WO2000049128A1 - Colourfast detergent and cleanser shaped bodies - Google Patents

Abstract

The colourfastness of wholly or partially dyed detergent and cleanser shaped bodies which contain builders, bleaching agents and other conventional ingredients of detergents and cleansers, as well as at least one dye that is not resistant to bleaching can be significantly improved, if the areas of the shaped body, in which the dye that is not resistant to bleaching also contain paraffin. This effect of colour stabilisation is especially pronounced in shaped bodies which are free of phosphates and which contain citrates.

Description

 "Color-stable detergent tablets"

The present invention relates to colored detergent tablets. In particular, the present invention relates to detergent tablets which are used for cleaning dishes in dishwashers.

Mechanical cleaning agents are widely described in the prior art. These agents usually contain one or more builders, bleaches, bleach activators, corrosion inhibitors and surfactants. In order to provide the consumer with a typical and distinctive product, these agents are usually both perfumed and colored. A whole series of requirements are placed on the dyes: they have to dye the detergent to be dyed permanently and visually, even at low concentrations, and must not discolor or discolor even after prolonged storage or at elevated temperatures. For this it is necessary that the dyes used are chemically inert to the sometimes aggressive ingredients (e.g. bleach, alkali carriers) and do not decompose themselves or other ingredients. Since the detergent tablets on the market are often designed in two colors for aesthetic reasons, no fading of the colored phase or a transition of color into lighter or uncolored areas may occur at the phase boundary of differently colored areas.

A high profile of requirements is placed on the dyes: Although the agents have to be colored in a contrasting manner, the dye must not stain the dishwasher or the dishes to be cleaned, even if the same agent is used for a long time. The dyes must therefore not have a pronounced substantivity towards metal or plastic surfaces. It is also necessary that the dyes are completely removed from the dishwasher in the rinse cycle and do not leave a film or colored lime stains on the dishes or in the machine when the water runs off. Since the wash ware will later be used for the preparation and storage of food, the dyes must continue to be completely toxicologically safe.

The older German patent application DE 198 21 695.5 (Henkel KGaA) describes the use of special dyes in detergents and cleaning agents in order to overcome the problems mentioned above. The dyes mentioned in this document are also suitable for coloring detergent tablets or individual areas in detergent tablets.

In the compact "tablet" form, however, the contact between the dye and other dye-destabilizing ingredients (in particular bleach) is so intimate that changes in color can occur with prolonged storage, which impair the appearance of the molded articles. Especially when using dyes in phosphate-free formulations, in which citrates are used as builders, the partially insufficient bleaching stability of the dyes was found to be serious. It has also been shown here that the obvious separation of bleach and dye into different areas of the tablet is not a solution in itself: at the phase boundary, the problems of bleaching and color transition also occur with this technical measure and lead to optically unacceptable tablets .

It was now the task of finding recipe adjustments which would make it possible to use non-bleach-stable dyes even in compact detergent tablets without having to accept the disadvantages mentioned above. In particular, also in phosphate-free and / or citrate-containing formulations, the requirement profile mentioned above should be fully met It has now been found that the addition of paraffin to the shaped body or to the region of the shaped body which contains the non-bleach-stable dye solves the problems mentioned above.

The present invention relates to detergent tablets made of compressed, particulate detergent and detergent, containing builders, bleaches and other conventional detergent ingredients which contain at least one non-bleach-stable dye and in which the areas of the tablet in which the dye not stable to bleaching, additionally contain paraffin.

Detergent tablets according to the invention contain, in addition to the constituents, builders and bleaches and the non-bleach-stable dye paraffin. In the context of the present invention, paraffin is the name for a mixture of purified, saturated aliphatic hydrocarbons (paraffins) which is colorless, odorless and tasteless. These alkane mixtures can be obtained commercially in various forms and can be used in the context of the present invention - from the low viscosity to the more viscous to the pasty or solid paraffin. Low-viscosity paraffins usually have densities between 0.81 and 0.875 ^"3 and viscosities between 25 and 80 mPas, while viscous paraffins can have densities from 0.827 to 0.89 ^{" 3} and viscosities from 110 to 230 mPas. In the technical field, the liquid paraffin forms are often added to the mineral oils and are referred to collectively as paraffm oil or as white oil, the density of such technical products usually being at least 0.88 ^"3 and the boiling point> 360 ° C.

