WO2000031231A1

WO2000031231A1 - Additive granule for moulded bodies having a detergent and cleaning action

Info

Publication number: WO2000031231A1
Application number: PCT/EP1999/008648
Authority: WO
Inventors: Gerhard Blasey; Hans-Friedrich Kruse; Andreas Lietzmann; Wilfried Rähse; Markus Semrau
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1998-11-19
Filing date: 1999-11-10
Publication date: 2000-06-02
Also published as: DE19853173A1

Abstract

The inventive additive granulate enables moulded bodies having a detergent and cleaning action, e.g. detergent tablets, dishwashing tablets, stain remover tablets or water softener tablets, to be used in household washing appliances on account of their decomposition rate. According to the invention, the additive granules contain 10-99 wt. % cellulose with a particle size of 100 νm and 1-90 wt. % of one or more solubilizers with a solubility of more than 200 g per litre of water at 20 °C and, on account of their physical and washing properties, are superior to traditional, additional cellulose-based disintegrating additives.

Description

"Aid granules for washing and cleaning-active molded articles"

The present invention is in the field of disintegration aids for compact moldings which have washing and cleaning properties. In particular, the invention relates to so-called disintegrant granules for use in washing and cleaning-active moldings, such as, for example, detergent tablets, dishwasher tablets, stain remover tablets or water softening tablets for use in the home, in particular for mechanical use.

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 ones: They are easier to dose and handle and, thanks to their compact structure, have advantages in terms of storage and transport. Detergent and cleaning agent tablets are consequently also comprehensively described in the patent literature. A problem that occurs again and again when using washing and cleaning active molded articles is the too slow disintegration and dissolving speed of the molded articles under application conditions. Since sufficiently stable, i.e. Shape and break resistant molded bodies can only be produced by relatively high pressure, there is a strong compression of the molded body components and a consequent delayed disintegration of the molded body in the aqueous liquor and thus to a slow release of the active substances in the washing or cleaning process .

In the field of washing or cleaning agents, according to the teaching of the European patent EP-B-0 523 099, the disintegrants which are known from the manufacture of pharmaceuticals can also be used. Swellable ones are mentioned as disintegrants Layered silicates such as bentonites, natural substances and natural substance derivatives based on starch and cellulose, alginates and the like, potato starch, methyl cellulose and / or hydroxypropyl cellulose. These disintegrants can be mixed with the granules to be pressed, but can also be incorporated into the granules to be pressed.

International patent application WO-A-96/06156 also states that the incorporation of disintegrants in detergent or cleaning agent tablets can be advantageous. Again, microcrystalline cellulose, sugars such as sorbitol, but also sheet silicates, in particular finely divided and swellable sheet silicates of the bentonite and smectite type, are mentioned as typical disintegrants. Substances contributing to gas formation such as citric acid, bisulfate, bicarbonate, carbonate and percarbonate are also listed as possible disintegration aids.

In the two last-mentioned documents of the prior art, no explicit information is given as to what exact particle size distribution the disintegrants that are to be used should have; Information regarding the microcrystallinity of cellulose and the fine particle size of the layered silicates, however, indicate to the person skilled in the art, especially in connection with the literature known from the manufacture of pharmaceutical tablets, that conventional disintegrants should be used in fine particle form.

According to EP-A-0 711 827, the use of particles, which predominantly consist of citrate, which has a certain solubility in water, also leads to an accelerated disintegration of the tablets. It is believed that the dissolution of the citrate locally increases the ionic strength during a transition period, which suppresses the gelling of surfactants and, as a result, does not hinder the disintegration of the tablet. According to this patent application, citrate is therefore not a classic explosive, but serves as an anti-gelling agent.

Detergent tablets containing cellulose disintegrants in granular or optionally cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and international patent application WO98 / 40463 (Henkel). These writings are also Information on the manufacture of granulated, compacted or cogranulated cellulose disintegrants can be found here. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm.

While the abovementioned documents disclose disintegration aids, which for the most part consist of cellulose or its derivatives, the older German patent application DE 197 23 028.8 (Henkel) discloses auxiliary granules for detergent tablets which contain 10 to 95% by weight of cellulose Contain particle sizes below 100 microns and 5 to 90 wt .-% microcrystalline cellulose and / or one or more ingredients of detergents. The disintegrants disclosed here are produced by compacting.

