EP1123381B1 - Detergent and cleaning agent shaped body/packaging combination - Google Patents

Abstract

The present invention describes a combination consisting of detergent and cleaning agent shaped body or bodies that contains alkyl benzole sulfonate(s) and cellulose-based disintegration auxiliary agents and a packaging system containing the detergent and cleaning shaped body or bodies, having a moisture vapor permeability rate ranging between 0.1 g/m<2>/day and less than 20 g/m<2>/day when the packaging system is stored at 23 DEG C and with a relative equilibrium moisture of 85 %. The detergent and cleaning agent shaped bodies exhibit high hardness and short disintegration period in said combinations.

Description

The present invention relates to tablets containing alkylbenzenesulfonate (s) and disintegration aids based on cellulose and to ensure better disintegration times combined with a special packaging system at the same time high hardness become. In particular, the invention relates to such specially packaged tablets as Detergent tablets, detergent tablets, bleach tablets or water softener tablets with alkylbenzenesulfonate (s) and disintegration aid (s) based on cellulose.

Detergent and detergent compositions in the form of tablets are known The technique has long been known and broadly described, although this form of supply on the Market so far has no outstanding significance. This is due to the fact that the Offering form of the tablet in addition to a number of advantages also has drawbacks, both affect the manufacture and use as well as consumer acceptance. The main advantages of tablets such as the elimination of the size of the needed Quantity of product by the consumer, the higher density and thus the reduced packaging and storage costs and a not to be underestimated aesthetic aspect doing with disadvantages such as the dichotomy between acceptable hardness and enough faster disintegration and dissolution of the tablets as well as numerous technological Difficulties in production and packaging relativized.

In particular, the dichotomy between a sufficiently hard tablets and a sufficient fast disintegration time is a central problem. Since sufficiently stable, i. Shaped and break-resistant tablets produced only by relatively high pressures can be, it comes to a strong compaction of the tablet components and a consequent delayed disintegration of the tablet in the aqueous Liquor and thus too slow a release of the active substances in the washing or

Cleaning process. The delayed disintegration of the tablet also has the disadvantage that usual detergent tablets are not on the Einspülkammer of household washing machines Rinse, as the tablets are not in a sufficiently fast time in Secondary particles, which are small enough to disintegrate from the dispenser compartment, decay Wash tub to be washed.

In the prior art, there is often some instability of detergent ingredients, especially bleaches, highlighted. Solutions to this Problems are, for example, in the coating of the crystalline bleach, in the addition of stabilizing agents during the manufacturing process or in a combination of these two measures. The stabilizer and / or coating bleaching technology does not deal with the dichotomy between Hardness and disintegration times of detergent tablets. Problems that the Incorporation of certain anionic surfactants in detergent tablets especially if these cellulose-based disintegrating agents are included hitherto neither acknowledged in the prior art, nor are solution approaches described.

An interesting approach to ensuring the stability of sodium percarbonate over extended periods of storage is given in EP-B-0 634 484 (Procter & Gamble): This document describes the combination of a granular detergent composition and a packaging system to provide active oxygen To avoid losses from the percarbonate. Also in this document, there is neither information on detergent tablets, nor is the problem of high disintegration times at high hardness mentioned.

The international patent application WO98 / 40464 (Unilever) describes a combination of at least one tablet of compressed particulate detergent, which is stored at least 24 hours h in a packaging system having a moisture permeability rate of less than 20 g / m ^2/24 h. According to this document, this combination increases the hardness of the tablets during storage, while the dissolution times are reduced. Although the disintegration time of the tablets according to the information in this document under mechanical action (stirring) is measured, all disintegration times are well over 2 minutes. Such high disintegration times make the tablets disclosed in this document unusable for metering via the dispensing chamber of household washing machines, since they do not disintegrate sufficiently quickly and thus can not be flushed. The use of disintegration aids based on cellulose is also not mentioned in this document.

US Pat. No. 4,099,912 (Colgate) discloses combination products based on detergent tablets of different composition. The different tablets can be combined as needed to a washing or cleaning agent adapted to the respective needs. Information about the packaging of these tablets does not make this document.

Phosphate and chlorine-free detergent tablets are the subject of WO95 / 04804 (La Marina). The tablets disclosed in this document likewise contain no cellulose-based disintegration aids such as the detergent tablets based on effervescent systems described in WO 97/35955 (Kärcher).

Finally, tablets in which microcrystalline to fibrous cellulose is used are disclosed in DE 2321693 (Henkel). The fibrous cellulose acts as a binder depending on the fiber length, for example, and is used in the tablets without prior granulation.

The present invention was based on the object, the advantages of the use of alkylbenzenesulfonates also to use in detergent tablets, which Contain cellulosic disintegration aids while providing tablets, which are characterized by high hardness with short decay times. In addition to the Overcoming this dichotomy between hardness and disintegration time the tablets should be so Have short disintegration times that a dosage on the dispenser usually household Washing machines easily and residue-free is possible.

Surprisingly, it has now been found that the above-mentioned objects by the packaging of one or more alkylbenzenesulfonate and cellulose-containing detergent tablets can be solved in special packaging systems.

The subject of the present invention is a combination of a detergent tablet (s); containing alkylbenzenesulfonate (s) and cellulose-based disintegration aids in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, and a packaging system containing the detergent tablet (s), characterized in that the packaging system has a moisture vapor transmission rate from 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system is stored at 23 ° C and a relative equilibrium moisture content of 85%.

The packaging system of the detergent tablet (s) combination and packaging system according to the invention has a moisture vapor transmission rate of 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system is at 23 ° C and a relative equilibrium moisture content of 85 % is stored. The temperature and humidity conditions mentioned are the test conditions specified in DIN standard 53122, with minimum deviations permissible according to DIN 53122 (23 ± 1 ° C, 85 ± 2% relative humidity). The moisture vapor transmission rate of a given packaging system or material can be determined by other standard methods and is also, for example, in the ASTM standard E-96-53T (test for measuring water vapor transmission of material in sheet form) and TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at High Temperature Humidity"). The measuring principle of common methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container is sealed at the top with the material to be tested. From the surface of the container, which is closed with the material to be tested (permeation surface), the increase in weight of the calcium chloride and the exposure time, the moisture vapor transmission rate decreases FDDR = 24 · 10000 A · x y [ G / m 2 / 24 H ] where A is the area of the material to be tested in cm ² , x is the weight gain of calcium chloride in g and y is the exposure time in h.

