WO1999041350A1 - Multi-phase shaped body with optimized phase split - Google Patents

Abstract

The invention relates to two-phase or multi-phase washing and cleaning agent shaped bodies consisting of compacted, particle-shaped washing and cleaning agents, comprising builder(s), bleaching agents, bleach activator(s) and optionally other washing and cleaning agent components. Optimum stability of oxidation-sensitive materials is achieved by physically separating the bleach activator(s) from the oxidation-sensitive materials in a defined region of the shaped body.

Description

 1 "Multi-phase molded article with optimized phase split"

The present invention relates to detergent tablets which contain bleach. In particular, the invention relates to moldings such as detergent tablets, detergent tablets, bleach tablets or water softener tablets with bleach.

Detergent and cleaning agent compositions in the form of moldings, in particular tablets, have long been known in the prior art and have been widely described, although this form of supply has so far not been of outstanding importance on the market. The reason for this is that, in addition to a number of advantages, the form in which the shaped body is offered also has disadvantages which impair production and use, as well as consumer acceptance. The main advantages of moldings such as the fact that the consumer does not have to measure the required amount of product, the higher density and thus the reduced packaging and storage costs, and an aesthetic aspect that should not be underestimated are offset by disadvantages such as the dichotomy between acceptable hardness and sufficiently rapid disintegration and Dissolution of the moldings and numerous technological difficulties in production and packaging put into perspective.

A particular problem results from the incorporation of bleaching agents into detergent tablets, in particular when active ingredients and auxiliaries sensitive to oxidation are to be introduced into the tablets in addition to the bleaching agent. Due to the high density, which is achieved through a strong compression of the particulate premixes, substances that are incompatible with each other are in closer contact with one another than is the case, for example, in a loose powder. This closer contact means that chemical incompatibilities of individual ingredients have a far more drastic effect than with conventional powdery agents.

In the prior art there are proposed solutions for detergent tablets containing bleach, which aim to remove the bleach from the l separate other ingredients that can affect its stability. In particular, the separation of bleach and bleach activator is a frequently pursued solution.

The European patent application EP 481 792 (Unilever) describes detergent tablets which contain a persalt and a bleach activator, the bleach activator having to have a certain pseudo-first-order perhydrolysis constant. This document teaches that the bleach should preferably be separated from bleach destabilizing ingredients. If the bleaching agent is perborate and a di- or polyacylated amine bleach activator is used, this measure is even mandatory.

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

European patent application EP 395 333 (Unilever) describes tabletted detergent compositions which contain sodium perborate and one or more substances from the group of di- or polyacylated amine bleach activators, enzymes and optical brighteners, the persalt not being separated from the substances from this group . The tablets disclosed in this application are stable and have no loss of bleach or enzyme activity.

In the prior art, the problems of bleach stability and the stability of oxidation-sensitive substances in detergent tablets are caused by the contact of bleach with the substances in question. The separation of the bleaching agent from the bleach activator or from oxidation-sensitive substances is repeatedly proposed as a solution. None of the documents mentioned deals with other solutions 3 Stability problems of oxidation-sensitive substances and the loss of activity of the bleach in detergent tablets have to be overcome at the same time.

The present invention was based on the object of providing detergent tablets which overcome the problems mentioned. In particular, the stability problems of oxidation-sensitive substances such as dyes, optical brighteners, fragrances and enzymes should be overcome and the loss of activity of the bleach should also be overcome over long periods of time.

It has now been found that oxidation-sensitive substances are not oxidized and destroyed by contact with the bleaching agent, the bleaching agent losing activity, but that the contact between bleach activator and oxidation-sensitive substance is the cause of the problems mentioned.

The invention now relates to two-phase or multi-phase detergent tablets made of compressed particulate detergent and detergent, comprising builders, bleaching agents, bleach activator (s) and, if appropriate, further detergent and detergent components in which the bleach activator (s) ( en) is / are spatially separated from oxidation-sensitive substances in a defined region of the molded body.

The detergent tablets of the present invention solve the problem of inadequate stability of both the bleach and the oxidation-sensitive substances by spatially separating oxidation-sensitive components that can be destroyed by the bleach and thereby "consume" the bleach from the bleach activator.

