WO2000039272A2 - Washing detergent shaped bodies comprising an optimized shape - Google Patents

Abstract

The invention relates to washing detergent tablets (1, 2) exhibiting improved mechanical stability and yet decreased disintegration times which make it possible to carry out washing by being placed in the drum of household washing machines. The inventive tablets can be produced by compacting a premix having a content of surfactants of greater than 10 wt. % in order to form washing detergent shaped bodies (1, 2) whose top side and/or bottom side (3, 4; 9, 10), at least in areas (7, 8; 14, 15), are/is concave in a uniformly cross-sectional manner or convex in a uniformly cross-sectional manner.

Description

 , Shape-optimized detergent tablets "

The invention is directed to detergent tablets with a volume of 15-80 cm ³ , preferably 30-40 cm ³ , in particular in a circular cylindrical basic form made of compressed particulate detergent, containing more than 10% by weight of surfactants, which has a jacket surface and the top and bottom has and a method for its production and use.

The invention relates to the technical field of detergent tablets for washing textiles in washing machines, in particular household washing machines, which are usually referred to as detergent tablets.

Detergent tablets are widely described in the prior art and have become firmly established as a form of offer for detergents and cleaning products in addition to the usual powdery products, in particular in the dishwasher detergent segment. Machine dishwashing detergents have a number of differences from detergents for washing textiles. So they have extremely low surfactant contents (usually well below 5 wt .-%) and have disintegration or dissolution times that are adapted to the conditions in dishwashers, where they have to survive a pre-wash at a lower temperature in order to be during a main wash at temperatures of 55 to 70 ° C slowly dissolve. While machine dishwashing detergents in tablet form come into contact with large amounts of hot water, the conditions for textile detergents and textile washing machines are different: Here cold water is washed into the machine so that the detergent is conveyed from the detergent dispenser into the machine or in the machine submitted detergent dissolves. In addition, the amounts of water are significantly lower, so that a form of “molded body” cannot be pressed so hard in order not to increase the disintegration time or solubility too drastically. While hardness above 150 N is the rule for dishwasher detergent tablets, detergent tablets may only have a hardness of up to 80 N to ensure sufficient disintegration times. In addition to the advantage of improved disintegration times, these low hardnesses have disadvantages in the production and handling of the tablets. Modern tableting machines have an output of up to 1000 molded articles per minute, which then have to be braked laterally and / or frontally and fed to a packaging unit. The tablets must not break or rub under mechanical stress, which is a greater technical problem for detergent tablets because of their lower hardness than for detergent tablets. Detergent tablets for machine dishwashing, but also water softening tablets, are mainly available in the market in round or rectangular form, the former, the flat cylinder, being of little importance compared to the second, the orthorhombus. The rectangular base of these moldings is due to the technical necessity that the moldings have to fit into the dosing chambers of the dishwashers, which open after the prewash cycle. Since these chambers are rectangular in shape, rectangular shaped bodies fit better into them. Shaped articles with a rectangular base are unknown in the field of detergent tablets for textile laundry. Only round detergent tablets in the shape of a circular cylinder with a flat top and bottom and possibly a chamfer in the transition from the cylinder jacket surface to the top and bottom are available on the market. To ensure sufficiently short disintegration times, these flat cylinders may only have a hardness of max. 80 N.

The object of the present invention is to provide a detergent tablet which has high hardness and short disintegration times.

In particular, it should quickly disintegrate into its secondary particles, so that it can find out about the

Allow the washing-in chamber to wash in household washing machines.

Furthermore, it should withstand the mechanical loads during the manufacturing process and should have the greatest possible variability in terms of its composition, if not

Recipe components of the detergent through useless in the washing process

To have to replace tabletting additives. In the case of a detergent tablet of the type mentioned at the outset, this object is achieved according to the invention in that the top and / or bottom of the tablet are / are at least partially uniformly cross-sectionally concave or uniformly cross-sectionally convex.

