WO2000060037A2 - Detergent forms with special bleach activators - Google Patents

Abstract

The invention relates to detergent forms with a good bleaching capacity and short decomposition times, even with high degrees of hardness. The detergent forms contain bleach activators in the form of cationic nitriles of formula (I), wherein R<1> represents -H, -CH3, a C2-24-alkyl or alkenyl radical, a substituted C2-24-alkyl or alkenyl radical with at least one substituent from the following group: -Cl, -Br, -OH, -NH2, -CN; an alkyl or alkenylaryl radical with a C1-24-alkyl group, or a substituted alkyl- or alkenylaryl radical with a C1-24-alkyl group and at least one other substitute on the aromatic ring; R<2> and R<3>, independently of each other, are selected from the following -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 with n=1, 2, 3, 4, 5 or 6 and X is an anion.

Description

 , Detergent tablets with special bleach activators "

The present invention relates to detergent tablets which contain so-called nitrile quats as bleach activators. In particular, the invention relates to shaped articles such as detergent tablets, detergent tablets, bleach tablets or water softener tablets with the bleach activators mentioned.

Detergent and cleaning agent compositions in the form of moldings, in particular tablets, have long been known in the prior art and have been widely described, although this form of supply has so far not been of outstanding importance on the market. The reason for this is that, in addition to a number of advantages, the form in which the shaped body is offered also has disadvantages which impair production and use, as well as consumer acceptance. The main advantages of moldings such as the fact that the consumer does not have to measure the required amount of product, the higher density and thus the reduced packaging and storage costs, and an aesthetic aspect that should not be underestimated are offset by disadvantages such as the dichotomy between acceptable hardness and sufficiently rapid disintegration and Dissolution of the moldings and numerous technological difficulties in production and packaging put into perspective.

In particular, the dichotomy between a sufficiently hard molded body and a sufficiently fast disintegration time is a central problem. Since sufficiently stable, that is to say shape and break-resistant molded articles can only be produced by relatively high compression pressures, there is a strong compression of the molded article components and consequent delayed disintegration of the molded article in the aqueous liquor and thus to a slow release of the active substances in the Washing or Cleaning process. The delayed disintegration of the molded body continues to have Disadvantage that conventional detergent tablets cannot be washed in via the induction chamber of household washing machines, since the tablets do not disintegrate into secondary particles in a sufficiently quick time that are small enough to be washed out of the induction chamber into the washing drum.

To overcome the dichotomy between hardness, i.e. Transport and handling stability, and easy disintegration of the moldings, many solutions have been developed in the prior art. A particularly well-known approach from the pharmaceutical industry and extended to the field of detergent tablets is the incorporation of certain disintegration aids which facilitate the access of water or which swell or develop gas or other forms upon access of water. Other proposed solutions from the patent literature describe the compression of premixes of certain particle sizes, the separation of individual ingredients from certain other ingredients, and the coating of individual ingredients or of the entire shaped body with binders.

Bleaching agent compositions containing nitrile quat type bleach activators are described in the prior art. For example, European patent application EP 303 520 (Kao Corp.) discloses bleaching compositions which contain a peroxide and a peracid precursor which contain at least one group N ⁺ -CH ₂ -CN or one N ⁺ (CH CN). Detergent tablets are not mentioned in this document.

European patent application EP 458 396 (Unilever) also describes bleaching agent compositions which contain a peroxy bleaching agent and a peracid precursor with at least one group N ⁺ - CH - CN or N ⁺ (CH ₂ CN). Neither particle sizes nor detergent tablets are mentioned in this document either.

Cationic nitriles of the general formula R ¹ R ¹¹ R ^{11 1} N ⁺ CR ¹ R ² -CN and their use as bleach activators are described in European patent application EP 464 880 (Unilever). This document also lacks any information on detergent tablets and particle sizes of the activators. Detergent tablets in which individual ingredients are present separately from others are described, for example, in EP-A-0 481 793 (Unilever). The detergent tablets disclosed in this document contain sodium percarbonate, which is spatially separated from all other components that could influence its stability (for example bleach activators). Information on the particle size of the bleach activator cannot be found in this document, nor are bleach activators of the nitrile quat type mentioned.

European patent application EP-A-0 466 484 (Unilever) claims detergent tablets which are produced by compressing particulate material which has particle sizes in the range from 200 to 2000 μm, the upper and lower limits of the particle sizes being not more than 700 μm should differ. The use of bleach activators is only mentioned as optional in this document, particle size ranges for the bleach activators are not specified.

Detergent tablets in which the bleach activators are used within a certain particle size range are described in the unpublished German patent application DE 198 47 277.3 (Henkel KGaA). In the case of the detergent tablets made of compressed particulate detergent and detergent disclosed herein, which contain bleach, bleach activator (s) and optionally further detergent components, at least 80% by weight of the bleach activator particles have a particle size above 0. 6 mm on. So-called nitrile quats are not mentioned in this document either.

