WO2000058435A1

WO2000058435A1 - Tablet containing a builder

Info

Publication number: WO2000058435A1
Application number: PCT/EP2000/002335
Authority: WO
Inventors: Mike PÜTZ; Harald Volk; Peter Jeschke
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1999-03-25
Filing date: 2000-03-16
Publication date: 2000-10-05
Also published as: AU3290300A; CA2302141A1

Abstract

The invention relates to tablets containing a builder as well as an additive which contains crystalline layered sodium silicate and a (co) polymere polycarboxylic acid. Said tablets can be prepared without the use of additional tabletting aids or additional disintegrating agents and still present a dissolution behaviour comparable to that of tablets to which such components are individually added but which also contain tabletting aids and disintegrating agents. Such tablets furthermore present comparable hardness with lower compacting pressures. This makes it possible notably for water-softening tablets to contain particularly large quantities of active substances since there is little need for additives which do not have an accessory water-softening function.

Description

"Builder-containing tablet"

The invention relates to builder-containing tablets which contain crystalline layered silicates and are suitable for washing or cleaning or for water softening.

Tablets have a number of advantages over powdered agents, such as simple dosing and low packaging volume requirements. Problems arise, however, in that relatively high compression pressures have to be used to achieve adequate dimensional stability and fracture resistance when pressing the powdery constituents. Because of the high degree of compaction, such tablets often have inadequate disintegration and dissolving properties during use. In order to get such problems under control, tableting aids are usually added to the actual active substances. These are, for example, polyethylene glycols, typically with molar masses of 1000 to 6000 g / mol, which usually make up 2 to 6% by weight of the total tablet formulation. So-called disintegrants are also added to enable the tablets to be dissolved quickly. Such disintegrants, which are usually used in amounts of 3 to 30% by weight of the tablets, are, for example, microcrystalline cellulose or swellable synthetic polymers such as polyvinylpyrrolidone. Both the tabletting aids and the disintegrants are additives which do not themselves contribute to the action of the respective tableted agents. Therefore, these additives reduce the active ingredient content of the tablets.

Accordingly, there is still a need for active ingredients which simultaneously act as tableting aids or disintegrants and thus make the use of special tableting aids and disintegrants superfluous.

It has now been found that in tablets which contain crystalline layered silicates and certain copolymers in the form of a suitably prepared compound, manage without the use of such additional aids and yet can be produced at relatively low compression pressures while maintaining their fracture resistance. The tablets also have excellent loose behavior without the use of separate disintegrants

Tablets which contain crystalline layered silicates have long been known per se. Patent application WO 95/21908 already describes tablets which are amorphous, partially stable and / or crystalline layered sodium silicates of the formula

Na ₂ Sι _x O _{2x + 1} yH ₂ O

Contained in amounts of 2 to 100% by weight, where x is a number from 1, 9 to 4 and y is a number from 0 to 20. A water softening tablet described in the application contains, for example, 20 to 80% by weight of the crystalline layered silicates, and if appropriate up to 80% by weight of zeolite and / or phosphate, possibly up to 50% by weight of polycarboxylate, up to 15% by weight of polymeric polycarboxylates and up to 30% by weight of surfactants The tablet specified in an example contains methylhydroxypropyl cellulose as disintegrant

EP-A-812 808 discloses water softener tablets which can contain up to 45% by weight of crystalline layered silicates, in addition they contain a polyfunctional carboxylic acid or its salt, carbonate and / or bicarbonate and polymer. The tablets further contain 1 to 6 % By weight of binder and up to 15% by weight of disintegrant

It has now been found that tablets which, in addition to other ingredients, contain a granular additive which contains a crystalline layered silicate and (co) polymeric polycarboxylic acid as essential constituents, can also be prepared without the use of additional tabletting aids or disintegrants at moderate compression pressures and are readily soluble are

Accordingly, a first subject of the invention are tablets which contain builder substances and optionally further ingredients of washing or cleaning agents, or phases of such tablets which are characterized in that they contain a powdery to granular additive which as essential components is a crystalline layered silicate of the general formula (I)

NaMSι _x O _{2x + 1} y H ₂ O (I),

where M is sodium or hydrogen, x is a number from 1.9 to 22 and y is a number from 0 to 33, and contains (co) polymeric polycarboxylic acid, but the tablets do not contain any additional disintegrant which has no builder action, and contain a maximum of 2% by weight of additional tabletting aid

Such crystalline layered silicates of the formula (I) are sold by Claπant GmbH (Germany) under the trade name Na-SKS. Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ xH ₂ O, Kenyait), Na are to be mentioned here, for example -SKS-2 (Na ₂ Sι ₁₄ O ₂₉ xH ₂ O, Magadnt), Na-SKS-3 (Na ₂ Sι ₈ O ₁₇ xH ₂ O) or Na-SKS-4 (Na ₂ Sι ₄ O ₉ xH ₂ O, makatite)

