DE19907411A1 - Compacted detergent tablets for dishwashers contain bleach-sensitive dye protected by addition of paraffin oil or wax to prevent color loss - Google Patents

Abstract

A compressed particulate detergent washing composition containing a builder, bleach, etc is such that paraffin is added to any regions containing a dye which is unstable in presence of the bleach. An Independent claim is also included for a multi-phase composition in which the bleach and the sensitive dye are in separate phases, with the dye-containing phase also containing paraffin.

Description

The present invention relates to colored detergent tablets. In particular, the present invention relates to detergent tablets for Cleaning dishes can be used in dishwashers.

Mechanical cleaning agents are widely described in the prior art. Usually these agents contain one or more builders, bleaches, bleach activators, Corrosion protection agents and surfactants. To give the consumer a typical and These funds are usually used to provide distinctive product both perfumed and colored. A whole range is added to the dyes Requirements: You have to add the detergent to be colored color and use low concentrations permanently and visually perceptible do not discolor or discolor even after prolonged storage or at elevated temperatures. For this purpose, it is necessary that the dyes used compared to some aggressive ingredients (e.g. bleach, alkali carriers) are chemically inert and neither decompose itself other ingredients. Because the ones in the market Detergent tablets are often designed in two colors for aesthetic reasons, there may also be no areas of different colors at the phase boundary Fading of the colored phase or a change of color to lighter or uncolored Areas result.  

The dyes have a high profile of requirements: they have to Medium can be colored in a contrasting manner, but the dye can also be used for a long time Use of one and the same means neither the dishwasher nor that Stain cleaning dishes. The dyes must therefore not have a pronounced substantivity compared to metal or plastic surfaces. It is also necessary that the dyes are completely removed from the dishwasher in the rinse cycle and There is no film or colored lime stains on the dishes or in the water Leave the machine. Since the wash ware later for the preparation and storage of food is used, the dyes must continue to be completely toxicologically safe his.

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

In the compact offer form "tablet" is the contact between dye and other dye-destabilizing ingredients (especially bleach) intimate that color changes can occur with prolonged storage, the Impact the appearance of the molded body. Especially when using Dyes in phosphate-free formulations in which citrates are used as builders become, the z. T. insufficient bleaching stability of the dyes as serious exposed. It has also been shown here that the obvious separation of No bleach and dye in different areas of the tablet alone Solution represents: At the phase boundary there are problems of bleaching and Color transition even with this technical measure and lead to visual unacceptable tablets.

The task now was to find recipe adjustments that it enable non-bleach-stable dyes even in compact washing and  To be able to use detergent tablets without the aforementioned Having to accept disadvantages. In particular also in phosphate-free and / or formulations containing citrate should fully meet the requirement profile mentioned above become.

It has now been found that the addition of paraffin to the shaped body or to the area of the shaped body containing the non-bleach-stable dye, the above Solves problems.

The present invention relates to detergent tablets compressed, particulate detergent and cleaning agent containing builders, Bleach and other common ingredients in detergents and cleaning agents contain at least one non-bleach-stable dye and in which the areas of Shaped body in which the non-bleach-stable dye is present, additionally paraffin contain.

In addition to the constituents, the detergent tablets according to the invention contain 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 g / cm ^-3 and viscosities between 25 and 80 mPa.s, while viscous paraffins have densities from 0.827 to 0.89 g / cm ^-3 and viscosities from 110 to 230 mPa. can have s. In the technical field, liquid paraffin forms are often added to mineral oils and are referred to collectively as paraffin oil or white oil, the density of such technical products usually being at least 0.88 g / cm ^-3 and the boiling point <360 ° C.

For semi-solid paraffin qualities with melting points of 45-65 ° names are like soft paraffin, for those with densities of 0.82 to 0.88 g / cm ^-3 and melting points of 38 to 60 ° C and boiling points <300 ° C names are like Petrolatum in use; a well-known trademark for the latter is petroleum jelly. We also know hard paraffin (Paraffinum solidum), a solid crystalline mass with a solidification temperature of 50 to 62 ° C.

Paraffin oils are particularly preferred in the context of the present invention used. Preferred washing and Detergent tablets 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.

