DE19919444A1 - Detergent tablets with binder compound - Google Patents

Abstract

The invention relates to detergent forms containing 0.1 to 20 wt. % of one or more binding agent compounds. The inventive detergent forms have advantageous technical application properties such as increased resistance to abrasion and stability. The binding agent compounds contain 10 to 99 wt. % of one or more support materials with an oil adsorption capacity of more than 20 g per 100 g and 1 to 90 wt. % of one or more non-surfactant liquid binding agents.

Description

The present invention is in the field of compact molded articles which are washable. and have cleaning-active properties. Such washing and Detergent tablets include detergent tablets for the Washing of textiles, detergent tablets for automatic dishwashing or cleaning hard surfaces, bleach tablets for use in laundry or dishwashers, water softening tablets or stain remover tablets. In particular, the invention relates to detergent tablets which are used for Washing textiles used in a household washing machine and briefly as Detergent tablets are called.

Detergent tablets are widely described in the prior art are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents and cleaning agents have a number of powdered detergents Advantages: They are easier to dose and handle and because of their compact structure Advantages in storage and transport. Also in the Patent literature therefore includes detergent tablets described. A problem with the application of washing and cleaning active Shaped bodies occur again and again, is the slow decay and dissolution rate the molded body under conditions of use. Because sufficiently stable, d. H. form and break-resistant molded articles only produced by relatively high pressure  can, there is a strong compression of the molded parts and resulting in a delayed disintegration of the shaped body in the aqueous Liquor and thus too slow a release of the active substances in the washing or Cleaning process. The delayed disintegration of the molded body continues to have Disadvantage that conventional detergent tablets do not have the Have the detergent dispenser washed in by household washing machines as the tablets are not in decay into secondary particles sufficiently small time that are small enough to get out Detergent dispenser to be washed into the washing drum. Another problem that occurs particularly with detergent tablets, the friability of Moldings or their often insufficient stability against abrasion. So can sufficiently break-stable, d. H. hard detergent tablets made often, however, these are the burdens of packaging, transport and handling, d. H. Falling and rubbing stresses, not sufficiently grown so that edge breakage and signs of abrasion adversely affect the appearance of the molding or even lead to a complete destruction of the molded structure.

To overcome the dichotomy between hardness, i. H. Transport and Handling stability and easy disintegration of the moldings are state of the art many solutions have been developed. A well-known in particular from pharmacy and is an extensive approach in the field of detergent tablets the incorporation of certain disintegration aids that prevent the entry of water facilitate or swell upon entry of water or gas evolving or in another form act disintegrating. Other proposed solutions from the patent literature describe the Compression of premixes of certain particle sizes, the separation of individual ones Ingredients of certain other ingredients as well as the coating of individual ones Ingredients or the entire molded body with binders.

EP 687 464 (Allphamed Arzneimittel-Gesellschaft) describes effervescent tablets, consisting of at least one active ingredient or combination of active ingredients, at least a binder, possibly carriers such as flavors, colors, fragrances, Plasticizers, bleaches and effervescent additives, with propylene glycol as the binder or glycerin, preferably in amounts of 0.004 to 2.5% by weight. Methods for producing these effervescent tablets are also claimed. After the  Statements of this document can also be made with the teaching according to the invention Prepare detergent effervescent tablets without the binders used becoming one Loss of carbon dioxide would result in the effervescent additives.

European patent application EP 711 828 (Unilever) describes detergent tablets, which contain surfactant (s), builders (e) and a polymer; that as a binding and Disintegration aid works. The binders disclosed in this document are intended to Room temperature be solid and fed to the premix to be pressed as a melt become. Preferred binders are the higher molecular weight polyethylene glycols.

The use of solid polyethylene glycols is also in the German patent application DE 197 09 411.2 (Henkel). This document teaches synergistic effects between the polyethylene glycols and over-dried amorphous silicates.

Solutions to the problem of friability and abrasion stability of washing and Detergent tablets are not in the prior art, for example in the Pre-published German patent application DE 198 41 146.4 (Henkel KGaA) disclosed. This document teaches the premix to be tabletted based on the Molded body weight 0.25 to 10 wt .-% of one or more non-surfactant, Add water-soluble, liquid binder.

The addition of liquids to tableting premixes is due to the ease and exact dosing advantageous, but also leads to technical problems and undesirable side effects. For one, tableting premixes are common made from different powders and granules, so that dosing points for Liquids mean an additional investment in the plant, on the other hand, a liquid Binder when sprayed or sprayed over the entire premix, so that higher amounts of binder are required. Another problem is that the liquids added to the premix during the pressing process tend to "sweat it out" and in this way lead to caking of the stamp.

The present invention was based on the object of providing moldings which are characterized by short disintegration times with a given hardness and are thus  also have it dispensed via the induction chamber of household washing machines. In addition to these requirements, the moldings should have increased stability against falling and friction loads, d. H. an improved, d. H. neglected Have friability and reduced abrasion behavior. This beneficial Shaped body properties should be in contrast to the proposed solutions of the stand the technology can be achieved by adding solids, whereby dosing and Press problems should be minimized.

It has now been found that the addition of binder compounds from non-surfactant, liquid binders and carriers with high oil absorption capacity for washing and Detergent tablets pre-mixes molded articles that are significantly more abrasion-resistant and are considerably less valuable than the previously known shaped bodies. The use of the The additives mentioned do not influence the fracture hardness of the molded articles or only in minor dimensions. The problems with the pressing process, especially that This additive "sweats" the liquid binder into the die avoided.

The present invention relates to detergent tablets made of compressed, particulate detergent, comprising surfactant (s), builder (s) and optionally further customary detergent ingredients which, based on the weight of the tablet, 0.1 to 20 wt .-% of one or more binder compounds

• a) 10 to 99 wt .-% of one or more carrier materials with one Oil absorption capacity of more than 20 g per 100 g,
• b) 1 to 90% by weight of one or more non-surfactant liquid binders contain.

In the context of the present invention, binder compounds include Mixtures of the above composition understood, which per se in finely divided Powder form available. These can be spray dried, granulated, Agglomeration, compacting, pelleting or extrusion process into a coarser-grained form be transferred if so desired.  