Agents which contain crystalline phyllosilicates of the formula (I) in which x is 2 are particularly suitable for the purposes of the present invention. Of these, Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na are particularly suitable -SKS-7 (ß-Na ₂ Sι ₂ O ₅ , Natrosi t), Na-SKS-9 (NaHSι ₂ O ₅ H ₂ O), Na-SKS-10 (NaHSι ₂ O ₅ 3H ₂ O, Kanemit), Na-SKS-11 (t-Na ₂ Sι ₂ O ₅ ) and Na-SKS-13 (NaHSι ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Sι ₂ O ₅ ) An overview of crystalline layered silicates For example, the articles published in "Hoechst High Chem Magazin 14/1993" on pages 33 - 38 and in "Seifen-Ole-Fette-Wwachs, 116 vol., No. 20/1990" on pages 805 - 808 are at least inventive some of the crystalline layered silicates of the formula (I) are introduced into the tablets according to the invention via the builder additive used in the invention. In a preferred embodiment of the invention, the crystalline layered silicates of the formula (I) a introduced exclusively into the tablets according to the invention via the builder additive used according to the invention. The tablets advantageously contain the crystalline layered silicate of the formula (I) in amounts of 2 to at most 50% by weight, preferably in amounts of 5 to 45% by weight and in particular in amounts of 10 to 40% by weight

In the context of the present invention, a (co) polymeric polycarboxylic acid is understood to mean a homopolymer or copolymer which is not or only partially neutralized. These include the homopolymers of acrylic acid or methacrylic acid or their copolymers with further ethylenically unsaturated monomers such as, for example Acrolein, dimethylacrylic acid, ethylacrylic acid, vinyl acetic acid, allylacetic acid, maleic acid, fumaric acid, itaconic acid, meth (-allylsulfonic acid), vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid as well as monomers containing phosphorus groups such as vinylphosphonic acid, allylphosphoric acid and acrylate methacrylate, acrylate (meth) acrylate, acrylate (meth) acrylate, acrylate (meth) acrylate, Allyl alcohol sulfates and allyl alcohol phosphates. Such polymers are described, for example, in German patent applications DE-A-23 57 036, DE-A-44 39 978 and European patent applications EP-A-0 075 820 or EP-A-0 451 508.

Preferred (co) polymers have an average molecular weight of 1000 to 100000 g / mol, preferably of 2000 to 75000 g / mol and in particular of 2000 to 35000 g / mol. The degree of neutralization of the acid groups is advantageously from 0 to 90%, preferably from 10 to 80% and in particular from 30 to 70%.

Suitable polymers include above all homopolymers of acrylic acid and copolymers of (meth) acrylic acid with maleic acid or maleic anhydride.

Further suitable copolymers are derived from terpolymers which are obtained by polymerizing 10 to 70% by weight of monoethylenically unsaturated dicarboxylic acids with 4 to 8 C atoms or salts thereof, 20 to 85% by weight of monoethylenically unsaturated monocarboxylic acids with 3 to 10 C atoms or their salts, 1 to 50% by weight of monounsaturated monomers which release hydroxyl groups on the polymer chain after saponification, and 0 to 10% by weight of further free-radically copolymerizable monomers. For the application according to the invention, saponification of the monounsaturated monomers which release a hydroxyl group on the polymer chain after saponification is preferred in an acidic environment. Products of the type mentioned above are described in German patent applications DE-A-43 00 772 and DE-A-195 16 957 and in WO-A-94/15978.

Graft polymers of monosaccharides, oligosaccharides, polysaccharides and modified polysaccharides are also suitable, as are described in German patent applications DE-A-40 03 172 and DE-A-44 15 623. The graft polymers with proteins of animal or vegetable origin, in particular with modified proteins, disclosed in the European patent application are also well suited. From the group of graft copolymers, copolymers of sugar and other polyhydroxy compounds and a monomer mixture of the following composition are preferably used: 45 to 96% by weight of monoethylenically unsaturated C ₃ to C ₁₀ monocarboxylic acid or mixtures of C ₃ to C ₁₀ monocarboxylic acids and / or their salts with monovalent cations, monomers containing 4 to 55% by weight of monoethylenically unsaturated monosulfonic acid groups, monoethylenically unsaturated sulfuric acid esters, vinylphosphonic acid and / or the salts of these acids with monovalent cations and 0 to 30% by weight of water-soluble, monoethylenically unsaturated compounds, which are modified with 2 to 50 moles of alkylene oxide per mole of monoethylenically unsaturated compound. Such compounds are described in DE-A-42 21 381 and in DE-A-43 43 993.

Other suitable polymers are polyaspartic acids or their derivatives in non-neutralized or only partially neutralized form. The polyaspartic acids are usually obtained in the form of their alkali metal or ammonium salts. The products which are not or only partially neutralized can be obtained from this by adding appropriate amounts of organic or inorganic acids and, if appropriate, separating off the salts formed.

Such products can also be obtained by the thermal reaction of maleic acid and ammonia or by the condensation of aspartic acid and the subsequent hydrolysis of the polysuccinimide formed. The production of such products is described, for example, in DE-A-36 26 672, DE-A-43 07 114, DE-A-44 27 287, EP-A-0 612 784, EP-A-0 644 257 and WO -A-92/14753.

