CA2314363A1

CA2314363A1 - A detergent/cleaner portion with a new pack and a pack for detergent/cleaner

Info

Publication number: CA2314363A1
Application number: CA 2314363
Authority: CA
Inventors: Bernd Larson; Christian Block; Jens Bode; Wilfried Raehse
Original assignee: Henkel AG and Co KGaA
Priority date: 1999-07-21
Filing date: 2000-07-20
Publication date: 2001-01-21
Also published as: AU6272800A; DE19934254A1; WO2001007560A1

Abstract

The invention relates to a detergent/cleaner portion, more particularly for placing in a washing/dishwashing machine for a program taking place in an aqueous phase, containing at least one measured quantity of at least one active washing preparation and at least one water-soluble polymer material surrounding the measured quantity(ies) of at least one active washing preparation, one or more component(s) of at least one of the active washing preparations also being present in the water-soluble polymer material and/or one or more component(s) of the water-soluble polymer material also being present in at least one of the active washing preparations. The invention also relates to a wrapper for the detergent portion and to a washing/cleaning process.

Description

A DETERGENT/CLEANER PORTION WITH A NEW PACK AND A PACK
FOR DETERGENT/CLEANERS
Field of the Invention This invention relates to a detergent or cleaner portion (hereinafter referred to as a detergent/cleaner portion) with a new pack, preferably with a water-soluble pack and more preferably which dissolves in water at a certain temperature but which does not enter into any adverse interaction with the ingredients of the detergent/cleaner portion. The invention also relates to a new pack for detergents/cleaner having improved properties in relation to the prior art.
Background of the Invention Detergents and processes for their production have been known for some considerable time and, accordingly, are widely described in the prior art literature. Detergents are normally marketed in the form of spray-dried or granulated solid products or as liquids. In response to consumer demand for easy dosing, products in pre-portioned form have established themselves on the market alongside these two conventional variants and have also been described in the prior art literature, detergents in the form of press-agglomerated shaped bodies, i.e. tablets, blocks, briquettes, rings and the like, and portions of solid and/or liquid detergents packed in bags being described in particular.
In the case of individual doses of detergents which are packed in bags for marketing, bags of water-soluble film, i.e. bags which do not have to be torn open by the user, have proved successful. In this way, an individual portion can be conveniently dosed by directly placing the bag in the washing machine or dishwashing machine, particularly in the dispensing compartment thereof, or by throwing the bag into a predetermined quantity of water, for example in a bucket or in a handwashing or rinsing bowl. The bag surrounding the detergent dissolves completely when a certain temperature is reached. Detergents packed in bags of water-soluble film are also described in large numbers in the prior art literature.
Thus, earlier patent application DE 198 31 703 discloses a portioned detergent prepar;~tion in a bag of water-soluble film, more particularly a bag of (optionally acetalized) polyvinyl alcohol (PVAL) in which at least 70% by weight of the particles of the detergent preparation have particle sizes above 800 Nm.
The water content and the content of other components present in the film material is in equilibrium with the content of water (atmospheric moisture) and optionally other compounds in the surrounding atmosphere.
The same also happens between the film and the interior of the bag. In other words, a phase equilibrium is gradually established.
Moisture in environment = water content of film = moisture in bag.
So far as the packed product is concerned, this situation is virtually equivalent to storage of the product in the open air.
This situation brings problems, particularly in connection with the moisture content or rather the water content of the film, and is particularly undesirable where percarbonates are used as bleaching agents in the washing/cleaning formulation. Percarbonates are not permanently stable in the presence of moisture and undergo significant losses of activity through the absorption of water. Under certain humidity conditions, therefore, washing/cleaning preparations containing percarbonate as bleaching agent are not stable in storage. Although the perborates suitable as alternatives are less sensitive to moisture than percarbonates, they cannot be used on account of esterification with the polyvinyl alcohol of the films.

A known solution is to coat the water-soluble film material with another layer, for example a vapor barrier layer, which leads to limited permeability of the pack to water vapor. For example, vapor barrier layers may be used to protect percarbonate against moisture. In another example, mechanical and chemical separation of the polyvinyl alcohol (PVAL) forming the outer pack from the ester with PVAL-forming perborate can be achieved by an additional layer on the inside of the pack, so that the pack is stabilized.
Thus, WO 98/40464 (Unilever N.V.) describes combinations of at least one tablet of a compressed particulate detergent/cleaner preparation with a closed pack surrounding the tablet which has a water vapor transmission rate of less than 20 g/m2 per day and, ideally, 5 g/m2 per day.
This pack is said to improve the physical properties of the packed tablet in storage and to provide the tablet with improved dissolving kinetics on contact with water.
EP-A 0 899 208 (The Procter & Gamble Company) describes combinations of detergent/cleaner preparations in the form of a stack of tablets containing a moisture-sensitive bleaching agent and a water-insoluble pack surrounding the tablets with a water vapor transmission rate of less than 20 g/m2 per day and, ideally, 0.5 g/m2 per day. The pack con-sists, for example:, of monolayers or co-extruded or laminated films of poly-ethylene, polypropylene, polystyrene and/or polyethylene terephthalate.
A distinct disadvantage of the solutions described in the prior art is that the production of a film material consisting of one or more (for example two) layers is complicated and considerably increases the price of the products. On the other hand, the complete solubility of the pack in water is generally relinquished in favor of impermeability to water vapor which is also undesirable ~on account of the residues of the pack accumulating in the washing/cleaning process.

A logical alternative to the above-described proposals of the prior art is to use an outer pack. acting as a vapor barrier for moisture-sensitive and/or hygroscopic products. Although the product is then optimally protected against water or moisture, a very low equilibrium moisture content by comparison with the normal air humidity is established in the container. This equilibrium moisture content is determined by the packed detergent/cleaner preparation. Water is almost completely removed from the water-soluble film material so that it becomes brittle and mechanically sensitive. The bag surrounding detergent/cleaner portions can thus tear, despite careful handling by the consumer, and releases its contents into the outer pack forming a vapor barrier. The advantages of a detergent/
cleaner portion packed in a water-soluble film for direct use in a washing or dishwashing machine are thus lost.
Summary of the Invention It has now surprisingly been found that both ideal packaging materials for detergents or cleaners and practical easy-to-dose detergent/
cleaner portions surrounded by the packaging materials mentioned can be obtained either when detergent/cleaner ingredients which are also present in the detergent/cleaner to be wrapped are incorporated in the water-soluble films or when detergent/cleaner-compatible plasticizers which are also present in the water-soluble film are compounded into the detergent/
cleaner.
The present invention relates to a detergent/cleaner portion, more particularly for placing in a washing/dishwashing machine for a program taking place in an aqueous phase, containing at least one measured quantity of at least one active washing preparation and at least one water-soluble polymer rnaterial surrounding the measured quantity(ies) of at least one active washing preparation, one or more components) of at least one of the active washing preparations also being present in the water-soluble polymer material.
The invention also relates to a detergent/cleaner portion, more particularly for placing in a washing/dishwashing machine for a program taking place in an aqueous phase, containing at least one measured 5 quantity of at least one active washing preparation and at least one water-soluble polymer material surrounding the measured quantity(ies) of at least one active washing preparation, one or more components) of the water-soluble polymer materiaN also being present in at least one of the active washing preparations.
In addition, the invention relates to a wrapper for at least one measured quantity of an active washing preparation of a detergent/cleaner portion suitable in particular for placing in a washing/dishwashing machine in the form of a water-soluble polymer material, one or more components) of at least one of the active washing preparations also being present in the water-soluble polymer material.
The invention also relates to a wrapper for at least one measured quantity of an active washing preparation of a detergent/cleaner portion suitable in particular for placing in a washing/dishwashing machine in the form of a water-soluble polymer material, one or more components) of the water-soluble poNymer material also being present in at least one of the active washing preparatians.
In addition, the present invention relates to a process for the production of a detergent/cleaner portion, more particularly for placing in a washing/dishwashing machine for a program taking place in an aqueous phase, containing at least one measured quantity of at least one active washing preparation and at least one water-soluble polymer material surrounding the measured quantity(ies) of at least one active washing preparation, characterized by the steps of - making ready at least one measured quantity of at least one active washing preparation;
- making ready at least one water-soluble polymer material, at least one water-soluble polymer material containing one or more components of at least one of the active washing preparations; and/or - making ready at least one water-soluble polymer material, at least one measured quantity of at least one active washing preparation containing one or more components) of the water-soluble polymer material; and - at least one measured quantity of at least one active washing preparation being enveloped in the at least one water-soluble polymer material.
The present invention also relates to a washing/cleaning process in which a detergent portion corresponding to the above definition is placed in a washing/dishwashing machine;
- at least one active washing preparation is released into the wash liquor by addition of water and adjustment of the temperature to a first temperature value at which at least one water-soluble polymer material surrounding a measured quantity of the active washing preparation of the detergent portion dissolves; and optionally - one or more other active washing preparations is/are released into the wash liquor Iby further additions) of water and adjustment of the temperature to one or more other temperature values) above the first temperature value and optionally above other previous temperature values.
Detailed Description of the Invention A "detergent portion" in the context of the present invention is understood to be a dose of a laundry or dishwashing detergent which is sufficient for a washing or cleaning process taking place in an aqueous phase. This may be, for example, a machine washing or dishwashing process carried out in commercially available washing or dishwashing machines. However, the expression "detergent portion" is also understood to encompass handwashing (carried out for example in a handwashing basin or in a bowl) or manual dishwashing or any other washing or cleaning process. According to the invention, the detergent portions are preferably used in machine washing or cleaning processes. Detergent portions according to the invention may also be used, for example, for cleaning floors and glass, for cleaning fittings, appliances and surfaces in the kitchen, for cleaning fittings, furniture and surfaces in the bathroom and for washing the hands. According to the invention, the detergent portions are preferably used in machine washing or cleaning processes.
A "detergent part-portion" in the context of the invention is understood to bs~ part of a detergent portion which is present in a phase separated from other detergent part-portions in spatial combination with other detergent part-portions of the same detergent portion and which is prepared by suitable measures in such a way that it can be introduced into the wash liquor separately from other part-portions of the same detergent portion and dissolved or suspended therein. A detergent part-portion can contain the same ingredients as another part-portion of the same detergent portion. Alternatively, two detergent part portions of the same detergent portion may contain different ingredients, more particularly different active washing preparations. However, the invention also encompasses detergent portions with only one detergent part-portion of uniform composition, for Example of powders, particles or tablets.
According to the invention, the detergent portions contain measured quantities of active washing preparations. The detergent portions may only contain active washing preparations having a particular composition.
According to the invention, however, several, normally at least two, active washing preparations differing in their composition are preferably present in the detergent portions. The composition may differ both in regard to the concentration of the individual components of the active washing preparation (i.e. quantitatively) and/or in regard to the nature of the individual components of the washing preparation (i.e. qualitatively). In one particularly preferred embodiment, the components are adapted in regard to type and concentration to the functions the detergent part-portions are intended to perform in the washing or cleaning cycle. According to the present invention, the part-portions are preferably the first, second and optionally third or' even faurth, fifth etc. measured quantities of one or more active washing preparations which are combined to form a detergent portion according to the invention.
In the context of the present invention, "active washing preparations"
are understood to be preparations of any conceivable substances that are relevant to a washing or cleaning process. These are primarily the actual laundry or dishwashing detergents themselves with their individual components explained in more detail hereinafter. These include such active ingredients as surfactants (anionic, nonionic, cationic and amphoteric surfactants}, builders (inorganic and organic builders), bleaching agents (for example peroxo bleaching and chlorine bleaching agents), bleach activators, bleach stabilizers, bleach catalysts, enzymes, special polymers;, dyes and perfumes, although the expression "active washing preparation" is by no means confined to substances belonging to these groups.
However, the expression "active washing preparations" is also understood to encompass washing and cleaning aids. Laundry treatment compositions, such as fabric softeners, and dishwasher detergent additives, such as rinse aids, are also regarded as active washing preparations in the context of the present invention.
According to the invention, the detergent/cleaner portion contains at least one water-soluble polymer material surrounding the measured quantity(ies) of at least one active washing preparation. This polymer material is preferably a pack surrounding at least one active washing preparation. A pack in the context of the invention is understood to be a flat or three-dimensional structure which completely surrounds at least one measured quantity of at least one active washing preparation and thus forms a detergent/cleaner part-portion which is normally (but not necessarily) arranged very close to another quantity - optionally surrounded by another water-soluble pack, but at all events measured - of another active washing preparation in the form of a detergent/cleaner portion. The exact form of such a pack is not critical and may largely be adapted to the conditions of uses. For example, plastic films processed to various forms (such as tubes, pouches" cylinders, bottles, disks or the like), capsules and other possible forms are suitable. According to the invention, films which may be bonded ;and/or sealed, for example, to form such packs as tubes, pouches or the like after they have been filled with part-portions of the detergent/cleaner portions according to the invention are preferred.
In one preferred embodiment of the invention, the wrapper consists of a water-soluble polymer material. More preferably, the wrapper is a sheet-form plastic part. Plastic capsules or bottles and, more particularly, packs in the form of a water-soluble polymer film are preferred. Among the plastic film packs, bonded and/or sealed plastic film packs are preferred. In one particularly advantageous embodiment, the wrapper is a water-soluble polymer film bonded with a water-soluble adhesive.
Such films are known in principle from the prior art and belong to the group consisting of (optionally acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble polyacrylates, water-soluble polyurethanes, polyethylene oxide, gelatine, cellulose and mixtures thereof.
Polyvinyl alcohols, referred to in short as PVALs, are polymers with the following general structure:

