WO2000027985A1 - Moulded cleaning agent and detergent bodies containing fine-particle solubility promoters - Google Patents

Abstract

The invention relates to moulded cleaning agent and detergent bodies having advantageous properties, which consist of compacted, particulate cleaning agent and detergent and as fine-particle solubility promoters contain between 0.5 and 20 % by weight, in relation to the moulded body, substances having a solubility of more than 200 g per litre of water at 20 DEG C. At least 30 % by weight of the solubility promoter particles are smaller than 200 mu m.

Description

 "Detergent tablets with finely divided solubilizers"

The present invention is in the field of compact moldings which have washing and cleaning properties. Such detergent tablets comprise, for example, detergent tablets for washing textiles, detergent tablets for machine dishwashing or hard surface cleaning, bleach tablets for use in washing machines or dishwashers, water softening tablets or stain remover tablets. In particular, the invention relates to detergent tablets which are used for washing textiles in a household washing machine and are briefly referred to as detergent tablets.

Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents and cleaning agents have a number of advantages over powdered detergents: they are easier to dose and handle and, thanks to their compact structure, have advantages for storage and transportation. Detergent tablets are therefore also comprehensively described in the patent literature. A problem that occurs again and again when using shaped articles which are active in washing and cleaning is the insufficient rate of disintegration and dissolution of the shaped articles under conditions of use. Since sufficiently stable, that is to say shape and break-resistant molded articles can only be produced by relatively high compression pressures, there is a strong compression of the molded article constituents and a consequent delayed disintegration of the molded article in the aqueous liquor and thus a too slow release of the Active substances in the washing or cleaning process. The delayed disintegration of the moldings also has the disadvantage that they are customary Do not allow detergent tablets to be washed in via the induction chamber of household washing machines, since the tablets do not disintegrate into secondary particles that are small enough to be washed into the washing drum from the induction chamber. In addition, there is the problem of adjusting the formulation in the production of washing and cleaning-active moldings. While in the case of powdery or liquid detergents and cleaning agents, the formulations can be adapted with little effort, for example to changing requirements with regard to washing or cleaning ability or to national circumstances, changing the ingredients or their quantities in premixes to be compressed often leads to that the tabletting properties of the mixture change drastically and result in moldings which, with the desired hardness, no longer have sufficient disintegration times.

To overcome the dichotomy between hardness, i.e. Transport and handling stability, and easy disintegration of the moldings, many solutions have been developed in the prior art. A particularly well-known approach from the pharmaceutical industry and extended to the field of detergent tablets is the incorporation of certain disintegration aids which facilitate the access of water or which swell or develop gas or other forms upon access of water. Other proposed solutions from the patent literature describe the compression of premixes of certain particle sizes, the separation of individual ingredients from certain other ingredients, and the coating of individual ingredients or of the entire shaped body with binders.

The addition of easily soluble substances to premixes for detergent tablets is described in some special cases in the prior art. DE 11 91 509 (Henkel) describes detergent tablets containing tripolyphosphate of modification I and conventional organic detergent substances, preferably 10 to 35 wt.% Detergent substances, 35 to 65 wt.% Tripolyphosphate, 1 to 6 wt.% Silica or magnesium silicate, 3 to 10% by weight of alkaline inorganic salts, 3 to 10% by weight of urea and up to 10% by weight of other constituents are contained. No information is given in this document about the particle sizes of the readily soluble substances. European patent application EP 711 827 (Unilever) discloses detergent tablets which contain particles which consist of 50 to 100% by weight of a citrate which has a solubility of at least 50 g per 100 g of water at 20 ° C., preferably sodium citrate Dihydrate is used. No information is given in this document either about the particle size of the particles which contain the readily soluble citrate.

The improvement in the solubility of water softening tablets by the addition of sodium acetate trihydrate, potassium acetate or mixtures thereof and optionally sodium citrate dihydrate is described in European patent application EP 838 519 (Unilever). In this document the use of a sodium acetate trihydrate is described, which has an average particle size of 625 μm and has hardly any fines.