Graft polymers of acrylic acid, methacrylic acid, maleic acid and other ethylenically unsaturated monomers on salts of polyaspartic acid, as are usually obtained in the previously described hydrolysis of the polysuccinimide, are also particularly suitable. The otherwise necessary addition of acid to produce the only partially neutralized form of polyaspartic acid can be dispensed with here. The amount of polyaspartate is usually chosen so that the degree of neutralization of all carboxyl groups incorporated in the polymer does not exceed 80%, preferably 60%. Products of the type mentioned are described in more detail in international patent application WO-A-94/01486.

The amounts in which the (co) polymeric polycarboxylates which are not or only partially neutralized are contained in the agents according to the invention are determined by the content of the builder additives used according to the invention and their content of these polymers.

The builder additive used according to the invention contains the crystalline layered silicate of the formula (I) and the (co) polymeric polycarboxylic acid preferably in weight ratios of (40 to 1): 1, in particular of (20 to 2): 1, ratios of 7 : 1 to about 3: 1, based in each case on the anhydrously calculated active substances, can be particularly advantageous. The water content of the builder additives used according to the invention is preferably 4 to 20% by weight, the upper meaningful value for the water content being made dependent on the builder additive still being stable even after storage at elevated temperatures of, for example, 40 ° C. and should be free-flowing and should not clump together. It has been shown that the lower value for the water content influences the dissolving behavior of the builder additive. For reasons of the higher dissolution rate of the builder additive, additives are therefore preferred which have 5 to 15% by weight of water and in particular 7 to 12% by weight of water. The water content is determined at a temperature of 140 ° C and a duration of 4 hours.

The builder additives used according to the invention can be prepared by simply bringing the crystalline layered silicate of the formula (I) into contact with an aqueous solution, preferably a concentrated aqueous solution of the (co) polymeric polycarboxylic acid and, if appropriate, then drying to the desired water content. Usual mixing and granulating devices, such as the ploughshare mixer from Lödige or a Schugi mixer or an Eirich mixer or a Lödige recycler CB 30, as well as other apparatuses known to the person skilled in the art, which in particular allow a liquid to be sprayed onto a solid, are also suitable Fluidized bed apparatus. The polymer solution serves as an agglomeration aid. It is assumed that in the reaction of the crystalline layered sodium silicate of the formula (I) with the acidic polymer, in particular at pH values of the polymer solution used of less than 4, part of the sodium ions of the silicate is replaced by protons. However, the silicate framework with its layer structure and the majority of the sodium ions remain unchanged. This leads to the fact that the builder additives used according to the invention have only a slightly reduced initial alkalinity, but a significantly lower residual alkalinity compared to the pure crystalline layered silicate of the formula (I). The residual alkalinity can be adjusted accordingly by the polymeric acid content of the additives can be set. The builder additive can therefore be used as a buffer substance in machine dishwashing detergents.

The builder additives can contain large amounts of (co) polymeric polycarboxylic acid, with amounts between 2 and 40% by weight being preferred and amounts between 5 and 30% by weight being particularly preferred and amounts between 10 and 25% by weight entirely are particularly preferred. The content of the crystalline layered silicates of the formula (I) in the builder additives is preferably 50 to 90% by weight, particularly preferably 60 to 90% by weight and very particularly preferably 65 to 85% by weight. The calcium binding capacity of the additives is preferably above 185 mg CaCO ₃ / g. The pH of a 0.1% by weight aqueous solution is preferably above 10 but below 12 at 20.degree. C. The bulk density of the additives used according to the invention varies depending on the type of preparation and is usually in the range from above 400 to about 700 g / l. While pure crystalline layered silicate of the formula (I) such as SKS6® is usually obtained in very fine particles and also has large amounts of dust constituents, the builder additive used according to the invention is a coarser powder to agglomerate / granulate, which is more finely divided when it is produced in the fluidized bed and coarser when it was made, for example, in a high speed mixer. Coarse-grained additives, for example, have an average particle size (d ₅₀ ) of approximately 450 to 900 μm, while more finely divided additives have an average particle size (d ₅₀ ) of between approximately 280 and 330 μm. But even with the fine-particle additives, the dust content is significantly lower than with the commercially available pure crystalline layered silicates of the formula (I), in particular than with SKS6®.

The content of these builder additives in the tablets according to the invention can be varied within a wide range and depends on the desired function of the tablets. Typical levels of these builder additives are> approximately 20-60% by weight, levels of 25-55% by weight and in particular up to 45% by weight being preferred.

Disintegrants which, according to the invention, should not be contained in the tablets or the tablet phases are auxiliary substances which have a positive influence on the dissolving or disintegrating process in the aqueous application phase, but which otherwise have no effect in the sense of the tableted agent as a builder. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182-184), tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form. These substances, which are also referred to as "explosives" due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling) and on the other hand a pressure can be generated by the release of gases, which breaks the tablet into smaller particles disintegrates.

