DE19908022A1 - Storage-stable detergent tablets - Google Patents

Abstract

The activity loss of washing and cleaning agent shaped bodies which contain bleaching agents, builders and other conventional constituents can be significantly improved if the water absorption of the shaped body is greater than 2g per 10g during a week of open storage at a temperature of 30 DEG C and with a relative humidity of 80 %. Washing and cleaning agent shaped bodies which contain enzymes, builders and other conventional constituents can significantly improve the stability in storage if the water absorption of the shaped body is less than 2g per 10g during a week of open storage at a temperature of 30 DEG C and with a relative humidity of 80 %. Washing and cleaning agent shaped bodies which contain enzymes and bleaching agents are thus advantageously prepared as multiphase shaped bodies, whereby one phase contains the enzyme, another phase contains the bleaching agent, and both phases have different degrees of water absorption.

Description

The present invention is in the field of compact moldings, the washing and cleaning properties. Such washing and Detergent tablets include detergent tablets for example Washing of textiles, automatic dishwashing detergent tablets or the cleaning of hard surfaces, bleach moldings for use in washing or dishwashers, water softening tablets or patch salt tablets. In particular, the invention relates to detergent tablets which are suitable for machine Cleaning dishes used in a household dishwasher and often short as Detergent tablets are called.

Depending on the intended use of the molded bodies, their composition varies. So detergent tablets for laundry of textiles contain high amounts of surfactants, whereas automatic dishwasher detergents contain these only in minor amounts and bleach tablets are often completely free of surfactants. Ingredients used in both detergent tablets and detergent tablets and bleach tablets are especially builders, bleaches and Enzymes, bleach tablets also being free from the latter.

Both in the use of bleaching agents and in the use of enzymes in washing and detergent tablets, the problem of stability also exists over longer  Time periods. Thus, the shaped bodies need not only immediately after manufacture high level of performance, but also after storage, transport and eventual Residence times at the end user. This problem is reinforced by the narrow Contact, in which the substances in question are in the form of other substances which are their constituents Affect stability. Incompatibilities of ingredients are in the compact offer form "tablet" more noticeable than, for example, in powders. Such incompatibilities exist for. B. between oxidation-sensitive substances (Dyes, enzymes, etc.) and bleaches, between bleach and bleach activator etc. The storage stability of bleaching agents and enzymes in washing and To increase detergent tablets was therefore an object of the present invention Invention.

To improve the stability of enzymes in detergent tablets There is little prior art prior to the loss Active oxygen in bleach-containing moldings subject more numerous Suggested solutions is.

Thus, the European patent application EP 481 792 (Unilever) describes Detergent tablets containing a persalt and a bleach activator, wherein the Bleach activator have a certain pseudo-first-order perhydrolysis constant got to. This document teaches that the bleaching agent is preferably bleached destabilizing ingredients should be separated. If the bleach is perborate and a di- or polyacylated amine bleach activator is used, this measure is even compelling.

European patent application EP 481 793 (Unilever) also describes Detergent tablets. These contain sodium percarbonate as a bleaching agent by all Substances that can affect its stability is spatially delineated. These too Scripture explicitly refers to the separation of bleach and bleach activator or substances,  which can be attacked by bleach and thereby to a loss of bleaching activity lead, go.

European Patent Application EP 395 333 (Unilever) describes tabletted Detergent compositions, the sodium perborate and one or more substances the group of di- or polyacylated amine bleach activators, enzymes and optical Whitener, wherein the persalt is not separated from the substances in this group becomes. The tablets disclosed in this application are stable and have no loss of bleach or enzyme activity.

The older German patent application DE 198 06 220.6 (Henkel KGaA) describes two or multi-phase detergent tablets of compacted particulate detergents and cleaners, which builder (s), bleach, Bleach activator (s) and optionally further washing and Contain detergent ingredients in which the bleach activator (s) spatially separated from oxidation - sensitive substances in a delimited region of the Molded body is present / present.

The prior art addresses the problems of bleach stability and stability oxidation-sensitive substances in detergent tablets causal on the contact of bleach with the substances concerned recycled. The proposed solution is again and again the separation of the bleaching agent proposed by the bleach activator or by oxidation-sensitive substances. None The mentioned documents deals with other solutions Stability problems of oxidation-sensitive substances and the loss of activity of the Bleaching agent or other active substances such as enzymes, in washing and To overcome detergent moldings simultaneously.

The present invention was based on the object, washing and To provide detergent tablets, which overcome the problems mentioned. In particular, the stability problems of oxidation-sensitive substances such as  For example, dyes, optical brighteners, fragrances and enzymes overcome and the loss of activity of the bleaching agent is overcome even over long periods of time be without necessarily a division of the molding in several areas is required.

It has now been found that the hygroscopicity of the moldings, or to compressing premixes have a decisive influence on both the decomposition oxidation-sensitive substances than on the loss of activity of the bleaching agent.

The invention now detergent and detergent tablets are made compacted, particulate detergent and cleaner containing builders, Bleaching agents and other common ingredients in which the water absorption of the Shaped body during one week of open storage at 30 ° C and 80% relative Humidity is more than 2 g per 10 g.

In the context of the present invention, the term "washing and cleaning agent shaped article" is not to be understood as limiting - as already mentioned, the term "washing and cleaning agent shaped article" also means washing, rinsing, cleaning agent and washing aid molding. The water uptake of the moldings, which is also referred to as hygroscoping of the moldings in the context of the present invention and is abbreviated by the symbol H _F , can be determined experimentally by one week open storage of a molded body which is balanced after preparation at 30 ° C. and 80% relative humidity, then weighing and subtraction of the mass values are determined. Shaped body hygroscopy is reported in grams of weight gain (water uptake) per 10 g of body weight.