The addition of finely divided processing components to compressible premixes for the production of detergent tablets is also described in the unpublished German patent application DE 198 43 773.0 (Henkel). The alkali metal and / or alkaline earth metal silicates and / or hydrogen carbonates disclosed in this document are contained in the shaped bodies in amounts of 1 to 20% by weight, based on the shaped body, and have at least 60% by weight of particle sizes below 600 μm. The addition of the alkali and / or alkaline earth metal silicates and / or hydrogen carbonates mentioned, which are for the most part less water-soluble, with at least 30% by weight of grain fractions below 200 μm is not disclosed in this document.

The present invention was based on the object of providing moldings which, given a given hardness, are distinguished by short disintegration times and can therefore also be metered via the dispensing chamber of household washing machines. Since the amounts of surfactant in a detergent and cleaning agent in particular are set within narrow limits, on the other hand the surfactants are often introduced via surfactant granules or compounds with defined surfactant proportions, substances should be found which are mixed with the premix to be pressed Granules of surfactant can be added without being found in varying amounts of surfactant granules and the substance negatively changes the tableting properties of the premix, but on the contrary improves it even further. Since auxiliary agents and fillers customary in detergents and cleaning agents cannot readily be incorporated into pre-mixes for tableting, there was also the need to find a way of incorporating these auxiliary agents and fillers that would allow these substances to be added to tablet mixtures.

The invention relates to detergent tablets made from compressed, particulate detergents and cleaning agents which, as finely divided solubilizers, have substances with a solubility of more than 200 g per liter of water at 20 ° C. in amounts of 0.5 to 20% by weight, based on the molded article, wherein at least 30% by weight of the particles of the solubilizers have particle sizes below 200 μm.

By using these finely divided solubilizers with the stated solubility, the proportion of certain ingredients, in particular the surfactant granules, can be reduced in a tablettable premix and replaced by these substances. The substances mentioned are commercially available in a wide variety of qualities, and the grain sizes also vary widely.

The amounts in which the finely divided solubilizers mentioned are contained in the shaped bodies are, according to the invention, between 0.5 and 20% by weight, in each case based on the weight of the shaped body. Detergent tablets preferred in the context of the present invention contain the finely divided solubilizer (s) in amounts of 1 to 15% by weight, preferably 1.5 to 10% by weight and in particular 2 to 5% by weight, based on the weight of the molded article.

It is preferred according to the invention if the finely divided solubilizers contained in the moldings according to the invention have a solubility of more than 250 g per liter of water at 20 ° C., preferably of more than 300 g per liter of water at 20 ° C. and in particular of more than 350 g per Have liters of water at 20 ° C.

It is further preferred if at least 35% by weight, preferably at least 40% by weight, particularly preferably at least 45% by weight and in particular at least 50 % By weight of the particles of the solubilizers have particle sizes below 200 μm. The particle size range in which the particle sizes of the finely divided solubilizers contained in the moldings according to the invention are preferably limited to an upper limit and is preferably within narrow limits. Preference is given to detergent tablets in which a maximum of 20% by weight, preferably a maximum of 10% by weight and in particular a maximum of 5% by weight of the particles of the solubilizers have particle sizes above 400 μm.

The finely divided solubilizers contained in the moldings according to the invention have solubilities above 200 grams of solubilizer in one liter of deionized water at 20 ° C. A very large number of compounds which can originate both from the group of the covalent compounds and from the group of the salts are suitable as finely divided solubilizers in the context of the present invention. As already mentioned, it is preferred if the finely divided solubilizers have even higher solubilities. The following list provides an overview of the solubilities of solubilizers suitable in the context of the present invention. Unless other temperatures are explicitly mentioned, the solubility values given in this table refer to the solubility at 20 ° C.

In the context of the present invention, it is preferred to use finely divided solubilizers which, in addition to their fine particle size and water solubility and the associated improvement in the physical properties of the detergent tablets, have further positive effects. This means that in the context of the present invention, the use of finely divided solubilizers is preferred which additionally have washing and cleaning-active or supporting properties in the washing or cleaning process. Another property of the finely divided solubilizers can be the adjustment of the pH of the washing or cleaning liquor, but they can also improve the primary or secondary washing ability of the detergent tablets.