The relative equilibrium moisture, often referred to as "relative humidity", in the measurement of moisture vapor transmission rate in the present invention is 85% at 23 ° C. The absorption capacity of air for water vapor increases with the temperature up to a respective maximum content, the so-called saturation content, and is expressed in g / m ³ . For example, 1 m ^{3 of} air is saturated by 17 ° with 14.4 g of water vapor, at a temperature of 11 ° saturation is already present with 10 g of water vapor. The relative humidity is the percentage expressed ratio of the actually existing water vapor content to the saturation content corresponding to the prevailing temperature. For example, if air at 17 ° contains 12 g / m ^{3 of} water vapor, then the relative humidity is (12 / 14.4) x 100 = 83%. If this air is cooled off, the saturation (100% RH) is reached at the so-called dew point (in the example: 14 °), ie, upon further cooling, a precipitate forms in the form of mist (dew). Hygrometers and psychrometers are used to quantify moisture.

The relative equilibrium humidity of 85% at 23 ° C can be, for example, in laboratory chambers with humidity control to +/- 2% r.L. depending on the device type. set exactly. Also over saturated solutions of certain salts form in closed systems at a given temperature constant and well-defined relative humidities, the on the phase equilibrium between partial pressure of the water, saturated solution and soil body based.

The combinations of laundry detergent tablets and packaging system according to the invention can, of course, in turn in secondary packaging, such as cardboard or trays, with no secondary requirements on the secondary packaging have to be asked. The secondary packaging is therefore possible, but not necessary.

Packaging systems preferred in the present invention have a moisture vapor transmission rate of from 0.5 g / m ² / day to less than 15 g / m ² / day.

The packaging system of the combination according to the invention encloses depending on the embodiment the invention one or more detergent tablets. It is according to the invention preferred to make either a tablet such that it is an application unit of the washing and cleaning agent, and to pack this tablet individually, or to pack the number of tablets in a single packaging unit Application unit includes. At a nominal dosage of 80 g washing and cleaning agent So it is possible according to the invention to produce a tablet weighing 80 g and individually pack, but it is also possible according to the invention, two each 40 g heavy Pack detergent tablets in a package to form a present invention Combination to arrive. Of course, this principle can be extended so that According to the invention combinations also three, four, five or more detergent tablets contained in a packaging unit. Of course, two or three more tablets in a package have different compositions. On this way it is possible to spatially separate certain components from one another For example, to avoid stability problems.

The packaging system of the combination according to the invention can be made of the most diverse Materials exist and assume any external forms. For economic reasons However, for reasons of ease of processing, packaging systems are preferred in which the packaging material has a low weight, easy to process and is inexpensive. In preferred combinations according to the invention the packaging system from a bag or sack. single layer or laminated Paper and / or plastic film.

In doing so, the detergent tablet may be unsorted, i. as loose bulk, in one Pouch can be filled from the mentioned materials. It is for aesthetic reasons and preferred for sorting the combinations in secondary packaging, the detergent tablet one by one or several sorted into sacks or bags to fill. For individual Application units of detergent tablets, which are in a bag or sack, the term "flow pack" has become common in the art. Such "flow packs" can then - optionally again sorted - optionally packed in outer packaging become what the compact offering form of the tablet underlines.

The preferably used as packaging system bags or bags of single-layer or laminated paper or plastic film can be designed in a variety of ways, such as inflated bag without center seam or bags with center seam, which closed by heat (heat fusion), adhesives or adhesive tapes become. Single-layer bag or bag materials are the known papers, which may optionally be impregnated, as well as plastic films, which may optionally be coextruded. Plastic films which can be used in the context of the present invention as a packaging system, for example, in Hans Domining House "The Plastics and their properties", 3rd edition, VDI Verlag, Dusseldorf, 1988, page 193 indicated. The figure 111 shown there also provides clues to the water vapor permeability of the materials mentioned.

In the context of the present invention, particularly preferred combinations as a packaging system, a bag or bags of single-layer or laminated Plastic film with a thickness of 10 to 200 .mu.m, preferably from 20 to 100 .mu.m and in particular from 25 to 50 microns.

Although it is possible, in addition to the films or papers mentioned also wax-coated To use paper in the form of cardboard packaging as a packaging system for the detergent tablet, It is preferred in the context of the present invention, when the packaging system does not include boxes of wax-coated paper. The term "packaging system indicates in the context of the present invention always the primary packaging of the tablets, i. the packaging, which on its inside directly with the tablet surface is in contact. At an optional secondary packaging are no requirements so that all the usual materials and systems are used here can.

As already mentioned above, the detergent tablets of the invention Combination depending on their intended use further ingredients of washing and Detergents in varying amounts. Regardless of the purpose of the According to the invention, tablets are preferred in that the detergent tablets have a relative Equilibrium moisture content of less than 30% at 35 ° C / exhibit.

The relative equilibrium moisture content of the detergent tablet can be standardized Be determined in the context of the present investigations A water-impermeable 1-liter jar with a lid, which has a closable opening for the introduction of samples has been filled with a total of 300 g detergent tablets and kept at a constant 23 ° C for 24 h to ensure a uniform temperature of vessel and substance - The water vapor pressure in the room above the tablets can then with a hygrometer (Hygrotest 6100, Testoterm Ltd., England). The water vapor pressure is now every 10th Minutes until two consecutive values show no deviation (Equilibrium moisture). The o.g. Hygrometer allows a direct display of the recorded Values in% relative humidity.

In combinations preferred in the context of the present invention contains / contain the detergent tablet (s) other surfactant (s) and builder (s).

In order to facilitate the disintegration of the laundry detergent tablets according to the invention, these contain a disintegration aid based on cellulose. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.