(-CH2-CH(OH)-]"
which also contain small amounts of structural units of the following type:
10 [-CH2-CH(OH)-CH(OH)-CH2]
Since the corresponding monomer (vinyl alcohol) is not stable in free form, polyvinyl alcohols are praduced via polymer-analog reactions by hydrolysis and - on an industrial scale - above all by alkali-catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol) in solution.
PVALs with a predetermined residual percentage of acetate groups -sometimes also referred to as "acetalized" PVAL - can also be obtained by these industrial processes.
Commercially available PVALs (for example Mowiol~ types, products of Hoechst) are marketed as white-yellowish powders or granules with degrees of polymerization of ca. 500 to 2,500 (corresponding to molecular weights of ca. 10,000 to 100,000 g/mole) and have different degrees of hydrolysis of about 70 mole-% or higher, for example 98-99 or 87-89 mole-%. ~4ccordingly, they are partly saponified polyvinyl acetates with a residual content of acetyl groups of ca. 1-2 or 11-13 mole-%.
The solubility of PVALs in water can be reduced and thus selectively adjusted to required values by aftertreatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax. Films of PVAL are largely impervious to ' 11 gases, such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but are permeable to water vapor.
Examples of suitable water soluble PVAL films are the PVAL films obtainable under the name of "SOLUBLONO" from Syntana Handelsgesellschaft E. Harke GmbH & Co. Their solubility in water can be very precisely adjusted and films of this product series soluble in water in all the temperature ranges relevant to practical application are obtainable.
PolyvinyN pyrrolidones, referred to in short as PVPs, correspond to the following general formula:

