DE19919444B4 - Detergent tablets with binder compound, process for its preparation and use of binder compounds - Google Patents

Abstract

Detergent tablets of compacted, particulate detergent and cleaner containing surfactant-containing granules and builder (s), characterized in that, based on the molding weight, from 1.1 to 20 wt .-% of one or a plurality of binder compounds consisting of a) from 10 to 99% by weight of one or more support materials having an oil adsorption capacity of more than 20 g per 100 g, from the group of silicas, alkali metal silicates and alkali aluminum silicates, b) from 1 to 90% by weight one or more non-surfactant liquid (25 ° C and 1013.25 mbar) binder from the group of di-, tri- and polyols, the carbonic acid esters containing polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate, ethylene glycol, propylene glycol and propylene carbonate.

Description

The present invention is in the field of compact moldings having washing and cleaning properties. Such detergent tablets comprise, for example, laundry detergent tablets for washing textiles, automatic dishwashing detergent tablets or hard surface cleaning agents, bleach tablets for use in dishwashers or dishwashers, water softening tablets or patch salt tablets. In particular, the invention relates to detergent tablets which are used for washing textiles in a household washing machine and are referred to as detergent tablets for short.

Detergent tablets are widely described in the art and are becoming increasingly popular with consumers because of their ease of use. Tableted detergents and cleaners have a number of advantages over powdered ones: they are easier to dose and to handle and, due to their compact structure, have advantages in storage and transport. Also in the patent literature washing and cleaning agent tablets are thus described comprehensively. A problem which occurs again and again in the application of washing and cleaning-active moldings is the too low disintegration and dissolution rate of the moldings under conditions of use. Because sufficiently stable, d. H. Form-resistant and fracture-resistant molded body can be produced only by relatively high pressing pressures, there is a strong compaction of the molding constituents and a consequent delayed disintegration of the molding in the aqueous liquor and thus to a slow release of the active substances in the washing or cleaning process , The delayed disintegration of the moldings also has the disadvantage that conventional detergent tablets can not be flushed in via the dispensing chamber of domestic washing machines, since the tablets do not disintegrate in sufficiently fast time into secondary particles which are small enough to move out of the dispensing chamber into the washing drum to be flushed. Another problem which occurs in particular with detergent tablets is the friability of the tablets or their often insufficient stability to abrasion. Thus, although sufficiently break-resistant, d. H. hard detergent tablets are often produced, but these are often the burden of packaging, transport and handling, d. H. Falling and rubbing stresses, not sufficiently grown, so that Kantenbruch- and Abrieberscheinungen affect the appearance of the molding or even lead to a complete destruction of the molding structure.

To overcome the dichotomy between hardness, d. H. Transport and handling stability, and easy disintegration of the moldings, many approaches have been developed in the prior art. An approach known in particular from the pharmaceutical industry and extended to the field of detergent tablets is the incorporation of certain disintegration aids which facilitate the ingress of water or which swell or become gas-evolved or otherwise disintegrate upon the ingress of water. Other proposed solutions from the patent literature describe the compression of premixes of certain particle sizes, the separation of individual ingredients of certain other ingredients and the coating of individual ingredients or the entire molded article with binders.

That's how it describes EP 687 464 A2 (Allphamed Arzneimittel-Gesellschaft) Effervescent tablets, consisting of at least one active ingredient or combination of active ingredients, at least one binder, optionally excipients such as flavors, dyes, fragrances, plasticizers, bleaching agents and effervescent additives, wherein as a binder propylene glycol or glycerol, preferably in amounts of 0.004 to 2.5% by weight. Also claimed are methods of making these effervescent tablets. According to the statements of this document can be prepared with the teaching of the invention also a detergent effervescent tablet without the binder used would lead to a loss of carbon dioxide in the effervescent additives.

The European patent application EP 711 828 A2 (Unilever) describes laundry detergent tablets containing surfactant (s), builder (s), and a polymer that acts as a binder and disintegration aid. The binders disclosed in this document should be solid at room temperature and fed to the premix to be compressed as a melt. Preferred binders are the relatively high molecular weight polyethylene glycols.

The use of solid polyethylene glycols is also disclosed in the German patent application DE 197 09 411 A1 (Henkel). This document teaches synergistic effects between the polyethylene glycols and overdried amorphous silicates.

Solutions to the problem of friability and abrasion stability of detergent tablets are known in the art, for example in the non-prepublished German patent application DE 198 41 146 A1 (Henkel KGaA). This document teaches to add 0.25 to 10 wt .-% of one or more non-surfactant, water-soluble, liquid binder to the tabletting premix based on the molding body weight.

In GB 2320255 A describes a production process for detergent tablets in which a portion of the particulate detergent composition having a high porosity is treated with a nonaqueous liquid having a viscosity below 1000 cp, mixed with the other ingredients and compressed into tablets.

WO 95/07976 A2 teaches detergent tablets made of a hydratable corrosive substance, a water hardness complexing agent, less than 10% by weight of water of crystallization, and 2 to 10% by weight of liquid components. Furthermore, surfactants and water-soluble polyhydric alcohols may preferably be contained. During production, portions of the solid components are blended into a premix and liquid surfactant, polycarboxylic acid and polyhydric water-soluble alcohol are made into a liquid mixture, the liquid mixture is sprayed onto the premix, additional etchant is added and the final mixture is compressed.

The older German patent application DE 19855676 A1 discloses a process for the preparation of a detergent additive in which a solid ingredient is mixed with carrier materials and one or more non-surfactant, water-soluble liquid binders are applied to the mixture. Subsequently, the resulting additives can be used as Abwuderungsmittel for detergent particles and pressed them into moldings.

In the European patent application EP 0737738 A2 Bleach tablets are described which contain paraffin oil, polyethylene glycol or glycerol as a binder.

The subject of the European patent application EP 0812808 A1 are tablets against water hardness, which contain, among other phyllosilicates or alkali metal silicates and binders, preferably polyethylene glycol.

WO 97/03177 A1 describes dishwasher tablets containing disilicate, surfactants and glycerin among others.

Although the addition of liquids to tableting premixes is advantageous due to its easy and exact meterability, it also leads to technical problems and undesired side effects. On the one hand Tablettiervorgemische are usually prepared from different powders and granules, so that liquid metering means an additional capital investment, on the other hand, a liquid binder is distributed during spraying or nozzles over the entire premix, so that higher amounts of binder are needed. Another problem is that the fluids added to the premix tend to "sweat out" during the pressing process, leading to stamp caking.

The present invention has now the object to provide moldings that are characterized by short decay times for a given hardness and thus can be dosed via the dispensing chamber household washing machines. In addition to these requirements, the moldings should have an increased stability against drop and friction loads, d. H. an improved, d. H. have reduced friability and have a reduced abrasion behavior. In contrast to the proposed solutions of the prior art, these advantageous molded body properties should be able to be achieved by adding solids, which should minimize dosing and pressing problems.