The proposed solutions lead to the desired success in the manufacture of pharmaceutical tablets. In the area of detergents and cleaning agents, they do contribute to an improvement in the disintegration properties of tablets that are active in washing or cleaning; however, the improvement achieved is not sufficient in many cases. This applies in particular if the proportion of sticky organic substances in the tablets, for example anionic and / or nonionic surfactants, increases. In addition, the use of disintegrants in washing and cleaning-active moldings can lead to specific problems that are completely unknown to drugs.

A particular problem results from the use of cellulose as a disintegration aid in molded bodies which are active in washing and cleaning. If the primary particle size of the cellulose is too large, the problem of residue formation on the treated textiles arises. In the case of dark textiles in particular, the deposits of the comparatively large cellulose primary particles which are released from the disintegrant compact in the wash liquor after the mold has disintegrated can be clearly seen after drying. To avoid the formation of residues on textiles, it is advisable to use a more finely divided cellulose, which does not have this problem. But also fine Partial celluloses can only be mixed up to a certain amount, otherwise residues can be seen on the textiles.

Accordingly, the object of the invention was to provide auxiliary granules for washing and cleaning-active molded articles which, on the one hand, do not have the residue problem, but on the other hand can be incorporated in granular form into the mixtures to be treated, without losing their effective form. Compared to the disintegrants described in the prior art, the effectiveness should be further improved with a constant amount of cellulose in order to enable the detergent tablets containing the auxiliary granules to be dosed via the induction chamber of household washing machines. It was also the object of the invention to develop a process for the production of such disintegrant granules for incorporation into shaped detergents and cleaners.

It has now been found that the residue problems of an explosive granulate based on cellulose with particle sizes below 100 μm can be avoided by granulating the cellulose with substances which have a solubility of more than 200 g per liter of water at 20 ° C.

The invention therefore relates in a first embodiment to an auxiliary granulate for washing and cleaning-active molded articles which has a content of

a) 10 to 99 wt .-% cellulose with particle sizes below 100 microns b) 1 to 90 wt .-% of one or more solubilizers with a solubility of more than 200 g per liter of water at 20 ° C.

is marked.

In the context of the present invention, auxiliary granules are understood to mean all those auxiliary and in particular disintegrating agents which per se are in finely divided powder form. lie and were converted into a coarser form by a spray drying, granulating, agglomerating, compacting, pelleting or extrusion process.

The terms “particle size” and “primary particle size” are used as synonyms in the context of the present invention if they are used to describe the cellulose in powder form. The granules obtained by granulating the cellulose powder naturally have particle sizes which are larger than the primary particle size of the cellulose powder used. The term “particle size” or “primary particle size” means that the corresponding powders pass completely through a sieve of the specified mesh size and leave less than 1% by weight of residue, based on the sieved powder, on the sieve.

The auxiliary granules of the present invention have a number of advantages which make them stand out over conventional disintegrants. So there are no problems with residues on laundry that has been washed with detergent tablets containing the auxiliary granules according to the invention.

The cellulose, which is contained as component a) in the auxiliary granules according to the invention, has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally considered, is a β-1,4-polyacetal of cellobiose, which in turn consists of two molecules Glucose is built up. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. A particle size of the cellulose prior to granulation of less than 100 μm is essential to the invention, primary particle sizes below 70 μm or below 50 μm being preferred. Cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions can also be used as component a) in the context of the present invention. 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, calicelluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers as well as amino celluloses.

The cellulose derivatives mentioned are preferably not used alone as component a), but are used in a mixture with cellulose. The cellulose derivative content of these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on component a). Pure cellulose which is free from cellulose derivatives is particularly preferably used as component a). In a particularly preferred embodiment, the auxiliary granules contain as component a) 20 to 95% by weight, preferably 30 to 90% by weight and in particular 40 to 85% by weight of cellulose with a particle size below 70 μm, preferably below 50 μm.

Within the scope of the present inventions, two types of material have emerged in particular as advantageous component a) or as a component thereof, namely TMP (thermo mechanical pulp) and CTMP (chemo thermo mechanical pulp). The substances mentioned are types of so-called wood pulp. In the TMP process, wood chips are shredded to TMP at approx. 130 ° C in pressure regulators. The use of chemicals in wood chip pre-damping results in CTMP. Further details can be found, for example, in "Römpps Chemie-Lexikon", 9th edition, Georg Thieme Verlag, Stuttgart, 1995, page 3207, keyword "paper".