N
~O
n ~ PVPs are produced by radical polymerization of 1-vinyl pyrrolidone.
Commercially available PVPs have molecular weights of ca. 2,500 to 750,000 g/mole and are commercially available as white hygroscopic powders or as aqueous solutions.
Polyethylene oxides, referred to in short as PEOXs, are polyalkylene glycols corresponding to the following general formula:
H-[O-CH2-CH2]~-~OH
which are produced on an industrial scale by base-catalyzed polyaddition of ethylene oxide (oxirane) with ethylene glycol as starter molecule in systems generally containing small quantities of water. They have molecular weights in the range from ca. 200 to 5,000,000 g/mole, corresponding to degrees of polymerization n of ca. 5 to >100,000.
Polyethylene oxides have an extremely low concentration of reactive terminal hydroxy groups and possess only weak glycol properties.
Gelatine is a polypeptide (molecular weight ca. 15,000 - >250,000 g/mole) which is mainly obtained by hydrolysis of the collagen present in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of gelatine largely corresponds to that of the collagen from which it was obtained and varies according to its provenance. The use of gelatine as a water-soluble capsule material is particularly widespread in pharmacy (hard or soft gelatine capsules).
Gelatine is rarely used in the form of films on account of its high price compared with the polymers mentioned above.
Other preferred detergent portions according to the present invention are those of which the bag consists of water-soluble film of at least one polymer from the group of starch and starch derivatives, cellulose and cellulose derivatives, more especially methyl cellulose and mixtures thereof.
Starch is a homoglycan in which the glucose units are attached by a-glycoside bonds. Starch is made up of two components of different molecular weight, namely ca. 20-30% straight-chain amylose (molecular weight ca. 50,00() to 150,000) and 70-80% of branched-chain amylopectin (molecular weight ca. 300,000 to 2,000,000). Small quantities of lipids, phosphoric acid and cations are also present. Whereas the amylose - on account of the bond in the 1,4-position - forms long, helical entwisted chains containing about 300 to 1,200 glucose molecules, the amylopectin chain branches through a 1,6-bond after - on average - 25 glucose units to form a branch-like structure containing about 1,500 to 12,000 glucose molecules. Besides pure starch, starch derivatives obtainable from starch by polymer-analog reactions may also be used in accordance with the invention for thE; production of water-soluble bags. Such chemically modified starches include, for example, products of esterification or etherification reactions in which hydroxy hydrogen atoms were substituted.
However, starches in which the hydroxy groups have been replaced by functional groups that are not attached by an oxygen atom may also be used as starch derivatives. The group of starch derivatives includes, for example, alkali metal starches, carboxymethyl starch (CMS), starch esters and ethers and amino starches.
Pure cellulose has the formal empirical composition (CsH~pO5)n and, in formal terms, its a ~3-1,4-polyacetal of cellobiose which, in tum, is made up of two molecules of glucose. Suitable celluloses consist of ca. 500 to 5,000 glucose units and, accordingly, have average molecular weights of 50,000 to 500,000. Other cellulose-based disintegrating agents which may be used in accordance with the present invention are cellulose derivatives obtainable from cellulose by polymer-analog reactions. Such chemically modified celluloses include, for example, products of esterification or etherification reactions in which hydroxy hydrogen atoms were substituted.
However, celluloses in which the hydroxy groups have been replaced by functional groups that are not attached by an oxygen atom may also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and also aminocelluloses.
Preferred wrappers of water-soluble film consist of a polymer with a molecular weight in the range from 5,000 to 500,000 dalton, preferably in the range from 7,500 to 250,000 dalton and more preferably in the range from 10,000 to 100,000 dalton. The water-soluble film which forms the wrapper has a thickness of 1 to 150 Nm, preferably 2 to 100 Nm, more preferably 5 to 75 Nm and most preferably 10 to 50 Nm.
The water-soluble films may be produced by various processes. In principle, they rnay be produced by blowing, extrusion and casting processes. In one preferred process, which starts out from a melt and uses a blowing mandrel, the films are blown with air to form a tube. In the extrusion process, which is another preferred production process, the raw materials plasticised by suitable additives are sprayed to form the films. It may be necessary in the extrusion process to dry the films after spraying.
In the casting process, which is another preferred production process, an aqueous polymer preparation is applied to a heatable drying roller, optionally cooled after evaporation of the water and the film formed is removed from the roller. This film may optionally be powdered before or during its removal from the roller.
According to the invention, the polymer material forming the wrapper of at least one active washing preparation does not consist solely of one of the polymers mentioned or a mixture of several polymers, but essentially contains other substances. According to the invention, there are at least two possible alternatives in this regard:
- one or more components) of at least one of the active washing preparations is/are also present in the water-soluble polymer material;
and/or - one or more c;omponent(s) of the water-soluble polymer material is/are also present in at least one of the active washing preparations.
According to the invention, either one of the two states prevails as an alternative, i.e. either one or more components) of at least one of the active washing preparations is/are also present in the water-soluble polymer material or, alternatively, one or more components) of the water-soluble polymer material is/are also present in at least one of the active washing preparations. In another preferred embodiment of the invention, however, both states prevail at the same time, in other words both one or more components) of at least one of the active washing preparations is/are also present in the water-soluble polymer material and, at the same time, one or more components) of the water-soluble polymer material is/are also present in at least one of the active washing preparations. In one particularly preferred embodiment of the invention, both alternatives are 5 applied at the same time.
According to the invention, the fact that one or more components) of at least one of the active washing preparations is/are also present in the water-soluble polymer material and/or one or more components) of the water-soluble polymer material is/are also present in at least one of the 10 active washing preparations ensures that, from the production stage onwards, a phase equilibrium is established between the ingredients of an active washing preparation and the water-soluble polymer material surrounding at least this active washing preparation. Although there is a continuous exchange of material between these two phases, it does not 15 lead to the enrichment of the particular materials) in one phase exceeding the concentration of the phase equilibrium and to a resulting depletion of the particular materials) in another phase which is generally accompanied by an unwanted change in the particular properties. The repeatedly observed changes in the properties of one or more ingredients) of one or even more activE: washing preparations) in regard to the properties, for example washing or cleaning activity, in the washing/cleaning process and/or changes in the properties of one or more wrappers) or packs) surrounding the active washing preparations in regard to the properties, for example solubility in water or brittleness, do not occur with the detergent/
cleaner portion according to the invention or its wrapper/pack.
Basically, no compulsory limitations emanating from the perspective of the particular components present in both phases are imposed on the fact that one or more components) of at least one of the active washing preparations is/are also present in the water-soluble polymer material and/or that one or mare components) of the water-soluble polymer material is/are ;also present in at least one of the active washing preparations. Basically, each of the components of the active washing preparation is suitable for incorporation in the water-soluble polymer materials) and for the establishment of a phase equilibrium between an active washing preparation and a polymer material in exactly the same way as each of the components of the polymer material is suitable for compounding into the active washing preparations) and for the establishment of a phase equilibrium between a polymer material and an active washing preparation.
According to the invention, however, certain ingredients of the particular phases are advantageous for establishing the equilibrium. The main advantage is that no other materials foreign to the film need be incorporated in tlhe film, thus avoiding a complicated production process and an increase in the weight of the film and also an increase in the cost of producing of thE; film. In addition, certain ingredients are particularly suitable becausE: the phase equilibrium can be rapidly and, hence, advantageously established in regard to such materials so that the advantages of thE: invention are quickly brought to bear. However, this may also be due to the fact that the material present in both phases (active washing preparation and water-soluble polymer material) in one particular case can be conveniently incorporated in both phases.
In another preferred embodiment of the invention, the materials present in at least two phases are materials which are liquid or paste-like or wax-like at room temperature, optionally after the addition of small quantities of water (less than 20% by weight and advantageously less than 10% by weight, based on the preparation). Substances selected according to this requirement - to be viewed from the application perspective - lead to detergent/cleaner portions with full activity of the active washing substances and to storage-stable wrappers with improved properties.
According to the invention, one particularly preferred embodiment of the detergent/cleaner portions is characterized in that the components) of at least one of the active washing preparations) present in the water-soluble polymer material is/are selected from the group consisting of nonionic and anionic surfactants as defined in detail in the following.
Suitable anionic surfactants are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are preferably cumene sulfonate, C9_~3 alkyl benzenesulfonates, olefin sulfonates, i.e.
mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C~2_~s monoolefins with an internal or terminal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Other suitable surfactants of the sulfonate type are the alkane sulfonates obtained from C~2_~$ alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. The esters of a-sulfofatty acids (ester sulfonates), for example the a-sulfonated methyl esters of hydrogenated coconut oil, palm kernel oil or tallow fatty acids, are also suitable.
Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters in the context of the present invention are the monoesters, diesters and triesters and mixtures thereof which are obtained where production is carried out 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 sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids containing 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
Preferred alk(en)yl sulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric acid semiesters of C~2_~$ fatty alcohols, for example cocofatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C~o_2o oxoalcohols and the corresponding semiesters of secondary alcohols with the same chain length. Other preferred alk(en)yl sulfates are those with the chain length mentioned which contain a synthetic, linear alkyl chain based on a petrochemical and which are similar in their degradation behavior to the corresponding compounds based on oleochemical raw materials. C~2_~6 alkyl sulfates, C~2_~5 alkyl sulfates and C~4_~5 alkyl sulfates are preferred from the point of view of washing technology. Other suitable anionic surfactants are 2,3-alkyl sulfates which may be produced, for example, in accordance with US
3,234,258 or US 5,075,041 and which are commerially obtainable as products of the Shell Oil Company under the name of DAN~.
The sulfuric acid monoesters of linear or branched C~_2~ alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C~» alcohols containing on average 3.5 moles of ethylene oxide (EO) or C~2_~8 fatty alcohols containing 1 to 4 EO, are also suitable. In view of their high foaming capacity, they are only used in relatively small quantities, for example in quantities of 1 to 5% by weight, in dishwashing detergents.
Other suitable anionic surfactants are the salts of alkyl sulfosuccinic acid which are ;also known as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and, more particula~iy, ethoxylated fatty alcohols. Preferred sulfosuccinates contain C8_~8 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols which, considered in isolation, represent nonionic surfactants (for a description, see below). Of these sulfosuccinates, those of which the fatty alcohol residues are derived from narrow-range ethoxylated fatty alcohols are particularly preferred. Alk(en)yl succinic acid preferably containing 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof may also be used.
Other suitable anionic surfactants are, in particular, soaps. Suitable soaps are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and soap mixtures derived in particular from natural fatty acids, for example coconut oil, palm kernel oil or tallow fatty acids.
The anionic surfactants, including the soaps, may be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts and, more preferably, in the form of their sodium salts. In another embodiment of t;he invention, surfactants are used in the form of their magnesium salts,.
According to the invention, preferred detergent/cleaner portions are those which contain 5 to 50% by weight, preferably 7.5 to 40% by weight and more preferably 15 to 25% by weight of anionic surfactant(s), based on the detergent portion.
So far as the choice of anionic surfactants used in the detergent portions according to the invention is concerned, there are no basic requirements to restrict the freedom of formulation. However, preferred detergent/cleaner portions according to the invention do have a soap content in excess of 0.2% by weight, based on the total weight of the detergent portion. Preferred anionic surfactants are alkyl benzene-sulfonates and fatty alcohol sulfates, preferred detergent portions containing 2 to 20% by weight, preferably 2.5 to 15% by weight and more preferably 5 to '10% by weight of fatty alcohol sulfate(s), based on the weight of the the detergent/cleaner portion.
Preferred nonionic surfactants are alkoxylated, advantageously ethoxylated or propoxylated, more especially primary alcohols preferably containing 8 to 18 carbon atoms and, on average, 1 to 80 and preferably 3 5 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical may be linear or, preferably, methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the form of the mixtures typically present in oxoalcohol radicals. However, alcohol ethoxylates containing linear radicals of alcohols of native origin with 12 to 18 carbon 10 atoms, for example coconut oil, palm oil, tallow or oleyl alcohol, and on average 1 to 80 and preferably 2 to 8 EO per mole of alcohol are partic-ularly preferred. Preferred ethoxylated alcohols include, for example, C~2_~4 alcohols containing 3 EO or 4 EO, Cg» alcohol containing 7 EO, C~3-15 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C~2-~8 alcohols containing 3 15 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C~2-~a alcohol containing 3 EO and C~2_,8 alcohol containing 5 EO. The degrees of ethoxylation mentioned represent statistical mean values which, for a special product, can be a whole number or a broken number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range 20 ethoxylates, NRE:). In addition to these nonionic surfactants, fatty alcohols containing more 'than 12 EO may also be used, examples including tallow alcohol containing 14 EO, 25 EO, 30 EO, 40 EO or up to 80 EO.
Another class of preferred nonionic surfactants which may be used either as sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters preferably containing 1 to 8 carbon atoms in the alkyl chain and 3 to 80 and preferably up to 20 alkoxy groups, preferably ethoxy groups, in the molecule, more especially the fatty acid methyl esters which are described, for example, in Japanese patent application JP 581217598 or which are preferably produced by the process described in International patent application WO-A-90113533.
Another class of nonionic surfactants which may advantageously be used are the alkyl polyglycosides (APGs). Suitable alkyl polyglycosides correspond to thE; general formula RO(G)Z where R is a linear or branched, more particularly 2-methyl-branched, saturated or unsaturated aliphatic radical containing 8 to 22 and preferably 12 to 18 carbon atoms and G
stands for a glycose unit containing 5 or 6 carbon atoms, preferably glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and more preferably between 1.1 and 1.4.
Linear alkyl polyglucosides, i.e. alkyl polyglycosides in which the polyglycosyl component is a glucose unit and the alkyl component is an n-alkyl group, are preferably used.
The detergent/cleaner portions according to the invention may advantageously contain alkyl polyglycosides, APG contents in the detergent/cleaner portions of more than 0.2% by weight, based on the tablet as a whole, being preferred. Particularly preferred detergent/cleaner portions according to the invention contain APGs in quantities of 0.2 to 10% by weight, preferably in quantities of 0.2 to 5% by weight and more preferably in quantities of 0.5 to 3% by weight.
Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethyl-amine oxide, and the fatty acid alkanolamide type are also suitable. The quantity in which these nonionic surfactants are used is preferably no more than the quantity in which the ethoxylated fatty alcohols are used and, more preferably, no more than half that quantity.
Other suitable surfactants are polyhydroxyfatty acid amides corresponding to formula (I):

R' R-CO-N-[Z] ( I ) in which RCO is an aliphatic acyl group containing 6 to 22 carbon atoms, R' is hydrogen, an alkyl or hydroxyalkyl group containing 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group containing 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxyfatty acid amides are known substances which may normally be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
The group of polyhydroxyfatty acid amides also includes compounds corresponding to formula (II):
R'-O-R2 R-CO-N-[Z] (I I) in which R is a linear or branched alkyl or alkenyl group containing 7 to 12 carbon atoms, R' is a linear, branched or cyclic alkyl group or an aryl group containing 2 to 8 carbon atoms and R2 is a linear, branched or cyclic alkyl group or an aryl group or an oxyalkyl group containing 1 to 8 carbon atoms, C~~ alkyl or phenyl groups being preferred, and [Z] is a linear polyhydroxy-alkyl group, of which the alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of that group.
[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds may then be converted into the required polyhydroxyfatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst, for example in accordance with the teaching of International patent application WO-A-95/07331.
According to the invention, nonionic surfactants from the group of alkoxylated fatty alcohols containing 8 to 20 carbon atoms in the fatty alcohol alkyl group are even more preferred, fatty alcohols of natural origin, i.e. linear fatty alcohols predominantly having an even number of carbon atoms in the alkyl group, being preferred to synthetic fatty alcohols (for example branched fatty alcohols or fatty alcohols containing an odd number of carbon atoms). Examples of the fatty alcohols from the perspective of the availability of the compounds are lauryl alcohol (C~2), myristyl alcohol (C~4), cetyl alcohol (C~6) etc. and mixtures emanating from native sources. 'The number of alkoxy groups, above all ethoxy groups or propoxy groups, more preferably ethoxy groups, may vary within wide limits and, in one particularly preferred embodiment, is between 3 and 80.
According to the invention, other nonionic surfactants which may also be present in the water-soluble polymer material are alkoxylated C&2o fatty acid alkyl esters containing 1 to 8 carbon atoms in the alkyl group and 3 to 80 and preferably up to 20 alkoxy groups in the molecule, the alkoxy groups preferably being ethoxy groups. From the practical standpoint, a factor to be advantageously taken into account is that compounds from the above-mentioned groups which are still liquid or paste-like at the applica-tion temperatures, despite considerable chain lengths, are used.
According to the invention, anionic surfactants may also preferably be used for the purpose mentioned. Within the group of these compounds, alkyl benzenesulfonic acids containing 9 to 13 carbon atoms in the alkyl groups and salts thereof (mainly present in alkaline medium), cumene sulfonic acid and salts thereof, fatty alcohol sulfates containing 12 to 18 carbon atoms in the fatty alcohol alkyl group and C8_2o fatty acids and salts thereof are particularly suitable.