The powdery carrier materials contained according to the invention 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 using standardized methods. For example, the British standard methods BS1795 and BS3483: Part B7: 1982 exist, both of which refer to the ISO 787/5 standard. In the test methods, a balanced sample of the substance in question is placed on a plate and refined flaxseed oil (density: 0.93 gcm ^-3 ) from a burette is added dropwise. After each addition, the powder is thoroughly mixed with the oil using a spatula, the addition of oil being continued until a paste of smooth consistency is obtained. This paste should flow or run without crumbling. The oil absorption capacity is now the amount of the added oil, based on 100 g of absorbent, and is given in ml / 100 g or g / 100 g, conversions about the density of the linseed oil being possible without any problems. A whole series of compounds which can originate both from the group of covalent compounds and from the group of salts are suitable as powdery components in the context of the present invention. As already mentioned, it is preferred if the powdery 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 of 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" characterizes in the context of the present Registration binders that do not belong to the class of surfactants. The term "liquid Binder "refers to the physical state of the binder at 25 ° C and 1013.25 mbar. Substances that only melt or soften at higher temperatures are therefore in the Cannot be used within the scope of the present invention.

Preferred amounts in which the binder compound or compounds are used are within a narrow range, so that preferred washing and Detergent tablets contain a content of the binder compound (s) of  0.5 to 15% by weight, preferably from 1 to 10% by weight and in particular from 2 to 7.5 % By weight, based in each case on the molding weight.

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

• a) 20 to 90% by weight, preferably 30 to 80% by weight, particularly preferably 40 to 70 % By weight and in particular 40 to 60% by weight of one or more carrier materials with an oil absorption capacity of more than 20 g per 100 g,
• b) 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-surfactants liquid binder.

The contained in the detergent tablets according to the invention Binder compounds contain binders applied to carrier materials. As According to the invention, carrier materials become substances with an oil adsorption capacity of more than 20 g used per 100 g, the values of preferred carrier materials are significantly above this value. In preferred washing and Detergent tablets are the carrier material (s) selected from the Group of silicas, alkali silicates and alkali aluminum silicates.

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

Silicas are compounds of the general formula SiO ₂ .n H ₂ O. While the lower members such as orthosilicic acid and pyro silicic acid are only stable in aqueous solution, the formal end product of the condensation is silicon dioxide, (SiO ₂ ) _x , the anhydride of the silicic acid. In the condensation, chain-extending, ring-forming and branching processes run side by side, so that the polysilicic acids are amorphous. With all silicas, the Si atoms are at the center of irregularly linked tetrahedra, at the four corners of which are the O atoms, which at the same time belong to the neighboring wheels. The silicas have a particular ability to form colloidal solutions of polysilicic acids in which the silica particles have particle sizes between 5 and 150 nm. These are called silica brines. They are unstable against further condensation and can be converted into silica gels by aggregation.

With regard to the technical scope of production, the precipitated silicas are by far the most important. They are produced from an aqueous alkali silicate solution by precipitation with mineral acids. This creates colloidal primary particles that agglomerate as the reaction progresses and eventually grow into aggregates. The powdery, voluminous forms have pore volumes of 2.5-15 ml / g and specific surfaces of 30-800 m ² / g. The term pyrogenic silicas is used to summarize highly disperse silicas which are produced by flame hydrolysis. Silicon tetrachloride is decomposed in a detonating gas flame. Pyrogenic silicas have significantly fewer OH groups on their almost non-porous surface than precipitated silicas. Known pyrogenic silicas available on an industrial scale are, for example, Aerosil® (Degussa), Cab-O-Sil® (Cabot Corporation, Waltham, Massachusetts) and HDK (highly disperse silicas).

In addition to the silicas and the silicates and described in detail below Aluminum silicates (zeolites) are also suitable for highly porous polymers and dried ones Polymer gels, such as polymer powder from the group of polyvinyl alcohols, Polyacrylates, polyurethanes and polyvinyl pyrrolidones, as carrier materials for the Binder compounds.

Suitable non-surfactant liquid binders in the context of the present Invention of a variety of substances as long as they are not from the group of surfactants originate and are liquid at 25 ° C and standard pressure. Are preferred as binders 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, in the aforementioned Conditions liquid polyols, carbonic acid esters such as propylene carbonate or Glycerine carbonate and paraffin oil are used. Preferred washing and  Detergent tablets are therefore characterized in that the non-surfactant (s) liquid binder (s) is / are selected from the group consisting of di-, tri- and polyols, the carbonic acid ester and the paraffin oils.

In preferred detergent tablets, as Binder compounds such compounds are used, the water-soluble binders contain. "Water-soluble" binders in the sense of the present application are Binders that 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 glycerin and 1,2-6-hexanetriol, under the conditions mentioned liquid polyols, carbonic acid esters such as propylene carbonate or glycerine carbonate. In washing machines preferred in the context of the present invention and detergent tablets is / are the non-surfactant (s) liquid (s) Binders selected from the group of polyethylene glycols and polypropylene glycols, Glycerin, glycerol carbonate, ethylene glycol, propylene glycol and propylene carbonate.

Polyethylene glycols (abbreviation PEG) which can be used according to the invention in the binder compounds are polymers of ethylene glycol which have the general formula I

H- (O-CH ₂ -CH ₂ ) _n -OH (I)

are sufficient, n taking values between 1 (ethylene glycol, see below) and approx. 16 can. Decisive in the evaluation of whether a polyethylene glycol according to the invention is usable, the physical state of the PEG at room temperature, i. H. the The freezing point of the PEG must be below 25 ° C. For polyethylene glycols exist different nomenclatures that can lead to confusion. Technically common is the indication of the average relative molecular weight after the indication "PEG", so that "PEG 200" is a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210 characterized. According to this nomenclature in the context of the present invention technically common polyethylene glycols PEG 200, PEG 300, PEG 400 and PEG 600 applicable.  

A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number which corresponds to the number n in the formula I mentioned above. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th 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.

Polyethylene glycols are commercially available, for example, under the trade names Carbowax® PEG 200 (Union Carbide), Emkapol® 200 (ICI Americas), Lipoxol® 200 MED (HÜLS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 (Rhone- Poulenc), Lutrol® E300 (BASF) and the corresponding trade names with higher Numbers.

Polypropylene glycols (abbreviation PPG) which can be used according to the invention in the binder compounds are polymers of propylene glycol which have the general formula II

are sufficient, with n assuming values between 1 (propylene glycol, see below) and approx. 12 can. Technically important here are in particular di-, tri- and tetrapropylene glycol, i.e. H. the representatives with n = 2, 3 and 4 in formula II.

Glycerin is a colorless, clear, difficult to move, odorless, sweet-tasting hygroscopic liquid with a density of 1.261 that solidifies at 18.2 ° C. Glycerin was originally only 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 intermediate stages allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO ₃ contact via the glycide stage.

Glycerol carbonate can be obtained by transesterification of ethylene carbonate or dimethyl carbonate with glycerin, ethylene glycol or methanol being obtained as by-products. Another synthetic route starts from glycidol (2,3-epoxy-1-propanol), which is converted under pressure in the presence of catalysts with CO ₂ to form glycerol carbonate.

