EP1165742B1 - Single or multi-phase detergent forms with special bleach activators - Google Patents

Description

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

Detergent compositions in the form of shaped articles, in particular tablets, have long been known and broadly described in the prior art, although this form of supply has hitherto had no outstanding importance on the market. This is due to the fact that the offer form of the molded body in addition to a number of advantages also has disadvantages that affect both the production and use as well as consumer acceptance. The main advantages of moldings such as the elimination of the metering of the required amount of product by the consumer, the higher density and thus the reduced packaging and storage costs and a not to be underestimated aesthetic aspect are disadvantages such as the dichotomy between acceptable hardness and sufficiently fast disintegration and Dissolution of the moldings and numerous technological difficulties in the production and Verpakkung relativized.

In particular, the dichotomy between a sufficiently hard molded body and a sufficiently fast disintegration time is a key problem. Since sufficiently stable, ie shape and break resistant moldings can be produced only by relatively high compression pressures, there is a strong compaction of the molding constituents and a consequent delayed disintegration of the molding in the aqueous liquor and thus to a slow release of the active ingredients in washing or cleaning process. The delayed disintegration of the moldings also has the disadvantage that conventional detergent tablets can not be flushed in via the dispensing chamber of household washing machines, since the tablets do not disintegrate in sufficiently fast time into secondary particles which are small enough from the dispensing chamber into the washing drum to be flushed.

To overcome the dichotomy between hardness, i. Transport and handling stability, and easy disintegration of the moldings, many approaches have been developed in the prior art. An 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 ingress of water or which swell or become gas-evolved or otherwise disintegrate upon the ingress of water. Other proposed solutions from the patent literature describe the compression of premixes of certain particle sizes, the separation of individual ingredients of certain other ingredients and the coating of individual ingredients or the entire molded article with binders.

Bleaching compositions containing nitrile quat-type bleach activators are described in the prior art. Thus, European Patent Application EP 303 520 (Kao Corp.) discloses bleaching compositions containing a peroxide and a peracid precursor containing at least one N ⁺ -CH ₂ -CN or one N ⁺ (CH ₂ CN) _{2 group} . Detergent tablets are not mentioned in this document.

European Patent Application EP 458 396 (Unilever) also describes bleaching compositions containing a peroxy bleach and a peracid precursor having at least one N ⁺ -CH ₂ -CN or N ⁺ (CH ₂ CN) _{2 group} . Also in this document neither single nor multi-phase detergent tablets are mentioned.

Cationic nitriles of the general formula R ¹ R ¹¹ R ¹¹¹ N ⁺ CR ¹ R ² -CN and their use as bleach activators are described in European patent application EP 464 880 (Unilever). Also in this document is missing any information on 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 containing sodium percarbonate, which is spatially separated from all other components that might affect its stability (for example, bleach activators). Nitrile quat-type bleach activators are not mentioned in this document. Information on pH values of the solution of individual layers or of the entire molding are also not found in this document.

None of the cited prior art documents dealing with laundry detergents and cleaning compositions describe detergent tablets containing "nitrile quat" -based bleach activators. Nowhere is a well-defined pH range given for moldings or regions of moldings containing "nitrile quat" -based bleach activators. None of the cited documents deals with improving the stability of detergent tablets by specifically using these particular bleach activators in areas of defined pH.

Accordingly, it is the object of the present invention to provide laundry detergent and cleaner tablets which contain, as bleach activators, nitrile quats and have a high hardness and outstanding disintegration properties. This washing and cleaning agent tablets should also be able to be dosed via the dispenser, without the consumer thereby disadvantages by residues in the dispenser and insufficient detergent in the wash liquor grown. In addition to these molding-specific properties, the washing and cleaning performance of the moldings according to the invention should also be exemplary. In particular, the storage stability of the moldings and the preservation of the bleaching performance even with long storage should be ensured.

It has now been found that the stability of "nitrile quat" -based bleach activators in laundry detergent and cleaner moldings can be increased by using these bleach activators be used in moldings or molded body areas, which after dissolution in water have a pH below 7.

enthalten/enthält, in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH_2-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist, wobei der pH-Wert der 1 Gew.-%igen wäßrigen Lösung des Formkörpers bzw. der Phase, die das Nitrilquat enthält, kleiner 7 ist.The invention relates to single- or multi-phase detergent tablets made of compacted particulate detergent and cleaner, comprising bleach, bleach activator (s) and optionally further detergent and cleaner ingredients, which are characterized in that the moldings or at least one phase thereof as Bleach activator a cationic nitrile of the formula (I)

in which R ^{1 is} -H, -CH ₃ , a C _2-24 -alkyl or -alkenyl radical, a substituted C _2-24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical having a C _1-24 alkyl group, or a substituted alkyl or alkenylaryl radical having a C _1-24 alkyl group and at least one further substituent on the aromatic ring, R ² and R ³ are independently selected from -CH ₂ -CN, -CH _3, -CH ₂ -CH _3, -CH _2- CH ₂ -CH _3, -CH (CH ₃₎ -CH _3, -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion, the pH of the 1 wt. -% aqueous solution of the molding or the phase containing the nitrile quat, is less than 7.

Inventive moldings can be configured as single or multi-phase. The individual phases of the shaped body can have different roughness forms in the context of the present invention. The simplest realization possibility lies in two-layered or multi-layered tablets, each layer of the shaped article representing one phase. However, it is also possible according to the invention to produce multiphase moldings in which individual phases have the form of inclusions in (a) other phase (s).

In addition to so-called "ring-core tablets", coated tablets or combinations of the aforementioned embodiments are possible, for example. Examples of multiphase moldings can be found in the drawings of EP-A-0 055 100 (Jeyes) which describes toilet cleaning blocks. The technically most common spatial form of multiphase moldings is the two-layer or multi-layer tablet. In the context of the present invention it is therefore preferred that the phases of the shaped body have the form of layers. Two-, three- and four-layer tablets are preferred within the scope of the present invention.