Well-known disintegrants are, for example, carbonate / citric acid systems, although other organic acids can also be used. However, in addition to the explosive action, these systems have a builder action and are therefore expressly not among the disintegrants which have no action in the sense of the tableted agent, and may accordingly be present in the tablets or tablet phases according to the invention. Preferred embodiments of the invention even contain large amounts of organic carboxylic acids and carbonates. These preferred embodiments are water softening tablets, which are described in detail below.

Swelling disintegrants which should not be included according to the invention 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.

In particular, the tablets or tablet phases according to the invention should not contain any cellulose-based disintegrants. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _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. In the context of the present invention, cellulose-based disintegrants also mean cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products 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, carboxymethyicellulose (CMC), cellulose esters and ethers and aminocelluloses. Such compounds do indeed have effects in the sense of the tableted agent, but in particular if the agent is a laundry detergent, the tablets or tablet phases according to the invention are, however, preferably not present. Microcrystalline cellulose can be mentioned as a further disintegrant based on cellulose 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.

Tableting aids, which are contained in the tablets or tablet phases according to the invention to a maximum of 2% by weight, are substances which ensure better cohesion of the individual powdery or granular constituents and thus contribute to the stability of the tablet.

The tablets or tablet phases preferably contain only dust binders as tableting aids. Short-chain polyethylene glycols with molar masses less than 800 g / mol and paraffins, in particular paraffin oils, are to be mentioned here in particular.

The undesirable tabletting aids include, in particular, polyethylene glycols with molecular weights in the range from 1000 to 10,000 g / mol, starch, cellulose, starch and cellulose derivatives, but also gelatin and polyvinylpyrrolidone. Some detergent ingredients, such as certain liquid to pasty nonionic surfactants, also act as tableting aids. These can be contained in tablets according to the invention, if the intended action of the tablets as a detergent so requires However, they do not require tableting aids. Preferred embodiments of the invention are therefore also free from such nonionic surfactants.

Tablets or tablet phases with these ingredients can be pressed at moderate pressing presses and still show high edge abrasion resistance. The tablets are readily soluble, the solubility of the tablets known from the prior art, which can contain both large amounts of tableting aids and the disintegrants described above, at least comparable. In contrast to these, the tablets or tablet phases according to the invention allow a very high active ingredient content, since it is precisely these disintegrants or the described tableting aids that are contained only in very small amounts.

In addition to the ingredients already described, the tablets can contain other ingredients. These can preferably be substances which have (co) builder properties. The tablets may also contain the builders already listed, crystalline layered sodium silicates and polymeric polycarboxylic acids, in addition to the additive, and also in separate form. In particular, this can be the case if the tablets have several “phases” or “layers” which are composed in themselves homogeneously. In the case of such multi-phase tablets, it can be preferred if the different phases, which can contain different active substances, dissolve at different speeds. Accordingly, it may be preferred to use the additive only in one phase according to the invention, while the other phase contains no or another disintegrant. However, it may be desirable if the other phase (s) contain the same builder substances, but in a form that does not have the explosive effect of the additive.

The tablets according to the invention can also contain other builders and cobuilder substances:

Other builder substances are primarily aluminosilicates and phosphates. The aluminosilicate is preferably finely crystalline, synthetic and bound water-containing zeolites, in particular Zeolite A, X and / or P. As zeolite P, for example, zeolite MAP ^(R) (commercial product from Crosfield) is used. However, zeolite Y and mixtures of A, X, Y and / or P are also suitable. Such a mixture of zeolite A and zeolite X is commercially available, for example, under the name Vegobond AX® (from Condea Augusta SpA). The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. 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.

The possible builder substances also include 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, which are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can have been caused in various ways, for example by surface treatment, compounding, compaction / 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 provide 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. Ins compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

Of course, it is also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. Their content is generally not more than 25% by weight, preferably not more than 20% by weight, based in each case on the finished composition. In some cases, it has been shown that tripolyphosphates in particular, even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing ability. It may also be preferred to use phosphate in the form of the phosphate compound described in the earlier German patent application DE 198 59 807.6.

In addition to the polymeric polycarboxylic acids used according to the invention, usable organic builders are, for example, also the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), 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. The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Other suitable builder substances are polyacetals, which are produced by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as in the European patent application EP-A-0 280 223 can be obtained. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders. Ethylenediamine N, ^{N'-disuccinate} (EDDS), whose synthesis is described for example in US 3,158,615, preferably in the form of its sodium or magnesium salts. Also preferred in this connection are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP-A-0 150 930 and Japanese Patent Application JP 93/339896 become. Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight.

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1 J-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP) and diethylene triamine pentamethylene phosphonate

(DTPMP) and their higher homologues in question. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it is preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as cobuilders.

In a preferred embodiment of the invention, the tablets are water softening tablets. Such tablets contain a very high proportion of builder substances. Preferred water softener tablets consist of 60 to 100% by weight, in particularly advantageous embodiments even more than 80% by weight, of builders and cobuilder substances. Although active substance contents of more than 90% by weight, in particular more than 95% by weight, are also preferred in these builder tablets, these can only be achieved with difficulty since the individual ingredients also introduce water into the tablets.