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 β- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ . yH ₂ O is preferred, wherein β-sodium disilicate can be obtained, for example, by the process described in international patent application WO-A-91/08171.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ , 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, can also be used, which are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “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 (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula

n Na ₂ O. (1-n) K ₂ O. Al ₂ O _3. (2-2.5) SiO _2. (3.5-5.5) H ₂ O

can be described. The zeolite can be used both as a builder in one granular compound used, as well as a kind of "powdering" of the entire pressing mixture are used, usually both ways to Incorporation of the zeolite into the premix can be used. Suitable zeolites have an average 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% by weight of bound water.

It goes without saying that the generally known phosphates are also used as Builder substances possible, provided that such use is not for ecological reasons should be avoided. The sodium salts are particularly suitable Orthophosphate, the pyrophosphate and especially the tripolyphosphate.

Usable organic builders are, for example, those in the form of their Polycarboxylic acids that can be used in sodium salts, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that such use is not for ecological reasons objectionable, 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. Are considered to be alkali carriers Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, Alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the the aforementioned substances, in the context of this invention preferably the alkali metal carbonates, especially sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate be used.

In moldings according to the invention for machine dishwashing Water-soluble builders preferred because they usually appear on dishes and hard surfaces less tend to form insoluble residues. Usual builders working in  machine dishwasher tablets according to the invention between 10 and 90 wt .-% based on the premix to be compressed, are the low molecular weight polycarboxylic acids and their salts, the homopolymers and copolymers Polycarboxylic acids and their salts, the carbonates, phosphates and silicates. Prefers are used for the production of moldings for machine dishwashing 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 metasilicates used. A builder system is particularly preferred containing a mixture of tripolyphosphate and sodium carbonate. Also special a builder system is preferred which comprises a mixture of tripolyphosphate and Contains sodium carbonate and sodium disilicate.

Preferred detergent tablets are within the scope of the present Invention characterized in that it 20 to 95 wt .-%, preferably 30 to 90 % By weight and in particular 40 to 85% by weight of one or more builders from the Group of phosphates, in particular pentasodium tripolyphosphate, of silicates, in particular the disilicates and / or metasilicates, the zeolites, the carbonates and / or Hydrogen carbonates, the low molecular weight polycarboxylic acids and their salts, especially the citrates, the homo- and copolymeric polycarboxylic acids and their salts and the gluconate.

The incorporation of paraffin into the shaped body has particular advantages or to the region of the shaped body in which the dye which is not bleach-stable is present, if the builder system contains citrate and is free of phosphates. In these moldings the problems that the present invention solves are otherwise very clear. in the Preferred detergent tablets in the context of the present invention do not contain phosphates.

As mentioned above, the use of citrate carbonate builder systems is in machine dishwashing detergent is an advantage. Therefore, preferred washing and Detergent tablets, characterized in that they are 5 to 40 as builders  % By weight, preferably 10 to 35% by weight and in particular 15 to 30% by weight of one or several alkali metal citrates, 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 several alkali metal carbonates and / or hydrogen carbonates, preferably Sodium hydrogen carbonate.

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 which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, 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 bleaches are the diacyl peroxides, such as. B. 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, peroxystearic acid, ε-phthalimido [peroxycaproic acid] Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyocelaic acid diperoxyacid diperoxyacid diacid acid, diperoxyacid diacid acid diperoxyacid diacid acid, diperoxyacetic acid diperoxyacid diacid acid diperoxyacid diacid acid, diperoxyacid diacid acid diperoxyacid diacid acid, diperoxyacid diacid acid diperoxyacid diacid acid, diperoxyacid diacid acid, diperoxyacid diacid acid, diperoxyacid diacid acid, diperoxyacid diacid acid, diperoxyacid diacid acid, diperoxyacid diacid acid, diperoxyacid diacid acid, diperoxyacid acid diperoxyacid, , 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or. Can also be used as bleaching agents in moldings for automatic dishwashing Bromine-releasing substances are used. Among the appropriate chlorine or bromine releasing materials come for example heterocyclic N-bromine and N- Chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DIGA) 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 washing and Detergent tablets are characterized in that the bleach is selected from the groups of oxygen bleaches, especially sodium perborate Monohydrate, sodium perborate tetrahydrate and sodium percarbonate and / or the Halogen bleach, especially chlorine bleach with particular preference of trichlocyanuric acids, dichloro- or monochlorocyanurates and hypochlorites.

The fourth essential ingredient contains the washing and Detergent tablets (or areas thereof) in addition to builder (s), Bleach (s) and paraffin one or more non-bleachable dye (s).