For semi-solid paraffin qualities with melting points of 45-65 ° names like soft paraffin, for those with densities from 0.82 to 0.88 like ^"3 and melting points from 38 to 60 ° C and boiling points> 300 ° C names like petrolatum in Use, a well-known trademark for the latter is petroleum jelly and hard paraffm (Paraffinum solidum), a solid crystalline mass with a solidification temperature of 50 to 62 ° C. Paraffin oils are used with particular preference in the context of the present invention. Detergent tablets preferred in the context of the present invention contain 0.1 to 5% by weight, preferably 0.25 to 4% by weight and in particular 0.5 to 3% by weight of paraffin oil and / or paraffin wax, preferably low viscosity Paraffin oil.

The other ingredients that are mandatory in the moldings according to the invention are described below:

In the detergent tablets according to the invention, all builders customarily used in detergents, in particular thus zeolites, silicates, carbonates, organic cobuilders and also the phosphates, can be present as builders.

' yH₂O bevorzugt, wobei ß-Natrium- disilikat beispielsweise nach dem Verfahren erhalten werden kann, das in der internationalen Patentanmeldung WO-A-91/08171 beschrieben ist.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. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ß- and δ-sodium disilicate

'yH ₂ O is preferred, it being possible for β-sodium disilicate to be obtained, for example, by the process described in international patent application WO-A-91/08171.

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

The finely crystalline, synthetic and bound water-containing zeolite that can be used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X) , which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa.0 ^• (ln) K ₂ O ^• Al ₂ O ₃ ^• (2 - 2.5) SiO ₂ ^• (3.5 - 5.5) H ₂ O can be described. The zeolite can be used both as a builder in a granular compound and can also be used for a type of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water. Of course, it is also possible to use the generally known phosphates as builders, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

Alkali carriers can be present as further constituents. Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates,

Alkali metal sesquicarbonates, alkali silicates, alkali metasilicates, and mixtures of the abovementioned substances, the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, preferably being used for the purposes of this invention.

Water-soluble builders are preferred in moldings according to the invention for machine dishwashing, since they generally have less tendency to form insoluble residues on dishes and hard surfaces. Customary builders, which may be present in the dishwasher tablets according to the invention of between 10 and 90% by weight, based on the premix to be compressed, are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and silicates. For the production of moldings for automatic dishwashing, preference is given to trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of Disilicates and / or Metasihkate used. A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred. A builder system which contains a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.

Preferred detergent tablets are characterized in the context of the present invention in that they contain 20 to 95% by weight, preferably 30 to 90% by weight and in particular 40 to 85% by weight of one or more builders from the group of the phosphates , in particular pentasodium tripolyphosphate, the silicates, in particular the disilicates and / or metasihkates, the zeolites, the carbonates and / or hydrogen carbonates, the low molecular weight polycarboxylic acids and their salts, in particular the citrates, the homo- and copolymeric polycarboxylic acids and their salts and the gluconates .

The incorporation of paraffin according to the invention into the shaped body or to the region of the shaped body in which the dye which is not bleachable is present is particularly advantageous if the builder system contains citrate and is free of phosphates. The problems which the present invention solves are otherwise very clearly apparent in these moldings. Detergent tablets preferred in the context of the present invention contain no phosphates.