Those water softening tablets which contain a carbonate / polycarboxylic acid system already described above are particularly preferred. Such water softening systems react bubbly with each other when they come into contact with water, thus contributing to the disintegration of the tablets, softening the water and also dissolving without residue. Any alkali carbonate, bicarbonate or sesquicarbonate, alone or in mixtures with others, can be used as the carbonate. However, the use of bi- and sesquicarbonates is particularly preferred. In this context, polycarboxylic acids are understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof are particularly preferred. All or some of these acids can also be used in the form of their salts. Preferred water softener tablets contain 10 to 40% by weight, in particular 15 to 30% by weight, of such polycarboxylic acids or Polycarboxylic acid salts and 10 to 50% by weight, in particular 20 to 45% by weight, of alkali carbonate, bicarbonate or sesquicarbonate.

In another embodiment of the invention, the tablets are detergent tablets.

Such tablets can preferably contain surface-active substances. These surface-active substances come from the group of anionic, nonionic, zwitterionic or cationic surfactants, anionic surfactants being clearly preferred for economic reasons and because of their range of services.

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, as obtained, for example, from C _12-18 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products, into consideration. Alkanesulfonates which are derived from C ₁₂ are also suitable. ₁₈ -alkanes can be obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. 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 sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. The 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 fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of 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. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ 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 ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol ethylene oxide (EO) or C ₁₂ . ₁₈ fatty alcohols with 1 to 4 EO are suitable.

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

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

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.

When selecting the anionic surfactants, there are no basic conditions to be observed that prevent freedom of formulation. The preferred anionic surfactants to be used in detergent tablets are the alkylbenzenesulfonates and fatty alcohol sulfates, preferred detergent tablets being 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight of fatty alcohol sulfate (s) on the weight of the detergent tablets.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ . ₁₄ - alcohols with 3 EO or 4 EO, C ^ 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as them are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Usable alkyl polyglycosides 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 C atoms, and G is the Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.

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

The tablets can preferably contain alkylpolyglycosides, with APG contents of more than 0.2% by weight, based on the entire molded body, being preferred. Particularly preferred detergent tablets contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.

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

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

R-CO-N- [Z] (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)

R ¹ -OR ²

I 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 aikyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic aikyl radical or Aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, where C ₁ . ₄ -alkyl or phenyl radicals are preferred and [Z] stands for a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of this radical.

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

The surfactant content of detergent tablets is usually between 10 and 40% by weight, preferably between 12.5 and 30% by weight and in particular between 15 and 25% by weight, bleach tablets and water softener tablets are usually free of surfactants.

In addition to the builder constituents and surfactants mentioned, the tablets according to the invention can additionally contain one or more substances from the groups of bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors and Color transfer inhibitors included. These substances are described below.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, irrespective of which other ingredients are contained in the shaped bodies. In principle, bleaches from the group of organic bleaches can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoxy acid panoic acid (PAP) )], o- Carboxybenzämidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperocysebacic acid, diperoxydodiacodoxydiperylpiperyldiacyldiperoxybutyldiacid, 4-diperoxybutyldiacid-2-diperoxybutyldiacid-2-diperoxybutyldiacid, , N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

In order to achieve an improved bleaching effect during washing or cleaning at temperatures of 60 ° C. and below, bleach activators can be incorporated into the tablets according to the invention. 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 multiply acylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetyloxy and 2,5-diacetyloxy and 2,5-glycolacetyl, ethylene glycol 2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the tablets. 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.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Bakery terienstämmeri or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus, enzymatic active ingredients obtained. 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 and / or embedded in coating substances in order 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. The most commonly used enzymes include lipases, amylases, cellulases and proteases. Preferred proteases are e.g. B. BLAP®140 from Biozym, Optimase®-M-440 and Opticlean®-M-250 from Solvay Enzymes; Maxacal®CX and Maxapem® or Esperase® from Gist Brocades or Savinase® from Novo. Particularly suitable cellulases and lipases are Celluzym® 0.7 T and Lipolase® 30 T from Novo Nordisk. Duramyl® and Termamyl® 60 T and Termamyl® 90 T from Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades find particular use as amylases. Other enzymes can also be used.

As optical brighteners, the tablets can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-aniiino-4-morphoiino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly structured compounds 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 aicalis salts of 4,4'-bis (2-suifostyryl) 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.

Dyes and fragrances are added to the moldings according to the invention in order to improve the aesthetic impression of the products and to the consumer in addition to the Softness performance to provide a visually and sensorially "typical and distinctive" 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, allyl cyclohexyl benzylatepylpionate, allyl cyclohexyl propyl pionate. The ethers include, for example, benzylethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones include, for example, the jonones, Is-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 colorant content of the tablets according to the invention is usually less than 0.01% by weight, while fragrances can make up 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 by 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. In order to improve the aesthetic impression of the agents 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 towards textile fibers in order not to dye them. Another object of the present invention is a process for the production of tablets containing builder substances and possibly other ingredients of detergents or cleaning agents, or phases of such tablets, characterized in that a powdery to granular additive, which as a constituent components is a crystalline layered Silicate of the general formula (I)

NaMSi _x O _{2x + 1} y H ₂ O (1),

where M represents sodium or hydrogen, x is a number from 1.9 to 2.2 and y is a number from 0 to 33, and contains (co) polymeric polycarboxylic acid, with further builder substances and, if appropriate, ingredients of washing and cleaning agents is mixed into a premix and this premix is pressed into tablets or phases of tablets without the addition of additional disintegrants which have no builder action and with a maximum of 2% by weight of tabletting aid.