The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives. The cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. Detergent tablets containing disintegrating agents in granular or optionally cogranulated form are described in German Patent Application DE 197 10 254 (Henkel). Such tablets are preferred in the context of the present invention. Accordingly, according to the invention, a combination is particularly preferred in which the detergent tablet (s) comprises the disintegration aid based on cellulose in granular, cogranulated or compacted form, in amounts of from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case on tablet weight, contains / contains.

Another disintegrating agent based on cellulose or as part of this component Microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only the amorphous regions (about 30% of the total cellulose mass) attack the celluloses and completely dissolve, leaving the crystalline areas (about 70%) undamaged. A subsequent deaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses having primary particle sizes of about 5 microns and, for example, compactable into granules with an average particle size of 200 microns are.

Disintegration-promoting systems are often also called "detergent tablets" "Showering systems" used. Usually, in effervescent systems oligomeric oligocarboxylic acids such as succinic acid, maleic acid and especially citric acid in combination used with carbonates or bicarbonates. In preferred embodiments However, according to the present invention, the detergent tablet is not a "effervescent tablet", i.e. preferred detergent tablets are free of oligomeric oligocarboxylic acids, especially citric acid.

Technically also possible is the coating of the tablet, with a coating that covers the entire Tablet covers. Such coated detergent tablets can be sprayed on a melt or solution of the coating material on the tablet body or Immerse the tablet body in the melt or solution are prepared.

By the use according to the invention of the disintegration aid based on cellulose and the alkylbenzenesulfonate in combination with the packaging system and optionally supported by the use of further disintegration aids (see above) According to the invention, detergent tablets are produced which at high hardnesses in water extremely quickly disintegrate into their components.

For the development of the washing or cleaning performance, the inventive Combinations of alkylbenzenesulfonate (s). Alkylbenzenesulfonates as powerful anionic Surfactants have been known since the thirties of this century. At that time were by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation Alkylbenzenes prepared that sulfonated with oleum and neutralized with sodium hydroxide solution were. In the early fifties was for the production of alkylbenzenesulfonates Propylene to tetramerized branched α-dodecylene and the product over a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride converted to tetrapropylene benzene, which was subsequently sulfonated and neutralized. This economical way of producing tetrapropylene benzenesulfonates (TPS) led to the breakthrough of this class of surfactants, which subsequently used the soaps as the main surfactant in Washing and cleaning agents displaced.

Due to the lack of biodegradability of TPS, there was a need represent new alkylbenzenesulfonates, characterized by an improved ecological behavior distinguished. These requirements are met by linear alkylbenzenesulfonates, which are today almost exclusively produced alkylbenzenesulfonates and with the abbreviation ABS.

Linear alkylbenzenesulfonates are prepared from linear alkylbenzenes, which in turn are accessible from linear olefins. For this purpose, petroleum fractions are industrially separated with molecular sieves into the n-paraffins of the desired purity and dehydrogenated to the n-olefins, resulting in both α- and i-olefins. The resulting Olefins are then in the presence of acidic catalysts with benzene to the alkylbenzenes implemented, with the choice of Friedel-Crafts catalyst influence the isomer distribution of the resulting linear alkylbenzenes has: When using Aluminum trichloride, the content of the 2-phenyl isomers in the mixture with the 3-, 4-, 5 and other isomers at about 30 wt .-%, however, is hydrogen fluoride as a catalyst used, the content of 2-phenyl isomer can be reduced to about 20 wt .-%. The Sulfonation of linear alkylbenzenes finally succeeds on an industrial scale with oleum, Sulfuric acid or gaseous sulfur trioxide, the latter by far the most significant Has. For the sulfonation special film or tube bundle reactors are used, which provide as product a 97 wt .-% alkylbenzenesulfonic acid (ABSS), the so marketed with NaOH to give aqueous ABS pastes with active substance contents around 60 % By weight is neutralized, which then go on sale.

in der die Summe aus x und y üblicherweise zwischen 5 und 13 liegt. Im Rahmen der vorliegenden Erfindung sind Kombinationen bevorzugt, in denen die Waschmitteltabletten die Alkalimetall-, vorzugsweise Natriumsalze, von C_8-16-, vorzugsweise C_9-13-Alkybenzolsulfonsäuren enthalten, die sich von Alkylbenzolen ableiten, welche einen Tetralingehalt unter 5 Gew.-%, bezogen auf das Alkylbenzol, aufweisen.By choosing the neutralizing agent, a wide variety of salts, ie alkylbenzenesulfonates, can be obtained from the ABSS. For reasons of economy, it is preferred in this case to prepare and use the alkali metal salts and, among these, preferably the sodium salts of ABSS. These can be described by the general formula I:

in which the sum of x and y is usually between 5 and 13. In the present invention combinations are preferred in which the detergent tablets of the alkali metal, preferably sodium salts, of C _8-16 - containing, preferably C _9-13 -alkylbenzenesulfonic acids derived from alkylbenzenes having a tetralin content below 5 wt %, based on the alkylbenzene.

It is further preferred to use in the combinations according to the invention alkylbenzenesulfonates whose alkylbenzenes were prepared by the HF process, so that combinations are preferred in which the alkylbenzenesulfonate compounds, the alkali metal, preferably sodium, of C _8-16 -, preferably C _9-13 -Alkybenzolsulfonsäuren containing a content of 2-phenyl isomer below 22 wt .-%, based on the alkylbenzenesulfonic acid.

In the combinations according to the invention, the detergent tablet (s) contains / Alkylbenzenesulfonates in amounts preferably from 0.5 to 30 wt .-%, very preferably from 1 to 25 wt .-%, particularly preferably from 2 to 20% by weight and in particular from 5 to 15% by weight, respectively based on the weight of the tablet.

In addition to the alkylbenzenesulfonates, the detergent tablets in the inventive Combination other surfactants (surfactants) containing, preferably come from the groups of anionic and / or nonionic surfactants. The total surfactant content of the tablets is from 5 to 60% by weight, based on the tablet weight, wherein surfactant contents above 15 wt .-% are preferred.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. Examples of surfactants of the sulfonate type are olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Among fatty acid glycerine esters are the mono-, di- and triesters and their mixtures to understand, as with the preparation by esterification of a monoglycerol with 1 to 3 mol fatty acid or obtained 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 with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also, 2,3-alkyl sulfates prepared, for example, according to U.S. Patents 3,234,258 or 5,075,041, which can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 . Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

As further anionic surfactants are particularly soaps into consideration. Are suitable saturated fatty acid soaps, 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 may be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or Triethanolamine. Preferably, the anionic surfactants are in the form of their Sodium or potassium salts, especially 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 on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _{12- 18} alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and _C12-18 alcohol containing 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. 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 include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Another class of preferred nonionic surfactants 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 having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as they are for example, in Japanese Patent Application JP 58/217598 , or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533 .

