WO2000060035A2

WO2000060035A2 - Single or multi-phase detergent forms with special bleach activators

Info

Publication number: WO2000060035A2
Application number: PCT/EP2000/002533
Authority: WO
Inventors: Horst-Dieter Speckmann; Monika Böcker; Andreas Lietzmann; Christian Nitsch; Jörg Poethkow
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1999-03-31
Filing date: 2000-03-22
Publication date: 2000-10-12
Also published as: AU3814200A; JP2002541302A; DE19914812A1; DE50012128D1; EP1165742A2; KR20010110469A; WO2000060035A3; CA2303638A1; EP1165742B1; ES2255995T3

Abstract

The invention relates to detergent forms which have an excellent bleaching capacity, even after long storage periods; and short decomposition times, even with high degrees of hardness. The inventive detergent forms contain a bleach activator 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 group -C1, -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 substituent on the aromatic ring, R<2> and R<3> are selected independently of each other 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, the pH-value of the 1 wt. % aqueous solution of the form or the phase containing the nitrile quat being less than 10.

Description

“Single- or multi-phase 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 moldings such as detergent tablets, detergent tablets, in particular detergent tablets for machine dishwashing, bleaching tablets or water softening 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 Laundry or cleaning process. The delayed disintegration of the moldings has the further 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 articles that are small enough to pass from the induction chamber into the washing drum in a sufficiently rapid time to be washed in.

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. One approach known in particular 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 ₂ CN) ₂ . 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 ₂ -CN or N ⁺ (CH ₂ CN) ₂ . In this document, too, neither single-phase nor multi-phase detergent tablets are mentioned.

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). In this document, too, there is no indication of detergent tablets. 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). Nitrile quat type bleach activators are not mentioned in this document. Information on the pH values of the solution of individual layers or of the entire molded body cannot be found in this document either.

None of the cited documents of the prior art, which deal with detergent tablets, describe detergent tablets which contain bleach activators based on "nitrile quat". Nowhere is a well-defined pH range for tablets or areas of tablets which contain bleach activators based on “nitrile quaf.” None of the documents mentioned deals with the improvement of the stability of detergent tablets by targeted use of these special bleach activators in areas with a defined pH value.

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 a high hardness and have excellent disintegration properties. These laundry detergent and cleaning product form bodies should also be able to be metered through the dispensing chamber without the consumer suffering disadvantages as a result of residues in the dispensing chamber and too little detergent in the wash liquor. In addition to these molded body-specific properties, the washing and cleaning performance of the molded body according to the invention should also be exemplary. In particular, the storage stability of the molded articles and the preservation of the bleaching performance even with long storage should be ensured.

It has now been found that the stability of bleach activators based on “nitrile quat” in detergent tablets can be increased by using these bleach activators. gates in molded bodies or molded body areas are used which, after dissolving in water, have a pH below 10.

The invention relates to single-phase or multi-phase detergent tablets made of compressed particulate detergent and detergent, comprising bleach, bleach activator (s) and, if appropriate, further detergent components, which are characterized in that the tablets or at least one phase thereof as Bleach activator a cationic nitrile of formula (I)

R ¹

R -N - (CH ₂ ) -CN X (.--).

(I),

R ³

contain / contains, in which R ^{1 represents} -H, -CH, a C ₂ - ₂ alkyl or alkenyl radical, a substituted C. ₂ -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- ₂₄ - alkyl group, or for a substituted alkyl or Alkenylaryl residue with a C]. ₂₄ - alkyl group and at least one further substituent on the aromatic ring, R ² and R ³ are selected independently of one another from -CH ₂ -CN, -CH, -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 the pH of the 1 wt .-% aqueous solution of the molded body or the phase containing the nitrile quat is less than 10.

Shaped bodies according to the invention can be configured with one or more phases. In the context of the present invention, the individual phases of the film body can have different spatial shapes. 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", coated tablets or combinations of the above-mentioned embodiments are possible, for example. 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 molded bodies 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. Two-, three- and four-layer tablets are preferred in the context of the present invention.