None of the cited documents of the prior art, which deal with detergent tablets, describe detergent tablets which contain "nitrile quaf" -based bleach activators. Nowhere is a well-defined particle size range specified for bleach activators based on “nitrile quaf”. None of the documents mentioned deals with the improvement of the solubility of detergent tablets through the targeted use of these special bleach activators within certain particle size ranges. The present invention is therefore based on the object of providing detergent tablets which contain so-called nitrile quats as bleach activators and which have high hardness and have excellent disintegration properties. These laundry detergent and cleaning product tablets should also be able to be metered through the induction chamber without the consumer suffering disadvantages as a result of residues in the induction chamber and too little detergent in the detergent solution. In addition to these molded article-specific properties, the washing and cleaning performance of the molded articles according to the invention should also be exemplary.

The invention relates to detergent tablets made of compressed particulate detergent and detergent, comprising bleach, bleach activator (s) and, if appropriate, further detergent constituents which, as the bleach activator, contain a cationic nitrile of the formula (I)

R ¹

R ³

contain, in which R ¹ for -H, -CH ₃ , a C ₂ . ₂₄ alkyl or alkenyl radical, a substituted C ₂ . ₂₄ -Alkyl- or -Alkenylrest with at least one substituent from the group -Cl, - Br, -OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a Cι- ₄ alkyl group, or for a substituted alkyl or Alkenylarylrest with a Cι- ₂₄ alkyl group and at least one further substituent on the aromatic ring, R and R 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 with n = 1, 2, 3, 4, 5 or 6 and X is an anion.

The shaped bodies according to the invention can contain the cationic nitriles of the general formula (I) in varying amounts, the amount depending on the intended use of the shaped bodies. So contain detergent tablets and detergent tablets for the machine dishwashing usually less bleach activator than bleach tablets, for example, which largely consist of bleach and bleach activator. Preferred detergent tablets in the context of the present invention are characterized in that they contain the cationic nitrile of the formula (I) in amounts of 0.1 to 20% by weight, preferably 0.25 to 15% by weight and in particular from 0.5 to 10% by weight, based in each case on the weight of the shaped body.

It is particularly preferred if the detergent tablets according to the invention contain the cationic nitrile of the formula (I) in a coarser form. In preferred detergent tablets, at least 90% by weight of the particles of the cationic nitrile of the formula (I) have a particle size above 0.2 mm.

It is preferred in the context of the present invention if the particles of the cationic nitrile not only have more than 90% by weight of particles with sizes above 0.2 mm, but also to a large extent contain coarser particles. Preferred detergent tablets are characterized in that at least 40% by weight, preferably at least 50% by weight and in particular at least 60% by weight, of the particles of the cationic nitrile of the formula (I) have a particle size above 0.4 mm.

The proportion of particles with sizes above 200 μm should preferably be more than 90% by weight, based on the total of the particles of the cationic nitrile. In order to have an advantageous homogeneous particle size distribution, the bleach activators used should in particular be free of too fine or dust components, that is to say particularly preferably contain no particles of less than 0.2 mm in diameter. In particularly preferred detergent tablets, the cationic nitriles are substantially free of particles with sizes below 0.2 mm. In the context of the present invention, “substantially free” means contents below 2% by weight, preferably below 1% by weight and in particular below 0.5% by weight, in each case based on the totality of the particles. In particularly preferred laundry detergent and cleaning product tablets, the cationic nitrile of the formula (I) has an average particle size above 400 μm, preferably above 500 μm, particularly preferably above 600 μm and in particular above 700 μm.

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

For reasons of easier 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 ^" . Single- or multi-phase detergent tablets which, as the cationic nitrile of the formula (I), are a cationic nitrile of the formula (Ia)

R ⁴

R ⁵ -N ⁽⁺⁾ - (CH ₂ ) -CN X * (- ⁾ (Ia),

R °

included in the R> 4, R r.5. and. τ R6 are independently selected from -CH, -CH ₂ -

CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , where R ⁴ can also be -H and X is an anniioonn ,, wwoobbeeii vvoorrzzuuggsswweeiissee RR ⁵⁵ == RR ⁶⁶ == --CCH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ applies are particularly preferred according to the invention

Detergent tablets which contain as cationic nitrile (CH ₃ ) ₃ N ^<+) CH ₂ -CN X ^" , where X ^{" is} an anion selected from the group consisting of chloride, bromide, iodide, hydrogen sulfate, methosulfate, p- Toluene sulfonate (tosylate) or xylene sulfonate is selected are particularly preferred according to the invention.

The detergent tablets according to the invention contain a system for the “activated bleaching”, ie both bleach and bleach activator, cationic nitriles being used as the latter according to the invention in order to obtain advantageous tablets. to maintain properties. In addition to the cationic nitriles, the detergent tablets according to the invention can also contain further bleach activators and / or bleach catalysts, which are also described below. The detergent tablets according to the invention preferably contain the cationic nitriles of the general formula (I) in amounts such that 30 to 100% of the total bleach activators and bleach catalysts contained in the tablets are cationic nitrile. Bleach activators are added to detergents and cleaning agents containing bleach in order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below. In the context of the present invention, bleach activators to be used in addition to the cationic nitrile can be compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid become. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU ), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyl alcohols, especially triac 5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, in the context of the present invention, so-called bleach catalysts can also be incorporated into the moldings in addition to the cationic nitriles of the formula (I). These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts. Also bleach-enhancing combinations of active ingredients, which by intimately mixing a water-soluble salt of a divalent transition metal, selected from cobalt, iron, copper and ruthenium and mixtures thereof, a water-soluble ammonium salt and, if appropriate, an oxidizing agent based on peroxygen and inert support material, can be used as bleaching catalysts in the context of the present invention. If bleaching catalysts are used in the context of the present invention, the particle size restrictions mentioned above also apply to them.