In the molded articles of the present invention, at least one spatially delimited region contains the bleach activator and optionally further components which are not sensitive to oxidation. These non-oxidation-sensitive substances originate, for example, from the group of builders, cobuilders, surfactants, binders, Disintegration aids and complexing agents as well as other optional detergent and cleaning agent components.

The spatial delimitation of the bleach activator can be achieved in a variety of ways. The delimited region can have the form of a separate layer, an envelope or individual inserts, while the substances sensitive to oxidation can be present in other layers, in further envelopes or in the core or else in the main matrix of the shaped body. Another possibility is the production of comparatively large granules or extrudates which are protected by coating and which are distributed over the molded body or the tablet.

A preferred embodiment of the present invention provides that the delimited region which contains the bleach activator does not contain the bleach activator alone, but in a mixture with other substances which are not sensitive to oxidation. Preferred detergent tablets contain the bleach activator and other non-oxidation-sensitive ingredients of detergents in the defined region

Another preferred embodiment provides that the delimited region contains the bleach activator and at least part of the total amount of the builders and ionic surfactants contained in the molded body. Particularly preferred detergent tablets have a delimited region which, in addition to the bleach activator, contains one or more substances from the group of builders, cobuilders, surfactants, binders, disintegration aids and complexing agents.

Without wishing to be limited by theory, the applicant assumes that the separation of the oxidation-sensitive substances from the bleach activator has the effect that the entry of water or hydrogen peroxide into the oxidation-sensitive substances in the absence of bleach activators does not lead to a drastic destruction of these compounds. If, on the other hand, bleach activator and substances sensitive to oxidation are present within a region, then under the influence of the bleach activator from migrating HO or H ₂ O, significantly more bleach-active species (for example s

Peracetic acid), which lead to the destruction of the oxidation-sensitive compounds. Since H ₂ O _{2 is} consumed in this way, further bleaching agent disintegrates until an equilibrium concentration of H ₂ O _{2 is} reached again in the shaped body. This process is prevented by the separation of bleach activator and substances susceptible to oxidation, that the bleach activator does not migrate even in the molded body and that the bleach-active species that arise when bleach activator and H ₂ O _{2 come} into contact are obviously less likely to migrate.

Preferred moldings are not made from a mixture of individual powders, but at least partially from compounds, i.e. a mixture of fewer granules. The primary particles of the constituents are agglomerated into secondary particles, which in turn are compressed into tablets. The secondary particles, which contain the bleach activator, are separated from substances that are sensitive to oxidation and can therefore not contribute to the formation of highly bleach-active species in the vicinity of the substances sensitive to oxidation.

In the context of the present application, oxidation-sensitive substances are understood to mean those substances which can be oxidatively decomposed by H ₂ O ₂ or more bleach-active compounds which arise from H ₂ O ₂ and bleach activators. Such substances are, in particular, dyes which completely fade or change their color in an unacceptable manner, optical brighteners in which the destruction of the molecule leads to the loss of the brightening effect, fragrances which are decomposed oxidatively to odorless or even malodorous compounds and enzymes whose Oxidation products no longer show any catalytic activity.

While such oxidation-sensitive substances are necessarily separated from the bleach activator in the context of the present invention by the bleach activator being present in a delimited region of the shaped bodies, the oxidation-sensitive substances can easily be in intimate contact with the bleaching agent without being damaged. The defined region, which contains the bleach activator, can additionally contain bleaching agents, it being within the scope of the present invention έ it is preferred that the defined region (which contains the bleach activator) is free of bleaching agent (s).

The fact that the delimited region (which contains the bleach activator) is preferably free of bleach does not mean that the bleach must itself be in a region which is separate and delimited from substances other than the bleach activator. As explained above, the bleaching agent can be mixed with the oxidation-sensitive substances without any problems, so that detergent tablets are preferred in which bleaching agents and oxidation-sensitive substances are present together in one region of the tablets.

The essence of the present invention requires that the moldings contain substances sensitive to oxidation, since their destruction and the consequent loss of activity of the bleaching agent are to be prevented. These oxidation-sensitive substances have already been explained in more detail above, but can also be selected from groups other than those mentioned above. In the context of the present inventions, however, detergent tablets are preferred which contain one or more substances from the group of dyes, optical brighteners, fragrances and enzymes as oxidation-sensitive substances.