It has now been found that the addition of binder compounds consisting of non-surfactant, liquid binders and excipients with high oil adsorption capacity to wash and Reinigungsmittelformkörper premixes moldings provides that are significantly more abrasion resistant and considerably less friabel than the previously known moldings. The use of said additives does not affect the fracture hardness of the molding or only to a minor extent. The problems during the pressing process, namely the "sweating out" of the liquid binder in the die, are avoided by this addition.

• a) 10 bis 99 Gew.-% eines oder mehrerer Trägermaterialien mit einer Öladsorptionskapazität von mehr als 20 g pro 100 g aus der Gruppe der Kieselsäuren, der Alkalisilikate und der Alkalialuminiumsilikate,
• b) 1 bis 90 Gew.-% eines oder mehrerer nichttensidischer flüssiger (25°C und 1013,25 mbar) Bindemittel aus der Gruppe der Di-, Tri- und Polyole, der Kohlensäureester, der Polyethylenglycole und Polypropylenglycole, Glycerin, Glycerincarbonat, Ethylenglycol, Propylenglycol und Propylencarbonat

enthalten.The present invention relates to detergent tablets of compacted particulate detergent and cleaner containing surfactant-containing granules (e), builder (s). and optionally further customary detergent and cleaner ingredients which, based on the molding weight, 1.1 to 20 wt .-% of one or more binder compounds consisting of

• a) 10 to 99% by weight of one or more support materials having an oil adsorption capacity of more than 20 g per 100 g from the group of silicic acids, alkali metal silicates and alkali aluminum silicates,
• b) 1 to 90 wt .-% of one or more non-surfactant liquid (25 ° C and 1013.25 mbar) binder from the group of di-, tri- and polyols, carbonic acid esters, polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate, ethylene glycol , Propylene glycol and propylene carbonate

contain.

In the context of the present invention, binder compounds are understood as meaning the substance mixtures of the abovementioned composition which are present per se in finely divided powder form. These can be converted into a coarse-grained form by a spray-drying, granulating, agglomerating, compacting, pelleting or extrusion process, if desired.

The powdery carrier materials according to the invention contained in the binder compounds have oil absorption capacities above 20 grams per 100 g. The oil absorption capacity is a physical property of a substance that can be determined by standardized methods. For example, there are the British standard methods BS1795 and BS3483: Part B7: 1982, both of which refer to the ISO 787/5 standard. In the test methods, a well-balanced sample of the substance in question is placed on a plate and treated dropwise with refined linseed oil (density: 0.93 gcm ^-3 ) from a burette. After each addition, the powder is mixed thoroughly with the oil using a spatula, with the addition of oil continuing until a paste of smooth consistency is achieved. This paste should flow or run without crumbling. The oil absorption capacity is now the amount of oil dropped, based on 100 g of absorbent and is given in ml / 100 g or g / 100 g, with conversions on the density of linseed oil are easily possible. Within the scope of the present invention, a whole series of compounds which can originate both from the group of the covalent compounds and from the group of the salts are suitable as powdery components. As already mentioned, it is preferred if the pulverulent components have even higher oil absorption capacities, so that detergent tablets are preferred in which the carrier material (s) has an oil adsorption capacity of more than 25 g per 100 g, preferably more than 30 g per 100 g, particularly preferably more than 50 g per 100 g and in particular more than 75 g per 100 g. Examples of suitable substances are silicates, aluminum silicates and silicas, which are described in detail below.

The term "non-surfactant binder" in the context of the present application characterizes binders which do not belong to the class of surfactants. The term "liquid binder" refers to the aggregate state of the binder at 25 ° C and 1013.25 mbar. Substances which only melt or soften at relatively high temperatures are therefore not usable in the context of the present invention.

Preferred amounts using the binder compound (s) are within a narrower range such that preferred detergent tablets have a content of the binder compound (s) of from 2 to 7.5% by weight, based on the tablet weight , exhibit.

• a) 20 bis 90 Gew.-%, vorzugsweise 30 bis 80 Gew.-%, besonders bevorzugt 40 bis 70 Gew.-% und insbesondere 40 bis 60 Gew.-% eines oder mehrerer Trägermaterialien mit einer Öladsorptionskapazität von mehr als 20 g pro 100 g,
• b) 10 bis 80 Gew.-%, vorzugsweise 20 bis 70 Gew.-%, besonders bevorzugt 30 bis 60 Gew.-% und insbesondere 40 bis 60 Gew.-% eines oder mehrerer nichttensidischer flüssiger Bindemittel.

The binder compounds according to the invention contained in the detergent tablets also preferably have a composition which is within narrower limits. In the context of the present invention, preferred detergent tablets contain the binder compound (s), in each case based on the compound

• a) 20 to 90 wt .-%, preferably 30 to 80 wt .-%, particularly preferably 40 to 70 wt .-% and in particular 40 to 60 wt .-% of one or more support materials having an oil adsorption capacity of more than 20 g per 100 g,
• b) 10 to 80 wt .-%, preferably 20 to 70 wt .-%, particularly preferably 30 to 60 wt .-% and in particular 40 to 60 wt .-% of one or more non-surfactant liquid binder.

The binder compounds according to the invention contained in the washing and cleaning agent tablets contain (s) binder applied to carrier materials. The carrier materials used according to the invention are substances having an oil adsorption capacity of more than 20 g per 100 g, the values of preferred carrier materials being significantly above this value. In the detergent tablets, the carrier material (s) is / are selected from the group of silicic acids, alkali metal silicates and alkali aluminum silicates.

Alkali silicates and alkali aluminum silicates are described in detail below in the description of the builders.

Silicas are compounds of the general formula SiO ₂ .nH ₂ O. While the lower limbs such as orthosilicic acid and pyrosilicic acid are only stable in aqueous solution, the formal end product of the condensation is silicon dioxide (SiO ₂ ) _x , the silicic anhydride. During condensation, chain-extending, ring-forming and branching processes proceed side by side, so that the polysilicic acids are amorphous. The Si atoms are in the center of all silicic acids at the center of irregularly interconnected tetrahedra, at its four vertices are the O atoms, which belong simultaneously to the Nachbarterraedern. The silicas are particularly capable of forming colloidal solutions of polysilicic acids in which the silica particles have particle sizes between 5 and 150 nm. These are called silica sols. They are unstable against further condensation and can be converted by aggregation in silica gels.

With regard to the technical scope of production, precipitated silicas are by far the most important. They are prepared from an aqueous alkali silicate solution by precipitation with mineral acids. This forms colloidal primary particles, which agglomerate with progressive reaction and finally grow into aggregates. The powdery, voluminous forms have pore volumes of 2.5-15 ml / g and specific surface areas of 30-800 m ² / g. The term pyrogenic silicas combines highly disperse silicas which are prepared by flame hydrolysis. In this case, silicon tetrachloride is decomposed in a blast gas flame. Pyrogenic silicas have significantly less OH groups than precipitated silicas on their virtually pore-free surface. Known available on an industrial scale fumed silicas are, for example, Aerosil ^® (Degussa), Cab-O-Sil ^® (Cabot Corporation, Waltham, Massachusetts), and HDK (fumed silicas).