The pH of a 1% strength by weight aqueous solution can be determined in the context of the present invention by preparing a solution of the molding or the phase which contains the cationic nitrile of the formula (I) in demineralized water. For this purpose, the appropriate amount of the molding or the phase is dissolved or suspended in water and determines the pH by known methods such as indicator papers or combination electrodes. Since certain methods of pH determination are temperature-dependent, the values given 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% strength by weight aqueous solution of the shaped body or the phase containing the nitrile quatate is less than 6.

Within the stated pH range, preference is given to single-phase or multi-phase detergent tablets in which the pH of the 1% strength by weight aqueous solution of the tablet or the phase containing the nitrile quatate is less than 6.5, preferably less than 6.0, more preferably less than 5.5 and in particular less than 5.

The moldings according to the invention may contain the cationic nitriles of the general formula (I) in varying amounts, the amount depending on the intended use of the moldings. So include detergent tablets and detergent tablets for the Machine dishwashing usually less bleach activator than, for example, bleach tablets, which consist largely of bleach and bleach activator. Detergent tablets and detergent tablets which are preferred for the purposes of the present invention are characterized in that they contain the cationic nitrile of the formula (I) in amounts of from 0.1 to 20% by weight, preferably from 0.25 to 15% by weight, and in particular from 0.5 to 10 wt .-%, each based on the molding weight.

It is particularly preferred if the detergent tablets according to the invention contain the cationic nitrile of the formula (I) in 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 of more than 0.2 mm.

It is preferred in the context of the present invention for the particles of the cationic nitrile not only to have more than 90% by weight of particles with sizes above 0.2 mm, but also to contain a relatively high proportion of coarser particles. Preferred washing and cleaning agent 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 have.

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 homogenous particle size distribution, the bleach activators used should in particular be free of too fine or dust fractions, that is to say particularly preferably contain no particles smaller 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" is understood to mean contents of less than 2% by weight, preferably less than 1% by weight and in particular less than 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, more preferably above 600 μm and in particular above 700 μm.

The general formula (I) includes a variety of cationic nitriles useful in the present invention. With particular advantage, the detergent tablets according to the invention comprise cationic nitriles in which R ^{1 represents} methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-butyl Tetradecyl, n-hexadecyl or n-octadecyl stands. R ² and R ³ are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, wherein one or both radicals may advantageously also be a Cyanomethylenrest. In the following table, preferred cationic nitriles of the formula (I) according to the invention are characterized by their radicals R ¹ , R ² and R ³ : R ¹ R ² R ³ -H -CH ₃ -CH ₃ -H -CH ₂ -CH ₃ -CH ₃ -H -CH ₂ -CH ₂ -CH ₃ -CH ₃ -H -CH (CH ₃ ) -CH ₃ -CH ₃ -H -CH ₂ -OH -CH ₃ -H -CH ₂ -CH ₂ -OH -CH ₃ -H -CH (OH) -CH ₃ -CH ₃ -H -CH ₂ -CH ₂ -CH ₂ -OH -CH ₃ -H -CH ₂ -CH (OH) -CH ₃ -CH ₃ -H -CH (OH) -CH ₂ -CH ₃ -CH ₃ -H - (CH ₂ CH ₂ -O) ₁ H -CH ₃ -H - (CH ₂ CH ₂ -O) ₂ H -CH ₃ -H - (CH ₂ CH ₂ -O) ₃ H -CH ₃ -H - (CH ₂ CH ₂ O) ₄ H -CH ₃ -H - (CH ₂ CH ₂ O) ₅ H -CH ₃ -H - (CH ₂ CH ₂ O) ₆ H -CH ₃ -CH ₃ -CH ₃ -CH ₃ -CH ₃ -CH ₂ -CH ₃ -CH ₃ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₃ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₃ -CH ₃ -CH ₂ -OH -CH ₃ -CH ₃ -CH ₂ -CH ₂ -OH -CH ₃ -CH ₃ -CH (OH) -CH ₃ -CH ₃ -CH ₃ -CH ₂ -CH ₂ -CH ₂ -OH -CH ₃ -CH ₃ -CH ₂ -CH (OH) -CH ₃ -CH ₃ -CH ₃ -CH (OH) -CH ₂ -CH ₃ -CH ₃ -CH ₃ - (CH ₂ CH ₂ -O) ₁ H -CH ₃ -CH ₃ - (CH ₂ CH ₂ -O) ₂ H -CH ₃ -CH ₃ - (CH ₂ CH ₂ -O) ₃ H -CH ₃ -CH ₃ - (CH ₂ CH ₂ O) ₄ H -CH ₃ -CH ₃ - (CH ₂ CH ₂ O) ₅ H -CH ₃ -CH ₃ - (CH ₂ CH ₂ O) ₆ H -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₃ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -OH -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -OH -CH ₃ -CH ₂ -CH ₃ -CH (OH) -CH ₃ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₂ -OH -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH (OH) -CH ₃ -CH ₃ -CH ₂ -CH ₃ -CH (OH) -CH ₂ -CH ₃ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -OH -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -OH -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH (OH) -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₂ -OH -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH (OH) -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH (OH) -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -OH -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -OH -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH (OH) -CH ₃ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₂ -OH -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH (OH) -CH ₃ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH (OH) -CH ₂ -CH ₃ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -OH -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -OH -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH (OH) -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₂ -OH -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH (OH) -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH (OH) -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -OH -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH ₂ -OH -CH ₃ -CH (CH ₃ ) -CH ₃ -CH (OH) -CH ₃ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH ₂ -CH ₂ -OH -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH (OH) -CH ₃ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH (OH) -CH ₂ -CH ₃ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₃ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -OH -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH ₂ -OH -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH (OH) -CH ₃ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH ₂ -CH ₂ -OH -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH (OH) -CH ₃ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH (OH) -CH ₂ CH ₃ -CH ₂ -CH ₃

enthalten, in der R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt sind aus -CH₃, -CH_2-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, wobei R⁴ zusätzlich auch -H sein kann und X ein Anion ist, wobei vorzugsweise R⁵ = R⁶ = -CH₃ und insbesondere R⁴ = R⁵ = R⁶ = -CH₃ gilt, sind erfindungsgemäß besonders bevorzugtFor ease of synthesis, preference is given to compounds in which the radicals R ¹ to R ^{3 are} identical, for example (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^-, (CH ₃ CH ₂ CH _{2) 3} N ⁽⁺⁾ CH ₂ -CN X ^-, (CH ₃ CH (CH _{3)) 3} N ⁽⁺⁾ CH ₂ -CN X ^-, or (HO -CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- . Single- or multi-phase detergent tablets which as cationic nitrile of the formula (I) are a cationic nitrile of the formula (Ia)