In the context of the present invention, the pH of a 1% strength by weight aqueous solution can be determined by preparing a solution of the molded article or the phase which contains the cationic nitrile of the formula (I) in demineralized water. For this purpose, the corresponding amount of the shaped body or the phase is dissolved or suspended in water and the pH value is determined by means of known methods such as indicator paper or combination electrodes. Since certain methods of determining the pH value are temperature-dependent, the values mentioned in the context of the present invention apply to a temperature of the solution or suspension of 20 ° C.

In preferred single- or multi-phase detergent tablets, the pH of the 1% by weight aqueous solution of the tablet or the phase which contains the nitrile quat is less than 9, preferably less than 8, particularly preferably less than 7 and especially less 6.

Within the pH range mentioned, single- or multi-phase detergent tablets are preferred, in which the pH of the 1% by weight aqueous solution of the tablet or the phase which contains the nitrile quat is less than 6.5. is preferably less than 6.0, particularly preferably less than 5.5 and in particular less than 5.

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. Detergent tablets preferred 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 molded 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 detergent 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 following table, preferred cationic nitriles of the formula (I) are characterized by their radicals R ¹ , R ² and R ³ :

For reasons of easier synthesis, compounds are preferred in which the radicals R ¹ to R ^{3 are} identical, for example (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X \ (CH ₃ CH ₂ ) ₃ N ^(+, CH ₂ -CN X ^" , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH (CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X-, or (HO- CH ₂ - CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" . 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 ° -N τ ( ⁽⁺ ) '- (CH ₂ ) -CN X ⁽ (-) (Ia),

R °

contain, in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ - CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , where R ^{4 can} additionally also be -H and X is an anion, R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ° = -CH ₃ preferably being 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 bleaching agent and bleach activator, cationic nitriles being used as the latter according to the invention in order to obtain advantageous molded articles. to maintain properties. In addition to the cationic nitriles, the detergent tablets according to the invention can also contain further bleach activators, which are also described below. However, the detergent tablets according to the invention preferably contain the cationic nitriles of the general formula (I) as the sole or main bleach activator, ie at least 50% by weight of the total bleach activators contained in the laundry detergent tablets according to the invention are cationic nitriles of the formula ( I). 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. 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 polyacylated alkylenediamines, especially tetraacetylethylene diamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, especially triacetine, Diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, in the context of the present invention, in addition to the canonical nitriles of the formula (I), so-called bleach catalysts can also be incorporated into the moldings. 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. In such combinations, 1/3 to 2/3 of the total amount of bleach activator of cationic nitrile of the formula (I) is particularly preferred.

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 washing and cleaning agent molded article, 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 molded articles 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 (s) 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 molded articles. If cleaning tablets or bleach tablets are produced for machine dishwashing, 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 monophosphate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthaloxyhexanoic acid (ε-phthaloxyhexanoic 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 are considered. 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, but also for detergent tablets for automatic dishwashing, 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 C0 ₃ -3 H ₂ O ₂ and is therefore not peroxycarbonate. 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. It was not until 1909 that the compound was recognized as a hydrogen peroxide addition compound, but the historical name "sodium percarbonate" has become established 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 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 weight of the finished Depending on the manufacturing process, the product can fluctuate between 800 and 1200 g / 1. 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, two- or multi-phase detergent tablets are preferred in which one phase contains the cationic nitrile of the formula (I) in amounts of 2.5% by weight, preferably 5% by weight and in particular 7 , 5 wt .-%, each based on the weight of the phase, while the other phase (s) is preferably free of the cationic nitrile of the formula (I) and in particular free of all bleach activators.

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.

Multi-phase molded bodies have the advantage over single-phase molded bodies that the pH criterion according to the invention can be implemented more easily and universally in one phase than for the entire molded body. Due to the low pH that the phase should have after dissolving in water, the use of more alkaline raw materials fen not possible in unlimited quantities, or to be avoided according to the invention. It may be necessary to add acidifying agents in order to have the cationic nitriles of the formula (I) in the mildly alkaline to slightly acidic medium desired according to the invention. If, however, alkaline raw materials, which cannot be dispensed with, are to be incoφorated in the agents, then a single-phase tablet would require the use of high amounts of acidifying agents. A phase split enables both the stabilization of the cationic nitrile, which is advantageous according to the invention, and the use of alkaline raw materials to be achieved, in that the alkaline raw materials such as carbonates, phosphates, silicates etc. are present in the phase (s) which are free of the cationic nitrile of the formula (I) are.

