be combined. Particularly preferred polymers have certain structural units on, which are described below.

Thus, for example, preferred are compositions according to the invention which are characterized in that they contain one or more copolymers which contain structural units of the formula V - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (V), in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, are preferred.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. Copolymerizing the sulfonic acid-containing acrylic acid derivative with methacrylic acid, one arrives at another polymer whose use in the compositions of the invention is also preferred and characterized in that the compositions contain one or more copolymers, the structural units of formula VI - (CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VI), in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, compositions according to the invention which comprise one or more copolymers which are structural units of the formula VII - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (VII) in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) where n = 0 to 4, -O- (C ₆ H ₄ ) -, -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - Also preferred is a preferred embodiment of the present invention, just as preferred are compositions characterized in that they contain one or more copolymers containing structural units of formula VIII [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (VIII) in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) where n = 0 to 4, -O- (C ₆ H ₄ ) -, -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , are preferred.

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). In this way, one obtains according to the invention preferred compositions, which are characterized in that they contain one or more copolymers, the structural units of the formula VIII - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VIII) in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred and to 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 (O) OY-SO ₃ H] _p - (IX), in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) where n = 0 to 4, -O- (C ₆ H ₄ ) -, -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , are preferred.

In summary, compositions according to the invention which contain one or more copolymers which contain 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 (O) -Y-SO ₃ H] _p - (IV), - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VI), - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (VI), - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (VII) - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VIII) - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (IX), in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) where n = 0 to 4, -O- (C ₆ H ₄ ) -, -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , are preferred.

In the polymers can the sulfonic acid groups wholly or partly in neutralized form, i. that the acidic Hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups against metal ions, preferably alkali metal ions and in particular against sodium ions, can be replaced. Corresponding compositions, which are characterized in that the sulfonic acid groups in Copolymer partially or fully neutralized, are preferred according to the invention.

The Monomer distribution of those used in the compositions of the invention Copolymer is for copolymers containing only monomers from groups i) and ii), preferably in each case from 5 to 95% by weight of i) or ii), particularly preferably 50 to 90% by weight of monomer from group i) and 10 to 50% by weight Monomer from group ii), in each case based on the polymer.

at Terpolymers are particularly preferred which contain from 20 to 85% by weight. Monomer from group i), 10 to 60 wt .-% monomer from the group ii) and 5 to 30 wt .-% of monomer from group iii).

The molecular weight of the above-described sulfo-copolymers used in the compositions according to the invention can be varied in order to adapt the properties of the polymers to the desired use. Preferred compositions are characterized in that the copolymers have molecular weights of from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

The The polymers mentioned above are also outstandingly suitable Perfume carrier, provided the perfume not by spraying on a particulate Would like to incorporate premix - more details this can be found below in the presentation of the method according to the invention.

In a further preferred embodiment of the present application will be referred to as polymers below used as co-builders polymeric carboxylates.

• – die Verkapselung der Polymere mittels wasserlöslicher oder wasserdispergierbarer Beschichtungsmittel, vorzugsweise mittels wasserlöslicher oder wasserdispergierbarer natürlicher oder synthetischer Polymere;
• – die Verkapselung der Polymere mittels wasserunlöslicher, schmelzbarer Beschichtungsmittel, vorzugsweise mittels wasserunlöslicher Beschichtungsmittel aus der Gruppe der Wachse oder Paraffine mit einem Schmelzpunkt oberhalb 30°C;
• – die Cogranulation der Polymere mit inerten Trägermaterialien, vorzugsweise mit Trägermaterialien aus der Gruppe der wasch- oder reinigungsaktiven Substanzen, besonders bevorzugt aus der Gruppe der Builder (Gerüststoffe) oder Cobuilder.

In a particularly preferred embodiment of the present invention, the polymers present in the agents according to the invention are present in prefabricated form. For the preparation of the polymers is suitable inter alia

• The encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;
• - The encapsulation of the polymers by means of water-insoluble, fusible coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C;
• - The cogranulation of the polymers with inert support materials, preferably with support materials from the group of washing or cleaning-active substances, particularly preferably from the group of builders (builders) or cobuilders.

The according to the invention or detergent tablets can next to perfume and polymer in addition further one or more surfactants). These come from the groups of anionic, nonionic, cationic and / or amphoteric surfactants, wherein in the context of automatic dishwashing nonionic Surfactants are clearly preferred and the surfactants from the others Groups only in minor amounts or preferably not at all be used.

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

Further Suitable anionic surfactants are sulfated fatty acid glycerol esters. Among fatty acid glycerol esters are to understand the mono-, di- and triesters and their mixtures, such as they are produced by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained. Preferred sulfated fatty acid glycerol esters are included the sulphonated products of saturated fatty acids with 6 to 22 carbon atoms, for example the caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or Behenic acid.

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

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

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

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

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

Another group of detergent substances are the nonionic surfactants. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG). Usable Alkypolyglycoside meet the general formula RO (G) _z , in which R is a linear or branched, especially in the 2-position methyl branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4. Preference is given to using linear alkyl polyglucosides, that is to say alkyl polyglycosides which consist of a glucose residue and an n-alkyl chain.