Suitable non-surfactant liquid binders in the context of the present invention are a multiplicity of substances, as long as they do not originate from the group of surfactants and are liquid at 25 ° C. and standard pressure. Preferred binders are diols, such as ethanediol (ethylene glycol, glycol), 1,2-propanediol, 1,3-propanediol, 1,2-, 1,3-, 2,3- and 1,4-butanediol, 1,2- and 1,5-pentanediol, but also polyethylene glycols and polypropylene glycols, triols such as glycerol and 1,2-6-hexanetriol, liquid polyols used in the conditions mentioned and carbonic acid esters such as propylene carbonate or glycerol carbonate. Furthermore, such compounds are used as binder compounds which contain water-soluble binders. "Water-soluble" binders for the purposes of the present application are binders which are miscible with water at room temperature. These substances are, for example, the diols mentioned, such as ethanediol (ethylene glycol, glycol), 1,2-propanediol, 1,3-propanediol, 1,2-, 1,3-, 2,3- and 1,4-butanediol, 1, 2- and 1,5-pentanediol, but also polyethylene glycols and polypropylene glycols, triols such as glycerol and 1,2-6-hexanetriol, at the conditions mentioned liquid polyols, carbonic acid esters such as propylene carbonate or glycerol carbonate. The non-surfactant liquid binder (s) are therefore selected from the group consisting of di-, tri- and polyols, carbonic acid esters, polyethylene glycols and polypropylene glycols, glycerine, glycerol carbonate, ethylene glycol, propylene glycol and propylene carbonate.

Polyethylene glycols (abbreviated to PEG) which can be used according to the invention in the binder compounds are polymers of ethylene glycol corresponding to general formula I H- (O-CH ₂ -CH ₂ ) _n -OH (I) n, where n can assume values between 1 (ethylene glycol, see below) and about 16. Decisive in the assessment of whether a polyethylene glycol is used according to the invention, is the state of aggregation of the PEG at room temperature, ie the solidification point of the PEG must be below 25 ° C. For polyethylene glycols there are various nomenclatures that can lead to confusion. Technically common is the indication of the average relative molecular weight following the indication "PEG", so that "PEG 200" characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210. According to this nomenclature, the commercially available polyethylene glycols PEG 200, PEG 300, PEG 400 and PEG 600 can be used in the context of the present invention. For cosmetic ingredients, another nomenclature is used in which the abbreviation PEG is hyphenated and directly followed by the hyphen followed by a number corresponding to the number n in formula I above. According to this nomenclature (so-called INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) according to the invention, for example, PEG-4, PEG-6, PEG-8, PEG- 9, PEG-10, PEG-12, PEG-14 and PEG-16 can be used according to the invention. Commercially available polyethylene glycols, for example, under the trade names Carbowax ^® PEG 200 (Union Carbide) Emkapol ^® 200 (ICI Americas), Lipoxol ^® 200 MED (Huls America), polyglycol ^® E-200 (Dow Chemical), Alkapol ^® PEG 300 (Rhone-Poulenc), Lutrol ^® E300 (BASF) and the corresponding trade names with higher numbers ,

genügen, wobei n Werte zwischen 1 (Propylenglycol, siehe unten) und ca. 12 annehmen kann. Technisch bedeutsam sind hier insbesondere Di-, Tri- und Tetrapropylenglycol, d. h. die Vertreter mit n = 2, 3 und 4 in Formel II.Polypropylene glycols (abbreviated PPG) which can be used according to the invention in the binder compounds are polymers of propylene glycol which correspond to the general formula II

n, where n can assume values between 1 (propylene glycol, see below) and about 12. Of particular technical importance here are di-, tri- and tetrapropylene glycols, ie the representatives with n = 2, 3 and 4 in formula II.

Glycerin is a colorless, clear, heavy-bodied, odorless sweet-tasting hygroscopic liquid of density 1.261 that solidifies at 18.2 ° C. Glycerol was originally a by-product of fat saponification but is now technically synthesized in large quantities. Most technical processes are based on propene, which is processed into glycerol via the intermediates allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO ₃ contact via the step of the glycide.

Glycerol carbonate is accessible by transesterification of ethylene carbonate or dimethyl carbonate with glycerol, as by-products of ethylene glycol or methanol incurred. Another synthetic route is based on glycidol (2,3-epoxy-1-propanol), which is converted under pressure in the presence of catalysts with CO ₂ to glycerol carbonate. Glycerine carbonate is a clear, easily agitated liquid with a density of 1.398 gcm ^-3 , which boils at 125-130 ° C (0.15 mbar).

Ethylene Glycol (1,2-Ethanediol, "Glycol") is a colorless, viscous, sweet-tasting, highly hygroscopic liquid that is miscible with water, alcohols and acetone and has a density of 1.113. The solidification point of ethylene glycol is -11.5 ° C, the liquid boils at 198 ° C. Technically, ethylene glycol is recovered from ethylene oxide by heating with water under pressure. Promising manufacturing processes can also be built on the acetoxylation of ethylene and subsequent hydrolysis or on synthesis gas reactions.

There are two isomers of propylene glycol, 1,3-propanediol and 1,2-propanediol. 1,3-Propanediol (trimethylene glycol) is a neutral, colorless and odorless, sweet-tasting liquid of density 1,0597, which solidifies at -32 ° C and boils at 214 ° C. The preparation of 1,3-propanediol succeeds from acrolein and water with subsequent catalytic hydrogenation. Technically much more significant is 1,2-propanediol (propylene glycol), which is an oily, colorless, almost odorless liquid, density 1.0381, which solidifies at -60 ° C and boils at 188 ° C. 1,2-Propanediol is prepared from propylene oxide by water addition.

Propylene carbonate is a water-bright, easily agitated liquid, with a density of 1.2057 gcm ^-3 , the melting point is -49 ° C, the boiling point at 242 ° C. Also propylene carbonate is industrially accessible by reaction of propylene oxide and CO ₂ at 200 ° C and 80 bar.

Regardless of the composition of the binder compounds detergent and cleaner tablets are preferred, the total content of non-surfactant, liquid binders 0.1 to 7.5 wt .-%, preferably 0.25 to 5 wt .-% and in particular 0.5 to 3 wt .-%, in each case based on the molding weight is.

In addition to the binder compounds used according to the invention, the detergent tablets according to the invention contain surfactant (s) and builder (s) as the most important ingredients of detergents and cleaners and optionally further ingredients. As further additives, which are usually not used in detergents and cleaners, but can develop beneficial effects in moldings, disintegration aids should be mentioned.