It is also possible according to the invention to release the activated bleaching system in a delayed or accelerated manner in order to achieve further advantages in washing or cleaning performance. Delayed release can be achieved, for example, by coating particles or the entire phase, while accelerated release can be achieved, for example, by adding disintegration aids to a phase. With such measures, it is possible, for example, to release the cationic nitrile of the formula (I) at the start of the washing or cleaning cycle, the washing or Cleaning liquor has a weakly alkaline or neutral to slightly acidic pH value if only the phase that contains the nitrile dissolves. After dissolving the other phase (s), the pH can then be increased drastically depending on the composition of the phase (s). Conversely, the late release of the cationic nitrile of the formula (I) can also be achieved. If the accelerated dissolution of the other phase (s) compared to the nitrile-containing phase is to provide a high pH value, this must be compensated for by acidifying agents in the nitrile-containing phase, if it is desired that the nitrile should be released in a neutral to slightly acidic medium.

The separation of the molded body into two or more phases can also be used to separate incompatible ingredients. Two-phase or multi-phase detergent tablets in which one phase contains the cationic nitrile of the formula (I) while another phase contains the total amount of the bleaching agents contained in the tablets are preferred according to the invention. If, in addition to bleaching agents and the cationic nitrile of the formula (I), further ingredients are used, it is also preferred to separate certain ingredients from one another. In the case of detergent tablets for machine dishwashing and detergent tablets for textile washing, preference is given to two-phase or multi-phase detergent tablets which contain the cationic nitrile of the formula (I), bleaching agents and enzymes, the enzymes not being in one phase together with the Bleach and the cationic nitrile are included.

Furthermore, in the case of detergent tablets for automatic dishwashing, two- or multi-phase detergents and cleaning agents are preferred, which contain the cationic nitrile of the formula (I), bleach and silver protection agent, the silver protection agent not in one phase together with the bleaching agent and the cationic nitrile is included.

The ingredients mentioned are described in detail below. 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 θ ₂ χ ₊ ι 'HO, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Such crystalline layered silicates are described, for example, in 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 Na2Si2θ ₅ 'yH ₂ θ are preferred, wherein β-sodium disilicate can 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 deliver 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. Zeolite P is 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 can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® 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, in Water easily soluble powder, which lose the water of crystallization when heated and at 200 ° C in the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ Ü), at higher temperature in sodium trimetaphosphate (Na P ₃ O) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it occurs when phosphoric acid is adjusted to a pH of 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 gcm ^"3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 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 gcm ^"3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to the diphosphate Na P ₂ θ ₇ with greater heating. 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) 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 like ^{" 3} , melting point 94 ° with loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (Kahumpyrophosphat), KP ₂ O _7, exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^"-3, which is soluble in water, wherein the pH of the solution at l% 25 ° is 10.4.

Condensation of the NaH ₂ PO 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 P ₃ Oιo (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] n-Na that crystallizes with 6 H ₂ O. 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, K ₅ P ₃ Oιo (potassium tripolyphosphate), for example in the form of a 50 wt .-% solution (> 23% P ₂ θ ₅ , 25% K ₂ O) on the market. The potassium polyphosphates are widely used in the detergent and cleaning agent industry. Further exist too Sodium potassium tripolyphosphates, which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH - Na ₃ K ₂ P3θ ₁₀ + HO