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, where preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ , are particularly preferred according to the invention

Detergent tablets containing 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, hydrogensulfate, 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 bleach", ie both bleach and bleach activator, cationic nitriles being used as the latter according to the invention in order to obtain advantageous shaped body properties to obtain. In addition to the cationic nitriles, the detergent tablets according to the invention may 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 sole or as main bleach activator, ie at least 50% by weight of the total bleach activators contained in the detergent tablets according to the invention are cationic nitriles of the formula ( I). Bleach activators are added to bleach-containing detergents and cleaners to achieve improved bleaching performance when washed at temperatures of 60 ° C and below. As bleach activators to be used in addition to the cationic nitrile, it is possible in the context of the present invention to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, in the context of the present invention, in addition to the cationic 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 Mn, Fe, Co, Ru or Mo saline complexes or - carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts. Also, bleach-enhancing active ingredient combinations obtained by intimately mixing a water-soluble salt of a divalent transition metal, can be selected from cobalt, iron, copper and ruthenium and mixtures thereof, a water-soluble ammonium salt and optionally a peroxygen-based oxidizing agent and inert carrier material are available, can be used as bleach catalysts in the present invention. If bleach catalysts are used in the context of the present invention, the abovementioned particle size restrictions also apply to them.

A bleach activator particularly preferably used in addition to the cationic nitrile of formula (I) is N, N, N ', N'-tetraacetylethylenediamine, which is widely used in detergents and cleaners. Accordingly, preferred detergent tablets are characterized in that they contain as bleach activators a cationic nitrile of the formula (I) and tetraacetylethylenediamine (TAED).

In such "nitrile quat" -TAED combinations, the weight ratios of "nitrile quat" to TAED are preferably in the range of 1: 2 to 10: 1. Particularly preferred in such combinations are 1/3 to 2/3 of the total amount of bleach activator cationic nitrile of the formula (I).

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

Depending on the intended use of the molded articles produced, the total amounts of bleach activators may vary. Thus, in typical universal detergent tablets bleach activator levels between 0.5 and 10 wt .-%, preferably between 2 and 8 wt .-% and in particular between 4 and 7 wt .-% usual, while bleach tablets quite higher levels, for example between 5 and 30 wt .-%, preferably between 7.5 and 25 wt .-% and in particular between 10 and 20 wt .-% may have. The skilled person is not limited in its formulation freedom and can in this way stronger or weaker bleaching detergent tablets, detergent tablets or bleach tablets by varying the levels of bleach activator and bleach.

The bleach activator (s) serve in the detergent tablets according to the invention to activate the bleach or bleach at lower washing or cleaning temperatures and thus to ensure a high bleaching performance even at low temperatures. As a bleaching agent, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. 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, regardless of which other ingredients are contained in the tablets. When cleaning or bleaching tablets for automatic dishwashing are prepared, it is also possible to use bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)] , o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutan-1,4-diene diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

Chlorinating or bromine-releasing substances can also be used as bleaching agents in machine dishwashing moldings. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

In laundry detergent tablets for textile laundry, which are referred to as laundry detergent tablets for short, but also for automatic dishwashing detergent tablets, sodium percarbonate is the preferred bleaching agent to be used. Here, "sodium percarbonate" is a non-specific term used for sodium carbonate peroxohydrates, which strictly speaking are not "percarbonates" (ie salts of percarbonate) but hydrogen peroxide adducts of sodium carbonate. The commodity has the average composition 2 Na ₂ CO ₃ .3 H ₂ O ₂ and is therefore not peroxycarbonate. Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm ^-3 , which readily decomposes into sodium carbonate and bleaching or oxidizing oxygen.

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

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

The detergent tablets according to the invention may be monophasic, i. be pressed from a premix to a homogeneous molding. However, it is also possible and preferred according to the invention to provide multi-phase shaped bodies, it being possible to divide active substances into spatially delimited areas where this appears expedient. In the context of the present invention, two-phase 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% by weight, based in each case on the weight of the phase, while the other phase (s) is / are 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 shaped 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 in the other phase (s) is correspondingly reduced without the Total content of the shaped body of this active substance varies. As is evident from the abovementioned amounts of bleach activator (s) in the overall shaped body 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 shaped body so that the corresponding phase has high bleach activator levels.

Multiphase moldings have the advantage over single-phase moldings that the pH criterion according to the invention can be realized more easily and universally in one phase than for the entire molding. Due to the low pH that the phase should have after dissolution in water, is a use of higher alkaline raw materials not possible in unlimited quantities, or to avoid according to the invention. Optionally, an addition of acidifying agents is required in order to have the cationic nitriles of the formula (I) present in the weakly alkaline to slightly acidic medium desired according to the invention. However, if alkaline raw materials that can not be dispensed with are to be incorporated into the compositions, a single-phase tablet would require the use of high amounts of acidifying agent. By means of a phase split, it is possible to realize both the stabilization of the cationic nitrile advantageous according to the invention and the use of alkaline raw materials, in that the alkaline raw materials such as carbonates, phosphates, silicates, etc. are present in the phase (s) free of the cationic nitrile of the formula (I) are.

It is also possible according to the invention to release the system of activated bleach in a delayed or accelerated manner in order to achieve further advantages in the 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 for example possible to release the cationic nitrile of the formula (I) at the beginning of the washing or cleaning cycle, wherein the washing or cleaning liquor has a weakly alkaline or neutral to slightly acidic pH, if only the phase which contains the nitrile. After dissolution of the other phase (s), the pH can then be drastically increased, depending on the composition of the phase (s). Conversely, the delayed release of the cationic nitrile of the formula (I) can be realized. If in this case the resolution of the other phase (s) accelerated in relation to the nitrile-containing phase should yield a high pH, this must be compensated by acidifying agent in the nitrile-containing phase, if it is desired that the nitrile should be released in the neutral to slightly acidic medium.