Bleach activators are incorporated into detergents and cleaning agents in order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below. According to the invention, these bleach activators are present in a delimited region of the shaped bodies. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are polyacylated alkylenediamines, especially 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 1-

(NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxy-benzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially 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, 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.

In the context of the present invention, substances from the group of bleach catalysts are bleach activators, i.e. the bleaching catalysts are also accommodated in the or a delimited region of their shaped bodies. The moldings according to the invention contain, based in each case on the entire mold, between 0.5 and 30% by weight, preferably between 1 and 20% by weight and in particular between 2 and 15% by weight, of one or more bleach activators or bleach catalysts. These amounts can vary depending on the intended use of the moldings produced. For example, bleach activator contents of between 0.5 and 5% by weight, preferably between 1 and 4% by weight and in particular between 2 and 3.5% by weight, are common in typical universal detergent tablets, while bleach tablets contain quite high contents, for example between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular between 10 and 20% by weight. The person skilled in the art is not restricted in its freedom of formulation and can thus produce more or less bleaching detergent tablets, detergent tablets or bleach tablets by varying the bleach activator and bleach content.

A particularly preferred bleach activator is N, N, N ', N'-tetraacetylethylenediamine, which is widely used in detergents and cleaning agents. Preferred detergent and cleaning product tablets are accordingly 8 characterized in that tetraacetylethylenediamine is used as the bleach activator in the amounts mentioned above.

To develop the desired bleaching performance, the detergent tablets of the present invention contain one or more bleaches. 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. Other useful bleaches are, for example, sodium percarbonate. Peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -supplying acidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Depending on the desired product, the bleaching agents are also used in varying amounts in the detergent tablets according to the invention. Usual contents are between 5 and 50% by weight, preferably between 10 and 40% by weight and in particular between 15 and 35% by weight, in each case based on the entire molded body.

In the case of bleaching agents, too, the content of these substances in the shaped bodies depends on the intended use of the shaped bodies. While conventional universal detergents in tablet form contain between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular between 12.5 and 22.5% by weight of bleaching agent, the contents of bleaching agent or bleach booster tablets are between 15 and 50% by weight, preferably between 22.5 and 45% by weight and in particular between 30 and 40% by weight.

As already explained above, the oxidation-sensitive substances preferably come from the group of dyes, optical brighteners, fragrances and enzymes. These groups are specified in more detail below.

In order to improve the aesthetic impression of the detergent tablets according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity 3 compared to textile fibers so as not to stain them. Since the subject matter of the present invention relates to multi-phase detergent tablets, the coloring of individual phases is of greater importance in order to underline the different active character of individual phases. Examples of the effectiveness of such coloring and of the success of statements on this are well known from the denture cleaner advertising.

Preferred for use in the laundry detergent tablets according to the invention are all colorants which can be oxidatively destroyed in the washing process, and also mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. For example, anionic colorants, e.g. anionic nitroso dyes. A possible colorant is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part

2: 10020), which is available as a commercial product, for example as Basacid Green 970 from BASF, Ludwigshafen, and mixtures of these with suitable blue dyes. Other colorants are Pigmosol Blue 6900 (CI 74160), Pigmosol ^® Green 8730 (CI 74260), Basonyl ^® Red 545 FL (CI 45170), Sandolan ^®

Rhodamine EB400 (CI 45100), Basacid ^® Yellow 094 (CI 47005), Sicovit ^® Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160) , Supranol Blue ^® GLW (CAS 12219-32-8, CI Acidblue 221)), Nylosan Yellow ^®

N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan ^® Blau (CI Acid Blue 182, CAS 12219-26-0).

When choosing the colorant, care must be taken to ensure that the colorants do not have too strong an affinity for the textile surfaces and in particular for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stability to oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant varies in the ΛO

Detergents or cleaning agents. In the case of readily water-soluble colorants, for example the above-mentioned basacid green or the above-mentioned sandolan blue, colorant concentrations in the range from a few 10 ^* to 10 ^" % by weight are typically chosen. In the case of those which are particularly preferred on account of their brilliance, but less so In contrast, readily water-soluble pigment dyes, for example the pigmosol dyes mentioned above, the suitable concentration of the colorant in washing or cleaning agents is typically a few 10 ^"3 to 10 ^{" 4} % by weight.