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 establish a lower and milder pH value for washing or Detergents. 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 respective acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UN 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 processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. Here is 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 common 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-0427 349, EP-A-0 472 042 and EP-A-0 542 496 and 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 are known. 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 ammoalkane phosphonates. Among the hydroxyalkane phosphonates is l-hydroxyethane-l, l-diphosphonate (HEDP) from of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred ammoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The ammoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, especially if the agents also contain bleach, it may be preferred to use ammoalkane phosphonates, 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 articles is 5 to 60% by weight, based on the molded article weight, in the case of detergent tablets, surfactant contents above 15% by weight are preferred and Detergent tablets for machine dishwashing usually contain less than 3% by weight of surfactant.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are preferably C _{_9-13} - alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example from

with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates, which are obtained from Ci ₂ - _.8 alkanes, for example by sulfochlorination or sulfoxidation with 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 Ci ₂ -C ₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁ -C ₂ o-oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The Ci ₂ -C ₆ alkyl sulfates and C ₁₂ -C ₅ alkyl sulfates and C] ₄ -Ci ₅ alkyl sulfates are preferred from a washing-technical point of view. Also 2,3-alkyl sulfates, which For example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN, suitable anionic surfactants are.

The sulfuric acid monoesters of the straight-chain or branched C ₇ ethoxylated with 1 to 6 mol of ethylene oxide. ₂ ι alcohols, such as 2-methyl-branched C .n alcohols with an average of 3.5 moles of ethylene oxide (EO) or Ci ₂ -ι ₈ 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 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 radical has a methyl or linear branching in the 2-position can be or can contain linear and methyl branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow 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, Cπ-π alcohols with 3 EO or 4 EO, C ₉ . _π alcohol with 7 EO, Cι ₃ . _{] 5} alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Cι ₂ . is alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci ₂ -ι alcohol with 3 EO and Ci ₂ -ι 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, such as are described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared according to the 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

I.

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 with 2 to 8 carbon atoms and R is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical with 1 to 8 carbon atoms, C - alkyl or phenyl radicals being preferred and [Z] for a linear polyhydroxyalkyl radical stands, the 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 wt .-%, each 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 not included in some phases of the detergent tablets or in the entire molded article, ie in all phases. Another important embodiment of the present invention therefore provides that at least one phase of the molded article is free of 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 to be advantageous, 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, p. 182-184), tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in 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 Hι ₀ θ ₅ ) _n and formally represents 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 writings are also details on Manufacture of granulated, compacted or cogranulated cellulose disintegrants. 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 and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30 HG from Rettenmaier available in the present invention.

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.

Within the scope of the present invention are single- or multi-phase detergent tablets 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 of 3 to 7 wt .-% and in particular from 4 to 6 wt .-%, based in each case 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 and silicone oils , Anti-redeposition agents, optical brighteners, graying inhibitors, Color transfer inhibitors and corrosion inhibitors included. 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 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.

The selection of the relevant enzymes is also dependent on the intended use of the detergent tablets according to the invention. In detergent tablets for machine dishwashing, the enzymes in particular include those from the hydrolase classes such as proteases, esterases, lipases or lipolytically active enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as stains containing protein, fat or starch. Oxidoreductases can also be used for bleaching. 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. Here are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytic enzymes or of protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.

Even with detergent tablets, 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 also be, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight.

Detergent tablets according to the invention for machine dishwashing can contain corrosion inhibitors to protect the wash ware or the machine, silver protection agents in particular being particularly useful in the area of machine dishwashing Have meaning. The known substances of the prior art can be used. In general, silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Benzotriazole and or alkylaminotriazole are particularly preferably to be used. In addition, active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

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 if 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, for example, salts of 4,4'-bis (2-anilino-4-moφholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the Moφholino- Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

Dyes and fragrances are added to the detergent tablets according to the invention in order to improve the aesthetic impression of the products and 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, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexyl benzylatepylpropionate, stylate propionate, stylate propionate. The ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones, for example, the jones, etc. -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 or dishes, so as 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 which is to be tabletted directly must have sufficient plastic deformability and have good flow properties, and furthermore it must not show any tendency to separate during storage, transport and filling of the die. These three prerequisites are extremely difficult to master with many substance mixtures, so that direct tableting is not often the case, particularly in the manufacture of detergent tablets is applied. The usual way of producing detergent tablets is therefore based on powdery components (“primary particles”) which are agglomerated or granulated by suitable processes to form secondary particles with a larger particle diameter. 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 single or multi-phase detergent tablets by shaping molding one or more particulate premixes in a manner known per se, which is characterized in that the premix for the entire molded article or for at least one of the phases 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 ₃ , a C ₂ . ₂ alkyl or alkenyl radical, a substituted C ₂ . ₂ 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 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 , -CH2-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 -O) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion, contains, wherein the pH of a 1 wt .-% aqueous solution of the premix in question is below 10.