In order to facilitate the disintegration of highly compacted moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrating agents, in order to shorten the disintegration times. Among tablet disintegrants and disintegrants according to Römpp (9th edition, Vol. 6, p 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, pp. 182-184) understood excipients that provide for the rapid disintegration of tablets in water or gastric juice and for the release of drugs in resorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume upon ingress of water, on the one hand increasing the intrinsic volume (swelling), and on the other hand creating a pressure via the release of gases which can break 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 substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

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

Disintegrating agents based on cellulose are used as preferred disintegrating agents in the context of the present invention, so that preferred washing and cleaning agent tablets use such cellulose-based disintegrating agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular 4 contain up to 6 wt .-%. 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. Detergents and cleaning agent tablets containing disintegrators in granular or optionally cogranulated form are described in the German patent applications DE 197 09 991 A1 (Stefan Herzog) and DE 197 10 254 A1 (Henkel) and the international patent application WO98 / 40463 A1 (Henkel). Further details of the production of granulated, compacted or cogranulated cellulose explosives can be found in these publications. The particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns. The above and described in more detail in the documents cited coarser disintegration aids, are preferred in the present invention as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier.

As a further disintegrating agent based on cellulose or as a component of this component, microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact. Subsequent deaggregation of the microfine celluloses resulting from the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 μm and can be compacted, for example, into granules having an average particle size of 200 μm.

In the context of the present invention, preferred detergent tablets also contain a disintegration aid, preferably a cellulose-based disintegration assistant, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight. -% and in particular from 4 to 6 wt .-%, each based on the molding weight.

The detergent tablets according to the invention also contain one or more builders. In the detergent tablets according to the invention all builders commonly used in detergents and cleaning agents may be present, in particular zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - 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 the European patent application EP 0 164 514 A1 described. 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, wherein β-sodium disilicate can be obtained, for example, by the process described in International Patent Application WO 91/08171 A1 is described.

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 which have 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, with 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 the German patent application DE 44 00 024 A1 described. 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) ), produced by CONDEA Augusta S. p. A. sold 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 microns (volume distribution, measuring method: Counter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.

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 high 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 5H ₂ O) and 12 moles of water (density 1.52 gcm ^-3 , melting point 35 ° with the loss of 5H ₂ O), becomes anhydrous at 100 ° C. and on more intense 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 z. 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 results in higher mol. 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 6H 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 ° about 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 + 2KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are used according to the invention exactly as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; 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 also be used according to the invention.

Particularly suitable organic co-builders in the detergent tablets according to the invention are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if 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 thereof.

The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 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 weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

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

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

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

Further preferred copolymers are those described in the German patent applications DE 44 00 024 A1 and DE 44 17 734 A1 be described and as monomers preferably 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. Particularly preferred are polyaspartic acids or their salts and derivatives, of which in the German patent application DE 195 40 086 A1 is disclosed that they also have a bleach-stabilizing effect in addition to Cobuilder properties.

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

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and 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 methods of their preparation are, for example, from the European patent applications EP 232 202 A2 . EP 0 427 349 A2 . EP 0 472 042 A1 and EP 0 542 496 A1 as well as the international patent applications WO 92/18542 A1 . WO 93/08251 A1 . WO 93/16110 A1 . WO 94/28030 A1 . WO 95/07303 A1 . WO 95/12619 A1 and WO 95/20608 A1 known. Also suitable is an oxidized oligosaccharide according to the German patent application DE 196 00 018 A1 , A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is 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 in 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 the international patent application WO 95/20029 A1 described.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the 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 aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds capable of forming complexes with alkaline earth ions can be used 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 .-%. Again, the amount of builders used depends on the intended use, so that bleach tablets may 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 wt .-%, preferably 12.5 to 45 wt .-%, in particular between 17.5 and 37.5 wt .-%).

Preferred detergent tablets also contain one or more surfactants. In the detergent tablets according to the invention anionic, nonionic, cationic and / or amphoteric surfactants or mixtures thereof may be used. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants. The total surfactant content of the tablets in the case of detergent tablets is preferably from 5 to 60% by weight, based on the weight of the tablet, surfactant contents above 15% by weight being preferred. Detergent tablets for automatic dishwashing may contain surfactants in smaller amounts, for example below 2% by weight.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, 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 acid hydrolysis of the sulfonation products into consideration. 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), z. As the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids suitable.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation 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.

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, which, for example, according to the U.S. Patents 3,234,258 A or 5,075,041 A are manufactured and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C _7-21 -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). Again, sulfosuccinates whose fatty alcohol residues are constricted with ethoxylated fatty alcohols Derive homolog distribution, 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. Suitable are 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, for. 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. The anionic surfactants are preferably present 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 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 native origin having 12 to 18 carbon atoms, for. From coconut, palm, tallow or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol. 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 of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical 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 the Japanese patent application JP 58/217598 A are described or preferably according to the in the international patent application WO 90/13533 Already described methods are produced.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

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 (III)

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 (V),

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 can then be used, for example, according to the teaching of the international application WO 95/07331 A1 be converted by conversion with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired Polyhydroxyfettsäureamide.

In the context of the present invention, detergent tablets are preferred which contain anionic (s) and nonionic (s) surfactant (s), wherein technical advantages can result from certain proportions in which the individual classes of surfactants are used. Particular preference is given to detergent tablets which contain anionic and / or nonionic surfactant (s) and total surfactant contents of above 2.5% by weight, preferably above 5% by weight and in particular above of 10 wt .-%, each based on the molding weight, have.

For example, washing and cleaning agent tablets are particularly preferred in which 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. Preference is also given to washing and cleaning agent tablets containing surfactant (s), preferably anionic (s) and / or nonionic surfactant (s), in amounts of from 5 to 40% by weight, preferably from 7.5 to 35% by weight .-%, particularly preferably from 10 to 30 wt .-% and in particular from 12.5 to 25 wt .-%, in each case based on the weight of the molded article.

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 entire molding, d. H. in all phases, not included. Another important embodiment of the present invention therefore provides that at least one phase of the shaped bodies is free of nonionic surfactants.

Conversely, however, can also by the content of individual phases or the entire molding, d. H. all phases, on certain surfactants a positive effect can be achieved. The incorporation of the alkylpolyglycosides described above has proved to be advantageous, so that detergent tablets are preferred in which at least one phase of the moldings contains alkylpolyglycosides.

Similar to the nonionic surfactants, the omission of anionic surfactants from individual or all phases may result in washing and cleaning agent tablets which are more suitable for certain fields of application. It is therefore within the scope of the present invention also possible to use detergent tablets in which at least one phase of the tablets is free of anionic surfactants.

In addition to the constituents mentioned surfactant, builder and disintegration aid and in addition to the invention contained in the moldings paraffin can be used in the inventive Detergents and cleaning agents contain other substances from the group of bleaches, bleach activators, enzymes, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, dye transfer inhibitors and corrosion inhibitors.

In addition to the constituents mentioned surfactant, builder and disintegration aid and in addition to the present invention in the moldings binder compound in the detergent tablets according to the invention further substances from the group of bleach, bleach activators, enzymes, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, Foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, grayness inhibitors, color transfer inhibitors and corrosion inhibitors.

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. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of which other ingredients are contained in the tablets. When cleaning or bleaching tablets for automatic dishwashing are prepared, it is also possible to use bleaching agents from the group of organic bleaching agents. Typical organic bleaching agents are the diacyl peroxides, such as. B. 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-aminopercapronate) can be used.