The separation of the molding in two or more phases can also be used to separate incompatible ingredients. Two- or multi-phase detergent tablets in which one phase contains the cationic nitrile of formula (I) while another phase contains the total amount of bleach contained in the tablets are preferred in the present invention.

If, in addition to bleaching agents and the cationic nitrile of the formula (I), further ingredients are used, it is also preferable to separate certain ingredients from each other. In the case of automatic dishwashing detergent tablets and laundry detergent tablets for laundry use, two- or more-phase detergent tablets are preferred which contain the cationic nitrile of formula (I), bleaching agents and enzymes, which enzymes do not co-incipient in one phase Bleaching agent and the cationic nitrile are included.

Furthermore, in the case of automatic dishwashing detergent tablets, two- or more-phase detergent tablets are preferred which contain the cationic nitrile of formula (I), bleach and silver protectants, the silver protectant not being in phase together with the bleach and cationic nitrile is included.

The ingredients mentioned are described in detail below. In addition to the ingredients bleach activator and bleach mentioned, the detergent tablets according to the invention may contain further ingredients whose amounts are determined by 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. It will also be difficult for the person skilled in the art to select the individual components and their quantitative contents. Thus, a universal detergent tablet will contain higher levels of surfactant (s), while a bleach tablet may even be dispensed with altogether. Also, the amount of builder (s) used will vary according to the intended use.

In the detergent tablets according to the invention, all builders commonly used in detergents and cleaners may be present, in particular zeolites, silicates, carbonates, organic co-builders and, where there are no ecological prejudices against their use, also the phosphates.

Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _{2x + 1} ˙H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are. Such crystalline sheet silicates are described, for example, in European Patent Application EP-A-0 164 514 . Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ ˙yH ₂ O are preferred, whereby β-sodium disilicate can be obtained, for example, by the process described in international patent application WO-A-91/08171 .

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray-amorphous silicates, which likewise have a dissolution delay compared to the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 . Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous 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 the company Crosfield) particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula

nNa ₂ O˙ (1-n) K ₂ O˙Al ₂ O ₃ ˙ (2 - 2.5) SiO ₂ ˙ (3.5-5.5) H ₂ O.

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

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.

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

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white, in Water very easily soluble powders which lose the water of crystallization on heating and at 200 ° C in the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in Natiumtrimetaphosphat (Na ₃ P ₃ O ₉ ) and Maddrellsches Salt (see below), go over. NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium phosphate, KDP), KH ₂ PO ₄ , is a white salt of 2.33 gcm ^-3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water.

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

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

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals. Na ₄ P ₂ O ₇ is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. Continue to exist Sodium potassium tripolyphosphates, which are also usable in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are used according to the invention exactly as 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.

Particularly suitable organic co-builders in the detergent tablets according to the invention are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if 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 thereof.

The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve for setting a lower and milder pH of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

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

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again 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 from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

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

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

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

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

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives, of which German Patent Application DE-A-195 40 086 discloses that they also have a bleach-stabilizing effect in addition to cobuilder properties.

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

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30, where DE is a common measure of the reducing effect of a polysaccharide compared to dextrose which has a DE of 100. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are described, for example, in European Patent Applications EP-A-0 232 202, EP-A-0 427 349, 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 . Also suitable is an oxidized oligosaccharide according to the German patent application DE-A-196 00 018. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

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

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such co-builders are 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 aminoalkanephosphonates. Among the hydroxyalkane phosphonates is the 1-hydroxyethane-1,1-diphosphonate (HEDP) of special importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). As Aminoallcanphosphonate preferably come Ethylenendiamintetramethylenphosphonat (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologues in question. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

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

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

Preferred detergent tablets also contain one or more surfactants. In the detergent tablets according to the invention anionic, nonionic, cationic and / or amphoteric surfactants or mixtures thereof may be used. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants. The total surfactant content of the molded articles is from 5 to 60% by weight, based on the weight of the molded article, surfactant contents of more than 15% by weight being preferred in the case of detergent tablets, and detergent tablets for automatic dishwashing usually less than 3 wt .-% surfactant.

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

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

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. From the washing are the C ₁₂ -C ₁₆ alkyl sulfates and C _12- C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates of preferably. Also 2,3-alkyl sulfates, which for example, according to US Pat. Nos. 3,234,258 or 5,075,041, which can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.

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

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

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

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

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

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as they are For example, in Japanese Patent Application JP 58/217598 are described or preferably after in the international Patent Application WO-A-90/13533.

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

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

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

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

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

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides according to the teaching of international application WO-A-95/07331, for example, 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 (s) 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 molding weight, have. In this case, application-related advantages can result from certain proportions in which the individual classes of surfactants are used.

For example, washing and cleaning agent tablets are particularly preferred in which the ratio of anionic surfactant (s) to nonionic surfactant (s) 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 have advantages if certain types of surfactant are not present in some phases of the detergent tablets or in the entire tablet, ie in all phases. Another important embodiment of the present invention therefore provides that at least one phase of the moldings is free of nonionic surfactants.

Conversely, however, the content of individual phases or of the entire molding, i. all phases, on certain surfactants a positive effect can be achieved. The incorporation of the above-described alkylpolyglycosides has proved to be advantageous, so that detergent tablets are preferred in which at least one phase of the tablets contains alkylpolyglycosides.

Similar to the nonionic surfactants, the omission of anionic surfactants from individual or all phases may result in washing and cleaning agent tablets which are more suitable for certain fields of application. It is therefore within the scope of the present invention also possible to use detergent tablets in which at least one phase of the tablets is free of anionic surfactants.

In order to facilitate the disintegration of highly compacted moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrating agents, in order to shorten the disintegration times. According to Römpp (9th edition, Vol. 6, p. 4440) and Voigt " Textbook of Pharmaceutical Technology " (6th edition, 1987, pp. 182-184), excipients are understood to mean excipients which are suitable for rapid disintegration of tablets in water or gastric juice and for the release of the drugs in resorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume upon ingress of water, on the one hand increasing the intrinsic volume (swelling), and on the other hand creating a pressure via the release of gases which can break the tablet into smaller particles decays. 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 substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
Preferred detergent tablets contain from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, of one or more disintegration aids, in each case based on the weight of the tablet.