The following substances are preferred finely divided solubilizers in the context of the present invention:

By using the finely divided solubilizers according to the invention in the particle size range mentioned and optionally supported by the use of disintegration aids (see below), detergent tablets can be produced according to the invention, which disintegrate into their constituents extremely quickly in water at high hardness. In the context of the present invention, particular preference is given to detergent tablets which disintegrate completely in water at 30 ° C. in less than 60 seconds into their secondary particles, which are so small that they can be washed in via the washing-in chamber of a household washing machine.

In addition to the finely divided solubilizers used according to the invention, the detergent tablets contain customary ingredients of detergents and cleaning agents, in particular from the groups of the surfactants and / or the builders and / or the bleaching agents. Further ingredients that can be used in the detergent tablets according to the invention are, for example, bleach activators, enzymes, dyes and fragrances, optical brighteners, polymers, foam inhibitors, etc.

To develop the washing performance, the detergent tablets according to the invention can contain surface-active substances from the group of anionic, nonionic, zwitterionic or cationic surfactants, anionic surfactants being clearly preferred for economic reasons and on the basis of their performance spectrum.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C - ₁₃ - alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates of the type obtained, for example, from C _{2-0 8} monoolefins with an end or internal double bond by sulfonation gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which are obtained from C ₁ -C ₈ -alkanes, 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 become. 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.

As alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the oC ^ oxo alcohols and those half esters secondary alcohols of these chain lengths 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 1 -C ₁₆ alkyl sulfates and C ₁₂ -C ₅ alkyl sulfates and C ₄ -C 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 straight-chain or branched C ₇ ethoxylated with 1 to 6 mol of ethylene oxide. ₁ -alcohols, such as 2 -methyl-branched C ₉ -π-alcohols with an average of 3.5 moles of ethylene oxide (EO) or Cι ₂ -ι ₈ fatty alcohols with 1 to 4 EO, are is suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

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

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

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

In the context of the present invention, detergent tablets are preferred which contain 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 10 to 20% by weight of anionic surfactant (s), based in each case on the Molded body weight included.

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

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical has a linear or preferably 2-methyl branching may be 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 fat 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 ₂ -C ₄ alcohols with 3 EO or 4 EO, C ₉ n alcohol with 7 EO, C ₁₃ -C ₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO , C ₁₂ - ι ₈ - alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ - ₁₄ - alcohol having 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, as described, for example, in Japanese Patent Application JP 58/217598 or which are preferably according to that described in US Pat international patent application WO-A-90/13533.

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

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

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

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

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

R ¹

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

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

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 alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or represents an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 6 -alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated, derivatives of this rest.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. In addition to the wash-active substances, builders are the most important ingredients in detergents and cleaning agents. The detergent tablets according to the invention can contain all builders commonly used in detergents, especially zeolites, the silicates, carbonates, organic cobuilders used according to the invention within a certain particle size range and - where there are no ecological prejudices against their use - also the phosphates. The builders mentioned can also be used in surfactant-free molded articles, so that it is possible according to the invention to produce molded articles which can be used for water softening or as bleach tablets.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x +} 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 have been brought about in various ways, for example by surface treatment, compounding, compacting / sealing 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 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 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 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. Particularly preferred are compressed / 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 used, usually using both ways of incohering the zeolite into the nor mixture. 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.

It is of course 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. 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.

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 necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.

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

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

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred washing and cleaning agents contain such a cellulose-based disintegrant in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight. Pure cellulose has the formal gross composition (C ₆ HιoO 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. 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 hydroxyl hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.

The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be treated. Detergent tablets, which contain disintegrants in granular or optionally granulated form, are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular to 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 resulting from the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, to granules with an average particle size of 200 μm.

Detergent tablets particularly preferred in the context of the present invention are characterized in that they 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 from 3 to 7 wt .-% and in particular from 4 to 6 wt .-%, each based on the molded body weight.

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 good flow properties, such as furthermore, it must not show any tendency to separate during storage, transport and filling of the die. These three prerequisites are extremely difficult to master with many substance mixtures, so that the direct tablet rank is not often used, particularly in the manufacture 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.

The present invention therefore also relates to a process for the production of detergent shaped bodies by shaping molding a particulate premix, the finely divided solubilizer with a solubility of more than 200 g per liter of water at 20 ° C. in amounts of 0.5 to Contains 20 wt .-%, based on the premix, wherein at least 30 wt .-% of the particles of the solubilizers have particle sizes below 200 microns.