This ensures that the detergent tablet has a larger surface area, for example, compared to a flat cylindrical shape or a flat rectangular shape of the same amount of detergent. This leads to more detergent being released from the inflowing water in the washing-up chamber of a washing machine and the detergent tablet to disintegrate more quickly or, if the detergent tablet is tougher, to decay just as quickly as a softer detergent tablet. In other words, the detergent tablets can have a higher hardness at the same rate of disintegration, which makes them more resistant due to the associated higher abrasion resistance, in particular to mechanical stresses during the packaging and transport process.

In particular, the detergent tablet is one with a circular cylindrical basic shape.

In the case of a shaped detergent body with a convex upper and / or lower side, this also fits better in the commercial washing machine dispenser compartments to better conform to the bottom contour, thereby dipping deeper into the compartment and better wetted by the inflowing water. This leads to a further improvement in its disintegration and dissolution rate, the detergent tablet often being set in rotation by the inflowing water due to its unstable contact surface, which further promotes its disintegration.

In the case of a detergent tablet having a concave top and / or bottom, the concave surfaces act like water collectors, which means that the central region of the detergent tablet is severed relatively quickly. This severing then has an even larger one that is exposed to the water flow Surface result, which further promotes the rapid dissolution or disintegration of the molded body or its individual parts then existing.

To combine both effects, it may also be possible to make one side concave and one side convex.

In a further development, the invention provides that the respective transition from the outer surface to the concave or convex upper and / or lower side of the shaped body is designed as an annular chamfer.

A technical advantage of this training is the lower tendency to wear on the edges of the molded body.

Geometrically simple and technically inexpensive pressing tools are required for the production of the detergent tablet if the concave or convex surface area directly adjoins the respective chamfer, as provided by the invention in one embodiment.

For the stackability of detergent tablets, in particular those with a concavely shaped top and bottom, and for achieving the abrasion resistance required for stacking one on top of the other, it is advantageous according to a further development of the invention if the bevel is first connected to an annular surface area which is oriented perpendicularly to the lateral surface, which then merges into the concave or convex area from the top and / or bottom.

Detergent tablets according to the invention have surfactant contents which are above 10% by weight, based on the weight of the tablet. The surfactants they contain come from the group of anionic, nonionic, cationic and / or zwitterionic surfactants, mixtures of anionic and nonionic surfactants being preferred from an application point of view. In general, detergent tablets which contain anionic and / or nonionic surfactants and have a total surfactant content of at least 12.5% by weight, preferably at least 15% by weight and in particular at least 20% by weight, are preferred in the context of the present invention on the weight of the molded body.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C 1 -C 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 -CC ₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonyl methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures, as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the 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 1 -C ₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁ -C ₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which are a synthetic, petrochemical-based, straight-chain alkyl radical contain, which have a similar degradation behavior as the adequate compounds based on oleochemical raw materials. The Cj ₂ - C _{] 6} alkyl sulfates and C ₂ -C ₅ alkyl sulfates and Cj ₄ -C 1 alkyl sulfates are preferred for washing technology reasons. 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- ι alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C _9- n 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 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 ₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -i4 alcohols with 3 EO or 4 EO, C ₉ n alcohol with 7 EO, C ₃ - ₅ alcohols with 3 EO, 5 EO,

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

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

8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4. Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as them are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.

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 ^J

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 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or is an oxyalkyl radical having 1 to 8 carbon atoms, C _M - alkyl or phenyl radicals being preferred and [Z] being 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.

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

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

Since detergent tablets according to the invention can also be formulated in multiple phases, for example in multiple layers, from an application point of view it can be advantageous if certain classes of surfactant in some phases of the detergent tablet or in the entire molded body, ie in all phases, are not included. A further important embodiment of the present invention therefore provides that at least one phase of the shaped body is free from nonionic surfactants.

Conversely, the content of individual phases or the entire molded body, i.e. all phases, certain surfactants have a positive effect. The introduction of the alkyl polyglycosides described above has proven to be advantageous, so that detergent tablets are preferred in which at least one phase of the tablets contains alkyl polyglycosides.