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

Also 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 alkanolamide can 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 from that.

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

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

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

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

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

In detergents and cleaners for automatic dishwashing come as surfactants in general all surfactants in question. However, the nonionic surfactants described above and, above all, the low-foaming nonionic surfactants are preferred for this purpose. Particularly preferred are the alkoxylated alcohols, especially the ethoxylated and / or propoxylated alcohols. The person skilled in the art generally understands, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention, the longer-chain alcohols (C ₁₀ to C ₁₈ , preferably between C ₁₂ and C ₁₆ , such as, for example, C ₁₁ -, 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, depending on the reaction conditions, form a complex mixture of addition products of different degrees of ethoxylation. A further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Also, if desired, by a final etherification with short-chain alkyl groups, such as preferably the butyl group, the substance class of "closed" alcohol ethoxylates reach, which can also be used in the context of the invention. Very particularly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or mixtures thereof with end-capped fatty alcohol ethoxylates.

in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃; -CH₂CH₃, -CH₂CH₂-CH₃, -CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.In the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here, washing or cleaning compositions according to the invention are preferred which contain surfactants of the general formula III as nonionic surfactant (s)

in which R ^{1 is} 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 of one another are integers from 1 to 6.

The preferred nonionic surfactants of 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 the formula I above may 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 usually undisplayed, wherein the linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols accessible from sysnthetic sources are, for example, the Guerbet alcohols or in the 2-position methyl-branched or linear and methyl-branched radicals in a mixture, as they are usually present in Oxoalkoholresten. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, washing or cleaning agents according to the invention are preferred in which R ¹ in formula 1 is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or -CH (CH ₃ ) ₂ are suitable. Preferred detergents or cleaners are characterized in that R ² and R ³ are each a residue -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another represent values of 1 or 2.

In summary, nonionic surfactants which have a C _9-15 -alkyl radical with 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 are particularly preferred for use in the agents according to the invention.

When preferred additional Surfactants become low-foaming nonionic surfactants used. Included with special preference the washing or detergent, a nonionic surfactant having a melting point above room temperature. Accordingly, preferred means characterized in that nonionic) surfactants) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, contain.

suitable additionally to the invention in the Nonionic surfactants contained nonionic surfactants which or softening points in said temperature range, are, for example, low-foaming nonionic surfactants that are solid or highly viscous at room temperature could be. Become used at room temperature highly viscous nonionic surfactants, it is preferred that these a viscosity above of 20 Pas, preferably above 35 Pas and especially above 40 Pas. Also nonionic surfactants which are waxy at room temperature Consistency are preferred.

Prefers as at room temperature fixed to be used nonionic surfactants derived the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary Alcohols and mixtures of these surfactants with structurally complicated built-up surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control out.

In a preferred embodiment The present invention is the nonionic surfactant having a Melting point above room temperature an ethoxylated nonionic surfactant, that from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 moles, in particular at least 20 moles of ethylene oxide per Mol alcohol or alkylphenol emerged.

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

Accordingly, particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).

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

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

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

A further preferred washing or cleaning agent according to the invention contains nonionic surfactants of the formula R ¹ O (CH ₂ CH (CH ₃ ) O] _x (CH ₂ CH ₂ O) _y [CH ₂ CH (OH) R ² ], in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.

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

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

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is to R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

Summarizing the latter statements, washing or cleaning agents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

In Compounds with said surfactants may also be anionic, cationic and / or amphoteric surfactants are used, these because their foaming behavior in automatic dishwashing detergents only have subordinate importance and mostly only in quantities below of 10 wt .-%, usually even below 5 wt .-%, for example from 0.01 to 2.5 wt .-%, each based on the agent used. The agents according to the invention can Thus, as a surfactant also anionic, cationic and / or contain amphoteric surfactants.

in the Within the scope of the present invention, it is preferred that the washing or detergent tablets 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 included. With particular preference, the agents according to the invention contain exclusively nonionic) Surfactants) and are therefore free of anionic, cationic and anionic surfactants amphoteric surfactants. Particularly preferred washing or detergent tablets are characterized in that the moldings as surfactants) contain only nonionic surfactant (s), with the nonionic surfactant (s) preferably at least 40% more preferably at least 60% and especially at least 75% of its weight in the perfume-rich Phase is included. Especially preferred are those agent according to the invention, characterized in that the moldings as surfactants) contain only nonionic surfactant (s), with the nonionic surfactant (s) preferably at least 80%, more preferably at least 90% and in particular at least 95% of its weight in the perfume-rich Phase is included.

Prefers are in the context of the present application, in particular those two or more phases Detergent tablets of compressed particulate detergent or cleaner, comprising polymer (s), builder (s), Perfume, Surfactants) and optionally other detergent and cleaner ingredients, wherein a phase of the shaped body based on its weight contains more perfume than the other phase (s), characterized in that the perfume-rich phase of the shaped body based on their weight contains more polymer (s) and more surfactants) than the other phase (s).