In preferred detergent tablets, the hygroscopic value H _{F is} higher than the lower limit mentioned above. In the context of the present invention, detergent tablets are preferred in which the water absorption of the tablet during a week of open storage at 30 ° C. and 80% relative atmospheric humidity is more than 2.25 g, preferably more than 2.5 g and in particular more than 2.75 g per 10 g.

The hygroscopic value H _F is - as described above - an experimentally determined value, which is determined by storage and weighing of the finished molded body. A disadvantage of this method is that an already prepared molding whose water absorption is less than 2 g per 10 g molding weight, although can be recognized as "stability problems", but the production of this molding is not omitted. It is therefore desirable to be able to make statements, even before the preparation of the premixes to be compressed, whether the shaped bodies will fulfill the hygroscopicity criterion and, if appropriate, make formulation changes in order to fulfill them. In this way, incorrect batches could be avoided even before pressing by the premixes are mixed with other ingredients.

It has been shown that in addition to the experimental hygroscopy value H _F , a calculated hygroscopic value H _ber can also be used. In this way, the hygroscopy H _{raw material} can be determined for each individual raw material contained in the premix by storage at 30 ° C. and 80% relative humidity for one week. The calculated hygroscopic value H _over the premix to be compressed is then obtained as the sum of the individual hygroscopies that has been evaluated by proportions:

H _ber = Σx _{raw material} . H _{raw material}

For the calculated hygroscopic value H _over the premix, a different limit applies than for the experimentally determined hygroscopic value of the already pressed molded body H _F. This results from the stronger compression of the individual hygroscopic substances in the molding.

Another object of the present invention are washing and Detergent moldings in which the sum of the water absorption values of the individual raw materials of the molded article during one week of open storage at 30 ° C and 80% relative humidity multiplied by more than its proportion in the molding 5 g per 10 g.

With the calculated hygroscopy H _ber, it is thus possible to produce premixes whose compression yields shaped bodies which satisfy the criteria for the experimentally determined hygroscopy H _F. Even in the calculated hygroscopy, the hygroscopic value H _ber in preferred detergent tablets is higher than the lower limit mentioned above. In the context of the present invention, detergent tablets are preferred in which the sum of the water absorption values of the individual raw materials of the shaped body during one week of open storage at 30 ° C. and 80% relative humidity multiplied by their proportion in the shaped body is more than 5.25 g, preferably more than 5.5 g and in particular more than 5.75 g per 10 g.

In addition to builders and optional other common ingredients of washing and Detergents contain the washing and Detergent tablets bleach, whose stability by adhering to the Hygroscopic value limits is improved.

Among the compounds serving as bleaches in water H ₂ O ₂ , 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. 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 bleaching agents are the diacyl peroxides, such as. B. 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, diperocysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diene diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

As bleaching agents in machine dishwashing moldings, chlorine or may also be used Bromine releasing substances are used. Among the suitable chlorine or bromine releasing materials include, for example, heterocyclic N-bromo- and N- Chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof with Cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro 5,5-dimethylhydantoin are also suitable.

In preferred detergent tablets, the bleaching agent is selected from the groups of oxygen bleaching agents, in particular sodium perborate monohydrate, Sodium perborate tetrahydrate and sodium percarbonate and / or the halogen bleach, in particular the chlorine bleach with particular preference of Trichlorocyanuric acids, dichloro- or monochlorocyanurates and hypochlorites.

The stabilization of bleaches was one aspect of the present invention. On Another aspect was the stabilization of other sensitive ingredients, in particular of enzymes. It has been shown that the enzyme stability in contrast to Bleach stability is better at low hygroscopic levels. Another  The present invention therefore washing and Detergent tablets of compacted, particulate washing and Detergents containing builders, enzymes and other common ingredients which characterized in that the water absorption of the shaped body during a Week of open storage at 30 ° C and 80% relative humidity less than 2 g per 10 g.

The hygroscopic value H _F is therefore an upper limit in the case of enzyme-containing detergent tablets, while in the case of the above-described bleach-containing detergent tablets, it represents a lower limit. In preferred enzyme-containing moldings, the hygroscopic value is below that mentioned above. In the context of the present invention, detergent tablets are preferred in which the water absorption of the tablet during a week of open storage at 30 ° C. and 80% relative atmospheric humidity is less than 1.75 g, preferably less than 1.5 g and in particular less than 1.25 g per 10 g.

Completely analogous to the above-described bleach-containing washing and Detergent tablets can also be in the case of enzyme-containing washing and Detergent tablets the experimentally determined hygroscopy by a replace calculated hygroscopy. Another object of the present invention are thus also detergent tablets, in which the sum of the Water absorption values of the individual raw materials of the molding during one week open storage at 30 ° C and 80% relative humidity multiplied by their Proportion in the molding is less than 5 g per 10 g.

Even in these cases, the upper limit is preferably lower, so that washing and Detergent tablets are preferred in which the sum of the Water absorption values of the individual raw materials of the molding during one week open storage at 30 ° C and 80% relative humidity multiplied by their  Content in the molding less than 4.75 g, preferably less than 4.5 g and in particular less than 4.25 g per 10 g.

In addition to builders and optional other common ingredients of washing and Detergents contain the washing and Detergent tablets enzymes, their stability by adherence to the Hygroscopic value limits is improved.