The builder additive is the additive already described above. Since exactly those tablets or phases of tablets are to be obtained in the production process described here, as have also been described above, it goes without saying that the preferred embodiments already described for the tablets, correspondingly also preferably in the process getting produced.

As also mentioned above, the tablets according to the invention contain the builder additives according to the invention in varying amounts depending on the intended use. Processes according to the invention in which the builder additive is used in amounts of 20 to 60% by weight, preferably in amounts of 25 to 55% by weight and in particular in amounts of up to 45% by weight, are also completely analogous. The premixes containing the described builder additive already have advantages. These premixes have a very good flowability, which allows the filling shoe to be filled evenly, thus helping to ensure a uniform quality of the manufacturing tablets. Furthermore, the premix hardly clumps and accordingly does not bake on the walls of the tablet press. In addition, the builder additive according to the invention allows the premix to be compressed at moderate pressures. This protects the tabletting tools and increases their service life.

Depending on the application, the builder additive is mixed with other ingredients of detergents and cleaning agents and pressed into the molded body. Processes according to the invention are preferred here, which are characterized in that the builder additive is mixed with at least one oxygen bleaching agent selected from the group of alkali perborates, alkali percarbonates, organic peracids and hydrogen peroxide. The bleaches in question were described above.

The bleaching performance of moldings containing bleach, such as water softener tablets, detergent tablets or bleach tablets, is preferably increased by using bleach activators. Processes according to the invention are preferred in which the builder additive with at least one bleach activator, preferably from the group of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), the N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methylsulfate (MMA) and / or the bleach-enhancing transition metal complexes, especially with the central atoms Mn, Fe, Co, Cu, Mo, V , Ti and / or Ru, preferably from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the Chlorides of cobalt or manganese and / or manganese sulfate is mixed. As already mentioned above, the tablets or phases of tablets according to the invention can contain further ingredients of detergents and cleaning agents, so that preferred process variants can be carried out analogously.

It is particularly preferred that the premix additionally contains one or more substances from the group of enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors and color transfer inhibitors.

Before the particulate premix is pressed into shaped articles, the premix can be "powdered" with finely divided surface treatment agents. This can be advantageous for the nature and physical properties of both the premix (storage, compression) and the finished 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. In the context of the present invention, the term “faujasite-type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4 (compare Donald W. Breck: “Zeolite Molecular Sieves”, John Wiley & Sons, New York , London, Sydney, Toronto, 1974, page 92). In addition to the zeolite X, 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.

The moldings according to the invention are first produced by dry mixing the constituents, which can be wholly or partially pregranulated, and then providing them, in particular pressing them into tablets, using conventional methods. To produce the moldings according to the invention, the premix is compacted in a so-called die between two punches to form a solid compressed product. This process, which takes place in The following, briefly referred to as tableting, is divided into four sections: dosage, compression (elastic deformation), plastic deformation and ejection.

First of all, the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molding being formed being determined by the position of the lower punch and the shape of the pressing tool. The constant metering, even at high molding throughputs, is preferably achieved by volumetric metering of the premix. As the tableting continues, the upper punch touches the premix and lowers further in the direction of the lower punch. During this compression, the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix) the plastic deformation begins, in which the particles flow together and the molded body is formed. Depending on the physical properties of the premix, some of the premix particles are also crushed and sintering of the premix occurs at even higher pressures. With increasing pressing speed, that is to say high throughput quantities, the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities. In the last step of tableting, the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.).

Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down. For small production quantities, eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine. The pressing can be done with an upper and lower stamp However, several punches can also be attached to an eccentric disk, the number of die holes being correspondingly expanded. 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 around a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation. 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 premix. The pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers.

Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet. For the production of two-layer and multi-layer molded articles, several filling shoes are arranged one after the other without the slightly pressed first layer being ejected before the 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 for pressing at the same time. The throughputs of modern rotary tablet presses are over one million tablets 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 moldings can be manufactured in a predetermined spatial shape and a predetermined size. Practically all practical configurations can be considered as the spatial shape, for example, the design as a board, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with 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 textile detergents in machines of the type customary in Europe with horizontally arranged mechanics, the portioned compacts can be designed as tablets, in cylindrical or cuboid form, 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 compacts.

The spatial shape of another embodiment of the shaped bodies is adapted in its dimensions to the induction chamber of commercial household washing machines, 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, the use of water softener or detergent tablets via a dosing aid is also possible without any problems and is preferred in the context of the present invention.