Preferred disintegrating agents in the context of the present invention are cellulose-based disintegrating agents, so that preferred washing and cleaning agent tablets contain such cellulose-based disintegrating agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular 4 contain up to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.

The cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. Detergents and cleaning agent tablets which contain disintegrating agents in granular or optionally cogranulated 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). described. These writings are also details to Production of granulated, compacted or cogranulated cellulose explosives to remove. The particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns. The above-mentioned coarser disintegration aids based on cellulose described in more detail in the cited documents are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel® TF-30-HG from Rettenmaier.

As a further disintegrating agent based on cellulose or as a component of this component, microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact. Subsequent deaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 μm and can be compacted, for example, into granules having an average particle size of 200 μm.

In the context of the present invention, single- or multi-phase detergent tablets are additionally a disintegration assistant, preferably a disintegration assistant based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably 3 to 7 wt .-% and in particular from 4 to 6 wt .-%, each based on the molding weight.

In addition to the constituents bleach activator, bleach, builder, surfactant and disintegration aid, the detergent tablets according to the invention may contain one or more substances from the group of builders, enzymes, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, antiredeposition agents , optical brighteners, grayness inhibitors, Color transfer inhibitors and corrosion inhibitors. These substances will be described below.

Particularly suitable enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or 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 enzymatically-derived variants derived from their genetically modified variants. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. These are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases. Cellulases used are preferably cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures of these. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
The enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation. The proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt%, preferably 0.5 to about 4.5 wt%.

The selection of the relevant enzymes is likewise dependent on the intended use of the detergent tablets according to the invention. In detergent tablets for automatic dishwashing come as enzymes in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, Glykosylhydrolasen and mixtures of said enzymes in question. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains. For bleaching and oxidoreductases can be used. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens, as well as enzymatically-derived variants derived from their genetically modified variants. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.

Even with detergent tablets, the enzymes may be adsorbed to carriers or embedded in coating substances to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can also be, for example, about 4.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-% amount.

Detergent shaped bodies according to the invention for machine dishwashing can contain corrosion inhibitors for protecting the items to be washed or the machine, with particular silver protectants in the area of automatic dishwashing being particularly special Have meaning. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

In addition, the detergent tablets may also contain components which positively influence the oil and grease washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty, which has been previously washed several times 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 methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic Cellulose ethers, as well as known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

The shaped bodies may contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed compounds which, instead of the morpholino group, a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl). Mixtures of the aforementioned brightener can 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 visual and sensory "typical and unmistakable" product in addition to performance. As perfume oils or fragrances, individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, α-isomethylionone and Methylcedrylketon to the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.

The content of the detergent tablets according to the invention is usually less than 0.01% by weight of dyes, while fragrances may account for up to 2% by weight of the total formulation.

The fragrances can be incorporated directly into the compositions of the invention, but it may also be advantageous to apply the fragrances on carriers, which enhance the adhesion of the perfume on the laundry and provide by a slower release of fragrance for long-lasting fragrance of the textiles. Cyclodextrins, for example, have proven useful as such carrier materials, wherein 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 dyed with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to textile fibers or dishes, so as not to stain them.

The production of washing and cleaning active moldings is done by applying pressure to a mixture to be pressed, which is located in the cavity of a press. In the simplest case of the production of shaped bodies, which is referred to below as simplifying tableting, the mixture to be tableted is compressed directly, ie without preceding granulation. The advantages of this so-called Direkttablettierung are their simple and cost-effective application, since no further process steps and consequently no other systems are needed. However, these advantages are also faced with disadvantages. Thus, a powder mixture, which is to be tabletted directly, have sufficient plastic deformability and have good flow properties, furthermore, it must not show any separation tendencies during storage, transport and filling of the die. These three conditions are extremely difficult to control in many mixtures of substances, so that the direct tableting, especially in the production of detergent tablets and detergent often not is applied. The usual way of producing washing and cleaning agent tablets is therefore based on pulverulent components ("primary particles") which are agglomerated or granulated by suitable processes to form secondary particles having a relatively high particle diameter. These granules or mixtures of different granules are then mixed with individual powdered additives and fed to the tableting.

enthält, in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃,-CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist, enthält, wobei der pH-Wert einer 1 Gew.-%igen wäßrigen Lösung des betreffenden Vorgemischs unter 7 liegt.
Werden einphasige Wasch- und Reinigungsmittelformkörper hergestellt, so muß das gesamte Vorgemisch dem genannten pH-Wert-Kriterium entsprechen. Bei der Herstellung mehrphasiger Formkörper, die durch Aufeinander- oder Ineinanderpressen verschiedener Vorgemische erhalten werden, muß lediglich das Vorgemisch, das das kationische Nitril der Formel (I) enthält, in 1 Gew.-%iger wäßriger Lösung einen pH-Wert unter 7 aufweisen.Another object of the present invention is a process for the preparation of single- or multi-phase detergent tablets by molding one or more particulate premixes in a conventional manner, which is characterized in that the premix for the entire molding or for at least one of the phases is a cationic nitrile of the formula (I)

contains, in the R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl, a substituted C _2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br , -OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C _1-24 -alkyl group and at least one further substituent on the aromatic ring , R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH ) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion, wherein the pH of a 1 wt. % aqueous solution of the premix concerned is less than 7.
If single-phase detergent tablets are prepared, the entire premix must comply with the said pH criterion. In the production of multiphase moldings, by juxtaposing or pressing each other different Vorgemische be obtained, only the premix containing the cationic nitrile of formula (I), in 1 wt .-% aqueous solution has a pH below 7.

Preferred embodiments of the method according to the invention can be seen analogously to the detergent tablets according to the invention. Thus, processes in which the pH of a 1% strength by weight aqueous solution of the premix for the entire molding or for the phase which contains the cationic nitrile of the formula (I) is below 6 are preferred according to the invention.