A particularly preferred bleach activator used in addition to the cationic nitrile of the formula (I) is N, N, N ', N'-tetraacetylethylene diamine, which is widely used in detergents and cleaners. Accordingly, preferred detergent tablets are characterized in that they contain a cationic nitrile of the formula (I) and tetraacetylethylene diamine (TAED) as bleach activators. In such “nitrile quat” TAED combinations, the weight ratios of “nitrile quat” to TAED are preferably in the range from 1: 2 to 10: 1. Particularly preferred in such combinations is 1/3 to 2/3 of the total amount of bleach activator Nitrile of the formula (I).

The detergent tablets according to the invention contain the bleach activator (s) in amounts of 0.5 to 30% by weight, preferably 1 to 20% by weight and in particular 2 to 15% by weight, in each case based on the entire detergent tablets, reference being made to the above quantities for the cationic nitrile.

The total amounts of bleach activators can vary depending on the intended use of the moldings produced. For example, bleach activator contents of between 0.5 and 10% by weight, preferably between 2 and 8% by weight and in particular between 4 and 7% by weight, are common in typical universal detergent tablets, while bleach tablets contain quite high contents, for example between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular between 10 and 20% by weight. The person skilled in the art is not restricted in its freedom of formulation and can in this way bleach more or less bleaching detergent tablets, detergent tablets or make bleach tablets by varying the levels of bleach activator and bleach.

The bleach activator (s) in the detergent tablets according to the invention serve to activate the bleach or detergents at lower washing or cleaning temperatures and thus to ensure high bleaching performance even at low temperatures. Sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important as bleaching agents. Further usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and HO ₂ -supplying acidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, irrespective of which other ingredients are contained in the moldings. If cleaning tablets or bleach tablets for machine dishwashing are manufactured, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoxy acid perooxyperaproic acid (ε-phthalimidoperoxy-capoic acid) . 1, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used. Chlorine or bromine-releasing substances can also be used as bleaching agents in molded articles for automatic dishwashing. Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid,

Dibromo isocyanuric acid and or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

In detergent tablets for textile laundry, which are briefly referred to as detergent tablets, sodium percarbonate is the preferred bleaching agent. “Sodium percarbonate” is a non-specific term for sodium carbonate peroxohydrates, which strictly speaking are not “percarbonates” (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate. The merchandise has the average composition 2 Na ₂ CO ₃ -3 H ₂ O ₂ and is therefore not peroxy carbonate. Sodium percarbonate often forms a white, water-soluble powder with a density of 2.14 ^"3 , which easily breaks down into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first obtained in 1899 by ethanol precipitation from a solution of sodium carbonate in hydrogen peroxide, but was mistakenly regarded as peroxy carbonate. Until 1909 the connection as W ^τ asserstoffperoxid- addition compound was detected, yet the historical name "sodium" has prevailed in practice.

The industrial production of sodium percarbonate is mainly produced by precipitation from an aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg ²⁺ ions). The precipitated salt, which still contains 5 to 12% by weight of mother liquor, is then filtered off and dried in fluidized bed dryers at 90.degree. The bulk density of the finished product can vary between 800 and 1200 g / 1 depending on the manufacturing process. In the As a rule, the percarbonate is stabilized by an additional coating. Coating processes and materials used for coating are widely described in the patent literature. In principle, according to the invention, all commercially available percarbonate types can be used, such as those offered by the companies Solvay Interox, Degussa, Kemira or Akzo.

The detergent tablets according to the invention can be single-phase, i.e. from a premix to a homogeneous molded body. According to the invention, however, it is also possible and preferred to provide multi-phase shaped bodies, where active ingredients can be divided into spatially delimited areas where this appears reasonable. In the context of the present invention, detergent tablets are preferred which consist of several phases, preferably layers, with the cationic nitrile of the formula (I) in at least one of the phases being more than 2.5% by weight, preferably more than 5% by weight and in particular more than 7.5% by weight, in each case based on the weight of the phase.

By dividing the total mass of a molded body into different phases, an increased content of certain ingredients, in particular bleach activators, can be achieved in a single phase if the content of this ingredient is correspondingly reduced in the other phase (s) without the Total content of the shaped body in this active ingredient varies. As is evident from the abovementioned amounts of bleach activator (s) in the overall molded article and from the abovementioned amounts of bleach activator (s) in a single phase, it is preferred according to the invention to concentrate the bleach activator (s) in one phase of the molded article , so that the corresponding phase has high bleach activator contents.

