DE10338044A1 - Process for the preparation of detergents or cleaners - Google Patents

Abstract

Casting process for washing or cleaning active preparations, which are carried out in molds which consist at least partially of elastic material, are characterized by a simpler mold release of the moldings.

Description

These Application relates to detergents or cleaners. In particular, it concerns This application is a process for the preparation of detergents or cleaning agents.

washing or detergents are available to the consumer in a variety of forms today available. In addition to washing powders and granules, this offer includes, for example also detergent concentrates in the form of extruded or tableted Compositions. These solid, concentrated or compacted Forms of supply are characterized by a reduced volume per Dosing and thus reduce the cost of packaging and transport. In particular, the washing or cleaning agent tablets meet here additionally the desire of the consumer for simple dosage. The corresponding Agents are comprehensively described in the art.

Except in the described fixed forms of supply can be washing or cleaning agents continue to make up as gels or pastes.

Thus, the granted European patent EP 331 370 (Unilever) a process for producing stable, viscous liquid compositions for use in automatic dishwashers. Subject of the European patent EP 797 656 (Unilever) are nonaqueous liquid detergent compositions containing polymeric hydrotropes.

For the packaging solid or liquid Detergents or cleaning agents are also particularly water-soluble or water-dispersible films. The way to single dosing units packaged cleaning products can in a simple manner by inserting one or more bags directly in the washing machine or dishwasher or in their Einspülkammer, or by injection into a predetermined amount of water, for example in a bucket or in hand washing or sink, be dosed. such packaged detergents and cleaners are the subject of numerous Publications.

The granted European patent EP 700 989 B1 claims, for example, a unitarily packaged detergent for dishwashing wherein the unitized detergent is enveloped by a package of a water-soluble material which is tacky on its outside.

The Application WO 02/616222 (Reckitt-Benckiser) discloses water-soluble packaging for aqueous detergent compositions, the content of free water is at least 3% by weight.

object WO 02/11541 (Reckitt-Benckiser) are liquid detergent compositions with a water content between 20 and 50 wt .-%, which in one water-soluble or water-dispersible material, at least a polyphosphate builder and by a certain ratio of those contained in the agent Potassium and sodium ions are characterized.

In spite of the numerous publications in the field of detergents or cleaning agents persists a need after improving the cleaning performance of these agents, in particular while maintaining or reducing the per wash or cleaning cycle used quantities of washing or cleaning substances. Furthermore, there is a need the amount of packaging and packaging of these products non-washing or cleaning active materials (e.g. water-soluble or non-water-soluble Polymer films of the outer packaging).

task The present application was to provide an optimized casting process for the production of detergent or cleaning agent hollow bodies, in which the cast body can be removed from the molds without breakage. It was surprising found that through the use of elastic materials cast in the production Detergent or cleaner body the above object can be achieved.

• a) Gießen einer wasch- oder reinigungsaktiven Zubereitung in ein Formwerkzeug,
• b) Entformen des gegossenen Körpers aus dem Formwerkzeug,

dadurch gekennzeichnet, daß das Formwerkzeug wenigstens anteilsweise aus elastischem Material gefertigt ist.A first subject of the present application is therefore a process for producing a cast body from a washing or cleaning active preparation, comprising the steps:

• a) pouring a washing or cleaning active preparation into a mold,
• b) demolding the cast body from the mold,

characterized in that the molding tool is at least partially made of elastic material.

The inventive method allows not only the demolding of the cast body without breakage. The used elastic materials are also characterized by a reduced adhesion especially in contact with builder-containing Recipes out.

As a "molding tool" is under the present application denotes a tool which has cavities, the pourable ones Filled substances can be. Such tools can for example in the form of individual cavities but also in the form of plates with several cavities be educated. The single cavities or cavity plates are preferably circulating horizontally in industrial processes Mounted conveyor belts, which a continuous or discontinuous transport the cavities for example, along a number of different workstations (eg: casting, Cool, To fill, Seal, demould, etc.).

In a preferred embodiment is not the entire mold made of elastic material. Rather, it is preferred that only the receiving trough of the mold, that is, the cavity, made of elastic Material is made. Such an embodiment, in which one made of elastic material receiving cavity / cavity of a preferably rigid body surrounded or held by a rigid device allows to one the safe demolding of the cast body, gives the mold but at the same time, especially for industrial production in high quantities necessary stiffness and robustness. In a preferred embodiment the method according to the invention be made of elastic material receiving trough can in the form of single insert in one with corresponding recesses fitted plate inserted. Such deposits can in a simple manner, for example when changing the spatial shape of the cast body or replaced or repaired for repair. However, it is also possible and in the context of the present application preferred, the mold coat with elastic material.

Prefers used elastic materials come from the group of plastics. The term "plastics" characterizes in the context of the present invention, materials whose essential Ingredients of such macromolecular organic compounds that exist synthetically or by altering natural products arise. They are in many cases under certain conditions (heat and Pressure) meltable and moldable. So plastics are basically organic Polymers and can either according to their physical properties (thermoplastics, Thermosets and elastomers), according to the nature of the reaction of their preparation (Polymers, polycondensates and polyadducts) or according to their chemical Nature (polyolefins, polyesters, polyamides, polyurethanes, etc.) classified become.

Elastomers are particularly preferably used as elastic materials. For the purposes of this application, "elastomers" are polymers having rubber-elastic behavior, elastomers being characterized in that they can be repeatedly stretched at least twice their length due to their rubber-elastic behavior at 20.degree The elastomers are wide-meshed, high-polymer materials, which can not flow viscously at the temperature of use due to the linking of the individual polymer chains at the crosslinking sites Irreversible, ie crosslinked via covalent chemically bonded bonds Elastomers have a glass transition temperature T _g (dyn) (in the case of amorphous polymers) or melting temperature T _m (dyn) (in the case of semicrystalline polymers) generally below 0 ° C. Below this temperature, only energy-elastic and energy / entropy-elastic shapes are used possible, while above this temperature up to the decomposition temperature rubber-elastic (entropy-elastic) deformations are allowed. Irreversibly crosslinked elastomers are generally made by vulcanization of natural and synthetic rubbers.

In the context of the present application, particular preference is given to elastic materials from the group of elastomers, in particular from the group of acrylate rubber, polyester urethane rubber, brominated butyl rubber, polybutadiene, chlorinated butyl rubber, chlorinated polyethylene, epichlorohydrin (homopolymer). , Polychloroprene, sulfurized polyethylene, ethylene-acrylate rubber, epichlorohydrin (copolymers), ethylene-propylene terpolymer (sulfur-crosslinked), ethylene-propylene copolymer (peroxide crosslinked), polyether-urethane rubber, ethylene-vinyl acetate copolymer, fluorine Rubber, fluorosilicone rubber, hy nitrated rubber, butyl rubber, dimethyl polysiloxane (vinyl-containing), natural rubber, synthetic rubber (synthetic polyisoprene), thioplasts, polyfluorophosphazenes, polynorbornene, styrene-butadiene rubber, nitrile rubber (carboxy group-containing).

Acrylic rubber is a collective name for rubber elastomers, vulcanizable copolymers based on Acrylsäureestern (especially ethyl and butyl acrylates) containing small amounts of comonomers such as Ethylene or methacrylic acid contain the rapid vulcanization of acrylic rubbers favor.

polybutadiene is the collective name for Polymers of 1,3-butadiene. The polymerization of the monomer can under 1,4- or 1,2-linkage respectively. The basic units can furthermore in cis or trans configuration in the polymer chain available. Polybutadienes can from 1,3-butadiene by free-radical, anionic, coordination or by Alfin initiators initiated polymerizations (Alfin polymerization) become.

Poly (2-chloro-1,3-butadiene) e is the name for Polymers of chloroprene (2-chloro-1,3-butadiene), which are technically by Emulsion polymerization are prepared.

Fluororubbers are thermoplastic fluoropolymers which are converted to fluoroelastomers by vulcanization. Of particular industrial importance are the copolymers poly (vinylidene fluoride-co-hexafluoropropylene), poly (vinylidene fluoride-co-hexafluoropropylene-co-tetrafluoroethylene), poly (vinylidene fluoride-co-tetrafluoroethylene-co-perfluoromethylvinyl ether), poly (tetrafluoroethylene-co-propylene) and poly (vinylidene fluoride -co-chlorotrifluoroethylene). Preferred production method for fluorinated rubbers is the polymerization of the monomers in aqueous emulsion in the temperature range of 80-125 ° C and 2-10 × 10 ⁶ Pa.

Butyl rubbers are copolymers of isobutylene and »0.5-5 wt .-% isoprene, by cationic polymerization at temperature of about -40 ° C to -100 ° C in the solution (Lsm .: Hexane) or precipitation method (Lsm .: Methylene chloride). Thus, butyl rubbers contain over the built in trans-1,4 configuration isoprene double bonds, the for vulcanization or modification of the butyl rubbers Chlorination (chlorobutyl rubber, short CIIR) or bromination (Bromobutyl rubber, short BIIR) can be used. vulcanized Butyl rubber characterized by very low gas permeability, high resistance across from Oxygen, ozone, acids, Bases and polar organic solvents and can be used in the temperature range from approx. -30 ° C to 190 ° C.

Nitrile rubber is the name for a synthetic rubber obtained by copolymerization of acrylonitrile and butadiene in proportions from about 52:48 to 82:18. Its production takes place practically exclusively in water Emulsion. The resulting emulsions are used as such (NBR latex) used or worked up to solid rubber. The properties of nitrile rubber off from the relationship the starting monomer and its molecular weight. Made of nitrile rubber accessible Vulcanizates have high resistance across from Fuels, oils, Fats u. Hydrocarbons and are distinguished over such from natural rubber by cheaper Aging behavior, lower abrasion and reduced gas permeability out.

Natural rubber is the name - hereinafter the abbreviation NR (according to DIN ISO 1629: 1981-10, derived from natural rubber) is used - for rubber, which occurs in the white latex (latex) of the milk tubes of numerous dicotyledons. However, NR is almost exclusively extracted (almost 99%) from the latex which flows out when scoring the secondary bark of the trunks of rubber or paraclyme trees (Hevea brasiliensis, family Wolfmilch Family, Euphorbiaceae). Like the synthetic rubber, NR is a polyisoprene whose enzymatically catalyzed biosynthesis proceeds via isopentyl and farnesyl pyrophosphate as precursors. Raw NR undergoes prolonged storage under the influence of light and air as a result of crosslinking u. Oxidation reactions adverse changes. NR became a valuable engineering product after American Goodyear introduced hot air vulcanization in 1840, still the most important NR vulcanization process. In this Verf. The crude rubber is heated after kneading with sulfur to 130-140 ° C (about 1 h). By reacting the sulfur with a part of the double bonds of the polyisoprene chains, the individual macromolecules of the NR are linked to each other via mono- or polyatomic (S or S _x ) sulfur bridges. This intermolecular crosslinking reaction eventually results in an insoluble and thermoplastic non-processable product called gum. Depending on the amount of sulfur used in the vulcanization, soft rubber (1-4 parts sulfur) or hard rubber (> 20 parts sulfur) is obtained. The sulfur can also be intramolecular from the NR-Mole be bound to reduce the tensile and structural strength of the vulcanizate. Depending on the nature of the rubber (natural and / or synthetic rubber) and the intended use of the rubber, the rubber processing requires the addition of numerous other substances; Inevitably, a highly specialized rubber technology has developed in view of the many variables (order and duration of exposure, temperature, reciprocal influence of additives). As such, as well as the above-mentioned additives, some of which are treated in single keywords and often generalized as rubber chemicals, NR (also synthetic rubbers) are mainly: fillers (carbon black, among others carbon blacks, silica gel, silicates like kaolin, chalk, talc etc.), Pigments (organic dyes, lithopones, titanium dioxide, iron oxides, chromium and cadmium compounds), plasticizers (mineral oils, ethers and thioethers, esters and other elastomers, factives), mastics (thiophenols, optionally chlorinated, and their zinc salts) , Anti-aging agents, which include the antioxidants, heat, ozone, light, fatigue and hydrolysis protectants (aromatic amines, phenols, phosphites, waxes and many others), blowing agents for porous articles (hydrazides, nitrosoamines, azodicarboxylic acid Derivatives), flame retardants (chlorinated alkanes, haloalkyl phosphates), preservatives and termites (chlorpheholes, phosphoric acid esters), odor-improving agents, Antistatic agents, release agents to reduce stickiness u. for easier replacement of the material to be processed by rollers u. Forms (waxes, fats, stearates, silicone oils), adhesives for improving the adhesion of NR to metals or fabrics (cobalt naphthenate, resorcinol-formaldehyde resins, phenolic resins, isocyanates, protein). For less frequently applied cold vulcanization, which is limited to thin NR articles, the raw rubber products are immersed in a solution of disulfur dichloride (S ₂ Cl ₂ ) in carbon disulfide (CS ₂ ), in benzene or benzene for a few to several minutes and then brought to ammonia Atmosphere to neutralize the resulting hydrochloric acid u. to decompose the excess disulfur dichloride.