As enzymes are in particular those from the classes of hydrolases such as Proteases, esterases, lipases or lipolytic enzymes, amylases, Glykosylhydrolasen and mixtures of the enzymes mentioned in question. All these hydrolases contribute to the removal of stains such as protein, fat or starchy Stains in. 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 from their genetically modified variants obtained enzymatic Agents. Preferably, subtilisin-type proteases and in particular Proteases derived from Bacillus lentus. There 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 acting 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 known Cutinases. Peroxidases or oxidases have also proved suitable in some cases proved. Suitable amylases include, in particular, alpha-amylases, iso- Amylases, pullulanases and pectinases.

The enzymes may be adsorbed to carriers or embedded in encapsulating substances to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures  or enzyme granules may, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-% amount.

In preferred detergent tablets, the enzymes are selected from the groups of proteases, lipases, amylases, glycosyl hydrolases and their Mixtures.

Both the bleach and the enzyme-containing wash and Detergent tablets contain builder (s) as further ingredient (s). Next the washing-active substances, builders are the most important ingredients of laundry detergents. and detergents. In the washing and Detergent tablets can all usually in washing and Be used detergents used, in particular zeolites, Silicates, carbonates, organic cobuilders and phosphates.

Crystalline, layered sodium silicates suitable as builders 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 are 2, 3 or 4. Such crystalline sheet silicates are described, for example, in European Patent Application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-Natriundisilikate Na ₂ Si ₂ O ₅ . yH ₂ O, wherein β-sodium disilicate can be obtained, for example, by the method 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 with 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.

If desired, may be introduced via the usually introduced by the surfactant granules Amount of zeolite of the P and / or X type addition zeolite in the premix be incorporated by adding zeolite as a treatment component. The used fine crystalline, synthetic and bound water-containing zeolite is preferably a type A, P, X or Y zeolite. However, zeolite X is also suitable and mixtures of A, X and / or P. Suitable zeolites have a mean Particle size of less than 10 μm (volume distribution, measurement method: Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% on bound water.

Of course, a use of the well-known phosphates as Builders possible, provided such use is not for environmental reasons should be avoided. Particularly suitable are the sodium salts of Orthophosphates, the pyrophosphates and in particular the tripolyphosphates.  

As organic cobuilders in the washing and Detergent tablets, in particular polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These substance classes will be described below.

Useful organic builders are, for example, in the form of their Sodium salts usable polycarboxylic acids, among polycarboxylic acids such Carboxylic acids are understood to carry more than one acid function. For example these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, Maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such an operation is not objectionable for ecological reasons, as well as Mixtures of these. Preferred salts are the salts of polycarboxylic acids such as Citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and Mixtures of these.

The acids themselves can also be used. The acids are next to theirs Builder effect also typically the property of an acidifying component and thus also serve to set a lower and milder pH of laundry detergents. or detergents. In particular, here are citric acid, succinic acid, Glutaric acid, adipic acid, gluconic acid and any mixtures of these.

As a builder further polymeric polycarboxylates are suitable, these are for example the Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.

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

Suitable polymers are, in particular, polyacrylates which preferably have a molecular mass of 2000 to 20,000 g / mol. Because of their superior solubility can be this group in turn the short-chain polyacrylates, the molecular weights of 2000 to 10,000 g / mol, and more preferably from 3000 to 5000 g / mol, are preferred his.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. When Copolymers of acrylic acid with maleic acid which have proved particularly suitable Contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative Molecular weight, based on free acids, is generally 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

To improve the solubility in water, the polymers may also be allyl sulfonic acids, such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer contain.

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

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 as monomers Acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, as further preferred builder substances are polymeric aminodicarboxylic acids, to mention their salts or their precursors. Particularly preferred Polyaspartic acids or their salts and derivatives, of which in the German Patent Application DE-A-195 40 086 discloses that in addition to cobuilder properties also have a bleach-stabilizing effect.

Further suitable builder substances are polyacetals which are obtained by reaction of Dialdehydes with Polyolcarbonsäuren, which 5 to 7 C-atoms and at least 3 Hydroxyl groups can be obtained. Preferred polyacetals are made Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained 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 obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to customary, for example acid or enzymkata lysed procedures are carried out. Preferably, it is hydrolysis pro having average molecular weights in the range of 400 to 500,000 g / mol. There is one Polysaccharide with a dextrose equivalent (DE) in the range 0.5 to 40, especially preferred from 2 to 30, where DE is a common measure of the reducing effect of a polysaccharide compared to dextrose, which is a DE of Owns 100 is. Useful 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 of 2000 to 30,000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. 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.

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

Other useful organic cobuilders are, for example, acetylated Hydroxycarboxylic acids or their salts, which may also be in lactone form and which at least 4 carbon atoms and at least one Hydroxy group and a maximum of two acid groups. Such co-builders will be For example, described in international patent application WO 95/20029.

Another class of substances with co-builder properties are the phosphonates. These are in particular hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a co-builder. It is preferably used as the sodium salt, wherein the disodium salt neutral and the tetrasodium salt alkaline (pH 9). When Aminoalkane phosphonates are preferably ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Homologous in question. They are preferably in the form of neutral reacting Sodium salts, e.g. B. as hexasodium salt of EDTMP or as hepta- and octa Sodium salt of DTPMP. As a builder it is from the class of  Phosphonates preferably used HEDP. The aminoalkane phosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may, in particular if the agents also contain bleach, it is preferable to use aminoalkanephosphonates, in particular DTPMP, or mixtures of said phosphonates use.

In addition, all compounds that are able to complexes with Form alkaline earth ions, are used as co-builders.

In detergent tablets of the invention can - as described above - Water-soluble and water-insoluble builders especially for binding calcium and water Magnesium be used. In this case, water-soluble builders are preferred because of Dishes and hard surfaces tend to be less susceptible to insolation To form residues. Typical builders used in the invention between 10 and 90% by weight, based on the total preparation, may be present low molecular weight polycarboxylic acids and their salts, the homopolymers and copolymers Polycarboxylic acids and their salts, the carbonates, phosphates and silicates. To water-insoluble builders include the zeolites, which can also be used as well as mixtures of the aforementioned builders.