The individual phases of the molded body can have different spatial shapes within the scope of the present invention. The simplest possible implementation is in two- or multi-layer tablets, with each layer of the molded body representing a phase. However, it is also possible according to the invention to produce multi-phase molded bodies in which individual phases have the form of inclusions in (another) phase (s). In addition to so-called "ring core tablets", for example, abletten or combinations of the embodiments mentioned possible. Examples of multi-phase molded bodies can be found in the illustrations in EP-A-0 055 100 (Jeyes), which describes toilet cleaning blocks. The most widespread spatial form of multi-phase tablets is the two- or multi-layer tablet. In the context of the present invention it is therefore preferred that the phases of the molded body have the shape of layers.

In extreme cases, the above-described principle of concentrating the bleach activator (s) in one phase can be carried out in such a way that only one phase contains bleach activator, while all other phases are free of bleach activator (s). Detergent shaped articles which consist of two or three phases, preferably layers, and only one phase contains the cationic nitrile of the formula (I), while the remaining phase (s) are free from bleach activator are preferred according to the invention .

In addition to the ingredients mentioned, bleach activator and bleach, the detergent tablets according to the invention can contain further ingredients, the amounts of which depend on the intended use of the tablets. In particular, substances from the groups of surfactants, builders and polymers are suitable for use in the detergent tablets according to the invention. Here too, the person skilled in the art will have no difficulty selecting the individual components and their amounts. For example, a universal detergent tablet will contain higher amounts of surfactant (s), while bleach tablets may even be dispensed with. The amount of builder (s) used also varies depending on the intended use.

The detergent tablets according to the invention can contain all of the builders customarily used in detergents and cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _2x + ι ^' H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline sheet silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ 'yH ₂ O are preferred, with β-sodium disilicate being able to be obtained, for example, by the method described in international patent application WO-A-91/08171 .

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

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and within the scope of the present Invention is preferably usable, for example, also a co-crystallizate of zeolite X and zeolite A (ca. 80 wt .-% zeolite X) which is marketed by CONDEA Augusta SpA under the trade name AX VEGOBOND ^® and by the formula

nNa ₂ O ^• (ln) K ₂ O 'Al ₂ O ₃ ' (2 - 2.5) SiO ₂ ^■ (3.5 - 5.5) H ₂ O

can be described. The zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be used, usually both ways of incohering the zeolite into the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid 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 and lime incrustations in tissues and also contribute to cleaning performance.

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

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly ^"3 , water loss at 95 °), 7 mol. (Density 1.68 gladly ^{" 3} , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 ^"3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na P ₂ O ₇ when heated more. Disodium hydrogen phosphate is used by neutralizing phosphoric acid with soda solution Made from phenolphthalein as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

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

Tetrasodium diphosphate (sodium pyrophosphate), Na P ₂ O ₇ , exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also given 880 °) and as decahydrate (Density 1.815-1.836 gladly ^"3 , melting point 94 ° with loss of water). In the case of substances there are colorless crystals which are soluble in water with an alkaline reaction. Na PO is formed when disodium phosphate is heated to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and the solution is spray-dried. the decahydrate complexes heavy metal salts and hardness salts and, therefore, reduces the hardness of the water. potassium diphosphate (potassium pyrophosphate), ΛO- _/, exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gladly represents ^"3 , which is soluble in water, the pH of the 1% solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P Oι ₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O - Well with n = 3. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K5P ₃ O1 ₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates, which are also within the scope of the present invention can be used. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH - Na ₃ K ₂ P ₃ O, ₀ + H ₂ O

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

Organic cobuilders which can be used in the detergent tablets according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. In addition to their builder effect, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular. Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

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

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.

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

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight. To improve water solubility, the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.

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

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

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

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

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, methods. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

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

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, l-hydroxyethane-l, l-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as cobuilders.

The amount of builder is usually between 10 and 70% by weight, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight. Again, the amount of builders used depends on the intended use, so that bleach tablets can have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular between 30 and 55% by weight) ), for example detergent tablets (usually 10 to 50% by weight, preferably 12.5 to 45% by weight and in particular between 17.5 and 37.5% by weight).

Preferred detergent tablets also contain one or more surfactant (s). Anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these can be used in the detergent tablets according to the invention. Mixtures of anionic and nonionic surfactants are preferred from an application point of view. The total surfactant content of the molded article is 5 to 60% by weight, based on the molded article weight, with surfactant contents above 15% by weight being preferred in the case of detergent tablets. Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C. ₁₃ - Alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from C _2. ] ₈ monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products , into consideration. Also suitable are alkanesulfonates, which are for example obtained from Cι ₂ .ι ₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production 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 become. Preferred sulfated fatty acid glycerol esters are the sulfate products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₂ -C ₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 1 -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. For reasons of washing technology, the C ₂ -C ₆ alkyl sulfates and C ₂ -C ₅ alkyl sulfates and C] ₄ -C ₄ alkyl sulfates are preferred. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants. The sulfuric acid monoesters of the straight-chain or branched C ethoxylated with 1 to 6 mol of ethylene oxide. ₂ -Alcohols, such as 2-methyl-branched C ₉ -n alcohols with an average of 3.5 mol of ethylene oxide (EO) or -C ₂ -ι fatty alcohols with 1 to 4 EO, are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _{8-0 8} fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

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

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

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

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

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533. Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

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

R ^J

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

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

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

R ^] -OR ²

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

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

or phenyl radicals are preferred and [Z] for a linear poly is a hydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.