Also in the method according to the invention, the pH is more preferably within a narrower range, so that processes in which the pH of a 1 wt .-% aqueous solution of the premix for the entire molding or for the phase containing the cationic Contains nitrile of formula (I), less than 6.5, preferably less than 6.0, more preferably less than 5.5 and in particular less than 5.0, according to the invention further preferred.

With regard to further preferred embodiments of the process according to the invention, reference is made to the above information on the detergent tablets according to the invention. Thus, contents of the pre-mixture of cationic nitrile of 0.25 to 15 and especially from 0.5 to 10 wt .-%, each based on the premix, are preferred.

Also with regard to the particle sizes of the cationic nitrile analogously applies the above. 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 the particles of the cationic nitrile of the formula (I) having a particle size above 0.4 mm, are likewise preferred according to the invention. Particularly preferred are process variants in which the cationic nitrile of the formula (I) a average particle size above 400 microns, preferably above 500 microns, more preferably above 600 microns and in particular above 700 microns.

With regard to the cationic nitriles preferably used, reference may be made to the above statements. In particularly preferred processes, the premix comprises 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.

In the context of the present invention, preferred detergent tablets are obtained by compressing a particulate premix of at least one surfactant-containing granulate and at least one subsequently admixed pulverulent component. The preparation of the surfactant-containing granules can be carried out by conventional industrial granulation processes such as compaction, extrusion, mixer granulation, pelleting or fluidized bed granulation. It is advantageous for the later detergent tablets if the premix to be compressed has a bulk density which approximates the conventional compact detergent. In particular, it is preferred that the particulate premix additionally contains surfactant-containing granules and has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.

The surfactant-containing granules in preferred process variants also satisfy certain particle size criteria. For example, preferred processes according to the invention are those 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 excipients, which more preferably originate 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 compressed into detergent tablets, the premix can be "powdered" with finely divided surface treatment agents. This may be advantageous for the nature and physical properties of both the premixture (storage, compression) and the final detergent and cleaning products. Fine particulate powdering agents are well known in the art, with mostly zeolites, silicates or other inorganic salts are used. Preferably, however, the premix is "powdered" with finely divided zeolite, with faujasite-type zeolites 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 structural group 4 (cf. Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York , London, Sydney, Toronto, 1974, page 92). In addition to zeolite X, it is thus also possible to use zeolite Y and faujasite and also mixtures of these compounds, the pure zeolite X being preferred.
Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which need not necessarily belong to the Zealith structural group 4, can be used as a powdering agent, it being advantageous if at least 50 wt .-% of the powdery powder of a zeolite of faujasite Type persist.

In the context of the present invention, preference is given to detergent tablets which consist of a particulate premix containing granular components and subsequently admixed pulverulent substances, the one or more subsequently admixed pulverulent components comprising a faujasite-type zeolite having particle sizes of less than 100 μm, preferably below 10 μm and in particular below 5 μm and makes up 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 tabletted.

In addition to the constituents surfactant, builder and disintegration aid, the premixes to be compressed may additionally contain one or more substances from the group of bleaches, bleach activators, enzymes, pH adjusters, fragrances, perfume carriers, Fluorescers, dyes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, color transfer inhibitors and corrosion inhibitors. These substances have been described above.

The production of the shaped bodies according to the invention takes place firstly by the dry mixing of the constituents, which may be completely or partially pre-granulated, and subsequent informing, in particular pressing into tablets, wherein conventional methods can be used. To produce the shaped bodies according to the invention, the premix is compacted in a so-called matrix between two punches to form a solid compressed product. This process, hereinafter referred to as tabletting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting shaped body are determined by the position of the lower punch and the shape of the pressing tool. The constant dosage even at high molding throughputs is preferably achieved via a volumetric metering of the premix. As the tableting progresses, the upper punch contacts the pre-mix and continues to descend toward the lower punch. In this compression, the particles of the premix are pressed closer to each other, with the void volume within the filling between the punches decreasing continuously. From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it comes to the formation of the molding. Depending on the physical properties of the premix, some of the premix particles are also crushed, and even higher pressures cause sintering of the premix. With increasing pressing speed, so high throughput amounts, the phase of the elastic deformation is shortened more and more, so that the resulting moldings may have more or less large cavities. In the last step of tableting, the finished molded body is pushed out of the die by the lower punch and carried away by subsequent transport means. At this time, only the weight of the molding is finally determined, since the compacts due to physical Processes (re-stretching, crystallographic effects, cooling, etc.) can change their shape and size.

The tabletting is carried out in commercial tablet presses, which can be equipped in principle with single or double punches. In the latter case, not only the upper punch is used to build up pressure, and the lower punch moves during the pressing on the upper punch, while the upper punch presses down. For small production quantities, eccentric tablet presses are preferably used in which the die or punches are attached to an eccentric disc, which in turn is mounted on an axis at a certain rotational speed. The movement of these punches is comparable to the operation of a conventional four-stroke engine. The compression can be done with a respective upper and lower punch, but it can also be attached more stamp on an eccentric disc, the number of Matrizenbohrungen is extended accordingly. The throughputs of eccentric presses vary depending on the type of 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 are arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are commercially available. Each die on the die table is assigned an upper and lower punch, in turn, the pressing pressure can be actively built only by the upper or lower punch, but also by both stamp. The die table and the punches move about a common vertical axis, the punches are brought by means of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection. At the points where a particularly serious increase or decrease of the stamp is required (filling, compaction, ejection), these curved paths are supported by additional low-pressure pieces, Nierderzugschienen and lifting tracks. The filling of the die via a rigidly arranged supply device, the so-called filling shoe, which is connected to a reservoir for the premix. The pressing pressure on the premix is individualized via the pressing paths for upper and lower punches adjustable, wherein the pressure build-up occurs by the Vorbeirollen the stamp shank heads on adjustable pressure rollers.