If single-phase detergent tablets are produced, the entire premix must meet the pH criterion mentioned. In the production of multi-phase moldings, which are pressed together or are intermixed differently Premixes must be obtained, only the premix containing the cationic nitrile of the formula (I) must have a pH below 7 in a 1% strength by weight aqueous solution.

Preferred embodiments of the method according to the invention are to be seen analogously to the detergent tablets according to the invention. For example, processes in which the pH of a 1% by weight aqueous solution of the premix for the entire molded article or for the phase which contains the cationic nitrile of the formula (I) are below 9, preferably below 8, particularly is preferably below 7 and in particular below 6, preferred according to the invention.

Also in the process according to the invention, the pH is more preferably within a narrow range, so that processes in which the pH of a 1% by weight aqueous solution of the premix for the entire molded article or for the phase which is the cationic Nitrile of the formula (I) contains below 6.5, preferably below 6.0, particularly preferably below 5.5 and in particular below 5.0, are further preferred according to the invention.

With regard to further 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 wt .-%, in each case based 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 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) is a 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 N ^{+ +} CH2-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.

Detergent tablets preferred in the context of the present invention are obtained by pressing 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 particulate premix additionally contains granule (s) containing surfactant and has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1.

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 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 and shaped body, the premix can be "powdered" with finely divided surface treatment agents. This can be of advantage for the nature and physical properties of both the premix (storage, pressing) and the finished detergent tablets. Finely divided powdering agents are well known in the art, mostly zeolites, silicates or other inorganic salts being 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 (compare 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. contains optical brighteners, 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. To produce the shaped bodies according to the invention, the premix is compacted in a so-called die between two punches to form a solid compressed product. This process, which is briefly referred to as tableting in the following, 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 time, only the weight of the molded body is finally determined, because the compacts are due to physical Processes (stretching, crystallographic effects, cooling etc.) can still change their shape and size.

Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down. For small production quantities, eccentric tablet presses are preferably used, in which the punch or stamps are fastened 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 pressure on the premix is individual via the press paths for the upper and lower punches adjustable, whereby the pressure builds up by rolling the stamp 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, jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or the core layers not being covered in the case of the dot tablets and thus remaining visible. Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing. The throughputs of modern rotary tablet presses are over one million 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 should. 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 in the context of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Hörn & Noack Pharmatechnik GmbH, Worms, IMA 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, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm 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, Hörn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers are e.g. Senss AG, Reinach (CH) and Medicopharm, Kamnik (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 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 as tablets, in cylinder or cuboid form can be expedient, a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such 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 single tablet, but that shaped bodies are obtained which have several layers. ten, i.e. 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 ) can be achieved by the outer layer (s), which prevents the premature dissolving of components of the inner layer (s).

In a further preferred embodiment of the invention, a molded body consists of at least three layers, i.e. 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 cover layers and in the case of the shell-shaped molded body the outermost layers, however, 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

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

Claims

Claims:

1. Single-phase or multi-phase detergent and cleaning agent shaped body made of compressed particulate detergent and cleaning agent, including bleach, bleach activators) and optionally further detergent and cleaning agent components, characterized in that the shaped body or at least one phase thereof as a bleach activator is a cationic nitrile of the formula (I)

R ¹

R ^Z -N ^ - (CH ₂ ) -CN X '.-.

(I)

R ³

contain / contains in which R ^{1 represents} -H, -CH ₃ , a C ₂ - ₄ alkyl or alkenyl radical, a substituted C ₂ - ₂ alkyl or alkenyl radical with at least one substituent from the group --Cl, -Br, -OH, -NH2, -CN, an alkyl or alkenylaryl radical with a Ci- ₂ alkyl group, or for a substituted alkyl or alkenylaryl radical with a C). ₂ 4-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, wherein the pH of the 1 wt .-% aqueous solution of the molded body or the phase containing the nitrile quat is less than 10.