In another particularly preferred embodiment of the detergent/
cleaner portions according to the invention, the components) of the water-soluble polymer material also present in at least one active washing preparation is/are selected from the group of hydrophilic plasticizers.
According to the invention, polyols containing 1 to 20 carbon atoms and 2 to 6 hydroxy groups, polyalkylene glycols containing 2 to 4 (preferably linear) alkylene carbon atoms (i.e. ethylene groups, propylene groups or butylene groups) in the molecule, preferably polyethylene glycols and/or polypropylene glycols and more preferably polyethylene glycols and/or polypropylene glycols with molecular weights of 200 to 12,000 and preferably with molecular weights of less than 1500 are particularly preferred. Amines structurally analogous to the polyalkylene glycols mentioned above, i.e. compounds in which the glycol -O- group is replaced by an amine -NH~- group, may also be used with advantage. The molecular weight ranges mentioned above also apply to the amines. From the practical perspective, compounds which are still liquid or paste-like at the (elevated) application temperatures may be used with advantage.
In another preferred embodiment of the detergent/cleaner portions according to the invention, the components) of the water-soluble polymer material also prEaent in at least one active washing preparation is/are selected from the group of perfumes and perfume preparations. Suitable perfume oils or perfumes include individual perfume compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Perfume compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.butyl cyclohexyl acetate, linalyl acetate, dimethyl benzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include, for example, the linear alkanals containing 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxy-citronellal, lilial and bourgeonal.
The ketones include, for example, the ionones, a-isomethyl ionone 5 and methyl cedryl ketone. The alcohols include anethol, citronellol, eugenol, geraniol, linalool, phenyl ethyl alcohol and terpineol. The hydrocarbons include, above all, the terpenes, such as limonene and pinene. However, mixtures of various perfumes which together produce an attractive perfume note are preferably used. Perfume oils such as these 10 may also contain natural perfume mixtures obtainable from vegetable sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are clary oil, camomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroli oil, 15 orange peel oil and sandalwood oil.
In another preferred embodiment of the invention, low molecular weight polyacrylates or polymethacrylates or polymaleates (acids or - under the alkaline in-use conditions - preferably their salts, including their amine or (even organic) ammonium salts) or copolymers of polyacrylates/
20 polymethacrylates and polymaleates may also be used.
The concentrations of the particular compounds in the particular phases, i.e. in the active washing preparations) and in the water-soluble polymer materials) surrounding them, depend entirely on the particular individual case. The concentration values are of course influenced by the 25 character of the material present in the two phases in question, optionally interactions between two or more materials present, interactions) thereof with the other components of the particular phase, the temperature, the pressure and optionally other parameters. The phase equilibrium concentration in one of the two phases in question is generally between 0.5 and 50% by weight, based on the total weight of the particular phase, preferably between 1 and 30% by weight and more preferably between 3 and 25% by weight. The only critical factor so far as the concentration of a suitable substance is concerned is that a phase equilibrium of the concentration of 'the particular substance(s), at which the properties of the active washing preparations) on the one hand and the water-soluble polymer materials) on the other hand are in a desirable range, is established between the phases.
According to the invention, it is of course also possible to design the detergent/cleaner portion and/or its pack or the wrapper surrounding a part-portion in such a way that one of the two phases does not contain any of the substances subsequently producing the expected property(ies) in the equilibrium whereas the other phase contains so much that, over a controlled period (for example of a few hours or a few days), a phase equilibrium is established between the two phases (at least one active washing preparation and/or at least one wrapper) without the substance in question being so heavily depleted in the phase in which it is initially present that its desired or already optimized properties unacceptably deteriorate or without the properties of the phase in which the substance in question is initially not present at all or in a quantity below the equilibrium concentration deteriorating so seriously that subsequent establishment of a phase equilibrium no longer improves the properties to an acceptable extent. In this case, one or more components) alone may also be incorpo-rated in one of the two phases while one or more other substances) alone is/are incorporatf:d in the other phase. After the two phases have been combined in the production of the detergent/cleaner portion according to the invention by introducing one or more active washing preparations) into one or more wrappers) of one or more water-soluble polymer material(s), a phase equilibrium of the particular substance in the two phases (active washing substance or water-soluble polymer material), which does not adversely affect the required properties of the two phases, even in the event of prolonged storage, is established under control through diffusion or adsorption effects.
In the detergent/cleaner portions according to the invention, the water-soluble material surrounding the active washing preparations) is in the form of a film, capsule or coating.
According to the invention, particularly preferred wrappers for the at least one active washing preparation are polyvinyl alcohol films. The PVAL
films preferably used are soluble at the temperature of cold water, i.e. at about 12 to 18°C. In another preferred embodiment, the PVAL films used are soluble at a temperature in a range which corresponds to the temperature range of the washing/dishwashing cycle in which the second measured quantity of a washing preparation is used. The temperature in question, for example in the case where the measured quantity of an active washing preparation in question is a preparation for the main wash cycle of a dishwashing machine, is the temperature of the main wash cycle, for example a temperature in the range from > about 20 to about 55°C, preferably >25°C to below 45°C and more preferably a temperature above 30°C to, for example, 40°C. In the case where the particular measured quantity of an active washing preparation is a preparation for the clear-rinse cycle of a dishwashing machine, the temperature at which the film dissolves in water is the temperature of the clear-rinse cycle, for example a temperature of >45°C, for example in the range from 50 to 55°C
or even higher. In line with the requirements and typical settings of the machines, other temperature ranges are relevant to washing processes carried out in washing machines, for example up to about 25°C for the prewash cycle, up to about 90°C for the main wash cycle and up to about 30°C for the final wash cycle. The temperatures at which the water-soluble ~Im dissolves can of course be adjusted within wide limits. In addition, films adjusted to a certain water-solubility temperature range (cf. the above-mentioned films of the MOWIOL~ type or the SOLUBLON~ type) are commercially obtainable. The expert is thus able to select such films according to requirements and to incorporate the components used in the films in accordance with the invention in those films or to allow them to enter the films through establishment of the phase equilibrium.
In another preferred embodiment of the present invention, the water-soluble material surrounding the particular measured quantity of an active washing preparation is a water-soluble capsule. Such capsules are also known from the prior art. They may be, for example, capsules of PVAL, gelatine or similar materials, but are by no means confined to materials such as these. Such capsules are commercially obtainable and are widely used in connection with pharmaceutical preparations and food additives.
Capsules of hard gelatine or soft gelatine have proved to be particularly successful and, accordingly, are particularly preferred for the purposes of the invention.
In another preferred embodiment of the invention, the water-soluble material surrounding the particular measured quantity of an active washing preparation is a water-soluble coating. Such coatings or membrane materials are used for coating washing substances in the prior art and, like the film materials, may be adjusted in their physical and chemical properties, for example their solubility in water, melting point or melting range, to meet certain technical requirements. For the purposes of the present invention, coatings soluble in water in the narrower sense are as suitable for coating active washing preparations as coatings which dissolve in an aqueous environment providing certain physical or chemical conditions, for example a certain temperature or a certain pH, are established because, for example, they melt and the membrane materials are then dispersE:d in water so that the ingredients, i.e. the active washing preparation(s), previously surrounded by the coating or membrane are released.
In this sense, the term "water-soluble" in the context of the present invention generally encompasses not only the ability of the coatings/
membranes of the active washing preparations to be dissolved by an aqueous medium (in the narrower sense), but also their ability (in the broader sense) to change when certain or physical or chemical conditions are established in the aqueous environment so that their physical integrity is lost and the coating/membrane releases the ingredients into the aqueous phase. The melting and subsequent dispersion of the membrane/coating material in the aqueous phase is a typical (but non-limiting) example of this.
Basically, the coatings or capsule materials should have a melting range at temperatures at which the active substances to be coated/encapsulated are not exposed to significant thermal stressing. On the other hand, however, the melting range must be high enough still to afford the encapsulated active washing preparations effective protection at at least slightly elevated temperatures. According to the invention, the coating/encapsulating materials have melting ranges between about 45°C
and about 75°C., The expression "melting range" in the present case means that the melting range lies within the temperature range mentioned and does not denote the width of the melting range. Coatings of waxes have proved to be particularly effective in this connection where they can be directly applied to the active washing preparation or its individual components. Accordingly, such coatings are particularly preferred because they are easy to apply and because their solubility in water can be exactly adjusted and hence optimally adapted to meet particular requirements and a phase equilibrium can be established between the coating and the coated active washing preparation.