Another preferred molded body that can be produced has a plate-like or sheet-like structure with alternating thick and short short segments, so that individual segments of this "Riege!" at the predetermined breaking points, which represent the short, thin segments, can be broken off and entered into the machine. This principle of the "bar-shaped" shaped body detergent can also be implemented in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side.

However, it is also possible that the different components are not pressed into a uniform tablet, but that tablets are obtained which have several layers or “phases”, ie at least two layers. It is also possible for these different layers to be different This can preferably be achieved, in particular, if one of the layers now contains the builder additive according to the invention, while the other may contain no or any other disintegrant, which can result in advantageous performance properties of the shaped bodies, for example if components in the shaped bodies are contained, which mutually influence each other negatively, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted, when the second goes into solution. The layer structure of the shaped bodies can be stacked, with the inner layer (s) already loosening at the edges of the shaped body when the outer layers have not yet been completely detached, but it is also possible for the inner layer (s) to be completely encased ) can be achieved by the layer (s) lying further outwards, which leads to the premature dissolution of components of the inner layer (s).

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

Similar effects can also be achieved by coating individual components of the composition to be pressed or of the entire molded body. For this purpose, the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else they can be coated using the method of melt coating.

After compression, the tablets are extremely stable. 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 σ 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 is the Height of the molded body. Examples

Water softener tablets were produced from the ingredients listed in Table 1 on a rotary press (from Fette). For this purpose, the individual components were mixed and pressed with a pressure according to Table 2. All tablets had a weight of 18 g, the compression pressure was chosen so that all tablets had the same height. A layered silicate polymer compound was used in Examples E1 to E3 according to the invention. This compound was formed when SKS-6® (Clariant) was reacted with a terpolymer in accordance with the disclosure of patent application EP-A-849 355. The terpolymer used in accordance with the disclosure in WO 94/15978 was obtained from 80% by weight. Acrylic acid and maleic acid in a weight ratio of 7: 3 and 20% by weight of vinyl acetate were produced and then saponified in an acidic environment (commercial product from Stockhausen). The resulting builder additive contained 71% by weight of SKS-6, 20% by weight of the terpolymer and 9% by weight of water. In Example E2, as in the comparative examples, copolymer, which is an acrylic acid / maleic acid copolymer, was also used (Sokalan CP5®; trade name from BASF). Comparative examples V1 and V3 contained layered silicate in the form of SKS-6 powder. The comparative examples also contained microcrystalline cellulose as disintegrant and a polyethylene glycol with a molecular weight of 4000 g / mol as tabletting aid. The paraffin oil used in the examples according to the invention, like the polyethylene glycol used in the comparative examples with a molar mass of 400 g / mol, serves as a dust-binding agent. Differences from 100% by weight in Table 1 result from additionally contained water and salts.

In the examples according to the invention, tablets of greater hardness and edge breaking stability than in the comparative examples could be obtained at lower compression pressures. The tablets according to the invention had dissolution times comparable to those of the comparative tests. Less caking on the filling shoes and in the die was also observed in the production of the tablets according to the invention (see Table 2).

The hardness of the tablets was measured by deforming the tablet to fracture, the force acting on the side surfaces of the tablet and the maximum force that the tablet was able to withstand. The measurement was carried out on a hardness tester CT5 (Holland) with punch diameters of 8 mm.

The edge break test was carried out in a rectangular plastic container with edge lengths from 18 to 14 to 22 cm. 5 tablets were weighed into this container and rotated at 40 rpm for 1 minute. The tablets were then weighed again and, as a result, the weight of the tablets after the test was given as a percentage of the weight of the tablets before the test (Table 2).

The dissolution test in the beaker was carried out at 20 ° C. For this purpose, a tablet with the dimensions 14.8 x 34.4 mm was placed on a sieve with a mesh size of 0.6 x 0.6 cm and this sieve was hung in a 1000 ml beaker filled with water. The time until the tablet fell through the sieve was measured with stirring. For the dissolution test in the washing machine, three tablets were placed in a washing machine drum filled with laundry. The machine was then started in the 30 ° C wash program without prewash. The time is stopped as soon as the drum begins to circulate. The washing process was then stopped after 1 or 2 or 3 or 4 or 5 min and the water was pumped out. The dissolution time was then the time after which no residues from the tablets could be found. The values given in Table 2 are mean values from duplicate determinations.

The caking on the tablet press was assessed visually. The assessment was based on the following key: very good (++): no significant caking; good (+): visible caking, but does not affect the tableting; satisfactory (0): visible caking, minor impairment of the tableting; bad (-): massive impairment of tableting.

The experimental data of the individual tablet series are shown in Table 2.

Table 2: Properties of the tablets

Claims

P a t e n t a n s r u c h e

1. tablet which contains builder substances and, if appropriate, further ingredients of washing or cleaning agents, or phase of such a tablet, characterized in that it contains a powdery to granular additive which comprises, as essential components, a crystalline layered silicate of the general formula (I)

NaMSi _x O _{2x + 1} y H ₂ O (I),

where M represents sodium or hydrogen, x is a number from 1.9 to 2.2 and y is a number from 0 to 33, and contains (co) polymeric polycarboxylic acid, but the tablet does not contain an additional disintegrant which does not have a builder effect has, and contains a maximum of 2 wt .-% additional tableting aid.