Trisodium citrate and / or pentasodium tripolyphosphate and / or are preferred Sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate Builder from the class of disilicates and / or metasilicates used.

As further constituents alkali carriers may be present. To be considered as alkali carriers Alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, Alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the abovementioned substances, preference being given in the context of this invention to the alkali metal carbonates, especially sodium carbonate, sodium bicarbonate or sodium sesquicarbonate be used.

Particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate.  

Also particularly preferred is a builder system comprising a mixture of Tripolyphosphate and sodium carbonate and sodium disilicate.

In summary, in the context of the present invention, washing and Detergent tablets which are characterized in that they have 20 to 95 wt .-%, preferably 30 to 90 wt .-% and in particular 40 to 85 wt .-% of one or several builders from the group of phosphates, in particular Pentasatrium tripolyphosphate, the silicates, especially the disilicates and / or Metasilicates, zeolites, carbonates and / or bicarbonates, the low molecular weight polycarboxylic acids and their salts, in particular citrates, the homo- and copolymeric polycarboxylic acids and their salts and the gluconates.

In addition to the bleaching agent and / or the enzymes and builders, the detergent tablets according to the invention further customary ingredients of detergents and cleaners. These substances include in particular Surfactants, bleach activators, corrosion inhibitors or silver protectants, pH adjusters, Perfumes, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, Anti redeposition agents, optical brighteners, grayness inhibitors and Dye transfer inhibitors.

The detergent tablets according to the invention can be used as surfactants For example, anionic and nonionic surfactants, the amount of which depending on desired use of the shaped body varies greatly. The mentioned Surfactant classes are described below.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. As surfactants of the sulfonate type are preferably C _9-13 - alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and Hydroxyalkansul fonates and disulfonates, such as those from C _12-18 monoolefins with terminal or internal double bond by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. 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), z. As the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids suitable.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Under Fatty acid glycerol esters are the mono-, di- and triesters and mixtures thereof as understood 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 to be obtained. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example the capron 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 a washing-technical point of view, the C ₁₂ -C ₁₆ -alkyl sulfates and C ₁₂ -C ₁₅ -alkyl sulfates and also C ₁₄ -C ₁₅ -alkyl sulfates are preferred. Also, 2,3-alkyl sulfates, which are prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and 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. Are suitable 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 from natural Fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants including 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. Preferably, the anionic surfactants are in the form of their Sodium or potassium salts, especially in the form of the sodium salts.

If laundry detergent tablets according to the invention are produced, then the content of the Shaped body of anionic surfactants preferably above 5 wt .-%, preferably above 7.5% by weight and in particular above 10% by weight, in each case based on the molding body weight.  

When selecting the anionic surfactants, the freedom from formulation is none to be observed in the way. Preferred detergent tablets have However, a content of soap, which is 0.2 wt .-%, based on the total weight of Detergent tablets, exceeds. Preferred anionic surfactants are included the alkylbenzenesulfonates and fatty alcohol sulfates, with preferred detergent tablets 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight Fatty alcohol sulfate (e), in each case based on the weight of the washing and Detergent tablets, included.

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

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

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

Preferably used are linear alkyl polyglucosides, ie alkyl polyglycosides, in where the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

In particular detergent tablets according to the invention may be preferred Containing alkylpolyglycosides, wherein levels of APG over 0.2 wt .-%, based on the entire shaped body, are preferred. Particularly preferred washing and Detergent tablets contain APG in amounts of from 0.2 to 10% by weight, preferably 0.2 to 5 wt .-% and in particular from 0.5 to 3 wt .-%.

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 be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of them.

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

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

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

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

[Z] is preferably 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 may then be used, for example the teaching of the international application WO-A-95/07331 by reaction with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxyfatty acid amides are transferred.

When detergent tablets according to the invention are prepared, it is preferred that the Content of the molded article of nonionic surfactants above 2 wt .-%, preferably above 5 wt .-% and in particular above 7.5 wt .-%, each based on the molded body weight lies.

To wash or clean at temperatures of 60 ° C and below To achieve improved bleaching effect, bleach activators may be the sole one Component or as an ingredient of component b) are incorporated. When Bleach activators may be compounds which are aliphatic under perhydrolysis conditions Peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms Atoms, and / or optionally substituted perbenzoic acid, are used. Suitable substances are the O- and / or N-acyl groups of said C atom number and / or optionally substituted benzoyl groups. Preference is given several times acylated alkylenediamines, especially 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, especially n- Nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5- dihydrofuran.

In addition to the conventional bleach activators or in their place may also so-called bleach catalysts are incorporated into the moldings. In these Substances are bleach-enhancing transition metal salts or Transition metal complexes such as Mn, Fe, Co, Ru or Mo  Salicene complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu Complexes containing N-containing tripod ligands and Co, Fe, Cu, and Ru ammine complexes are useful as bleach catalysts.

For the purposes of the present invention, preferred washing and Detergent tablets additionally contain a bleach activator, preferably from Group of polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonate, in particular n-nonanoyl or Isononanoyloxybenzolsulfonat (n- or iso-NOBS), MMA and / or the group of manganese and / or cobalt salts and / or complex, more preferably the cobalt (ammin) complexes, the cobalt (acetate) Complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, the Manganese sulfate, preferably in amounts of 1 wt .-% to 10 wt .-%, in particular 2 wt .-% to 8 wt .-%, based on the molding weight.