"Waxes" in the context of the present invention are understood to be any of a number of natural or synthetic substances which generally melt above 40°C without decomposing and, even just above their melting point, are of relatively low viscosity and non-stringing. Their consistency and 5 solubility are dependent to a large extent on temperature.
Waxes are divided into three groups according to their origin, namely: natural waxes, chemically modified waxes and synthetic waxes.
The natural waxes include, for example, vegetable waxes, such as candelilla wax, carnauba wax, Japan wax, esparto grass wax, cork wax, 10 guaruma wax, rice oil wax, sugar cane wax, ouricury wax or montan wax, animal waxes, such as bees wax, shellac wax, spermaceti, lanolin (wool wax) or uropygial fat, mineral waxes, such as ceresine or ozocerite (earth wax), or petrochemical waxes, such as petrolatum, paraffin waxes or microwaxes.
15 The chemically modified waxes include, for example, hard waxes, such as montan f;ster waxes, sassol waxes or hydrogenated jojoba waxes.
Synthetic waxes are generally understood to be polyalkylene waxes or polyalkylene glycol waxes.
Compounds from other classes which satisfy the above-mentioned 20 softening point requirements may also be used as coating/encapsulating materials. For example, higher esters of phthalic acid, more particularly the dicyclohexyl phthalate commercially available under the name of Unimoll~
66 (Bayer AG), have proved to be suitable synthetic compounds. Synthetic waxes of lower carboxylic acids and fatty alcohols, for example the 25 dimyristyl tartrate commercially available under the name of Cosmacol~ETLP (Condea), are also suitable. Conversely, synthetic or partly synthetic esters of lower alcohols with fatty acids from native sources may also be used. This class of substances includes, for example, Tegin~
90 (Goldschmidt), a glycerol monostearate palmitate. Schellack-KPS-Dreiring-SP (Kalkhoff GmbH) may also be used as a coating/encapsulating material in accordance with the invention.
In the context of the invention, the waxes also include, for example, the so-called wax alcohols. Wax alcohols are relatively high molecular weight water-insoluble fatty alcohols generally containing about 22 to 40 carbon atoms. 'The wax alcohols are used as a principal constituent of many natural waxes, for example in the form of wax esters of relatively high molecular weighs: fatty acids (wax acids). Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating of the washing preparations may also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example the lanolin obtainable, for example, under the name of Argowax~ (Pamentier ~ Co.). According to the invention, fatty acid glycerol esters or fatty acid alkanolamides and also water-insoluble or substantially water-insoluble polyalkylene glycol compounds may also be used at least partly as an encapsulating material.
In one preferred embodiment, the coatings used in accordance with the invention prE;dominantly contain paraffin wax. In another preferred embodiment, at least 50% by weight of the total of encapsulating materials present and preferably more consists of paraffin wax. Paraffin wax contents (based on total enapsulating material) of about 60% by weight, about 70% by weight or about 80% by weight are particularly suitable, even higher contents of, for example, more than 90% by weight being particularly preferred. In one: particular embodiment of the invention, the total quantity of encapsulating material used consists of paraffin wax. So far as the present invention is concerned, paraffin waxes have the advantage over the other natural waxes mentioned that the waxes do not undergo hydrolysis in an alkaline detergent environment (as might be expected, for example, in the ease of the wax esters), because a paraffin wax does not contain any hydrolyzable groups.
Paraffin waxes consist principally of alkanes and small amounts of iso- and cycloalkanes. The paraffin waxes preferably used in accordance with the invention preferably contain virtually no constituents with a melting point above 70°C: and, more preferably, above 60°C. If the temperature in the washing/cleaning solution falls below this melting temperature, high-melting alkanes in the paraffin can leave unwanted wax residues behind on the laundry to be washed or the ware to be cleaned. Wax residues such as these generally leave the cleaned surface with an unattractive appearance and should therefore be avoided. The encapsulating substances used in accordance with the invention contain a paraffin wax with a melting range of 50°C to 60°C.
The paraffin wax used preferably has a high content of alkanes, isoalkanes and cycloalkanes solid at ambient temperature (generally about 10 to about 30°(:). The higher the percentage of solid wax constituents present in a wax at room temperature, the more useful that wax is for the purposes of the present invention. The higher the percentage of solid wax constituents, the greater the resistance of the coated particles to impact or friction with othe~~r surfaces, which leads to better protection of the active washing substances present in the particles.
Besides paraffin as principal constituent, the coating material may also contain one or more of the waxes or wax-like substances mentioned above. Basically, the composition of the mixture forming the encapsulating/coating material should be such that the coated particles are at least substantially insoluble in water. Their solubility in water should not exceed about 10 mg/l at a temperature of about 30°C and should preferably be below 5 mg/l. At all events, the coating should have very low solubility in water, even in water at elevated temperature, in order largely to avoid the active washing substances being released independently of temperature.
The principle described above facilitates the delayed release of active washing preparations at a certain time in the washing or cleaning cycle and may be applied with particular advantage when the main wash cycle, for example in dishwashing, is carried out at a relatively low temperature (for example 45°C), so that the active washing substance is only released from the coated particles comprising a rinse aid in the final rinse cycle at relatively high temperatures (for example > 55°C).
Membrane materials or coatings preferably used in accordance with the invention comprise one or more substances with a melting range of 40°C to 75°C in quantities of 6 to 30% by weight, preferably 7.5 to 25% by weight and more preferably 10 to 20% by weight, based on the weight of the particles.
In another preferred embodiment of the invention, the detergent/
cleaner portion in which one or more components) of at least one of the active washing preparations is/are also present in the water-soluble polymer material and/or in which one or more components) of the water-soluble polymer material is/are also present in at least one of the active washing preparations additionally comprises a wrapper or outer pack which, in one particular embodiment, is less permeable to water vapor and/or to the particular components) present in the phase equilibrium and/or subjected to the establishment of a phase equilibrium than the wrappers) immediately surrounding the active washing preparation(s).
This additional wrapper may be a wrapper surrounding only one detergent/
cleaner portion or a wrapper surrounding several detergent/cleaner portions. The second of these two cases is preferred: several detergent portions may be offered to the consumer so to speak in a "portion pack".
Not only does this solve a transport-related problem of simultaneously supplying several (for example six, ten or more) detergent/cleaner portions, it also affords the individual detergent/cleaner portions optimal protection against exchange with water vapor or substances from the interior of the wrapper or substances from the surrounding environment. Particularly high stability in storage can thus be guaranteed. The permeability of this additional wrapper to water and to the components) present in the phase equilibrium in accordance with the invention may be entirely different.
Thus, the permeability to one or more of the components may (optionally) be slightly greater or smaller than to water. In another preferred embodiment of the invention, the additional wrapper in question is reclosable after opening and removal of one or more detergent portions.
This can be guaranteed in known manner, for example as described in EP-A 0 899 208. 'The expert in this packaging field is familiar with such devices for reclosing a wrapper of the type in question and may select them unconditionally according to his own expert knowledge.
In another preferred embodiment of the invention, an outer pack as described herein with only limited permeability to water vapor is used.
Desirable packs which may be used with particular advantage in accordance with 'the invention have a water vapor transmission rate of <_ 10 g/m2 per day at 23°C/85% relative humidity and preferably a water vapor transmission rate of <_ 5 g/m2 per day. Outer packs which do not have an measurable permeability to water vapor as measured to DIN EN 53122 are particularly preferred. Suitable materials for these purposes are also known from the prior art and may be, for example, single-layer, multilayer, laminated or co-extruded films of such materials as polyethylene, poly-propylene, polystyrene, polyethylene terephthalate, copolymers thereof or mixtures thereof. Polyethylene or polypropylene films with one or more layers are particularly advantageous.
In the detergent/cleaner portions according to the invention, several, for example first, second and optionally further (third, fourth, etc.), measured quantities of active washing preparations independently of one another are preferably laundry/ dishwasher detergent formulations in the form of shaped bodies, powders, gels or liquids. Detergent/cleaner preparations in the form of shaped bodies may be present as granules, 5 tablets, blocks, briquettes, rings or other shaped bodies. More particularly, tablets, blocks or briquettes may be plain shaped bodies or shaped bodies with depressions, cavities, grooves or the like which are used to accommodate particular components of the preparations or which may even have a performance-related function. Liquid detergent/cleaner 10 preparations may be solutions, suspensions or other liquid systems known for washing and cleaning purposes.
The deterc~ent/cleaner portions contain one or more ingredients from the group of surfactants, surfactant compounds, builders, bleaching agents, bleach activators, enzymes, foam inhibitors, dyes and perfumes and -15 where the detergent/cleaner portions are at least partly present as tablets -binders and disintegration aids. These classes of ingredients are described in the following.
In order to develop their washing effect, the laundry/dishwasher detegent portions according to the invention contain surfactants from the 20 group of anionic:, nonionic, zwitterionic or cationic surfactants, anionic surfactants being greatly preferred both for economic reasons and by virtue of their performance spectrum.
The anionic and nonionic surfactants suitable for use in the detergent portions according to the invention were broadly described in the 25 foregoing. As mE:ntioned, anionic surfactants are preferably used.
In another preferred embodiment, cationic surfactants may be used in addition to anionic and nonionic surfactants. They are mainly used as detergency boosters and need only be used in small quantities. If cationic surfactants are used, they are present in the detergents in quantities of preferably 0.01 to 10% by weight and more preferably in quantities of 0.1 to 3.0% by weight.
In cases where the detergent/cleaner portions according to the invention are laundry detergents, they normally contain one or more surfactants) in total quantities of 5 to 50% by weight and preferably 10 to 35% by weight, surfactants optionally being present in relatively large or relatively small quantities in part-portions of the laundry detergent portions according to the invention. In other words, the quantity of surfactant is not the same in all portions, instead part-portions with a relatively large surfactant content and part-portions with a relatively small surfactant content may be provided., In cases where the detergent/cleaner portions according to the invention are cleaning compositions, more particularly dishwashing detergents, they normally contain one or more surfactants in total quantities of 0.1 to 10% by weight and preferably in quantities of 0.5 to 5% by weight, surfactants optionally being present in relatively large or relatively small quantities in part-portions of the laundry detergent portions according to the invention. In other words, with dishwashing detergents also, the quantity of surfactant is not the same in all portions, instead part-portions with a relatively large surfactant content and part-portions with a relatively small surfactant content may be provided.
Besides the active washing ingredients, builders are the most important ingredients of detergents. Any of the builders normally used in detergents may be present in the detergent/cleaner portions according to the invention, including in particular zeolites, silicates, carbonates, organic co-builders and also - providing there are no ecological objections to their use - phosphates.
Suitable crystalline layer-form sodium silicates correspond to the general formula f~aMSiXO~+~y H20, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x being 2, 3 or 4. Crystalline layer silicates such as these are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layer silicates corresponding to the above formula are those in which M is sodium and x assumes the value 2 or 3. Both Vii- and 8-sodium disilicates Na2Si;z05y H20 are particularly preferred, ~-sodium disilicate being obtainable, for example, by the process described in International patent application WO-A- 91108171.
Other useful builders are amorphous sodium silicates with a modulus (Na20:Si02 ratio) of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and more preferably 1:2 to 1:2.6 which dissolve with delay and exhibit multiple wash cycle properties. The delay in dissolution in relation to conventional amorphous sodium silicates can have been obtained in various ways, for example by surface treatment, compounding, compacting or by overdrying.
In the context of the invention, the term "amorphous" is also understood to encompass "X-ray amorphous". In other words, the silicates do not produce any of the sharp X-ray reflexes typical of crystalline substances in X-ray diffraction experiments, but at best one or more maxima of the scattered X-radiation which have a width of several degrees of the diffraction angle. However, particularly good builder properties may even be achieved where the silicate particles produce crooked or even sharp diffraction maxima in electron diffraction experiments. This may be interpreted to mean that the products have microcrystalline regions between 10 and a few hundred nm in size, values of up to at most 50 nm and, more particularly, up to at most 20 nm being preferred. So-called X-ray amorphous silicates such as these, which also dissolve with delay in relation to conventional waterglasses, are described for example in German patent application DE-A-44 00 024. Compacted amorphous silicates, compounded amorphous silicates and overdried X-ray-amorphous silicates are particularly preferred.
A finely crystalline, synthetic zeolite containing bound water optionally is preferably zeolite A and/or zeolite P. Zeolite MAP~ (for example Doucil A24, a Crosfield product) is a particularly preferred P-type zeolite. However, zeolite X and mixtures of A, X and/or P are also suitable.
According to thE: invention, it is also possible to use, for example, a commercially obtainable co-crystallizate of zeolite X and zeolite A (ca. 80%
by weight zeolite X) which is marketed by CONDEA Augusta S.p.A. under the name of VEGOBOND AX~ and which may be described by the following formula:
nNa20 ~ (1-n)K2O ~ AI203 ~ (2 - 2.5)Si02 ~ (3.5 - 5.5) H20 Suitable zeolites have a mean particle size of less than 10 pm (volume distribution, as rneasured by the Coulter Counter Method) and contain preferably 18 to 22% by weight and more preferably 20 to 22% by weight of bound water.
The generally known phosphates may of course also be used as builders providinc,~ their use should not be avoided on ecological grounds.
The sodium salty of the orthophosphates, the pyrophosphates and, in particular, the trip~olyphosphates are particularly suitable.
Useful organic builders are, for example, polycarboxylic acids usable in the form of their sodium salts, polycarboxylic acids in this context being those carboxylic acids which carry more than one acid function. These include, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, malefic acid, fumaric acid, sugar acids, amino-carboxylic acids,, nitrilotriacetic acid (NTA) - providing its use is not ecologically unsafe - and mixtures thereof. Preferred salts are the salts of the polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. The acids per se may also be used. Besides their builder effect, the acids also typically have the property of an acidifying component and, hence, also serve to establish a relatively low and mild pH value in detergent portions according to the invention. Citric; acid, succinic acid, glutaric acid, adipic acid, gluconic acid and mixtures thereof are particularly mentioned in this regard.
Other suitable builders are polymeric polycarboxylates such as, for example, the alkali metal salts of polyacrylic or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g/mole.
The molecular weights mentioned in this specification for polymeric polycarboxylates are weight-average molecular weights MW of the particular acid form which, basically, were determined by gel permeation chromatography (GPC) using a UV detector. The measurement was carried out against an external polyacrylic acid standard which provides realistic molecular weight values by virtue of its structural similarity to the polymers investiclated. These values differ distinctly from the molecular weights measured against polystyrene sulfonic acids as standard. The molecular weights measured against polystyrene sulfonic acids are generally higher than the molecular weights mentioned in this specification.
Particularlyr suitable polymers are polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g/mole. By virtue of their superior solubility, preferred representatives of this group are the short-chain polyacrylates which have molecular weights of 2,000 to 10,000 g/mole and, more: particularly, 3,000 to 5,000 g/mole.
Also suitable are copolymeric polycarboxylates, particularly those of acrylic acid with methacrylic acid and those of acrylic acid or methacrylic acid with malefic <~cid. Acrylic acid/maleic acid copolymers containing 50 to 90% by weight of acrylic acid and 50 to 10% by weight of malefic acid have proved to be particularly suitable. Their relative molecular weights, based on the free acids, are generally in the range from 2,000 to 70,000 g/mole, preferably in the range from 20,000 to 50,000 g/mole and more preferably in the range from 30,000 to 40,000 g/mole.
The (co)polymeric polycarboxylates may be used either in the form 5 of an aqueous solution or in powder form. The detergent/cleaner portions according to the invention preferably contain 0.5 to 20% by weight and more particularly 3 to 10% by weight of (co)polymeric polycarboxylates.
In order to improve solubility in water, the polymers may also contain allyl sulfonic acids, such as for example allyloxybenzene sulfonic acid and 10 methallyl sulfonic acid (cf. EP-B-727 448), as monomer.
Other particularly preferred polymers are biodegradable polymers of more than two different monomer units, for example those which contain salts of acrylic acid and malefic acid and vinyl alcohol or vinyl alcohol derivatives as monomers according to DE-A-43 00 772 or those which 15 contain salts of acrylic acid and 2-alkylallyl sulfonic acid and sugar derivatives as monomers according to DE-C-42 21 381.
Other preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid/acrylic acid salts or 20 acrolein and vinyl acetate as monomers.
Other preferred builders are polymeric aminodicarboxylic acids, salts or precursors thereof. Particular preference is attributed to polyaspartic acids or salts and derivatives thereof which, according to German patent application DE-A-195 40 086, are also said to have a bleach-stabilizing 25 effect in addition to their co-builder properties.
Other suitable builders are polyacetals which may be obtained by reaction of dialdehydes with polyol carboxylic acids containing 5 to 7 carbon atoms and at least three hydroxyl groups, for example as described in European patent application EP-A-0 280 223. Preferred polyacetals are obtained from dialdehydes, such as glyoxal, glutaraldehyde, terephthal-aldehyde and mixtures thereof and from polyol carboxylic acids, such as gluconic acid and/or glucoheptonic acid.
Other suitable organic builders are dextrins, for example oligomers or polymers of carbohydrates which may be obtained by partial hydrolysis of starches. ThE: hydrolysis may be carried out by standard methods, for example acid- or enzyme-catalyzed methods. The end products are preferably hydrolysis products with average molecular weights of 400 to 500,000 g/mole. A polysaccharide with a dextrose equivalent (DE) of 0.5 to 40 and, more particularly, 2 to 30 is preferred, the DE being an accepted measure of the reducing effect of a polysaccharide by comparison with dextrose which has a DE of 100. Both maltodextrins with a DE of 3 to 20 and dry glucose sirups with a DE of 20 to 37 and also so-called yellow dextrins and while dextrins with relatively high molecular weights of 2,000 to 30,000 g/mole may be used. A preferred dextrin is described in British patent application 9419 091.
The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Dextrins thus oxidized and processes for their production are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and from International patent applications WO 92/18542, WO 93108251, WO 93116110, WO 94128030, WO 95107303, WO 95/12619 and WO 95120608. An oxidized oligosaccharide corresponding to~ German patent application DE A-196 00 018 is also suitable. A product oxidized at C6 of the saccharide ring can be particularly advantageous.
Other suitable co-builders are oxydisuccinates and other derivatives of disuccinates, G>referably ethylenediamine disuccinate. Ethylenediamine-N,N'-disuccinate (EDDS), of which the synthesis is described for example in US 3,158,615, is preferably used in the form of its sodium or magnesium salts. The glycerol disuccinates and glycerol trisuccinates described, for example, in US 4,524,009, in US 4,639, 325, in European patent application EP-A-0 150 930 and in Japanese patent application JP
931339,896 are also particularly preferred in this connection. The quantities used in zeolite-containing and/or silicate-containing formulations are from 3 to 15% by weight.
Other useful organic co-builders are, for example, acetylated hydroxycarboxylic acids and salts thereof which may optionally be present in lactone form and which contain at least 4 carbon atoms, at least one hydroxy group and at most two acid groups. Co-builders such as these are described, for example, in International patent application WO-A-95120029.
Another class of substances with co-builder properties are the phosphonates, more particularly hydroxyalkane and aminoalkane phos phonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1 diphosphonate (HEDP) is particularly important as a co-builder. It is preferably used in the form of a sodium salt, the disodium salt showing a neutral reaction and the tetrasodium salt an alkaline reaction (pH 9).
Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and higher homologs thereof. They are preferably used in the form of the neutrally reacting sodium salts, for example as the hexasodium salt of EDTMP and as the hepta- and octasodium salt of DTPMP. Within the class of phosphonates, HEDP is preferably used as builder. The aminoalkane phosphonates also show a pronounced heavy metal binding capacity. Accordingly, it can be of advantage to use aminoalkane phosphonates, more especially DTPMP, or mixtures of the phosphonates mentioned, particularly if the detergent/cleaner portions according to the invention also contain bleach.
In addition, any compounds capable of complexing alkaline earth metal ions may be used as co-builders.
In addition to the ingredients - surfactants and builders - mentioned above, the dete~rgentlcleaner portions according to the invention may contain other typical detergent ingredients, for example from the group of bleaching agents, bleach activators, enzymes, perfumes, perfume carriers, fluorescing agents, dyes, foam inhibitors, silicone oils, redeposition inhibitors, optical brighteners, discoloration inhibitors, dye transfer inhibitors and corrosion inhibitors.
Among the compounds yielding H202 in water which serve as bleaching agents, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate pefiy-drates and H~~02-yielding peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecane dioic acid. If detergent or bleaching compositions for dishwashing machines are being produced, bleaching agents from the group of organic bleaches may also be used. Typical organic bleaching agents are diacyl peroxides, such as dibenzoyl peroxide for example.
Other typical organic bleaching agents are the peroxy acids, of which alkyl peroxy acids and aryl peroxy acids are particularly mentioned as examples.
Preferred representatives are (a) peroxybenzoic acid and ring-substituted derivatives thereof, such as alkyl peroxybenzoic acids, but also peroxy-a-naphthoic acid and magnesium monoperphthalate, (b) aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, s-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid, N,N-terephthaloyl-di(~i-aminopercaproic acid).
Other suitable bleaching agents in compositions for dishwashing machines are chlorine- and bromine-releasing substances. Suitable chlorine- or bromine-releasing materials are, for example, heterocyclic N-bromamides and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanurlc acid, dibromoisocyanuric acid and/or dichloro-isocyanuric acid (DICA) and/or salts thereof with cations, such as potassium and sodium. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethyl hydantoin, are also suitable.
In order to obtain an improved bleaching effect where washing is carried out at temperatures of 60°C or lower, bleach activators may be incorporated in l:he detergents according to the invention. The bleach activators may be compounds which form aliphatic peroxocarboxylic acids containing preferably 1 to 10 carbon atoms and more preferably 2 to 4 carbon atoms and/or optionally substituted perbenzoic acid under perhydrolysis conditions. Substances bearing O- and/or N-acyl groups with the number of carbon atoms mentioned and/or optionally substituted benzoyl groups are suitable. Preferred bleach activators are polyacylated alkylenediamines, more particularly tetraacetyl ethylenediamine (TAED), acylated triazine derivatives, more particularly 1,5-diacetyl-2,4-dioxohexa-hydro-1,3,5-triazine (DADHT), acylated glycolurils, more particularly tetraacetyl glycoluril (TAGU), N-acylimides, more particularly N-nonanoyl succinimide (NOSI), acylated phenol sulfonates, more particularly n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, more particularly phthalic anhydride, acylated polyhydric alcohols, more particularly triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
In addition to or instead of the conventional bleach activators mentioned above, so-called bleach catalysts may also be incorporated in the detergent/cleaner portions. Bleach catalysts are bleach-boosting 5 transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl comple:Kes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and cobalt-, iron-, copper- and ruthenium-ammine complexes may 10 also be used as bleach catalysts.
Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi,, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus, are particularly suitable. Proteases of the subtilisin 15 type are preferred, proteases obtained from Bacillus lentus being particularly preferred. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or of protease, lipase and cellulase, but especially cellulase-containing mixtures, are of particular 20 interest. Peroxidases or oxidases have also proved to be suitable in some cases. The enzymes may be adsorbed to supports and/or encapsulated in membrane materials to protect them against premature decomposition.
The percentage content of the enzymes, enzyme mixtures or enzyme granules in the compositions according to the invention may be, for 25 example, from about 0.1 to 5% by weight and is preferably from 0.1 to about 2% by weight.
In one p<~rticularly preferred embodiment, the detergent/cleaner portions according to the invention contain other additives known from the prior art as additives for laundry-dishwasher detergent preparations. These other additives may either be added to one or more, if necessary even all, of the part-portions (active washing preparations) of the detergent/cleaner portions according to the invention or, as described in co-pending patent application 199 29 098.8 with the title "Active-substance portion pack", may be incorporated in the water-soluble wrappers surrounding the active washing preparations, i.e. for example in the water-soluble films, but also in the capsules or coatings according to the invention.
A preferred group of additives used in accordance with the invention are optical brighteners. The optical brighteners normally present in detergents may be used. They are added in the form of an aqueous solution or in the form of a solution in an organic solvent to the polymer solution which i~; converted into the film or are added to a part-portion (active washing preparation) of a detergent/cleaner in solid or liquid form.
Examples of optical brighteners are derivatives of diamino-stilbenedisulfonic acid or alkali metal salts thereof. Suitable optical brighteners are, for example, salts of 4,4'-bis-(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)-stilbene-2,2'-disulfonic acid or compounds of similar composition which contain a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group. Brighteners of the substituted Biphenyl styryl type, for example alkali metal salts of 4,4'-bis-(2-sulfostyryl)-Biphenyl, 4,4'-bis-(4-chloro-3-sulfostyryl)-Biphenyl or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)-Biphenyl, may also be present in the part-portions (active washing preparations) of the detergent/cleaner portions according to the invention. Mixtures of the brighteners mentioned above may also be used.
According to the invention ,another preferred group of additives are UV filters. These are substances which are released into the wash liquor during the washing process or in the subsequent fabric-softening process and accumulate on the fibers where they have a UV-filtering effect. The products commercially available under the name of Tinosorb from Ciba Speciality Chemicals are suitable UV filters.
Other possible additives - preferred in special embodiments - are foam inhibitors and also bitter substances for preventing children from accidentally swallowing the packs or parts thereof.
Another group of additives preferably used in accordance with the invention are dyes, more particularly water-soluble or water-dispersible dyes. Dyes of the type normally used to improve visual product appeal in detergents/cleaners are preferred. Such dyes are not difficult for the expert to choose, above all because they have high stability in storage, are not affected by the other ingredients of the active washing preparations or by light and do not have any pronounced substantivity for textile fibers so as not to color them. According to the invention, the dyes are present in the detergent/cleaner portions in quantities of less than 0.01 % by weight.
Another class of additives which may be added to the detergentlcleaner portions according to the invention are polymers.
Suitable polymers are; on the one hand, polymers which show co-builder properties during washing, dishwashing or cleaning, i.e. for example polyacrylic acids, modified polyacrylic acids and corresponding copolymers.
Another group of polymers are polyvinyl pyrrolidone and other redeposition inhibitors, such as copolymers of polyvinyl pyrrolidone, cellulose ethers and the like. In another embodiment of the invention, the polymers may also be soil repellents. Soil repellents are polymers which are absorbed onto fibers or hard surfaces where they counteract resoiling. Relevant compounds of this type are known to the expert on detergents. They are polyesters of terephthalic acid and ethylene glycol partly modified with sulfonic acid groups.
Another group of additives are bleach catalysts, more particularly bleach catalysts; for dishwasher detergents or laundry detergents.