As mentioned above, the use of citrate-carbonate builder systems in automatic dishwashing detergents is advantageous. Preferred detergent tablets are therefore characterized in that they contain 5 to 40% by weight, preferably 10 to 35% by weight and in particular 15 to 30% by weight, of one or more alkali metal citrates, preferably trisodium citrate dihydrate, as the builder 5 to 50 wt .-%, preferably 10 to 45 wt .-% and in particular 15 to 40 wt .-% of one or more alkali metal carbonates and / or hydrogen carbonates, preferably sodium hydrogen carbonate, contain. Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid 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, the use of sodium percarbonate is preferred, irrespective of which other ingredients are contained in the moldings. If cleaning tablets or bleach tablets for machine dishwashing are manufactured, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) 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, peroxy stearic acid, ε-phthalimido peroxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamidoperadipinic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxy acid, 1, 9-diperoxyacid acid, 1, 9-diperoxyacid, diperoxyacid acid, 1, 9-diperoxyacid acid, 1, 9-diperoxyacid acid, 1, 9-diperoxyacid acid, 1, 9-diperoxyacid acid, 1, 9-diperoxyacid diacid acid, 1, 9-diperoxyacid acid, 1, 9-diperoxyacid diacid acid, 1, 9-diperoxyacid acid, 1, 9-diperoxyacid acid, 1, 9-diperoxyacid diacid acid, 1, 9-diperoxyacid acid, 1, 9-diperoxyacid acid, 1, 9-diperacid acid, diperoxyacid, phthalic acids, 2-decyldiperoxybutane-l, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents in moldings for automatic dishwashing. Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid,

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

Preferred detergent tablets in the context of the present invention are 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 halogen bleaching agents, in particular chlorine bleaching agents, with particular preference for trichlocyanuric acids, Dichloro- or monochlorocyanurates and hypochlorites.

As a fourth essential constituent, the detergent tablets (or areas thereof) according to the invention contain one or more non-bleach-stable dye (s) in addition to builders, bleaching agents and paraffin.

Such dyes which can be used for coloring washing and cleaning agents are colorants which are soluble in solvents and / or binders. Due to the structural diversity of these dyes (e.g. azo, azine, anthraquinone, acridine, cyanine, oxazine, polymethine, thiazine, triarylmethane dyes, etc.) several tens of thousands of different dyes are known, of which about 5000 are commercially available and only around 500 are produced in technical quantities. In addition to the structural systematization, the dyes are systematically classified according to the so-called Color Index with its number system (C.I. xxxxx) or the word / number system (Acid Red xxx). In the case of dyes that have become widely accepted, the fantasy names and trade names protected as trademarks can also be used for characterization.

Dyes used in laundry detergent and cleaning product tablets should have a long shelf life and are not sensitive to the other ingredients of the products and to light, and should not have a pronounced substantivity towards textile fibers or dishes, so as not to stain them. In detergent tablets for automatic dishwashing, the colorants used in the initially cited state of the art Dyes proven technology, whose bleach stability was improved in the context of the present invention. The dyes Ponceau 4R (CAS No. 2611-82-7, CI 16255), Allura Red 40 (CAS No. 25956-17-6, CI 16035), aluminum red RLW (CI Mordant Red 83), Supranol ^® Red GW (CAS No. 61901-44-8), Basantol ^® Red 310 (CAS No. 61951-36-8), Basacid ^® Green 970 (CAS No. 19381-50-1) , Supranol ^® Green 6 GW (anthraquinone dye preparation with Acid Green 81), Supranol ^® Green BW (anthraquinone dye preparation with Acid Green 84), Ultramarine Blue-6394 (CAS No. 57455-37-5, CI 77007 ), Acid Yellow 17 (CAS No. 6359-98-4, CI 18965) and Acid Yellow 23 (CAS No. 1934-21-0, CI 19140).

The amounts of the dyes used in the detergent tablets according to the invention can vary depending on the desired color impression and intended use. Preferred detergent tablets in the context of the present invention contain the non-bleach-stable dye (s) in amounts of 0.01 to 1% by weight, preferably 0.02 to 0.5% by weight and in particular 0.05 up to 0.25% by weight, based in each case on the shaped body.

In addition to the ingredients mentioned, the detergent tablets according to the invention can contain, depending on their intended use, further ingredients, in particular from the groups of bleach activators, disintegration aids, surfactants, enzymes, silver protection agents, fragrances, polymers, pH regulators, fluorescent agents, foam inhibitors, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors and mixtures thereof.