Inventive detergent tablets for automatic dishwashing can be used as an ingredient to protect the items to be washed or the machine Corrosion inhibitors, with particular silver protectants in the range of machine dishwashing have a special meaning. Generally, you can All silver protectants selected from the group of triazoles, the benzotriazoles, the Bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the Transition metal salts or complexes can be used. Particularly preferred too use are benzotriazole and / or alkylaminotriazole. It can according to the above Especially oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. Hydroquinone, pyrocatechol, Hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these Classes of compounds. Also salt and complex inorganic compounds, such as salts The metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred are here the transition metal salts, which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides  of cobalt or manganese and manganese sulfate. Likewise, zinc compounds be used to prevent corrosion of items to be washed.

For the purposes of the present invention, preferred washing and Detergent tablets are characterized in that additionally at least one Silver protectants selected from the group of triazoles, benzotriazoles, the Bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole.

In addition to the builders, the bleach and / or the enzymes as well as the optional surfactants and bleach activators to be used, the washing and Detergent tablets of the present invention contain further ingredients of laundry detergents. and detergents, for example, disintegration aids, dyes and detergents Fragrances, etc. These substances are described below.

In order to facilitate the disintegration of highly compressed moldings, it is possible Disintegration aids, so-called tablet disintegrants to incorporate into this to shorten the disintegration times. Among tablet disintegrants and decay accelerators are according to Römpp (9th edition, Bd. 6, p. 4440) and Voigt "textbook of Pharmaceutical Technology "(6th edition, 1987, pp. 182-184) understood excipients which for rapid disintegration of tablets in water or gastric juice and for release provide the pharmaceuticals in resorbable form.

These substances, which are also called "explosives" because of their effect, enlarge their volume when water enters, on the one hand increases the intrinsic volume (Swelling), on the other hand also on the release of gases pressure to be generated may cause the tablet to disintegrate into smaller particles. Well-known Disintegration aids are, for example, carbonate / citric acid systems, wherein also other organic acids can be used. overflowing 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 3 to 7 wt .-% and in particular 4 to 6 wt .-% of one or more Disintegration aids, in each case based on the molding body weight.

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 disintegration aid is preferably not in used finely divided form, but before admixing to be pressed Premixes converted into a coarser form, for example, granulated or compacted. Detergents and cleaning products, granular or explosive optionally contain cogranulated form are in the German Patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) as well as International Patent Application WO 98/40463 (Henkel). These writings are also details of the production of granulated, compacted or cogranulated Remove cellulose explosives. The particle sizes of such disintegrating agents are usually above 200 microns, preferably at least 90 wt .-% between 300 and 1600 microns and in particular at least 90 wt .-% between 400 and 1200 microns. The mentioned above and described in more detail in the cited documents coarser Cellulosic disintegration aids are within the scope of the present invention preferably used as a disintegration aid and in the trade, for example, under the name Arbocel® TF-30-HG of the company Rettenmaier available.

Another disintegrating agent based on cellulose or as part of this Component may be used microcrystalline cellulose. This microcrystalline Cellulose is produced by partial hydrolysis of celluloses under such conditions containing only the amorphous regions (about 30% of the total cellulose mass) of the Celluloses attack and completely dissolve, but the crystalline areas (about 70%) leave undamaged. Subsequent deaggregation by hydrolysis resulting micro-fine celluloses provides the microcrystalline celluloses, the Primary particle sizes of about 5 microns and, for example, to granules with a average particle size of 200 microns are compacted.

In addition, laundry detergent tablets according to the invention may also contain components which positively influence the oil and grease washability of textiles (so-called soil repellents). This effect is particularly evident when a textile is soiled already before several times with a detergent according to the invention, this oil and fat dissolving component, was washed. Among 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 from 15 to 30% by weight and of hydroxypropoxyl groups of from 1 to 15% by weight, in each case based on the nonionic cellulose ether, as well as those of the prior Technically known polymers of phthalic acid and / or terephthalic acid or of their Derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionic and / or nonionic modified Derivatives of these. Particularly preferred of these are the sulfonated derivatives of Phthalic and terephthalic acid polymers.

Detergent tablets according to the invention can be used as optical brightener derivatives of Diaminostilbendisulfonsäure or their alkali metal salts. Suitable z. B. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfo nsäure or similar compounds, which instead of the morpholino group a Diethanolamino group, a methylamino group, an anilino group or a 2- Wear methoxyethylamino group. In addition, brighteners of the substituted type can be used Diphenylstyryl be present, for. 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) - biphenyl. Mixtures of the aforementioned brightener can be used.

Dyes and fragrances are the washing and Detergent tablets added to the aesthetic impression of the products improve and the consumer in addition to product performance visually and sensory to provide a "typical and unmistakable" product. As perfume oils or Fragrances can be individual fragrance compounds, eg. B. the synthetic products of Type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons used become. Fragrance compounds of the ester type are e.g. B. benzyl acetate, Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl carbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. To the Ethern For example, include benzyl ethyl ether to the aldehydes z. B. with the linear alkanals  8-18 C-atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, α- Isomethylionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons mainly include the terpenes such as limes and pinene. However, preference is given Used mixtures of different fragrances, which together create an appealing Create a fragrance. Such perfume oils can also be natural fragrance mixtures contained in plant sources, e.g. Pine, citrus, jasmine, Patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, Juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroliol, orange peel oil and sandalwood oil.

Usually, the content of the washing and Detergent tablets on dyes below 0.01 wt .-%, while perfumes up to 2 wt .-% of the total formulation can make.