Complexes of manganese and cobalt, more particularly with nitrogen-containing ligands, are used for this purpose.
Another group of additives preferably used in accordance with the invention are silver corrosion inhibitors, i.e. any of various, mostly cyclic organic compounds which are also familiar to the expert and which contribute towards preventing silver-containing articles from tarnishing during the dishwashing process.
Other additives which may be present in the detergent/cleaner portions according to the invention are components which positively influence the removal of oils and fats from textiles, so-called soil repellents.
This effect becomes particularly clear when a textile which has already been repeatedly washed with a detergent according to the invention containing this oil- and tat-dissolving component is soiled. Preferred oil-and fat-dissolving components include, for example, nonionic cellulose ethers, such as methyl cellulose and methyl hydroxypropyl cellulose containing 15 to 30% by weight of methoxy groups and 1 to 15% by weight of hydroxypropo~;y groups, based on the nonionic cellulose ether, and the polymers of phthalic acid and/or terephthalic acid known from the prior art or derivatives thereof, mare particularly polymers of ethylene terephthalates and/or polyethylene glycol terephthalates or anionically and/or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
All these additives are added to the detergent/cleaner portions according to the invention in quantities of up to at most 30% by weight and preferably 2 to 20% by weight. As already mentioned, they may also be added to a material of a water-soluble wrapper which comprises the, or one of the, active washing preparation(s). In order to balance the formulation, therefore, the expert may also increase the weight of the plastic material for the wrapper in order thus to utilize the storage effect obtained in accordance with the invention by incorporating the additives in the wrappers) or additionally to keep the additives mentioned at least partly in the remaining active washing preparation. However, this is less preferred.
Perfumes are added to the detergent/cleaner portions according to the invention to improve the aesthetic impression created by the products and to provide the consumer not only with the required technical performance (fabric softening result) but also with a visually and sensorially "typical and unmistakable" product.
The perfumes and perfume preparations suitable for use in the detergent/cleaner portions according to the invention were broadly described in the foregoing.
The perfume content is normally up to 2% by weight, based on the detergent/cleaner portion as a whole.
The perfumes may be directly incorporated in the active washing preparations according to the invention, although it can also be of advantage to apply the perfumes to supports which strengthen the adherence of thE; perfume to the washing and which provide the textiles with a long-lasting perfume through a slower release of the perfume.
Suitable support materials are, for example, cyclodextrins, the cyclodextrin/perfume complexes additionally being coated with other auxiliaries. ' Basically, the perfumes may be present in each of the part-portions (active washing preparations) of the detergent/cleaner portions according to the invention. In one particularly preferred embodiment, however, they are present in a detergent in a laundry detergent part-portion intended for the final wash cycle or fabric-softening cycle or in a cleaner, particularly a dishwashing detergent, in a cleaner part-portion, particularly a dishwashing detergent part-portion, intended for the final rinse or clear rinse cycle.
According to the invention, therefore, they have to be surrounded by a material which only dissolves in water under the conditions (more particularly at the temperature) of the final wash or final rinse cycle, but which is insoluble in water under the conditions (more particularly at the temperature) of the preceding wash cycles, more particularly a 5 corresponding film or capsule. According to the invention, this is possible for example with a multi-compartment bag of films differing in their water solubility.
The detergent/cleaner portions according to the invention may be present in a wide variety of forms. These various forms are dependent on 10 the particular Components used, more particularly by the washing preparations, but may also be freely selected within certain limits.
Thus, numerous active washing preparations are present in the form of powders, powder mixtures or in the form of particles, for example beads or granules, so that detergent/cleaner portions according to the invention 15 may be made up as single-portion packs or as packs of combinations of powder-form or particulate components, for example as combinations of powder-form or particulate components in film bags with one or more compartments or layers or as single portions or combinations of powder-form components in capsules. In another preferred embodiment of the 20 invention, the solid, for example powder-form, components may be present as granules or beads and - like the powders - may be packed in the form of granules or beads in film bags with several layers or compartments or in capsules and may then be directly used in this form for washing or cleaning.
25 In another preferred embodiment of the invention, the detergent/cleaner portions may also be present in the form of solids compressed to form shaped bodies of any form; such shaped bodies (such as tablets, blocks, briquettes, rings or the like) are known from the prior art and may also bE~ used within the scope of the present invention. More particularly, shaped bodies of the type in question may also have cavities, depressions, indentations or the like for accommodating individual washing substances. Shaped bodies in combination with powders, in combination with liquids (for example in a wrapper of a water-soluble material according to the invention) or in combination with an active washing preparation embedded in a fusible matrix are of course also within the scope of the present invention.
The following are preferred, but not limiting examples of active washing preparations which may be combined to form detergent/cleaner portions according to the invention:
- one or more active washing preparations in powder, particulate or granular form and/or liquid form for one or more cycles of the washing/
cleaning process in one or more wrappers of one or more water-soluble polymer material(s), preferably in an individual bag of polymer material or in interconnected bags of polymer material differing in their solubility in water, preferably as a function of temperature; active washing preparations differing in their composition for one and the same washing/cleaning cycle may be surrounded by one of these prepara-tions, i.e. for example three active washing preparations of which, for example, one is intended for the preliminary (washing or cleaning) cycle and two for the main (washing or cleaning) cycle or, for example, two for the main (washing or cleaning) cycle and one for the final (washing or cleaning) cycle;
- an active washing preparation in powder form and an active washing preparation in the form of a body melting at high temperature in a wrapper which dissolves in water at the temperature at which the detergent/cleaner part-portion present in powder form is needed in the liquor;