The moldings can contain optical brighteners of the derivative type of diaminostilbenedisulfonic acid or their alkali metal salts as oxidation-sensitive substances. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which, instead of the morpholino group, have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can also be used. The optical brighteners are used in the detergent tablets according to the invention in concentrations between 0.01 and 1% by weight, preferably between 0.05 and 0.5% by weight and in particular between 0.1 and 0.25% by weight. %, each based on the entire molded body, used.

Fragrances are added to the agents according to the invention in order to improve the aesthetic impression of the products and, in addition to the softness, to provide the consumer with a visually and sensorially "typical and unmistakable" product. Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexyl benzylatepylpionate, allylcyclohexyl propyl pionate. The ethers include, for example, benzyl ethyl ether and the aldehydes eg the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal. the ketones, for example, the jonones, cc-isomethylionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrance content of the laundry detergent tablets according to the invention is usually up to 2% by weight of the total formulation. The fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. 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 protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers Oil and / or embedded in enveloping substances to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules in the shaped bodies according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

In the context of the present invention, spatial separation is understood to mean that the separate layer, covering or individual insert which contains the bleach activator is completely free of the oxidation-sensitive substances mentioned. As already mentioned above, this can be achieved, for example, by producing a separate secondary granulate which, in addition to the bleach activator, contains only non-oxidation-sensitive substances and, after mixing with other constituents and / or compounds, is pressed to give shaped articles. The production of a two- or multi-layer tablet in which only one layer contains bleach activator is also conceivable. Oxidation-sensitive substances can then be used in the other layer (s). It is preferred in the context of the present invention that the delimited region of the shaped bodies is in the form of a separate layer, an envelope or individual inserts, the design as a multilayer shaped body being particularly preferred. Thus, the individual phases of the molded body can have different spatial shapes within the scope of the present invention. As already explained, the simplest possible implementation is in two- or multi-layer tablets, each layer of the shaped body representing a phase. However, it is also possible, according to the invention, to produce multiphase molded articles in which individual phases have the form of inclusions in (another) phase (s). In addition to so-called "ring core tablets", coated tablets or combinations of the above-mentioned embodiments are possible, for example. Examples of multi-phase moldings can be found in the illustrations in EP-A-0 055 100 (Jeyes), which describes toilet cleaning blocks. The currently most widespread spatial form of multi-phase tablets is the two- or multi-layer tablet.

In addition to the ingredients mentioned, the detergent tablets according to the invention may contain further ingredients, the amounts of which depend on the intended use of the tablets. So are especially fabrics from the 13

Groups of surfactants, builders and polymers are suitable for use in the detergent tablets according to the invention. The specialist will also have no difficulty in selecting the individual components and their quantities. For example, a universal detergent tablet will contain higher amounts of surfactant (s), while bleach tablets may even be dispensed with. The amount of builder (s) used also varies depending on the intended use.

The detergent tablets according to the invention can contain all of the builders customarily used in detergents and cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.

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

Amorphous sodium silicates with a module Na ₂ O: SiO from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which 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 / compacting or by overdrying. In the context of this invention, the term "amoφh" is also understood to mean "roentgenamoφh". This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more 11,

Maxima of the scattered X-rays which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be integrated in such a way that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. 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

nNa ₂ O ^■ (ln) K ₂ O 'Al ₂ O ₃ ' (2 - 2.5) SiO ₂ "(3.5 - 5.5) H ₂ O

can be described. The zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be veφressed, usually both ways of incoφoration of the zeolite in 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. 15

It goes without saying that the generally known phosphates are also used as

Builder substances possible if such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

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

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.

Anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these can be used in the detergent tablets according to the invention. Mixtures of anionic and nonionic surfactants are preferred from an application point of view. The total surfactant content of the molded article is from 5 to 60% by weight, based on the weight of the molded article, with surfactant contents above 15% by weight being preferred.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are preferably C _9- thereby ι ₃ - alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C _12-18 monoolefins with a terminal 6 or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates, which are of C _l2 ι ₈ alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization obtained. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

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

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid half esters of the C ₂ -C _{18 fatty} alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₀ -C ₂ o- Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. The Cj ₂ - Cj ₆ alkyl sulfates and C ₁₂ -Ci ₅ alkyl sulfates and C _{] 4} -Ci ₅ alkyl sulfates are preferred from the point of view of washing technology. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with 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.