Concentric presses can be provided with two Füllschuhen to increase the throughput, with the production of a tablet only a semicircle must be traversed. To produce two-layered and multi-layered shaped bodies, several filling shoes are arranged one after the other without the slightly pressed-on first layer being ejected before further filling. By suitable process control are on this. It is also possible to produce coat and point tablets which have an onion-shell-like construction, wherein in the case of the point tablets the top side of the core or the core layers is not covered and thus remains visible. Even rotary tablet presses can be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes are used simultaneously for pressing. The throughputs of modern rotary tablet presses amount to over one million moldings per hour.

• Verwendung von Kunststoffeinlagen mit geringen Dickentoleranzen
• Geringe Umdrehungszahl des Rotors
• Große Füllschuhe
• Abstimmung des Füllschuhflügeldrehzahl auf die Drehzahl des Rotors
• Füllschuh mit konstanter Pulverhöhe
• Entkopplung von Füllschuh und Pulvervorlage

When tableting with rotary presses, it has proven to be advantageous to carry out the tableting with the lowest possible weight fluctuations of the tablet. In this way, the hardness fluctuations of the tablet can be reduced. Small variations 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
• Tuning of the filling paddle speed to the speed of the rotor
• Filling shoe with constant powder height
• Decoupling of filling shoe and powder template

To reduce Stempelanbackungen offer all known from the art non-stick coatings. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotary punches have also proved to be advantageous, with upper and lower punches being designed to be rotatable if possible should. With rotating punches can be dispensed with a plastic insert usually. Here, the stamp surfaces should be electropolished.

It has also been shown that long pressing times are advantageous. These can be adjusted with pressure rails, several pressure rollers or low rotor speeds. Since the variations in the hardness of the tablet caused by the fluctuations of the pressing forces, systems should be applied, which limit the pressing force. Here, elastic punches, pneumatic compensators or resilient elements in the force path can be used. Also, the pressure roller can be stirred out resiliently.

Tableting machines suitable for the purposes of the present invention are obtainable, for example, from Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Verpackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell on the lake, KORSCH presses AG, Berlin, as well as Romaco GmbH, Worms. Other providers include Dr. med. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Berne (CH), BWI Manesty, Liverpool (GB), 1st Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (SI ). Particularly suitable is, for example, the hydraulic double pressure press HPF 630 LAEIS, D. Tablettierwerkzeuge are for example from the company Adams tabletting tools, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Sons GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers are e.g. Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

The moldings can be made in a predetermined spatial form and predetermined size. As a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section. This last embodiment detects the presentation form of the tablet to compact cylinder pieces with a ratio of height to diameter above 1.

The portioned compacts can be designed in each case as separate individual elements, which corresponds to the predetermined dosage amount of the washing and / or cleaning agent. However, it is also possible to form compacts which connect a plurality of such mass units in a compact, wherein in particular by predetermined predetermined breaking points the easy separability portioned smaller units is provided. For the use of laundry detergents in machines of the type commonly used in Europe with horizontally arranged mechanism, the formation of the portioned compacts as tablets, in cylindrical or cuboidal form may be appropriate, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred. Commercially available hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for producing such compacts.

The spatial form of another embodiment of the moldings is adapted in their dimensions of Einspülkammcr of commercial household washing machines, so that the moldings can be metered without dosing directly into the dispenser, where it dissolves during the Einspülvorgangs. Of course, however, a use of the detergent tablets via a dosing is easily possible and preferred in the context of the present invention.

Another preferred molded article which can be produced has a plate-like or tabular structure with alternately thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, which are the short thin segments, broken and in the Machine can be entered. This principle of the "bar-shaped" shaped body wash can also be realized in other geometric shapes, for example vertical triangles, which are joined together only on one side thereof.

But it is also possible that the various components are not pressed into a single tablet, but that moldings are obtained, the several layers, So at least two layers. It is also possible that these different layers have different dissolution rates. This can result in advantageous performance properties of the molded body. If, for example, components are contained in the moldings which interact negatively, it is possible to integrate one component in the faster soluble layer and to incorporate the other component into a slower soluble layer, so that the first component has already reacted, when the second goes into solution. The layer structure of the moldings can be carried out both in a staggered manner, wherein a dissolution process of the inner layer (s) takes place at the edges of the molded body already when the outer layers are not completely dissolved, but it can also be a complete coating of the inner layer (s ) are reached through the respective outer layer (s), which leads to a prevention of premature dissolution of constituents of the inner layer (s).

In a further preferred embodiment of the invention, a shaped body consists of at least three layers, ie two outer and at least one inner layer, at least in one of the inner layers containing a peroxy bleach, while the stacked shaped body, the two outer layers and the envelope-shaped body However, outermost layers are free of peroxy bleach. Furthermore, it is also possible to separate peroxy bleach and optionally present bleach activators and / or enzymes spatially in a molding from each other. Such multilayer moldings have the advantage that they can be used not only via a dispensing compartment or via a metering device, which is placed in the wash liquor; Rather, it is also possible in such cases, to give the molding in direct contact with the textiles in the machine without stains caused by bleach and the like to be feared.

Similar effects can also be achieved by coating ("coating") individual constituents of the washing and cleaning agent composition to be tabletted or of the entire shaped body. For this purpose, the bodies to be coated can be sprayed, for example, with aqueous solutions or emulsions, or obtained by the process of melt coating a coating.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be detected by the measurand of the diametric breaking load. This is determinable $$\sigma =\frac{2P}{\mathit{\pi Dt}}$$

Herein, σ is the diametrical fracture stress (DFS) in Pa, P is the force in N which results in the pressure applied to the molded article causing the breakage of the molded article, D is the molded article diameter in meters and t the height of the moldings.