Glycerol carbonate is a clear, easily movable 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, strong hygroscopic liquid which is miscible with water, alcohols and acetone and a Density of 1.113. The freezing point of ethylene glycol is -11.5 ° C, the Liquid boils at 198 ° C. Technically, ethylene glycol is made from ethylene oxide Heating with water obtained under pressure. Promising manufacturing processes leave also on the acetoxylation of ethylene and subsequent hydrolysis or on Build 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 with a density of 1.0597, which solidifies at -32 ° C and boils at 214 ° C. 1,3-propanediol can be prepared from acrolein and water, followed by catalytic hydrogenation.

Technically far more important is 1,2-propanediol (propylene glycol), which is an oily, colorless, almost odorless liquid, the density 1.0381, which solidifies at -60 ° C and boils at 188 ° C. 1,2-propanediol is made from propylene oxide by adding water manufactured.

Propylene carbonate is a bright, easily moving liquid with a density of 1.2057 gcm ³ , the melting point is -49 ° C, the boiling point is 242 ° C. Large quantities of propylene carbonate can also be obtained by reacting propylene oxide and CO ₂ at 200 ° C and 80 bar.

Regardless of the composition of the binder compounds, washing and Preferred detergent tablets, 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% by weight, based in each case on the weight of the shaped body.

In addition to the binder compounds used according to the invention, the Detergent tablets according to the invention surfactant (s) and builders (e) as the most important ingredients of detergents and cleaning agents and optionally others Ingredients. As other additives that are common in washing and cleaning agents cannot be used, but can have advantageous effects in moldings, disintegration aids are to be mentioned.

In order to facilitate the disintegration of highly compressed moldings, it is possible to Disintegration aids, so-called tablet disintegrants, to be incorporated into them in order to to shorten the disintegration times. Under tablet disintegrants or disintegrators according to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology "(6th edition, 1987, pp. 182-184) understood auxiliary substances that for the rapid disintegration of tablets in water or gastric juice and for the release of the pharmaceuticals in a resorbable form.

These substances, which are also known as "explosives" due to their effectiveness, increase their volume when water enters, and on the one hand increases their own volume (Swelling), on the other hand, a pressure can be generated via the release of gases which can break the tablet into smaller particles. Well-known Disintegration aids are, for example, carbonate / citric acid systems, wherein other organic acids can also be used. Swell end 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 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more Disintegration aid, each based on the weight of the molded body.  

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets have such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 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, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.

The cellulose used as disintegration aid is preferably not in finely divided form used, but before mixing to the to be pressed Premixes are converted into a coarser form, for example granulated or compacted. Detergent tablets, the explosives in granular or optionally contain cogranulated form, are in the German Patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) as well the international patent application WO 98/40463 (Henkel). These writings are also more details on the production of granulated, compacted or co-granulated To remove cellulose disintegrant. The particle sizes of such disintegrants  are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 µm and in particular at least 90% by weight between 400 and 1200 µm. The coarser mentioned above and described in more detail in the cited documents Disintegration aids based on cellulose are within the scope of the present invention preferably used as a disintegration aid and commercially, for example, at the name Arbocel® TF-30-HG available from Rettenmaier.

As a further disintegrant based on cellulose or as part of it Component can be used microcrystalline cellulose. This microcrystalline Cellulose is made by partial hydrolysis of celluloses under such conditions get that only the amorphous areas (about 30% of the total cellulose mass) of the Attack and completely dissolve celluloses, but the crystalline areas (approx. 70%) leave undamaged. A subsequent disaggregation by hydrolysis emerging micro-fine cellulosic supplies the microcrystalline celluloses that Have primary particle sizes of about 5 microns and, for example, to granules with a average particle size of 200 microns are compactible.

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

The detergent tablets according to the invention also contain one or more builders. In the washing and Detergent tablets can all usually be found in detergents and cleaning agents builders used, in particular zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use exist - also the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta S. pA 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 (3.5-5.5) H ₂ O

can be described. The zeolite can be used both as a builder in one granular compound used, as well as a kind of "powdering" of the entire pressing mixture are used, usually both ways to Incorporation of the zeolite into the premix can be used. Suitable zeolites have an average particle size of less than 10 µm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22% by weight of bound water.

It goes without saying that the generally known phosphates are also used as Builder substances possible, provided that such use is not for ecological reasons should be avoided. Have among the variety of commercially available phosphates the alkali metal phosphates with particular preference for pentasodium or Pentapotassium triphosphate (sodium or potassium tripolyphosphate) in the washing and Detergent industry the most important.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to 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, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic 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 occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^-3 , 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 easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5H ₂ O) and 12 mol. Water (density 1.52 gcm ^-3 , melting point 35 ° with the loss of 5H ₂ O), becomes anhydrous at 100 ° and changes into the diphosphate Na ₄ P ₂ O ₇ when heated to a greater extent. Disodium hydrogen phosphate is prepared by neutralizing 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 easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) 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 with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) . Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ , is formed by heating disodium phosphate to <200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers 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 value being 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's 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 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 about 17 g of the crystal water-free salt dissolve at room temperature, about 20 g at 60 ° and about 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (<23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

According to the invention, these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures of Sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of Potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of Sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

As organic cobuilders in the washing and Detergent tablets, in particular polycarboxylates 1, polycarboxylic acids, polymers Polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances will described below.

Usable organic builders are, for example, those in the form of their Polycarboxylic acids that can be used are sodium salts, with polycarboxylic acids being such Carboxylic acids are understood that carry more than one acid function. For example these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, Maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and Mixtures of these. Preferred salts are the salts of polycarboxylic acids such as Citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and Mixtures of these.

The acids themselves can also be used. The acids have besides theirs Builder effect typically also the property of an acidifying component and thus also serve to set a lower and milder pH value of washing or detergents. In particular, citric acid, succinic acid, To name glutaric acid, adipic acid, gluconic acid and any mixtures of these.  

Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{W of} the respective acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, can this group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As Copolymers of acrylic acid with maleic acid have proven particularly suitable Contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative Molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

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

Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which are salts of the monomers Acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or the as monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar Derivatives included.

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

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Are particularly preferred Polyaspartic acids or their salts and derivatives, of which in the German Patent application DE-A-195 40 086 is disclosed; that besides Cobuilder- Properties also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups can be obtained. Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme lysed procedures are carried out. It is preferably hydrolysis pro Products with average molecular weights in the range of 400 to 500,000 g / mol. There is one Polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, particularly preferred from 2 to 30, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which have a DE of  100 owns. Both maltodextrins with a DE between 3 and 20 can be used and dry glucose syrups with a DE between 20 and 37 as well as so-called Yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol.