- an active washing preparation in the form of a shaped body and an active washing preparation in the form of a body melting at high temperature in a wrapper which dissolves in water at the temperature at which the detergent/cleaner part-portion present in solid form is needed in the liquor; this embodiment may encompass a shaped body which dissolves partly or completely with delay, for example by compression or coating with a coating resistant to water for a certain time or at a certain temperature; if, in this case, the wrapper is soluble in cold water, the tablet is released into the liquor early in the washing/cleaning cycle and may contain quick-dissolving components for a preliminary (washing or cleaning) cycle and (through the delay in dissolution) slowly dissolving components for a main (washing or cleaning) cycle or even quick-dissolving components for a first part of the main (washing or cleaning) cycle and (through the delay in dissolution) slowly dissolving components for a second part of the main (washing or cleaning) cycle;
at all events, the active washing preparation emanating from the fusible body is intended for the final (washing or cleaning) cycle;
- an active washing preparation in the form of a shaped body (optionally surrounded by a water-soluble polymer material and optionally dissolv-ing with delay) in combination with an active washing preparation, for example in liquid form, surrounded by a water-soluble polymer material;
- an active washing preparation in the form of a shaped body (optionally dissolving with delay) with a cavity in which another active washing preparation is held in the form of a powder of a polymer material dissolving in water at a certain temperature;
- an active washing preparation in the form of a shaped body (optionally dissolving with delay) with a cavity in which another active washing preparation is held in the form of a shaped body of a polymer material dissolving in water at a certain temperature; by adjusting the solubility of the second shaped body, components dissolving under certain conditions (for example at a certain temperature) can be dosed into the wash liquor; several active washing preparations in the form of shaped bodies (optionally dissolving with delay) are combined in water-soluble polymer materials differing in their solubility in water to form a detergent/
cleaner portion, optionally together with other components in other polymer materials soluble in water (under different conditions).
As mentioned above, these cases are non-limiting examples of detergent portions according to the invention.
The process for the production of a detergent/cleaner portion, more particularly for placing in a washing/dishwashing machine for a program taking place in an aqueous phase, containing at least one measured quantity of at lea t one active washing preparation and at least one water-soluble polymer material surrounding the measured quantity(ies) of at least one active washing preparation is characterized by the steps of - making ready at least one measured quantity of at least one active washing preparation;
- making ready at least one water-soluble polymer material, at least one water-soluble polymer material containing one or more components of at least one of the active washing preparations; and/or - making ready at least one water-soluble polymer material, at least one measured quantity of at least one active washing preparation containing one or more components) of the water-soluble polymer material; and - at least one measured quantity of at least one active washing preparation being enveloped in the at least one water-soluble polymer material.
The process steps depend on whether a single measured quantity or whether several measured quantities of active washing preparations is/are present in the detergent/cleaner portion to be produced. Basically, the processes suitable for the production of detergent/cleaner portions comprising one active washing preparation or detergent/cleaner portions comprising several active washing preparations. The second case is the preferred case according to the invention. Detergent/cleaner portions in which several active washing preparations are combined to form a portion are generally produced.
In the most simple method of production, each active washing preparation is surrounded by a separate water-soluble polymer material.
However, several active washing preparations may also be surrounded by a polymer material. The particular water-soluble polymer material used in the production process according to the invention must be selected according to the temperature at which the particular polymer material is intended to dissolve in the washing/cleaning liquor and thus to release the contents of the part-pack into the liquor. According to the invention, however, another criterion governing the choice of the water-soluble polymer material is what active washing preparation is to be surrounded by the particular polymer material. This is important because it determines the decision as to which components) of the active washing preparation, for which the polymE;r material is intended to serve as a "pack", is/are also to be present in the polymer material or alternatively or additionally which components) of the water-soluble polymer material is/are also to be present in the active washing preparation.
Accordingly, the invention provides at least one water-soluble polymer material for the active washing preparations) which contains one or more components) that is/are present in at least one of the packed active washing preparations. Alternatively or even at the same time, one or more active washing preparations is/are compounded so that they contain at least one or Even several components) of the water-soluble polymer material surrounding them. In one particularly preferred embodiment, one or more of the components mentioned which are present in both phases (polymer materials) and active washing preparation(s)) is/are selected from the group of hydrophilic plasticizers and substances which are present 5 in liquid or paste-like or wax-like form at room temperature, optionally after addition of small quantities of water (less than 20% by weight and advantageously less than 10% by weight, based on the preparation).
Particular preference is attributed to the above-mentioned surfactant components or polyols, polyalkylene glycols and structurally analogous 10 amines, particularly the representatives specially described above. One or more of these may be present in both phases.
The content of one or more of the components mentioned in the process according to the invention is selected so that it corresponds to the particular concentration of the phase equilibrium in each of the phases.
15 Accordingly, both phases may be involved in a reciprocal dynamic ex-change of the particular components) from the outset. In another embodi-ment of the invention, however, the concentration of the components) is selected so that one phase contains the predominant quantity or even the entire quantity of the particular components) while the other phase 20 contains a relatively small quantity of the same component or does not contain the components) in question at all when the equilibrium between the two phases involved (active washing preparation and water-soluble polymer material) is established under controlled conditions after produc-tion of the detergent/cleaner portion according to the invention. Through 25 diffusion and/or adsorption, the component in question migrates, for example (but not necessarily) in hours or a few days into the phase in which the concentration is below the phase equilibrium concentration.
Thus, the phase equilibrium is established after a short time acceptable for practical purposE;s, so that both stable active washing preparations and storage-stable wrappers for the active washing preparations) are thus obtained in combination.
It is of course also possible in the production process according to the invention for several active washing preparations to be surrounded by one water-soluble polymer material. Corresponding examples were mentioned in the foregoing. In this case, the polymer material may contain one or more components of one or more active washing substances;
alternatively or at the same time, several active washing substances may also contain one or more components of the polymer material.
The invention also relates to the new wrappers for the detergent portions according to the invention.
These wrappers are particularly suitable for wrapping the detergent/
cleaner portions according to the invention or part-portions thereof. These wrappers are either designed in such a way that one or more components) of at least one of the (subsequently wrapped) active washing preparations is/are also present in the water-soluble polymer material of the wrapper or in such a way that one or more components) of the water-soluble polymer material is/are also present in at least one of the "subsequently wrapped"
active washing preparations. In another preferred embodiment of the invention, both one or more components) of at least one of the active washing preparations is/are also present in the water-soluble polymer material and one or more components) of the water-soluble polymer material is/are also present in at least one of the active washing preparations.
In preferred embodiments of the wrappers which may be used with advantage, the components) which is/are also present in the water-soluble polymer material is/are selected from the group of substances which are present in liquid or paste-like or wax-like form at room temperature, optionally after addition of small quantities of water.