In the process according to the invention, too, the use of the finely divided solubilizers mentioned is preferred in a particle size distribution in which at least 40% by weight, preferably at least 45% by weight and in particular at least 50% by weight of the particles of the solubilizers have particle sizes below 200 μm. It is also preferred if the premix contains the finely divided solubilizer (s) in amounts of 1 to 15% by weight, preferably 1.5 to 10% by weight and in particular 2 to 5% by weight. Processes which are preferred according to the invention are characterized overall in that the premix contains the finely divided solubilizer or solubilizers in amounts of 1 to 15% by weight, preferably 1.5 to 10% by weight and in particular 2 to 5% by weight, based on the molded body weight, contains and have at least 35% by weight, preferably at least 40% by weight, particularly preferably at least 45% by weight and in particular at least 50% by weight of the particles of the solubilizers, particle sizes below 200 μm. Preferred detergent tablets in the context of the present invention are obtained by squeezing a particulate premix consisting of at least one surfactant-containing granulate and at least one subsequently admixed powdery component. The granules containing surfactant can be produced by conventional industrial granulation processes such as compacting, extrusion, mixer granulation, pelletization or fluidized bed granulation. It is advantageous for the later detergent tablets if the premix to be veφresses has 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.

In preferred process variants, the surfactant-containing granules also meet certain particle size criteria. Methods according to the invention are preferred in which the surfactant-containing granules have particle sizes between 100 and 2000 μm, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 μm. Overall, there is therefore a preference for processes according to the invention in which the particulate premix additionally contains surfactant-containing granules (e) and has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1, where the surfactant-containing granules preferably have particle sizes between 100 and 2000 μm, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 μm.

In addition to the active substances (anionic and / or nonionic and / or cationic and / or amphoteric surfactants), the surfactant granules preferably also contain carriers which particularly preferably come from the group of builders. Particularly advantageous processes are characterized in that the surfactant-containing granules contain anionic and / or nonionic surfactants and builders and have total surfactant contents of at least 10% by weight, preferably at least 20% by weight and in particular at least 25% by weight. Before the particulate premix is pressed into detergent and shaped body, the premix can be "powdered" with finely divided surface treatment agents. This can be of advantage for the nature and physical properties of both the premix (storage, pressing) and 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. In the context of the present invention, the term “zeolite of the faujasite type” 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 faujasite-type zeolites with other zeolites which do not necessarily have to belong to zeolite structure group 4 can also be used as powdering agents, it being advantageous if at least 50% by weight of the powdering agent is removed a zeolite of the faujasite type.

In the context of the present invention, detergent tablets are preferred which consist of a particulate premix containing 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.

In addition to the above-mentioned constituents surfactant, builder and solubilizer, the premixes to be veφress and thus the detergent tablets according to the invention can additionally include one or more substances from the group of bleaching agents, bleach activators, disintegration aids, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, Dyes, foam inhibitors, silicone oils, anti- contain deposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

Among the compounds which serve as bleaching agents and provide water H O, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and HO-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for washing textiles, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of which other ingredients are contained in the moldings. If cleaning tablets or bleach tablets for machine dishwashing are manufactured, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, e.g. Dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monophthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidopercapid [Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1, 9-diperoxyacelic acid oxyacid, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents in moldings for automatic dishwashing. Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromo isocyanuric acid and or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

In order to achieve an improved bleaching effect when washing or cleaning at temperatures of 60 ° C. and below, bleach activators can be incorporated as the sole component or as an ingredient of component b). 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 are substances which carry O- and / or N-acyl groups of the stated number of carbon atoms and / or optionally substituted benzoyl groups. Multi-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, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, ethylene glycol, 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.

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. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures of cellulase containing 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.

In addition, the detergent tablets can also contain components that positively influence the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and hydroxypropoxyl groups of 1 to 15% by weight, in each case based 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 shaped bodies can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-moφholino-l, 3,5-triazinyl-6-amino) stilbene-2,2 ^l -disulfonic acid or compounds of the same structure which instead of the Moφholino- Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) - diphenyls, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can also be used.