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

Oxydisuccinates and other derivatives of disuccinates are also preferred Ethylene diamine disuccinate are other suitable cobuilders. Here, ethylenediamine N, N'-disuccinate (EDDS) preferably in the form of its sodium or magnesium salts used. Glycerol disuccinates are also preferred in this context and glycerol trisuccinates. Suitable amounts are in zeolite and / or formulations containing silicate at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated Hydroxycarboxylic acids or their salts, which may also be in lactone form and which have at least 4 carbon atoms and at least one Contain hydroxy group and a maximum of two acid groups. Such cobuilders will described for example in international patent application WO 95/20029.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). As  Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Homologues in question. They are preferably in the form of neutral reactions Sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta- and octa- DTPMP sodium salt used. As a builder, the class becomes the Phosphonates preferably used HEDP. The aminoalkane phosphonates also have a pronounced heavy metal binding capacity. Accordingly, it can, in particular if the agents also contain bleach, aminoalkanephosphonates are preferred, use in particular DTPMP, or mixtures of the phosphonates mentioned use.

In addition, all compounds that are able to complex with To train alkaline earth ions are used as cobuilders.

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

Preferred detergent tablets furthermore contain one or more Surfactant (s). Can in the detergent tablets according to the invention anionic, nonionic, cationic and / or amphoteric surfactants respectively Mixtures of these are used. Are preferred from application technology View mixtures of anionic and nonionic surfactants. The total surfactant content in the case of detergent tablets, the shaped body is preferably 5 to 60% by weight. %, based on the weight of the shaped body, with surfactant contents above 15% by weight being preferred are. Detergent tablets for automatic dishwashing can contain tensides contain smaller amounts, for example less than 2 wt .-%.  

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from C _12-18 monoolefins having a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under Fatty acid glycerol esters are the mono-, di- and triesters as well as their mixtures understand how they are produced by esterification of a monoglycerin with 1 up to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerin be preserved. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example the Capron acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil 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 this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

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

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

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

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

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linearly or preferably 2-branched methyl or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

Another class of preferred non-ionic surfactants, which either sole nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the Alkyl chain, especially fatty acid methyl esters, such as those found in Japanese Patent application JP 58/217598 are described or preferably according to the in the international patent application WO-A-90/13533 become.  

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the Fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.

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

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

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

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C ₁₄ -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 rest.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example, according to the teaching of the international application WO-A-95/07331 by implementation with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

In the context of the present invention, detergent tablets are shaped preferred which contain anionic (s) and nonionic (s) surfactant (s), wherein application technology advantages from certain proportions, in which the individual classes of surfactants can be used. Are particularly preferred Detergent tablets, the anionic and / or nonionic (s) Contain surfactant (s) and total surfactant contents above 2.5 wt .-%, preferably above 5% by weight and in particular above 10% by weight, in each case based on the molded body weight.

For example, detergent tablets are particularly preferred where the ratio of anionic surfactant (s) to nonionic surfactant (s) is between 10: 1 and 1:10, is preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2. Preference is also given to detergent tablets, the surfactant (s), preferably anionic (s) and / or nonionic (s) surfactant (s), in amounts of 5 to 40 % By weight, preferably from 7.5 to 35% by weight, particularly preferably from 10 to 30% by weight and in particular from 12.5 to 25% by weight, in each case based on the molding weight, contain.

From an application point of view, it can be advantageous if certain classes of surfactants in some phases of the detergent tablets or in whole Molded articles, d. H. in all phases, are not included. Another important one  Embodiment of the present invention therefore provides that at least one phase the molded body is free of nonionic surfactants.

Conversely, the content of individual phases or the entire phase can also be used Molded body, d. H. all phases, achieved a positive effect on certain surfactants become. The introduction of the alkyl polyglycosides described above has proven to be proven to be advantageous, so that detergent tablets are preferred, in which contains at least one phase of the shaped body alkyl polyglycosides.

Similar to the non-ionic surfactants, the omission of anionic surfactants from individual or all phases of washing and Detergent tablets result, which are better for certain areas of application own. It is therefore also within the scope of the present invention Detergent tablets are conceivable in which at least one phase of the tablets is free of anionic surfactants.

In addition to the ingredients mentioned surfactant, builder and disintegration aid and in addition to the paraffin contained in the moldings according to the invention, the Detergent tablets according to the invention further substances from the Group of bleaching agents, bleach activators, enzymes, pH regulators, fragrances, Perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, Anti-redeposition agents, optical brighteners, graying inhibitors, Color transfer inhibitors and corrosion inhibitors may be included.

In addition to the ingredients mentioned surfactant, builder and disintegration aid and in addition to the binder compound contained in the moldings according to the invention can further in the detergent tablets according to the invention Substances from the group of bleaching agents, bleach activators, enzymes, pH adjusting agents, Fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, Anti-redeposition agents, optical brighteners, graying inhibitors, Color transfer inhibitors and corrosion inhibitors may be included.  

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for washing textiles, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, irrespective of which other ingredients are contained in the moldings. If cleaning tablets or bleach tablets for machine dishwashing are manufactured, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) 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-phthalimidoxy acid perooxyperaproic acid (ε-phthalimidoperoxyiminoproic acid) . 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or. Can also be used as bleaching agents in moldings for automatic dishwashing Bromine-releasing substances are used. Among the appropriate chlorine or bromine releasing materials come for example heterocyclic N-bromine and N- Chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with Cations such as potassium and sodium are considered. Hydantoin compounds such as 1,3-dichloro-5,5- dimethylhydanthoin are also suitable.  

To be one when washing or cleaning at temperatures of 60 ° C and below To achieve improved bleaching effects, bleach activators can be used in the washing and Detergent tablets are incorporated. Can be used as bleach activators Compounds containing aliphatic peroxocarboxylic acids under perhydrolysis conditions preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or result in optionally substituted perbenzoic acid can be used. Are suitable Substances containing O and / or N-acyl groups with the number of carbon atoms mentioned and / or against also carry substituted benzoyl groups. Multiple acylates are preferred Alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated Triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n- Nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5- dihydrofuran.