Such dyes which can be used for coloring detergents and cleaning agents are shown in Solvents and / or binders soluble colorants. Because of the structural Diversity of these dyes (e.g. azo, azine, anthraquinone, acridine, cyanine, oxazine, Polymethine, thiazine, triarylmethane dyes, etc.) are tens of thousands various dyes known, of which about 5000 are commercially available and only approx. 500 are produced in technical quantities. A systematic structure of the In addition to the structural systematization, dyes also follow 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 are as Trademark protected fantasy names and trade names for Characterization can be used.  

Dyes used in detergent tablets should have a high level Storage stability and insensitivity to the other ingredients of the agent and against light as well as no pronounced substantivity towards textile fibers or Have dishes so that they do not stain. In detergent tablets for that automatic dishwashing have become the colorants in the initially cited state of the art Dyes proven technology, their bleach stability in the context of present invention has been improved. For example, those are to be mentioned explicitly 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® Rot 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 dyes used in the washing and Detergent tablets can, depending on the desired color impression and Purpose vary. Preferred laundry detergents within the scope of the present invention and detergent tablets contain the non-bleachable 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 washing and Detergent tablets depending on their intended use Contain ingredients that are especially from the groups of bleach activators, Disintegration aids, surfactants, enzymes, silver protection agents, fragrances, polymers, pH Adjusting agents, fluorescent agents, foam inhibitors, anti-redeposition agents, optical Brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors gates and mixtures come from this.  

To be one when washing or cleaning at temperatures of 60 ° C and below To achieve improved bleaching effect, bleach activators can be pressed into the Be premixed. As bleach activators, compounds that are under Perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 C- Atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted Perbenzoic acid result, are used. Suitable substances are O- and / or N- Acyl groups of the number of carbon atoms mentioned and / or optionally substituted Wear benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylene diamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl 2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, Ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, too so-called bleaching catalysts can be incorporated into the moldings. With these Fabrics are bleach-enhancing transition metal salts or Transition metal complexes such as Mn, Fe, Co, Ru or Mo Salene complexes or carbonyl complexes. Also 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 be used as bleaching catalysts.

Preferred washing and Detergent tablets additionally contain a bleach activator, preferably from the Group of polyacylated alkylenediamines, especially 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 - complex, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) -  Complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, des Manganese sulfate, preferably in amounts of 1% by weight to 10% by weight, in particular 2 wt .-% to 8 wt .-%, based on the weight of the molded body.

In order to facilitate the disintegration of highly compressed moldings, it is possible to Disintegration aids, so-called tablet disintegrants, to be incorporated into them in order to to shorten the disintegration times. Under tablet disintegrants or disintegrators according to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology "(6th edition, 1987, pp. 182-184) understood auxiliary substances that for the rapid disintegration of tablets in water or gastric juice and for the release of the pharmaceuticals in a resorbable form.

These substances, which are also known as "explosives" due to their effectiveness, increase their volume when water enters, and on the one hand increases their own volume (Swelling), on the other hand, a pressure can be generated via the release of gases which can break the tablet into smaller particles. Well-known Disintegration aids are, for example, carbonate / citric acid systems, wherein other organic acids can also be used. Swell end 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 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 aid, each based on the weight of the molded body.

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, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy 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 cellulose-based disintegrant.

The cellulose used as disintegration aid is preferably not in finely divided form used, but before mixing to the to be pressed Premixes are converted into a coarser form, for example granulated or compacted. Detergent tablets, the explosives in granular or optionally contain cogranulated form, are in the German Patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) as well of international patent application WO98 / 40463 (Henkel). These writings are also more details on the production of granulated, compacted or co-granulated To remove cellulose disintegrant. 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 coarser mentioned above and described in more detail in the cited documents  Disintegration aids based on cellulose are within the scope of the present invention preferably used as a disintegration aid and commercially, for example, at the name Arbocel® TF-30-HG available from Rettenmaier.

As a further disintegrant based on cellulose or as part of it Component can be used microcrystalline cellulose. This microcrystalline Cellulose is made by partial hydrolysis of celluloses under such conditions get that only the amorphous areas (about 30% of the total cellulose mass) of the Attack and completely dissolve celluloses, but the crystalline areas (approx. 70%) leave undamaged. A subsequent disaggregation by hydrolysis emerging micro-fine cellulosic supplies the microcrystalline celluloses that Have primary particle sizes of about 5 microns and, for example, to granules with a average particle size of 200 microns are compactible.