Next the absolute content of the individual phases of perfume and polymer, which refers to the composition of each phase, is also the relationship the amounts in the individual phases to each other variable. As part of detergent tablets are preferred in the present invention, which consist of two phases and in which the quotient of the Difference of perfume contents and the difference of the polymer contents less than 2, preferably smaller is 1 and in particular less than 0.5.

attracts for clarification, the example of a two-layer tablet, in which the content of the one phase of perfume p1 wt .-%, that of the other Phase p2 wt .-% is and refers analogously to the polymer content of the perfume-rich Phase with d1, that of the more perfumed phase with d2, in preferred embodiments the present invention applies Invention the mathematical relationship (p1 - p2) / (d1 - d2) <2, preferably <1 and in particular <0.5.

The according to the invention or detergent tablets contain builders as another ingredient. preferred Washing according to the invention or detergent tablets contain in addition to the ingredients listed above one more or more substances from the group of co-builders, bleaches, Bleach activators, enzymes, dyes, corrosion inhibitors, or another usual Component of detergents and cleaners. These ingredients will be described below.

Builder

According to the present invention, all builders commonly used in detergents and cleaners, in particular silicates, can be incorporated into the detergents and cleaners te, organic cobuilders and also the phosphates.

Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that in X-ray diffraction experiments the silicates do not give sharp X-ray reflections typical of crystalline substances, but at best one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties 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 regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred.

Especially preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried roentgenoamorphous Silicates.

When Carbonates can both the monoalkali metal salts and the dialkali metal salts the carbonic acid and sesquicarbonates may be included in the compositions. preferred Alkali metal ions represent sodium and / or potassium ions. In an embodiment it may be preferred that the carbonate and / or bicarbonate at least partly as a further component separately or subsequently admixed. Also compounds from, for example, carbonate, silicate and optionally other excipients such as anionic surfactants or others, especially organic builders, may be used as a separate component present in the finished means.

Of course it is also a use of the well-known phosphates as builders possible, if such use is not avoided for environmental reasons should be. Among the variety of commercially available Phosphates have the alkali metal phosphates, with particular preference of Pentasodium or pentakalium triphosphate (sodium or potassium tripolyphosphate) in the washing and cleaning industry the greatest importance.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits on machine parts or limescale deposits on the items to be washed and also contribute to the cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; It is formed when phosphoric acid is adjusted to pH 4.5 with narcotic eye and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt of density 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , loss of water at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. dipotassium (Secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) aufeisen a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 gcm ^-3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.

Tetrasodium disphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals. Na ₄ P ₂ O ₇ is formed on heating of 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 agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, where one can distinguish cyclic representatives, the sodium or Kaliummetaphoshate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches 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 with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are exact according to the invention such as sodium tripolyphosphate, potassium tripolyphosphate or mixtures can be used from these two; also 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 used according to the invention.

in the Within the scope of the present invention preferred detergents or cleaners do not contain sodium and / or potassium hydroxide. A waiver Sodium and / or potassium hydroxide as alkali source has particular proved to be advantageous if, as zinc salts, zinc gluconate, Zinc formate and zinc acetate can be used.

builders

When organic cobuilders can in the cleaning agents in the context of the present invention in particular Polycarboxylates / polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates used become. The polymers can It may also be part of the active substance-containing matrix, but they can also completely independently from this in the inventive compositions be included. The mentioned classes of substances are described below.

useful organic builders For example, they can be used in the form of their sodium salts polycarboxylic where among polycarboxylic acids such carboxylic acids be understood that 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), if such an application for ecological reasons not is objectionable, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids like citric acid, adipic acid, Succinic acid, glutaric, Tartaric acid, methylglycine, sugar acids and mixtures of these.

Also the acids in itself can be used. The acids In addition to their builder effect, they also typically have the property an acidifying component and thus serve to set a lower and milder one pH value of detergents or cleaning agents. In particular, here are citric acid, Succinic acid, glutaric, adipic acid, gluconic and to name any mixtures of these.

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

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

suitable Polymers are in particular polyacrylates, which preferably have a molecular mass of 1000 to 20,000 g / mol. Because of their superior solubility can from this group again the short-chain polyacrylates, the molecular weights from 1000 to 10000 g / mol, and more preferably from 1200 to 4000 g / mol, may be preferred.

Especially Both polyacrylates are preferred in the agents according to the invention as well as copolymers of unsaturated Carboxylic acids, Containing sulfonic acid Monomers and optionally further ionic or nonionic Monomers used. The sulfonic acid-containing copolymers are in detail in detail described.

Besides can Of course also the sulfonic acid group-containing polymers described above in the inventive compositions be included, without necessarily part of the active ingredient To be a matrix.

As already mentioned above, in the agents according to the invention it is particularly preferable to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers. The polyacrylates were described in detail above. Particularly preferred are combinations of the above-described sulfonic acid-containing copolymers with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons. Such polyacrylates are commercially available under the trade name Sokalan ^® PA15 and 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. Particularly suitable Co Polymers of acrylic acid with maleic acid containing 50 to 90 wt .-% of acrylic acid and 50 to 10 wt .-% of maleic acid. Their molecular weight relative to free acids is generally from 2000 to 100,000 g / mol, preferably from 20,000 to 90,000 g / mol and in particular from 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 the (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%.

to Improvement of water solubility can the polymers also include allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as Contain monomer.