In addition to the conventional bleach activators or in their place, too so-called bleaching catalysts can be incorporated into the moldings. With these Fabrics are bleach-enhancing transition metal salts or Transition metal complexes such as Mn, Fe, Co, Ru or Mo Salene complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu Complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts. Also bleach-enhancing Active ingredient combinations by the intimate mixing of a water-soluble salt of a divalent transition metal, selected from cobalt, iron, copper and ruthenium as well as their mixtures, a water-soluble ammonium salt and optionally an oxidizing agent based on peroxygen as well as inert carrier material are can be used as bleaching catalysts in the context of the present invention. Enzymes in particular come from the hydrolase classes such as that Proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases  or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases contribute to the removal of stains such as protein, greasy or starchy stains and graying. Cellulases and others Glycosyl hydrolases can also be removed by removing pilling and Microfibrils help to maintain color and increase the softness of the textile. Oxidoreductases can also be used for bleaching or for inhibiting color transfer be used. Bacterial strains or fungi such as are particularly well suited Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and those obtained from its genetically modified variants enzymatic agents. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are used. Are there Enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and Lipase or enzymes with a tipolytic action or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic Enzymes and cellulase, but especially protease and / or lipase-containing Mixtures or mixtures with Iipolytic enzymes of particular Interest. Examples of such lipolytically active enzymes are the known ones Cutinases. Peroxidases or oxidases have also been found to be suitable in some cases proven. Suitable amylases include in particular alpha-amylases, iso- Amylases, pullulanases and pectinases. As cellulases are preferred Cellobiohydrolases, endoglucanases and glucosidases, also called cellobiases are used, or mixtures of these. Because there are different types of cellulase can distinguish through their CMCase and Avicelase activities, through targeted Mixtures of cellulases to set the desired activities.

The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5% by weight.

The selection of the relevant enzymes also depends on the intended use of the Detergent tablets according to the invention. In detergent tablets for machine dishwashing, the enzymes in particular come from the  Classes of hydrolases such as proteases, esterases, lipases or lipolytic Enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of soiling such as protein, fat or starchy stains. Oxidoreductases can also be used for bleaching become. Bacterial strains or fungi such as Bacillus are particularly suitable subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic derived from their genetically modified variants Active ingredients. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Are there Enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic Enzymes, but especially protease and / or lipase-containing mixtures or Mixtures with lipolytically active enzymes of particular interest. examples for Such lipolytic enzymes are the well-known cutinases. Peroxidases too or oxidases have been found to be suitable in some cases. To the appropriate ones Amylases include in particular alpha-amylases, iso-amylases, pullulanases and Pectinases.

Even with detergent tablets, the enzymes can be adsorbed on or in carrier substances Envelope substances must be embedded to protect them against premature decomposition. The Proportion of enzymes, enzyme mixtures or enzyme granules can also be found here for example about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight.

Detergent tablets according to the invention for machine dishwashing may contain corrosion inhibitors to protect the dishes or the machine, especially silver protection agents in the field of automatic dishwashing have special meaning. The known substances of the prior art can be used Technology. In general, silver protection agents can be selected from the group of Triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the Alkylaminotriazoles and the transition metal salts or complexes are used. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. Man often finds active chlorine-containing agents in detergent formulations Can significantly reduce corroding of the silver surface. In chlorine-free cleaners  organic and redox-active compounds containing oxygen and nitrogen, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, Hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives thereof Connection classes. Also salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Are preferred the transition metal salts selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

In addition, the detergent tablets can also contain components contain, which positively influence the oil and fat washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is soiled, which has previously been repeatedly washed with a detergent according to the invention, that contains this oil and fat-dissolving component. Among the preferred Oil and fat-dissolving components include, for example, nonionic cellulose ethers such as Methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl Groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, each based on the nonionic cellulose ether, and those from the prior art Technically known polymers of phthalic acid and / or terephthalic acid or their Derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionically and / or nonionically modified Derivatives of these. Of these, the sulfonated derivatives of are particularly preferred Phthalic acid and terephthalic acid polymers.

The moldings can be derivatives of diaminostilbenedisulfonic acid as optical brighteners or their alkali metal salts. Are suitable for. B. Salts of 4,4'-bis (2-anilino-4- morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or the like Compounds which instead of the morpholino group a diethanolamino group, a Carry a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -  diphenyls, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can be used.

Dyes and fragrances are the washing and Shaped detergent tablets added to the aesthetic impression of the products improve and give the consumer a visual and sensory "typical and distinctive "product. As perfume oils or fragrances individual fragrance compounds, e.g. B. the synthetic products of the type Esters, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are e.g. B. benzyl acetate, Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl carbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. To the ethers include, for example, benzyl ethyl ether, the aldehydes z. B. the linear alkanals 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, ∝- Isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons mainly include the terpenes like limes and pinene. However, are preferred Mixtures of different fragrances are used, which together make an appealing Generate fragrance. Such parflime oils can also contain natural fragrance mixtures contain as they are accessible from plant sources, e.g. B. Pine, Citrus, Jasmine Patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, Juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The content of the inventive washing and Detergent tablets on dyes below 0.01 wt .-%, while fragrances up to Can make up 2% by weight of the total formulation.

The fragrances can be incorporated directly into the agents according to the invention but can also be advantageous to apply the fragrances to the carrier, which increase the liability  of the perfume on the laundry and by a slower fragrance release for long-lasting fragrance of the textiles. As such carrier materials have become For example, cyclodextrins have proven to be the cyclodextrin-perfume complexes can also be coated with other auxiliaries.

In order to improve the aesthetic impression of the agents according to the invention, they can can be colored with suitable dyes. Preferred dyes, the selection of which Expert has no difficulty, have a high storage stability and Insensitivity to the other ingredients of the agent and to light as well no pronounced substantivity towards textile fibers in order not to dye them.

The production of washable and cleaning-active molded articles takes place by application pressure on a mixture to be pressed, which is located in the cavity of a press. In the simplest case of molded article production, the subsequent simplified tableting is called, the mixture to be tabletted directly, i. H. without previous Granulation pressed. The advantages of this so-called direct tableting are yours simple and inexpensive to use, since no further process steps and consequently, no further systems are required. But these advantages stand also disadvantages. A powder mixture that is to be tabletted directly must have sufficient plastic deformability and good flow properties furthermore, it may be used during storage, transport and filling of the Matrix do not show any tendency to segregate. These three requirements are met many substance mixtures are extremely difficult to master, so that the Direct tableting, especially in the manufacture of detergents and cleaning agents tablets is not used often. The usual way to make laundry and Detergent tablets therefore go from powdered components ("primary particles") from that by suitable methods to secondary particles with higher Particle diameter can be agglomerated or granulated. These granules or Mixtures of different granules are then powdered with individual Additives mixed and fed to the tableting.

The present invention therefore also relates to a process for the production of detergent tablets by compression molding a particulate premix in a manner known per se, in which the premix comprises one or more binder compounds

• a) 10 to 99 wt .-% of one or more carrier materials with one Oil absorption capacity of more than 20 g per 100 g,
• b) 1 to 90% by weight of one or more non-surfactant liquid binders contains.

For preferred embodiments of the method according to the invention, here above, the same applies to the Detergent tablets according to the invention. So z. B. preferred method according to the invention, characterized in that the premix or the binder compound (s) in amounts of 0.5 to 15% by weight, preferably 1 up to 10 wt .-% and in particular from 2 to 7.5 wt .-%, each based on the weight of the premix.