The fragrances can be incorporated directly into the compositions according to the invention But it may also be advantageous to apply the fragrances on carriers, which the adhesion of the Intensify perfumes on the lingerie and through a slower release of fragrance for long-lasting fragrance of the textiles. As such carrier materials have become For example, cyclodextrins have proven useful, with the cyclodextrin-perfume complexes additionally can be coated with other excipients.

In order to improve the aesthetic impression of the agents according to the invention, they can dyed with suitable dyes. Preferred dyes, the selection of which Professional no difficulty, have a high storage stability and Insensitivity to the other ingredients of the agent and against light as well no pronounced substantivity to textile fibers or harness to the treated Do not stain substrates.  

Before the compression of the particulate premix to wash and Detergent tablets, the premix with finely divided Surface treatment agents are "powdered". This may be for the condition and physical properties of both the premix (storage, compression) as Also the finished detergent tablets are advantageous. finely divided Abwuderungsmittel are well-known in the art, with mostly zeolites, silicates or other inorganic salts. However, the premix is preferred "powdered" with finely divided zeolite, wherein faujasite-type zeolites are preferred. In the context of the present invention, the term "zeolite from faujasite Type "all three zeolites forming the faujasite subgroup of zeolite structure group 4 (Compare Donald W. Breck: "Zeolite Molecular Sieves," John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92). In addition to the zeolite X are also Zeolite Y and faujasite and mixtures of these compounds can be used, wherein the pure Zeolite X is preferred.

In the context of the present invention are methods for the preparation of washing and Preferred detergent tablets in which the or one of the later admixed finely divided treatment components with a faujasite-type zeolite with Particle sizes below 100 microns, preferably below 1 micron and in particular is below 5 microns and at least 0.2 wt .-%, preferably at least 0.5 wt .-% and in particular more than 1 wt .-% of the premix to be compressed.

The present invention provides on the one hand bleach-containing wash and Detergent tablets ready for excellent bleach stability Hygroscopicity values above 2 g per 10 g of molding have, on the other hand, the The present invention provides enzyme-containing detergent tablets according to the invention excellent enzyme stability through hygroscopicity values below 2 g per 10 g Shaped body, said experimentally determined Hygroscopicity values can also be replaced by calculated ones, as above was explained in detail.  

It is now possible to apply the above principles in a molding realize by dividing the molding into at least two areas whose one containing the bleaching agent and having a water absorption capacity of more than 2 g per 10 g, while another area contains the enzymes and a Water absorption capacity of less than 2 g per 10 g.

Another object of the present invention is therefore a multiphase washing and detergent tablets of compacted, particulate wash and Detergents containing builders, bleaches, enzymes and other common Ingredients characterized in that the bleaching agent (s) and the enzymes are present in separate phases and the water absorption of the bleach-containing Phase (s) during one week of open storage at 30 ° C and 80% relative Humidity is more than 2 g per 10 g, while the water absorption of the enzyme-containing phase (s) during one week of open storage at 30 ° C and 80% relative humidity is less than 2 g per 10 g.

Hygroscopicity values refer to the invention Mehrphasenformkörpern always on a phase or on the premix, whose Compression provides this phase. For the premixes, the calculation of the Hygroscopic values the above; for the individual phases applies that experimental hygroscopic values for each phase individually, d. H. after separation of the Shaped body in its phases, to be determined.

Of course, according to the invention, any of those described above may also be used "Single principles", d. H. excellent bleach stability through Hygroscopicity values above 2 g per 10 g of molding, on the other hand an excellent Enzyme stability by hygroscopicity values below 2 g per 10 g of molded body, in multiphase moldings are realized, either bleach only or only Contain enzymes. In multi-phase moldings in which, for example, only one phase Contains bleach, then only this phase must hygroscopicity criteria  suffice. The term "shaped body" is then mutatis mutandis by "phase" to replace, so that Another object of the present invention are also multiphase moldings, where only one phase contains bleach and this phase contains hygroscopicity values above 2 g per 10 g of the phase weight, resulting in an excellent Bleach stability results. Analogous are also multiphase moldings in which only contains a phase of enzymes and this phase hygroscopicity values below 2 g per 10 g the phase weight, subject of the present invention. This will be a achieved excellent enzyme stability.

The individual phases of the shaped body can be used in the context of the present invention have different spatial forms. The easiest way to realize it lies thereby in two- or multi-layered tablets, each layer of the molding a Phase represents. But it is also possible according to the invention, multiphase moldings in which individual phases take the form of incorporation into (another) one Phase (s). In addition to so-called "ring-core tablets" are, for example Sheath tablets or combinations of the aforementioned embodiments possible. Examples of multiphase moldings can be found in the drawings of EP-A-0 055 100 (Jeyes) describing toilet cleaning blocks. The technically most widespread Raumform multiphase molding is the two- or multi-layer tablet. As part of Therefore, in the present invention, it is preferable that the phases of the molded article have the Have the form of layers.

The abovementioned total contents of the molding of bleaching agents and enzymes are related in multi-phase moldings on the weight of each phase. Here, multi-phase detergent tablets are preferred in which the content of the bleach-containing phase of bleach, based on the phase 5 bis 50 wt .-%, preferably 7.5 to 40 wt .-% and in particular 10 to 30 wt .-% and the Content of the enzyme-containing phase of enzymes, based on the phase 1 to 20 wt .-%, preferably 1.5 to 15 wt .-% and in particular 2 to 10 wt .-%, is.  

For the preparation of the single-phase moldings of the invention, the premix is in a so-called matrix between two stamps compacted into a solid compressed. This process, which is referred to below as tabletting, is divided into four sections: metering, compaction (elastic deformation), plastic deformation and Ejecting.