Especially Biodegradable polymers of more than two are also preferred various monomer units, for example, those as monomers Salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers Salts of acrylic acid and 2-alkylallyl sulfonic acid and sugar derivatives.

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

As well are as further preferred builders polymeric aminodicarboxylic acids whose Salts or their precursors to call. Particular preference is given to polyaspartic acids or their salts and derivatives.

Further Suitable builders are polyacetals, which by reaction of dialdehydes with polyol carboxylic acids containing 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained. preferred Polyacetals are from dialdehydes such as glyoxal, glutaraldehyde, Te phthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic receive.

Further suitable organic builders are dextrins, for example Oligomers or polymers of carbohydrates by partial Hydrolysis of starches can be obtained. The hydrolysis can be carried out according to usual, for example acidic or enzyme-catalyzed processes. Preferably These are hydrolysis products with average molecular weights in the range from 400 to 500,000 g / mol. It is a polysaccharide with a Dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 preferred where DE is a common one Measure of the reducing Effect of a polysaccharide compared to dextrose, which DE of 100 is. Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrup with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher Molar masses in the range of 2000 to 30,000 g / mol.

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 to C _{6 of} the saccharide ring may be particularly advantageous.

Also Oxydisuccinates and other derivatives of disuccinates, preferably Ethylenediamine disuccinate are other suitable cobuilders. there becomes ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. As a builder is from the class of Phos phonate prefers HEDP ver used. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

Furthermore can all compounds that are capable of complexes with alkaline earth ions train as co-builders.

Compositions according to the invention are characterized in the context of the present application characterized that she Builders, preferably from the group of silicates, carbonates, organic Cobuilders and / or phosphates in amounts of from 0.1 to 99.5% by weight, preferably from 1 to 95% by weight, more preferably from 5 to 90 Wt .-% and in particular from 10 to 80 wt .-%, each based on the means included.

bleach

Bleaching agents and bleach activators are important constituents of detergents and cleaners, and a washing and cleaning agent may in the context of the present invention contain one or more substances from the groups mentioned. Among the compounds which serve as bleaches and deliver H ₂ O ₂ in water, sodium percarbonate has particular significance. Further useful bleaching agents are, for example, sodium perborate tetrahydrate and the sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

"Sodium percarbonate" is a term used in unspecified form for sodium carbonate peroxohydrates, which strictly speaking are not "percarbonates" (ie salts of percarbonic acid) but hydrogen peroxide adducts of sodium carbonate. The commercial product has the average composition 2 Na ₂ CO ₃ · 3 H ₂ O ₂ and is therefore no peroxycarbonate. Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm ^-3 , which readily decomposes into sodium carbonate and bleaching or oxidizing oxygen.

sodium carbonate peroxyhydrate was first made in 1899 by precipitation with ethanol from a solution obtained from sodium carbonate in hydrogen peroxide, but erroneously as Peroxycarbonate considered. It was not until 1909 that the compound became a hydrogen peroxide addition compound recognized, yet the historical term "sodium percarbonate" is in practice enforced.

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

cleaning supplies for the automatic dishwashing can also contain bleaches from the group of organic bleaches. Typical organic bleaches as ingredients in the frame can be used in the present invention are the diacyl peroxides, such as. Dibenzoyl. Other typical organic bleaches are the peroxyacids, Examples being the alkyl peroxyacids and the aryl peroxyacids become. Preferred representatives are (a) the peroxybenzoic acid and their ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and Magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, like peroxylauric acid, Peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic, such as 1,12-diperoxy carboxylic acid, 1,9-diperoxyazelaic acid, Diperocysebacinsäure, diperoxybrassylic, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid, N, N-Terephthaloyl-di (6-aminopercapronate) can be used become.

When Bleach for automatic dishwashing can according to the present Invention also used chlorine or bromine releasing substances become. Among the suitable chlorine or bromine releasing materials for example, heterocyclic N-bromo and N-chloroamides, for example, trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

advantageous Means in the context of the present invention contain one or more Bleaching agent, preferably from the group of oxygen or halogen bleaches, in particular the chlorine bleach, with particular preference of sodium percarbonate and / or sodium perborate monohydrate, in amounts of from 0.5 to 40 Wt .-%, preferably from 1 to 30 wt .-%, particularly preferably from 2.5 to 25 wt .-% and in particular from 5 to 20 wt .-%, respectively based on the total mean.

Bleach activators

Around when cleaning at temperatures of 60 ° C and below an improved Bleaching effect can achieve Cleaning Agents in the Present Invention Bleach activators contain. As bleach activators, compounds mentioned in U.S. Pat Perhydrolysis aliphatic peroxycarboxylic acids preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid be used. Suitable substances are the O and / or N-acyl groups of said carbon atom number and / or optionally substituted Wear benzoyl groups. Preference is given to polyacylated 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 Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place can according to the present Invention also called bleach catalysts in the detergents be incorporated. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe-Cu and Ru-amine complexes are used as bleach catalysts usable.