Dyes and fragrances are added to the detergent tablets 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. As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexylpropionate, styrallyl propionate and styrallyl propionate. The ethers include, for example, benzyl ethyl ether, the aldehydes, for example. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, cc-isomethylionon and methyl-cedrylketone, to the alcohols anethol, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and Teφineol, to the hydrocarbons belong mainly the Teφene like Limonen and Pinen. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, Citras, 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, lentil flower 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 dye content of the detergent 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 through a slower fragrance release for long-lasting fragrance of the textiles. 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 to textile fibers, in order not to dye them.

The molded articles according to the invention are first produced by dry mixing the constituents, which can be wholly or partially pregranulated, and then providing information, in particular feeding them into tablets, whereby conventional methods can be used. To produce the shaped bodies according to the invention, the premix is compacted in a so-called die between two punches to form a solid compact. This process, which is briefly referred to below as the tableting line, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molded body being formed being determined by the position of the lower punch and the shape of the pressing tool. The constant dosing, even at high mold throughputs, is preferably achieved by volumetric dosing of the premix. As the tableting continues, the upper punch touches the premix and lowers further in the direction of the lower punch. During this compression, the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix), the plastic deformation begins, in which the particles flow together and the molded body is formed. Depending on the physical properties of the premix, some of the premix particles are also crushed and sintering of the premix occurs at even higher pressures. at increasing pressing speed, that is 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 the tabletting process, the finished molded body is pressed out of the die by the lower punch and is conveyed 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 punch used to build up the drain, the lower punch also moves towards the upper punch during the pressing process, while the upper punch 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 punch, but several punches can also be attached to one eccentric disc, the number of die bores being increased accordingly. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available. Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps. The die table and the stamps move about 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 increase or decrease in the stamp is required is necessary (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 pressure on the premix can be individually adjusted via the press paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable drape rollers.

Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet. For the production of two-layer and multi-layer molded bodies, several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling. Using 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 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-press HPF 630 from LAEIS, D. is particularly suitable.

The molded body can be manufactured in a predetermined spatial shape and a predetermined size. Practically all sensibly manageable configurations come into consideration as the spatial form, for example the design as a board, the rod or bar form, 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. However, it is also possible to form compacts which combine a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined breaking points. For the use of laundry detergents in machines of the type customary in Europe with horizontally arranged mechanics, the portioned compacts as tablets, in cylinder or cuboid form can be expedient, with a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such pressed articles.

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

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

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

Similar effects can also be achieved by coating individual constituents of the detergent and cleaning agent composition to be treated or the entire molded article. For this purpose, the bodies to be coated can be coated with, for example aqueous solutions or emulsions are sprayed, or else a coating is obtained via the process of melt coating.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be determined by means of the measured quantity of the diametrical field response. This can be determined according to

2R

TtDt

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

Another object of the present invention is the use of finely divided solubilizers, which have a solubility of more than 200 g per liter of water at 20 ° C, with at least 30 wt .-% of the particles of the solubilizers have particle sizes below 200 microns to improve physical properties of laundry detergent and cleaning product. By using the finely divided solubilizers with the stated solubility and in the specified particle size range in premixes for detergent tablets, the physical properties of the tablets can be improved, as the following examples show:

Examples:

Granulation in a 50-liter ploughshare mixer from Lödige produced granules containing tensides (for composition, see Table 1), which was used as the basis for a particulate premix. Following the granulation, the granules were dried in a fluidized bed apparatus from Glatt at a supply air temperature of 60 ° C. over a period of 30 minutes. After drying, fine particles <0.4 mm and coarse particles> 1.6 mm were screened off.

This premix was prepared by mixing the surfactant-containing granules with bleach, bleach activator and other processing components. As a further processing component, the shaped bodies El and E2 ammonium chloride (solubility: 370 g / 1 H O at 20 ° C.) according to the invention were mixed in finely divided form, while the comparative shaped bodies V were free of ammonium chloride.

The premixes were pressed in a Korsch eccentric press into tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g). The press was set so that three series of moldings were obtained (El, El ', El ", E2, E2', E2" and V, V, V ") which differ in their hardness Premixes to be pressed (and thus the molded article) are shown in Table 2, the particle size distribution of the ammonium chloride added is given in Table 3, and the particle size distribution of the other processing components is shown in Table 4.