The unsaturated nature of the NR allows not only the preparation of vulcanizates, but also of addition derivatives such as hydrochlorinated NR (addition of HCl), chlorinated rubber (addition of Cl ₂ ), cyclo rubber (exposure to acids or metal halides), AC rubber.

Thioplasts or polysulfide rubbers is the name for polycondensates of organic dihalides u. Alkali metal polysulfides, which are marketed under the name Thiokol ^®.

polynorbornene [Poly (1,3-cyclopentylenevinylene) is the name given to the Polyalkenameren counting, polymers obtainable by metathesis polymerization of norbornene. polynorbomenes be as amorphous white Traded powder. They have molecular weights of about 2,000,000 g / mol, one Glass transition temperature of 35-45 ° C u. one high proportion (about 80%) of double bonds in the trans position. You can as When processed by addition of mineral oils to the rubber Lowering the glass transition temperature be plasticized to elastomers.

Styrene-butadiene is the collective name for Copolymers of styrene and butadiene, which are the two monomers mostly in the weight ratio of about 23.5: 76.5, in exceptional cases also included from 40:60. They are produced by methods the emulsion polymerization or solution polymerization. The emulsion polymerization in water with redox initiators at low temperatures (cold rubber; rubber) or at higher Temperatures (hot-rubber; hot rubber) is started with persulfates, provides latices that used as such or worked up to solid rubber. The molecular weights of emulsion styrene-butadiene rubber are in the Range of about 250000-800000 g / mol; Differentiate between cold and hot rubbers in terms of the degree of branching. In the solution polymerization become aliphatic or aromatic hydrocarbons as solvent and e.g. Alkyllithium used as an initiator. The rubbers are as such od. blended with oil or filled with blacks markets u. represent the most important synthetic rubbers. Special Advantages of the post-vulcanization of emulsion SBR Products are high resistance to dynamic fatigue and Aging and heat resistance. Against weather u. They must be ozone-influenced by antioxidants be stabilized. They are resistant to many non-polar organic Solvent, diluted acids u. Bases, but swell strongly in contact with fuels, oils od. Fats.

The washing or cleaning-active preparations are poured in the process according to the invention and solidify subsequently to a dimensionally stable body. In the context of the present invention, "solidification" characterizes any curing mechanism which delivers a solid, solid-state body from a deformable, preferably flowable mixture or substance or mass, without the need for pressing or compacting forces The purpose of the present invention is therefore, for example, the curing of melts of solid substances at room temperature by cooling. "Solidification processes" in the sense of the present application are also the curing of formable materials by time-delayed water binding, by evaporation of solvents, by chemical reaction, crystallization, etc., as well as the reactive hardening of flowable powder mixtures to form stable hollow bodies.

In summary are methods according to the invention preferred in which the cast body by delayed water binding, by cooling below the melting point, by evaporation of solvents, by crystallization, by chemical reaction (s), in particular polymerization, by change the rheological properties, for example by altered shear, by sintering or by radiation curing, in particular produced by UV, alpha-beta or gamma rays becomes.

in the For the purposes of the present application, preference is given to processes which the solidification of the cast body by cooling under the melting point. The cooling below the melting point can, for example, by heat to the environment, in particular to the mold done. Especially however, it is preferably the heat release by using a cooling medium to support. Consequently, such methods according to the invention are particularly preferred. where the mold cooled becomes. As a cooling medium For example, (dried) cold air, dry ice or liquid nitrogen. With particular preference, however, circulating in the mold, preferably liquid coolant used. The cooling of the mold is preferably carried out at temperatures below 20 ° C, preferably below 17 ° C, more preferably below 14 ° C, most preferably below 11 ° C and especially below 8 ° C. In In another preferred variant of the method, the cooling takes place Temperatures between 5 and 20 ° C, especially preferred at temperatures between 8 and 19 ° C, especially preferably at temperatures between 11 and 18 ° C and in particular at temperatures between 14 and 17 ° C.

The inventive method serves the production of casting bodies. It it was found that the breaking hardness the surface optics the by means of this casting process manufactured body thereby improving that the washing or cleaning active preparation after pouring and is vibrated before solidification. Another subject of the present Application is therefore an inventive method in which the washing or cleaning active substance mixture after the to water is vibrated in the mold.

As "vibration" or "vibration" is in the context of referred to in this application a time-periodic process, in which the mold is reciprocated within certain limits. The vibration can be both horizontal and vertical Direction. Preferred are methods in which horizontal and superimpose vertical vibrations. In preferred methods of the invention Accordingly, the vibration of the mold is done in horizontal and / or vertical spatial direction.

The Vibrational motion is characterized by its amplitude and frequency. The "amplitude" is the maximum Deflection of the mold referred to from the rest position. The amplitude the vibration movement is in a preferred embodiment the present invention in the horizontal direction less than 10 cm, preferably less than 7 cm, more preferably less than 4 cm and in particular less than 2 cm. In the vertical direction is the amplitude the vibration movement preferably less than 4 cm, especially preferably less than 2 cm and in particular less than 1 cm.

The Number of vibration movements per unit time determines the "frequency" of this vibration. Amplitude, frequency and duration of the vibratory motion are in the inventive method et al by the viscosity and composition (for example, the solids content) of the processed washing or cleaning active preparations determined. In the method according to the invention are preferably frequencies between 0.1 and 1000 Hz, preferably between 0.2 and 800 Hz, more preferably between 0.4 and 500 Hz and in particular between 0.8 and 300 Hz implemented.

In A preferred variant of the method according to the invention are amplitude and / or frequency of the vibration used infinitely adjustable. Through a stepless regulation of amplitude and / or frequency The vibration movement can easily meet the requirements the respective processed washing or cleaning active preparation customized become. The need for Such adjustments can occur, for example, in the case of recipe changes or changes in the process temperature (For example: temperature of the poured washing or cleaning activity Preparation; outside temperature in production). In the context of the present application For example, the amplitude and the frequency of the vibration used are preferable constant. However, it may also be advantageous, the amplitude and / or to change the frequency of the vibration. Process in which Changing the amplitude and / or frequency of the vibration are preferred according to the invention.

there For example, it is conceivable that at constant frequency, the amplitude of the vibration decreases or increases. It can but also performed procedures in which at constant amplitude the frequency of the vibration elevated or decreased. Process in which in the course of degassing at constant amplitude the frequency of the vibration is increased, are particularly preferred in the context of the present application.

• i) 10 bis 85 Gew.-% Dispersionsmittel und
• ii) 15 bis 90 Gew.-% dispergierte Stoffe

enthalten, besonders bevorzugt werden.For processing in the process according to the invention are generally all washing or cleaning active preparations that can be processed by casting techniques. In the process according to the invention, particular preference is given to using washing- or cleaning-active preparations in the form of dispersions. In a particularly preferred embodiment of the present application, the washing or cleaning-active preparation poured into the receiving recess of the molding tool is a dispersion of solid particles in a dispersion medium, dispersions based on their total weight

• i) from 10 to 85% by weight of dispersant and
• ii) 15 to 90% by weight of dispersed substances

contain, are particularly preferred.

When Dispersion in this application is a multi-phase system one of which is continuous (dispersing agent) and at least one more is finely dispersed (dispersed substances). Particularly preferred washing or cleaning active according to the invention Preparations are characterized in that they are the dispersant in amounts above 11 wt .-%, preferably above 13 wt .-%, particularly preferably above 15% by weight, most preferably above 17% by weight and in particular above 19 wt .-%, each based on the total weight the dispersion. Preference is furthermore given to using dispersions, which is a dispersion with a proportion by weight of dispersant above 20 wt .-%, preferably above 21 wt .-% and in particular above 22% by weight, in each case based on the total weight of the dispersion, exhibit. The maximum content of preferred dispersions of dispersant is, preferably less based on the total weight of the dispersion as 63% by weight, preferably less than 57% by weight, more preferably less than 52% by weight, most preferably less than 47% by weight and in particular less than 37 wt .-%. In the context of the present Invention are especially those washing or cleaning active Preparations based on their total weight, dispersing agent in amounts of from 12 to 62% by weight, preferably from 17 to 49% by weight and in particular from 23 to 38 wt .-%. Especially preferred are dispersions containing a dispersion medium between 16 and 30 wt .-%, preferably between 16 and 26 wt .-% and in particular between 16 and 22 wt .-%, each based on the total weight the dispersion.

The The dispersants used are preferably water-soluble or water-dispersible. The solubility this dispersant is at 25 ° C preferably more than 200 g / l, preferably more than 300 g / l, especially preferably more than 400 g / l, most preferably between 430 and 620 g / l and in particular between 470 and 580 g / l.

When Dispersants are suitable in the context of the present invention preferably the water-soluble or water-dispersible polymers, in particular the water-soluble or water-dispersible nonionic polymers. With the dispersant This can be both a single polymer and mixtures different water-soluble or water-dispersible polymers. In a further preferred embodiment In the present invention, the dispersing agent is at least 50 wt .-% of the polymer mixture of water-soluble or water-dispersible nonionic polymers from the group of polyvinylpyrrolidones, Vinylpyrrolidone / vinyl ester copolymers, cellulose ethers, polyvinyl alcohols, Polyalkylene glycols, in particular polyethylene glycol and / or polypropylene glycol.

Particular preference is given to using dispersions which contain, as dispersants, a nonionic polymer, preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol, the weight fraction of the poly (ethylene) glycol being based on the total weight of all dispersing agents is preferably between 10 and 90% by weight, more preferably between 30 and 80% by weight and in particular between 50 and 70% by weight. Particular preference is given to dispersions in which the dispersant contains more than 92% by weight, preferably more than 94% by weight, more preferably more than 96% by weight, very particularly preferably more than 98% by weight. and in particular to 100 wt .-% of a poly (alkylene) glycol, preferably poly (ethylene) glycol and / or poly (propylene) glycol, but in particular consists poly (ethylene) glycol. Dispersing agents which, in addition to poly (ethylene) glycol, also contain poly (propylene) glycol, preferably have a ratio of the weight proportions of poly (ethylene) glycol to Po ly (propylene) glycol between 40: 1 and 1: 2, preferably between 20: 1 and 1: 1, more preferably between 10: 1 and 1.5: 1 and in particular between 7: 1 and 2: 1.

Further preferred dispersants are the nonionic surfactants which both alone, but more preferably in combination with a nonionic polymer can be used. Detailed versions to the usable nonionic surfactants can be found in the frame the description of washing- or cleaning-active substances below.

Prefers used dispersions are characterized in that at least a dispersant has a melting point above 25 ° C, preferably above 35 ° C and especially above 40 ° C having. Particularly preferred is the use of dispersants with a melting point or melting range between 30 and 80 ° C, preferably between 35 and 75 ° C, more preferably between 40 and 70 ° C and in particular between 45 and 65 ° C, these dispersants being based on the total weight of the used dispersing agent, a weight fraction above 10 Wt .-%, preferably above 40 wt .-%, more preferably above 70 wt.% And in particular between 80 and 100 wt .-% have.

When dispersed substances are suitable in the context of the present application all washing or cleaning substances which are solid at room temperature, but especially washing or cleaning substances from the group of builders (Builder and Cobuilder), the washing or cleaning active polymers, bleach, bleach activators, glass corrosion inhibitors, the silver protection agent and / or the enzymes. A more detailed description these ingredients can be found below in the text.

Of the Water content of preferably in the process according to the invention used dispersions, based on their total weight, preferably less than 30% by weight, preferably less than 23% by weight, preferably less than 19% by weight, more preferably less than 15% by weight and especially less as 12% by weight. According to the invention preferred used Disperisonen are low in water or anhydrous. Especially preferably used dispersions are characterized that they, based on their total weight, a content of free water below 10 wt .-%, preferably below 7 wt .-%, more preferably below 3 wt .-% and in particular below 1 wt .-% have.