With the wood pulp TMP and CTMP a certain leaching of the material has taken place, but the lignins, resins and other wood accompanying substances have not been completely removed, in particular not as completely as in the cellulose production. So these wood pulps are cellulose-containing materials that can still have a rest of the wood character. The aforementioned two materials have proven to be particularly effective as component a) in the auxiliary granules according to the invention.

The finely divided solubilizers contained according to the invention in the auxiliary granules have solubilities above 200 grams of solubilizer in one liter of deionized water at 20 ° C. Suitable as fine-particle solubilizers are men of the present invention, a whole series of compounds that can come from both the group of covalent compounds and the group of salts. As already mentioned, it is preferred if the finely divided solubilizers have even higher solubilities, so that auxiliary granules are preferred in which the solubilizer or 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. 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.

Preferred auxiliary granules contain the solubilizers in amounts between 5 and 70% by weight, preferably between 10 and 60% by weight and in particular between 20 and 50% by weight, based on the auxiliary granules.

In the context of the present invention, it is preferred to use finely divided solubilizers which do not originate from the groups of builders, bleaching agents and bleach activators, foam inhibitors and soil-release polymers. In particular, it is preferred that component b) is not a common ingredient of detergents and cleaning agents. The following substances are preferred finely divided solubilizers in the context of the present invention:

The auxiliary granules according to the invention preferably have no fines below 0.1 mm and preferably contain a total of only 0 to 5% by weight of particles with particle sizes below 0.2 mm. Preferred granules consist of at least 90% by weight of particles with a size of at least 0.3 mm and at most 2.0 mm.

In a further embodiment, the invention relates to a method for producing auxiliary granules for washing and cleaning-active molded articles, in which

granulated under compacting conditions.

To this end, components a) and b) are mixed, the cellulose having to meet the particle size criteria mentioned because of the residue problem, while component b) is not subject to any restrictions with regard to the particle size. In the interest of an intensive and homogeneous mixing of the two components however, it may be advantageous to also grind component b) to particle size ranges below 1 mm, in particular below 500 μm and particularly preferably below 200 μm, before the compacting process.

The granulation under compacting conditions can be carried out by all processes familiar to the person skilled in the art, with a wide variety of apparatuses being suitable for carrying out the process according to the invention. In the context of this application, the granulation under compacting conditions can be equated with terms such as granulation, agglomeration, compacting, extrusion and pelletizing. Suitable pelletizers are pellet presses, which in preferred embodiments are used as ring die presses. Roller compacting has proven to be particularly advantageous and particularly preferred in the context of the present invention, in which the dry premix of components a) and b) is compacted by two rollers rotating in opposite directions to form a sheet-like slug, which is then broken down by grinding and sieving Granules with particle sizes below 2 mm is brought.

In a further embodiment, the invention provides the use of auxiliary granules for detergent-active molded articles as disintegration accelerators in detergent tablets, in particular detergent tablets.

The invention therefore also relates to detergent-active molded articles, in particular detergent tablets, containing 1 to 40% by weight, preferably 2.5 to 30% by weight and in particular 5 to 20% by weight of an auxiliary granulate.

These shaped bodies are obtained by mixing the auxiliary granules with the other constituents of the detergent and cleaning agent and subsequent molding.

The molded body can be manufactured in a predetermined spatial shape and a predetermined size. Practically all sensibly manageable designs come as a room shape tions into consideration, for example, the design as a board, the shape of bars or bars, 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 approximately 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such pressed articles.

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

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

However, it is also possible that the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous application properties of the molded body. If, for example, components are contained in the moldings that mutually influence one another negatively, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted. when the second goes into solution. The layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely removed, but it is also possible for the inner layer (s) to be completely encased ) can be achieved by the layer (s) lying further outwards, which leads to the premature dissolution of components of the inner layer (s).