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

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further suitable surfactants are polyhydroxy fatty acid amides of the formula (II)

wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 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.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (III)

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C _1-4 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 residue.

[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 may then be used, for example the teaching of international application WO-A-95/07331 by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides be transferred.

In the context of the present invention, combinations are preferred in which the Detergent tablets containing anionic (s) and nonionic (s) surfactant (s), with application technology Benefits of certain proportions, in which the individual Surfactant classes can be used, can result.

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

It may have advantages from an application point of view, if certain classes of surfactants in some phases of the detergent tablets or in the whole tablet, i. in all Phases are not included. Another important embodiment of the present invention The invention therefore provides that at least one phase of the tablet is free of nonionic Is surfactants.

Conversely, however, the content of individual phases or of the entire tablet, i.e. all phases, on certain surfactants a positive effect can be achieved. The introduction The alkylpolyglycosides described above have proved to be advantageous, so that detergent tablets are preferred in which at least one phase of the tablet Alkylpolyglycoside contains.

Similar to the nonionic surfactants can also be removed from the omission of anionic Surfactants resulting from single or all phases of detergent tablets, resulting better suited for certain applications. It is therefore within the scope of the present Detergent tablets also conceivable in which at least one phase of Tablet is free of anionic surfactants.

In the detergent tablets of the combination according to the invention, all can usually Be contained in detergents and cleaning agents builders, in particular So zeolites, silicates, carbonates, organic cobuilders and -where no ecological Prejudices against their use exist - also the phosphates.

Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are. Such crystalline sheet 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 is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, whereby β-sodium disilicate can be obtained, for example, by the process described in international patent application WO-A-91/08171 .

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification 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 do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray-amorphous silicates, which likewise have a dissolution delay compared to the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 . Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula nNa ₂ O • (1-n) 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, as well as to a kind of "powdering" of the entire mixture to be pressed, wherein usually both ways for incorporating the zeolite are used in the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course, a use of the well-known phosphates as builders possible, unless such use is avoided for environmental reasons should be. Among the large number of commercially available phosphates, the Alkalimetallphosphate with particular preference of pentasodium or Pentakaliumtriphosphat (Sodium or potassium tripolyphosphate) in the detergents and cleaners industry the biggest meaning.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium phosphate, KDP), KH ₂ PO ₄ , is a white salt of 2.33 gcm ^-3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , loss of water at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 gcm ^-3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals. Na ₄ P ₂ O ₇ is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ gives rise to moles of moles. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are according to the invention just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

As organic cobuilders in the laundry detergent tablets according to the invention, in particular Polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) and phosphonates used become. These classes of substances are described below.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, wherein among polycarboxylic acids such carboxylic acids be understood that carry more than one acid function. For example, these are citric acid, Adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if one such use is not objectionable for environmental reasons, as well as mixtures from 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 thereof.

The acids themselves can also be used. The acids have besides their builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.

As a builder further polymeric polycarboxylates are suitable, these are for example the Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are, in particular, polyacrylates which preferably have a molecular mass of 2000 to 20,000 g / mol. Because of their superior solubility, this can be Group again the short-chain polyacrylates, the molar masses from 2000 to 10000 g / mol, and more preferably from 3000 to 5000 g / mol, are preferred be.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As special Copolymers of acrylic acid with maleic acid have proven to be suitable, the 50 to Containing 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution be used. The content of the (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%.

To improve the solubility in water, the polymers may also be allyl sulfonic acids, such as For example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

Also particularly preferred are biodegradable polymers of more than two different Monomer units, for example those containing as monomers salts of acrylic acid and the maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives contain.

Further preferred copolymers are those which are described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives, of which German Patent Application DE-A-195 40 086 discloses that they also have a bleach-stabilizing effect in addition to cobuilder properties.

Further suitable builder substances are polyacetals, which are prepared by reaction of dialdehydes with polyol carboxylic acids having 5 to 7 C atoms and at least 3 hydroxyl groups can be obtained. Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from Polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out by conventional, for example acid or enzyme catalyzed Procedures are performed. Preferably, they are hydrolysis products with average molecular weights in the range of 400 to 500,000 g / mol. This is a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30, where DE is a common measure of the reducing effect of a polysaccharide compared to dextrose which has a DE of 100. Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are described, for example, in European Patent Applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and International Patent Applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 . Also suitable is an oxidized oligosaccharide according to the German patent application DE-A-196 00 018. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable cobuilders. This is ethylenediamine-N, N'disuccinat (EDDS) preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are zeolithhaltigen and / or silicate-containing Formulations at 3 to 15 wt .-%.

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

Another class of substances with co-builder properties are the phosphonates these are in particular hydroxyalkane or aminoalkanephosphonates. Under the hydroxyalkane phosphonates is the 1-hydroxyethane-1,1-diphosphonate (HEDP) of special importance as a co-builder. It is preferably used as the sodium salt, wherein the disodium salt neutral and the tetrasodium salt alkaline (pH 9). When Aminoalkane phosphonates are preferably ethylenediamine tetramethylene phosphonate (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologues in question. They are preferably in the form of neutral sodium salts, z. B. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP, used. The builder used here is preferably HEDP from the class of phosphonates. The Aminoalkanphosphonate also have a pronounced Schwerinetallbindeabmögen. Accordingly, especially if the agents also contain bleach, be preferred to use Aminoalkanphosphonate, in particular DTPMP, or Use mixtures of the above phosphonates.

In addition, all compounds that are capable of complexes with alkaline earth ions train as co-builders.