2. tablet or phase of a tablet according to claim 1, characterized in that it contains the crystalline layered silicate of formula (I) in amounts of 2 to a maximum of 50 wt .-%, preferably in amounts of 5 to 45 wt .-% and in particular contains in amounts of 10 to 40 wt .-%.

3. tablet or phase of a tablet according to one of claims 1 or 2, characterized in that it contains the builder additive in amounts of 20 to 60 wt .-%, preferably in amounts of 25-55 wt .-% and in particular in amounts contains up to 45 wt .-%.

4. tablet or phase of a tablet according to any one of claims 1 to 3, characterized in that it contains a builder additive which 50 to 90 wt .-%, preferably 60 to 90 wt .-% and in particular 65 to 85 wt. % crystalline layered silicate of the formula (I), 2 to 40% by weight, preferably 5 to 30% by weight and in particular 10 to 25% by weight of polymeric polycarboxylic acid and 4 to 20 % By weight, preferably 5 to 15% by weight and in particular 7 to 12% by weight of water.

5. tablet or phase of a tablet according to any one of claims 1 to 4, characterized in that the (co) polymeric polycarboxylic acid in the builder additive has a molecular weight of 1000 to 100000 g / mol, preferably from 2000 to 75000 g / mol and in particular from 2000 to 35000 g / mol, the degree of neutralization of the acid groups being 0 to 90%, preferably 10 to 80% and in particular 30 to 70%.

6. tablet or phase of a tablet according to any one of claims 1 to 5, characterized in that the tablet no disintegrant based on polyvinylpyrrolidone or natural polymers or modified natural products such as cellulose and starch or their derivatives such as algae or casein derivatives, especially no microcrystalline Cellulose, and as a tabletting aid only contains dust binders, in particular short-chain polyethylene glycols with molar masses <800 g / mol or paraffins.

7. tablet or phase of a tablet according to any one of claims 1 to 6, characterized in that the tablet is a water softener tablet which preferably contains 60-100% by weight of builder substances, particularly preferably more than 80% by weight of builder substances .

8. tablet or phase of a tablet according to claim 7, characterized in that the tablet 10 to 40 wt .-%, in particular 15 to 30 wt .-% of polycarboxylic acids or polycarboxylic acid salts and 10 to 50 wt .-%, in particular 20 to 45 Contains% by weight alkali carbonate, bicarbonate or sesquicarbonate.

9. tablet or phase of a tablet according to any one of claims 1 to 6, characterized in that the tablet is a detergent tablet.

10. tablet or phase of a tablet according to claim 9, characterized in that the tablet contains alkylbenzenesulfonate and 2 to 20 wt .-%, preferably 2.5 to 15 wt .-% and in particular 5 to 10 wt .-% fatty alcohol sulfate.

11. Tablet or phase of a tablet according to one of claims 1 to 10, characterized in that it additionally contains one or more substances from the groups of bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils , Contains anti-redeposition agents, optical brighteners, graying inhibitors and color transfer inhibitors.

12. A process for the preparation of tablets which contain builder substances and, if appropriate, further ingredients of detergents or cleaning agents, or phases of such tablets, characterized in that a powdery to granular additive which comprises a crystalline layered silicate of the general formula (I )

NaMSi _x O _{2x + 1} y H ₂ O (I),

13. The method according to claim 13, characterized in that the builder additive is used in amounts of 20 to 60 wt .-%, preferably in amounts of 25 to 55 wt .-% and in particular in amounts up to 45 wt .-%.

14. The method according to any one of claims 13 or 14, characterized in that a builder additive is used, which 50 to 90 wt .-%, preferably 60 to 90 wt .-% and in particular 65 to 85 wt .-% crystalline layered silicate Formula (I), 2 to 40% by weight, preferably 5 to 30% by weight and in particular 10 to 25% by weight of (co) polymeric polycarboxylic acid and 4 to 20% by weight, preferably 5 to 15% by weight .-% and in particular 7 to 12 wt .-% water, the (co) polymeric polycarboxylic acid having a molar mass of 1000 to 100000 g / mol, preferably from 2000 to 75000 g / mol, in particular from 2000 to 35000 g / mol and the degree of neutralization of the acid groups is 0 to 90%, preferably 10 to 80% and in particular 30 to 70%.

16. The method according to any one of claims 13 to 15, characterized in that the premix additionally one or more substances from the group of enzymes, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors and contains color transfer inhibitors.

17. Use of a powdery to granular additive which as essential constituents is a crystalline layered silicate of the general formula (I)

NaMSi _x O _{2x + 1} y H ₂ O (I),

wherein M represents sodium or hydrogen, x is a number from 1.9 to 2.2 and y is a number from 0 to 33, and contains (co) polymeric polycarboxylic acid, as tabletting aid and disintegrant in tablets or individual phases of Tablets.