With regard to preferred compositions of the binder compounds used according to the invention, the above applies analogously. Preferred processes are therefore characterized in that the binder compound or compounds, in each case based on the compound

• a) 20 to 90% by weight, preferably 30 to 80% by weight, particularly preferably 40 to 70 % By weight and in particular 40 to 60% by weight of one or more carrier materials with an oil adsorption capacity of more than 20 g per 100 g, preferably of more than 25 g per 100 g, particularly preferably more than 30 g per 100 g preferably of more than 50 g per 100 g and in particular of more than 75 g per 100 g, wherein the carrier materials are preferably selected from the group of Silicas, alkali silicates and alkali aluminum silicates,
• b) 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-surfactants liquid binder, preferably from the group of silicas, the Alkali silicates and the alkali aluminum silicates with particular preference for Polyethylene glycols and polypropylene glycols, glycerin, glycerol carbonate, Ethylene glycol, propylene glycol and propylene carbonate, contain.

In preferred process variants, the binder compounds are sufficient Particle size criteria. Methods according to the invention are preferred in which the Binder compounds, in each case based on the compound, at least 60% by weight, preferably at least 75% by weight and in particular at least 90% by weight Particles with particle sizes below 600 microns exist. It is special here preferred if the binder compounds have an average particle size below 400 µm.

Preferred washing and Detergent tablets are made by pressing a particulate Premix of at least one surfactant-containing granulate and at least one subsequently added powdered component. The manufacture of the Granules containing surfactant can be prepared using conventional industrial granulation processes such as Compacting, extrusion, mixer granulation, pelleting or Fluidized bed granulation takes place. It is there for later washing and Detergent tablets are advantageous if the premix to be pressed is Has bulk density that comes close to the usual compact detergent. In particular it is preferred that the particulate premix additionally contain surfactant (s) Contains granulate (s) and a bulk density of at least 500 g / l, preferably has at least 600 g / l and in particular at least 700 g / l.

In preferred process variants, the granules containing surfactant are also sufficient certain particle size criteria. Thus methods according to the invention are preferred for where the surfactant-containing granules have particle sizes between 100 and 2000 µm, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 µm and in particular between 600 and 1400 µm.

In addition to the active substances (anionic and / or nonionic and / or cationic and / or amphoteric surfactants) preferably also contain the surfactant granules Carriers that particularly preferably come from the group of builders. Particularly advantageous processes are therefore characterized in that the surfactant Granules contain anionic and / or nonionic surfactants and builders and  Total surfactant contents of at least 10% by weight, preferably at least 20% by weight and in particular at least 25% by weight.

Before pressing the particulate premix to wash and The pre-mix with fine particles can form detergent tablets Surface treatment agents are "powdered". This can affect the texture and physical properties of both the premix (storage, compression) as the finished detergent tablets may also be advantageous. Finely divided Powdering agents are well known in the prior art, mostly zeolites, silicates or other inorganic salts can be used. However, the premix is preferred "powdered" with finely divided zeolite, faujasite type zeolites being preferred. In the context of the present invention, the term "zeolite from faujasite Type "all three zeolites that form the faujasite subgroup of zeolite structure group 4 (Compare Donald W. Breck: "Zeolite Molecular Sieves," John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92). In addition to the Zeolite X are also Zeolite Y and faujasite and mixtures of these compounds can be used, the pure Zeolite X is preferred.

Mixtures or cocrystallizates of zeolites of the faujasite type with others Zeolites, which do not necessarily have to belong to the zeolite structure group 4, are as Powdering agent can be used, it being advantageous if at least 50% by weight of the Powdering agent consist of a zeolite of the faujasite type.

In the context of the present invention, detergent tablets are shaped preferred, which consist of a particulate premix, the granular Contains components and subsequently mixed powdery substances, the or one of the subsequently mixed powdered components is a zeolite from Faujasite type with particle sizes below 100 microns, preferably below 10 pm and is in particular below 5 μm and is at least 0.2% by weight, preferably at least 0.5 % By weight and in particular more than 1% by weight of the premix to be pressed matters.

In addition to the ingredients mentioned, surfactant, builder and disintegration aid can the premixes to be pressed additionally include one or more substances from the group  bleaching agents, bleach activators, enzymes, pH adjusting agents, fragrances, perfume carriers, Fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and Contains corrosion inhibitors. These substances have been described above.

The moldings according to the invention are first produced by dry means Mixing of the components, which can be partially or completely pre-granulated, and on concluding information, in particular pressing into tablets, with conventional che procedures can be used. For the production of the invention The pre-mix is molded in a so-called die between two stamps compacted into a solid compressed. This process, briefly referred to below as Tabletting is divided into four sections: dosage, compression (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting molded body through the position of the lower one Stamp and the shape of the press tool can be determined. The constant one Dosage even at high molding throughputs is preferably over a volumetric dosage of the premix reached. In the further course of tableting the upper stamp touches the premix and continues to lower in the direction of the Lower stamp. With this compression, the particles of the premix become closer pressed together, the void volume within the filling between the Stamping decreases continuously. From a certain position of the upper stamp (and from a certain pressure on the premix) begins the 17899 00070 552 001000280000000200012000285911778800040 0002019919444 00004 17780plastic Deformation in which the particles flow together and it to form the molded body is coming. Depending on the physical properties of the premix, a part also becomes the premixed particles are crushed and there is a pressure at even higher pressures Sintering the premix. With increasing press speed, i.e. high Throughput quantities, the phase of elastic deformation is shortened more and more, so that the resulting shaped bodies can have more or less large cavities. In the last step of tableting, the finished molded article is made using the lower stamp pressed out of the die and by subsequent transport devices transported away. At this point, only the weight of the molded body is final  determined because the compacts due to physical processes (stretching, crystallographic effects, cooling etc.) can still change their shape and size. Tableting takes place in commercially available tablet presses, which are basically or double stamps can be equipped. In the latter case, not only Upper stamp used to build up pressure, the lower stamp also moves during of the pressing process towards the upper punch, while the upper punch presses down. Eccentric tablet presses are preferably used for small production quantities, where the stamp or stamps are attached to an eccentric disc, which in turn an axis with a certain rotational speed is mounted. The movement this ram is comparable to the operation of a conventional four-stroke engine. The pressing can be done with an upper and lower stamp, but it can also several stamps can be attached to an eccentric disc, the number of Die holes are expanded accordingly. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected, on which one so-called die table a larger number of dies is arranged in a circle. The number of matrices varies between 6 and 55, depending on the model, with larger ones as well Matrices are commercially available. Each die on the die table is a top and Assigned lower stamp, whereby again the pressure is active only by the upper or Lower stamp, but can also be built up by both stamps. The matrix table and the stamps move about a common vertical axis, the Stamp with the help of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection. To the Places where there is a particularly serious increase or decrease in the stamp is necessary (filling, compacting, ejecting), these cam tracks are additional low-pressure pieces, low-tension rails and lifting tracks supported. The The die is filled via a rigidly arranged feed device so-called filling shoe, which is connected to a reservoir for the premix. The pressure on the premix is via the press paths for upper and lower punches individually adjustable, the pressure build-up by rolling the Stamp shaft heads happen on adjustable pressure rollers.  