The amount of builder is usually between 10 and 70 wt .-%, preferably between 15 and 60 wt .-% and in particular between 20 and 50 wt .-%. In turn the amount of Buildem used depends on the purpose, so that Bleaching agent tablets may have higher amounts of builders (for example between 20 and 70 wt .-%, preferably between 25 and 65 wt .-% and in particular between 30 and 55% by weight), for example detergent tablets (usually 10 to 50 wt .-%, preferably 12.5 to 45 wt .-% us and in particular between 17.5 and 37.5% by weight).

Except for the alkylbenzene sulfonate (s), the cellulose disintegration aid (s) and the optionally used further surfactants and builders the detergent tablets in the combinations according to the invention further in washing and Detergents conventional ingredients from the group of bleaches, bleach activators, Dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, anti redeposition agents, Graying inhibitors, color transfer inhibitors and corrosion inhibitors contain.

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [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, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutan-1,4-diene diacid, N, N-terephthaloyl-di (6-antinopercapronate) can be used.

Also useful as bleaching agents in automatic dishwashing compositions Chlorine or bromine releasing substances are used. Under the appropriate chlorine or bromine-releasing materials include, for example, heterocyclic N-bromo and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof with Cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Combinations preferred in the context of the present invention are packaged Detergent tablets that are suitable for washing colored textiles and no bleach contain. A particularly preferred combination is therefore characterized that the detergent tablet (s) is / are free of bleach (s).

To improve when washing or cleaning at temperatures of 60 ° C and below To achieve bleaching effect, bleach activators can be incorporated. When Bleach activators may be compounds which are aliphatic under perhydrolysis conditions Peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, can be used. Suitable substances are the O- and / or N-acyl groups of said C atom number and / or optionally substituted benzoyl groups. Preference is given several times 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, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place may also so-called bleach catalysts are incorporated. These substances are to bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are useful as bleach catalysts.

It is - similar to the bleaching agents - preferred when the tablets in the inventive Combinations are free of bleach activator (s). In the context of the present Invention preferred combinations are characterized in that the Detergent tablet (s) free of bleach activator (s) is / are.

In order to improve the aesthetic impression of the detergent tablets according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the funds and against Light and no pronounced substantivity to textile fibers, not these to stain.

Preferred for use in the detergent tablets of the combination according to the invention are all colorants that can be oxidatively destroyed in the washing process and mixtures the same with suitable blue dyes, so-called Blautönem. It turned out to be have proven advantageous to use colorants which are in water or at room temperature in liquid organic substances are soluble. Suitable examples are anionic Colorants, e.g. anionic nitrosofarads. A possible colorant is, for example Naphthol green (Color Index (CI) Part 1: Acid Green 1, Part 2: 10020), which is a commercial product for example, as Basacid® Green 970 from BASF, Ludwigshafen, available is, as well as mixtures of these with suitable blue dyes. As further colorants Pigmosol® Blue 6900 (CI 74160), Pigmosol® Green 8730 (CI 74260), Basonyl® Red 545 FL (CI 45170), Sandolan® Rhodamine EB400 (CI 45100), Basacid® Yellow 094 (CI No. 47005), Sicovit® Patent Blue 85 E 131 (Cl 42051), Acid Blue 183 (CAS 12217-22-0, CI Acid Blue 183), Pigment Blue 15 (CI 74160), Supranol® Blue GLW (CAS 12219-32-8, CI Acidblue 221)), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan® Blue (CI Acid Blue 182, CAS 12219-26-0).

When choosing the colorant, it must be taken into account that the colorants do not have too high an affinity for the textile surfaces and, in particular, for synthetic fibers. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, for example the abovementioned Basacid® Green or the abovementioned Sandolan® Blue, colorant concentrations in the range from a few 10 ^-2 to 10 ^-3 % by weight are typically selected. In the case of the particularly preferred, but less readily water-soluble, pigment dyes, for example the abovementioned Pigmosol® dyes, the suitable concentration of the colorant in detergents or cleaners is typically between 10 ^-3 and 10 ^-4 % by weight. ,

The tablets may be optical brighteners of the diaminostilbene disulfonic acid type or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar compounds which, instead of the morpholino group, have a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group wear. Furthermore, brighteners of the type of substituted Diphenylstyryle present be, 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-sulfosylryl) -diphenyls. Also mixtures The aforementioned brightener can be used. The optical brighteners are in the laundry detergent tablets according to the invention in concentrations between 0.01 and 1 Wt .-%, preferably between 0.05 and 0.5 wt .-% and in particular between 0.1 and 0.25 wt .-%, each based on the total tablet used, if their use desired becomes. In preferred combinations, the packaged detergent tablets however, free of optical brighteners, so that preferred combinations are characterized are that the detergent tablet (s) is / are free of optical brighteners.

Fragrances are added to the compositions according to the invention to give the aesthetic impression to improve the products and give the consumer a visual and in addition to performance sensory "typical and distinctive" product to provide. As perfume oils or fragrances may be individual fragrance compounds, e.g. the synthetic one Products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type be used. Fragrance compounds of the ester type are known e.g. benzyl acetate, Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. To the Ethem include, for example, benzyl ethyl ether, to the aldehydes e.g. the linear alkanals with 8-18 C-atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the ionone, α-isomethylionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, Phenylethyl alcohol and terpineol, the hydrocarbons belong mainly the terpenes like limonene and pinene. However, mixtures of various are preferred Uses fragrances that together create a pleasing fragrance. Such Perfume oils may also contain natural fragrance mixtures, such as those from vegetable Sources are accessible, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Muskateller, sage oil, chamomile oil, clove oil, lemon balm oil, Mint oil, cinnamon leaf oil, lime 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 content of detergent tablets is usually in the combinations according to the invention perfumes up to 2% by weight of the total formulation. The perfumes can be incorporated directly into the compositions of the invention, but it can also be advantageous to apply the fragrances on carriers that the adhesion of the perfume intensify the wash and by a slower release of fragrance for long-lasting Fragrance of the textiles provide. Examples of such carrier materials are cyclodextrins proven, wherein the cyclodextrin-perfume complexes additionally with other Excipients can be coated.

Enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof in question. Particularly suitable are from bacterial strains or Fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents. Preferably, subtilisin-type proteases and in particular Proteases derived from Bacillus lentus. These are enzyme mixtures, for example from protease and amylase or protease and lipase or Protease and cellulase or cellulase and lipase or protease, amylase and lipase or protease, lipase and cellulase, but especially cellulase-containing mixtures of special interest. Peroxidases or oxidases have also been found in some Cases proved to be suitable. The enzymes can be adsorbed to carriers and / or embedded in encapsulants to protect against premature decomposition. Of the Proportion of the enzymes, enzyme mixtures or enzyme granules in the tablets of the invention Combinations may, for example, be about 0.1 to 5% by weight, preferably 0.1 to about 2 wt .-% amount.

In addition, the detergent tablets may also contain components containing the oil and Soil repellents from textiles positively influence (so-called soil repellents). This effect becomes particularly clear when a textile is soiled before several times with a detergent according to the invention, this oil and fat dissolving Component contains, was washed. Among the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and at hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic cellulose ethers, as well as the polymers known from the prior art phthalic acid and / or terephthalic acid or their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. Especially preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

The use of dye transfer inhibiting agents is preferred in the packaged detergent tablets of the present invention. Color transfer inhibitors have the task, possibly from colored textiles dissolved dyes from the wash liquor to keep or suspend them suspended in the fleet and so prevent re-application to the fiber. As color transfer inhibitors, in particular polymers have proven, with the polyvinylpyrrolidone (PVP) plays an outstanding role. Combinations preferred in the context of the present invention are characterized in that the detergent tablet (s) additionally comprises color transfer inhibitors, preferably polyvinylpyrrolidone, in amounts of from 0.1 to 2.0% by weight, preferably from 0.2 to 1.5% by weight. and in particular from 0.5 to 1.0 wt .-%, each based on the tablet weight.
The preparation of washing and cleaning active tablets is done by applying pressure to a mixture to be compressed, which is located in the cavity of a press. In the simplest case of tablet production, which is referred to as tableting in a simplified manner below, the mixture to be tableted is compressed directly, ie without prior granulation. The advantages of this so-called Direkttablettierung are their simple and cost-effective application, since no further process steps and consequently no other systems are needed. However, these advantages are also faced with disadvantages. Thus, a powder mixture, which is to be tabletted directly, have sufficient plastic deformability and have good flow properties, furthermore, it must not show any separation tendencies during storage, transport and filling of the die. These three conditions are extremely difficult to control in many mixtures of substances, so that the direct tabletting is not often used, especially in the production of detergent tablets. The usual way of producing washing and cleaning agent tablets is therefore based on pulverulent components ("primary particles") which are agglomerated or granulated by suitable processes to form secondary particles having a relatively high particle diameter. These granules or mixtures of different granules are then mixed with individual powdered additives and fed to the tableting.

In the context of the present invention, detergent tablets are preferred Pressing a particulate premix of at least one surfactant-containing granules and at least one subsequently admixed powdered component. The surfactant-containing granules can be processed by conventional granulation processes such as mixing and plate granulation, fluidized bed granulation, extrusion, pelletizing or compaction getting produced. It is advantageous for the later detergent tablets, if the premix to be compressed has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular above 700 g / l. Another Advantage can be gained from a narrower particle size distribution of the surfactant granules used result. Detergent tablets are preferred in the context of the present invention, in which the granules particle sizes between 10 and 4000 microns, preferably between 100 and 2000 microns and in particular between 600 and 1400 microns have.

Prior to compression of the particulate premix to detergent tablets, the Premix be "powdered" with finely divided surface treatment agents. This can for the nature and physical properties of both the premix (Storage, compression) and the finished detergent tablets are beneficial. Fine particulate powdering agents are well known in the art, with mostly zeolites, Silicates or other inorganic salts are used. Preference is given to the premix but "powdered" with finely divided zeolite, wherein zeolites of the faujasite type are preferred. In the context of the present invention, the term "zeolite of the faujasite type "all three zeolites containing the faujasite subgroup of the zeolite structure group 4 (Compare Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92). In addition to the zeolite X are therefore also zeolite Y and faujasite and mixtures of these compounds used, wherein the pure zeolite X is preferred.

Also mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which do not necessarily belong to the zeolite structure group 4 are as powdering agents can be used, wherein it is advantageous if at least 50 wt .-% of the powdering agent consist of a zeolite of the faujasite type.

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

The finely divided treatment components with the above particle sizes can while being dry admixed to the pre-mix to be compressed. It is also possible and preferred, they by adding small amounts of liquid substances to the surface of the coarser particles "stick". These Abpuderungsverfahren are in the state of Technique widely described and familiar to the expert. As liquid components, the suitable for the adhesion of the powdering agent, for example, nonionic Surfactants or aqueous solutions of surfactants or other detergent and cleaner ingredients be used. It is within the scope of the present invention preferably, as a liquid adhesion promoter between finely divided Abwuderungsmittel and the coarse particle to use perfume.

To prepare the tablets of the invention, the premixes in a so-called Matrix compressed between two punches to a solid compressed. This Process, which is referred to below as tableting, is divided into four Sections: dosage, compaction (elastic deformation), plastic deformation and Ejection.

The tabletting is carried out in commercial tablet presses, which in principle with single or Double stamping can be equipped. In the latter case, not only the upper punch used for pressure build-up, also the lower punch moves during the Pressing on the upper punch, while the upper punch presses down. For small production quantities are preferably used in eccentric tablet presses the one or more stamps are attached to an eccentric disc, which in turn to a Axis is mounted at a certain rotational speed. The movement of this Preßstempel is similar to the operation of a conventional four-stroke engine. The compression can be done with a top and bottom stamp, but it can also be several Stamp be attached to an eccentric disc, the number of die holes is extended accordingly. The throughputs of eccentric presses vary according to type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs you can choose rotary tablet presses, where on a so-called Matrizentisch a larger number of matrices is arranged in a circle. The Number of matrices varies depending on the model between 6 and 55, with larger matrices are commercially available. Each die on the die table is a top and bottom stamp assigned, in turn, the pressing pressure active only by the upper or lower punch, but can also be built by both stamps. The die table and the Stamps move around a common perpendicular axis, with the stamp by means of rail-like cam tracks during circulation in the positions for filling, Compression, plastic deformation and ejection are brought. In the places where a particularly serious increase or decrease of the stamp required is (filling, compaction, ejection), these curved paths are supplemented by Low pressure pieces, Nierderzugschienen and Aushebebahnen supported. The filling the die is made via a rigidly arranged supply device, the so-called Fill shoe connected to a pre-mix reservoir. Of the Pressing pressure on the premix is individualized via the pressing paths for upper and lower punches adjustable, wherein the pressure build-up by the Vorbeirollen the stamp shank heads happens on adjustable pressure rollers.