In a further preferred embodiment of the invention, a molded body consists of at least three layers, i.e. two outer and at least one inner layer, at least one of the inner layers containing a peroxy bleaching agent, while in the case of the stacked molded body the two cover layers and in the case of the shell-shaped molded body the outermost layers, however, are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in a molded body. Such multilayer molded bodies have the advantage that they can be used not only via a dispensing chamber or via a metering device which is added to the washing liquor; rather, in such cases it is also possible to put the molded body into direct contact with the textiles in the machine without the risk of bleaching from bleaching agents and the like. Similar effects can also be achieved by coating individual constituents of the detergent and cleaning agent composition to be treated or the entire molded body. For this purpose, the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else using the process of melt coating Received coating.

In addition to the auxiliary granulate according to the invention, which facilitates and accelerates the disintegration of the washing and cleaning-active molded articles, the molded articles according to the invention can contain all the usual constituents of detergents and cleaning agents. If auxiliary granules according to the invention are used which contain certain ingredients of detergents and cleaning agents as component b), it is possible to dispense with the further addition of these substances in the production of the molded article. However, it may also be preferred to incorporate such constituents of detergents and cleaning agents both as component b) into the auxiliary granules and additionally into the molded body. In addition to the constituents already mentioned above as part of the auxiliary granulate, the shaped bodies according to the invention can contain further constituents which are not introduced into the shaped body via the auxiliary granules. Surfactants and enzymes should be mentioned here in particular as substances which are active in washing and cleaning and which are incorporated into the molded body.

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

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C ₉ . ₁₃ - alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates fonaten and disulfonates, such as those obtained, for example, from C _12.18 monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Alkanesulfonates which are derived from C ₁₂ are also suitable. ₁₈ -alkanes can be obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. 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 sulfated fatty acid glycerol esters are the sulfate 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 oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C _I0 -C ₂₀ -oxoalcohols 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 which is produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. From the washing are the C ₁₂ -C _I6 alkyl sulfates and C ₁₂ -C ₁₅ - alkyl sulfates and preferably C, _4-C, ₅ alkyl sulfates. 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 ethoxylated with 1 to 6 mol of ethylene oxide. ₂₁ alcohols, such as 2-methyl-branched C _{9 u} alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ₁₂ . ₁₈ fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

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

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

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

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol Holrest may be linearly branched or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, such as are usually present in oxo alcohol residues. 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 _{12, 14} alcohols with 3 EO or 4 EO, C ₉ , alcohol with 7 EO, C ₁₃ , ₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO , C _12. _I8 - 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.

In addition, alkyl glycosides of the general formula RO (G) can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533. 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-CO-N- [Z] (I)

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

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

R ^! -OR ^2nd

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

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical with 1 to 8 carbon atoms, where C,. ₄ -alkyl or phenyl radicals are preferred and [Z] represents a linear polyhydroxyalkyl radical whose alkyl chain is substituted by 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, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers 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 shaped bodies can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Salts of 4,4'-bis (2-anilino-4- moφholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which instead of the Moφholino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

The invention can also take advantage of the fact that acidifying agents such as citric acid, tartaric acid or succinic acid, but also acidic salts of inorganic acids (“hydrogen salts”), for example bisulfates, especially in combination with carbonate-containing systems, contribute to improving the disintegration properties of the shaped bodies In the context of this invention, however, it is then provided that these acidifying agents are also present in coarse-grained, in particular granular form, which have as little dust as possible and are adapted in particle size distribution to those of the auxiliary granules. The granular acidifying agents can be used, for example, in amounts of 1 to 10 % By weight can be contained in the shaped bodies.

The shaped articles according to the invention, in particular the previously poorly disintegrating and poorly soluble detergent shaped articles and bleached shaped articles, have excellent disintegration properties due to the use of the auxiliary granulate according to the invention. By compacting the disintegration aid with a detergent ingredient, a wider distribution of the aid granules is achieved in the entire molded body. The improved disintegration can be tested, for example, under critical conditions in a conventional household washing machine (use directly in the washing liquor using a conventional dosing device, delicates program or colored laundry, washing temperature maximum 40 ° C) or in a beaker at a water temperature of 25 ° C. The execution of the corresponding tests is described in the example section. Under these conditions, the shaped bodies according to the invention not only completely disintegrate within 10 minutes; the preferred embodiments have disintegration times in the beaker test of less than 3 minutes, in particular less than 2 minutes on. Particularly advantageous embodiments even have disintegration times of less than 1 minute. Disintegration times of less than 1 minute in the beaker test are usually sufficient to allow the detergent tablets or the washing additive tablets to be rinsed into the washing liquor via the rinsing chamber of conventional household washing machines, even in so-called "critical machines" that wash in with a little water. In another embodiment The invention therefore claims a washing process using a molded body according to the invention, which is characterized in that the molded body is introduced into the washing liquor via the induction device of a household washing machine.