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 .n alcohols ff with an average of 3.5 moles of ethylene oxide (EO) or Cπ-is 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. used.

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- ] ₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

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

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

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear 13 and methyl-branched radicals in the mixture, as usually in

Oxo alcohol residues are present. 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. Preferred ethoxylated alcohols include, for example, Cι ι _{2- 4} - alcohols with 3 EO or 4 EO, C _9-1 alcohol with 7 EO, C _13- ι ₅ alcohols containing 3 EO, 5 EO,

7 EO or 8 EO, Cι -ι ₈ - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12- ι ₄ alcohol with 3 EO and Cι _2- ι ₈ alcohol with 5 EO . The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R has a primary straight-chain or methyl-branched radical, in particular in the 2-position methyl-branched aliphatic radical

8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as 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. 13

Also 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 may 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 the RCO for an aliphatic acyl radical having 6 to 22 carbon atoms. R ^ represents hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] stands 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 ²

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 oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical, the alkyl chain of which has at least two Hydroxyl groups is substituted, or alkoxylated, preferably ethoxylated or propylated derivatives of this radical.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

For the purposes of the present invention, detergent tablets are preferred which contain anionic (s) and nonionic (s) surfactant (s), with application technology advantages being able to result from certain quantitative ratios in which the individual classes of surfactants are used.

For example, detergent tablets are particularly preferred in which the ratio of anionic surfactant (s) to nonionic surfactant (s) is between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2.

From an application point of view, it can be advantageous if certain classes of surfactant are present in some phases of the detergent tablets or in the entire molded article, i.e. in all phases, are not included. A further important embodiment of the present invention therefore provides that at least one phase of the molded article is free from nonionic surfactants.

Conversely, a positive effect can also be achieved by the content of individual phases or the entire molded article, ie all phases, of certain surfactants. The introduction of the alkyl polyglycosides described above has proven to be advantageous, so that detergent tablets are preferred in which at least one phase of the tablets contains alkyl polyglycosides. Similar to the nonionic surfactants, the omission of anionic surfactants from individual or all phases can result in detergent tablets which are better suited for certain fields of application. It is therefore also conceivable within the scope of the present invention for detergent tablets to be made in which at least one phase of the tablet is free from anionic surfactants.

In order to facilitate the disintegration of highly compressed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt ^' "Textbook of pharmaceutical technology ^" "(6th edition, 1987, p. 182-184), tablet disintegrants or disintegrants are understood as auxiliary substances which are suitable for the rapid disintegration of tablets in water or gastric juice and release of the pharmaceuticals in an absorbable form.

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

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

Disintegration agents based on cellulose are used as preferred disintegration agents in the context of the present invention, so that preferred detergent tablets form such a disintegration agent based on cellulose in zt

Contain amounts of 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ Hι ₀ O) _n and, formally speaking, is a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound by an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.

The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be treated. Detergent tablets containing 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 PCT / EP 98/1203 (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.

Detergent tablets, which additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular of 4 to 6 wt .-%, each based on the molded body weight, are particularly preferred in the context of the present invention.

In addition to the above-mentioned components of bleach activator, bleaching agent, oxidation-sensitive substance, surfactant, builder and disintegration aid, the detergent tablets according to the invention can contain further ingredients customary in detergents and cleaning agents from the group of foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

In addition, the detergent tablets can also contain components that 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 from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

The production of washable and cleaning-active molded articles takes place by applying pressure to a mixture to be veφressing, which is located in the cavity of a press. In the simplest case of molded article production, which is referred to simply as tableting below, the mixture to be tabletted is pressed directly, ie without prior granulation. The advantages of this so-called direct tableting are its simple and inexpensive application, since no further process steps and consequently no further plants are required. However, these advantages are offset by disadvantages. For example, a powder mixture that is to be tabletted directly must have sufficient plastic deformability and have good flow properties; furthermore, it must not show any tendency to segregate during storage, transport and filling of the die. These three requirements are extremely difficult to master with many substance mixtures, so that direct tableting is not often used, particularly in the production of detergent tablets. The usual way of producing detergent tablets is therefore based on powdery components (“primary particles”) which are agglomerated or granulated by suitable processes to form secondary particles with a larger particle diameter. These granules or mixtures of different granules are then mixed with individual powdery additives and fed to the tableting. Each For example, after designing the phases of the multi-phase detergent and detergent tablets, the die is gradually filled with different premixes. In the manufacture of multi-layer tablets, a slight application of pressure between the pre-mix filling can have advantages for the next layer. In the production of ring-core shaped bodies or coated tablets, such pre-evaporation with shaping is almost indispensable.