The dispersions used with preference as washing or cleaning active preparation are characterized by a high density. Particular preference is given to using dispersions having a density of above 1.040 g / cm ³ . Preferred processes according to the invention are characterized in that the washing and cleaning active preparation has a density above 1.040 g / cm ³ , preferably above 1.15 g / cm ³ , more preferably above 1.30 g / cm ³ and in particular above 1.40 g / cm ³ . This high density not only reduces the total volume of a molded body dosing unit but also improves its mechanical stability. Particularly preferred methods according to the invention are therefore characterized in that the dispersion has a density of 1050-1670 g / cm ^3, preferably 1.120 to 1.610 g / cm ^3, particularly preferably 1.210 to 1.570 g / cm ^3, most preferably between 1,290 and 1.510 g / cm ³ , and in particular between 1.340 and 1.480 g / cm ³ The information on the density in each case refer to the densities of the agent at 20 ° C. In order to avoid segregation during processing of these dispersions, particularly in the course of vibration of the dies, preferably dispersants and dispersed materials have densities less than 0.6 g / cm ³ , preferably less than 0.4 g / cm ³ and especially differing by less than 0.3 g / cm ³ .

According to the invention preferred Draw as dispersions used as washing or cleaning active preparation characterized by the fact that they in water (40 ° C) in less than 9 minutes, preferably less than 7 minutes in less than 6 minutes, more preferably in less than 5 minutes and in particular dissolve in less than 4 minutes. For determination of solubility 20 g of the dispersion in the interior of a dishwasher (Miele G 646 PLUS) introduced.

It becomes the main rinse a standard rinse program (45 ° C) started. The determination of solubility takes place by the measurement of the conductivity, which via a conductivity sensor is recorded. The dissolution process is when the maximum conductivity is reached completed. In the Leittähigkeitsdiagramm corresponds this maximum a plateau. The conductivity measurement starts with the insertion of the circulation pump in the main rinse. The amount of water used is 5 liters.

By means of the method according to the invention, both compact casting bodies and cast hollow molds can be produced. Leaving a potted washing or cleaning active preparation in the cavity solidify the mold, so simple, compact body are made. However, more advantageous and preferred within the scope of the present application are those processes in which the first washing- or cleaning-active preparation is brought into shape before demolding. In the context of the present application, methods for producing cast hollow bodies are particularly preferred.

• a) Gießen einer wasch- oder reinigungsaktiven Zubereitung in ein Formwerkzeug;
• b) In Form bringen der wasch- oder reinigungsaktiven Zubereitung;
• c) Entformen des gegossenen Körpers aus dem Formwerkzeug,

dadurch gekennzeichnet, daß das Formwerkzeug wenigstens anteilsweise aus elastischem Material gefertigt ist.A preferred subject of the present application is therefore a process for producing a cast hollow body from a washing or cleaning active preparation, comprising the steps:

• a) pouring a washing or cleaning active preparation into a mold;
• b) shaping the washing or cleaning active preparation;
• c) demolding the cast body from the mold,

characterized in that the molding tool is at least partially made of elastic material.

The Production of the poured hollow body in step a) of this preferred process variant can with different Techniques are done. In the simplest case, a flowable mixture filled into a suitable mold, allowed to harden there and subsequently removed from the mold. The disadvantage here is the design of the form because the desired wall thickness the resulting hollow body a quick filling do not allow complicated geometries.

alternative For example, the solidifying mixture can be filled into a mold that is merely intended as a cavity is trained. Would If you let the mixture solidify there, you would get a compact Body, no mold. By appropriate process management can be guaranteed be that the Mixture first solidified on the wall of the mold. Do you turn the Form after a certain time t um, so the excess mixture flows off and leaves a Lining of the form, which itself represents a mold, the after complete Freezing can be demoulded. As already mentioned, but the filling can also take place before demolding; also a filling during the solidification process is possible.

• a) Gießen einer wasch- oder reinigungsaktiven Zubereitung in die Kavität eines Formwerkzeugs;
• b) Wenden der Kavität und ausgießen der überschüssigen Zubereitung;
• c) Entformen des gegossenen Körpers aus dem Formwerkzeug,

dadurch gekennzeichnet, daß das Formwerkzeug wenigstens anteilsweise aus elastischem Material gefertigt ist.A further preferred subject matter of the present application is therefore a process for producing a cast hollow body from a washing or cleaning-active preparation, comprising the steps:

• a) pouring a washing or cleaning active preparation in the cavity of a mold;
• b) turning the cavity and pouring out the excess preparation;
• c) demolding the cast body from the mold,

characterized in that the molding tool is at least partially made of elastic material.

In dependence From the solidification mechanism, the turning of the mold takes place preferably after a time t between 0 and 20 minutes, preferably after a time t between 1 and 17 minutes, especially preferred after a time of between 2 and 14 minutes, most preferably between 3 and 11 minutes and especially between 4 and 8 minutes.

alternative to the full fill the cavity and pouring off excess mixture can the cavity only partially filled become. The mixture is in these cases with a matching stamp to the wall of the cavity pressed where they go to the hollow body stiffens. This variant of the method is quasi an intermediate form between the "casting technique" and the casting technique in negative forms of the hollow body represents.

• a) Gießen einer wasch- oder reinigungsaktiven Zubereitung in die Kavität eines Formwerkzeugs;
• b) Verdrängen der wasch- oder reinigungsaktiven Zubereitung mittels eines Stempels;
• c) Entformen des gegossenen Körpers aus dem Formwerkzeug,

dadurch gekennzeichnet, daß das Formwerkzeug wenigstens anteilsweise aus elastischem Material gefertigt ist, sind im Rahmen der vorliegenden Anmeldung besonders bevorzugt.Corresponding methods for producing a cast hollow body from a washing or cleaning-active preparation, comprising the steps:

• a) pouring a washing or cleaning active preparation in the cavity of a mold;
• b) displacing the washing or cleaning active preparation by means of a punch;
• c) demolding the cast body from the mold,

characterized in that the mold is at least partially made of elastic material, are particularly preferred in the context of the present application.

Particularly advantageous in this process procedure, which is also referred to as "cold stamp method", is the ability to produce even large quantities with a precisely defined wall thickness of the hollow body.In addition, the method is largely insensitive to fluctuating flow properties and in higher viscosity mixtures applicable. In a preferred embodiment of this preferred process variant, a cooled stamp is used. The temperature of this cooled stamp is preferably between 5 and 20 ° C, more preferably between 8 and 19 ° C, most preferably between 11 and 18 ° C and especially between 14 and 17 ° C.

The The methods described above are particularly suitable for hollow body produce, which have a shape without undercuts, that is, the shape of a "shell," i.e., an opening surface, which the largest horizontal Cross sectional area equivalent. These "bowls" can be filled and optionally closed.

Regarding The shape of the shells are the expert in the selection no limits set. From the hemisphere over angular ("carton-like") cups all the way up to complicated structures with pronounced surface structure (e.g. of nutshells or animal forms) are all hollow body produced.

While or after solidification, in a preferred process variant according to the invention by turning or displacing produced hollow bodies the hanging out of the mold Noses or edges solidified washing or cleaning active preparation by knife. cut or scraped and / or removed with a roller. In a particularly preferred embodiment of the method according to the invention be used for cutting or scraper or rolling heated knife or Scrapers or rollers used. The temperature of this heated Knife, scraper or rollers amounts preferably at least 35 ° C, preferably at least 45 ° C and in particular between 50 and 90 ° C.

• a) Gießen einer wasch- oder reinigungsaktiven Zubereitung in eine schließbare Doppelform;
• b) Bewegen der Doppelform während einer Zeit t zwischen 0 und 20 Minuten;
• c) Entformen des gegossenen Körpers aus dem Formwerkzeug,

dadurch gekennzeichnet, daß das Formwerkzeug wenigstens anteilsweise aus elastischem Material gefertigt ist, sind im Rahmen der vorliegenden Anmeldung besonders bevorzugt.However, according to the invention it is also possible to produce hollow bodies which have only a small opening and to fill the resulting hollow mold later through this small "bunghole." Corresponding processes are usually carried out industrially with closable double molds which have a wall lining of the desired thickness In this case, all shapes are possible, from the ball over egg shapes to complex hollow structures such as animal shapes, company logos, etc. A further preferred embodiment of the present invention therefore provides a method for producing a cast Hollow body of a washing or cleaning active preparation, comprising the steps:

• a) pouring a washing or cleaning active preparation in a closable double mold;
• b) moving the double-shape during a time t between 0 and 20 minutes;
• c) demolding the cast body from the mold,

characterized in that the mold is at least partially made of elastic material, are particularly preferred in the context of the present application.

The according to the inventive method produced molded hollow body can during the or following the preparation filled with detergent or cleaning agent. in this connection can all ready prefabricated washing or cleaning agent in liquid, pasty, gelatinous, powdery, extruded, granulated, pelleted, scaly or tableted Form are introduced into the mold. It is not required to fill a finished washing or cleaning agent, rather can also individual washing or cleaning agent ingredients or precursors of it in the hollow body filled become.

in the Within the scope of the present applications, such processes are particular preferred in which the cast hollow body with at least one other washing or cleaning active preparation is filled.

To the filling becomes the hollow body preferably sealed or closed. Suitable for sealing There are a number of different approaches that can be found in dependence of the desired look of the process product or its intended use differ can. The preferred methods of sealing described below the molded hollow body are with any of the manufacturing methods disclosed above for such hollow body combined.

In a first preferred variant of the method for sealing filled, cast hollow bodies, the filled, cast hollow body is closed with a water-soluble or water-dispersible polymer. The sealing of the hollow body by means of a water-soluble or water-dispersible polymer can be carried out, for example, by spraying the filled hollow body with a liquid polymer preparation. However, preferred are sealing methods in which the hollow body is sealed with a film of water-soluble or water-dispersible material. As film materials are there in particular (optionally acetalated) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof, in particular methylcellulose, and mixtures thereof.

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs

enthalten."Polyvinyl alcohols" (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure

in small proportions (about 2%) also structural units of the type

contain.

Commercially available polyvinyl alcohols, the as white-yellowish Powders or granules with degrees of polymerization in the range of approx. 100 to 2500 (molecular weights of about 4000 to 100,000 g / mol) offered have degrees of hydrolysis of 98-99 or 87-89 mol%, so they still contain a residual content of acetyl groups. The polyvinyl alcohols are characterized from the manufacturer by specifying the degree of polymerization the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

polyvinyl alcohols are dependent soluble in the degree of hydrolysis in water and a few highly polar organic solvents (Formamide, dimethylformamide, dimethyl sulfoxide); of (chlorinated) Hydrocarbons, esters, fats and oils are not attacked. Polyvinyl alcohols are classified as toxicologically harmless and are at least partially biodegradable biologically. The water solubility can be by post-treatment with aldehydes (acetalization), by Complexation with Ni or Cu salts or by treatment with dichromates, boric acid od. Borax decrease. The coatings are made of polyvinyl alcohol largely impenetrable for Gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, however allow water vapor to pass through.

in the Within the scope of the present invention it is preferred that the in the Verafahren invention used wrapping material at least partially comprises a polyvinyl alcohol whose Degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, especially preferably 81 to 89 mole and especially 82 to 88 mol%. In a preferred embodiment this is the case in the process according to the invention used first wrapping material at least 20% by weight, more preferably at least 40% by weight, entirely particularly preferably at least 60% by weight and in particular at least 80 Wt .-% of a polyvinyl alcohol whose degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, more preferably 81 to 89 mol% and in particular 82 to 88 mol%.

Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the containers, it being preferred according to the invention that the coating material comprises a polyvinyl alcohol whose molecular weight is in the range of 10,000 to 100,000 gmol ^-1 , preferably 11,000 to 90,000 gmol ^-1 , particularly preferably 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 .

Of the Degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680 and especially between about 260 to about 1500th

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® particularly suitable in the context of the present invention, polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88, Mowiol ^® 8-88 and L648 , L734, Mowiflex LPTC 221 ex KSE and the compounds of Texas Polymers such as Vinex 2034.

Further polyvinyl alcohols which are particularly suitable as shell material are shown in the following table:

Other suitable polyvinyl alcohols are as shell material ^® ELVANOL 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX 72.5 ^®, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ^® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK).

Examples of suitable water PVAL films are those available under the name "SOLUBLON® ^®" from Syntana Handelsgesellschaft E. Harke GmbH & Co. PVAL films. Their solubility in water can be adjusted to the exact degree, and films of this product series are available which are soluble in aqueous phase in all temperature ranges relevant for the application.