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

In the context of the present invention, detergent tablets are preferred which contain anionic and / or nonionic surfactant (s) and total surfactant contents above 2.5% by weight, preferably above 5% by weight. % and in particular above 10% by weight, in each case based on the molded body weight. Here, application-related advantages can result from certain quantitative ratios in which the individual classes of surfactants are used.

For example, detergent tablets are particularly preferred in which the ratio of anionic surfactant (s) to nonionic surfactant (s) is between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2.

From an application point of view, it can be advantageous if certain classes of surfactant are present in some phases of the detergent tablets or in the entire molded article, i.e. in all phases, are not included. A further important embodiment of the present invention therefore provides that at least one phase of the molded article is free from nonionic surfactants.

Conversely, a positive effect can also be achieved by the content of individual phases or the entire molded article, ie all phases, of certain surfactants. The introduction of the alkyl polyglycosides described above has proven advantageous pointed out, so that detergent tablets are preferred in which at least one phase of the tablets contains alkyl polyglycosides.

Similar to the nonionic surfactants, the omission of anionic surfactants from individual or all phases can result in detergent tablets which are better suited for certain areas of application. It is therefore also conceivable within the scope of the present invention for detergent tablets to be made in which at least one phase of the tablet is free from anionic surfactants.

In order to facilitate the disintegration of highly compressed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology ^' '^'' (6th edition, 1987, pp. 182-184), tablet disintegrants or accelerators of disintegration are understood as auxiliary substances which are suitable for ensure the rapid disintegration of tablets in water or gastric juice and the release of pharmaceuticals in an absorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling) and on the other hand a pressure can be generated by the release of gases, which breaks the tablet into smaller particles disintegrates. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.

Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the molded article weight. Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred washing and cleaning agent shaped bodies such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 contain up to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ HιoO ₅ ) _n and, formally speaking, is a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.

The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be treated. Detergent tablets which contain disintegrants in granular or optionally granulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO-A-98/40463 ( Henkel). These documents are also to be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. to take. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The above-mentioned coarser disintegration aids based on cellulose and described in more detail in the cited documents are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel TF-30-HG from Rettenmaier.

Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, to granules with an average particle size of 200 μm.

In the context of the present invention, detergent tablets are preferred which additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 up to 7% by weight and in particular from 4 to 6% by weight, in each case based on the molded body weight.

In addition to the above-mentioned components of bleach activator, bleach, builder, surfactant and disintegration aid, the detergent tablets according to the invention can contain one or more substances from the group of builders, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils and anti-redeposition agents , optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors. These substances are described below. Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxidoreductases can also be used for bleaching or for inhibiting color transfer. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight. In addition, the detergent tablets can also contain components that positively influence the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

The shaped bodies can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-moφholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which, instead of the Moφholino group, have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can also be used.

Dyes and fragrances are added to the washing and cleaning agent moldings according to the invention in order to improve the aesthetic impression of the products and, in addition to the performance, to provide the consumer with a visually and sensorially "typical and unmistakable" product. Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.- Butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate. Styrallyl propionate and benzyl salicylate. The ethers include, for example, benzylethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, oc -Isomethyl ionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include tephenols such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The dye content of the detergent tablets according to the invention is usually less than 0.01% by weight, while fragrances can make up up to 2% by weight of the total formulation.

The fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to textile fibers, in order not to dye them. The production of washable and cleaning-active molded articles takes place by applying pressure to a mixture to be veφressing, which is located in the cavity of a press. In the simplest case of molded article production, which is referred to simply as tableting below, the mixture to be tabletted is pressed directly, ie without prior granulation. The advantages of this so-called direct tableting are its simple and inexpensive application, since no further process steps and consequently no further plants are required. However, these advantages are offset by disadvantages. For example, a powder mixture that is to be tabletted directly must have sufficient plastic deformability and have good flow properties; furthermore, it must not show any tendency to segregate during storage, transport and filling of the die. These three requirements are extremely difficult to master with many substance mixtures, so that direct tableting is not often used, particularly in the production of detergent tablets. Therefore, the usual way for the production of washing and cleaning agent tablets is based on pulverfb ^'shaped components ( "primary"), which are agglomerated by suitable methods to Sekundäφartikeln higher particle diameter and granulated. These granules or mixtures of different granules are then mixed with individual powdery additives and fed to the tableting.

Another object of the present invention is a process for the production of detergent tablets by molding a particle-shaped premix in a manner known per se, the premix being a cationic nitrile of the formula (I)

R ¹

R ² -N ⁽⁺⁾ - (CH ₂ ) -CN X ^{• (} -) (I),

R ³ contains, in which R ¹ for -H, -CH, a C ₂ . ₂₄ alkyl or alkenyl radical, a substituted C ₂ . ₂₄ alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a Cι_ ₂₄ alkyl group, or for a substituted alkyl or alkenylaryl radical with a C ₂₄ alkyl group and at least one further substituent on the aromatic ring, R and R 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 with n = 1, 2, 3, 4, 5 or 6 and X is an anion, in amounts of 0.1 to 20% by weight, based on the premix.