In order to achieve an improved bleaching effect when washing or cleaning at temperatures of 60 ° C. and below, bleach activators can be incorporated into the premix to be pressed. Bleach activators which can be used are compounds which, under perhydrolysis conditions, aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted Perbenzoic acid result, are used. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetoxy and 2,5-diacetyloxy and 2,5-glycethylacetyl, ethylene glycol 2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the moldings. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

Preferred detergent tablets in the context of the present invention additionally contain a bleach activator, preferably from the group of polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), MMA and / or the group of manganese and / or cobalt salts and / or - complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (Carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the weight of the shaped body. In order to facilitate the disintegration of highly compressed moldings, disintegration aids, so-called tablet disintegrants, can be incorporated into them in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182-184), tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.

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

Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the weight of the tablet.

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

The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be pressed. Detergent tablets which contain disintegrants in granular or, if appropriate, 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 WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier available in the present invention. Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, into granules with an average particle size of 200 μm.

In addition to the builders described above, the premix can also contain the above-mentioned detergent substances, which are particularly important ingredients for detergent tablets. Depending on the molded article to be produced, different answers are possible when answering the questions as to whether and if so which surfactants are used. Moldings for washing textiles can usually contain a wide variety of surfactants from the groups of anionic, nonionic, cationic and amphoteric surfactants, while moldings for machine dishwashing preferably contain only low-foaming nonionic surfactants and water softening tablets or bleach tablets are free of surfactants. When incorporating the surfactants into the premix to be pressed, the person skilled in the art has no limits with regard to the freedom of formulation.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C ₉ . ₁₃ - Alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C ₁₂ . _{] 8-} Monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Alkanesulfonates which are derived from C ₁₂ are also suitable. ₁₈ -alkanes can be obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), for example 15

the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures, as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfonated 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) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₀ -C ₂₀ - Oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. From the washing, the C ₁₂ are - C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates of preferably. 2,3-Alkyl sulfates, which are manufactured according to the US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

Also, the Schwefelsäuremonoester the ethoxylated with 1 to 6 moles of ethylene oxide, linear or branched C ₇ _ ₂₁ alcohols such as 2-methyl-branched C. _{9 n} -Alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ₁₂ . ₁₈ fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight. Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8.18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

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

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

If detergent tablets are produced in the context of the present invention, it is preferred that they each contain 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 10 to 20% by weight of anionic surfactant (s) based on the weight of the molded body.

When selecting the anionic surfactants that are used in the detergent tablets according to the invention, there are no general conditions to be observed that prevent freedom of formulation. Preferred detergent tablets, however, have a soap content of 0.2% by weight, based on the total weight of the molded body. The preferred anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, preferred detergent tablets 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight of fatty alcohol sulfate (s), based in each case on the Molded body weight included

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12.14 alcohols with 3 EO or 4 EO, C ₉ "alcohol 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 averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as them are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533. Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkypolyglycosides which can be used satisfy the general formula RO (G) _z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for 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.

Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.

The detergent tablets according to the invention can preferably contain alkyl polyglycosides, APG contents of the tablets more than 0.2% by weight, based on the entire tablet, being preferred. Particularly preferred detergent tablets contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

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

R ¹

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

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

R ^! -OR ^2nd

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

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, with C _M alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives thereof Rest.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. In principle, all surfactants can also be used as surfactants in the production of moldings for automatic dishwashing. However, the nonionic surfactants described above, and above all the low-foaming nonionic surfactants, are preferred for this purpose. The alkoxylated alcohols are particularly preferred, especially the ethoxylated and / or propoxylated alcohols. The person skilled in the art generally understands alkoxylated alcohols to mean the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the sense of the present invention the longer-chain alcohols (C ₁₀ to C ₁₈ , preferably between C ₁₂ and C ₁₆ , such as C _u -, C ₁₂ -, C ₁₃ -, C ₁₄ -, C ₁₅ -, C ₁₆ -, C ₁₇ - and C ₁₈ -alcohols). As a rule, a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. A further embodiment consists in using mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. If desired, final etherification with short-chain alkyl groups, such as preferably the butyl group, can also give the class of "closed" alcohol ethoxylates, which can also be used in the context of the invention. Highly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.

Suitable enzymes in detergent tablets are, in particular, those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases help to remove stains such as protein, fat or starchy stains. Oxidoreductases can also be used for bleaching. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytically active enzymes or of protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.

The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight.