Similar to the nonionic surfactants, the omission of anionic surfactants from individual or all phases can result in detergent tablets which are more suitable for certain fields of application. In the context of the present invention, therefore, detergent tablets are also conceivable in which at least one phase of the tablet is free from anionic surfactants.

Surfactants from the groups of the cationic and / or zwitterionic or amphoteric surfactants can be used as further surfactants in the detergent tablet.

In addition to the surfactants, builders are the most important ingredients in detergent tablets. All of the builders commonly used in detergents can be contained in the detergent tablet, in particular thus zeolites, silicates, carbonates, organic cobuilders and — where there are no ecological prejudices against their use — the phosphates.

Detergent tablets preferred in the context of the present invention additionally contain one or more builders, preferably from the group of silicates and aluminosilicates, in amounts of 10 to 40% by weight, preferably 15 to 35% by weight and in particular 20 to 30% by weight .-%, each based on the weight of the molded body.

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 are preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na Si ₂ O ₅ 'yH 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 Na ₂ O: SiO modulus of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, which delay the dissolution, can also be used are and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles are added

Electron diffraction experiments provide washed-out or even sharp diffraction maxima. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, are also suitable Zeolite X and mixtures of A, X and / or P. Commercially available and preferably used in the context of the present invention is, for example, a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which of is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and through 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 type of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

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.

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

Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that 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.

If universal detergents are to be produced within the scope of the present invention, the use of bleaching agents is recommended in the detergent tablets according to the invention. Among the compounds which provide HO in water and provide bleaching agents, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and HO ₂ -supplying acidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced.

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 monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidopercapate

[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-diperoxyazelaic acid diperidic acid, diperacid acid, diperidic acid, diperacid acid

Diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid) can be used. Detergent tablets preferred in the context of the present invention additionally contain one or more bleaching agents, preferably from the group of peroxy bleaching agents, with particular preference for one or more substances from the group of sodium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate, in amounts of 5 to 30% by weight. %, preferably from 10 to 25% by weight and in particular from 15 to 20% by weight, in each case based on the weight of the shaped body.

In order to facilitate the disintegration of highly compressed moldings, disintegration aids, so-called tablet disintegrants, can be incorporated into them 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 accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling) and on the other hand a pressure can be generated by the release of gases, which breaks the tablet into smaller particles disintegrates. Well-known 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 weight of the tablet.

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets have such a disintegrant based on cellulose Contain amounts of 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ 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 pressed. Detergent tablets which contain disintegrants in granular or, if appropriate, cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application 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 at least 90% by weight between 400 and 1200 μm. The above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier available in the present invention.

Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, into granules with an average particle size of 200 μm.

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

The detergent tablets with surfactant contents above 10% by weight, based on the weight of the tablet, can contain further conventional detergent ingredients, bleach activators, enzymes, polymers, foam inhibitors, graying inhibitors, colorants and fragrances being particularly mentioned.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated. Compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used as bleach activators become. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (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 triacetoxy and 2,5-diacetyloxy and 2,5-glycethylacetyl, ethylene glycol 2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the 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. 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. In addition, the detergent tablets can also contain components which have a positive effect on the ability to wash out oil and fat from textiles (so-called soil repellents). This effect becomes particularly clear if a textile is soiled that has already been washed several times with a detergent containing this oil and fat-dissolving component. The preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or of 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 of these. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

The moldings can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which, instead of the morpholino group, have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can also be used.

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

The 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, but it can also be advantageous to apply the fragrances to supports which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance for the textiles due to the slower release of the fragrance. 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 moldings, 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 long shelf life and are non-sensitive compared to the other ingredients of the agents and against light and no pronounced substantivity towards textile fibers, so as not to stain them.