Chlorinating or bromine-releasing substances can also be used as bleaching agents in machine dishwashing moldings. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

In order to achieve an improved bleaching effect during washing or cleaning at temperatures of 60 ° C. and below, bleach activators can be incorporated into the detergent tablets. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated 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, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place also so-called bleach catalysts can be incorporated into the moldings. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts. Bleach-enhancing active ingredient combinations which are obtainable by intimately mixing a water-soluble divalent transition metal salt selected from cobalt, iron, copper and ruthenium and mixtures thereof, a water-soluble ammonium salt and optionally a peroxygen-based oxidizing agent and inert carrier material can also be used in the context of the present invention use as bleach catalysts.

Particularly suitable enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases carry in the laundry for removal from stains such as proteinaceous, fatty or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens, as well as enzymatically-derived variants derived from their genetically modified variants. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases. Cellulases used are preferably cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures of these. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases. The enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation. The proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-%.

The selection of the relevant enzymes is likewise dependent on the intended use of the detergent tablets according to the invention. In detergent tablets for automatic dishwashing come as enzymes in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, Glykosylhydrolasen and mixtures of said enzymes in question. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains. For bleaching and oxidoreductases can be used. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens, as well as enzymatically-derived variants derived from their genetically modified variants. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases. Even with detergent tablets, the enzymes may be adsorbed to carriers or embedded in coating substances to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can also be, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-% amount.

Detergent shaped bodies according to the invention for machine dishwashing can contain corrosion inhibitors for the protection of the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

In addition, the detergent tablets may also contain components which positively influence the oil and grease washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component. The preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxy-propylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, as well as the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

The shaped bodies may contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable z. B. salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure, instead of the morpholino group a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the type of substituted Diphenylstyryle be present, for. 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). Mixtures of the aforementioned brightener can be used.

Dyes and fragrances are added to the detergent tablets according to the invention in order to improve the aesthetic impression of the products and to provide the consumer with a visual and sensory "typical and unmistakable" product in addition to performance. As perfume oils or perfumes, individual fragrance compounds, eg. As the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl carbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether to the aldehydes z. B. the linear alkanals with 8-18 C-atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones z. As the Jonone, α-isomethylionone and methyl cedrylketone to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons include mainly the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.

The content of the detergent tablets according to the invention is usually less than 0.01% by weight of dyes, while fragrances may account for up to 2% by weight of the total formulation.

The fragrances can be incorporated directly into the compositions of the invention, but it may also be advantageous to apply the fragrances on carriers, which enhance the adhesion of the perfume on the laundry and provide by a slower release of fragrance for long-lasting fragrance of the textiles. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.

In order to improve the aesthetic impression of the agents according to the invention, they can be dyed 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 agents and to light and no pronounced substantivity to textile fibers so as not to stain them.

The production of washing and cleaning active moldings is done by applying pressure to a mixture to be pressed, which is located in the cavity of a press. In the simplest case of the production of shaped bodies, which is referred to below as simplifying tableting, the mixture to be tableted is compressed directly, ie without prior granulation. The advantages of this so-called Direkttablettierung are their simple and inexpensive application, since no further process steps and consequently also no further equipment is 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 show during storage, transport and filling of the die no segregation tendencies. These three conditions are extremely difficult to control in many mixtures of substances, so that 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.

• a) 10 bis 99 Gew.-% eines oder mehrerer Trägermaterialien mit einer Öladsorptionskapazität von mehr als 20 g pro 100 g aus der Gruppe der Kieselsäuren, der Alkalisilikate und der Alkalialuminiumsilikate,
• b) 1 bis 90 Gew.-% eines oder mehrerer nichttensidischer flüssiger (25°C und 1013,25 mbar) Bindemittel aus der Gruppe der Di-, Tri- und Polyole, der Kohlensäureester, der Polyethylenglycole und Polypropylenglycole, Glycerin, Glycerincarbonat, Ethylenglycol, Propylenglycol und Propylencarbonat

enthält.The present invention is therefore also a process for the preparation of detergent tablets by molding a particulate premix in a conventional manner in which the premix next to at least one surfactant-containing granules further 1.1 to 20 wt .-% of one or more Binder compounds off

• a) 10 to 99% by weight of one or more support materials having an oil adsorption capacity of more than 20 g per 100 g from the group of silicic acids, alkali metal silicates and alkali aluminum silicates,
• b) 1 to 90 wt .-% of one or more non-surfactant liquid (25 ° C and 1013.25 mbar) binder from the group of di-, tri- and polyols, carbonic acid esters, polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate, ethylene glycol , Propylene glycol and propylene carbonate

contains.

For preferred embodiments of the method according to the invention, reference may be made here to the above statements: The same applies analogously to what has been said for the washing and cleaning agent tablets according to the invention. So z. For example, preferred method according to the invention characterized in that the premix contains the binder compound (s) in amounts of 2 to 7.5 wt .-%, based on the weight of the premix.

• a) 20 bis 90 Gew.-%, vorzugsweise 30 bis 80 Gew.-%, besonders bevorzugt 40 bis 70 Gew.-% und insbesondere 40 bis 60 Gew.-% eines oder mehrerer Trägermaterialien mit einer Öladsorptionskapazität von mehr als 20 g pro 100 g, vorzugsweise von mehr als 25 g pro 100 g, besonders bevorzugt von mehr als 30 g pro 100 g, weiter bevorzugt von mehr als 50 g pro 100 g und insbesondere von mehr als 75 g pro 100 g, 10 bis 80 Gew.-%, vorzugsweise 20 bis 70 Gew.-%, besonders bevorzugt 30 bis 60 Gew.-% und insbesondere 40 bis 60 Gew.-% eines oder mehrerer nichttensidischer flüssiger Bindemittel,

enthalten.Also with regard to preferred compositions of the binder compounds used according to the invention, the above statements apply completely analogously. Preferred methods are therefore characterized in that the binder compound or compounds, in each case based on the compound

• a) 20 to 90 wt .-%, preferably 30 to 80 wt .-%, particularly preferably 40 to 70 wt .-% and in particular 40 to 60 wt .-% of one or more support materials having an oil adsorption capacity of more than 20 g per 100 g, preferably more than 25 g per 100 g, more preferably more than 30 g per 100 g, more preferably more than 50 g per 100 g and in particular more than 75 g per 100 g, 10 to 80% by weight. %, preferably 20 to 70% by weight, particularly preferably 30 to 60% by weight and in particular 40 to 60% by weight of one or more non-surfactant liquid binders,

contain.

The binder compounds satisfy preferred particle size criteria in preferred process variants. Thus, preference is given to processes according to the invention in which the binder compounds, in each case based on the compound, comprise at least 60% by weight, preferably at least 75% by weight and in particular at least 90% by weight, of particles having particle sizes of less than 600 μm consist. It is particularly preferred here for the binder compounds to have an average particle size below 400 μm.