In addition to the builders described above, the premix can also already contain mentioned detergent substances, especially for detergent tablets are important ingredients. Depending on the molded body to be produced, the Answering the questions of whether and if so which surfactants to use, different Answers possible. Shaped articles for washing textiles can usually be used various surfactants from the groups of anionic, nonionic, cationic and contain amphoteric surfactants, while moldings for mechanical Dishwashing preferably contain only low-foaming nonionic surfactants and Water softening tablets or bleach tablets are free of tensides. The A person skilled in the art is responsible for incorporating the surfactants into the premix to be pressed there are no limits 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, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from C _12-18 monoolefins having a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under Fatty acid glycerol esters are the mono-, di- and triesters as well as their mixtures understand how they are produced by esterification of a monoglycerin with 1 up to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerin be preserved. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 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) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil 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 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 produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol 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 -C ₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, viewed in isolation, 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. 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. B. 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 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, especially in the form of the sodium salts.

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

When selecting the anionic surfactants that are used in the washing and Detergent tablets are used, freedom of formulation no framework conditions to be observed in the way. 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 Alkylbenzenesulfonates and fatty alcohol sulfates, preferred detergent tablets 2 up to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight Fatty alcohol sulfate (s), each based on the weight of the molded body.

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 linearly or preferably 2-branched methyl or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 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 thereof, 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 include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferably used nonionic surfactants, which 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, especially fatty acid methyl esters, such as those found in Japanese Patent application JP 58/217598 are described or preferably according to the in the international patent application WO-A-90/13533 become.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkypolyglycosides that 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, are preferably used where the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

The detergent tablets according to the invention can be preferred Contain alkyl polyglycosides, the APG contents of the shaped bodies being above 0.2% by weight, based on the entire molded body, are preferred. Particularly preferred washing and Detergent tablets contain APG in quantities of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the Fatty acid alkanolamides can 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 it.

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

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

The group of polyhydroxy fatty acid amides also includes compounds of the formula (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 oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by 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 can then, for example, according to the teaching of the international application WO-A-95/07331 by implementation with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

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 by alkoxylated alcohols 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 ₁₁ -, 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 for the purposes 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.

In enzymes in detergent tablets, there are in particular those from the class hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, Amylases, glycosyl hydrolases and mixtures of the enzymes mentioned in question. All these Hydrolases help remove stains such as protein, fat or starchy stains. Oxidoreductases can also be used for bleaching become. Bacterial strains or fungi such as Bacillus are particularly suitable subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola  insolens as well as enzymatic derived from their genetically modified variants Active ingredients. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Are there Enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic Enzymes, but especially protease and / or lipase-containing mixtures or Mixtures with lipolytically active enzymes of particular interest. examples for Such lipolytic enzymes are the well-known cutinases. Peroxidases too or oxidases have been found to be suitable in some cases. To the appropriate ones Amylases include in particular alpha-amylases, iso-amylases, pullulanases and Pectinases. The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5% by weight.

In addition to the enzymes mentioned above, detergent tablets also contain still consider cellulases. Cellulases and other glycosyl hydrolases can by the Removing pilling and microfibrils to maintain color and increase color Contribute to the softness of the textile. Cellobiohydrolases are preferably used as cellulases, Endoglucanases and glucosidases, which are also called cellobiases, or Mixtures of these are used. Because different types of cellulase are characterized by their CMCase and Avicelase activities can be distinguished by targeted mixtures of the Cellulases the desired activities can be set.

Shaped body according to the invention for machine cleaning of dishes can be manufactured to protect the dishes or the machine Contain corrosion inhibitors, silver protection in the field of mechanical Dishwashing have a special meaning. The known ones can be used State of the art substances. In general, silver protection agents in particular  selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, Aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes be used. Benzotriazole and / or are particularly preferably to be used Alkylaminotriazole. You will also often find it in detergent formulations Agents containing active chlorine, which significantly reduce the corrosion of the silver surface can. Chlorine-free cleaners especially contain oxygen and nitrogenous ones organic redox-active compounds, such as di- and trihydric phenols, e.g. B. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic Compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often found Use. The transition metal salts selected from are preferred the group of manganese and / or cobalt salts and / or complexes, particularly preferred the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) - Complexes, chlorides of cobalt or manganese and manganese sulfate. Likewise Zinc compounds can be used to prevent corrosion on the wash ware.