With regard to preferred embodiments of the method according to the invention, reference is made to the above information on the detergent tablets according to the invention. So contents of the premix of cationic nitrile from 0.25 to 15 and particularly from 0.5 to 10% by weight, based in each case on the premix, are preferred.

The statements made above also apply analogously to the particle sizes of the cationic nitrile. Processes in which at least 90% by weight of the particles of the cationic nitrile of the formula (I) have a particle size above 0.2 mm, it being preferred that at least 40% by weight, preferably at least 50% by weight and In particular, at least 60% by weight of which the particles of the cationic nitrile of the formula (I) have a particle size above 0.4 mm are likewise preferred according to the invention. Process variants are particularly preferred in which the cationic nitrile of the formula (I) has an average particle size above 400 μm, preferably above 500 μm, particularly preferably above 600 μm and in particular above 700 μm.

With regard to the cationic nitriles to be preferably used, reference can also be made to the above statements. In particularly preferred processes, the premix contains as cationic nitrile (CH ₃ ) ₃ N ^{+ +} CH ₂ -CN X ^" , where X ^{" is} an anion selected from the group consisting of chloride, bromide, iodide, hydrogen sulfate, methosulfate, p- Toluene sulfonate (tosylate) or xylene sulfonate is selected. Detergent tablets preferred in the context of the present invention are obtained by squeezing a particulate premix comprising at least one surfactant-containing granulate and at least one subsequently admixed powdery component. The granules containing surfactant can be produced by conventional industrial granulation processes such as compacting, extrusion, mixer granulation, pelletization or fluidized bed granulation. It is advantageous for the later detergent tablets if the premix to be veφresses has a bulk density that comes close to the usual compact detergent. In particular, it is preferred that the teilchenfb ^'-shaped premix addition tensidhalti- ge (s) containing granule (s) and a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and especially at least 700 g / 1 has.

In preferred process variants, the surfactant-containing granules also meet certain particle size criteria. Methods according to the invention are preferred in which the surfactant-containing granules have particle sizes between 100 and 2000 μm, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 μm.

In addition to the active substances (anionic and / or nonionic and / or cationic and / or amphoteric surfactants), the surfactant granules preferably also contain carriers which particularly preferably come from the group of builders. Particularly advantageous processes are therefore characterized in that the surfactant-containing granules contain anionic and or nonionic surfactants and builders and have total surfactant contents of at least 10% by weight, preferably at least 20% by weight and in particular at least 25% by weight.

Before the particulate premix is pressed into detergent tablets, the premix can be "powdered" with finely divided surface treatment agents. This can be of advantage for the quality and physical properties of both the premix (storage, molding) as well as the finished detergent tablets. Finely divided powdering agents are well known in the prior art, mostly zeolites, silicates or other inorganic salts be used. However, the premix is preferably “powdered” with finely divided zeolite, zeolites of the faujasite type being preferred. In the context of the present invention, the term “faujasite-type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4 (see Donald W. Breck: “Zeolite Molecular Sieves”, John Wiley & Sons, New York) , London, Sydney, Toronto, 1974, page 92). In addition to the zeolite X, zeolite Y and faujasite and mixtures of these compounds can also be used, the pure zeolite X being preferred.

Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites which do not necessarily have to belong to the zeolite structural group 4 can also be used as powdering agents, it being advantageous if at least 50% by weight of the powdering agent is used a zeolite of the faujasite type.

In the context of the present invention, detergent tablets are preferred which consist of a particulate premix which contains granular components and subsequently admixed powdery substances, the or one of the subsequently admixed powdery components being a zeolite of the faujasite type with particle sizes below 100 μm, is preferably below 10 μm and in particular below 5 μm and is at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be treated.

In addition to the constituents mentioned, surfactant, builder and disintegration aid, the premixes to be treated can additionally include one or more substances from the group of bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, Contains graying inhibitors, color transfer inhibitors and corrosion inhibitors. These substances have been described above.

The molded articles according to the invention are first produced by dry mixing the constituents, which can be wholly or partially pregranulated, and then providing information, in particular feeding them into tablets, whereby conventional methods can be used. For the production of the invention The pre-mix is compacted in a so-called die between two punches to form a solid compressed body. This process, which is briefly referred to below as tabletting, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molded body being formed being determined by the position of the lower punch and the shape of the pressing tool. The constant dosing, even at high mold throughputs, is preferably achieved by volumetric dosing of the premix. As the tableting continues, the upper punch touches the premix and lowers further in the direction of the lower punch. During this compression, the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix), the plastic deformation begins, in which the particles flow together and the molded body is formed. Depending on the physical properties of the premix, some of the premix particles are also crushed and sintering of the premix occurs at even higher pressures. With increasing pressing speed, that is to say high throughput quantities, the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities. In the last step of tableting, the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.).