In the context of the present invention, preferred detergent tablets are obtained by compressing a particulate premix of at least one surfactant-containing granulate and at least one subsequently admixed pulverulent component. The preparation of the surfactant-containing granules can be carried out by conventional industrial granulation processes such as compaction, extrusion, mixer granulation, pelleting or fluidized bed granulation. It is advantageous for the later detergent tablets if the premix to be compressed has a bulk density which approximates the conventional compact detergent. In particular, it is preferred that the particulate premix additionally contains surfactant-containing granules and has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.

The surfactant-containing granules in preferred process variants also satisfy certain particle size criteria. Thus, methods according to the invention are preferred in which the surfactant-containing granules Particle sizes between 100 and 2000 .mu.m, preferably between 200 and 1800 .mu.m, more preferably between 400 and 1600 .mu.m and in particular between 600 and 1400 .mu.m.

In addition to the active substances (anionic and / or nonionic and / or cationic and / or amphoteric surfactants), the surfactant granules preferably also contain excipients, which more preferably originate from the group of builders. Particularly advantageous processes are therefore characterized in that the surfactant-containing granules contain anionic and / or nonionic surfactants and builders and total surfactant contents of at least 10 wt .-%, preferably at least 20 wt .-% and in particular at least 25 wt .-% having ,

Before the particulate premix is compressed into detergent tablets, the premix can be "powdered" with finely divided surface treatment agents. This may be advantageous for the nature and physical properties of both the premix (storage, compression) and the finished detergent tablets. Fine particulate powdering agents are well known in the art, with mostly zeolites, silicates or other inorganic salts are used. Preferably, however, the premix is "powdered" with finely divided zeolite, with faujasite-type zeolites being preferred. In the context of the present invention, the term "faujasite-type zeolite" denotes all three zeolites which form the faujasite subgroup of the zeolite structural group 4 (cf. Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York , London, Sydney, Toronto, 1974, page 92). In addition to zeolite X, it is thus also possible to use zeolite Y and faujasite and also mixtures of these compounds, the pure zeolite X being preferred. Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which need not necessarily belong to the zeolite structure group 4, can be used as a powdering agent, it being advantageous if at least 50 wt .-% of the powdery powder of a zeolite of faujasite Type persist.

In the context of the present invention, preference is given to detergent tablets which consist of a particulate premix containing granular components and subsequently admixed pulverulent substances, the one or more subsequently admixed pulverulent components comprising a faujasite-type zeolite having particle sizes of less than 100 μm , preferably below 10 microns and especially below 5 microns 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.

In addition to the constituents surfactant, builder and disintegration assistant, the premixes to be compressed additionally contain one or more substances from the group of bleaches, bleach activators, enzymes, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, Contains grayness inhibitors, color transfer inhibitors and corrosion inhibitors. These substances have been described above.

The production of the shaped bodies according to the invention takes place firstly by the dry mixing of the constituents, which may be completely or partially pre-granulated, and subsequent informing, in particular pressing into tablets, wherein conventional methods can be used. To produce the shaped bodies according to the invention, the premix is compacted in a so-called matrix between two punches to form a solid compressed product. This process, hereinafter referred to as tabletting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting shaped body are determined by the position of the lower punch and the shape of the pressing tool. The constant dosage even at high molding throughputs is preferably achieved via a volumetric metering of the premix. As the tableting progresses, the upper punch contacts the pre-mix and continues to descend toward the lower punch. In this compression, the particles of the premix are pressed closer to each other, with the void volume within the filling between the punches decreasing continuously. From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it comes to the formation of the molding. Depending on the physical properties of the premix, some of the premix particles are also crushed, and even higher pressures cause sintering of the premix. With increasing pressing speed, so high throughputs, the phase of the elastic deformation is shortened more and more, so that the resulting moldings may have more or less large cavities. In the last step of tabletting the finished molded body is pushed out of the die by the lower punch and through subsequent transport facilities carried away. At this time, only the weight of the molded article is finally determined, since the compacts due to physical processes (re-expansion, crystallographic effects, cooling, etc.) can change their shape and size. The tabletting is carried out in commercial tablet presses, which can be equipped in principle with single or double punches. In the latter case, not only the upper punch is used for pressure build-up, also the lower punch moves during the pressing operation on the upper punch, while the upper punch presses down. For small production quantities, eccentric tablet presses are preferably used in which the die or punches are attached to an eccentric disc, which in turn is mounted on an axis at a certain rotational speed. The movement of these punches is comparable to the operation of a conventional four-stroke engine. The compression can be done with a respective upper and lower punch, but it can also be attached more stamp on an eccentric disc, the number of Matrizenbohrungen is extended accordingly. The throughputs of eccentric presses vary depending on the type of 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 are 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 commercially available. Each die on the die table is assigned an upper and lower punch, in turn, the pressing pressure can be actively built only by the upper or lower punch, but also by both stamp. The die table and the punches move about a common vertical axis, the punches are brought by means of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection. At the points where a particularly serious raising or lowering of the punches is required (filling, compaction, ejection), these curved paths are supported by additional low-pressure pieces, Niederzugschienen and lifting tracks. The filling of the die via a rigidly arranged supply device, the so-called filling shoe, which is connected to a reservoir for the premix. The pressing pressure on the premix is individually adjustable via the pressing paths for upper and lower punches, the pressure being built up by the rolling of the punch shaft heads on adjustable pressure rollers. Concentric presses can be provided to increase the throughput with two filling shoes, which only a semicircle must be run through to produce a tablet. To produce two-layered and multi-layered shaped bodies, several filling shoes are arranged one after the other without the slightly pressed-on first layer being ejected before further filling. By suitable process control coat and point tablets can be produced in this way, which have a zwiebelschalenartigen structure, wherein in the case of the point tablets, the top of the core or the core layers is not covered and thus remains visible. Even rotary tablet presses can be equipped with single or multiple tools, so that, for example, an outer circle with 50 holes and an inner circle with 35 holes are used simultaneously for pressing. The throughputs of modern rotary tablet presses amount to over one million moldings 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
• - Matching of the Füllschuhflügeldrehzahl on 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. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotary punches have also proved to be advantageous, wherein, if possible, upper and lower punches should be rotatable. With rotating punches can be dispensed with a plastic insert usually. Here, the stamp surfaces should be electropolished.

It also showed that long press times are advantageous. These can be adjusted with pressure rails, several pressure rollers or low rotor speeds. Since the hardness variations of the tablet are caused by the fluctuations of the pressing forces, systems should be used which limit the pressing force. Here, elastic punches, pneumatic compensators or resilient elements in the force path can be used. Also, the pressure roller can be made resilient.

Tableting machines suitable for the purposes of the present invention are obtainable, for example, 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 on the lake, KORSCH presses AG, Berlin, as well as Romaco GmbH, Worms. Other providers include Dr. med. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Berne (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (SI ). Particularly suitable is, for example, the hydraulic double pressure press HPF 630 LAEIS, D. Tablettierwerkzeuge are for example from the company Adams tabletting tools, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Sons GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharmatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers are z. Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

The moldings can be made in a predetermined spatial form and predetermined size. As a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section. This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.