First, the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting molded body by the position of the lower Stamp and the shape of the press tool can be determined. The consistent one Dosage even at high molding throughputs is preferably via a achieved volumetric dosing of the premix. In the further course of tableting the upper punch touches the premix and descends further in the direction of the Lower stamp. In this compression, the particles of the premix become closer pressed together, wherein the void volume within the filling between the Stamping decreases continuously. From a certain position of the upper punch (and thus starting from a certain pressure on the premix) the plastic begins Deformation, in which the particles flow together and it to form the shaped body comes. Depending on the physical properties of the premix is also a part the Vorgemischpartikel crushed and it comes at even higher pressures to a 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 farm body can have more or less large cavities. In the last step of the tableting, the finished shaped body is replaced by the lower punch pushed out of the die and by subsequent transport facilities carried away. At this time, only the weight of the molded article is final determined because the compacts due to physical processes (rear expansion, crystallographic effects, cooling etc.) can change their shape and size. The tabletting is carried out in commercially available tablet presses, which are in principle or double stamping. In the latter case, not only the Upper punch used to build pressure, also the lower punch moves while Pressing on the upper punch, while the upper punch presses down. For small production quantities, eccentric tablet presses are preferably used,  in which the one or more stamps are attached to an eccentric disc, in turn to an axle with a certain rotational speed is mounted. The movement This ram is comparable to the operation of a conventional four-stroke engine. The compression can be done with a top and bottom stamp, but it can also a plurality of punches attached to an eccentric disc, the number of Matrizenbohrungen is extended accordingly. The throughputs of eccentric presses vary according to type from a few hundred to a maximum of 3000 tablets per hour. For larger throughputs you can choose rotary tablet presses, where on one so-called die table a larger number of matrices is arranged in a circle. The number of matrices varies depending on the model between 6 and 55, and larger Matrices are commercially available. Each die on the die table is a top and bottom Assigned lower punch, in turn, the pressing pressure active only by the upper or Lower stamp, but can also be built by both stamps. The die table and the punches move about a common vertical axis, the Stamp with the aid of rail-like cam tracks during the circulation in the positions for filling, compaction, plastic deformation and ejection. To the Areas where a particularly serious increase or decrease of the stamp is required (filling, compaction, ejection), these curved paths are through additional low pressure pieces, Nierderzugschienen and Aushebebahnen supported. The Filling of the die takes place via a rigidly arranged feed device, the so-called filling shoe, which is connected to a reservoir for the premix. The pressing pressure on the premix is on the pressing paths for upper and lower punch individually adjustable, wherein the pressure build-up by the Vorbeirollen the Stamping heads on adjustable pressure rollers happens.

Concentric presses can be used to increase throughput even with two filling shoes be provided, wherein for the preparation of a tablet to go through only a semicircle must become. For the production of two- and multi-layered moldings are several Füllschuhe arranged one behind the other, without the slightly pressed first layer before the further filling is ejected. By suitable process control are in this way coat and point tablets produced, the onion-like structure have, in the case of the point tablets, the top of the core or the core layers  is not covered and thus remains visible. Rotary tablet presses are also available 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.

Tableting machines suitable for the purposes of the present invention are, for example available from Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy N.V., Halle (BE / LU). For example, the hydraulic double pressure press HPF is particularly suitable 630 of the company LAEIS, D.

The moldings can be in a predetermined spatial form and predetermined size be made. As a form of space virtually all useful manageable Embodiments into consideration, for example, the training as a blackboard, the rod or Barrel shape, cubes, cuboids and corresponding room 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 up to compact cylinder pieces with a ratio of height to diameter above 1.

The portioned compacts can each as separate individual elements be formed, the predetermined dosage of the washing and / or Cleaning agent corresponds. Likewise, it is possible to form briquettes, the one Join plurality of such mass units in a compact, in particular by predetermined breaking points the easy separability of portioned smaller units is provided. For the use of laundry detergents in machines in Europe usual type with horizontally arranged mechanics can the training of the portioned compacts in the form of tablets, in cylindrical or cuboidal form, a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred  is. Commercially available hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for producing such compacts.

Another preferred molded article which can be produced has a plate or panel-like 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 ones Segments, aborted and entered into the machine. This Principle of the "bar-shaped" molding detergent can also be used in other geometric Shapes, such as vertical triangles, only on one side alongside each other, be realized.

But it is possible - as described above - also that the various Components are not compressed into a single tablet, but that Shaped bodies are obtained, the several layers, so at least two layers, respectively. It is also possible that these different layers different Have dissolution rates. This can be advantageous application technology Properties of the moldings result. For example, if components in the Formed bodies are included, which influence each other negatively, so it is possible to integrate one component in the faster soluble layer and 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 Shaped body can be done both stack-like, with a solution process of the inner Layer (s) already takes place at the edges of the shaped body when the outer Layers are not yet completely dissolved, but it can also be a complete Envelopment of the inner layer (s) by the respective outer layer (s) be achieved, resulting in a prevention of the early release of components of the inner layer (s) leads.

Similar effects can also be achieved by coating individual constituents the laundry and cleaning composition to be compressed or the entire Reach shaped body. For this purpose, the body to be coated, for example, with  aqueous solutions or emulsions, or via the process of Melt coating received 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

Here, σ stands for the diametrical fracture stress (DFS) in Pa, P is the force in N which leads to the pressure exerted on the molding, which is the pressure Rupture of the molding caused, D is the molding diameter in meters and t is the Height of the moldings.  