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

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

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

When tableting with concentricity presses, it has proven to be advantageous to carry out the tabletting with the smallest possible fluctuations in the weight of the tablet. The fluctuations in hardness of the tablet can also be reduced in this way. Small fluctuations in weight can be achieved in the following ways:

- Use of plastic inserts with small thickness tolerances

- Low number of revolutions of the rotor

- Big filling shoes

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

- Filling shoe with constant powder height

- Decoupling of filling shoe and powder feed

All non-stick coatings known from the art are suitable for reducing stamp caking. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotating punches have also proven to be advantageous, with the upper and lower punches being designed to be rotatable if possible. In the case of rotating stamps, a plastic insert can generally be dispensed with. The stamp surfaces should be electropolished here.

It was also shown that long pressing times are advantageous. These can be set with pressure rails, several pressure rollers or low rotor speeds. Since the fluctuations in the hardness of the tablet are caused by the fluctuations in the pressing forces, systems should be used which limit the pressing force. Here elastic stamps, pneumatic compensators or resilient elements can be used in the force path. The pressure roller can also be designed to be resilient. Tableting machines suitable within the scope of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Hörn & Noack Pharmatechnik GmbH, Worms, EMA Veφackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other providers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liveeool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Me- diopharm Kamnik (SI). For example, the hydraulic double pressure press HPF 630 from LAEIS, D. Tablettierwerkzeuge are for example from the companies Adams Tablettierwerkzeuge, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Hom & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers include Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

The molded body can be manufactured in a predetermined spatial shape and a predetermined size. Practically all practical configurations can be considered as the spatial shape, for example, the design as a board, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.

The portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. It is also possible, however, to form compacts which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points. For the use of textile detergents in machines of the type customary in Europe with horizontally arranged mechanics, the portioned compacts can be designed as tablets, in the shape of a cylinder or cuboid, with a diameter / height Ratio in the range of about 0.5: 2 to 2: 0.5 is preferred. Commercially available hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such pressed articles.

The spatial shape of another embodiment of the molded body is adapted in its dimensions to the detergent dispenser of commercially available household washing machines, so that the molded body can be metered directly into the dispenser without metering aid, where it dissolves during the dispensing process. However, it is of course also possible to use the detergent tablets without problems using a metering aid and is preferred in the context of the present invention.

Another preferred molded body that can be produced has a plate-like or plate-like structure with alternating thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, broken off and into the Machine can be entered. This principle of the "bar-shaped" shaped body detergent can also be realized in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side.

However, it is also possible that the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous application properties of the molded body. If, for example, components are contained in the moldings that mutually influence one another negatively, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted. when the second goes into solution. The layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely removed, but it is also possible for the inner layer (s) to be completely encased ) due to the more external Layer (s) can be reached, which leads to the premature release of components of the inner layer (s).

In a further preferred embodiment of the invention, a molded body consists of at least three layers, that is to say two outer and at least one inner layer, at least one of the inner layers containing a peroxy bleaching agent, while in the case of the stacked molded body, the two outer layers and in the case of the molded body however, the outermost layers are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in a molded body. Such multilayer molded bodies have the advantage that they can be used not only via a dispensing chamber or via a metering device which is added to the washing liquor; rather, in such cases it is also possible to put the molded body into direct contact with the textiles in the machine without the risk of bleaching from bleaching agents and the like.

Similar effects can also be achieved by coating individual constituents of the detergent and cleaning agent composition to be treated or the entire molded article. For this purpose, the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else they can be coated using the melt coating method.

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

2P σ = πDt

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

The present invention furthermore relates to the use of cationic nitriles of the formula (I)

R ¹

R ² -N ⁽⁺⁾ - (CH ₂ ) -CN X (-)

(I),

R ³

in the R ¹ for -H, -CH ₃ , a C ₂ . ₂₄ alkyl or alkenyl radical, a substituted C ₂ . ₂₄ - alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a Cι- ₂₄ alkyl group, or for a substituted alkyl or Alkenylarylrest with a Cι. ₂ 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 with n = 1, 2, 3, 4, 5 or 6 and X is an anion , wherein at least 90% by weight of the particles of the cationic nitrile have a particle size above 200 μm, in order to improve the hardness and disintegration time of detergent tablets.

With regard to preferred embodiments of the use according to the invention (particle sizes, further ingredients, composition of the premix, etc.), what has been said above for the method according to the invention applies analogously.

Claims

Claims:

1. washing and cleaning agent shaped body made of compressed particulate washing and cleaning agent, comprising bleach, bleach activator (s) and optionally further washing and cleaning agent components, characterized in that they are a cationic nitrile of the formula (I) as a bleach activator

R ¹

R -N ^l - (CH ₂ ) -CN X '(->)

0).

R ³

contain, in which R ¹ for -H, -CH, a C ₂ . ₂₄ alkyl or alkenyl radical, a substituted C ₂ . ₂₄ alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a Cι- ₂₄ - alkyl group, or for a substituted alkyl or Alkenylarylrest with a C 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 with n = 1, 2, 3, 4, 5 or 6 and X is an anion.