The production of wash-active molded articles is carried out by applying pressure to a mixture to be pressed, which is located in the cavity of a press. In the simplest case of molded article production, which is simply called tableting below, the mixture to be tabletted is directly, i.e. pressed without prior granulation. The advantages of this so-called direct tableting are its simple and inexpensive application, since no further process steps and consequently no further plants are required. However, these advantages are offset by disadvantages. For example, a powder mixture that is to be tabletted directly must have sufficient plastic deformability and have good flow properties; furthermore, it must not show any tendency to segregate during storage, transport and filling of the die. These three requirements are extremely difficult to master with many substance mixtures, so that direct tableting is not often used, particularly in the 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.

In one method, the above object is achieved in that a particulate premix with a surfactant content of more than 10% by weight, based on the premix, is pressed in a press, the pressing tools of which are convex to the top and / or bottom of the shaped body or have concave surface areas.

Detergent tablets are usually first produced by dry mixing the constituents, which can be wholly or partially pregranulated, and then providing information, in particular pressing them into tablets, using conventional methods. To make the Detergent tablets, the premix is compressed in a so-called matrix between two stamps to form a solid compressed product. This process, which is briefly referred to below as tabletting, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.

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

Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down. Eccentric tablet presses are preferred for small production quantities used, in which the stamp or stamps are attached 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 disk, the number of die holes being correspondingly increased. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available. Each die on the die table is assigned an upper and lower stamp, with the pressing pressure being active only by the upper or lower die. Lower stamp, but can also be built up by both stamps. The die table and the stamps move around a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation. Wherever a particularly serious lifting or lowering of the punches is required (filling, compacting, ejecting), these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks. The die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix. The pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers.

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

Tableting machines suitable within the scope of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy NV, Halle (BE / LU). For example, the hydraulic double pressure press HPF 630 from LAEIS, D. is particularly suitable.

In the method according to the invention, the pressing tools have a circular base. Since the pressing tools are positively immersed in the die or limit it if they are not moved, the die bore of the tablet press in the method according to the invention also has a circular cross section (horizontal section). If changes are made to the base surface of a pressing tool, these are to be carried out analogously both on the die and on the opposite pressing tool. In the method according to the invention, too, the configurations of the pressing tool and die referred to above as preferred, which lead to the advantageous detergent tablet shapes.

Detergent tablets with a concave or convex top and / or bottom have so far not been commercially available and the advantages in their handling are not described in the prior art.

Another object of the present invention is therefore the use of such detergent tablets for cleaning textiles in a washing machine. The present invention allows the production and safe packaging of detergent tablets; which are characterized by short disintegration times. Shatter-resistant molded articles are obtained, the dosing of which is possible without problems and without residues via the induction chamber of household washing machines.

A preferred embodiment according to an embodiment of the invention is therefore the use characterized in that the detergent tablet is added via the induction chamber of a household washing machine.

The invention is explained below using a drawing as an example. This shows in

Fig. 1 in cross section a cylindrical detergent tablet with a convex top and bottom and in Fig. 2 in cross section a cylindrical detergent body with a concave

Top and bottom.

The shaped detergent tablets generally designated 1 and 2 in FIGS. 1 and 2 are circular cylindrical in their basic shape.

The embodiment according to FIG. 1 shows in cross-section a detergent tablet with top and bottom surfaces 3, 4 which are uniformly convex in cross-sectional areas. Both on the top side 3 and on the bottom side 4 there is the transition from the cylinder jacket surface 5 to the respective cross-sectionally convex surface area 7, 8 a chamfer 6 is formed. Because of the circular cylindrical basic shape of the detergent shaped body 1, these bevels 6 are annular. The chamfers 6 are then directly adjoined by the uniform cross-sectional convex surface areas 7, 8 of the top and bottom. Due to the circular cylindrical base of the detergent tablet 1, these surface areas 7, 8 are raised in a dome-like manner with a circular base.