The molded articles according to the invention are actually produced first by dry mixing the auxiliary granules with the remaining constituents and then informing them, in particular feeding them into tablets, using conventional methods (for example as in the conventional patent literature for tablets, especially in the field of detergents or cleaning agents). in particular as can be used in the abovementioned patent applications and the article "Tablettierung: Stand der Technik", SÖFW-Journal, 122nd year, pp. 1016-1021 (1996)).

Examples:

A based on TMP / CTMP commercial granular cellulose disintegrant (Arbocel ^® TF 30 HG, Rettenmaier) was ground in a pinned-disk mill and defibered in the primary particles, which had a particle size <75 microns. These cellulose fibers were mixed with urea in a weight ratio of 75:25 and compacted on a roller compactor (Alexanderwerk) to form a sheet-like slug, which was brought to particle sizes between 400 and 1200 μm in a sieve granulator. The auxiliary granules according to the invention obtained in this way were incorporated into detergent tablets E. Served as controls detergent tablets V, which is a commercially available cellulose disintegrant contained (Arbocel ^® TF 30 HG, Rettenmaier). The proportion of cellulose in the overall formulation was kept in the same amount for the molded bodies E and V, respectively. The disintegrant used for the comparison was also screened for particle sizes between 400 and 1200 μm.

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. The auxiliary granules according to the invention were admixed to the shaped bodies E according to the invention as a further processing component, while the comparative shaped bodies V contained the commercially available cellulose disintegrant.

The premixes were pressed in a Korsch eccentric press into tablets (diameter: 44 mm, height: approx. 22 mm, weight: 37.5 g). The pressure was adjusted so that three series of molded bodies were obtained (El, El ', El ", E2, E2', E2 "or V, V, V") which differ in their hardness. The composition of the premixes to be treated (and thus the shaped body) is shown in Table 2, and the particle size distribution of the disintegration aids is given in Table 3.

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

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

Table 3: Sieving numbers of disintegration aids [% 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 3:

Table 4: Detergent tablets [physical data]

Table 4 shows that the disintegration times of detergent tablets are significantly reduced by using the auxiliary granules according to the invention.

Claims

Claims:

1. Aid granules for washing and cleaning-active molded articles, characterized by a content of

2. Auxiliary granules according to claim 1, characterized in that the solubilizer or 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.

3. Auxiliary granules according to claim 1 or 2, characterized in that the solubilizers in amounts between 5 and 70 wt .-%, preferably between 10 and 60 wt .-% and in particular between 20 and 50 wt .-%, based on the auxiliary granulate , are contained in the granulate.

4. Aid granules according to one of claims 1 to 3, characterized in that component b) does not originate from the groups of builders, bleaching agents and bleach activators, foam inhibitors and soil-release polymers.

5. Aid granules according to one of claims 1 to 4, characterized in that component b) is not a common ingredient of detergents.

6. Auxiliary granules according to one of claims 1 to 5, characterized in that as component a) 20 to 95 wt .-%, preferably 30 to 90 wt .-% and in particular 40 to 85 wt .-% cellulose with a particle size below 70 μm, preferably less than 50 μm, is used.

7. Process for the preparation of auxiliary granules for washing and cleaning-active molded articles, characterized in that

granulated under compacting conditions.

8. The method according to claim 7, characterized in that one

compacted by roller compaction to form a leaf-shaped slug, which is then ground and sieved to granules with particle sizes below 2 mm.

9. Use of auxiliary granules for washing and cleaning-active molded articles according to one of claims 1 to 6, as disintegration accelerators in detergent tablets, in particular detergent tablets.

10. washing and cleaning-active molded article, in particular detergent tablets, containing 1 to 40% by weight, preferably 2.5 to 30% by weight and in particular 5 to 20% by weight of an auxiliary granulate according to one of claims 1 to 6.

11. Washing method using a molded body according to claim 10, characterized in that the molded body is introduced into the washing liquor via the induction device of a household washing machine.