2. Detergent form according to claim 1, characterized in that they contain the cationic nitrile of the formula (I) in amounts of 0.1 to 20% by weight, preferably 0.25 to 15% by weight and in particular of 0.5 to 10 wt .-%, based in each case on the molded body weight.

3. Washing and cleaning agent molded article according to one of claims 1 or 2, characterized in that at least 90% by weight of the particles of the cationic nitrile of the formula (I) have a particle size above 0.2 mm.

4. Detergent form according to one of claims 1 to 3, characterized in that at least 40% by weight, preferably at least 50% by weight and in particular at least 60% by weight, of the particles of the cationic nitrile of the formula (I ) have a particle size above 0.4 mm.

5. Washing and cleaning agent molded article according to one of claims 1 to 4, characterized in that the cationic nitrile of the formula (I) has an average particle size above 400 μm, preferably above 500 μm, particularly preferably above 600 μm and in particular above 700 μm.

6. Detergent form according to one of claims 1 to 5, characterized in that they contain as the cationic nitrile (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , where X ^{" stands} for an anion from Group chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate is selected.

7. Detergent form according to one of claims 1 to 6, characterized in that they consist of several phases, preferably layers, the cationic nitrile of the formula (I) in at least one of the phases being more than 2.5% by weight. %, preferably more than 5% by weight and in particular more than 7.5% by weight, in each case based on the weight of the phase.

8. washing and cleaning agent form according to claim 7, characterized in that they consist of two or three phases, preferably layers, and only one phase contains the cationic nitrile of the formula (I), while the remaining phase (s) free of bleach activator.

9. Detergent form according to one of claims 1 to 8, characterized in that they contain a cationic nitrile of the formula (I) and tetraacetylethylene diamine (TAED) as bleach activators.

10. Detergent and molded article according to one of claims 1 to 9, characterized in that it additionally contains a disintegration aid, preferably a Disintegration aids based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight * and in particular 4 to 6% by weight, in each case based on the body weight, included.

11. Detergent form according to one of claims 1 to 10, characterized in that they contain anionic (s) and / or nonionic (s) surfactant (s) and total surfactant contents above 2.5 wt .-%, preferably above 5% by weight and in particular above 10% by weight, based in each case on the molding weight.

12. A process for the production of detergent tablets by molding a particulate premix in a manner known per se, characterized in that the premix is a cationic nitrile of the formula (I)

R ¹

R -N ^ - (CH ₂ ) -CN X '((->) (D,

R ³

contains, in which R ¹ for -H, -CH, a C ₂ . ₂₄ alkyl or alkenyl radical, a substituted C ₂ . ₂₄ - alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a Cι_ ₂₄ - alkyl group, or for a substituted alkyl or alkenylaryl radical with a C]. 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 -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 with n = 1, 2, 3, 4, 5 or 6 and X is an anion, in amounts of 0.1 to 20 wt .-%, based on the premix.

13. The method according to claim 12, characterized in that at least 90 wt .-% of the particles of the cationic nitrile of the formula (I) have a particle size above 0.2 mm, it being preferred that at least 40 wt .-%, preferably at least 50% by weight and in particular at least 60% by weight of the particles of the cationic nitrile of the formula (I) have a particle size above 0.4 mm.

14. The method according to any one of claims 12 or 13, characterized in that the cationic nitrile of formula (I) has an average particle size above 400 microns, preferably above 500 microns, particularly preferably above 600 microns and in particular above 700 microns .

15. The method according to any one of claims 12 to 14, characterized in that the premix contains as cationic nitrile (CH ₃ ) N ⁽⁺⁾ CH ₂ -CN X ^" , where X ^{" is} an anion selected from the group consisting of chloride, Bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate is selected.

16. The method according to any one of claims 12 to 15, characterized in that the particulate premix additionally contains surfactant-containing granules (s) and a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1.

17. The method according to claim 16, characterized in that the surfactant-containing granules have particle sizes between 100 and 2000 microns, preferably between 200 and 1800 microns, particularly preferably between 400 and 1600 microns and in particular between 600 and 1400 microns.

18. The method according to any one of claims 16 or 17, characterized in that the surfactant-containing granules contains anionic and / or nonionic surfactants and builders and total surfactant contents of at least 10 wt .-%, preferably at least 20 wt .-% and in particular at least 25 % By weight.

19. The method according to any one of claims 12 to 18, characterized in that the particulate premix additionally one or more substances from the group of bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils , Anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

20. Use of cationic nitriles of the formula (I)

R ¹

R ² -N ^<+) - (CH ₂ ) -CN X (I),

R ³

in the R ¹ for -H, -CH ₃ , a C ₂ . ₂₄ alkyl or alkenyl radical, a substituted C ₂ . ₂₄ - alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a Cι. ₂₄ alkyl group, or for a substituted alkyl or alkenylaryl radical with a C 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, - 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 with n = 1 , 2, 3, 4, 5 or 6 and X is an anion, with at least 90% by weight of the particles of the cationic nitrile having a particle size above 200 μm, for improving the hardness and disintegration time of detergent tablets.