FIG. 2 shows a shaped detergent body 2 with upper and lower sides 9, 10 which are concavely shaped in cross-section in certain areas. Both on the Top 9 and bottom 10 is in the transition from the cylinder surface

11 a chamfer 12 is initially formed on the top and bottom. As in the exemplary embodiment according to FIG. 1, these bevels 12 are also annular. To the bevels

12 are then connected in each case to annular surface areas 13 which are oriented perpendicular to the cylindrical surface area 11, before the surface areas 14, 15 which are concavely shaped in cross-section then connect to the interior of the shaped detergent body. Due to the circular cylindrical base of the detergent tablet 2, these surface areas are trough-shaped with a circular base.

The detergent tablets 1, 2 have a volume of 35-38 cm ³ .

The detergent tablets 1 and 2 were produced by granulation in a 50 liter ploughshare mixer from Lödige. A surfactant-containing granulate (for composition, see Table 1) was produced, 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.

A premix was prepared by mixing the granules containing the surfactant with bleach, bleach activator and other processing components, after which the premixes were compressed into tablets in a Korsch eccentric press. The composition of the premixes to be pressed (and thus the shaped body) is shown in Table 2.

In the exemplary embodiments, the surface regions 7, 8 are both convex and the surface regions 14, 15 are both concave. However, it is also possible to form one upper or lower side concave and the other convex, or one upper or lower side concave or convex and the other flat and without curvature. Table 1: Composition of the surfactant granules [% by weight]

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

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

Claims

Claims: 1. Detergent tablets (1, 2) with a volume of 15 - 80 cm ³ , preferably 30 - 40 cm, in particular in a circular cylindrical basic shape, made of compressed particulate detergent, containing more than 10% by weight of surfactants, which has a lateral surface (5, 11) and top and bottom, characterized in that the top and / or bottom (3, 4; 9, 10) of the shaped body (1, 2) at least in regions (7,8; 14, 15) have a uniformly concave cross section or are / are uniformly convex in cross section. 2. Detergent molded article according to claim 1, characterized in that the respective transition from the outer surface (5; 11) to the concave or convex shaped upper and / or lower side (3,4; 9,10) of the molded article (1,2) than annular chamfer (6, 12) is formed. 3. Detergent molded article according to claim 1 or 2, characterized in that the concave or convex surface area (7,8; 14,15) adjoins the respective chamfer (6, 12). 4. Detergent molded article according to claim 1 or 2, characterized in that the chamfer (12) is first connected to an annular surface area (13) which is oriented perpendicular to the lateral surface (11) and which then extends into the concave or convex area (14, 15). passes from the top and / or bottom (9, 10). 5. Detergent tablets according to one of claims 1 to 4, characterized in that it contains anionic and / or nonionic surfactants and a total surfactant content of at least 12.5% by weight, preferably at least 15% by weight and in particular at least 20% by weight .-%, each based on the molded body weight. 6. Detergent tablets according to one of claims 1 to 5, characterized in that it additionally contains one or more builders, preferably from the group of silicates and aluminosilicates, in amounts of 10 to 40% by weight, preferably 15 to 35% by weight. % and in particular from 20 to 30 wt .-%, each based on the molded body weight, contains. 7. Detergent form according to one of claims 1 to 6, characterized in that it additionally contains one or more bleaching agents, preferably from the group of peroxy bleaching agents, with particular preference for one or more substances from the group of sodium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate, in amounts of 5 to 30 wt .-%, preferably from 10 to 25 wt .-% and in particular from 15 to 20 wt .-%, each based on the molded body weight. 8. Detergent form according to one of claims 1 to 7, characterized in that it additionally contains a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably of 3 to 7 wt .-% and in particular from 4 to 6 wt .-%, each based on the molded body weight, contains. 9. A process for the preparation of a detergent molded article with the features according to one of claims 1 to 8, characterized in that a particulate premix with a surfactant content of more than 10% by weight, based on the premix, is pressed in a press, the pressing tools of which on the contrary, have convex or concave surface areas to the top and / or bottom of the molded body. 10. Use of a Waschmittelformköφers with the features of one of claims 1 to 9 for cleaning textiles in a washing machine. 1. Use according to claim 10, characterized in that the Waschmittelformköφer is added via the dispenser of a household washing machine.