Claims (19)

1. One-phase or multiphase laundry detergent and cleaning composition tablets composed of compacted particulate laundry detergent and cleaning composition, comprising bleach, bleach activator(s) and also optionally further laundry detergent and cleaning composition constituents, characterized in that the tablet or at least one phase thereof comprise(s), as the bleach activator, a cationic nitrile of the formula (I)

   

   
   in which R¹ is -H, -CH₃, a C_2-24-alkyl or -alkenyl radical, a substituted C_2-24-alkyl or -alkenyl radical having at least one substituent from the group of -Cl, -Br, -OH, -NH₂, -CN, an alkyl- or alkenylaryl radical having a C_1-24-alkyl group, or a substituted alkyl- or alkenylaryl radical having a C_1-24-alkyl group and at least one further substituent on the aromatic ring, R² and R³ are each independently selected from -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH (CH₃) -CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH where n = 1, 2, 3, 4, 5 or 6 and X is an anion, where the pH of the 1% by weight aqueous solution of the tablet or of the phase which comprises the nitrile quat is less than 7.
2. One-phase or multiphase laundry detergent and cleaning composition tablets according to Claim 1, characterized in that the pH of the 1% by weight aqueous solution of the tablet or of the phase which comprises the nitrile quat is less than 6.
3. One-phase or multiphase laundry detergent and cleaning composition tablets according to one of Claims 1 and 2, characterized in that they comprise the cationic nitrile of the formula (I) in amounts of 0.1 to 20% by weight, preferably of 0.25 to 15% by weight and in particular of 0.5 to 10% by weight, based in each case on the tablet weight.
4. One-phase or multiphase laundry detergent and cleaning composition tablets according to one of Claims 1 to 3, characterized in that they comprise, as the cationic nitrile of the formula (I), a cationic nitrile of the formula (Ia)

   

   
   in which R⁴, R⁵ and R⁶ are each independently selected from -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, where R⁴ may additionally also be -H and X is an anion, where, preferably, R⁵ = R⁶ = -CH₃ and, in particular, R⁴ = R⁵ = R⁶ = -CH₃.
5. One-phase or multiphase laundry detergent and cleaning composition tablets according to one of Claims 1 to 4, characterized in that they comprise, as the cationic nitrile, (CH₃)₃N⁽⁺⁾CH₂-CNX^- where X^- represents an anion which is selected from the group of chloride, bromide, iodide, hydrogensulphate, methosulphate, p-toluenesulphonate (tosylate) or xylenesulphonate.
6. One-phase or multiphase laundry detergent and cleaning composition tablets according to one of Claims 1 to 5, characterized in that they comprise, as bleach activators, a cationic nitrile of the formula (I) and tetraacetylethylenediamine (TAED).
7. One-phase or multiphase laundry detergent and cleaning composition tablets according to one of Claims 1 to 6, characterized in that they additionally comprise a disintegration assistant, preferably a disintegration assistant based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of from 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 tablet weight.
8. One-phase or multiphase laundry detergent and cleaning composition tablets according to one of Claims 1 to 7, characterized in that they comprise anionic and/or nonionic surfactant(s) and have overall surfactant contents above 2.5% by weight, preferably above 5% by weight and in particular above 10% by weight, based in each case on the tablet weight.
9. Two-phase or multiphase laundry detergent and cleaning composition tablets according to one of Claims 1 to 8, characterized in that one phase comprises the cationic nitrile of the formula (I) in amounts of 2.5% by weight, preferably of 5% by weight and in particular of 7.5o by weight, based in each case on the weight of the phase, while the other phase(s) is/are preferably free from the cationic nitrile of the formula (I) and in particular free from any bleach activators.
10. Two-phase or multiphase laundry detergent and cleaning composition tablets according to Claim 9, characterized in that one phase comprises the cationic nitrile of the formula (I), while another phase comprises the entirety of the bleaches present in the tablets.
11. Two-phase or multiphase laundry detergent and cleaning composition tablets according to one of Claims 9 or 10, characterized in that they comprise the cationic nitrile of the formula (I), bleach and enzymes, in which case the enzymes are not present in one phase together with the bleach and the cationic nitrile.
12. Two-phase or multiphase laundry detergent and cleaning composition tablets according to one of Claims 9 to 11, characterized in that they comprise the cationic nitrile of the formula (I), bleach and silver protectant, in which case the silver protectant is not present in one phase together with the bleach and the cationic nitrile.
13. Process for producing single-phase or multiphase laundry detergent and cleaning composition tablets by shaping compression of one or more particulate premixtures in a manner known per se, characterized in that the premixture for the entire tablet or for at least one of the phases comprises a cationic nitrile of the formula (I)

    

    
    in which R¹ is -H, -CH₃, a C_2-24-alkyl or -alkenyl radical, a substituted C_2-24-alkyl or -alkenyl radical having at least one substituent from the group of -Cl, -Br, -OH, -NH₂, -CN, an alkyl- or alkenylaryl radical having a C_1-24-alkyl group, or a substituted alkyl- or alkenylaryl radical having a C_1-24-alkyl group and at least one further substituent on the aromatic ring, R² and R³ are each independently selected from -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 where n = 1, 2, 3, 4, 5 or 6 and X is an anion, where the pH of a 1% by weight aqueous solution of the premixture in question is below 7.
14. Process according to Claim 13, characterized in that the pH of a 1% by weight aqueous solution of the premixture for the entire tablet or for the phase which comprises the cationic nitrile of the formula (I) is below 6.
15. Process according to one of Claims 13 and 14, characterized in that the premixture comprises, as the cationic nitrile, (CH₃)₃N⁽⁺⁾CH₂-CNX^- where X^- represents an anion which is selected from the group of chloride, bromide, iodide, hydrogensulphate, methosulphate, p-toluenesulphonate (tosylate) or xylenesulphonate.
16. Process according to one of Claims 13 to 15, characterized in that the particulate premixture additionally comprises surfactant-containing granule(s) and has a bulk density of at least 500 g/l, preferably at least 600 g/l and in particular at least 700 g/l.
17. Process according to Claim 16, characterized in that the surfactant-containing granule has particle sizes between 100 and 2000 µm, preferably between 200 and 1800 µm, more preferably between 400 and 1600 µm and in particular between 600 and 1400 µm.
18. Process according to one of Claims 16 and 17, characterized in that the surfactant-containing granule comprises anionic and/or nonionic surfactants and also builders, and has total surfactant contents of at least 10% by weight, preferably at least 20% by weight and in particular at least 25% by weight.
19. Process according to one of Claims 13 to 18, characterized in that the particulate premixture additionally comprises one or more substances from the group of the bleaches, bleach activators, enzymes, pH modifiers, fragrances, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, greying inhibitors, dye transfer inhibitors and corrosion inhibitors.