Preferred washing and Detergent tablets additionally contain at least one silver protective agent selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, Aminotriazoles, the alkylaminotriazoles, preferably benzotriazole and / or Alkylaminotriazole.

In addition, detergent tablets according to the invention can also contain components contain, which positively influence the oil and fat washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is soiled, which has previously been repeatedly washed with a detergent according to the invention, that contains this oil and fat-dissolving component. Among 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, each based on the nonionic cellulose ether, and those from the prior art  Technically known polymers of phthalic acid and / or terephthalic acid or their Derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionically and / or nonionically modified Derivatives of these. Of these, the sulfonated derivatives of are particularly preferred Phthalic acid and terephthalic acid polymers.

The premix to be pressed can be produced when manufacturing textile detergent tablets wants, as optical brightener derivatives of diaminostilbenedisulfonic acid or their Contain alkali metal salts. Are suitable for. B. Salts of 4,4'-bis (2-anilino-4-morpholino- 1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or a similar structure Ver bonds that replace the morpholino group with a diethanolamino group, a methyl wear amino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) - diphenyls, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can be used.

Perfumes can be used in the detergent tablets according to the invention can be added to improve the aesthetic impression of the resulting products and the consumer in addition to the cleaning performance and the color impression a sensory to provide "typical and distinctive" product. As perfume oils or Fragrances can individual fragrance compounds, e.g. B. the synthetic products from 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, Dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzyl formate, Ethyl methylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and Benzyl salicylate. The ethers include, for example, benzyl ethyl ether and the aldehydes e.g. B. the linear alkanals with 8-18 C atoms, citral, citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. B. the Jonone, ∝-isomethyl ionone and methyl cedryl ketone to the  Alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and Terpineol, the hydrocarbons mainly include terpenes such as limonene and pinene. However, mixtures of different fragrances are preferably used, which together create an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures as they are accessible from plant sources, e.g. B. 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 on carriers that affect the adhesion of the perfume reinforce the laundry and through a slower fragrance release for long-lasting Ensure the fragrance of the textiles. Such carrier materials have, for example Cyclodextrins have proven themselves, with the cyclodextrin-perfume complexes additionally other auxiliaries can be coated.

To produce the moldings according to the invention, the premix is in a so-called die between two stamps compressed into a solid compressed. This process, which is briefly referred to below as tabletting, is divided into four sections: metering, compression (elastic deformation), plastic deformation and expelling.

First, the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting molded body through the position of the lower one Stamp and the shape of the press tool can be determined. The constant one Dosage even at high molding throughputs is preferably over a volumetric dosage of the premix reached. In the further course of tableting the upper stamp touches the premix and continues to lower in the direction of the Lower stamp. With this compression, the particles of the premix become closer pressed together, the void volume within the filling between the  Stamping decreases continuously. From a certain position of the upper stamp (and from a certain pressure on the premix) the plastic begins Deformation in which the particles flow together and it to form the molded body is coming. Depending on the physical properties of the premix, a part also becomes the premixed particles are crushed and there is a pressure at even higher pressures Sintering the premix. With increasing press speed, i.e. high Throughput quantities, the phase of elastic deformation is shortened more and more, so that the resulting shaped bodies can have more or less large cavities. In the last step of tableting, the finished molded article is made using the lower stamp pressed out of the die and by subsequent transport devices transported away. At this point, only the weight of the molded body is final determined because the compacts due to physical processes (stretching, crystallographic effects, cooling etc.) can still change their shape and size. Tableting takes place in commercially available tablet presses, which are basically or double stamps can be equipped. In the latter case, not only Upper stamp used to build up pressure, the lower stamp also moves during of the pressing process towards the upper punch, while the upper punch presses down. Eccentric tablet presses are preferably used for small production quantities, where the stamp or stamps are attached to an eccentric disc, which in turn an axis with a certain rotational speed is mounted. The movement this ram is comparable to the operation of a conventional four-stroke engine. The pressing can be done with an upper and lower stamp, but it can also several stamps can be attached to an eccentric disc, the number of Die holes are expanded accordingly. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour. For larger throughputs, rotary tablet presses are selected, on which one so-called die table a larger number of dies is arranged in a circle. The number of matrices varies between 6 and 55, depending on the model, with larger ones as well Matrices are commercially available. Each die on the die table is a top and Assigned lower stamp, whereby again the pressure is active only by the upper or Lower stamp, but can also be built up by both stamps. The matrix table  and the stamps move about a common vertical axis, the Stamp with the help of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection. To the Places where there is a particularly serious increase or decrease in the stamp is necessary (filling, compacting, ejecting), these cam tracks are additional low-pressure pieces, low-tension rails and lifting tracks supported. The The die is filled via a rigidly arranged feed device so-called filling shoe, which is connected to a reservoir for the premix. The pressure on the premix is via the press paths for upper and lower punches individually adjustable, the pressure build-up by rolling the Stamp shaft heads happen on adjustable pressure rollers.