Preferred detergent tablets in the context of the present invention are obtained by squeezing particulate premixes from at least one surfactant-containing granulate and at least one subsequently admixed powdery component. The surfactant-containing granules can be produced using conventional granulation processes such as mixer and plate granulation, fluidized bed granulation, extrusion, pelletizing or compacting. It is advantageous for the later detergent tablets if the premixes to be veφressen have a bulk density that comes close to the usual compact detergent. In particular, it is preferred that the premix to be veφress has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular above 700 g / 1. Another advantage can result from a narrower particle size distribution of the surfactant granules used. In the context of the present invention, detergent tablets are preferred in which the granules have particle sizes between 10 and 4000 μm, preferably between 100 and 2000 μm and in particular between 600 and 1400 μm.

Before the particulate premix is pressed into detergent tablets, the premix can be "powdered" with finely divided surface treatment agents. This can be of advantage for the quality and physical properties of both the premix (storage, molding) as well as the finished detergent tablets. Finely divided powdering agents are well known in the art, mostly zeolites, silicates or other inorganic salts being used. However, the premix is preferably “powdered” with finely divided zeolite, zeolites of the faujasite type being preferred. As part of the In the present invention, the term "faujasite-type zeolite" denotes all three zeolites which form the faujasite subgroup of zeolite structure group 4 (see Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London) , Sydney, Toronto, 1974, page 92). In addition to the zeolite X, zeolite Y and faujasite and mixtures of these compounds can also be used, the pure zeolite X being preferred.

Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which do not necessarily have to belong to the zeolite structural group 4, can be used as powdering agents, it being advantageous if at least 50% by weight of the powdering agent from a zeolite of faujasite -Type exist.

In the context of the present invention, detergent tablets are preferred which consist of a particulate premix which contains granular components and subsequently admixed powdery substances, the or one of the subsequently admixed powdery components being a zeolite of the faujasite type with particle sizes below 100 μm, is preferably below 10 μm and in particular below 5 μm and is at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be treated.

The finely divided processing components with the above-mentioned particle sizes can be dry mixed into the premix to be treated. However, it is also possible and preferred to "stick" them to the surface of the coarser particles by adding small amounts of liquid substances. These powdering processes are widely described in the prior art and are familiar to the person skilled in the art. Non-ionic surfactants or aqueous solutions of surfactants or other detergent ingredients can be used as liquid components that are suitable for promoting the adhesion of the powdering agents. In the context of the present invention, it is preferred to use perfume as the liquid adhesion promoter between the finely divided powdering agent and the coarse-grained particles. The molded articles according to the invention are first produced by dry mixing the constituents of the individual phases, which can be wholly or partially pre-granulated, and then providing information, in particular compresses to tablets, whereby conventional methods for producing multi-phase molded articles can be used. To produce the multi-phase molded bodies according to the invention, the premixes are compressed in a so-called die between two punches to form a solid compressed product. This process, which is briefly referred to below as tabletting, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.

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 stamp, with the pressing pressure being active only by the upper or lower die. Lower stamp, but can also be built up by both stamps. The die table and the stamps move about a common vertical axis, the stamps being used with the aid of rail-like curved tracks during the rotation IS in the positions for filling, compression, plastic deformation and discharge. Wherever a particularly serious lifting or lowering of the punches is required (filling, compacting, ejecting), these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks. The die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premixes. The pressing pressure on the respective premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure building up by the rolling of the punch shaft heads past adjustable pressure rollers.

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

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 made in a predetermined spatial shape and size, whereby they always consist of several phases, ie layers, inclusions or cores and rings. Practically all of them come in useful form manageable configurations into consideration, for example, the design as a table, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to 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. Of course, the detergent tablets can also be used without problems using a dosing aid.