Polyvinylpyrrolidones, referred to as PVP for short, can be described by the following general formula:

PVP are prepared by radical polymerization of 1-vinylpyrrolidone. commercial PVP have molecular weights in the range of about 2,500 to 750,000 g / mol and be as white, hygroscopic powders or offered as aqueous solutions.

Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula H- [O-CH ₂ -CH ₂ ] _n -OH the technically by alkaline-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems are prepared with ethylene glycol as the starting molecule. They have molar masses in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.

gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), mainly by Hydrolysis of the collagen contained in the skin and bones of animals obtained under acidic or alkaline conditions. The amino acid composition The gelatin largely corresponds to that of the collagen from which they are made and varies depending on its provenance. The use of gelatin as the water-soluble coating material is in particular in pharmacy in the form of hard or soft gelatin capsules extremely far common. In the form of slides, gelatin is because of their compared to the above-mentioned polymers of high price only small Use.

Starch is a homoglycan, wherein the glucose units are linked α-glycosidically. Starch is composed of two components of different molecular weight: from about 20 to 30% straight chain amylose (MW about 50,000 to 150,000) and 70 to 80% branched chain amylopectin (MW about 300,000 to 2,000,000). In addition, small amounts of lipids, phosphoric acid and cations are still included. While the amylose forms long, helical, entangled chains with about 300 to 1,200 glucose molecules as a result of the binding in the 1,4-position, the chain branched in amylopectin after an average of 25 glucose building blocks by 1,6-bonding to a branch-like structure with about 1,500 to 12,000 molecules of gluco In addition to pure starch, starch-derivatives which are obtainable from starch by polymer-analogous reactions are also suitable for the preparation of water-soluble coatings of the detergent, detergent and cleaner portions in the context of the present invention. Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino starches.

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

In a second preferred method variant for sealing filled, cast Hollow body, will the filled, cast hollow bodies with a washing or cleaning substance or a washing or cleaning agent closed cleaning substance mixture.

The washing or cleaning-active substance used for the sealing is, for example, another castable washing or cleaning substance, for example one of the dispersions described above. However, active substance-containing preparations based on water-soluble or water-dispersible polymers can also be used as washing or cleaning-active substance mixture for sealing the filled hollow body. Particularly preferred is the seal by pouring a sugar, preferably a saccharide from the group glucose, fructose, ribose, maltose, lactose, sucrose, maltodextrin and Isomalt ^® .

In a third preferred method variant for sealing filled, cast Hollow body will the filled, cast hollow bodies closed with a pre-made pouch.

The prefabricated pouches used in this process variant can by any technical method known to the person skilled in the art, in particular by thermoforming or vacuum forming but also by vertical or horizontal tubular bag method be made. The attachment the pouch on the hollow body is preferably done by gluing or welding. Of the Pouch preferably has water-soluble or water-dispersible shell materials, preferably in film form, on. For a detailed description of these wrapping materials is given on above directed. The prefabricated pouch can be used unfilled for sealing become. Preferably, however, it is the pouch with one or more to fill washing or cleaning substances.

The inventive method is used to produce molded bodies from washing or cleaning active Preparations. The cast bodies can For example, have the form of hollow bodies, which in turn with washing or cleaning-active substances or substance mixtures filled become. In the context of the present application, all of them may be familiar to the person skilled in the art known washing or cleaning-active substances for the production of the casting and / or for filling a molded hollow body be used. With particular preference includes the potted wash or cleaning-active preparation and / or the filling of the hollow body used washing or cleaning substance / substance mixture at least one substance from the group of builders, surfactants, polymers, Bleaching agents, bleach activators, enzymes, dyes, fragrances, Electrolytes, pH adjusters, perfume carriers, fluorescers, hydrotopes, Foam inhibitors, silicone oils, Anti redeposition agents, optical brighteners, grayness inhibitors, Inlet preventer, anti-crease agents, color transfer inhibitors, antimicrobial Active ingredients, germicides, fungicides, antioxidants, corrosion inhibitors, Antistatic agents, ironing aids, Phobic and impregnating agents, Swelling and slip-resistant, plasticizers and / or UV absorbers included. These substances will be described in more detail below.

builders

To the builders counting in the context of the present application, in particular the zeolites, Silicates, carbonates, organic cobuilders and -where no ecological Prejudices against their use exist - also the phosphates.

Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

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

in the Within the scope of the present invention it is preferred that these Silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous alkali disilicates, in detergents or cleaners in amounts of from 10 to 60% by weight, preferably from 15 to 50% by weight and in particular from 20 to 40 wt .-%, each based on the weight of the washing or cleaning agent are included.

If the silicates are used as constituents of automatic dishwasher detergents, these compositions preferably contain at least one crystalline layered silicate of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22 , preferably from 1.9 to 4, and y is a number from 0 to 33. The crystalline layer-form silicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS, eg Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ · XH ₂ O, kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ · xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ · xH ₂ O) or Na-SKS 4 (Na ₂ Si ₄ O ₉ .xH ₂ O, Makatite).

Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula (I) in which x is 2. Of these, especially Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3H ₂ O, kanemite), Na-SKS-11 (t-Na ₂ Si ₂ O ₅₎ and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ).

If the silicates are used as a constituent of automatic dishwasher detergents, these compositions in the context of the present application contain a proportion _by weight of the crystalline layered silicate of the formula NaMSi _x O _{2x + 1} .yH ₂ O from 0.1 to 20% by weight, preferably from 0.2 to 15 wt .-% and in particular from 0.4 to 10 wt .-%, each based on the total weight of these agents. It is particularly preferred in particular if such automatic dishwashing agents have a total silicate content of less than 7% by weight, preferably less than 6% by weight, preferably less than 5% by weight, more preferably less than 4% by weight, most preferably less than 3% by weight % and in particular below 2.5 wt .-%, wherein it is in this silicate, based on the total weight of the silicate contained, preferably at least 70 wt .-%, preferably at least 80 wt .-% and in particular to At least 90 wt .-% is silicate of the general formula NaMSi _x O _{2x + 1} · y H ₂ O.

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 in the context of the present invention is preferably used, for example, a co-crystallizate of zeolite X and zeolite A (about 80 wt .-% zeolite X), which is sold by the company CONDEA Augusta SpA under the trade name VEGOBOND AX ^® and by the formula nNa ₂ O • (1-n) K ₂ O • Al ₂ O ₃ • (2 - 2.5) SiO ₂ • (3.5-5.5) H ₂ O can be described. The zeolite can be used both as a builder in a granular compound, as well as to a kind of "powdering" of the entire mixture to be pressed, wherein usually both ways for incorporating the zeolite are used in the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course it is also a use of the well-known phosphates as builders possible, if such use is not avoided for environmental reasons should be. This applies in particular to the use of agents according to the invention as automatic dishwashing detergent, which is particularly preferred in the context of the present application is. Among the large number of commercially available phosphates, the Alkali metal phosphates with particular preference for pentasodium or pentakalium triphosphate (sodium or potassium tripolyphosphate) in the wash and Detergent industry the biggest importance.

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

Suitable phosphates are, for example, the sodium dihydrogen phosphate, NaH ₂ PO ₄ , in the form of the dihydrate (density 1.91 gcm ^-3 , melting point 60 °) or in the form of the monohydrate (density 2.04 gcm ^-3 ), the disodium hydrogen phosphate (secondary sodium phosphate) , Na ₂ HPO ₄ , which is anhydrous or with 2 moles (density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water (density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) can be used, in particular however the Trisatriumphosphat (tertiary sodium phosphate) Na ₃ PO ₄ , which as Dodecahydrat, as Decahydrat (according to 19 -20% P ₂ O ₅ ) and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) can be used.

Another preferred phosphate is the tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ . Further preferred are the tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , which in anhydrous form (density 2.534 gcm, melting point 988 °, also 880 ° indicated) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° under Water loss), as well as the corresponding potassium salt potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₄ .

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

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. The corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is marketed, 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 washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are exact according to the invention such as sodium tripolyphosphate, potassium tripolyphosphate or mixtures can be used from these two; 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 used according to the invention.

Become in the context of the present application phosphates as washing or cleaning active Substances used in detergents or cleaners, so included preferred means these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 5 to 80 wt .-%, preferably from 15 to 75% by weight, in particular, from 20 to 70% by weight, respectively based on the weight of the washing or cleaning agent.

Prefers it is in particular potassium tripolyphosphate and sodium tripolyphosphate in a weight ratio of more than 1: 1, preferably more than 2: 1, preferably more than 5: 1, more preferably more than 10: 1 and in particular more than 20: 1 einsezten. Particularly preferred is exclusively potassium tripolyphosphate to use without admixtures of other phosphates.

Further builders are the alkali carriers. As alkali carrier For example, alkali metal hydroxides, alkali metal carbonates, Alkali metal bicarbonates, alkali metal sesquicarbonates, the mentioned alkali metal silicates, alkali metal silicates, and mixtures of aforementioned substances, wherein for the purposes of this invention preferably the Alkali carbonates, especially sodium carbonate, sodium bicarbonate or sodium sesquicarbonate. Especially preferred is a builder system containing a mixture of tripolyphosphate and Sodium. Also particularly preferred is a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate. Because of their compared with other builders low chemical compatibility with the rest Ingredients of detergents or cleaning agents, the alkali metal hydroxides preferably only in small amounts, preferably in amounts below 10 % By weight, preferably below 6% by weight, more preferably below 4 wt .-% and in particular below 2 wt .-%, each based on the total weight of the detergent or cleansing agent used. Particularly preferred are agents which, based on their total weight less than 0.5 wt .-% and in particular no alkali metal hydroxides contain.

Especially preference is given to the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of from 2 to 50% by weight, preferably from 5 to 40% by weight and in particular from 7.5 to 30 wt .-%, each based on the Weight of washing or cleaning agent. Particularly preferred Means, based on the weight of the detergent or cleaning agent (ie the total weight of the combination product without packaging) less than 20% by weight, preferably less than 17% by weight, is preferred less than 13% by weight and in particular less than 9% by weight of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonates, especially preferably contain sodium carbonate.

When Organic co-builders are in particular polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) as well as phosphonates. These classes of substances are hereafter described.

useful organic builders For example, they can be used in the form of their sodium salts polycarboxylic where among polycarboxylic acids such carboxylic acids be understood that carry more than one acid function. For example these are citric acid, adipic acid, Succinic acid, Glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such an application for ecological reasons not is objectionable, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids like citric acid, adipic acid, Succinic acid, glutaric, Tartaric acid, sugar acids and mixtures of these.

Also the acids in itself can be used. The acids In addition to their builder effect, they also typically have the property an acidifying component and thus serve to set a lower and milder one pH value of detergents or cleaning agents. In particular, here are citric acid, Succinic acid, glutaric, adipic acid, gluconic and to name any mixtures of these.

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

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

suitable Polymers are in particular polyacrylates, which preferably have a molecular mass of 2000 to 20,000 g / mol. Because of their superior solubility can from this group again the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and more preferably from 3000 to 5000 g / mol, may be preferred.

Suitable are furthermore copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and the acrylic acid or methacrylic acid with maleic acid. Particularly suitable are copolymers of acrylic acid with maleic which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid. Your molecular weight, based on free acids, is in general from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

to Improvement of water solubility can the polymers also include allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as Contain monomer.

Especially Biodegradable polymers of more than two are also preferred various monomer units, for example, those as monomers Salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers Salts of acrylic acid and 2-alkylallyl sulfonic acid and sugar derivatives.

Further preferred copolymers are those which are preferably used as monomers Acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

As well are as further preferred builders polymeric aminodicarboxylic acids whose Salts or their precursors to call. Particular preference is given to polyaspartic acids or their salts and.

Further Suitable builders are polyacetals, which by reaction of dialdehydes with polyol carboxylic acids containing 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained. preferred Polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic receive.

Further suitable organic builders are dextrins, for example Oligomers or polymers of carbohydrates by partial Hydrolysis of starches can be obtained. The hydrolysis can be carried out according to usual, for example acidic or enzyme-catalyzed processes. Preferably These are hydrolysis products with average molecular weights in the range from 400 to 500,000 g / mol. It is a polysaccharide with a Dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 preferred where DE is a common one Measure of the reducing Effect of a polysaccharide compared to dextrose, which DE of 100 is. Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrup with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher Molar masses in the range of 2000 to 30,000 g / mol.

at the oxidized derivatives of such dextrins are their reaction products with oxidants, which are able are at least one alcohol function of the saccharide ring to the carboxylic acid function to oxidize.

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

Further useful organic cobuilders are, for example, acetylated hydroxy or their salts, which may also be present in lactone form can and which at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups contain.

A another substance class with cobuilder properties are the phosphonates These are in particular hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a co-builder. It is preferably used as the sodium salt, wherein the disodium salt neutral and the tetrasodium salt is alkaline (pH 9). As aminoalkanephosphonates preferably ethylenediamine tetramethylenephosphonate (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reacting Sodium salts, e.g. B. as hexasodium salt of EDTMP or hepta- and octa-sodium salt the DTPMP. As a builder it is from the class of Phosphonates preferably used HEDP. The aminoalkane phosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it may, especially if the means also bleach be preferred, Aminoalkanphosphonate, in particular DTPMP, to use or mixtures of the phosphonates mentioned.

Furthermore can all compounds that are capable of complexes with alkaline earth ions train as builders be used.

surfactants

to Group of surfactants will continue next to the nonionic surfactants the anionic, cationic and amphoteric surfactants counted.

As nonionic surfactants are preferably used alkoxylated, preferably ethoxylated, especially 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 is linear or preferably methyl-branched in the 2-position may contain or linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

A another class of preferred nonionic surfactants, the either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.

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 alkanolamide can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half from that.

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

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

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

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having from 1 to 8 carbon atoms, with C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.

[Z] is preferably by reductive amination of a reduced sugar obtained, for example, glucose, fructose, maltose, lactose, galactose, Mannose or xylose. The N-alkoxy or N-aryloxy-substituted. links can by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxyfatty acid amides are transferred.

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, the machine dishwashing detergents according to the invention contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Especially preferred are nonionic surfactants which have a melting point above Have room temperature, wherein nonionic surfactants with a Melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, are particularly preferred.

suitable nonionic surfactants, the melting or softening points in said Temperature range, for example, low-foaming nonionic Surfactants which may be solid or highly viscous at room temperature. Become used at room temperature highly viscous nonionic surfactants, it is preferred that these a viscosity above 20 Pas, preferably above 35 Pas and especially above 40 Pas. Also nonionic surfactants which are waxy at room temperature Consistency are preferred.

Prefers as at room temperature fixed to be used nonionic surfactants derived the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary Alcohols and mixtures of these surfactants with structurally complicated built-up surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants stand out beyond that by good foam control.

In a preferred embodiment The present invention is the nonionic surfactant having a Melting point above room temperature an ethoxylated nonionic surfactant, that from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 moles, in particular at least 20 moles of ethylene oxide per Mol alcohol or alkylphenol emerged.

A particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Accordingly, particular preference is given to ethoxylated nonionic surfactants which are obtained from C _6-20 monohydroxyalkanols or C _6-20 -alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol of alcohol were.

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25% by weight, especially preferably up to 20 wt .-% and in particular up to 15 wt .-% of total molecular weight of the nonionic surfactant. Especially preferred nonionic surfactants are ethoxylated monohydroxyalkanols or Alkylphenols, in addition Having polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules makes preferably more than 30% by weight, more preferably more than 50 wt .-% and in particular more than 70 wt .-% of the total molecular weight such nonionic surfactants. Preferred dishwashing detergents are characterized that she contain ethoxylated and propoxylated nonionic surfactants in which the Propylene oxide units in the molecule up to 25% by weight, preferably up to 20% by weight and in particular to constitute 15% by weight of the total molecular weight of the nonionic surfactant, contain.

Further particularly preferred nonionic surfactants with melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-18 from Olin Chemicals.

In detergents or cleaners, preferably in dishwashing detergents, the nonionic surfactants of the formula (II) R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ], (II) in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15, used.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} N or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula may be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms particularly before are awarded. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = N) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is to R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

Summarizing the latter statements, the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O) _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, preference being given to surfactants of the type R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6–24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃; -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.As particularly preferred nonionic surfactants, low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have been found in the context of the present application. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Machine dishwashing agents according to the invention which contain surfactants of the general formula III as nonionic surfactants are preferred here

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently of one another are integers from 1 to 6.

The preferred nonionic surfactants of formula III can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in formula III above may vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually undisplayed, wherein the linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, automatic dishwasher detergents according to the invention are preferred in which R ¹ in formula III is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or CH (CH ₃ ) ₂ are suitable. Preferred automatic dishwasher detergents are characterized in that R ¹ or R ^{3 is} a radical -CH ₃ , w and x independently represent values of 3 or 4, and y and z independently represent values of 1 or 2.

In summary, particularly preferred are nonionic surfactants having a C _9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula (IV) R ¹ O [CH ₂ CH (R ³ ) O] _x R ² (IV) in which R ^{1 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{2 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably between 1 and have 5 hydroxy groups and are preferably further functionalized with an ether group, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2- Butyl radical, x for values between 1 and 40.

In particularly preferred nonionic surfactants of the above formula (IV), R ^{3 is} H. In the resulting end-capped poly (oxyalkylated) nonionic surfactants of the formula (V) R ¹ O [CH ₂ CH ₂ O] _x R ² (V) In particular those nonionic surfactants are preferred in which R ^{1 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, R ^{2 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxyl groups and x stands for values between 1 and 40.

In particular, those end-capped poly (oxyalkylated) nonionic surfactants are preferred, which according to the formula (VI) R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² (VI) in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical with 1 have up to 30 carbon atoms R ² , which is a monohydroxylated intermediate group -CH ₂ CH (OH) - adjacent. In this formula, x stands for values between 1 and 40. Such end-capped poly (oxyalkylated) nonionic surfactants can be prepared, for example, by reacting a terminal epoxide of the formula R ² CH (O) CH ₂ with an ethoxylated alcohol of the formula R ¹ O [CH ₂ CH ₂ O] _x-1 CH ₂ CH ₂ OH.

The specified C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned Nonionic surfactants represent statistical averages that are suitable for a specific Product can be a whole or a fractional number. by virtue of the manufacturing process consist of commercial products of the formulas mentioned mostly not from an individual representative, but from mixtures, which is responsible for both the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation averages and resulting in fractional numbers.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-8 -monoolefins having terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example, the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or Tallow fatty acids suitable.

Further Suitable anionic surfactants are sulfated fatty acid glycerol esters. Among fatty acid glycerol esters are to understand the mono-, di- and triesters and their mixtures, such as they are produced by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained. Preferred sulfated fatty acid glycerol esters are included the sulphonated products of saturated fatty acids with 6 to 22 carbon atoms, for example the caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or Behenic acid.

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

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

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

When other anionic surfactants are especially soaps into consideration. Suitable are saturated fatty acid soaps, like the salts of lauric acid, myristic, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow derived soap mixtures.

The including anionic surfactants the soaps can in the form of their sodium, potassium or ammonium salts and as soluble salts 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.

are the anionic surfactants component of automatic dishwashing detergents, so is their content, based on the total weight of the funds preferably less than 4% by weight, preferably less than 2% by weight and most especially preferably less than 1% by weight. Automatic dishwashing detergents, which do not contain anionic surfactants are particularly preferred.

At Place of said surfactants or in conjunction with them may also cationic and / or amphoteric surfactants are used.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1–6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8–28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_nT-R²; R⁴ = R¹ oder R² oder (CH₂)_n T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.As cationic active substances, it is possible, for example, to use cationic compounds of the formulas VII, VIII or IX:

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

In automatic dishwashing detergent, is the content of cationic and / or amphoteric surfactants preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. Automatic dishwashing detergents, which contain no cationic or amphoteric surfactants particularly preferred.

polymers

to Group of polymers count in particular the washing or cleaning Poylmere, for example the rinse aid polymers and / or as softening effective polymers. Generally in detergents or cleansers in addition to nonionic polymers also cationic, anionic and can be used amphoteric polymers.

When softeners effective polymers are, for example, the sulfonic acid-containing Polymers which are used with particular preference.

Especially preferably as Suldonsäuregruppen-containing Polymers can be used are copolymers of unsaturated carboxylic acids containing sulfonic acid groups Monomers and optionally further ionic or nonionic Monomers.

In the context of the present invention, unsaturated carboxylic acids of the formula X are preferred as the monomer, R ¹ (R ² ) C = C (R ³ ) COOH (X), in the R ¹ to R ³ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radicals having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or -COOH or -COOR ⁴ wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the formula X are in particular acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H, R ³ = CH ₃ ) and / or maleic acid (R ¹ = COOH; R ² = R ³ = H) is preferred.

In the sulfonic acid group-containing monomers, those of the formula XI are preferred, R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XI), in the R ⁵ to R ⁷ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -O-OH or -COOH-substituted alkyl or alkenyl radicals as defined above or -COOH or -COOR ⁴ , where R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group, which is selected from - (CH ₂ ) _n with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas XIa, XIb and / or XIc, H ₂ C = CH-X-SO ₃ H (XIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (XIb), HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XIc), in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n ; with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₂ CH ₃ ) in formula XIa), 2-acrylamido-2-propanesulfonic acid (X = -C ( O) NH-C (CH ₃ ) ₂ in formula XIa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula XIa), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CN ₃ ) CH ₂ - in formula XIb), 3-methacrylamido-2-hydroxypropanesulfonic acid (X = -C (O) NH-CH ₂ CH (OH) CH ₂ - in formula XIb), allylsulfonic acid (X = CH ₂ in formula XIIa), methallylsulfonic acid (X = CH ₂ in formula XIb), allyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula XIa), methallyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula XIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid (X = CH ₂ in formula XIb), styrenesulfonic acid (X = C ₆ H ₄ in formula XIa), vinylsulfonic acid (X not present in formula XIa), 3-sulfopropyl acrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in Formula XIa), 3-Su isopropyl methacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula XIb), sulfomethacrylamide (X = -C (O) NH- in formula XIb), sulfomethylmethacrylamide (X = -C (O) NH-) CH ₂ - in formula XIb) and water-soluble salts of said acids.

When other ionic or nonionic monomers are used in particular ethylenically unsaturated compounds into consideration. Preferably the content of the invention used Polymers to monomers of group iii) less than 20 wt .-%, based on the polymer. Particularly preferred polymers to use only from monomers of groups i) and ii).

• i) ungesättigten Carbonsäuren der Formel X. R¹(R²)C=C(R³)COOH (X),in der R¹ bis R³ unabhängig voneinander für -H -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,
• ii) Sulfonsäuregruppen-haltigen Monomeren der Formel XI R⁵(R⁶)C=C(R¹)-X-SO₃H (XI), in der R⁵ bis R⁷ unabhängig voneinander für -H -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R4 ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und – C(O)-NH-CH(CH₂CH₃)
• iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren besonders bevorzugt.

In summary, copolymers are made of

• i) unsaturated carboxylic acids of the formula X. R ¹ (R ² ) C = C (R ³ ) COOH (X), in the R ¹ to R ³ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or un saturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
• ii) sulfonic acid group-containing monomers of the formula XI R ⁵ (R ⁶ ) C = C (R ¹ ) -X-SO ₃ H (XI), in the R ⁵ to R ⁷ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -O-OH or -COOH-substituted alkyl or alkenyl radicals as defined above or -COOH or -COOR ⁴ , where R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group, which is selected from - (CH ₂ ) _n with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ )
• iii) optionally further ionic or nonionic monomers particularly preferred.

• i) einer oder mehrerer ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln XIa, XIb und/oder XIc: H₂C=CH-X-SO₃H (XIa), H₂C=C(CH₃)-X-SO₃H (XIb), HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H (XIc),in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂) mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)
• iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren.

Further particularly preferred copolymers consist of

• i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid
• ii) one or more sulfonic acid group-containing monomers of the formulas XIa, XIb and / or XIc: H ₂ C = CH-X-SO ₃ H (XIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (XIb), HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XIc), in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C ( O) -NH-CH (CH ₂ CH ₃ )
• iii) optionally further ionic or nonionic monomers.

The Copolymers can the monomers from groups i) and ii) and optionally iii) contained in varying amounts, all representatives from the group i) with all Representatives from group ii) and all representatives from the group Group iii) can be combined. Particularly preferred polymers have certain structural units on, which are described below.

Thus, for example, copolymers are preferred, the structural units of the formula XII - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XII), in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) where n = 0 to 4, -O- (C ₆ H ₄ ) -, -NH-C (CN ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , are preferred.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. When the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise preferred. The corresponding copolymers contain the structural units of the formula XIII - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XIII) wherein m and p are each an integer between 1 and 2,000, and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals containing from 1 to 24 carbon atoms, wherein: Y is -O - (CH ₂ ) _n where n = 0 to 4, -O- (C ₆ H ₄ ) -, -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) -, are preferred.

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, copolymers which are structural units of the formula XIV - (CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XIV), in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, as preferred as copolymers, the structural units of the formula XV - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H) _p - (XV), wherein m and p are each an integer between 1 and 2,000, and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals containing from 1 to 24 carbon atoms, wherein: Y is -O - (CH ₂ ) _n - where n = 0 to 4, -O- (C ₆ H ₄ ) -, -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - ,

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred copolymers, the structural units of the formula XVI - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XVI), in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms; where spacer groups in which Y is -O- (CH ₂ ) _n - where n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH- CH (CH ₂ CH ₃ ) -, are preferred and to inventively preferred copolymers, the structural units of the formula XVII - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (XVII), in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands.

In summary, such copolymers are preferred according to the invention, the structural units of the formulas XII and / or XIII and / or XIV and / or XV and / or XVI and / or XVII - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XII), - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XIII) - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XIV), - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XV), - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XVI), - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (XVII), in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands.

In the polymers can the sulfonic acid groups wholly or partly in neutralized form, i. that the acidic Hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups against metal ions, preferably alkali metal ions and in particular against sodium ions, can be replaced. The use of or fully neutralized sulfonic acid group-containing Copolymer is preferred according to the invention.

The Monomer distribution of the copolymers preferably used according to the invention is for copolymers containing only monomers from groups i) and ii), preferably in each case from 5 to 95% by weight of i) or ii), particularly preferably 50 to 90% by weight of monomer from group i) and 10 to 50% by weight Monomer from group ii), in each case based on the polymer.

at Terpolymers are particularly preferred which contain from 20 to 85% by weight. Monomer from group i), 10 to 60 wt .-% monomer from the group ii) and 5 to 30 wt .-% of monomer from group iii).

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred detergent or cleaning compositions are characterized in that the copolymers have molecular weights of from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

With Particular preference is furthermore given to amphoteric or cationic polymers used. These particularly preferred polymers are characterized that she have at least one positive charge. Such polymers are preferably water-soluble or water-dispersible, that is, they are in water 25 ° C one solubility above 10 mg / ml.

Particularly preferred cationic or amphoteric polymers contain at least one ethylenically unsaturated monomer unit of the general formula R ¹ (R ² ) C = C (R ³ ) R ⁴ in the R ¹ to R ⁴ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above, a heteroatomic group having at least one positively-ground group, a quaternized nitrogen atom or at least one amine group with a positive charge in the pH range between 2 and 11 or -COOH or -COOR ⁵ , wherein R ^{5 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Examples of the above-mentioned (unpolymersized) monomer units are diallylamine, methyldiallylamine, dimethyldimethylammonium salts, acrylamidopropyl (trimethyl) ammonium salts (R ¹ , R ² , and R ³ , = H, R ⁴ = C (O) NH (CH ₂ ) ₂ N ⁺ ( CH ₃ ) ₃ X ^- ), methacrylamidopropyl (trimethyl) ammonium salts (R ¹ and R ² = H, R ³ = CH ₃ H, R ⁴ = C (O) NH (CH ₂ ) ₂ N ⁺ (CH ₃ ) ₃ X ^- ).

Particularly preferred as part of the amphoteric polymers are unsaturated carboxylic acids of the general formula R ¹ (R ² ) C = C (R ³ ) COOH used in which R ¹ to R ^{3 are} independently -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Especially preferred amphoteric polymers contain as monomer units derivatives of diallylamine, in particular dimethyldiallylammonium salt and / or Methacrylamidopropyl (trimethyl) ammonium salt, preferably in the form of the chloride, bromide, iodide, hydroxide, phosphate, sulfate, Hydrosulfates, ethylsulfates, methylsulfate, mesylate, tosylate, Formate or acetate in combination with monomer units from the group the ethylenically unsaturated Carboxylic acids.

bleach

Among the compounds which serve as bleaches and deliver H ₂ O ₂ in water, sodium percarbonate has particular significance. Further useful bleaching agents are, for example, the sodium perborate tetrahydrate and the sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Bleaching agents from the group of organic bleaching agents can also be used according to the invention. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-Diperoxy carboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

When Bleach can Chlorine or bromine releasing substances are used. Among the suitable chlorine or bromine releasing materials come for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Bleach activators

Bleach activators are used, for example, in detergents or cleaners, to improve cleaning at temperatures of 60 ° C and below To achieve bleaching effect. As bleach activators, compounds, which under perhydrolysis aliphatic peroxycarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, are used. Suitable substances are the O- and / or N-acyl groups of the mentioned C atom number and / or optionally substituted benzoyl groups wear. Preference is given to polyacylated alkylenediamines, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

in der R¹ für -H, -CH₃, einen C_2–24-Alkyl- oder -Alkenylrest, einen substituierten C_2–24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1–24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1–24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist.Further bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula

in the R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C _1-24 -alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) - CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion.

in der R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt sind aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, wobei R⁴ zusätzlich auch -H sein kann und X ein Anion ist, wobei vorzugsweise R⁵ = R⁶ = -CH₃ und insbesondere R⁴ = R⁵ = R⁶ = -CH₃ gilt und Verbindungen der Formeln (CH₃)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂)₃N⁽⁺⁾CH₂-CN X^– , (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH(CH₃))₃N⁽⁺⁾CH₂-CN X^–, oder (HO-CH₂-CH₂)₃N⁽⁺⁾CH₂-CN X^– besonders bevorzugt sind, wobei aus der Gruppe dieser Substanzen wiederum das kationische Nitril der Formel (CH₃)₃N⁽⁺⁾CH₂-CN X^–, in welcher X^– für ein Anion steht, das aus der Gruppe Chlorid, Bromid, Iodid, Hydrogensulfat, Methosulfat, p-Toluolsulfonat (Tosylat) oder Xylolsulfonat ausgewählt ist, besonders bevorzugt wird.Particularly preferred is a cationic nitrile of the formula

in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , wherein R ⁴ additionally also -H may be and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ( CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{- are} particularly preferred, wherein in turn from the group of these substances the cationic nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , in which X ^{- is} an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate is particularly preferred.

When Bleach activators can furthermore compounds which are aliphatic under perhydrolysis conditions peroxycarboxylic with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, are used. Suitable substances are the O- and / or N-acyl groups of the mentioned C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methylsulfate (MMA) and acetylated sorbitol and mannitol or their Mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), Pentaacetylfruktose, Tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam. hydrophilic substituted acyl acetals and acyl lactams are also preferred used. Combinations of conventional bleach activators can also be used become.

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

Provided in addition to the Nitrilquats further bleach activators are used are preferred bleach activators from the group of multiple acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10 wt .-%, in particular 0.1 wt. % to 8 wt .-%, especially 2 to 8 wt .-% and particularly preferred 2 to 6 wt .-%, each based on the total weight of the bleach activator-containing Medium, used.

Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate in usual Quantities, preferably in an amount up to 5 wt .-%, in particular from 0.0025 wt.% to 1 wt.%, and more preferably from 0.01 Wt .-% to 0.25 wt .-%, each based on the total weight of bleach activator-containing agent used. But in special cases can also more bleach activator can be used.

Glass corrosion inhibitors

Glass corrosion inhibitors prevent the occurrence of cloudiness, Streaks and scratches but also iridescence of the glass surface of mechanically cleaned glasses. Preferred glass corrosion inhibitors come from the group of Magnesium and / or zinc salts and / or magnesium and / or zinc complexes.

A preferred class of compounds used to prevent glass corrosion can be used are insoluble Zinc salts.

Insoluble zinc salts in the context of this preferred embodiment are zinc salts which have a solubility of a maximum of 10 grams of zinc salt per liter of water at 20 ° C. Examples of particularly preferred insoluble zinc salts according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn ₂ (OH) ₂ CO ₃ ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn ₃ (PO ₄ ) ₂ ), and zinc pyrophosphate (Zn ₂ (P ₂ O ₇ )).

The zinc compounds mentioned are preferably used in amounts which have a content of the zinc ions of between 0.02 and 10% by weight, preferably between 0.1 and 5.0% by weight and in particular between 0.2 and 1.0 Wt .-%, in each case based on the total glass corrosion inhibitor-containing agent, be Act. The exact content of the agent on the zinc salt or zinc salts is naturally dependent on the type of zinc salts - the less soluble the zinc salt used, the higher its concentration should be in the funds.

There the insoluble Zinc salts during the Geschirreinigungsvorgangs mostly unchanged remain, is the particle size of the salts a criterion to be observed so that the salts do not affect glassware or attach machine parts. Here, agents are preferred in which the insoluble Zinc salts have a particle size below 1.7 millimeters.

If the maximum particle size of the insoluble Zinc salts below 1.7 mm are insoluble residues in the dishwasher not to be afraid. Preferably, the insoluble zinc salt a mean particle size, the well below this value, the risk is more insoluble Residues continue to minimize, for example, an average particle size smaller 250 μm. Again, this is even more true the less the zinc salt is soluble. In addition, the glass corrosion inhibiting effectiveness increases with decreasing Particle size. at very poorly soluble Zinc salts, the average particle size is preferably below 100 μm. For still poorly soluble Salts can be even lower; for example, that's for the very most poorly soluble Zinc oxide mean particle sizes below of 100 μm prefers.

A Another preferred class of compounds are magnesium and / or Zinc salts) of at least one monomeric and / or polymeric organic Acid. These cause that too when used repeatedly, the surfaces of glassware are not corrosively changed, in particular no cloudiness, Streaks or scratches but also no iridescence of the glass surfaces caused become.

Even though all magnesium and / or zinc salts) monomeric and / or polymeric used organic acids can be but, as described above, the magnesium and / or Zinc salts of monomeric and / or polymeric organic acids the groups of unbranched saturated or unsaturated Monocarboxylic acids, the branched saturated or unsaturated Monocarboxylic acids, the saturated one and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, of the amino acids and / or the polymeric carboxylic acids prefers.

The Spectrum of the invention preferred Zinc salts of organic acids, preferably organic carboxylic acids, ranges from salts that are heavy or insoluble in water, So a solubility below 100 mg / L, preferably below 10 mg / L, in particular no solubility up to such salts, which have a solubility in water above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and especially above 5 g / L (all solubilities at 20 ° C Water temperature). For example, the first group of zinc salts include the zinc citrate, the zinc oleate and the zinc stearate, to the group the soluble Zinc salts belong for example, zinc formate, zinc acetate, zinc lactate and the zinc gluconate.

With Particular preference is given as a glass corrosion inhibitor at least one Zinc salt of an organic carboxylic acid, more preferably in order a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, Zinc acetate, zinc lactate and / or zinc citrate used. Also zinc ricinoleate, Zinc abietate and zinc oxalate are preferred.

In the context of the present invention, the content of cleaning agents to zinc salt is preferably between 0.1 to 5 wt .-%, preferably between 0.2 to 4 wt .-% and in particular between 0.4 to 3 wt .-%, or the content of zinc in oxidized form (calculated as Zn ²⁺ ) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight. -%, in each case based on the total weight of the glass corrosion inhibitor-containing agent.

corrosion inhibitors

Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. Examples of the 3-amino-5-alkyl-1,2,4-triazoles preferably used according to the invention may be: 5-propyl, -butyl, -pentyl, -heptyl, -octyl, Nonyl, decyl, indodecyl, dodecyl, isononyl, versatic-10-alkyl, phenyl, p-tolyl, (4-tert-butylphenyl) -, - ( 4-methoxyphenyl) -, - (2-, -3-, 4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2-furyl) -, - (5-oxo-2- pyrrolidinyl) -, 3-amino-1,2,4-triazole. In dishwashing agents, the alkylamino-1,2,4-triazoles or their physiologically tolerated salts in a concentration of 0.001 to 10 wt .-%, preferably 0.0025 to 2 wt .-%, particularly preferably 0.01 to 0.04 wt.% Used. Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as vinegar, glycolic, citric, succinic acid. Especially effective are 5-pentyl, 5-heptyl, 5-nonyl, 5-undecyl, 5-isononyl, 5-versatic-10-alkyl-3-amino-1,2,4-triazoles and mixtures of these substances.

you In addition, cleaning agent formulations often contain active chlorine Means that can significantly reduce the corrosion of the silver surface. In Chlorine-free cleaners are especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, z. Hydroquinone, catechol, hydroxyhydroquinone, gallic acid, phloroglucinol, Pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic compounds, such as salts of metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Prefers here are the transition metal salts, which are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can help prevent it corrosion on the items to be washed be used.

Instead of from or in addition to the silver protectants described above, for example the Benzotriazoles, can redox-active substances are used. These substances are preferably inorganic redox-active substances from the group Manganese, Titanium, Zirconium, Hafnium, Vanadium, Cobalt and Cerium salts and / or complexes, wherein the metals are preferably in one of the oxidation states II, III, IV, V or VI.

The used metal salts or metal complexes should at least partially soluble in water be. The counterions suitable for salt formation include all common ones mono-, di- or tri-negatively charged inorganic anions, z. As oxide, sulfate, nitrate, fluoride, but also organic anions such as Stearate.

metal complexes in the context of the invention are compounds which consist of a central atom and one or more ligands and optionally in addition one or more of the o.g. Anions exist. The central atom is one the o.g. Metals in one of the above Oxidation states. The ligands are neutral molecules or anions which are monodentate or polydentate; the term "ligands" within the meaning of the invention is e.g. in "Römpp Chemie Lexicon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, Page 2507 " in a metal complex the charge of the central atom and the charge of the ligand (s) is not zero, so, depending on whether a cationic or an anionic charge excess is present, either one or more of the above. Anions or one or more Cations, z. As sodium, potassium, ammonium ions, for the charge balance. Suitable complexing agents are e.g. Citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.

The common in chemistry Definition for "oxidation state" is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1991, page 3168 "reproduced.

Particularly preferred metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ and mixtures thereof. so that preferred automatic dishwasher detergents according to the invention are characterized in that the metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1-diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ . In these metal salts or metal complexes are generally commercially available substances that can be used for the purpose of silver corrosion protection without prior purification in the compositions of the invention. Thus, for example, the mixture of pentavalent and tetravalent vanadium (V ₂ O ₅ , VO ₂ , V ₂ O ₄ ) known from the SO ₃ preparation (contact method) is suitable, as is the case by diluting a Ti (SO ₄ ) ₂ - Solution resulting titanyl sulfate, TiOSO ₄ .

The inorganic redox-active substances, in particular metal salts or metal complexes are preferably coated, ie completely coated with a waterproof material which is readily soluble in the cleaning temperatures, in order to prevent their premature decomposition or oxidation during storage. Preferred coating materials, which by known methods, such as melt coating method according to Sandwik from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids. The coating material which is solid at room temperature is applied in the molten state to the material to be coated, for example by spinning finely divided material to be coated in a continuous stream through a likewise continuously produced spray zone of the molten coating material. The melting point must be chosen so that the coating material easily dissolves or melts during the silver treatment. The melting point should ideally be in the range between 45 ° C and 65 ° C and preferably in the range 50 ° C to 60 ° C.

The mentioned metal salts and / or metal complexes are in cleaning agents, preferably in an amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, each based on the total corrosion inhibitor-containing Contain funds.

enzymes

To increase the washing or cleaning performance of detergents or cleaners enzymes can be used. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Agents of the invention preferably contain enzymes in total amounts of from 1 × 10 ^-6 to 5 weight percent based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferable. Examples thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg in a developed form under the trade names Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP ^® variants are derived.

Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® by the company Genencor, that under the trade name Protosol® ^® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ^® and protease P ^® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus and also their further developments improved for use in detergents and cleaners. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar® ^® ST. Development products of this α-amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ^®, and variants derived from the α-amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes.

Furthermore are for this purpose the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae. Another commercial product is, for example, the amylase ^LT® .

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. For this For example, include the lipases originally available from Humicola lanuginosa (Thermomyces lanuginosus), or further developed, in particular those with the amino acid exchange D96L. They are for example marketed by Novozymes under the trade names Lipolase ^®, Lipolase Ultra ^®, LipoPrime® ^®, Lipozyme® ^® and Lipex ^®. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. ^Lipase® , Lipase ^AP® , Lipase M- ^AP® and Lipase ^{AML® are} available. From the company Genencor, for example, the lipases, or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products, the preparations originally sold by Gist-Brocades M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention also the product Lumafast® ^® from Genencor.

Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, United States. The obtained from B. subtilis β-glucanase is available under the name Cereflo ^® from Novozymes.

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Suitable commercial products Denilite® ^® 1 and 2 from Novozymes should be mentioned. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

The For example, enzymes are either originally derived from microorganisms, about the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are used according to known biotechnological processes produced by suitable microorganisms, such as transgenic Expression hosts of the genera Bacillus or filamentous fungi.

The Purification of the enzymes concerned is preferably carried out by itself established methods, for example about precipitation, sedimentation, concentration, Filtration of the liquid Phases, microfiltration, ultrafiltration, exposure to chemicals, Deodorization or suitable combinations of these steps.

The Enzymes can used in any form established in the prior art become. These include for example, by granulation, extrusion or lyophilization obtained solid preparations or, especially in liquid or gelatinous Means, solutions the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers.

alternative can the enzymes for both the solid as well for the liquid Dosage form can be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural polymer or in the form of capsules, for example those in which the enzymes are as in enclosed in a solidified gel or in those of the core-shell type, in which a enzyme-containing core coated with a water, air and / or chemical impermeable protective layer is. In superimposed layers additional active ingredients, For example, stabilizers, emulsifiers, pigments, bleach or Dyes are applied. Such capsules are after known methods, for example by shaking or Roll granulation or applied in fluid-bed processes. Advantageously Such granules, for example by applying polymeric film-forming agents, low in dust and storage-stable due to the coating.

Farther Is it possible, to assemble two or more enzymes together, so that a single Granules several enzyme activities having.

A protein and / or enzyme may be particularly useful during storage against damage such as For example, inactivation, denaturation or decay be protected by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Compositions according to the invention may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.

A Group of stabilizers are reversible protease inhibitors. Become frequent Benzamidine hydrochloride, Borax, boric acids, boronic acids or their salts or esters, including derivatives in particular with aromatic groups, such as ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their Salts or esters. As peptidic protease inhibitors are under to mention other ovomucoid and leupeptin; an additional Option is the formation of fusion proteins from proteases and peptide inhibitors.

Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders are additionally capable of stabilizing a contained enzyme.

low aliphatic alcohols, but especially polyols, such as Glycerine, ethylene glycol, propylene glycol or sorbitol are other often used enzyme stabilizers. Likewise, calcium salts are used such as calcium acetate or calcium formate, and magnesium salts.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations. Polyamine N-oxide containing polymers act as enzyme stabilizers. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes. Alkylpolyglycosides can stabilize the enzymatic components of the agent according to the invention and even increase their performance. Crosslinked N-containing compounds also act as enzyme stabilizers.

reducing agent and increase antioxidants the stability of the enzymes oxidative decay. A sulfur-containing reducing agent is, for example Sodium sulphate.

Prefers Kombinatonen be used by stabilizers, for example made of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing Salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing Salt. The effect of peptide-aldehyde stabilizers is obtained by combination with boric acid and / or boric acid derivatives and polyols increased and by the additional use of divalent Cations, such as calcium ions further amplified.

Prefers are one or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, in Amounts of 0.1 to 5 wt .-%, preferably from 0.2 to 4.5 and in particular from 0.4 to 4 wt .-%, each based on the total enzyme-containing Medium, used.

disintegration aid

Around the disintegration of prefabricated moldings to facilitate, it is possible Disintegration aids, so-called tablet disintegrants, in to incorporate these agents to reduce disintegration times. Under Tablet disintegrants or disintegrants are used according to Römpp (9. Auflage, Bd. 6, p. 4440) and Voigt "textbook of pharmaceutical technology" (6th edition, 1987, Pp. 182-184) Understood excipients for the rapid disintegration of tablets in water or gastric juice and for release provide the pharmaceuticals in resorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume upon ingress of water, on the one hand increasing the intrinsic volume (swelling), and on the other hand creating a pressure via the release of gases which can break the tablet into smaller particles decays. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Prefers are disintegration aids in amounts of 0.5 to 10 wt .-%, preferably 3 to 7% by weight and in particular 4 to 6% by weight, respectively based on the total weight of the desintegrationshilfsmittelhaltigen By means of, used.

Preferred disintegrating agents used in the present invention are cellulose-based disintegrating agents, so that preferred washing and cleaning compositions comprise such a cellulose-based disintegrating agent in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular 4 contain up to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, more preferably below 20% by weight, based on the cellulose-based disintegration agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.

The cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. The particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns. The above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier available in the present invention.

When another disintegrating agent based on cellulose or as an ingredient This component can be used microcrystalline cellulose. This microcrystalline cellulose is made by partial hydrolysis of Celluloses obtained under such conditions, only the amorphous ones Areas (about 30% of the total cellulose mass) of the celluloses attack and completely dissolve, the crystalline areas (about 70%) but leave undamaged. A subsequent disaggregation of the resulting from the hydrolysis microfine celluloses provide the microcrystalline celluloses, the primary particle sizes of approx. 5 μm and compactable, for example, to granules having an average particle size of 200 microns are.

in the Within the scope of the present invention, preferred disintegration aids, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form in the disintegrating agent-containing agents in amounts of 0.5 to 10% by weight, preferably from 3 to 7% by weight and especially from 4 to 6% by weight, respectively based on the total weight of the disintegrant-containing By means of, included.

According to the invention preferred can about that in addition, gas-evolving effervescent systems as tablet disintegration aids be used. The gas-developing effervescent system can from a consist of a single substance which releases a gas on contact with water. Among these compounds is in particular the magnesium peroxide to call, which releases oxygen on contact with water. Usually However, the gas-releasing effervescent system in turn from at least two components that are together under gas formation react. While here a variety of systems is thinkable and executable, for example Nitrogen, oxygen or hydrogen will release the in the washing and cleaning compositions used effervescent system both economic and also on the basis of ecological Select points of view to let. Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifier, the is suitable to release carbon dioxide from the alkali metal salts in aqueous solution.

at The alkali metal carbonates or bicarbonates are the sodium and potassium salts for cost reasons across from the other salts clearly preferred. Of course you do not have to the respective pure alkali metal carbonates or bicarbonates be used; rather, you can Mixtures of different carbonates and bicarbonates preferred be.

Prefers be used as effervescent 2 to 20 wt .-%, preferably 3 to 15 wt .-% and in particular 5 to 10 wt .-% of a Aikalimetallcarbonats or bicarbonates and 1 to 15, preferably 2 to 12 and in particular 3 to 10 wt .-% of an Acidifizierungsmittels, in each case based Total weight of the agent used.

Acidifying agents which release carbon dioxide from the alkali metal salts in aqueous solution include, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts. However, preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. However, it is also possible in particular to use the other solid mono-, oligo- and polycarboxylic acids. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred from this group. Organic sulfonic acids such as sulfamic acid are also usable. A commercially available as an acidifier in the context of the present invention also preferably be used is Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) and adipic acid ( at most 33% by weight).

Prefers are in the context of the present invention Acidifizierungsmittel in the shower system from the group of organic di-, tri- and oligocarboxylic acids or Mixtures.

fragrances

When Perfume oils or Fragrances can individual perfume compounds, e.g. the synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons be used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, Dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, Benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and Benzylsalicylate. For example, the ethers include Benzyl ethyl ether, to the aldehydes e.g. the linear alkanals with 8-18 C-atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, α-isomethylionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons belong mainly the terpenes like limonene and pinene. However, mixtures are preferred different fragrances used, which together create an appealing Create a fragrance. Such perfume oils can also natural fragrance mixtures as available from plant sources, e.g. Pine, Citrus, Jasmine, patchouly, rose or ylang-ylang oil. Also suitable Muscat, sage oil, Chamomile oil, Clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil, and Orange blossom oil, neroliol, Orange peel oil and sandalwood oil.

The Fragrances can can be processed directly, but it can also be beneficial to the Fragrances on carrier The slow release of fragrance for long-lasting Provide scent. As such carrier materials For example, cyclodextrins have proven useful, with the cyclodextrin-perfume complexes additionally still can be coated with other excipients.

dyes

preferred Dyes whose selection does not present any difficulty to the skilled person have a high storage stability and insensitivity to the rest Ingredients of the agents and against light and no pronounced substantivity to the with the dye-containing agents to be treated substrates such as for example glass, ceramics, plastic dishes or textiles, so as not to stain them.

solvent

The solvents include, in particular, the nonaqueous organic solvents, particular preference being given to using nonaqueous solvents from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the given concentration range. Preferably, the solvents are selected from ethanol, n- or i-propanol, butano glycol, propane or butanediol, glycerol, diglycol, propyl or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, -ethyl or -propyl ether, dipropylene glycol methyl, or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents.

foam inhibitors

When Foam inhibitors are, for example, soaps, paraffins or silicone oils into consideration, optionally on support materials can be applied. Suitable anti redeposition agents, also called soil repellents are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion at methoxy groups of 15 to 30 wt .-% and hydroxypropyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether and the known from the prior art polymers of phthalic acid and / or terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. Especially preferred of these are the sulfonated derivatives of phthalic acid and Terephthalic acid polymers.

Optical brighteners

optical Brighteners (so-called "whiteners") can be used or detergents are added to reduce graying and yellowing of textiles treated with these funds. These substances attract to the fiber and cause a whitening and fake bleaching effect, by turning invisible ultraviolet radiation into visible longer wavelength Convert light, with the ultraviolet absorbed from sunlight Light as slightly bluish Fluorescence is emitted and with the yellow of the bated or yellowed laundry pure white results. Suitable compounds are derived, for example, from the substance classes 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyryl-biphenylene, methylumbelliferones, Coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, Benzoxazole, benzisoxazole and Benzimidazole systems and those substituted by heterocycles Pyrene derivatives.

graying

graying In textile cleaners have the job of the fiber detached dirt to keep suspended in the fleet and so the recovery of the Prevent dirt. For this purpose, water-soluble colloids are usually more organic Nature, for example the water-soluble salts of polymeric carboxylic acids, glue, Gelatin, salts of ether sulfonic acids the strength or the cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water-soluble, Acidic group-containing polyamides are suitable for this purpose. Farther can be soluble Starch preparations and other than the aforesaid starch products use, e.g. degraded starch, aldehyde etc. Also, polyvinylpyrrolidone is useful. As grayness inhibitors in the particular Cellulosic ethers such as carboxymethylcellulose can also be used (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as Methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and their mixtures.

Antimicrobial agents

antimicrobial Active substances serve to fight of microorganisms. Here one differentiates depending upon antimicrobial Spectrum and mechanism of action between bacteriostats and bactericides, fungistats and fungicides, etc. Important substances from these groups are, for example Benzalkonium chlorides, alkylaryl sulfonates, halophenols and phenol mercuriacetate, whereby the use of these funds can be completely dispensed with.

softener

The formulations may also comprise fabric softening clay minerals which may be selected from a variety of minerals, especially the layered silicates. The group of smectites has proved to be advantageous. The term smectite includes both clays in which alumina is present in a silicate lattice and clays in which magnesium oxide occurs in a silicate lattice. Typical smectites have the following general formula: Al ₂ (Si ₂ O ₅ ) ₂ (OH) ₂ .nH ₂ O and compounds having the following formula Mg ₃ (Si ₂ O ₅ ) ₂ (OH) ₂ .nH ₂ O. Smectites are usually in an extended three layer structure. Specific examples of suitable smectites include those selected from the class of montmorillonites, hectorites, volkonskites, nontronites, saponites, and sauconites, especially those having alkali or alkaline earth metal ions in the crystal lattice structure. Preferred is a three-layer, expandable aluminum silicate characterized by a dioctahedral crystal lattice, whereas the extended three-layer magnesium silicate structure has a trioctahedral crystal lattice. As mentioned previously, the clay minerals contain cationic counterions such as protons, sodium ions, potassium ions, calcium ion, magnesium ions, and the like. Usually, the clay minerals are distinguished by the cations that are predominantly or exclusively absorbed. For example, a sodium bentonot is such a clay mineral in which there is predominantly sodium as the absorbed cation. Such absorbed cations can undergo exchange reactions with other cations in aqueous solutions. A typical exchange reaction involving a smectite type is as follows: Smectite (Na) + NH ₄ OH → smectite (NH ₄ ) + NaOH

In the aforementioned equilibrium reaction becomes one equivalent Ammonium ion replaced by one equivalent Sodium ion. It is usual, the cation exchange capacity in milliequivalents / 100 g (meq / 100 g). The cation exchange capacity of the clays can be determined in different ways, for example by Electrodialysis or by exchange with ammonium ions, followed by a titration, as in the book by Grimshaw, "The chemistry and physics of clays ", Pages 264-265, Interscience 1971, is described. Smectites such as Nontonite has an ion exchange capacity of about 70 meq / 100 g, and Montmorillonite, which has an exchange capacity of above 70 meq / 100 g have been found to be extremely preferred in the context of the present invention, since they are particularly effectively on the textiles to be treated and give them the desired Give soft grip. Particularly preferred clay minerals in the frame The present invention is therefore expanded three-layered Smectite types with an ion exchange capacity of at least 50 meq / 100 g.

organophilic Clay minerals can also be used in the context of the present invention. Such hydrophobically modified clay minerals in which inorganic Metal ions are exchanged by organic ions through the previously described exchange process are also preferred. The modified clay minerals are very well miscible with organic solvents and have the property of organic solvents between layers store. Suitable examples of organophilic clay minerals are Benton SD-1, SD-2 and SD-3 from Rheox.

Out The group of smectites has been found to be particularly preferred for the bentonites exposed. Bentonites are contaminated clays caused by weathering volcanic tuffs have arisen. Because of their high salary Bentonites have valuable properties on montmorillonite, such as Swelling capacity, Ion exchange capacity and thixotropy. It is possible the properties of bentonites according to the intended use to modify. Bentonites are as an ingredient in tropical Soils frequent and are used as sodium bentonite e.g. mined in Wyoming / USA. Sodium bentonite has the best application properties (swelling capacity), so that its Use in the context of the present invention is preferred. Naturally occurring Calcium bentonites are from, for example, Mississippi / USA or Texas / USA or from Landshut / D. The course recovered Ca bentonites become artificial exchanged by Ca for Na in the swellable Na bentonites.

The main constituents of the bentonites form so-called montmorillonites, which can also be used in their pure form in the context of the present invention. Montmorillonites belong to the phyllosilicates and here to the dioctahedral smectites belonging clay minerals, which crystallize monoclinic pseudohexagonal. Montmorillonite form predominantly white, grayish-white to yellowish, completely amorphous appearing, easily friable, in the water swelling, but not plasticizing masses, by the general formulas Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ] .nH ₂ O or Al ₂ O ₃ · 4SiO ₂ · H ₂ O · nH ₂ O or Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ] (dried at 150 °) can be described.

Montmorillonites have a three-layer structure consisting of two tetrahedral layers, which are electrostatically crosslinked via the cations of an octahedral intermediate layer. The layers are not rigidly connected, but can swell by reversible incorporation of water (in 2-7 times the amount) and other substances such as alcohols, glycols, pyridine, ammonium compounds, hydroxy-aluminosilicate ions, etc. The above. Formulas are only approximate formulas since montmorillonites have a high ion exchange capacity. Thus, Al can be exchanged for Mg, Fe ²⁺ , Fe ³⁺ , Zn, Cr, Cu and other ions. As a result of such substitution, a negative charge of the layers results, which is balanced by other cations, especially Na ⁺ and Ca ²⁺ .

Calcium or magnesium bentonites are usually non-swellable and usually less effective plasticizers. However, it is advantageous to combine non-swellable bentonites with carrier materials, such as polyethylene glycol, to achieve a significantly improved softness of the textiles treated therewith. Also advantageous are calcium or magnesium bentonites, which are used in the presence of a sodium source, such as NaOH or NaCO ₃ .

• I) Montmorillonit-Gehalt von mindestens 85 % und
• II) wenn der mit Natriumionen aktivierte Ton, getrocknet und zu Partikeln gemahlen wird, dann quellen die gemahlenen Partikel nicht mehr als das zweieinhalbfache an innerhalb einer Zeit von 24 Stunden, wenn entionisiertes Wasser bei Raumtemperatur hinzugefügt wird.

In a particularly preferred embodiment, the clay is a treated montmorillonite-containing clay having the following properties:

• I) montmorillonite content of at least 85% and
• II) when the clay activated with sodium ions is dried and ground to particles, then the milled particles swell no more than two and a half times over a period of 24 hours when deionized water is added at room temperature.

• a) Trocknen des Tons auf einen Wassergehalt von 25 – 35 Gew.-%,
• b) Extrudieren des getrockneten Materials zu einer Paste;
• c) Trocknen der Paste auf einen Feuchtigkeitsgehalt von 10 – 14 Gew.-% und
• d) Kalzinieren bei einer Temperatur zwischen 120 und 250°C.

Particularly preferred is a montmorillonite-containing clay, which is obtained by the following process steps:

• a) drying the clay to a water content of 25-35 wt .-%,
• b) extruding the dried material into a paste;
• c) drying the paste to a moisture content of 10 - 14 wt .-% and
• d) calcining at a temperature between 120 and 250 ° C.

The chemical composition of the bentonite to be used as starting material is preferably the following: SiO ₂ : 55.0 - 61.0% by weight Al ₂ O ₃ : 14.5-17.6% by weight Fe ₂ O ₃ : 1.45-1.7% by weight CaO: 2.8 - 7.0% by weight MgO: 5.0-6.3% by weight K ₂ O: 0.5-0.58% by weight Na ₂ O: 0.25-0.3% by weight Mn ₃ O ₄ : 0.04-0.25% by weight

A detailed description of the process for the treatment of bentonite is found in WO 00/03959, the disclosure of which in this application full is incorporated.

The crystalline structure of montmorillonite is more or less resistant to Acid treatment.

Under acid treatment In the context of the invention, it is understood that a sample of the clay (for example 1 g / L) in a 1 N HCl solution for 15 Hours at a temperature of 80 ° C is exposed. It must be there mentioned be that the Most clays by acid treatment can be destroyed with, for example Flourwasserstoff. In the context of the present Invention is under acid treatment however, the HCl treatment meant. Montmorillonite (magnesium saturated / air dried) show for usually a maximum diffraction distance of 14-15 Å in the 001 plane when with X-rays be treated. This maximum diffraction distance changes usually too not by the fact that Clay is treated with HCl.

in the However, the scope of the present invention is acid-sensitive montmorillonites preferably, for example Montmorillonite whose crystalline Structure destroyed when treated with HCl. The use of such clay minerals has a softening effect and also makes for a better Dispersibility in the aqueous wash liquor or the aqueous textile treatment liquid. The destruction The crystalline structure can be measured by measuring the diffraction distance be determined so that at the destroyed one Montmorillonites expected in crystalline Montmoriloniten maximum diffraction distance in the 001 plane of 14-15 Å does not appear.

Without being bound by theory, it is believed that the acid sensitivity is related to increased exchange of aluminum by magnesium in the octahedral layer of the montmorillonite clay. Preferred is a ratio of Al ₂ O ₂ / MgO of less than 4, more preferably of less than 3. The aforementioned acid-sensitive montmorillonites have the advantage that they allow a reduced tendency to gel as well as an improved dispersibility in the wash liquor. In addition, it has been observed that such clay minerals produce improved softness.

Claims (10)

A process for producing a molded body from a washing or cleaning active preparation, comprising the steps of: a) pouring a washing or cleaning active preparation into a mold, b) demolding the molded body from the mold, characterized in that the mold is at least partially made of elastic material. Method according to claim 1, characterized in that that the Receiving trough of the mold made of elastic material is. Method according to one of claims 1 or 2, characterized that this Mold is coated with elastic material. Method according to one of claims 1 to 3, characterized that the first wash or cleaning active substance mixture after casting in the Mold is vibrated. Method according to one of claims 1 to 4, characterized that this Mold is cooled. Method according to one of claims 1 to 5, characterized that the first wash or cleaning-active preparation before demolding, preferably under Formation of a hollow body, is brought into shape. Method according to Claim 6, characterized that the cast hollow bodies with at least one further washing or cleaning active preparation filled becomes. Method according to one of claims 6 or 7, characterized that the molded hollow body with a water-soluble or water-dispersible polymer is sealed. Method according to one of claims 6 to 8, characterized that the molded hollow body with a washing or cleaning substance or a washing or detergent-active substance mixture is closed. Method according to one of claims 6 to 9, characterized that the molded hollow body with a prefabricated pouch is closed.