Examples

By compression of differently composed premixes were Detergent tablets prepared for automatic dishwashing. The purpose raw materials used and the experimentally determined hygroscopic values of the raw materials are summarized in Table 1. Table 2 presents calculated hygroscopies, experimental determined Formkörperhygroskopien and the active oxygen preservation degree of Bleaching agent-containing moldings. Table 3 presents calculated hygroscopies, experimentally determined form body hygroscopies and the degree of enzyme conservation of Enzyme-containing moldings.

Table 1 Hygroscopicity values of the raw materials used [g per 10 g at 1 week, 30 ° C, 80% r. F.]

ingredient hygroscopicity trisodium 1.97 Trisodium polyphosphate, fine 2.24 sodium 3.90 sodium 0.00 sodium silicate 5.80 Trisodium citrate dihydrate 0.01 Enzyme Granules I 0.56 Enzyme granules II 0.25 TAED granules 0.40 Sodium perborate monohydrate 3.33

Table 2: Hygroscopicity values of bleach-containing detergent tablets

Table 3: Hygroscopicity values of enzyme-containing detergent tablets

Claims (16)

1. detergent tablets of compacted, particulate detergent and cleaner, containing builders, bleach and other conventional ingredients, characterized in that the water absorption of the molding during one week of open storage at 30 ° C and 80% relative humidity more than 2 g per 10 g. 2. detergent tablets according to claim 1, characterized in that that the water absorption of the molding during a week of open storage at 30 ° C and 80% relative humidity more than 2.25 g, preferably more than 2.5 g and in particular more than 2.75 g per 10 g. 3. detergent tablets according to claim 1 or 2, characterized characterized in that the sum of the water absorption values of the individual raw materials of the molded article during a week of open storage at 30 ° C and 80% relative Humidity multiplied by its content in the molding more than 5 g per 10 g is. 4. detergent tablets according to claim 3, characterized that the sum of the water absorption values of the individual raw materials of the molding during one week of open storage at 30 ° C and 80% relative humidity multiplied by its content in the molding more than 5.25 g, preferably more than 5.5 g and in particular more than 5.75 g per 10 g. 5. detergent tablets according to one of claims 1 to 4, characterized in that the bleaching agent is selected from the groups of Oxygen bleaching agents, in particular sodium perborate monohydrate, sodium perborate Tetrahydrate and sodium percarbonate and / or the halogen bleach, in particular chlorine bleach, with particular preference to trichlorocyanuric acids, Dichloro- or monochlorocyanurates and hypochlorites.   6. Detergent tablets made of compacted, particulate washing and detergents containing builders, enzymes and other common ones Ingredients, characterized in that the water absorption of the shaped body during one week of open storage at 30 ° C and 80% relative humidity less than 2 g per 10 g. 7. detergent tablets according to claim 6, characterized that the water absorption of the molding during a week of open storage at 30 ° C and 80% relative humidity less than 1.75 g, preferably less than 1.5 g and in particular less than 1.25 g per 10 g. 8. detergent tablets according to claim 6 or 7, characterized characterized in that the sum of the water absorption values of the individual raw materials of the molded article during a week of open storage at 30 ° C and 80% relative Humidity multiplied by their proportion in the molding less than 5 g per 10 g is. 9. detergent tablets according to claim 8, characterized in that that the sum of the water absorption values of the individual raw materials of the molding during one week of open storage at 30 ° C and 80% relative humidity multiplied by its content in the molding less than 4.75 g, preferably less than 4.5 g and in particular less than 4.25 g per 10 g. 10. Washing and cleaning product molding according to one of claims 6 to 9, characterized characterized in that the enzymes are selected from the groups of proteases, Lipases, amylases, glycosyl hydrolases and mixtures thereof. 11. Washing and cleaning product molding according to one of claims 1 to 10, characterized characterized in that it is 20 to 95 wt .-%, preferably 30 to 90 wt .-% and in particular from 40 to 85% by weight of one or more builders from the group of  Phosphates, in particular pentasodium tripolyphosphate, silicates, in particular the Disilicates and / or metasilicates, zeolites, carbonates and / or Bicarbonates, the low molecular weight polycarboxylic acids and their salts, in particular the citrates, homo- and co-polymeric polycarboxylic acids and their Salts and the gluconates contains. 12. Washing and cleaning product molding according to one of claims 1 to 11, characterized in that it additionally contains a bleach activator, preferably from the group of multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), MMA and / or the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammin) complexes, the Cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of the manganese sulfate, preferably in amounts of 1% by weight to 10 wt .-%, in particular 2 wt .-% to 8 wt .-%, based on the Molded body weight, contains. 13. detergent tablets according to one of claims 1 to 12, characterized characterized in that additionally at least one silver protective agent selected from the Group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, Alkylaminotriazole, preferably benzotriazole and / or alkylaminotriazole is. 14. Multiphase detergent tablets of compacted, particulate detergents and cleaners containing builders, bleaches, Enzymes and other conventional ingredients, characterized in that the / Bleach and the enzymes are present in separate phases and the Water absorption of the bleach-containing phase (s) during a week open Storage at 30 ° C and 80% relative humidity is more than 2 g per 10 g, while the water uptake of the enzyme-containing phase (s) during a week  open storage at 30 ° C and 80% relative humidity less than 2 g per 10 g is. 15. Multiphase detergent tablets according to claim 14, characterized characterized in that the phases of the shaped body have the form of layers. 16. Multiphase detergent tablets according to one of claims 14 or 15, characterized in that the content of the bleach-containing phase Bleaching agent, based on the phase 5 to 50 wt .-%, preferably 7.5 to 40 wt .-% and in particular 10 to 30 wt .-% and the content of the enzyme-containing phase Enzymes, based on the phase 1 to 20 wt .-%, preferably 1.5 to 15 wt .-% and in particular 2 to 10 wt .-%, is.