2. Single or multi-phase detergent and cleaning mold according to claim 1, characterized in that the pH of the 1 wt .-% aqueous solution of the mold or the phase containing the nitrile quat, less than 9, preferably less than 8, is particularly preferably less than 7 and in particular less than 6.

3. single or multi-phase detergent and cleaning product according to one of claims 1 or 2, characterized in that it contains the cationic nitrile of the formula (I) in amounts of 0.1 to 20 wt .-%, preferably from 0.25 to 15 wt .-% and in particular from 0.5 to 10 wt .-%, each based on the molded body weight.

4. Single- or multi-phase detergent and cleaning product according to one of claims 1 to 3, characterized in that it is a cationic nitrile of the formula (I) as a cationic nitrile of the formula (Ia)

R ⁴

X γ ⁽ .-- ⁾ . (Ia),

R ^b

contain, in which R, R and R are independently selected from -CH ₃ , -

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 anion, preferably R ⁵ = R ⁶ - -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = - CH ₃ applies.

5. Single-phase or multi-phase detergent form according to one of claims 1 to 4, characterized in that they contain as cationic nitrile (CH ₃ ) ₃ N ⁽⁺⁾ CH2-CN X ^" , where X ^{" stands} for an anion, which is selected from the group consisting of chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate.

6. single-phase or multi-phase detergent form according to one of claims 1 to 5, characterized in that they contain a cationic nitrile of the formula (I) and tetraacetylethylene diamine (TAED) as bleach activators.

7. single or multi-phase detergent and cleaning agent molded article according to one of claims 1 to 6, characterized in that it additionally contains 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 from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the molded body weight.

8. single-phase or multi-phase detergent form according to one of claims 1 to 6, characterized in that they contain anionic (s) and / or nonionic (s) 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.

9. Two-phase or multi-phase washing and cleaning agent molded article according to one of claims 1 to 7, characterized in that one phase contains the cationic nitrile of the formula (I) in amounts of 2.5% by weight, preferably 5% by weight and in particular of 7.5% by weight, based in each case on the weight of the phase, while the other phase (s) is preferably free of the cationic nitrile of the formula (I) and in particular free of all bleach activators /are.

10. Two- or multi-phase washing and cleaning agent molded articles according to claim 6, characterized in that one phase contains the cationic nitrile of the formula (I), while another phase contains the total amount of bleaching agents contained in the molded articles.

11. Two-phase or multi-phase detergent and cleaning agent form according to one of claims 8 or 9, characterized in that they contain the cationic nitrile of the formula (I), bleaching agents and enzymes, the enzymes not being in one phase together with the bleaching agent and cationic nitrile are included.

12. Two-phase or multi-phase detergent and cleaning agent shaped body according to one of claims 8 to 10, characterized in that they contain the cationic nitrile of the formula (I), bleach and silver protection agent, the silver protection agent not in one phase together with the bleaching agent and cationic nitrile is included.

13. A process for the production of single-phase or multi-phase detergent tablets by shaping molding of one or more particulate premixes in a manner known per se, characterized in that the premix is a cationic nitrile of the formula for the entire molded article or for at least one of the phases (I)

R ¹

R ² _N < ⁺⁾ - (CH ₂ ) -CN X (i),

R ³

contains, in which R ¹ for -H, -CH ₃ , a C ₂ - ₂₄ alkyl or alkenyl radical, a substituted C ₂ - ₂₄ alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br , -OH, -NH _2, -CN, an alkyl or alkenylaryl radical with a C1 ₂ 4- alkyl group, or a substituted alkyl- or alkenylaryl radical 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 pH of which is 1% by weight aqueous solution of the premix in question is below 10.

14. The method according to claim 12, characterized in that the pH of a 1% by weight aqueous solution of the premix for the entire molded article or for the phase which contains the cationic nitrile of the formula (I) is below 9, is preferably below 8, particularly preferably below 7 and in particular below 6.

15. The method according to any one of claims 12 or 13, characterized in that the premix contains as cationic nitrile (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , where X ^{" is} an anion 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 14, 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 15, 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 15 or 16, 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 17, 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.