In addition to the enzymes mentioned above, cellulases can also be used in detergent tablets. By removing pilling and microfibrils, cellulases and other glycosyl hydrolases can help maintain color and increase the softness of the textile. Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different types of cellulase differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

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

Detergent tablets preferred in the context of the present invention additionally comprise at least one silver protective agent selected from the group consisting of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole.

In addition, detergent tablets according to the invention can also contain components which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case on the nonionic Cellulose ethers, as well as the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred. The premix to be pressed can, if one wishes to manufacture textile detergent tablets, contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-moφholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which instead of the Moφholino- Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

Fragrances can be added to the detergent tablets according to the invention in order to improve the aesthetic impression of the resulting products and to provide the consumer with a sensorically "typical and distinctive" product in addition to the cleaning performance and the color impression. As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate,

Dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzyl salicylate. The ethers include, for example, benzylethyl ether, the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones include, for example, the jonones, cc-isomethylionone and methyl cedryl ketone the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and teφineol, the hydrocarbons mainly include teφenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures, such as are available from 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, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

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

To produce the shaped bodies according to the invention, the premix is compacted in a so-called die between two punches to form a solid compressed product. This process, which is briefly referred to as tableting in the following, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molded body being formed being determined by the position of the lower punch and the shape of the pressing tool. The constant dosing, even at high mold throughputs, is preferably achieved by volumetric dosing of the premix. As the tableting continues, the upper punch touches the premix and lowers further in the direction of the lower punch. During this compression, the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix), the plastic deformation begins, in which the particles flow together and the molded body is formed. Depending on the physical properties of the premix, some of the premix particles are also crushed and an even higher pressure occurs Sintering the premix. With increasing pressing speed, that is to say high throughput quantities, the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities. In the last step of tableting, the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.). Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down. For small production quantities, eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine. The pressing can take place with one upper and one lower stamp, but several stamps can also be attached to one eccentric disc, the number of die holes being correspondingly increased. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour. For larger throughputs, rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available. Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps. The die table and the stamps move around a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation. At those points where a particularly serious lifting or lowering of the punches is required (filling, compacting, ejecting), these cam tracks are followed additional low-pressure pieces, low-tension rails and lifting tracks supported. The die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix. The pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers.

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

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

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

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

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

Another preferred molded body that can be produced has a plate-like or plate-like structure with alternating thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, broken off and into the Machine can be entered. This principle of the "bar-shaped" molded article washing agent can also be realized in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side. However, it is also possible that the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous application properties of the molded body. If, for example, components are contained in the moldings that mutually influence one another negatively, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted. when the second goes into solution. The layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely removed, but it is also possible for the inner layer (s) to be completely encased ) can be achieved by the layer (s) lying further outwards, which leads to the premature dissolution of components of the inner layer (s).

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

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

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

2P πDt

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

As stated above, molded bodies according to the invention can also be provided which comprise several phases, preferably several layers. The present invention therefore furthermore relates to multi-phase detergent shaped bodies made of compressed, particulate detergent and cleaning agent, comprising builders, bleaching agents, at least one dye which is not stable to bleaching, and other conventional ingredients in which the bleaching agent (s) and the non-bleaching agent ( n) dye (s) are present in separate phases and the phase which contains the non-bleach-stable dye additionally contains paraffin. As already mentioned, multi-phase washing and cleaning agent molded bodies are preferred in which the phases of the molded body have the shape of layers.

The ingredients and quantity ranges outlined above, within which they are used, are also preferred for multi-phase molded bodies. In particular for the ingredients bleaching agent and dye, multi-phase detergent and cleaning agent tablets are preferred, in which the content of the bleaching agents Phase of bleach, based on the phase 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 10 to 30% by weight and the dye content of the dye-containing phase based on phase 0, 01 to 2 wt .-%, preferably 0.05 to 1.5 wt .-% and in particular 0.1 to 1.0 wt .-%.

Examples:

By pressing different premixes, two-layer detergent tablets (1/3 upper phase, 2/3 lower phase) for machine dishwashing were produced. The respective premix for the lower phase was first metered into the die of a commercially available tablet press (Korsch TRP 700) and pre-pressed, after which the premix for the upper phase was filled in and the final addressing was carried out.