Another preferred multi-phase molded body that can be produced has a plate-like or panel-like structure with alternately thick long and thin short segments, so that individual segments of this "multi-phase lock" are broken off at the predetermined breaking points, which represent the short thin segments and can be entered into the machine. This principle of the "bar-shaped" shaped body detergent can also be used in other geometric shapes, for example vertically standing triangles, which are only along one side on one side 30 are connected to be realized. Here it lends itself for optical reasons

To form a triangular base, which connects the individual segments with one another, as one phase, while the triangle tip forms the second phase. Different coloring of both phases is particularly attractive in this embodiment. 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.

31 examples

By pressing particulate premixes, two-phase detergent tablets were produced, which were in the form of a two-layer tablet. By selecting the relevant premixes, one of the two phases was colored blue, while the other phase remained white. The blue coloring was achieved on the one hand by coloring a TAED-containing phase (VI, V2), the TAED being additionally colored blue in the case of comparative example 2. In example El according to the invention, the phase containing bleach was colored, while the phase which contained the bleach activator remains white. The composition of the detergent tablets, based in each case on the respective phase, is shown in Table 1.

Table 1: detergent tablets: Composition [wt ^'/ o]

VI V2 El blue white tab blue white tab blue white tab phase phase phase phase phase phase

Phase fraction [%] 23.3 76.6 100 23.3 76.6 100 28.0 72.0 100

Na percarbonate - 42.0 32.20 - 42.0 32.20 42.0 27.0 31.20

TAED 50.0 - 11.67 - - - - 13.5 9.73

TAED * - - - 50.0 - 11.67 - - -

Na-SKS6 5.84 5.84 5.84 5.84 3.49 4.04 5.84 3.49 4.15

NaHCO ₃ 16.0 26.16 23.79 16.0 28.51 25.59 24.33 30.0 28.41

Citric acid 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0

PEG 4000 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5

Disintegrant ** 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5

PEG 400 0.25-0.06 0.25-0.06 0.25-0.07

Enzyme 1.88-0.44 1.88-0.44 1.55-0.43

Supranol * Blue 0.03 - 0.01 0.03 - 0.01 0.03 - 0.01

TAED colored with 0.03% by weight Supranol ^® Blue GLW (anthraquinone dye, trademark of Bayer AG 3t

** compacted cellulose (particle size: 90% by weight> 400 μm) PEG: polyethylene glycol with molecular weights of -4000 or -400 gmol ^"1

The contact dye / bleach activator is therefore most intense in VI and V2, the contact dye bleach is most intense in El.

The tablets produced were individually packed in polypropylene bags (“flow pack”) and stored at 30 ° C. for 4 weeks. After storage, the blue phases of Comparative Examples VI and V2 show clear and uneven bleaching and white spots, while El shows a homogeneous blue phase without significant brightening.

The color retention is significantly better in the example according to the invention than in the comparative examples.

Claims

33 claims

1. Two-phase or multi-phase detergent and cleaning agent molded body made of compressed particulate detergent and cleaning agent, comprising builders (s), bleach, bleach activator (s) and optionally further detergent and cleaning agent components, characterized in that the bleach activator (s) ) is / are spatially separated from oxidation-sensitive substances in a defined region of the molded body.

2. Detergent and body form according to claim 1, characterized in that the delimited region contains the bleach activator and other non-oxidation-sensitive ingredients of detergents and cleaning agents.

3. Detergent and shaped body according to one of claims 1 or 2, characterized in that the defined region contains the bleach activator and one or more substances from the group of builders, cobuilders, surfactants, binders, disintegration aids and complexing agents.

4. Detergent and shaped article according to one of claims 1 to 3, characterized in that the defined region is free from bleach (s).

5. Detergent and molded article according to one of claims 1 to 4, characterized in that bleach and oxidation-sensitive substance (s) are present together in a region of the molded article.

6. Washing and cleaning agent shaped body according to one of claims 1 to 5, characterized in that the shaped body contains one or more substances from the group of dyes, optical brighteners, fragrances and enzymes as oxidation-sensitive substances.

7. washing and cleaning agent shaped body according to one of claims 1 to 6, characterized in that tetraacetylethylene diamine is used as the bleach activator.

8. washing and cleaning agent shaped body according to one of claims 1 to 7, characterized in that the delimited region of the tablet has the shape of a separate layer, an envelope or individual inserts.

9. Detergent form according to one of claims 1 to 8, characterized in that it additionally contains a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight. %, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the molded body weight.