Concentric presses can also be equipped with two filling shoes to increase throughput be, with the preparation of a tablet only a semicircle are passed through got to. To produce two- and multi-layered tablets, several filling shoes are used arranged one behind the other without the slightly pressed first layer before the other Filling is ejected. By suitable process control are in this way too Coat and point tablets can be produced, which have an onion-shell-like structure, wherein in the case of the point tablets, the top of the core or the core layers not is covered and thus remains visible. Rotary tablet presses are also available with or multiple tools can be equipped, so that, for example, an outer circle with 50 and an inner circle with 35 holes are used simultaneously for crimping. The Throughputs of modern rotary tablet presses amount to over one million tablets per Hour.

• Verwendung von Kunststoffeinlagen mit geringen Dickentoleranzen
• Geringe Umdrehungszahl des Rotors
• Große Füllschuhe
• Abstimmung des Füllschuhflügeldrehzahl auf die Drehzahl des Rotors
• Füllschuh mit konstanter Pulverhöhe
• Entkopplung von Füllschuh und Pulvervorlage

When tableting with rotary presses, it has proven to be advantageous to carry out the tableting with the lowest possible weight fluctuations of the tablet. In this way, the hardness fluctuations of the tablet can be reduced. Small variations in weight can be achieved in the following ways:

• Use of plastic inserts with small thickness tolerances
• Low number of revolutions of the rotor
• Big filling shoes
• Tuning of the filling paddle speed to the speed of the rotor
• Filling shoe with constant powder height
• Decoupling of filling shoe and powder template

To reduce Stempelanbackungen offer all known from the art Non-stick coatings on. Particularly advantageous are plastic coatings, Plastic inserts or plastic stamps. Even rotating stamps have proven to be beneficial proven, where possible upper and lower punch be made rotatable should. With rotating punches can be dispensed with a plastic insert usually become. Here, the stamp surfaces should be electropolished.

It has also been shown that long pressing times are advantageous. These can be with pressure rails, several pressure rollers or low rotor speeds are set. Because the Hardness fluctuations of the tablet caused by the fluctuations of the pressing forces, Systems should be used which limit the pressing force. Here can be elastic Used punches, pneumatic compensators or resilient elements in the force path become. Also, the pressure roller can be stirred out resiliently.

Tableting machines suitable for the purposes of the present invention are, for example available from Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Verpackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Press AG, Berlin, and Romaco GmbH, Worms. Further providers are, for example Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Berne (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (UK), Courtoy N.V., Halle (BE / LU) and Mediopharm Kamnik (SI). For example, the hydraulic double pressure press is particularly suitable HPF 630 from LAEIS, D. tabletting tools are, for example, from the companies Adams tabletting tools, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Sons GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers are e.g. the Senss AG, Reinach (CH) and the Medicopharm, Kamnik (SI).

The tablets can be made in a predetermined spatial form and predetermined size are always made up of several phases, i. Layers, inclusions or cores and wrestling exist. As a form of space virtually all useful manageable Embodiments into consideration, for example, the training as a blackboard, the rod or Barrel shape, cubes, cuboids and corresponding room elements with flat side surfaces and in particular cylindrical configurations with circular or oval Cross-section. This last embodiment detects the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.

The portioned compacts can each as separate individual elements be formed, the predetermined dosage of the detergent and / or detergent equivalent. However, it is also possible to form compacts, a plurality connect such mass units in a compact, in particular by predetermined Predetermined breaking points the easy separability of portioned smaller units provided is. For the use of textile detergents in machines of the type common in Europe with horizontally arranged mechanism, the formation of the portioned compacts as Tablets to be useful in cylindrical or cuboidal shape, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, Eccentric or rotary presses are suitable devices in particular for producing such compacts.

The spatial form of another embodiment of the tablets is in their dimensions of Einspülkammer adapted from commercial household washing machines, so that the Tablets without dosing aid can be metered directly into the dispenser, where they dissolves during the flushing process. Of course, but also a use of Detergent tablets easily possible via a dosing aid.

Another preferred multiphase tablet which can be prepared has one plate-like or tabular structure with alternately thick long and thin short segments, so that individual segments of this "multiphase bar" at the predetermined breaking points, which represent the short thin segments, canceled and entered into the machine can be. This principle of the "bar-shaped" tablet detergent can in other geometric shapes, such as vertical triangles, the are connected together only on one side, be realized. Here, for optical reasons, it is the triangle base that makes up the individual segments connects together to form as a phase, while the triangle tip the second phase forms. A different staining of both phases is in this embodiment especially sexy.

In addition to the layer structure, multiphase tablets can also be produced in the form of ring-core tablets, core-coat tablets or so-called "bulleye" tablets. An overview of such embodiments of multiphase tablets is described in EP 055 100 (Jeyes Group). This document discloses toilet cleaner blocks comprising a molded body of a slow-dissolving detergent composition in which a bleach tablet is embedded. This document simultaneously discloses the most varied embodiments of multiphase tablets from the simple multiphase tablet to complicated multi-layered systems with inserts.

After pressing, the detergent tablets have a high stability. The fracture strength of cylindrical tablets can be detected by the measurand of the diametric breaking stress. This is determinable σ = 2 P π dt

Here, σ stands for the diametrical fracture stress (DFS) in Pa, P is the force in N that leads to the pressure exerted on the tablets, which causes the pressure Breakage of the tablet causes, D is the diameter of the tray in meters and t is the height the tablet.