Rotary presses can also be used with two filling shoes to increase the throughput be provided, with only a semicircle to produce a tablet must become. Several are used to produce two-layer and multi-layer moldings Filling shoes arranged one behind the other without the slightly pressed first layer in front of the further filling is ejected. Appropriate litigation is based on this Way to produce coated and dot tablets, the onion-like Have a break, whereby in the case of the point tablets the top of the core or Core layers are not covered and thus remain visible. Also Rotary tablet presses can be equipped with single or multiple tools, so that for example, an outer circle with 50 and an inner circle with 35 holes can be used for pressing at the same time. The throughputs are more modern Rotary tablet presses are over one million tablets per hour.

When tableting with rotary presses, it has proven to be advantageous to carry out the tabletting with the smallest possible fluctuations in the weight of the tablet. The fluctuations in hardness of the tablet can also be reduced in this way. Small fluctuations 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 the filler paddle speed to the speed of the rotor Filling shoe with constant powder height
• - Decoupling of filling shoe and powder feed

All of the technology is available to reduce the build-up of stamps known non-stick coatings. Plastic coatings are particularly advantageous, Plastic inlays or plastic stamps. Rotating stamps have also turned out to be proven to be advantageous, the upper and lower punches being rotatable if possible should be. With rotating stamps, a plastic insert can usually be used to be dispensed with. The stamp surfaces should be electropolished here.  

It was also shown that long pressing times are advantageous. You can use Pressure rails, several pressure rollers or low rotor speeds can be set. Because the fluctuations in hardness of the tablet due to the fluctuations in the pressing forces systems should be used that limit the pressing force. Here can elastic stamps, pneumatic compensators or resilient elements in the Kraftweg be used. The pressure roller can also be designed to be resilient.

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

The moldings can be in a predetermined spatial shape and a predetermined size are manufactured. Practically all sensibly manageable come as a room shape Configurations into consideration, for example, the training as a board, the staff or Bar shape, cubes, cuboids and corresponding room elements with flat side surfaces as well as 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 each be separate individual elements be formed, the predetermined dosage of the washing and / or Corresponds to detergent. But it is also possible to form compacts, the one Connect a plurality of such mass units in one compact, in particular by predetermined breaking points make it easy to separate portioned smaller units is provided. For the use of textile detergents in machines of in Europe usual type with horizontally arranged mechanics can the training of portioned compacts as tablets, in cylindrical or cuboid form, are expedient, a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred is. Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices in particular for the production of such compacts.

The spatial shape of another embodiment of the shaped body is in its dimensions the induction chamber of commercial household washing machines adapted so that the Shaped bodies can be metered directly into the induction chamber without a metering aid, where it dissolves during the induction process. Of course, there is also a stake the detergent tablets are easily possible via a dosing aid and within the present invention preferred.

Another preferred shaped body that can be produced has a plate or panel-like structure with alternating thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, the short thin Display segments, can be canceled and entered into the machine. This Principle of the "bar-shaped" shaped body detergent can also be used in others geometric shapes, for example vertically standing triangles, which only appear one of its sides are connected to each other along the side, can be realized.

But it is also possible that the various components do not become one Tablet are pressed, but that shaped bodies are obtained, which several Have layers, that is, at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous performance properties of the shaped bodies result. If, for example, components are contained in the moldings, the  affect each other negatively, so it is possible to have one component in the faster integrate soluble layer and the other component into a slower soluble Work in layer so that the first component has already reacted when the second goes into solution. The layer structure of the moldings can be stacked, a dissolution process of the inner layer (s) at the edges of the molded body already then occurs when the outer layers are not yet completely dissolved, but it can also a complete covering of the inner layer (s) by the further outwards lying layer (s) can be reached, which prevents the early Solution of components of the inner layer (s) leads.

In a further preferred embodiment of the invention, a molded body consists of at least three layers, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while in the case of the stacked shaped body, the two outer layers and in the case of the shell-shaped one Shaped bodies, however, the outermost layers are free of peroxy bleach. Farther it is also possible to use peroxy bleach and any bleach activators present and / or to separate enzymes spatially from one another in a shaped body. Such multilayered moldings have the advantage that they do not have only one Detergent dispenser or via a metering device, which is added to the wash liquor will be used; rather, it is also possible in such cases, the Put molded articles in direct contact with the textiles in the machine without Stains from bleach and the like would be feared.

Similar effects can also be achieved by coating individual components of the detergent and cleaning agent composition to be pressed, or all of them Reach shaped body. For this purpose, the bodies to be coated can be coated with, for example aqueous solutions or emulsions are sprayed, or via the process of Get a coating on the melt coating.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to

Here σ stands for diametral fracture stress (DFS) in Pa, P is the force in N which leads to the pressure exerted on the molded body, which is the Breakage of the shaped body causes, D is the shaped body diameter in meters and t is the Height of the molded body.

Another object of the present invention is the use of binder compounds

• a) 10 to 99 wt .-% of one or more carrier materials with one Oil absorption capacity of more than 20 g per 100 g,
• b) 1 to 90% by weight of one or more non-surfactant liquid binders to improve the hardness and disintegration time and / or the abrasion resistance of laundry and detergent tablets. This inventive use of the above Binder compounds lead to moldings with advantageous properties, such as show examples below. Regarding preferred embodiments of the use according to the invention (particle sizes, further ingredients, The composition of the premix etc.) applies analogously to the above Method according to the invention said.

Examples

By granulation in a 5-liter ploughshare mixer from the company Lödige Granules containing surfactant (for composition, see Table 1), which are used as the basis for a particulate premix was used. Following the granulation the granules were in a fluidized bed apparatus from Glatt at a Supply air temperature of 60 ° C dried over a period of 30 minutes. After Drying fine parts <0.6 mm and coarse particles <1.6 mm were sieved.

This premix was mixed with the surfactant-containing granules Bleach, bleach activator and other processing components manufactured. The Example E according to the invention was 3% by weight in the preparation of the premix of a binder compound, the composition of which is shown in Table 2 is specified. The proportions of the other components therefore differ as a percentage of those of Comparative Example V, which contained no binder compound. Premixes E and V became tablets in a Korsch eccentric press (Diameter: 44 mm, height: 22 mm, weight: 37.5 g) pressed, but none "Sweating out" of the binder from the shaped body was observed. The Composition of the premixes to be pressed (and thus the shaped body) shows Table 3.