The tablets E according to the invention differ from the tablets V not according to the invention in that the colored layer (outer phase) additionally contains paraffin. The composition of the premixes to be dispensed, from which the composition of the molded bodies is directly derived, is given in the following table:

* Ponceau 4R (CI 16255): 7-hydroxy-8- [(4-sulfo-1-naphthalenyl) azo] - 1, 3 -naphthalenedisulfonic acid trisodium salt The tablets were assessed visually immediately after the pressing and after storage for one week; the results are summarized in the table below:

The use of paraffin oil in the colored layer leads to better color stability and higher color brilliance.

Claims

Claims: 1. washing and cleaning agent shaped body made of compressed, particulate washing and cleaning agent, containing builders, bleaching agents and other usual ingredients of washing and cleaning agents, characterized in that it contains at least one non-bleach-stable dye and the areas of the shaped body in which the bleach-stable dye is present, additionally contain paraffin. 2. Detergent form according to claim 1, characterized in that it contains 20 to 95% by weight, preferably 30 to 90% by weight and in particular 40 to 85% by weight of one or more builders from the group of the phosphates, in particular pentasodium tripolyphosphate, the silicates, in particular the disilicates and / or metasihkates, the zeolites, the carbonates and / or hydrogen carbonates, the low molecular weight polycarboxylic acids and their salts, in particular the citrates, the homo- and copolymeric polycarboxylic acids and their salts and the gluconates. 3. Detergent and shaped body according to one of claims 1 or 2, characterized in that it contains no phosphates. 4. Detergent and shaped article according to one of claims 1 to 3, characterized in that it contains 5 to 40% by weight, preferably 10 to 35% by weight and in particular 15 to 30% by weight of one or more alkali metal citrates as builders , preferably trisodium citrate dihydrate, and 5 to 50% by weight, preferably 10 to 45% by weight and in particular 15 to 40% by weight of one or more alkali metal carbonates and / or hydrogen carbonates, preferably sodium hydrogen carbonate. 5. Detergent form according to one of claims 1 to 4, characterized in that the bleaching agent is selected from the groups of oxygen bleaches, in particular sodium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate and / or the halogen bleach, in particular the chlorine bleach with particular preference for trichlocyanuric acids, dichloro- or monochlorocyanurates and hypochlorites. 6. Detergent form according to one of claims 1 to 5, characterized in that it contains the non-bleach-stable dye in amounts of 0.01 to 1 wt .-%, preferably 0.02 to 0.5 wt .-% and in particular 0.05 to 0.25 wt .-%, each based on the molded body, contains. 7. washing and cleaning agent molded article according to one of claims 1 to 6, characterized in that it 0.1 to 5 wt .-%, preferably 0.25 to 4 wt .-% and in particular 0.5 to 3 wt .-% Paraffmöl and / or paraffin wax, preferably low viscosity paraffmöl, contains. 8. Multi-phase detergent and shaped body made of compressed, particulate detergent and cleaning agent, containing builders, bleach, at least one non-bleach-stable dye and other customary ingredients, characterized in that the bleach and the non-bleachable dye (s) ( e) are in separate phases and the phase which contains the non-bleach-stable dye additionally contains paraffin. 9. Mehφhasiger washing and cleaning agent shaped body according to claim 8, characterized in that the phases of the shaped body have the shape of layers. 10. Mehφhasiger washing and cleaning agent shaped body according to one of claims 8 or 9, characterized in that the content of the bleach-containing phase of bleach, based on the phase 5 to 50 wt .-%, preferably 7.5 to 40 wt .-% and in particular 10 to 30% by weight and the dye content of the dye-containing phase, based on the phase 0.01 to 2% by weight, preferably 0.05 to 1.5% by weight and in particular 0.1 to 1 , 0% by weight. 11. Detergent form according to one of claims 1 to 10, characterized in that it additionally contains a bleach activator, preferably from the group of polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, especially 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, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight. -%, based on the molded body weight, contains. 12. Detergent form according to one of claims 1 to 11, characterized in that it additionally contains at least one silver protective agent selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole .