EP1309669B1 - Mechanically stable, liquid formulation washing, rinsing or cleaning agent doses - Google Patents

Abstract

The invention relates to a washing, rinsing or cleaning agent dose comprising a fully or partially water-soluble coating in the form of a capsule, a ball or a bag. Said coating completely surrounds a liquid-based formulation of at least one washing, rinsing or cleaning active ingredient having a crushing resistance of >1 N at 23° C. The invention also relates to a method for producing one such washing, rinsing or cleaning agent dose, in addition to a method for washing, rinsing or cleaning using said washing, rinsing or cleaning agent dose.

Description

The present invention relates to mechanically stable, liquid formulated detergent, detergent or detergent portions. In particular, the present invention relates to detergent, detergent or detergent portions in the form of formulations that are liquid in the production and filling and whose viscosity increases over time, resulting in that encapsulated formulations due to their thixotropic or pseudoplastic behavior are mechanically stable.

Detergents and cleaners and cosmetics with increased viscosity have been increasingly offered in recent years. Products with gel-like consistency are widely accepted by the consumer. In the field of liquid detergents, gel products with increased viscosity have the advantage that less non-aqueous solvents can be used in their preparation. Furthermore, the resulting product can be applied specifically to stains on the laundry without being lost. Conventionally, conventional liquid detergents based on aqueous formulations are converted by the use of thickeners into higher-viscosity products. Examples of such thickening agents are agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein, carboxymethyl cellulose and cellulose ethers, hydroxyethyl cellulose, hydroxypropyl cellulose and the like, gum ethers, polyacryl - u. Polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, polysilicic acids, clay minerals such as montmorillonites, zeolites and silicic acids. The use of these thickening agents for increasing the viscosity in a wide variety of liquids has long been State of the art. The use of polymers in liquid detergents has long been known.

The incorporation of thickeners such as the thickener mentioned leads in liquid detergents above certain surfactant contents to stable gels. Liquid detergents with surfactant contents below 35% by weight already show phase separation or agglomeration after a few days, which manifests itself in opaque ("clouding") of the formulation. In addition, with such products, the viscosity during storage sometimes drops drastically. Since gel formation usually only succeeds at surfactant contents above 35% by weight, high surfactant contents are therefore essential. Since higher-viscosity liquid detergents are usually offered in clear bottles to underline the aesthetic features, it is also necessary that the thickening agents used are stable to light, otherwise a radical decomposition of the polymers occurs, resulting in destruction of the product color and - also - expresses unwanted "clouding".

Liquid detergents having viscosities of between 500 and 20,000 mPas, preferably from 2,000 to 10,000 mPas, in which lamellar surfactant droplets are dispersed in an aqueous electrolyte phase are described in European Patent Application EP-A 691 399 (Colgate). These agents contain 10 to 45% by weight of surfactant (s), at least one builder, and 0.01 to 5% by weight of a mercapto-end-capped, intermediate molecular weight polymer of between 1,500 and 50,000 gmol ^-1 .

The use of boron compounds in aqueous liquid detergents is described in EP-A 381 262 (Unilever). The liquid detergents described contain the boron compounds and a polyol as enzyme stabilization system for a mixture of proteolytic and lipolytic enzymes, preferred stabilizer systems consisting of a sorbitol / borax mixture. About viscosity and stability of liquid detergents nothing is carried out in this document.

Liquid, aqueous detergent concentrates which maintain or increase their viscosity when diluted with water are described in EP-A 724 013 (Colgate). This effect is achieved by the use of two surfactants with different resistance to electrolytes and the addition of a dissolved electrolyte, wherein the concentrate has a viscosity of less than 2,500 mPas and when diluted with water loses its micellar structure in favor of the formation of a lamellar phase.

International Patent Application WO96 / 01305 (Unilever) describes an aqueous cleaning and liquid detergent which, when diluted with at least twice the amount of water, forms a microemulsion having particle sizes of 10 to 100 nm. The composition contains 20 to 70 wt .-% water, 15 to 40 wt .-% of a surfactant system containing at least one nonionic surfactant from the group of alkoxylated alcohols and not more than 20 wt .-% anion, cation, ampho- or contains zwitterionic surfactants, 5 to 30 wt .-% of solvent and 5 to 20 wt .-% water-insoluble oil.

EP 1 314 654 A, EP 1 120 459 A and WO 0 206 431 A disclose detergents; Detergent or detergent portions with liquid based formulation.

None of the mentioned documents deals with the problem of providing portioned, higher-viscosity liquid detergents which guarantee a stable viscosity, do not lead to agglomeration (so-called "clouding") or phase separation within one portion and show no reduction in the color stability of the composition under the influence of light.

Aqueous, highly viscous liquid detergents in bulk form with surfactants and other customary ingredients of detergents and cleaners and a thickening system of polyurethanes or modified polyacrylates, a boron compound and one or more complexing agents, in particular low molecular weight hydroxycarboxylic acids, are described in the document WO 99/28430. Portioned detergents, dishwashing detergents or detergents with thixotropic or pseudoplastic flow behavior of the wash-active, dishwashing or cleaning-active components contained therein can not be gathered from this prior art.

Aqueous, highly viscous liquid detergents in bulk form with surfactants and other customary ingredients of detergents and cleaners and a thickening system of a polymeric thickener or swelling agent, a boron compound and one or more complexing agents, in particular low molecular weight hydroxycarboxylic acids, are described in WO 99/27051 , Portioned detergents, dishwashing detergents or detergents with thixotropic or pseudoplastic flow behavior of the wash-active, dishwashing or cleaning-active components contained therein can not be gathered from this prior art.

WO 96/10072 and WO 96/10073 (Procter & Gamble) describe surfactant formulations for treating highly soiled laundry in the form of a stable suspension of a solid, substantially insoluble particulate material of an inorganic peroxide bleach and an anionic surfactant in one aqueous liquid phase of a fatty alcohol ethoxylate as a non-ionic surfactant and an anhydrous organic solvent of low polarity, and a method for producing such a surfactant preparation by mixing the solid components in a vigorously agitated mixture of the liquid components. With a water content of the suspension of <5% by weight, the preparations should have a viscosity of 300 to 5,000 cps (Brookfield, # 5 spindle at 50 rpm), without providing information on non-Newtonian behavior of the preparations.

EP-A-0 738 778 (Procter & Gamble) discloses non-aqueous liquid detergent compositions in the form of stable suspensions of solid particles of bleaches, bleach activators, alkalis, builders and anionic surfactants in non-aqueous mixtures of anionic (alkali metal or alkanolamine) surfactants. Alkyl polyalkoxylates) and nonionic (polyhydroxy fatty acid amides) surfactants and organic diluents (alcohol alkoxylates and low-polarity organic solvents). WO 97/00938 (Procter & Gamble) describes non-aqueous liquid detergent formulations in the form of stable dispersions of bleach (eg peroxy bleach) and optionally bleach activator and organic builders in non-aqueous mixtures of alkali metal salts of alkylbenzenesulfonates, Fatty alcohol ethoxylates and non-polar organic solvents. With a water content of the suspension of <5% by weight, the preparations should have a viscosity of 300 to 5,000 cps (Brookfield, # 5 spindle at 50 rpm), without providing information on non-Newtonian behavior of the preparations.

The references WO 97/00936 and WO 97/00937 (Procter & Gamble) describe non-aqueous (<5 wt .-% water) surfactant preparations in the form of liquids, gels or pastes, the anionic and / or nonionic surfactants , nonaqueous organic diluents (eg, fatty alcohol alkoxylates or nonpolar organic solvents) and clay soilings removing polymers (e.g., alkoxylated cationic diamines or polyamines (WO 97/00936) and bleaching agents and salts of divalent metals as bleach activators (WO 97/00937)). In terms of consistency comparable surfactant preparations with alkalis, organic builders, etc. in liquid mixtures of anionic and nonionic surfactants and non-aqueous organic diluents are described in WO 97/02336 (Procter & Gamble). Changes in the viscosity of the preparations as a function of applied shear forces can not be found in any of the cited documents.

WO 98/00507 to WO 98/00512 and WO 98/00514 to WO 98/00517 (Procter & Gamble) describe various non-aqueous (<5% by weight water) liquid detergents in which solid components (bleaching agents, bleaches Precursors, bleach activators, enzymes) are dispersed or suspended in anhydrous mixtures containing at least one surfactant and non-aqueous diluent or solvent. The viscosity behavior of such preparations is not addressed in any of the cited documents.

Preparations of the abovementioned type were usually given to the consumer in containers containing large quantities of liquid such as, for example, plastic bottles. The dosage was then as needed (degree of contamination of the washing, rinsing or cleaning, amount of washing, rinsing or cleaning) or experience in each individual case with suitable devices for measuring amounts of liquid.

Anhydrous alcohol ether sulfates (isopropanol ammonium ether sulfates) as components of highly concentrated detergent and cleaner systems are disclosed in the article "U. Schoenkaes et al., Water-free Alcohol Ether Sulfates - New High-Active Surfactants for Superconcentrated Detergent Formulations". Such systems are described as being excellent as wash-active and are suitable for stable incorporation of bleaches and other water-sensitive detergents, dishwashing detergent and detergent components.

It is also described that such formulations can be incorporated into water-soluble gelatin capsules or foil pouches and thus can be added to the laundry, rinsing or cleaning stock as a pre-dosed detergent, rinse or detergent portion.

In addition to the disadvantages of a possible chemical or physical instability of the respective portion constituting ingredients had in the cited document described detergent, detergent or detergent portions in capsule, ball or foil bag form but also the disadvantage of mechanical instability: In larger containers packaged capsules, balls or foil bags with liquid content always subject to the risk due to shock or bursting by the weight of adjacent portions and then draining their liquid contents into the package. Also was found to be disadvantageous that individual portions that were dropped either by carelessness or - if in ball shape - by rolling out of control or were - for example, children - mechanically damaged, their liquid content delivered even at the slightest damage in the environment , Of course, this was undesirable and the lack of resistance is a reason for many consumers to reject this new form of detergent, detergent or detergent portions.

Surprisingly, it has now been found that these disadvantages can be remedied by providing detergent, dishwashing or cleaning agent portions based on liquid formulations of washing-active, dishwashing or cleaning-active components, the formulations having a high viscosity. According to the invention, particularly advantageous detergent, detergent or cleaning agent portions result in cases in which the liquid formulations during processing, for example during manufacture from their detergent-active, rinse-active or detergent-active components, during stirring, during pumping and during filling of the the detergent, detergent or detergent portions provided sheaths (capsules, balls, bags) have a low, after release of the mechanical action, however, have a high viscosity. A thixotropic or pseudoplastic - in any case non-Newtonian - behavior of the liquid formulations of washing-active, dishwashing or cleaning-active components unexpectedly leads to detergent, detergent or cleaner portions with significantly improved performance properties.

The invention therefore relates to a detergent, dishwashing or cleaning agent portion comprising a completely or partially water-soluble casing with a thickness of 1 to 300 .mu.m in capsule form, which is a liquid-based formulation with non-Newtonian flow behavior at least one washing active, rinse or completely encloses cleaning active material, with a compression resistance of 10 to 10 ⁵ N at 23 ° C.

In an alternative embodiment, the invention relates to a detergent, detergent or cleaning agent portion comprising a completely or partially water-soluble coating with a thickness of 1 to 300 μm in spherical form, which completely surrounds a liquid-based formulation with non-Newtonian flow behavior of at least one washing-active, rinsing-active or cleaning-active material, with a compression resistance of 10 to 10 ⁵ N at 23 ° C.

In a further alternative embodiment, the invention relates to a detergent, detergent or cleaning agent portion comprising a wholly or partially water-soluble envelope having a thickness of 1 to 300 .mu.m in the form of a bag containing a liquid-based formulation with non-Newtonian flow behavior at least one wash-active, rinse-active or cleaning-active material completely surrounds, with a compression resistance of 10 to 10 ⁵ N at 23 ° C.

• (a) wenigstens eine flüssige Komponente der flüssig-basierten Formulierung mit nicht - newtonischen Fließverhalten wenigstens eines waschaktiven, spülaktiven oder reinigungsaktiven Materials vorlegt und diese unter Aufbringen einer bestimmten Scherkraft bewegt;
• (b) gegebenenfalls eine oder mehrere weitere flüssige Komponente(n) der flüssig-basierten Formulierung zusetzt;
• (c) in die so hergestellte flüssige Phase gegebenenfalls eine oder mehrere feste Komponente(n) der flüssig-basierten Formulierung einarbeitet und gegebenenfalls anschließend eine oder mehrere weitere feste und/oder flüssige Komponente(n) zusetzt und dabei eine bestimmte Scherkraft beibehält; und
• (d) gegebenenfalls die nach Schritt (c) hergestellte flüssige Mischung sofort in die Umhüllung mit einer Dicke von 1 bis 300 µm einbringt und diese um die flüssig-basierte Formulierung mit nicht - newtonischen Fließverhalten verschließt.

The invention further relates to a process for the preparation of a washing agent, detergent or cleaning agent portion which comprises a completely or partially water-soluble coating with a thickness of 1 to 300 μm in capsule form, in spherical form or in the form of a bag, which in turn is a liquid-based Completely surrounds the formulation with non-Newtonian flow behavior of at least one washing-active, rinsing-active or cleaning-active material, comprising the steps of

• (A) at least one liquid component of the liquid-based formulation with non-Newtonian flow behavior of at least one detergent, rinse active or cleaning active material presents and moves them under application of a certain shearing force;
• (b) optionally adding one or more further liquid component (s) to the liquid-based formulation;
• (c) optionally incorporating one or more solid component (s) of the liquid-based formulation into the liquid phase thus prepared, and then optionally adding one or more further solid and / or liquid component (s) while maintaining a certain shear force; and
• (d) optionally introducing the liquid mixture prepared according to step (c) immediately into the covering with a thickness of 1 to 300 μm and closing it around the liquid-based formulation with non-Newtonian flow behavior.

The invention also relates to a washing method, a rinsing method and a cleaning method using the detergent, detergent or detergent portions described in more detail below.

In the context of the present invention, the term "detergent, dishwashing or cleaning agent portion" is understood to mean a quantity of a detergent, dishwashing agent or cleaning agent which is sufficient for a washing, rinsing or cleaning process taking place in an aqueous phase. This can be, for example, a machine washing, rinsing or cleaning process, as is carried out with commercially available washing machines or dishwashers or cleaning machines. However, according to the invention, this term also refers to a hand washing cycle (performed, for example, in a hand basin or in a bowl) or a dishwashing process carried out by means of a cleaning liquor in a vessel, such as a bucket, or another process of washing, rinsing or cleaning Understood. According to the invention, the detergent, detergent or cleaner portions are preferably used in automatic washing, rinsing or cleaning operations.

In the context of the present invention, the term "detergent partial portion" or "detergent partial portion" or "detergent partial portion" is understood to mean a portion of a detergent, dishwashing or cleaning agent portion which is in one of other detergents, dishwashing detergents and detergents. or detergent sub-portions of separate phase is in spatial association with other detergent, rinse or detergent portions of the same detergent, rinse or detergent portion and is prepared by appropriate means so as to be separate from other detergents, dishwashing or cleaning agents Portions of the same detergent, detergent or detergent portion may be added to the liquor and optionally dissolved or suspended in it. In this case, a detergent, detergent or detergent partial portion may contain the same ingredients as another detergent, detergent or detergent portion of the same detergent, detergent or detergent portion; However, two detergent, detergent or detergent partial portions of the same detergent, detergent or cleaner portion preferably contain different ingredients, in particular different detergent-active, rinse-active or detergent-active preparations.

According to the detergent, detergent or cleaner portions contain measured amounts of at least one washing-active, rinsing-active or cleaning-active preparation, usually measured amounts of several washing-active, rinse-active or cleaning-active preparations. It is possible that the portions only Wash-active, rinse-active or cleaning-active preparations of a particular composition. According to the invention, however, it is preferred that several, usually at least two, washing active, rinse active or cleaning active preparations of different composition in the detergent, detergent or detergent portions are included. The composition may be (qualitatively) different with regard to the concentration of the individual components of the washing-active, rinsing-active or cleaning-active preparation (quantitatively) and / or with regard to the nature of the individual components of the washing-active, rinsing-active or cleaning-active preparation. It is particularly preferred that the components are adapted in terms of nature and concentration to the tasks that have to meet the detergent, detergent or detergent partial portions in the washing, rinsing or cleaning process.

In the context of the present invention, the term "wash-active preparation" or "rinse-active preparation" or "cleansing-active preparation" is understood as meaning preparations, materials or components of all conceivable ones understood with a washing, rinsing or cleaning process relevant substances. These are primarily the actual detergents, dishwashing detergents or cleaning agents with their individual components explained in the further course of the description. These include active ingredients such as surfactants (anionic, nonionic, cationic and amphoteric surfactants), builders (inorganic and organic builders), bleaches (such as peroxy bleach and chlorine bleach), bleach activators, bleach stabilizers, bleach catalysts, enzymes, specialty polymers ( for example, those with cobuilder properties), grayness inhibitors, dyes and fragrances (perfumes), without the term being limited to these substance groups.

However, constituents of such "wash-active preparations (materials, components)", "dishwashing preparations (materials, components)" or "cleaning-active preparations (materials, components)" may also be washing auxiliaries, rinse aids and cleaning aids, examples of which are optical brighteners, UV protective substances Soil repellents, ie polymers which counteract re-soiling of fibers or hard surfaces, as well as silver protectants are also considered laundry-active or dishwashing active preparations.

The detergent, rinse or detergent portion of the invention comprises a wholly or partially water-soluble wrapper. The shape of the envelope according to the invention is not limited to specific forms. Basically, all Archimedean and Platonic bodies, ie three-dimensional shaped bodies, come into question as forms of envelopment. Examples of the shape of the wrapper are capsules, cubes, spheres, ovoid moldings, cuboids, cones, rods or bags. Also hollow body with one or more compartments, as described in the co-pending patent application no. DE 100 33 827.5 entitled "compartment hollow body", are suitable as a sheath for the washing active, rinse or cleaning active materials. In preferred embodiments of the invention, the wrappers are in the form of capsules, such as those used in pharmacy for the administration of drugs, spheres or bags. The latter are preferably welded or glued on at least one side, wherein the adhesive used in particularly preferred embodiments of the invention is an adhesive that is water-soluble.

Suitable materials for the completely or partially water-soluble coating are in principle all materials in question, which under the given conditions of a washing process, rinsing or cleaning process (temperature, pH, concentration of detergent components) in aqueous phase can completely or partially dissolve. The polymer materials may particularly preferably the groups (optionally partially acetalized) polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, in particular modified starches, and mixtures (polymer blends, composites, co-extrudates, etc.) of the materials mentioned To belong. Particularly preferred are gelatin and polyvinyl alcohols and the two materials mentioned in each case in combination with starch or modified starch. There are also inorganic salts and mixtures thereof as materials for the at least partially water-soluble envelope in question.

Polyvinyl alcohols (abbreviated PVAL) are polymers of the general structure

[-CH ₂ -CH (OH) -] _n

in small quantities also structural units of the type

[-CH ₂ -CH (OH) -CH (OH) -CH ₂ -]

contain. Since the corresponding monomer (vinyl alcohol) is not stable in free form, polyvinyl alcohols are obtained via polymer-analogous reactions by hydrolysis, in particular by alkali-catalyzed transesterification of polyvinyl acetates with alcohols, preferably with methanol. By these technical methods, PVAL are also available which contain a predetermined residual amount of acetate groups.

Commercially available PVAL (eg Mowiol® grades from Hoechst) are commercially available as white-yellowish powders or granules with degrees of polymerization in the range of about 500 to 2500 (corresponding to molar masses of about 20,000 to 100,000 g / mol) and have different degrees of hydrolysis, for example 98 to 99 or 87 to 89 mol%. So you are partially hydrolyzed polyvinyl acetates with a residual content of acetyl groups, for example, about 1 to 2 or 11 to 13 mol%.

The water solubility of PVAL can be reduced by aftertreatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values. Films made of PVAL are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

Examples of suitable water-soluble PVAL films are the PVAL films available under the name "SOLUBLON®" from Syntana Handelsgesellschaft E. Harke GmbH & Co. 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. Commercially available PVP have molecular weights in the range of about 2,500 to 750,000 g / mol and are available as white, hygroscopic powders or 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), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of gelatin is broadly similar to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as water-soluble coating material is extremely widespread, especially in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin has little use because of its high price compared to the polymers mentioned above.

Also preferred within the scope of the present invention are detergent, detergent and cleaner portions whose packaging consists of at least partially water-soluble film of at least one polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methylcellulose and mixtures thereof.

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). There are still few Amounts of lipids, phosphoric acid and cations. 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 glucose. 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 bound by 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.

Preferred casings of at least partially water-soluble film consist of a polymer having a molecular weight between 5,000 and 500,000 g / mol, preferably between 7,500 and 250,000 g / mol and in particular between 10,000 and 100,000 g / mol. The water-soluble film forming the coating has a thickness of from 1 to 300 .mu.m, preferably from 2 to 200 .mu.m, particularly preferably from 5 to 150 .mu.m and in particular from 10 to 100 .mu.m.

These water-soluble films can be produced by various production methods. Blow molding, calendering and casting processes should be mentioned here in principle. In a preferred method, the films are blown starting from a melt with air through a mandrel to a hose. In the case of the calendering process, which is likewise one of the preferred production processes, the raw materials plasticized by suitable additives are atomized to form the films. In particular, it may be necessary to attach drying to the atomizations. In the casting process, which is also one of the preferred production methods, an aqueous polymer preparation is placed on a heatable drying roller, after the evaporation of the water is optionally cooled and the film is peeled off as a film. Optionally, this film is additionally powdered before or during the removal.

As materials for the coating of the detergent, detergent or cleaning agent portion according to the invention, organic and / or inorganic salts are also suitable. Examples of these are salts which can be formed into a coating, for example by crystallization, compression, compression or other suitable processes, and which dissolve under the conditions of the washing, rinsing or cleaning process in sufficient time in water or aqueous liquor. Ideally, in particularly preferred embodiments of the invention, those salts are used which can also assume further functions in a washing, rinsing or cleaning process.

According to the invention, an embodiment is preferred in accordance with which the wrapper is water-soluble as a whole, ie completely dissolves when used as intended during washing, rinsing or cleaning, for example during machine washing, rinsing or cleaning, when the conditions provided for dissolution have been reached. Particularly preferred as completely water-soluble coatings z. B. gelatin capsules, advantageously of soft gelatin, or bags of (optionally partially acetalized) PVAL or balls of gelatin or (optionally partially acetalized) PVAL or of one or more organic and / or inorganic salts, preferably spheres of soft gelatin. The essential advantage of this embodiment is that the sheath within a practically relevant short time - as a non-limiting example can be a few seconds to 5 min - under exactly defined conditions in the wash liquor, wash liquor or cleaning liquor at least partially dissolves and thus accordingly meets the requirements of the wrapped contents, ie the wash-active, rinse-active or cleaning-active material or several materials in the fleet.

In another embodiment of the invention, which is also preferred because of its advantageous properties, the water-soluble coating comprises regions which are less soluble or not water-soluble or only water-soluble at relatively high temperatures and regions which are readily soluble in water or soluble in water at low temperature. In other words, the coating does not consist of a uniform material that has the same water solubility in all areas, but of materials of different water solubility. On the one hand, areas of good water solubility are to be distinguished from areas with less good water solubility, with poor or even absent water solubility or areas in which the water solubility reaches the desired value only at a higher temperature or only at a different pH value or only when the electrolyte concentration has changed achieved, on the other hand. This may result in certain areas of the enclosure becoming disengaged under normal conditions of use, while other areas remain intact. Thus, an envelope provided with pores or holes is formed, into which water and / or liquor can penetrate, which can dissolve washing-active, rinse-active or cleaning-active ingredients and remove them from the casing. In the same way, wrapping systems in the form of multi-chamber bags or in the form of nested hollow bodies (eg balls: "onion system") can also be provided. Thus, controlled release systems of the detergent-active, rinse-active or cleaning-active ingredients can be produced.

To form such systems, the invention is not limited. Thus, wraps can be provided in which a uniform polymeric material comprises small areas of incorporated compounds (for example, salts) which are more rapidly soluble in water than the polymeric material. On the other hand, several polymer materials with different water solubility can be mixed (polymer blend); so that the faster soluble polymer material is disintegrated faster under defined conditions by water or the liquor than the slower soluble.

It is in accordance with a particularly preferred embodiment of the invention that the less readily water-soluble areas or areas which are not water-soluble or areas of the enclosure which are only water-soluble at higher temperatures are areas of a material which is essentially chemically that of the readily water-soluble areas or at lower temperature water-soluble areas, but has a higher layer thickness and / or a modified degree of polymerization of the same polymer and / or has a higher degree of crosslinking the same polymer structure and / or a higher degree of acetalization (PVAL) and / or a content of water-insoluble salt components and / or has a content of a water-insoluble polymer. Even taking into account the fact that the wrapper does not completely dissolve, it is possible to provide detergent, detergent or cleaner portions according to the invention which have advantageous properties in the release of the wash-active, rinse-active or cleaning-active components into the respective liquor.

A further embodiment of the invention, which is likewise preferred on account of the advantageous properties, provides detergent, detergent or cleaning agent portions in which the completely or partially water-soluble coating contains one or more washing-active, rinse-active or cleaning-active components, in particular those components which are incorporated in US Pat Detergents, detergents or cleaning agents are present in small quantities. Suitable components include, for example, bleaches or at least portions thereof, bleach activators, enzymes, dyes, fragrances, optical brighteners and / or soil repellents, but also other components of the detergent, dishwashing or cleaning agent portions.

According to the invention, the completely or partially water-soluble coating of the detergent, detergent or cleaner portions according to the invention completely surrounds a liquid-based formulation of at least one wash-active, rinse-active or cleaning-active material. In the context of the present invention, the term "liquid-based" is understood to mean that the formulation of a wash-active, rinse-active or cleaning-active material or several wash-active, rinse-active or cleaning-active materials, at least during production, is a formulation prepared on the basis of liquid components will be explained in detail below, even if this formulation contains in a larger amount of solid components (suspended or dispersed) and / or increases in viscosity after preparation in the absence of shear, for example by at least 10%, preferably by at least 50%, more preferably by at least 100%, so that it can no longer be called "liquid" in the narrower sense.

Liquid-based formulations of detergent, rinse or detergent portions according to the invention completely surrounded by the wraps can be either low-water formulations or substantially anhydrous formulations. Low-water formulations comprise water as an essential component in an amount of, for example, ≤15% by weight, based on the weight of all components of the formulation. On the other hand, non-aqueous or essentially anhydrous formulations comprise water only in small amounts, preferably in amounts of <5% by weight, more preferably in amounts of from 1 to 3% by weight, based in each case on the weight of all components of the formulation, non-aqueous or substantially anhydrous formulations being particularly preferred.

For the low-water as well as the anhydrous systems, the formulations contain surfactant (s) using anionic, nonionic, cationic and / or amphoteric surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants, the proportion of nonionic surfactants should be greater than the proportion of anionic surfactants. The total surfactant content of the detergent, dishwashing or cleaning agent portions is preferably above 30% by weight, based on the total liquid detergent.

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 from coconut, palm, tallow or oleyl alcohol and on average 2 to 8 moles of EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols containing 3 EO, 4 EO or 7 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 7 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. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, it is also possible to use mixed alkoxylated nonionic surfactants in which EO and PO units are not randomly distributed but statistically distributed. Such products are available by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

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

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters as they are for example, in Japanese Patent Application JP 58/217598, or which are preferably prepared according to the method described in International Patent Application WO 90/13533.

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

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z¹] 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 Zukkers 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,

in which RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z ¹ ] is a linear or branched polyhydroxyalkyl radical 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 Alkylenrest oder einen Arylenrest 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 [Z²] 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 II,

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

[Z ² ] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides according to the teaching of international application WO 95/07331, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

The content of preferred formulations of nonionic surfactants is 5 to 95 wt .-%, preferably 10 to 60 wt .-% and in particular 15 to 50 wt .-%, each based on the total agent.

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

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. From the washing are the C ₁₂ -C ₁₆ alkyl sulfates and C _12- C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates of preferably. Also 2,3-alkyl sulfates, which are prepared for example according to US Patents 3,234,258 or 5,075,041 and 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 radical which is derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (description see above). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases such as mono-, di- or triethanolamine, monoisopropanolamine or triisopropanolamine. The anionic surfactants are preferably present in the form of their ammonium salts, in particular their ammonium salts with at least one long-chain alkyl radical or alkanolamine radical on the ammonium nitrogen.

The content of preferred detergent, detergent or cleaner portions of anionic surfactants is 5 to 95 wt .-%, preferably 10 to 60 wt .-% and in particular 15 to 50 wt .-%, each based on the total portion.

In addition to the one or more surfactants, the detergent, rinse or detergent portions of the present invention, whether hydrous or low in water or substantially anhydrous, may contain other ingredients that further the performance and / or aesthetics of the composition improve. In the context of the present invention, preferred detergent, rinse or cleaning agent portions in addition to the surfactant (s) comprise one or more substances from the group of builders, bleaches, bleach activators, enzymes, electrolytes, nonaqueous solvents, pH adjusters, Fragrances, perfume carriers, fluorescers, dyes, hydrotropes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing auxiliaries, repellents and impregnating agents, swelling agents and Slip Resistant and UV absorber.

Suitable builders which may be present in the detergent, dishwashing or cleaning agent portions according to the invention are, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

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

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

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula

nNa ₂ O • (1-n) K ₂ O • Al ₂ O ₃ • (2 - 2.5) SiO ₂ • (3.5-5.5) H ₂ O

can be described. The zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols having 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated Isotridecanoles. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates.

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the detergent portions. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran, as well as triethylacetyl citrate (TEAC).

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the wash-active preparations for the portions according to the invention. These substances are bleach-enhancing Transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo-salene complexes or -carbonylkomplexe. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

Suitable enzymes for use in detergent, detergent or cleaner portions are, in particular, those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. The hydrolases contribute, for example, in the laundry for the removal of stains such as proteinaceous, fat or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. These are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest for the detergent, detergent or cleaner portions of the invention. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes may be adsorbed to carriers or embedded in encapsulating substances to protect them from premature decomposition, or may also be embedded in the water-soluble encapsulants of the present invention. The proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.12 to about 2 wt .-%.

As electrolytes from the group of inorganic salts, a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl ₂ in the agents according to the invention is preferred. The proportion of electrolytes in the inventive compositions is usually 0.5 to 5 wt .-%.

Non-aqueous solvents which can be used in the detergent, detergent or cleaner portions according to the invention are derived, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the concentration range indicated. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane- or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether , Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, Propylene glycol t-butyl ether, N-butoxypropoxypropanol and mixtures of these solvents. Non-aqueous solvents may be used in the inventive detergent, detergent or cleaner portions in amounts of between 0.5 and 90% by weight, but preferably below 80% by weight and in particular below 70% by weight.

In order to bring the pH of the agents according to the invention in the desired range, the use of pH adjusting agents may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited. Usually, the amount of these adjusting agents does not exceed 2% by weight of the total formulation.

In order to improve the aesthetic impression of the detergent, detergent or cleaner portions according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the formulation and to light and no pronounced substantivity to textile fibers so as not to stain them.

Suitable foam inhibitors which can be used in the detergent, dishwashing or cleaning agent portions according to the invention are, for example, soaps, paraffins or silicone oils, which may optionally be applied to carrier materials.

Suitable anti-redeposition agents, which are also referred to as "soil repellents", are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on nonionic cellulose ethers, and the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred among the compounds mentioned are the sulfonated derivatives of the phthalic and terephthalic acid polymers.

Optical brighteners (so-called "whiteners") can be added to the detergent portions according to the invention in order to eliminate graying and yellowing of the treated textiles. These fabrics impinge on the fiber and cause lightening and fake bleaching by converting invisible ultraviolet radiation into visible longer wavelength light, emitting ultraviolet light absorbed from the sunlight as faint bluish fluorescence, and pure yellow with the yellowed or yellowed wash White results. Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid imides, benzoxazole , Benzisoxazole and benzimidazole systems as well as heterocyclic substituted pyrene derivatives. The optical brighteners are usually used in amounts between 0.05 and 0.3 wt .-%, based on the formulation.

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatine, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful. However, preference is given to using cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the compositions. Grayness inhibitors based on optionally modified polyacrylates and their copolymers are also suitable according to the invention.

Since textile fabrics, in particular of Reyon®, rayon, cotton and their mixtures, can tend to wrinkle, because the individual fibers are sensitive to bending, buckling, pressing and squeezing transversely to the fiber direction, detergents of the invention may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

For controlling microorganisms, detergent, detergent or cleaner portions of the invention may contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, and the compounds according to the invention can be completely dispensed with.

In order to prevent undesirable changes to the detergent, detergent or cleaning agent portions and / or the treated fabrics caused by oxygen and other oxidative processes, the formulations may contain anti-oxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

An increased wearing comfort can result from the additional use of antistatic agents, which are additionally added to the detergent portions according to the invention. Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges. External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. External antistatic agents are described, for example, in patent applications FR 1,156,513, GB 873,214 and GB 839,407. The lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed herein are useful as antistatics for textiles or as additives to laundry detergents, with the additional benefit of providing a softening effect.

To improve the water absorbency or the rewettability of the treated textiles and to facilitate the ironing of the treated textiles, for example, silicone derivatives can be used in the detergent portions according to the invention. These additionally improve the rinsing behavior of the portions according to the invention by their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones are in the range between 100 and 100,000 mPas at 25 ° C., it being possible to use the silicones in amounts of between 0.2 and 5% by weight, based on the total agent.

Finally, the agents according to the invention may also contain UV absorbers which are absorbed by the treated textiles and improve the light resistance of the fibers. Links, which have these desired properties are, for example, the active by non-radioactive deactivation compounds and derivatives of benzophenone with substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.

In order to avoid the catalyzed by heavy metals decomposition of certain detergent ingredients, substances that complex heavy metals can be used. Suitable heavy metal complexing agents are, for example, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or of nitrilotriacetic acid (NTA) or of their derivatives or derivatives and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.

A preferred class of complexing agents are the phosphonates, which are in preferred detergent, detergent or detergent portions in amounts of 0.01 to 1.5 wt .-%, preferably 0.02 to 1 wt .-% and in particular of 0 , 03 to 0.5 wt .-% are included. These preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2 , 4-tricarboxylic acid (PBS-AM), which are used mostly in the form of their ammonium or alkali metal salts.

In further preferred embodiments of the detergent, rinse or detergent portions of the invention, the low-water formulation comprises a thickening system. This may consist of one or may consist of several component (s). Regularly, a component is a polymeric thickener. These high molecular weight substances, which are also called swelling agents and absorb liquids, swell up and finally pass into viscous true or colloidal solutions, originate from the groups of natural polymers, the modified natural polymers and the fully synthetic polymers.

Naturally derived polymers which are used as thickening agents are, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein.

Modified natural products come mainly from the group of modified starches and celluloses, examples include carboxymethyl cellulose and cellulose ethers, hydroxyethyl and propyl cellulose and core flour ethers.

A large group of thickeners, which find wide use in a variety of applications, are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.

Thickeners from the mentioned classes of substances are commercially widely available and are described, for example, under the trade names Acusol® -820 (methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral® GT -282-S (alkyl polyglycol ether, Akzo), Deuterol® polymer-11 (dicarboxylic acid copolymer, Schöner GmbH), Deuteron®-XG (anionic heteropolysaccharide based on β-D-glucose, D-manose, D-glucuronic acid, more beautiful GmbH), Deuteron®-XN (nonionic polysaccharide, Schöner GmbH), Dicrylan®-Verdicker-O (ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA®-81 and EMA® -91 (ethylene oxide). Maleic anhydride copolymer, Monsanto), thickener QR-1001 (polyurethane emulsion, 19 to 21% in water / diglycol ether, Rohm & Haas), Mirox®-AM (anionic acrylic acid-acrylic ester copolymer dispersion, 25% in Wasser, Stockhausen), SER-AD-FX-1100 (hydrophobic urethane polymer, Servo Delden), Shellflo® -S (high molecular weight polysaccharide stabilized with formaldehyde, Shell) and Shellflo®-XA (xanthan biopolymer stabilized with formaldehyde, Shell).

Preferred low-water formulations contain as a component of the thickening system 0.01 to 4% by weight, preferably 0.1 to 3% by weight and in particular 0.4 to 1.5% by weight, of a polysaccharide.

A preferred polymeric polysaccharide thickener is xanthan gum, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions, and a molecular weight from 2 to 15 million g / mole. Xanthan is formed from a chain of β-1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum.

It is particularly advantageous to use xanthans and modified xanthans because of their high acid stability and oxidation stability.

Xanthan can be described by the following formula:

Preferred aqueous formulations of the detergent, detergent or cleaner portions contain as component a) of the thickening system, in each case based on the total agent, 0.01 to 4 wt .-%, preferably 0.1 to 3 wt .-% and in particular 0.4 to 1.5% by weight, xanthan.

Other components of the thickening system are described in the prior art, for example in the publication WO 99/27051: There, the second component of the thickening system is a boron compound, which is used in amounts of 0.5 to 7 wt .-%. Examples of boron compounds useful in the present invention are boric acid, boric oxide, alkali metal borates such as ammonium, sodium and potassium ortho-, meta- and pyroborates, borax in its various stages of hydration and polyborates such as alkali metal pentaborates. Organic boron compounds such as esters of boric acid can also be used. Preferred liquid detergent portions contain from 0.0001 to 5 wt .-%, preferably 0.001 to 4 wt .-% and in particular 0.01 to 3 wt .-% of a boron compound.

As a third component of the thickening system, the detergent, dishwashing or cleaning agent portions according to the invention may contain from 0 to 20% by weight of a complexing agent. In the context of the present application, the term complexing agent is understood to mean low molecular weight hydroxycarboxylic acids, such as citric acid, tartaric acid, malic acid, or gluconic acid or salts thereof.

Particularly preferred liquid detergent portions contain as component c) of the thickening system citric acid or sodium citrate, wherein liquid detergent portions are preferred, the 1.0 to 15.0 wt .-%, preferably 2.0 to 10.0 wt .-% and in particular 2.0 to 7.0 wt .-%, sodium citrate.

• a) 0,2 bis 5 Gew.-% eines Polyurethans oder eines modifizierten Polyacrylats,
• b) 0,5 bis 7 Gew.-% einer Borverbindung sowie
• c) 1 bis 8 Gew.-% eines Komplexbildners,

wobei die Komponenten (b) und (c) qualitativ und gegebenenfalls auch quantitativ mit den Komponenten des oben beschriebenen Verdickungssystems übereinstimmen.Another thickening system is described in the publication WO 99/28430 and consists of (in each case based on the formulation of the detergent, detergent or cleaning agent portion)

• a) 0.2 to 5 wt .-% of a polyurethane or a modified polyacrylate,
• b) 0.5 to 7 wt .-% of a boron compound and
• c) 1 to 8% by weight of a complexing agent,

wherein the components (b) and (c) qualitatively and optionally also quantitatively agree with the components of the thickening system described above.

The first component of the thickening system is a polyurethane or a modified polyacrylate, which is used in amounts of 0.2 to 5 wt .-%, based on the total portion.

in der R³ für einen niedermolekularen oder polymeren Diol-Rest, R⁴ für eine aliphatische oder aromatische Gruppe und n für eine natürliche Zahl steht. R³ ist dabei vorzugsweise eine lineare oder verzweigte C_2-12-Alk(en)ylgruppe, kann aber auch ein Rest eines höherwertigen Alkohols sein, wodurch quervernetzte Polyurethane gebildet werden, die sich von der oben angegebenen Formel III dadurch unterscheiden, daß an den Rest R³ weitere ―O-CO-NH-Gruppen gebunden sind.Polyurethanes are prepared by polyaddition from dihydric and higher alcohols and isocyanates and are described by the general formula III:

in which R ^{3 is} a low molecular weight or polymeric diol radical, R ^{4 is} an aliphatic or aromatic group and n is a natural number. R ³ is preferably a linear or branched C _2-12 -alk (en) yl group, but may also be a radical of a higher-valent alcohol, whereby crosslinked polyurethanes are formed, which differ from the formula III given above in that the Rest R ³ more -O-CO-NH groups are bonded.

Technically important PU are from polyester and / or polyether diols and, for example, from 2,4- or 2,6-toluene diisocyanate (TDI, R ⁴ = C ₆ H ₃ -CH ₃ ), 4,4'-methylenedi (phenyl isocyanate) (MDI, R ⁴ = C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) or hexamethylene diisocyanate [HMDI, R ⁴ = (CH ₂ ) ₆ ].

Commercially available polyurethane-based thickeners are known, for example, under the names Acrysol® PM 12 V (3-5% modified starch mixture and 14-16% PUR resin in water, Rohm & Haas), Borchigel® L75-N (nonionic polyurethane Dispersion, 50% in water, Borchers), Coatex® BR-100-P (PUR dispersion, 50% in water / butylglycol, Dimed), Nopco® DSX-1514 (PUR dispersion, 40% in water / Butyltriglycol, Henkel-Nopco), thickener QR 1001 (20% PUR emulsion in water / digyl ether, Rohm & Haas) and Rilanit® VPW-3116 (PUR dispersion, 43% in water, Henkel).

Preferred detergent, detergent or cleaning agent portions contain 0.01 to 4 wt .-%, preferably 0.1 to 3 wt .-% and in particular 0.5 to 1.5 wt .-% of a polyurethane.

in der R⁵ für H oder einen verzweigten oder unverzweigten C₁- bis C₄-Alk(en)ylrest, X für N-R⁷ oder O, R⁶ für einen gegebenenfalls alkoxylierten verzweigten oder unverzweigten, eventuell substituierten C₈- bis C₂₂-Alk(en)ylrest, R⁷ für H oder R⁶ und n für eine natürliche Zahl steht. Allgemein sind solche modifizierten Polyacrylate Ester oder Amide von Acrylsäure bzw. einer α-substituierten Acrylsäure. Unter diesen Polymeren bevorzugt sind solche, bei denen R³ für H oder eine Methylgruppe steht. Bei den Polyacrylamiden (X = N-R⁵) sind sowohl einfach (R⁵ = H) als auch zweifach (R⁵ = R⁴) N-substituierte Amidstrukturen möglich, wobei die beiden Kohlenwasserstoffreste, die an das N-Atom gebunden sind, unabhängig voneinander aus gegebenenfalls alkoxylierten verzweigten oder unverzweigten C₈- bis C₂₂-Alk(en)ylresten ausgewählt werden können. Unter den Polyacrylestern (X = O) sind solche bevorzugt, in denen der Alkohol aus natürlichen oder synthetischen Fetten bzw. Ölen gewonnen wurde und zusätzlich alkoxyliert, vorzugsweise ethoxyliert ist. Bevorzugte Alkoxlierungsgrade liegen zwischen 2 und 30, wobei Alkoxylierungsgrade zwischen 10 und 15 besonders bevorzugt sind.Optionally modified polyacrylates which can be used in the context of the present invention are derived, for example, from acrylic acid or methacrylic acid and can be described by the general formula IV:

in the R ^{5 is} H or a branched or unbranched C ₁ - to C ₄ -alk (en) yl radical, X is NR ⁷ or O, R ^{6 is} an optionally alkoxylated branched or unbranched, possibly substituted C ₈ - to C ₂₂ - Alk (en) yl radical, R ^{7 is} H or R ⁶ and n is a natural number. In general, such modified polyacrylates are esters or amides of acrylic acid or of an α-substituted acrylic acid. Preferred among these polymers are those in which R ^{3 is} H or a methyl group. In the polyacrylamides (X = NR ⁵ ), both simple (R ⁵ = H) and also doubly (R ⁵ = R ⁴ ) N-substituted amide structures are possible, the two hydrocarbon radicals which are bonded to the N atom being independent of one another from optionally alkoxylated branched or unbranched C ₈ - to C ₂₂ -alk (en) ylresten can be selected. Among the polyacrylic esters (X = O), preference is given to those in which the alcohol was obtained from natural or synthetic fats or oils and additionally alkoxylated, preferably ethoxylated. Preferred alkoxylation levels are between 2 and 30, with degrees of alkoxylation between 10 and 15 being particularly preferred.

Since the polymers which can be used are technical compounds, the designation of the radicals bound to X represents a statistical mean value which, in individual cases, can vary with regard to chain length or degree of alkoxylation. Formula IV only gives formulas for idealized homopolymers. Can be used in the frame However, the present invention also copolymers in which the proportion of monomer units satisfying the formula IV, at least 30 wt .-% is. For example, it is also possible to use copolymers of modified polyacrylates and acrylic acid or salts thereof which still have acidic H atoms or basic -COO ^- groups.

in der R⁶ für einen vorzugsweise unverzweigten, gesättigten oder ungesättigten C₈- bis C₂₂-Alk(en)ylrest, R⁸ und R⁹ unabhängig voneinander für H oder CH₃ stehen, der Polymerisationsgrad n eine natürliche Zahl und der Alkoxylierungsgrad a eine natürliche Zahl zwischen 2 und 30, vorzugsweise zwischen 10 und 20 ist. R⁶ ist dabei vorzugsweise ein Fettalkoholrest, der aus natürlichen oder synthetischen Quellen gewonnen wurde, wobei der Fettalkohol wiederum bevorzugt ethoxyliert (R⁸= H) ist.In the context of the present invention preferably used modified polyacrylates are polyacrylate-polymethacrylate copolymers which satisfy the formula IVa

in which R ^{6 is} a preferably unbranched, saturated or unsaturated C ₈ - to C ₂₂ -alk (en) yl radical, R ⁸ and R ⁹ independently of one another are H or CH ₃ , the degree of polymerization n is a natural number and the degree of alkoxylation a natural number is between 2 and 30, preferably between 10 and 20. R ⁶ is preferably a fatty alcohol residue which has been obtained from natural or synthetic sources, the fatty alcohol in turn preferably ethoxylated (R ⁸ = H).

Products of the formula Iva are commercially available, for example, under the name Acusol® 820 (Rohm & Haas) in the form of 30% strength by weight dispersions in water. In said commercial product, R ^{6 is} a stearyl radical, R ⁸ is a hydrogen atom, R ⁹ is H or CH ₃ , and the degree of ethoxylation a is 20.

Preferred detergent, detergent or cleaner portions contain, based on the total agent, 0.01 to 4 wt .-%, preferably 0.1 to 3 wt .-% and in particular 0.5 to 2.0 wt. % of a modified polyacrylate of formula IV.

Other thickening systems are conceivable and can be used alone or in mixtures with any other systems within the scope of the invention.

In those instances where the formulation of the wash-active, rinse-active or cleaning-active materials is a low-water or anhydrous formulation, this low-water or anhydrous formulation preferably comprises one or more anionic surfactants (e) and / or one or more nonionic surfactants to adjust their rheological parameters ( e) comprehensive material. In a particularly preferred embodiment, the anionic surfactant (s) is / are selected from the group of the sulfonates and sulfates and mixtures thereof and / or the nonionic surfactant (s) selected from the group of alkoxylated alcohols, alkoxylated fatty acid alkyl esters, alkyl glycosides and their mixtures. The above connection groups have been explained in detail above.

In water-poor or essentially anhydrous formulations of washing-active, rinsing-active or cleaning-active materials which are contained in the detergent, dishwashing or cleaning agent portions according to the invention can in a preferred embodiment as anionic surfactants, optionally in the presence of further anionic and / or not ionic surfactants which use isopropanolammonium ether sulphates according to the article "U. Schoenkaes et al., Water-free Alcohol Ether Sulfates - New High-active Surfactants for Superconcentrated Detergent Formulations" already cited above, of which monoisopropanolammonium ether sulphate (MIPA ether sulphate) and triisopropanol ammonium ether sulphate (TIPA ether sulfate) are particularly preferred because of their excellent anionic surfactant properties.

Advantageously, polymers with thickening effect are used in low-water or substantially anhydrous systems, which can also be used as associative thickener. These may be, for example (but not limited to) acrylate based polymers, e.g. T. may have relatively high molecular masses in the range of> 1,000,000 g / mol. They are used in amounts of from 0.01 to 10% by weight, for example in amounts of from 0.5 to 4% by weight, in the wash-active, rinse-active or cleaning-active formulations. Suitable products are, for example, the products marketed by Rohm & Haas under the name Acusol ^R , which are predominantly polyacrylates with different alkylation or crosslinking or hydrophobically modified nonionic polyols, or the products marketed by BF Goodrich under the name Carbopol ^R , which Polyacrylates or copolymers of acrylic acid and alkylated (preferably C ₅ - to C ₁₀ -alkylated) acrylic acids, or the products marketed by BF Goodrich under the name Pemulen ^R , the high molecular weight acrylic acid copolymers of the type Acry-lat / C ₁₀ - to C ₃₀ -alkyl acrylate crosspolymer are. In addition to the aforementioned associative thickeners, polyacrylate or polyurethane thickeners can also be used in anhydrous or essentially anhydrous systems which offer the possibility of adjusting the viscosity via a different mechanism of action (ie not associative) in the presence of small amounts of water.

Furthermore, according to the invention, detergent, detergent or cleaner portions in which the liquid-based formulations exhibit non-Newtonian flow behavior preferably exhibit thixotropic or pseudoplastic flow behavior. In particularly preferred embodiments of the portions, the liquid-based formulations have a low viscosity during production, for example a viscosity in the range of 10 to 50 mPa · s, and the liquid-based formulations have a higher viscosity during storage, etc., for example in the range of 10 to 100,000 mPa · s, preferably 100 to 20,000 mPa · s, more preferably a viscosity in the range of 200 to 10,000 mPa · s. In the case of clearly present systems, the viscosity may be lower than in systems in which solid components (which are visually noticeable in a cloudiness) are present; The latter usually become thicker during storage ("setting") and may even become pasty.

Detergent, detergent or cleaning agent portions according to the present invention, which are present for example in capsule form, in spherical form or in the form of bags, have a high mechanical stability (depending on the particular shape), which results in that the portions much less likely to burst or burst. The mechanical stability can be measured according to per se known (and described in more detail in the examples) method as compression resistance. This is generally defined as the resistance that the molded article opposes to a stamping pressure applied to it (under standardized conditions) and, as stated above, is dependent on the shape of the portion, but also on the strength of its ingredients, on temperature and optionally of further parameters. Detergent, detergent or detergent portions in capsule form according to the invention have a compression resistance of from 10 to 10 ⁵ at 23 ° C. Spherical detergent, rinse or detergent portions in accordance with the invention have a crush resistance of 10 to 10 ⁵ N at 23 ° C and more preferably from 10 ² to 10 ⁴ N at 23 ° C. Detergent, detergent or detergent portions in the form of sachets according to the invention have an upset resistance of from 10 to 10 ⁵ N at 23 ° C and even more preferably from 10 ² to 10 ⁴ N at 23 ° C.

The liquid-based formulations of at least one wash-active, rinse-active or cleaning-active material contained in the wraps of the detergent, rinse or detergent portion may be clear solutions of one or more wash-active, rinse-active or cleaning-active component (s) or microemulsions. However, it is also possible according to the invention that the liquid-based formulations contain one or more solids suspended or dispersed, in particular when low-water or substantially anhydrous formulations are used. This is an advantage over the prior art because water-sensitive components of washing-active, rinse-active or cleaning-active materials can be stably and evenly distributed in the liquid phase and problems with activity reduction do not occur.

The process for the preparation of detergent, detergent or detergent portions is subject to no restrictions in principle. It is usually carried out by simply mixing the ingredients in stirred tanks, optionally present water, non-aqueous solvents and liquid surfactant (s) are suitably presented and the other ingredients are added in portions. Separate heating in the preparation is not required, if desired, the temperature of the mixture should not exceed 80 ° C.

• (a) wenigstens eine flüssige Komponente der flüssig-basierten Formulierung mit nicht-newtonischen Fließverhalten wenigstens eines waschaktiven, spülaktiven oder reinigungsaktiven Materials vorlegt und diese unter Aufbringen einer bestimmten Scherkraft bewegt;
• (b) gegebenenfalls eine oder mehrere weitere flüssige Komponente(n) der flüssig-basierten Formulierung zusetzt;
• (c) in die so hergestellte flüssige Phase gegebenenfalls eine oder mehrere feste Komponente(n) der flüssig-basierten Formulierung einarbeitet und gegebenenfalls anschließend eine oder mehrere weitere feste und/oder flüssige Komponente(n) zusetzt und dabei eine bestimmte Scherkraft beibehält; und
• (d) gegebenenfalls die nach Schritt (c) hergestellte flüssige Mischung sofort in die Umhüllung mit einer Dicke von 1 bis 300 µm einbringt und diese um die flüssig-basierte Formulierung verschließt.

In a preferred embodiment of the invention, the process comprises the preparation of a detergent, rinse or detergent portion which comprises a wholly or partially water-soluble casing having a thickness of 1 to 300 μm in capsule form, in spherical form or in the form of a bag in turn completely surrounds a liquid-based formulation having non-Newtonian flow behavior of at least one wash-active, rinse-active or cleaning-active material, the steps of

• (A) at least one liquid component of the liquid-based formulation with non-Newtonian flow behavior of at least one washing active, active washing or cleaning active material and moves them under application of a certain shearing force;
• (b) optionally adding one or more further liquid component (s) to the liquid-based formulation;
• (c) optionally incorporating one or more solid component (s) of the liquid-based formulation into the liquid phase thus prepared, and then optionally adding one or more further solid and / or liquid component (s) while maintaining a certain shear force; and
• (d) optionally introducing the liquid mixture prepared according to step (c) immediately into the covering with a thickness of 1 to 300 μm and closing it around the liquid-based formulation.

Alternatively, the liquid mixture prepared according to step (c) can be introduced into the coating only with a time lag and closed with the liquid-based formulation.

Of particular advantage, the particular shear force applied to the liquid-based formulation of at least one detergent-active, rinse-active or cleaning-active material to incorporate the remaining (particularly solid) components into this formulation, which is referred to herein as the shear rate, can be> 0 , 01 min ^-1 , preferably in the range of 0.1 to 50,000 min ^-1 , more preferably in the range of 5 to 20,000 min ^-1 , even more preferably in the range of 30 to 10,000 min ^-1 .

• (a) eine Waschmittel-Portion nach der obigen detaillierten Beschreibung in die Waschmaschine, insbesondere in die Einspülkammer oder in die Waschtrommel, eingibt;
• (b) über die Zugabe von Wasser einen Kontakt zwischen der Waschmittel-Portion und der Waschflotte herstellt;
• (c) die gewünschten Waschbedingungen einstellt; und
• (d) bei Eintreten der gewünschten Bedingungen das/die waschaktive(n) Material(ien) der Waschmittel-Portion in die Waschflotte freisetzt und diese mit dem zu waschenden Gut in Kontakt bringt.

The invention also relates to a washing process, in particular to a method of machine washing in a commercial washing machine, comprising the steps of

• (A) a detergent portion according to the above detailed description in the washing machine, in particular in the Einspülkammer or in the washing drum, inputs;
• (B) makes contact between the detergent portion and the wash liquor via the addition of water;
• (c) stops the desired wash conditions; and
• (d) Upon entering the desired conditions, the wash-active material (s) of the detergent portion releases into the wash liquor and brings them into contact with the material to be washed.

• (a) eine Spülmittel-Portion nach der obigen detaillierten Beschreibung in die Spülmaschine, insbesondere in die Einspülkammer oder in den Spülraum, eingibt;
• (b) über die Zugabe von Wasser einen Kontakt zwischen Spülmittel-Portion und der Spülflotte herstellt;
• (c) die gewünschten Spülbedingungen einstellt; und
• (d) bei Eintreten dieser Bedingungen das/die spülaktive(n) Material(ien) der Spülmittel-Portion in die Spülflotte freisetzt und diese mit dem zu spülenden Gut in Kontakt bringt.

The invention also relates to a rinsing method, in particular method for machine rinsing in a commercial dishwashing machine, comprising the steps of

• (A) a detergent portion according to the above detailed description in the dishwasher, in particular in the Einspülkammer or in the washing compartment, inputs;
• (b) making contact between the detergent portion and the rinse liquor via the addition of water;
• (c) sets the desired purge conditions; and
• (d) when these conditions enter the flushing (s) material (s) of the detergent portion in the wash liquor releases and brings them into contact with the material to be washed.

• (a) eine Reinigungsmittel-Portion nach der obigen detaillierten Beschreibung in die Reinigungsflotte eingibt;
• (b) die gewünschten Reinigungsbedingungen einstellt; und
• (c) bei Eintreten dieser Bedingungen die reinigungsaktive(n) Material(ien) der Reinigungsmittel-Portion in die Reinigungsflotte freisetzt und diese mit dem zu reinigenden Gut in Kontakt bringt.

The invention also relates to a purification process comprising the steps of

• (a) adding a detergent portion according to the above detailed description to the cleaning liquor;
• (b) sets the desired cleaning conditions; and
• (c) releases the cleaning-active material (s) of the cleaning agent portion into the cleaning liquor when these conditions occur and brings them into contact with the material to be cleaned.

In addition to the aforementioned areas, the portions according to the present invention can also be used in other areas. So they are, for example, as a cleaner for toilet cisterns for optionally continuous delivery of a cleaning and disinfecting agent to the toilet flushing water or as a cleaner for piping, etc. conceivable. For particular uses, such cleaners may also include gas (e) releasing systems (eg, an acid such as citric acid with a carbonate such as sodium carbonate).

The invention is further illustrated by the following examples, but without being limited thereto.

The strength of detergent, detergent or detergent portions according to the invention was determined by the following standardized method:

The determination was carried out with a universal testing machine from Zwick Type 1425.

At least 10 samples of each variety were tested. As a rule, the samples were tested immediately after conditioning. At the request of the client, however, a previous storage under different climatic conditions can take place.

Prior to testing or storage, all bags were checked for any damage. Furthermore, the gross weight was determined for the samples.

The samples were conditioned for at least 24 hours prior to each test. The test was carried out in a normal atmosphere at 23 ° C / 50% rel. Humidity.

The test samples were always tested in a plastic bag as splash protection. The thickness of the material of this bag should be at least 100 μm. For testing, the film bag was placed in the splash guard bag centered on the lower base plate. This was placed vertically below the upper baseplate.

The printing press was set at a compression speed of 10 mm / min. set. Afterwards the test procedure was started. The force [N] exerted on the bag at bursting moment was printed on the connected printer.

Bag burst strength is given in N. The tensile stress is given in N / cm ² .

For this purpose, in addition to the compression strength and the filled area of the bag is needed. This is calculated from the height and width of the entire bag, minus the respective welding or sealing edges. The two inside dimensions were measured to 0.1 cm and the area calculated.

Examples 1 to 7

The recipes resulting from the following Table 1 were realized with the introduction of the liquid components and subsequent addition of - optionally finely ground - solid components with agitation and so detergent-active or rinse-active formulations prepared according to the invention. The viscosity measurements were carried out according to Brookfield.

The formulations prepared according to Table 1 were filled into conventional gelatin washing balls (SwissCaps). <b> Table 1 </ b> Formulation examples for anhydrous liquid detergents as filling material for washing balls Recipe no. 1 2 3 4 5 6 7 ABS powder - 20 15.5 17.5 20 25 - Sulfopone 1218 G - - - - - - 1.5 Lutensol AO 7 - - - - 10 - - Lutensol AO 5 - - - - 15 - - Lutensol AO 3 - - - - 10 - - Dehydrol LT 7 - 35 27.6 5.2 - - - Dehydrol LS 5 38 - - - - 28 - Dehypon LS 54 17.73 21.85 - - 19 - - Dehypon LS 52 R - - - - - - 61.6 Genapol UD-079 - - - 25 - - Tixogel MP 250 - - - - - - 0.6 propylene carbonate 1.14 0.92 - - 0.8 - 1.8 Thixatrol Plus 0.29 0.23 - - 0.2 - perborate 15 - 19.3 18.2 - - 14 TAED granules 5 - - - - - 5.5 triacetin - - - - - 24 - triethyl - - 22.1 21.5 - - - Tri-sodium citrate anhydrous 15 10 - - - - 10 Na-SKS-6 - - 6.9 - - 10.3 - soda - - - - 13.2 - - Sokalan CP 5 3.2 5.2 5.5 5.8 5 5.5 - Turpinal 2 NZ 1 1.2 1.1 1.2 1.2 1 1 Velvetol 251 C - - - - - - 0.2 Tinosorb FD - - 0.1 - - - - Tinopal CBS-X 0.1 0.1 - 0.1 0.1 0.1 0.1 VP1132 0.5 0.5 0.3 0.5 0.5 0.5 0.2 Perfume + + + + + + + protease + + - + + + + amylase + + - + + + + dye + + - + + + + residual salts At 100 At 100 At 100 At 100 At 100 At 100 At 100 Viscosities in mPa · s After production 1 rpm - 24600 14400 20400 7300 18800 - 5 rpm 6600 8840 7240 7800 3260 9840 8660 20 rpm 2520 4470 4350 4030 2020 1340 2900 After storage RT 1 wk 1 rpm - 23200 13200 21800 - 35600 - Compression resistance at 23 ° C (in N) 99.1 129.7 118.6 109.5 85.4 96.8 95.2

ABS-Pulver

= Alkylbenzolsulfonat 90%ig, Firma Unger

Sulfopon 1218 G

= C₁₂- bisC₁₈-Fettalkoholsulfat Granulat, Firma Cognis

Lutensol AO7

= C₁₃- bis C₁₅-Oxoalkoholethoxylat mit 7 Mol EO

Lutensol AO5

= C₁₃- bis C₁₅-Oxoalkoholethoxylat mit 5 Mol EO

Lutensol AO3

= C₁₃- bis C₁₅-Oxoalkoholethoxylat mit 3 Mol EO

Dehydol LT7

= C₁₂- bis C₁₈-Fettalkoholethoxylat mit 7 Mol EO, Firma Cognis

Dehydol LS5

= C₁₂- bis C₁₄-Fettalkoholethoxylat mit 5 Mol EO, Firma Cognis

Dehypon LS54

= C₁₂- bis C₁₄-Fettalkoholethoxylat/propoxylat mit 5 Mol EO und 4 Mol PO, Firma Cognis

Dehypon LS 52R

= C₁₂- bis C₁₄-Fettalkoholethoxylat/propoxylat random mit 5 Mol EO und 2 Mol PO, Firma Cognis

Genapol UD-79

= C₁₁-Oxoalkoholethoxylat mit 7 Mol EO, Firma Clariant

Tixogel MP 250

= organisch modifiziertes Schichtsilicat, Firma Südchemie

Thixatrol Plus

= Diamidwachsmischung, Firma Rheox

TAED

= Tetraacetyldiamin, Firma Warwick

Triacetin

= Glycerintriacetat, Firma Cognis

Na-SKS-6

= Firma Clariant

Sokalan CP 5

= Polycarboxylat, Firma BASF

Turpinal 2NZ

= Hydroxyethandiphosphonsäure-di-Natrium-Salz, Firma Cognis

Velvetol 251 C

= Terephthalsäure-Ethyineglykol-PEG-Polyester, Firma Rhodia

Tinopal CBS-X

= opt. Aufheller, Firma CIBA

Tinosorb FD

= UV-Absorber, Firma CIBA

VP1132

= Siliconentschäumer, Firma Wacker

Marlox MO 124

= C₁₂- bis C₁₄-Fettalkoholethoxylat/propoxylat mit 2 Mol EO und 4 Mol PO, Firma Condea

Marlinat 242/90M

= C₁₂- C₁₄-Fettalkoholpolyethylenglycol-(2EO)-ethersulfat - Monoisopropanolaminsalz, Firma Condea

Edenor K12-18

= C₁₂- bis C₁₈-Fettsäure, Firma Cognis

Explanation of the trade names of Tables 1 and 2:

ABS powder

= 90% alkylbenzenesulfonate, Unger

Sulfopone 1218 G

= C ₁₂ bisC ₁₈ fatty alcohol sulfate granules, Cognis

Lutensol AO7

= C ₁₃ - to C ₁₅ oxo alcohol ethoxylate with 7 moles of EO

Lutensol AO5

= C ₁₃ - to C ₁₅ oxo alcohol ethoxylate with 5 moles EO

Lutensol AO3

= C ₁₃ - to C ₁₅ oxo alcohol ethoxylate with 3 moles of EO

Dehydrol LT7

= C ₁₂ - to C ₁₈ fatty alcohol ethoxylate with 7 moles of EO, Cognis

Dehydrol LS5

= C ₁₂ - to C ₁₄ fatty alcohol ethoxylate with 5 moles of EO, Cognis

Dehypon LS54

= C ₁₂ - to C ₁₄ -fatty alcohol ethoxylate / propoxylate with 5 moles of EO and 4 moles of PO, Cognis

Dehypon LS 52R

= C ₁₂ - to C ₁₄ fatty alcohol ethoxylate / propoxylate random with 5 moles EO and 2 moles PO, Cognis

Genapol UD-79

C ₁₁ oxo alcohol ethoxylate with 7 moles EO, from Clariant

Tixogel MP 250

= organically modified phyllosilicate, Südchemie

Thixatrol Plus

= Diamide wax blend, Rheox

TAED

= Tetraacetyldiamine, Warwick

triacetin

= Glycerol triacetate, Cognis

Na-SKS-6

= Company Clariant

Sokalan CP 5

= Polycarboxylate, BASF

Turpinal 2NZ

= Hydroxyethanediphosphonic acid di-sodium salt, Cognis

Velvetol 251 C

= Terephthalic acid-ethylene glycol PEG polyester, Rhodia company

Tinopal CBS-X

= opt. Brightener, company CIBA

Tinosorb FD

= UV absorber, company CIBA

VP1132

= Silicone defoamer, Wacker

Marlox MO 124

= C ₁₂ - to C ₁₄ -fatty alcohol ethoxylate / propoxylate with 2 moles of EO and 4 moles of PO, Condea

Marlinat 242 / 90M

= C ₁₂ -C ₁₄ fatty alcohol polyethylene glycol (2EO) ether sulfate monoisopropanolamine salt, Condea

Edenor K12-18

= C ₁₂ to C ₁₈ fatty acid, Cognis

The values of the measured viscosities of the formulations shown in Table 1 show that the formulations obtained are pseudoplastic with one exception and exhibit shear-thinning behavior.

Comparative example

A conventional free-flowing detergent formulation was filled into a gelatine ball of the Swisscaps company equivalent to Examples 1 to 7 above. The recipe is given in Table 2 below. Viscosity was also determined by Brookfield. <b> Table 2 </ b> Marlox MO 124 33 Marlinat 242 / 90M 40 Edenor K12-18 5 Monoethanolamine 6 Polyethylene glycol 400 14 hydroxyethane 1 Perfume 1 Viscosity in mPa · s 20 rpm 258 Compression resistance at 23 ° C (in N) 69.4

The crushing resistance of the filled gelatin spheres of Examples 1 to 7 and Comparative Example was measured by the method described above. The results show that the stability of spheres filled with non-Newtonian or higher viscosity liquids was greater than that of spheres filled with a free-flowing product.

Claims (22)

1. Washing or cleaning composition portion comprising a fully or partly water-soluble envelope which has a thickness of 1 to 300 µm in capsule form, fully surrounds a liquid-based formulation having non-newtonian flow behaviour of at least one washing-active or cleaning-active material and has a crush resistance of 10 to 10⁵ N at 23°C.
2. Washing or cleaning composition portion comprising a fully or partly water-soluble envelope which has a thickness of 1 to 300 µm in spherical form, fully surrounds a liquid-based formulation having non-newtonian flow behaviour of at least one washing-active or cleaning-active material and has a crush resistance of 10 to 10⁵ N at 23°C.
3. Washing or cleaning composition portion comprising a fully or partly water-soluble envelope which has a thickness of 1 to 300 µm in the form of a pouch, fully surrounds a liquid-based formulation having non-newtonian flow behaviour of at least one washing-active or cleaning-active material and has a crush resistance of 10 to 10⁵ N at 23°C.
4. Washing or cleaning composition portion according to one of Claims 1 to 3, wherein the value of the crush resistance is 10² to 10⁴ N and even more preferably 200 to 5000 N, in each case measured at 23°C.
5. Washing or cleaning composition portion according to one of Claims 1 to 4, comprising a fully or partly water-soluble envelope of a material from the group of (optionally partly acetalized) polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, blends and composites, inorganic salts and mixtures of the materials mentioned.
6. Washing or cleaning composition portion according to one of Claims 1 to 5, comprising a fully water-soluble envelope from the group of capsul of gelatin, preferably soft gelatin, sachet of (optionally partly acetalized) polyvinyl alcohol, sphere of (optionally partly acetalized) polyvinyl alcohol or gelatin, preferably soft gelatin, or an inorganic salt or a mixture of inorganic salts.
7. Washing or cleaning composition portion according to Claim 5 or Claim 6, wherein the water-soluble envelope includes regions which are less readily water-soluble or even water-insoluble, or are water-soluble only at high temperature, and regions which are readily water-soluble or water-soluble at low temperature.
8. Washing or cleaning composition portion according to Claim 7, wherein the regions which are less readily water-soluble or regions which are even water-insoluble or regions which are water-soluble only at higher temperature in the envelope are regions composed of a material which corresponds chemically essentially to that of the readily water-soluble regions or regions which are water-soluble at lower temperature, but have a higher layer thickness and/or have a changed degree of polymerization and/or have a higher degree of crosslinking and/or have a higher degree of acetalization and/or have a content of water-insoluble salt components and/or have a content of a water-insoluble polymer.
9. Washing or cleaning composition portion according to one of Claims 1 to 8, wherein the fully or partly water-soluble envelope comprises one or more washing-active or cleaning-active components, especially those components which are present only in small amounts in washing or cleaning compositions.
10. Washing or cleaning composition portion according to one of Claims 1 to 9, wherein the liquid-based formulation of at least one washing-active or cleaning-active material is a low-water formulation.
11. Washing or cleaning composition portion according to one of Claims 1 to 10, wherein the low-water formulation comprises a thickening system.
12. Washing or cleaning composition portion according to Claim 11, wherein the low-water formulation comprises, as the thickening system, a polymeric thickener and optionally further components which contribute to thickening.
13. Washing or cleaning composition portion according to one of Claims 1 to 9, wherein the liquid-based formulation of at least one washing-active or cleaning-active material is a nonaqueous or substantially anhydrous formulation, preferably a formulation comprising less than 5% by weight of water, more preferably a formulation comprising 1 to 3% by weight of water, more preferably an anhydrous formulation.
14. Washing or cleaning composition portion according to one of Claims 1 to 9 and 13, wherein the nonaqueous or substantially anhydrous formulation is a formulation containing anionic surfactant and/or nonionic surfactant.
15. Washing or cleaning composition portion according to one of Claims 1 to 9, 13 and 14, wherein the anionic surfactant(s) is/are selected from the group of the sulphonates and sulphates and mixtures thereof, and/or wherein the nonionic surfactant(s) is/are selected from the group of alkoxylated alcohols, alkoxylated fatty acid alkyl esters, alkyl glycosides and mixtures thereof.
16. Washing or cleaning composition portion according to one of Claims 1 to 15, wherein the liquid-based formulations exhibit thixotropic or pseudoplastic flow behaviour.
17. Washing or cleaning composition portion according to one of Claims 1 to 16, wherein the liquid-based formulations have a low viscosity in production and thereafter exhibit a rise in the viscosity by at least 10%, preferably by at least 50%, more preferably by at least 100%.
18. Process for producing a washing or cleaning composition portion which comprises a fully or partly water-soluble envelope in capsule form, in spherical form or in the form of a pouch, said envelope in turn fully surrounding a liquid-based formulation of at least one washing-active or cleaning-active material, comprising the steps of

    (a) initially charging at least one liquid component of the liquid-based formulation of at least one washing-active or cleaning-active material and moving it with application of a certain shear rate;

    (b) optionally adding one or more further liquid component(s) of the liquid-based formulation;

    (c) optionally incorporating one or more solid component(s) of the liquid-based formulation into the liquid phase thus produced and optionally subsequently adding one or more further solid and/or liquid component(s) while retaining a certain shear rate; and

    (d) optionally introducing the liquid mixture produced in step (c) immediately into the envelope and sealing it around the liquid-based formulation.
19. Process according to Claim 18, wherein the liquid mixture prepared in step (c) is introduced into the envelope only with a time delay and it is sealed around the liquid-based formulation.
20. Washing process, especially a process for machine-washing in a commercial washing machine, comprising the steps of:

    (a) introducing a laundry detergent portion according to one of Claims 1 to 17 into the washing machine, especially into the detergent compartment or into the washing drum;

    (b) forming a contact between the laundry detergent portion and the wash liquor by means of the addition of water;

    (c) establishing the desired washing conditions; and

    (d) when the desired conditions occur, releasing the washing-active material(s) of the laundry detergent portion into the wash liquor and contacting it/them with the material to be washed.
21. Washing process, especially a process for machine-dishwashing in a commercial machine dishwasher, comprising the steps of:

    (a) introducing a dishwasher detergent portion according to one of Claims 1 to 17 into the machine dishwasher, especially into the detergent compartment or into the wash chamber;

    (b) forming a contact between the dishwasher detergent portion and the wash liquor by means of the addition of water;

    (c) establishing the desired washing conditions; and

    (d) when these conditions occur, releasing the washing-active material(s) of the dishwasher detergent portion into the wash liquor and contacting it/them with the material to be washed.
22. Cleaning process, comprising the steps of:

    (a) introducing a cleaning composition portion according to Claims 1 to 17 into the cleaning liquor;

    (b) establishing the desired cleaning conditions; and

    (c) when these conditions occur, releasing the cleaning-active material(s) of the cleaning composition into the cleaning liquor and contacting it/them with the material to be cleaned.