Table 1

Composition of the surfactant granules [% by weight]

Table 2

Composition of the binder compound [% by weight]

Table 3

Composition of the premixes [% by weight]

The hardness of the tablets became after two days of storage by deforming the tablet measured to break, the force acting on the side surfaces of the tablet and the maximum force that the tablet withstood was determined.

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

The experimental data are shown in Table 4

Table 4

Detergent tablets with binder compound [physical data]

As can be seen from Table 4, the addition of the binder compound has hardly any Influence on the breaking hardness or the disintegration time of the detergent tablets. For determination the friability, the abrasion behavior and the brittle fracture behavior were the Tablets E according to the invention or the comparison tablets V in a Friabilator  (rotating, vertical glass drum, ∅ 180 mm, width 40 mm, with three across to the direction of rotation and at the same distance from each other triangular obstacle ribs 20 mm high and 15 mm wide was provided). At a revolution speed of 20 rpm, the time determined within which a tablet broke into several large parts. The results of the Table 5 shows measurements:

Table 5

Results from brittle fracture and friability measurements [s]

The data in Table 5 show that the addition of the binder compound leads to the fact that the detergent tablets only become clear when subjected to mechanical loads break up into several parts later, so they are more stable. In addition, the tendency to wear the molded body significantly reduced.

Claims (20)

1. Detergent tablets made of compressed, particulate detergent and detergent, containing surfactant (s), builders (e) and optionally other customary detergent ingredients, characterized in that, based on the weight of the tablet, 0.1 up to 20% by weight of one or more binder compounds

• a) 10 to 99% by weight of one or more carrier materials with an oil absorption capacity of more than 20 g per 100 g,
• b) contain 1 to 90% by weight of one or more non-surfactant liquid binders.

2. Detergent tablets according to claim 1, characterized in that they contain the binder compound (s) in quantities of 0.5 to 15% by weight, preferably from 1 to 10% by weight and in particular from 2 to 7.5% by weight, in each case based on the weight of the molded body. 3. Detergent tablets according to one of claims 1 or 2, characterized in that the or the binder compounds, each 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 carrier materials with an oil adsorption capacity of more than 20 g per 100 g,
• b) 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.

4. Detergent tablets according to one of claims 1 to 3, characterized characterized in that the carrier material (s) has an oil adsorption capacity of more more than 25 g per 100 g, preferably more than 30 g per 100 g, particularly preferred of more than 50 g per 100 g and in particular of more than 75 g per 100 g.   5. Detergent tablets according to one of claims 1 to 4, characterized characterized in that the carrier material (s) is / are selected from the group of Silicas, the alkali silicates and the alkali aluminum silicates. 6. Detergent tablets according to one of claims 1 to 5, characterized characterized in that the non-surfactant (s) liquid binder (s) is selected is / are from the group of di-, tri- and polyols, carbonic acid esters and Paraffin oils. 7. Detergent tablets according to one of claims 1 to 6, characterized characterized in that the non-surfactant (s) liquid binder (s) is selected is / are from the group of polyethylene glycols and polypropylene glycols, glycerol, Glycerine carbonate, ethylene glycol, propylene glycol and propylene carbonate. 8. Detergent tablets according to one of claims 1 to 7, characterized characterized in that the total content of the shaped body of non-surfactant, liquid Binder 0.1 to 7.5 wt .-%, preferably 0.25 to 5 wt .-% and in particular 0.5 to 3 wt .-%, based in each case on the weight of the shaped body. 9. Detergent tablets according to one of claims 1 to 8, characterized characterized in that they additionally contain a disintegration aid, preferably a Disintegration aids based on cellulose, preferably in granular form, cogranulated or compacted form, in quantities of 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the weight of the molded body. 10. Detergent tablets according to one of claims 1 to 9, characterized characterized in that they contain anionic (s) and / or nonionic (s) surfactant (s) and total surfactant contents above 2.5% by weight, preferably above 5 % By weight and in particular above 10% by weight, in each case based on the Molded body weight.   11. A process for the production of detergent tablets by molding a particulate premix in a manner known per se, characterized in that the premix comprises one or more binder compounds

• a) 10 to 99% by weight of one or more carrier materials with an oil absorption capacity of more than 20 g per 100 g,
• b) contains 1 to 90% by weight of one or more non-surfactant liquid binders.

12. The method according to claim 11, characterized in that the premix or the binder compound (s) in amounts of 0.5 to 15% by weight, preferably 1 up to 10 wt .-% and in particular from 2 to 7.5 wt .-%, each based on the Weight of premix; contains. 13. The method according to any one of claims 11 or 12, characterized in that the binder compound or compounds, in each case based on the compound

• 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 carrier materials with an oil absorption capacity of more than 20 g per 100 g, preferably more than 25 g per 100 g, particularly 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, the carrier materials preferably being selected are from the group of silicas, alkali silicates and alkali aluminum silicates,
• b) 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, preferably from the group of silicas , the alkali silicates and the alkali aluminum silicates with particular preference for the polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate, ethylene glycol, propylene glycol and propylene carbonate.

14. The method according to any one of claims 11 to 13, characterized in that the Binder compounds, in each case based on the compound, at least 60% by weight,  preferably at least 75% by weight and in particular at least 90% by weight consist of particles with particle sizes below 600 microns. 15. The method according to any one of claims 11 to 14, characterized in that the Binder compounds have an average particle size below 400 microns. 16. The method according to any one of claims 11 to 15, characterized in that the Particulate premix additionally contains granules (s) containing surfactant and a Bulk density of at least 500 g / l, preferably at least 600 g / l and in particular has at least 700 g / l. 17. The method according to claim 16, characterized in that the surfactant-containing granules Particle sizes between 100 and 2000 microns, preferably between 200 and 1800 µm, particularly preferably between 400 and 1600 µm and in particular between 600 and 1400 µm. 18. The method according to any one of claims 16 or 17, characterized in that the Granules containing surfactants, anionic and / or nonionic surfactants and builders contains and total surfactant contents of at least 10 wt .-%, preferably has at least 20% by weight and in particular at least 25% by weight. 19. The method according to any one of claims 11 to 18, characterized in that the Particulate premix additionally one or more substances from the group of Bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, Fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and Contains corrosion inhibitors. 20. Use of binder compounds

• a) 10 to 99% by weight of one or more carrier materials with an oil absorption capacity of more than 20 g per 100 g,
• b) 1 to 90 wt .-% of one or more non-surfactant liquid binders to improve the hardness and the disintegration time and / or the abrasion resistance of detergent tablets.