The portioned compacts can be designed in each case as separate individual elements, which corresponds to the predetermined dosage amount of the washing and / or cleaning agent. However, it is also possible to form compacts which connect a plurality of such mass units in a compact, wherein in particular by predetermined predetermined breaking points, the easy separability portioned smaller units is provided. For the use of laundry detergents in machines of the type commonly used in Europe with horizontally arranged mechanics, the formation of the portioned tablets as tablets, in cylindrical or cuboidal form may be appropriate, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred. Commercially available hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for producing such compacts.

The spatial form of another embodiment of the moldings is adapted in their dimensions of the dispenser of commercial household washing machines, so that the moldings can be metered without dosing directly into the dispenser, where it dissolves during the dispensing process. Of course, however, a use of the detergent tablets via a dosing is easily possible and preferred in the context of the present invention.

Another preferred molded article which can be produced has a plate-like or tabular structure with alternately thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, which are the short thin segments, broken and in the Machine can be entered. This principle of the "bar-shaped" shaped body wash can also be realized in other geometric shapes, for example vertical triangles, which are joined together only on one side thereof.

But it is also possible that the various components are not pressed into a single tablet, but that moldings are obtained which have multiple layers, ie at least two layers. It is also possible that these different layers have different dissolution rates. This can result in advantageous performance properties of the molded body. If, for example, components are contained in the moldings which interact negatively, it is possible to integrate one component in the faster soluble layer and to incorporate the other component into a slower soluble layer, so that the first component has already reacted, when the second goes into solution. The layer structure of the moldings can be carried out both in a staggered manner, wherein a dissolution process of the inner layer (s) takes place at the edges of the molded body already when the outer layers are not completely dissolved, but it can also be a complete coating of the inner layer (s ) are reached through the respective outer layer (s), which leads to a prevention of premature dissolution of constituents of the inner layer (s).

In a further preferred embodiment of the invention, a shaped body consists of at least three layers, ie two outer and at least one inner layer, at least in one of the inner layers containing a peroxy bleach, while the stacked shaped body, the two outer layers and the envelope-shaped body outermost layers but free of peroxygen Bleaching agents are. Furthermore, it is also possible to separate peroxy bleach and optionally present bleach activators and / or enzymes spatially in a molding from each other. Such multilayer molded articles have the advantage that they can be used not only via a dispensing chamber or via a metering device which is introduced into the wash liquor; Rather, it is also possible in such cases, to give the molding in direct contact with the textiles in the machine, without stains caused by bleach and the like were to be feared.

Similar effects can also be achieved by coating ("coating") individual constituents of the washing and cleaning agent composition to be tabletted or of the entire shaped body. For this purpose, the bodies to be coated can be sprayed, for example, with aqueous solutions or emulsions, or obtained by the process of melt coating a coating.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be detected by the measurand of the diametric breaking load. This is determinable σ = 2 P / πDt

Herein, σ is the diametrical fracture stress (DFS) in Pa, P is the force in N which results in the pressure applied to the molded article causing the breakage of the molded article, D is the molded article diameter in meters and t the height of the moldings.

• a) 10 bis 99 Gew.-% eines oder mehrerer Trägermaterialien mit einer Öladsorptionskapazität von mehr als 20 g pro 100 g aus der Kieselsäuren, der Alkalisilikate und der Alkalialuminiumsilikate,
• b) 1 bis 90 Gew.-% eines oder mehrerer nichttensidischer flüssiger Bindemittel aus der Gruppe der Di-, Tri- und Polyole, der Kohlensäureester, der Polyethylenglycole und Polypropylenglycole, Glycerin, Glycerincarbonat, Ethylenglycol, Propylenglycol und Propylencarbonat

zur Verbesserung der Härte und der Zerfallszeit und/oder der Abriebstabilität von Wasch- und Reinigungsmittelformkörpern. Dieser erfindungsgemäße Einsatz der genannten Bindemittelcompounds führt zu Formkörpern mit vorteilhaften Eigenschaften, wie die nachstehenden Beispiele zeigen. Hinsichtlich bevorzugter Ausführungsformen der erfindungsgemäßen Verwendung (Teilchengrößen, weitere Inhaltsstoffe, Zusammensetzung des Vorgemischs etc.) gilt analog das vorstehend für das erfindungsgemäße Verfahren Gesagte.Another object of the present invention is the use of binder compounds consisting of

• a) from 10 to 99% by weight of one or more support materials having an oil adsorption capacity of more than 20 g per 100 g of the silicic acids, the alkali metal silicates and the alkali aluminum silicates,
• b) 1 to 90 wt .-% of one or more non-surfactant liquid binder from the group of di-, tri- and polyols, carbonic acid esters, polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate, ethylene glycol, propylene glycol and propylene carbonate

for improving the hardness and the disintegration time and / or the abrasion stability of detergent tablets. This inventive use of said binder compounds leads to moldings having advantageous properties, as the examples below show. With regard to preferred embodiments of the use according to the invention (particle sizes, further ingredients, composition of the premix, etc.), the statements made above for the process according to the invention apply analogously.

Examples:

By granulation in a 5-liter ploughshare mixer company Lödige a surfactant-containing granules (composition see Table 1) was prepared, 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, fines <0.6 mm and coarse particles> 1.6 mm were sieved.

This premix was prepared by mixing the surfactant-containing granules with bleach, bleach activator and other treatment components. To Example E according to the invention, 3% by weight of a binder compound whose composition is given in Table 2 were added during the preparation of the premix. The proportions of the other components therefore differ in percentage from those of Comparative Example V, which contained no binder compound. Premixes E and V, respectively, were compressed into tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g) in a Korsch eccentric press, whereby no "sweating out" of the binder from the shaped body was observed. The composition of the premixes to be compressed (and thus of the molded article) is shown in Table 3. TABLE 1 Composition of the surfactant granules [% by weight] C _9-13 alkyl benzene sulphonate 18.6 C _12-18 fatty alcohol with 7 EO 5.7 C _12-18 fatty alcohol sulfate 5.4 Soap 1.6 optical brightener 0.3 sodium 16.6 sodium silicate 5.4 Acrylic acid-maleic acid copolymer 5.4 Zeolite A (anhydrous active substance) 29.9 Na-hydroxyethane-1,1-diphosphonate 0.8 Water, salts rest Table 2: Composition of binder compound [wt%]: over-dried water glass (sodium silicate, amorphous, <10% by weight water) 57.5 glycerin 42.5 Table 3: Composition of premixes [% by weight]: e V Surfactant granules (Table 1) 64.5 65.8 Sodium perborate monohydrate 15.0 15.8 TAED 5.0 5.3 foam inhibitor 3.0 3.2 polyacrylate 1.0 1.0 enzymes 2.0 2.1 Perfume 0.5 0.5 Wessalith ^® P (zeolite A) 1.0 1.0 Disintegration Aid (Cellulose) 5.0 5.3 binder compound 3.0 -

The hardness of the tablets was measured after two days of storage by deformation of the tablet until fracture, with the force acting on the side surfaces of the tablet and determining the maximum force that could withstand the tablet.