According to the invention Medium preferably, one or more substances from the group of Bleach activators, in particular from the groups of the multiply acylated Alkylenediamines, especially tetraacetylethylenediamine (TAED), the N-acylimides, especially N-nonanoylsuccinimide (NOSI), which are acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), in quantities from 0.1 to 20 wt .-%, preferably from 0.5 to 15 wt .-% and in particular from 1 to 10 wt .-%, each based on the total agent included.

in denen R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist.The bleach activators which are preferred in the context of the present invention furthermore include the "nitrile quats", cationic nitriles of the formula (IV),

in which R ^{1 is} -H, -CH ₃ , a C _2-24 -alkyl or -alkenyl radical, a substituted C _2-24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C _1-24 -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 -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion.

The general formula (XXI) includes a variety of cationic nitriles useful in the present invention. With particular advantage, the detergent tablets according to the invention comprise cationic nitriles in which R ^{1 represents} methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-butyl Tetradecyl, n-hexadecyl or n-octadecyl stands. R ² and R ³ are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, wherein one or both radicals may advantageously also be a Cyanomethylenrest.

For ease of synthesis, preference is given to compounds 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 ^- , wherein X is preferably an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is.

in the For the purposes of the present invention, preferred washing and cleaning agents are characterized in that they the cationic nitrile of the formula (XXI) in amounts of from 0.1 to 20 Wt .-%, preferably from 0.25 to 15 wt .-% and in particular of 0.5 to 10 wt .-%, each based on the molding weight, included.

enzymes

When Enzymes are especially those from the classes of hydrolases as the proteases, esterases, lipases or lipolytic acting Enzymes, amylases, cellulases or other Glykosylhydrola sen and mixtures the enzymes mentioned in question. All of these hydrolases carry in the Laundry to remove stains such as protein, fat or starch Stains and graying at. Cellulases and other glycosyl hydrolases can about that By removing pilling and microfibrils for color retention and to increase contribute to the softness of the textile. For bleaching or inhibition the color transfer can Oxidoreductases are also used. Particularly well suited from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens and their genetically modified variants obtained enzymatic agents. Preferably, subtilisin-type proteases and in particular Proteases derived from Bacillus lentus. These are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or Protease and cellulase or from cellulase and lipase or lipolytic acting enzymes or from protease, amylase and lipase or lipolytic acting enzymes or protease, lipase or lipolytic acting Enzymes and cellulase, but in particular protease and / or lipase-containing Mixtures or mixtures with lipolytic enzymes of special interest. Examples of such lipolytic acting Enzymes are the known cutinases.

Also Peroxidases or oxidases have in some cases as proved suitable. Suitable amylases include, in particular, alpha-amylases, Iso-amylases, pullulanases and pectinases. Being cellulases preferably cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures of these used. Because different types of cellulase are affected by their CMCase and avicelase activities can distinguish adjusted by targeted mixtures of cellulases the desired activities become.

The Enzymes can on carriers adsorbed or in enveloping substances be embedded to protect them against premature decomposition. preferred inventive agent contain enzymes, preferably in the form of liquid and / or solid enzyme preparations, in amounts of from 0.1 to 10% by weight, preferably from 0.5 to 8% by weight and in particular from 1 to 5 wt .-%, each based on the total Medium.

dyes

Around the aesthetic Impression of detergents and cleaners, they can improve dyed with suitable dyes. In the context of the present Invention preferred dyes whose selection the skilled person no Difficulty, possess a high storage stability and insensitivity across from the rest Ingredients of the agents and against light and no pronounced substantivity to textile fibers, so as not to stain them.

Preferred for use in the detergents and cleaning agents according to the invention are all colorants which can be oxidatively destroyed in the cleaning process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be advantageous to use colorants which are described in What or at room temperature in liquid organic substances are soluble. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe. 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. Further suitable colorants Pigmosol come ^® Blue 6900 (CI 74160), Pigmosol ^® Green 8730 (CI 74260), Basonyl ^® Red 545 FL (CI 45170), Sandolan® ^® rhodamine EB400 (CI 45100), Basacid® ^® Yellow 094 (CI 47005) Sicovit ^® Patentblau 85 e 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acidblue 183), pigment Blue 15 (Cl 74160), Supranol Blue ^® GLW (GAS 12219-32-8, Cl Acidblue 221 )), Nylosan Yellow ^® N-7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sardolan ^® Blue (Cl Acid Blue 182, CAS 12219-26-0) is used.

When choosing the colorant, it must be taken into account that the colorants do not have too high an affinity for the textile surfaces and, in particular, for synthetic fibers. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the 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 detergents or cleaners 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 a few 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 may contain corrosion inhibitors to protect the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) 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⁺ (PF6 ^- ) ₂ , [Me-MeTACN) Mn ^IV (m-0) ₃ Mn ^IV (Me-McTACN)] ²⁺ (PF ₆ ^- ) ₂ , [Me-TACN) Mn ^III (m-O) (m -OAc) ₂ Mn ^III (Me-TACN)] ²⁺ (PF 6 ^- ) ₂ and [Me-McTACN) Mn ^III (m-0) (m-OAc) ₂ Mn ^III (Me-McTACN)] ²⁺ (PF ₆ ^- ) ₂ , wherein Me-TACN is 1,4,7-trimethyl-1, 4,7-triazacyclononane and Me-McTACN stands for 1,2,4,7-tetramethyl-1,4,7-triazacyclononane. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

One preferred agent for providing corrosion protection for glassware at cleaning and / or Rinsing a dishwasher is zinc in oxidized form, i. Zinc compounds in which zinc cationic. Similarly, magnesium salts are also preferred. Here you can both soluble as bad or insoluble Zinc or magnesium compounds are used. Preferred compositions according to the invention contain one or more magnesium and / or zinc salts) at least one monomeric and / or polymeric organic acid.