Examples:

To prepare alkylbenzenesulfonate and cellulose-containing detergent tablets, a surfactant granulate was mixed with further treatment components and compressed on an eccentric tablet press into tablets. The composition of the surfactant granules is given in the following Table 1, the composition of the premix to be compressed (and thus the composition of the tablets) can be found in Table 2. Surfactant granules [% by weight] C _9-13 alkyl benzene sulphonate 19.4 C _12-18 fatty alcohol sulfate 5.2 C _12-18 fatty alcohol with 7 EO 4.8 C _12-16 alkyl-1,4-glycoside 1.0 Soap 1.6 sodium 17.2 sodium silicate 5.6 Zeolite A (anhydrous active substance) 28.5 Na-hydroxyethane-1,1-diphosphonate 0.8 Acrylic acid-maleic acid copolymer 5.6 Water, salts rest Premix [% by weight] Surfactant granules 87.3 foam inhibitor 3.5 enzymes 1.7 Perfume 0.5 Zeolite A (Wessalith® P, Degussa) 1.0 cellulose 5.0

The tabletting premixes were compressed in a Korsch eccentric press into tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g). In this case, the pressing pressure was adjusted so that in each case three series of tablets were obtained (E, E ', E "and V, V', V"), which differ in their hardness. The detergent tablets E according to the invention were packaged after manufacture for a combination of the invention by two tablets in a flow pack of laminate foil (aluminized film, thickness: 35 microns, the water vapor permeability of 1 g / m ^2/24 hr) were packed; Comparative Examples V were stored open. Of all the tablet series, hardness and disintegration time were measured before packaging. Both tablets (combination E according to the invention and comparison tablet V were stored for 14 days in a climate cell at 23 ° C. and 85% relative humidity (test conditions according to DIN 53122), after which the hardnesses and disintegration times were determined again the tablet measured to break, with the force acting on the side surfaces of the tablet and determining the maximum force that sustained the tablet.

To determine the tablet disintegration, the tablet was placed in a beaker with water (600 ml of water, temperature 30 ° C) and measured the time to complete tablet disintegration. To determine the Einspülbarkeit 3 tablets were placed in the Einspülkammer a household washing machine (AEG Öko Lavärnat) and started a 40 ° C program without prewash. After completion of the Einspülvorgangs the residues located in the Einspülkammer were dried and weighed. The experimental data of the individual tablet series are shown in Table 3: Detergent tablets [physical data] tablet e e ' e " V V ' V " before storage Tablet hardness [N] 39 49 62 39 49 62 Tablet disintegration [s] 14 26 49 14 26 58 dispensability
(Rest) [g] 6 4 8th 6 4 8th after storage Tablet hardness [N] 45 54 62 35 46 53 Tablet disintegration [s] 14 30 59 > 60 > 60 > 60 dispensability
(Rest) [g] 6 6 5 58 92 105

Table 3 shows impressively that the hardness and disintegration times of detergent tablets change only slightly in the combinations according to the invention, while the Tablets of Comparative Example V unacceptably aftercure and very bad or not decay anymore.

Claims (15)

1. Combination of (a) laundry detergent tablet(s), comprising alkylbenzenesulphonate(s) and cellulose-based disintegration assistant in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, and of a packaging system comprising the laundry detergent tablet(s), characterized in that the packaging system has a moisture vapour permeability rate of from 0.1 g/m²/day to less than 20 g/m²/day when stored at 23°C and a relative equilibrium humidity of 85%.
2. Combination according to Claim 1, characterized in that the packaging system has a moisture vapour permeability rate of from 0.5 g/m²/day to less than 15 g/m²/day.
3. Combination according to Claim 1 or 2, characterized in that the laundry detergent tablet(s) has/have a relative equilibrium humidity of less than 30% at 35°C.
4. Combination according to one of Claims 1 to 3, characterized in that the packaging system is composed of a bag or pouch of single-ply or laminated paper and/or polymeric film.
5. Combination according to Claim 4, characterized in that the packaging system is composed of a bag or pouch of single-ply or laminated polymeric film having a thickness of from 10 to 200 µm, preferably from 20 to 100 µm and in particular from 25 to 50 µm.
6. Combination according to one of Claims 1 to 5, characterized in that the packaging system does not comprise cartons made of wax-coated paper.
7. Combination according to one of Claims 1 to 6, characterized in that the laundry detergent tablet(s) comprises/comprise further surfactant(s) and builder(s).
8. Combination according to one of Claims 1 to 7, characterized in that the laundry detergent tablet(s) comprises/comprise the cellulose-based disintegration assistant in granular, cogranulated or compacted form in amounts of from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the tablet weight.
9. Combination according to one of Claims 1 to 8, characterized in that the laundry detergent tablet(s) is/are free from bleach(es).
10. Combination according to one of Claims 1 to 9, characterized in that the laundry detergent tablet(s) is/are free from bleach activator(s).
11. Combination according to one of Claims 1 to 10, characterized in that the laundry detergent tablet(s) is/are free from optical brightener.
12. Combination according to one of Claims 1 to 11, characterized in that the laundry detergent tablet(s) further comprises/comprise colour transfer inhibitors, preferably polyvinylpyrrolidone, in amounts of from 0.1 to 2.0% by weight, preferably from 0.2 to 1.5% by weight and in particular from 0.5 to 1.0% by weight, based in each case on the tablet weight.
13. Combination according to one of Claims 1 to 12, characterized in that the laundry detergent tablet(s) comprises/comprise the alkali metal salts, preferably sodium salts, of C_8-16, preferably C_9-13, alkylbenzenesulphonic acids deriving from alkylbenzenes having a tetralin content below 5% by weight, based on the alkylbenzene.
14. Combination according to one of Claims 1 to 13, characterized in that the laundry detergent tablet(s) comprises/comprise the alkali metal salts, preferably sodium salts, of C_8-16, preferably C_9-13, alkylbenzenesulphonic acids having a 2-phenyl isomer content below 22% by weight, based on the alkylbenzenesulphonic acid.
15. Combination according to one of Claims 1 to 14, characterized in that the laundry detergent tablet(s) comprises/comprise the alkylbenzenesulphonates in amounts of from 0.5 to 30% by weight, preferably from 1 to 25% by weight, more preferably from 2 to 20% by weight and in particular from 5 to 15% by weight, based in each case on the tablet weight.