Rotary presses can also be used with two filling shoes to increase the throughput be provided, with only a semicircle to produce a tablet must become. Several are used to produce two-layer and multi-layer moldings Filling shoes arranged one behind the other without the slightly pressed first layer in front of the further filling is ejected. By appropriate process control are in this way also coated and dot tablets can be produced, which have an onion skin-like structure have, whereby in the case of the point tablets the top of the core or the core layers is not covered and therefore remains visible. Rotary tablet presses are also included Single or multiple tools can be equipped 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 a million tablets per hour.

Tableting machines suitable for the purposes of the present invention are, for example available 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 N.V., Halle (BE / LU). The hydraulic double pressure press HPF, for example, is particularly suitable 630 from LAEIS, D.  

The moldings can be in a predetermined spatial shape and a predetermined size are manufactured. Practically all sensibly manageable come as a room shape Configurations into consideration, for example, the training as a board, the staff or Bar shape, cubes, cuboids and corresponding room elements with flat side surfaces as well as in particular cylindrical configurations with circular or oval Cross-section. This last embodiment covers 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 be separate individual elements be formed, the predetermined dosage of the washing and / or Corresponds to detergent. But it is also possible to form compacts, the one Connect a plurality of such mass units in one compact, in particular by predetermined breaking points make it easy to separate portioned smaller units is provided. For the use of textile detergents in machines of in Europe usual type with horizontally arranged mechanics can the training of portioned compacts as tablets, in cylindrical or cuboid form, are expedient, a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred is. Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices in particular for the production of such compacts.

The spatial shape of another embodiment of the shaped body is in its dimensions the induction chamber of commercial household washing machines adapted so that the Shaped bodies can be metered directly into the induction chamber without a metering aid, where it dissolves during the induction process. Of course, there is also a stake the detergent tablets are easily possible via a dosing aid and within the present invention preferred.

Another preferred shaped body that can be produced has a plate or panel-like structure with alternating thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, the short thin  Display segments, can be canceled and entered into the machine. This Principle of the "bar-shaped" shaped body detergent can also be used in other geometric Shapes, for example vertical triangles, only on one side are connected alongside each other, can be realized.

But it is also possible that the various components do not become one Tablet are pressed, but that shaped bodies are obtained, which several Have layers, that is, at least two layers. It is also possible that these different layers have different dissolving speeds. Out of this This may result in advantageous performance properties of the molded articles. If For example, components are contained in the moldings, which are mutually reciprocal affect negatively, so it is possible that one component is more soluble in the Integrate layer and the other component into a slower soluble layer to incorporate so that the first component has already reacted when the second in Solution goes. The layer structure of the moldings can be stacked, a dissolution process of the inner layer (s) at the edges of the molded body already then occurs when the outer layers are not yet completely dissolved, but it can also a complete covering of the inner layer (s) by the further outwards lying layer (s) can be reached, which prevents the early Solution of components of the inner layer (s) leads.

In a further preferred embodiment of the invention, a molded body consists of at least three layers, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while in the case of the stacked shaped body, the two outer layers and in the case of the shell-shaped one Shaped bodies, however, the outermost layers are free of peroxy bleach. Farther it is also possible to use peroxy bleach and any bleach activators present and / or to separate enzymes spatially from one another in a shaped body. Such multilayered moldings have the advantage that they do not have only one Detergent dispenser or via a metering device, which is added to the wash liquor will be used; rather, it is also possible in such cases, the  Put molded articles in direct contact with the textiles in the machine without Stains from bleach and the like would be feared.