The acids in question are preferably derived. from the group of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated Monocarbonsäu ren, 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 having at least 8 carbon atoms and / or resin acids.

Although all magnesium and / or zinc salts of monomeric and / or polymeric organic acids may be present according to the invention, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the groups of 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 are preferred. Within these groups, the acids mentioned below are again preferred in the context of the present invention:
From the group of unbranched saturated or unsaturated monocarboxylic acids: methanoic acid (formic acid), ethanoic acid (acetic acid), propionic 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 (arachidic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid) , Hexacosanoic acid (cerotic acid), triacotinic acid (melissinic acid), 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidinic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c Octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (linoleic acid ) and 9c, 12c, 15c-octadecatreic acid (linolenic acid).

Out the group of 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-decyltetradecanoic acid, 2-undecylpentadecanoic acid, 2-dodecylhexadecanoic acid, 2- Tridecylheptadecanoic acid, 2-tetradecyloctadecanoic acid, 2-pentadecylnonadecanoic acid, 2-hexadecyleicosanoic acid, 2-heptadecylheneicosanoic acid.

Out the group of unbranched saturated or unsaturated Di- or tricarboxylic acids: propanedioic (Malonic acid), Butandisäure (Succinic acid), pentanedioic (Glutaric acid), hexanedioic (Adipic acid), heptanedioic (Pimelic acid), octanedioic (Suberic acid), nonanedioic (Azelaic acid), decanedioic (Sebacic acid), 2c-butenedioic (Maleic acid), 2t-butenedioic (Fumaric acid), 2-butynedicarboxylic acid (acetylenedicarboxylic acid).

Out 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).

Out the group of sugar acids: galactonic, Manno acid, Fructonsäure, arabinonic, xylonic, ribonic, 2-deoxy-ribonic, Alginic acid.

Out the group of hydroxy acids: hydroxyphenylacetic (Mandelic acid), 2-hydroxypropionic acid (lactic acid), malic acid (malic acid), 2,3-dihydroxybutanedioic 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).

Out the group of oxo acids: 2-oxopropionic (Pyruvic acid), 4-oxopentanoic acid (Levulinic acid).

Out 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.

Out the group of polymeric carboxylic acids: polyacrylic acid, polymethacrylic Alkylacrylamide / acrylic acid copolymers, Alkylacrylamide / methacrylic acid copolymers, Alkyl acrylamide / methyl methacrylic acid copolymers, Copolymers of unsaturated Carboxylic acids, Vinyl acetate / crotonic acid copolymers, Vinylpyrrolidone / vinyl acrylate copolymers.

The spectrum of the inventively preferred zinc salts of organic acids, preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / L, preferably below 10 mg / L, in particular have no solubility, to such salts having a solubility in water above 100 mg / L, preferably above 500 mg / L, more 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, and 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, which is preferably at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt selected from zinc stearate, zinc oleate, zinc gluconate, zinc acetate , Zinc lactate and / or zinc citrate. Furthermore, zinc ricinoleate, zinc and zinc oxalate are preferably used.

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

The Perfume can be introduced in different ways in the moldings of the invention become. The simplest way is that the perfume by spraying on the premix (s) is introduced into the perfume-containing phase (s) becomes. Since the premixes to be compressed for the respective phases are usually Mixtures of different particulate and optionally liquid or pasty substances are, the perfume can simply added in the mixing step. This is a fine one Distribution, for example, a Verdüsen prefer the simple casting.

The Perfume can - in particular, if nonionic surfactants are used as surfactants - also with the surfactant mixed and mixed with this on the premixes be applied.

It but it is also possible the fragrances before adding to the respective premix on carriers to apply or extend in a suitable manner in their liability. For this offer, for example, cyclodextrin-perfume complexes or encapsulated perfumes at. Procedures in which the perfume by adding such solid perfume preparation forms the premix (s) are introduced into the perfume-containing phase (s) is, are also preferred.

When support materials For example, the builders mentioned above are suitable but also polymers from the group of the above-mentioned co-builders. A particularly suitable perfume carrier is the above-described sulfonic acid group-containing polymer.

In preferred method is a perfume and optionally surfactant or polymer-containing carrier material in the particulate Premix introduced. This preferably has perfume contents from 1 to 60 wt .-%, particularly preferably from 10 to 50 wt .-% and in particular from 12 to 40% by weight, in each case based on its weight, on. Unless the perfume-containing Material in addition Surfactant, preferably nonionic surfactant, the surfactant content is preferably from 20 to 60 wt .-%, particularly preferably from 25 to 55 wt .-% and in particular from 30 to 45% by weight, in each case based on the weight of the carrier material. In the latter cases lies the perfume content correspondingly at the lower end of the above range.

Provided loaded carrier materials as a perfume or surfactant carrier be used is the bulk density the loaded materials preferably at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.

In preferred method according to the invention indicates the loaded carrier material Particle sizes between 100 and 2000 μm, preferably between 200 and 1800 microns, more preferably between 400 and 1600 μm and in particular between 600 and 1400 microns, on.

The other ingredients of the detergent tablets according to the invention can also be introduced into the process according to the invention, to which reference is made to the above statements. Preferred processes are characterized in that the particulate premix is additional contains one or more substances from the group of bleaches, bleach activators, disintegration aids, enzymes, pH adjusters, fluorescers, dyes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, dye transfer inhibitors and corrosion inhibitors.

The Production of the shaped body according to the invention takes place first by dry blending the constituents of the individual phases, which may be pre-granulated in whole or in part, and subsequent informing, in particular compression to tablets, being conventional Method for producing multiphase moldings can be used. to Preparation of the multiphase invention moldings are the premixes in a so-called matrix between two Stamping compacted into a solid compressed. This process, the hereinafter referred to as tableting, is divided in four sections: metering, compaction (elastic deformation), plastic deformation and ejection.

The Tableting is done in commercial Tablet presses, in principle with single or double punches equipped could be. In the latter case, not only the upper punch for pressure build-up also the lower punch moves during the pressing process on the upper stamp too, during the Upper punch presses down. For small Production quantities are preferably used eccentric tablet presses, where the stamp or attached to an eccentric disc are, in turn, on an axis with a certain rotational speed is mounted. The movement of these punches is the way of working a usual one Four-stroke engine comparable. The compression can be done with one upper and stamped, it can but also several stamps attached to an eccentric disc, wherein the number of die holes is extended accordingly. The throughputs of eccentric presses vary from a few hundred to several depending on the type maximum 3000 tablets per hour.

For larger throughputs, choose Rotary tablet presses in which on a so-called die table A larger number of matrices circular is arranged. The number of matrices varies depending on the model 6 and 55, although larger matrices available in the stores are. Each die on the die table is a top and bottom stamp assigned, in turn, the pressing pressure active only by the Upper or lower stamp, but also constructed by both stamps can be. The die table and the stamps move around one common vertical axis, with the stamps with the help rail-like curved tracks during of circulation in the positions for filling, Compression, plastic deformation and ejection are brought. In the places where a particularly serious increase or decrease in the Stamp is required (filling, Compacting, ejecting), These curves are through additional low pressure pieces, Nierderzugschienen and lifting tracks supported. The filling the matrix is over a rigidly arranged supply device, the so-called filling shoe, the one with a reservoir for the Premix is connected. The pressing pressure on the premix is about the compression paths for upper and lower stamp individually adjustable, whereby the pressure build-up by the Vorbeirollen the stamp shank heads happens on adjustable pressure rollers.

Rotary presses can to increase the throughput with two filling shoes be provided, wherein for the preparation of a tablet only one Semicircle must be traversed. To produce two-layered and multi-layered shaped bodies, several filling shoes are used arranged one behind the other without the slightly pressed first Layer before further filling pushed out becomes. By suitable process control are on coat and point tablets produced this way, the one have onion-like structure, in the case of the point tablets not covering the top of the core or core layers and thus remains visible. Also rotary tablet presses are Equipped with single or multiple tools, so that, for example an outer circle with 50 and an inner circle with 35 holes at the same time for pressing to be used. The throughputs modern rotary tablet presses amount to over one million moldings per Hour.

• – Verwendung von Kunststoffeinlagen mit geringen Dickentoleranzen
• – Arbeitsweise ohne Einlagen mit minimalen Werkzeugtoleranzen und drehenden Stempeln
• – Geringe Umdrehungszahl des Rotors
• – Große Füllschuhe
• – Abstimmung des Füllschuhflügeldrehzahl auf die Drehzahl des Rotors
• – Füllschuh mit konstanter Pulverhöhe
• - Entkopplung von Füllschuh und Pulvervorlage

When tableting with rotary presses, it has proved to be advantageous to carry out the tableting with the lowest possible fluctuations in the hardness of the tablet. This is achieved by tableting with constant compressive forces. The readjustment of the pressing forces takes place via the filling quantity or the tablet height. Small variations in weight can be achieved in the following ways:

• - Use of plastic inserts with small thickness tolerances
• - Working without inserts with minimal tool tolerances and rotating punches
• - Low number of revolutions of the rotor
• - Big filling shoes
• - Matching of the Füllschuhflügeldrehzahl on the speed of the rotor
• - filling shoe with constant powder height
• - Decoupling of filling shoe and powder template

to Reduction of Stempelanbackungen offer all Non-stick coatings known in the art. Especially advantageous are plastic coatings, plastic inserts or plastic stamps. Rotary stamps have proved to be advantageous, wherein if possible Upper and lower punch should be rotatable. When turning Stamping can usually be dispensed with a plastic insert become. Here, the stamp surfaces should be electropolished.

It showed that long pressing times are advantageous. these can with pressure rails, multiple pressure rollers or low rotor speeds be set. Because the hardness fluctuations The tablet should be caused by the fluctuations of the pressing forces Systems are applied, which limit the pressing force. Here can be elastic Punches, pneumatic compensators or resilient elements in the force path be used. Also, the pressure roller can be made resilient.

in the According to the present invention suitable tabletting machines are available from, for example the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Verpackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Press AG, Berlin, and Romaco GmbH, Worms. Further providers are, for example Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Berne (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (UK), Courtoy N.V., Halle (BE / LU) and Mediopharm Kamnik (SI). Particularly suitable For example, the hydraulic double pressure press HPF 630 is the Company LAEIS, D. tabletting tools are for example of the Adams tabletting tools, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Sons GmbH, Hamburg, Hofer GmbH, Because, Horn & 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 the Medicopharm, Kamnik (SI).

The moldings can manufactured in a predetermined spatial form and predetermined size are always made up of several phases, i. Layers, inclusions or Cores and rings exist. As a form of space, practically all make sense manageable configurations into consideration, for example, the training as a blackboard, the bar or bar form, cubes, cuboids and the like Room elements with flat side surfaces and in particular cylindrical Embodiments with circular or oval section. This last embodiment detects the presentation form of the tablet to compact cylinder pieces with a relationship of height to diameter above 1.

The portioned compacts can each formed as separate individual elements be that of the predetermined dosage amount of detergents and / or cleaning agents equivalent. But it is also possible compacts form a plurality of such mass units in one compact connect, in particular by predetermined breaking points the easy separability of portioned smaller units provided is. For the use of laundry detergents in machines common in Europe Type with horizontally arranged mechanics can be the training of the portioned compacts be useful as tablets, in cylindrical or cuboidal form, being a diameter / height ratio in the Range of 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 Room shape of another embodiment the molded body is in its dimensions of the dispenser of commercial Household washing machines adapted, So that the moldings can be metered directly into the dispensing compartment without dosing aid, where she herself while the flushing process dissolves. Of course it is but also a use of detergent tablets via a dosing easily possible.

One further preferred multiphase moldings which are produced can, has a plate or panel-like structure with alternately thick long and thin short ones Segments, so that individual Segments of this "multi-phase bar" at the predetermined breaking points, the short ones thin Display segments, aborted and entered into the machine can be. This principle of the "bar-shaped" molding detergent can also be in other geometric shapes, such as vertical standing triangles, which alongside only one of their sides connected with each other, be realized. Here it offers for optical reasons on, the triangle base connecting the individual segments, to train as a phase while the triangle peak forms the second phase. A different one Staining both Phases is in this embodiment especially sexy.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be detected by the measurand of the diametric breaking load. This is determinable

Here in σ stands for the diametrical one Diametral fracture stress (DFS) in Pa, P is the force in N, which leads to the pressure exerted on the molded body, the the breakage of the molding D is the shape diameter in meters and t is the height the molded body.

Claims (11)

Two-phase or multi-phase detergent tablets made of compacted particulate detergent or cleaner, comprising polymer (s), builder (s), perfume and optionally further detergent and cleaner ingredients, one phase of the tablet containing more perfume than the weight of the tablet other phase (s), characterized in that the perfume-rich phase of the shaped body contains more polymer (s) relative to its weight than the other phase (s). Detergent or cleaning product according to claim 1, characterized characterized in that perfume content the individual phases of the molding, based on the weight of each phase to more than 0.1 wt .-%, preferably more than 0.25% by weight and in particular more than 0.5 wt .-%, varies. Detergent or cleaning product 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 the individual phase by more than 0.05 wt .-%, preferably by more as 0.1 wt .-%, more preferably more than 0.2 wt .-% and in particular by more than 0.5% by weight. Detergent or cleaning product molding according to one of claims 1 to 3, characterized in that the moldings have two phases, the same perfume in different amounts contain. Detergent or cleaning product according to claim 4, characterized characterized in that moldings have two layers, one of which is free of perfume. Detergent and cleaning product molding according to one of claims 1 to 5, characterized in that the moldings Total perfume levels from 0.05 to 10 wt .-%, preferably from 0.1 to 5 wt .-% and in particular from 0.25 to 1.5% by weight, in each case based on the molding weight, exhibit. Detergent or cleaning product molding according to one of claims 1 to 6, characterized in that the moldings furthermore surfactant (s), preferably only nonionic surfactant (s), wherein the surfactant (s) preferably at least 40%, more preferably at least 60% and in particular at least 75% of its weight in the perfumed Phase is included. Detergent or cleaning product molding according to one of claims 1 to 7, characterized in that the moldings consists of two phases and the quotient of the difference of the perfume contents and the difference of the polymer contents less than 2, preferably is less than 1 and in particular less than 0.5. Process for the preparation of multiphase washing and Cleaning tablets by per se known compression of different particulate premixes, which contain different amounts of perfume, characterized that this perfume richer Premix based on its weight contains more polymer (s) than the / the other premix (s). Method according to claim 9, characterized in that that this Perfume by spraying onto the premix (s) in the perfume-containing phase (s) becomes. Method according to one of claims 9 or 10, characterized that this Perfume by adding solid perfume preparation forms to the or the premix (s) into the perfume-containing (s) Phase (s) is introduced.