To determine the tablet disintegration, the tablet was placed in a beaker with water (600 ml of water, temperature 15 ° C) and measured the time to complete tablet disintegration.

The experimental data are shown in Table 4: Table 4: Detergent Tablets with Binder Compound [Physical Data] tablet e V Tablet hardness [N] 34 36 Tablet disintegration [sec] 22 23

As can be seen from Table 4, the addition of the binder compound has little effect on the fracture hardness or disintegration time of the detergent tablets. To determine the friability or the abrasion behavior and the brittle fracture behavior, the tablets according to the invention E or the comparative tablets V in a Friabilator (rotating, vertical glass drum, ⌀ 180 mm, width 40 mm, with three transverse to the direction of rotation and at the same distance provided triangular obstacle ribs of a height of 20 mm and a foot width of 15 mm was provided). At a rotational speed of 20 rpm, the time was determined within which a tablet broke into several large pieces. The results of the measurements are shown in Table 5: Table 5: Results from the brittle fracture and friability measurements [s] fracture toughness 26 N 37 N 47 N e 330 460 1000 V 20 60 100

The data in Table 5 show that the addition of the binder compound leads to the fact that the washing and cleaning agent moldings only break much later in mechanical stress on multiple parts, so are more stable. In addition, the abrasion tendency of the molded body is significantly reduced.

Claims (17)

Detergent tablets of compacted, particulate detergent and cleaner containing surfactant-containing granules and builder (s), characterized in that, based on the molding weight, from 1.1 to 20 wt .-% of one or a plurality of binder compounds consisting of a) from 10 to 99% by weight of one or more support materials having an oil adsorption capacity of more than 20 g per 100 g, from the group of silicas, alkali metal silicates and alkali aluminum silicates, b) from 1 to 90% by weight one or more non-surfactant liquid (25 ° C and 1013.25 mbar) binder from the group of di-, tri- and polyols, the carbonic acid esters, the polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate, ethylene glycol, propylene glycol and propylene carbonate. Detergent and detergent tablets according to Claim 1, characterized in that they contain the binder compound (s) in amounts of from 2 to 7.5% by weight, based on the weight of the tablet. Detergents and cleaning agent tablets according to one of claims 1 or 2, characterized in that the binder compound or compounds, in each case based on the compound a) from 20 to 90 wt .-%, preferably 30 to 80 wt .-%, particularly preferably 40 to 70 wt .-% and in particular 40 to 60 wt .-% of one or more support materials having an oil adsorption capacity of more than 20 g per 100 g, b) 10 to 80 wt .-%, preferably 20 to 70 wt .-%, especially preferably 30 to 60 wt .-% and in particular 40 to 60 wt .-% of one or more non-surfactant liquid binder. Detergent tablets according to any one of claims 1 to 3, characterized in that the carrier material (s) has an oil adsorption capacity of more than 25 g per 100 g, preferably more than 30 g per 100 g, more preferably more than 50 g per 100 g and in particular of more than 75 g per 100 g. Detergent tablets according to any one of claims 1 to 4, characterized in that the total content of the tablet of non-surfactant liquid binders is 0.1 to 7.5% by weight, preferably 0.25 to 5% by weight and in particular 0 , 5 to 3 wt .-%, each based on the molding weight, is. Detergents and cleaning tablets according to any one of claims 1 to 5, characterized in that they additionally comprise a disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 wt .-%, preferably of from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the molding weight. Detergent tablets according to any one of claims 1 to 6, characterized in that they contain anionic (s) and / or nonionic surfactant (s) and total surfactant contents above 2.5% by weight, preferably above 5 wt .-% and in particular above 10 wt .-%, each based on the molding weight, have. A process for the preparation of detergent tablets by molding a particulate premix in a conventional manner, characterized in that the premix next to at least one surfactant-containing granules further 1.1 to 20 wt .-% of one or more binder compounds from a) 10 bis 99% by weight of one or more support materials having an oil adsorption capacity of more than 20 g per 100 g, from the group of silicic acids, alkali metal silicates and alkali aluminum silicates, b) 1 to 90% by weight of one or more non-surfactant liquid (25 ° C) C and 1013.25 mbar) binders from the group of di-, tri- and polyols, the carbonic acid ester containing polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate, ethylene glycol, propylene glycol and propylene carbonate. A process according to claim 8, characterized in that the premix contains the binder compound (s) in amounts of from 2 to 7.5% by weight, based on the weight of the premix. Method according to one of claims 8 or 9, characterized in that the binder compound or compounds, in each case based on the compound, from a) 10 to 90 wt .-%, preferably 30 to 80 wt .-%, particularly preferably 40 to 70 Wt .-% and in particular 40 to 60 wt .-% of one or more support materials having an oil absorption capacity of more than 20 g per 100 g, preferably of more than 25 g per 100 g, more preferably of more than 30 g per 100 g, more preferably more than 50 g per 100 g and in particular more than 75 g per 100 g, b) 10 to 80 wt .-%, preferably 20 to 70 wt .-%, particularly preferably 30 to 60 wt .-% and in particular from 40 to 60% by weight of one or more non-surfactant liquid binders. Method according to one of claims 8 to 10, characterized in that the binder compounds, in each case based on the compound, at least 60 wt .-%, preferably at least 75 wt .-% and in particular at least 90 wt .-% of particles with Particle sizes below 600 microns exist. Method according to one of claims 8 to 11, characterized in that the binder compounds have an average particle size below 400 microns. Method according to one of claims 8 to 12, characterized in that the particulate premix has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l. A method according to claim 13, characterized in that the surfactant-containing granules particle sizes between 100 and 2000 .mu.m, preferably between 200 and 1800 .mu.m, more preferably between 400 and 1600 .mu.m and in particular between 600 and 1400 .mu.m. Method according to one of claims 8 to 14, characterized in that the surfactant-containing granules anionic and / or nonionic surfactants and builders and total surfactant contents of at least 10 wt .-%, preferably at least 20 wt .-% and in particular at least 25 wt. -%, having. Method according to one of claims 8 to 15, characterized in that the particulate premix additionally one or more substances from the group of bleaches, bleach activators, enzymes, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, anti redeposition agents, optical Brightener, grayness inhibitors, color transfer inhibitors and corrosion inhibitors contains. Use of binder compounds consisting of a) 10 to 99 wt .-% of one or more support materials having an oil adsorption capacity of more than 20 g per 100 g, from the group of silicic acids, alkali metal silicates and Alkalialuminiumsilikate, b) 1 to 90 wt. % of one or more non-surfactant liquid (25 ° C and 1013.25 mbar) binder from the group of di-, tri- and polyols, carbonic acid esters, polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate, ethylene glycol, propylene glycol and propylene carbonate to improve the hardness and the disintegration time and / or the abrasion stability of detergent tablets containing at least one surfactant-containing granules.