Similar effects can also be achieved by coating individual components of the detergent and cleaning agent composition to be pressed, or all of them Reach shaped body. For this purpose, the bodies to be coated can be coated with, for example aqueous solutions or emulsions are sprayed, or via the process of Get a coating on the melt coating.

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

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

As stated above, moldings according to the invention can also be provided, which comprise several phases, preferably several layers. Another item The present invention is therefore multi-phase washing and Detergent tablets made of compressed, particulate washing and Detergents containing builders, bleach, at least one not bleach-stable dye and other conventional ingredients in which the bleach (s) and the non-bleachable dye (s) are present in separate phases and the phase containing the non-bleach-stable dye additionally contains paraffin. As already mentioned, here are multiphase detergent tablets preferred, in which the phases of the shaped body have the form of layers.  

The ingredients and quantity ranges listed above, within which these are also preferred for multiphase molded articles. Especially for the Ingredients bleach and dye applies to multi-phase washing and Detergent tablets are preferred in which the content of the bleach-containing Bleach phase, 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 content of the dye-containing phase Dye, 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.

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-compressed, after which the premix was filled in for the upper phase and the final compression took place. The tablets E according to the invention differ from the tablets V not according to the invention in that the colored layer (upper phase) additionally contains paraffin. The composition of the premixes to be pressed, from which the composition of the moldings is directly derived, is given in the table below:

The tablets were assessed visually immediately after compression 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 (12)

1. Detergent tablets made of compressed, particulate detergents and cleaning agents, containing builders, bleaches and other usual ingredients of detergents and cleaning agents, characterized in that it contains at least one non-bleach-stable dye and the areas of the tablets in which the bleach-stable dye is present, additionally contain paraffin. 2. Detergent tablets according to claim 1, characterized in that it is 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 Metasilicates, zeolites, carbonates and / or hydrogen carbonates, the low molecular weight polycarboxylic acids and their salts, especially the citrates, the homo- and copolymeric polycarboxylic acids and their salts and the gluconates. 3. Detergent tablets according to one of claims 1 or 2, characterized characterized in that it contains no phosphates. 4. Detergent tablets according to one of claims 1 to 3, characterized characterized in that it contains 5 to 40 wt.%, preferably 10 to 35 wt. and in particular 15 to 30% by weight of one or more alkali metal citrates, 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 bicarbonate. 5. Detergent tablets according to one of claims 1 to 4, characterized characterized in that the bleach is selected from the groups of Oxygen bleach, especially sodium perborate monohydrate, sodium perborate Tetrahydrate and sodium percarbonate and / or the halogen bleach, in particular  chlorine bleach with particular preference for trichlocyanuric acids, Dichloro- or monochlorocyanurates and hypochlorites. 6. Detergent tablets according to one of claims 1 to 5, characterized characterized in that it contains the non-bleach-stable dye in amounts of 0.01 to 1 % By weight, preferably 0.02 to 0.5% by weight and in particular 0.05 to 0.25% by weight, each based on the shaped body. 7. Detergent tablets according to one of claims 1 to 6, characterized characterized in that it 0.1 to 5 wt .-%, preferably 0.25 to 4 wt .-% and in particular 0.5 to 3% by weight of paraffin oil and / or paraffin wax, preferably contains low viscosity paraffin oil. 8. Multi-phase detergent tablets made of compressed, particulate detergents and cleaning agents containing builders, bleach, at least one non-bleach-stable dye and other usual ingredients, characterized in that the bleaching agent (s) and the non-bleaching stable (s) Dye (s) are in separate phases and the phase that is not contains bleach-stable dye, additionally contains paraffin. 9. Multi-phase detergent tablets according to claim 8, characterized characterized in that the phases of the shaped body have the form of layers. 10. Multi-phase detergent tablets according to one of claims 8 or 9, characterized in that the content of the bleach-containing phase Bleaching agent, 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 content of the dye-containing phase Dye, 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 tablets according to one of claims 1 to 10, characterized characterized in that he additionally a bleach activator, preferably from the group of multiple acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenol sulfonates, 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 (ammin) 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 wt .-%, in particular 2 wt .-% to 8 wt .-%, based on the Molded body weight, contains. 12. Detergent tablets according to one of claims 1 to 11, characterized characterized in that he additionally selected at least one silver protection agent from the Group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the Alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole, contains.