Table 1: Composition of the surfactant granules [% by weight]

Table 2: Composition of the premixes [% by weight]:

* see table 3

** compacted cellulose (particle size: 90% by weight> 400 μm)

Table 3: Sieving numbers of ammonium chloride [% by weight]

Tabelle 4: Siebzahlen der übrigen Aufbereitungskomponenten [Gew.-%]

Table 4: Sieving numbers of the other treatment components [% by weight]

After two days of storage, the hardness of the tablets was measured by deforming the tablet until it broke, the force acting on the side surfaces of the tablet and the maximum force which the tablet withstood being determined.

To determine the tablet disintegration, the tablet was placed in a beaker with water (600 ml of water, temperature 30 ° C.) and the time until the tablet disintegrated completely. The experimental data are shown in Table 5:

Table 5: Detergent tablets with ammonium chloride [physical data]

Table 5 shows that the disintegration times of laundry detergent and cleaning agent shaped bodies are significantly reduced by the use of the finely divided solubilizer according to the invention.

Claims

Claims: 1. washing and cleaning agent molded body made of compressed, particulate washing and cleaning agent, characterized in that they, as finely divided solubilizers, have substances with a solubility of more than 200 g per liter of water at 20 ° C. in amounts of 0.5 to 20% by weight. %, based on the molded article, containing at least 30% by weight of the particles of the solubilizers having particle sizes below 200 μm. 2. Detergent and molded article according to claim 1, characterized in that it contains the finely divided solubilizer or solids in amounts of 1 to 15% by weight, preferably 1.5 to 10% by weight and in particular 2 to 5% by weight .-%, based on the molded body weight. 3. Washing and cleaning agent molded article according to one of claims 1 or 2, characterized in that the finely divided solubilizers have a solubility of more than 250 g per liter of water at 20 ° C, preferably of more than 300 g per liter of water at 20 ° C and in particular of more than 350 g per liter of water at 20 ° C. 4. Detergent and molded article according to one of claims 1 to 3, characterized in that at least 35% by weight, preferably at least 40% by weight, particularly preferably at least 45% by weight and in particular at least 50% by weight of Particles of the solubilizers have particle sizes below 200 microns. 5. Detergent and molded article according to one of claims 1 to 4, characterized in that a maximum of 20% by weight, preferably a maximum of 10% by weight and in particular a maximum of 5% by weight of the particles of the solubilizers have particle sizes above 400 μm. 6. Washing and cleaning agent molded article according to one of claims 1 to 5, characterized in that it additionally contains a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated ter or compacted form, in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7 wt .-% and in particular from 4 to 6 wt .-%, each based on the molded body weight. 7. A process for the production of detergent tablets by shaping a particulate premix, characterized in that the premix finely divided solubilizer with a solubility of more than 200 g per liter of water at 20 ° C in amounts of 0.5 to 20 wt. -%, based on the premix, contains, with at least 30 wt .-% of the particles of the solubilizers having particle sizes below 200 microns. 8. The method according spoke 7, characterized in that the premix or the finely divided solubilizer in amounts of 1 to 15 wt .-%, preferably from 1.5 to 10 wt .-% and in particular from 2 to 5 wt .-% %, based on the molding weight, contains and at least 35% by weight, preferably at least 40% by weight, particularly preferably at least 45% by weight and in particular at least 50% by weight of the particles of the solubilizers, particle sizes below 200 μm exhibit. 9. The method according to any one of claims 7 or 8, characterized in that the particulate premix additionally contains surfactant-containing granules (s) and a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1, the surfactant-containing granules preferably having particle sizes between 100 and 2000 μm, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 μm. 10. The method according spoke 9, characterized in that the surfactant-containing granules contains anionic and / or nonionic surfactants and builders and total surfactant contents of at least 10 wt .-%, preferably at least 20 wt .-% and in particular at least 25 wt .-% , having. 11. The method according to any one of claims 7 to 10, characterized in that the particulate premix additionally contains one or more substances from the group of bleaches, bleach activators, disintegration aids, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors , Silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors. 12. Use of finely divided solubilizers which have a solubility of more than 200 g per liter of water at 20 ° C., at least 30% by weight of the particles of the solubilizers having particle sizes below 200 μm, to improve the physical properties of washing and Detergent tablets.