In another' preferred embodiment of the wrappers according to the invention, the c:omponent(s) of at least one of the active washing preparations) also present in the water-soluble polymer material is/are selected from the group consisting of nonionic and anionic surfactants, as defined in detail in the foregoing. According to the invention, nonionic surfactants from the group of alkoxylated fatty alcohols containing 8 to 20 carbon atoms in the fatty alcohol alkyl group are more preferred, fatty alcohols of natural origin, i.e. linear fatty alcohols predominantly containing an even number of carbon atoms in the alkyl group, being preferred to synthetic fatty alcohols (for example branched fatty alcohols or fatty alcohols containing an odd number of carbon atoms). Examples of fatty alcohols from the perspective of availability of the compounds are lauryl alcohol (C~2), myristyl alcohol (C~4), cetyl alcohol (C~s) etc. or mixtures of such fatty alcohols emanating from native sources and correspondingly processed. The number of alkoxy groups - according to the invention primarily ethoxy or propoxy groups, preferably ethoxy groups - may vary within wide limits and, in one particularly preferred embodiment, is between 3 and 80. According to the invention, other nonionic surfactants which may also be present in the water-soluble polymer material are alkoxylated C&2o fatty acid alkyl esters containing 1 to 8 carbon atoms in the alkyl group and 3 to 80, preferably up to 20 alkoxy groups, preferably ethoxy groups, in the molecule. From the practical standpoint, a factor which may advanta-geously be taken into account is that substances from the above-mentioned groups which are still liquid or paste-like at the application temperatures, despite considerable chain lengths, are used.
According to the invention, anionic surfactants may also be used for the purpose mentioned. Within the group of anionic surfactants, alkyl benzenesulfonic .acids containing 9 to 13 carbon atoms in the alkyl groups and salts thereof (mainly present in alkaline medium), cumene sulfonic acid and salts thereof" C~2_~a fatty alcohol sulfates and C&zo fatty acids and salts thereof are particularly suitable.
Another particularly preferred embodiment of the wrappers for cleaner/detergent portions according to the invention is characterized in that the components) of the water-soluble polymer material which is/are also present in at least one active washing preparation is/are selected from the group of hydrophilic plasticizers.
According to the invention, particularly preferred hydrophilic plasti-cizers are polyols containing 1 to 20 carbon atoms and 2 to 6 hydroxy groups, polyalkylene glycols containing 2 to 4 (preferably linear) alkylene carbon atoms (i.e. ethylene groups, propylene groups or butylene groups) in the molecule, preferably polyethylene glycols and/or polypropylene glycols and more preferably polyethylene glycols and/or polypropylene glycols with molecular weights in the range from 200 to 12,000 and preferably with molecular weights of less than 1500. Amines structurally analogous to the polyalkylene glycols mentioned, i.e. compounds in which the glycol -O- group is replaced by an amine -NH- group, may also be used with advantage. The above-mentioned molecular weight ranges also apply to the amines. I=rom the practical standpoint, compounds which are still liquid or paste-like at the (high) application temperatures may be used with advantage in the wrapper according to the invention.
In another' preferred embodiment of the invention, low molecular weight polyacrylates or polymethacrylates or polymaleates (acids or - under the alkaline in-use conditions - preferably salts thereof, including amine or (even organic) ammonium salts) or copolymers of polyacrylates/polymeth-acrylates and polymaleates may also be used.
As mentioned above, the concentrations of the particular components) in the wrapper according to the invention are subjected to hardly any limitations, but do depend upon a number of parameters. In general, the pha;>e equilibrium concentration in the wrapper is between 0.5 and 50% by weight, based on the total weight of the material of the wrapper, preferably between 1 and 30% by weight and more preferably between 3 and 25% by weight. In the case discussed above where, in the production of the cleaner/detergent portion, the wrapper still contains none of the required components, the concentration at the beginning of the production step can of course be 0% by weight. However, a phase equilibrium concentration of the corresponding components) in the wrapper which corresponds to a concentration in the above-mentioned ranges will subsequently be established over a controllable, comparatively short period of time.
In another preferred embodiment of the invention, the material of the wrapper is a polymer material selected from the group consisting of (optionally acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin, starch, cellulose and derivatives and mixtures thereof.
Details of these materials were provided in the foregoing.
According to the invention, water-soluble polymer materials present in the form of films, Capsules or coatings are used with particular advantage. Particulars of these forms were also provided in the foregoing in connection with the detergent/cleaner portions.
The present invention also relates to a washing process using the above-described detergent portions and to a dishwashing process using the above-described detergent portions. Both processes are characterized by the use of wrappers in which one or more components) of at least one of the (subsequently wrapped) active washing preparations is/are also present in the water-soluble polymer material of the wrapper and/or in which one or more components) of the water-soluble polymer material is/are also present in at least one of the (subsequently wrapped) active washing preparations.

The washing process according to the invention is, in particular, a machine washing process, in which - a detergent portion as described in detail in the foregoing is placed in a washing machine;
5 - at least one active washing preparation is released into the wash liquor by addition of water and adjustment of the temperature to a first temperature value at which at least one water-soluble polymer material surrounding a measured quantity of the active washing preparation of the detergent portion dissolves; and optionally 10 - one or more other active washing preparations is/are released into the wash liquor by further additions) of water and adjustment of the temperature to one or more other temperature values) above the first temperature value and optionally above other previous temperature values.
15 The cleaning process according to the invention is, in particular, a machine dishwashing process, in which - a detergent portion as described in detail in the foregoing is placed in a dishwashing machine;
- at least one active washing preparation is released into the wash liquor 20 by addition of water and adjustment of the temperature to a first temperature value at which at least one water-soluble polymer material surrounding a~ measured quantity of the active washing preparation of the detergent portion dissolves; and optionally - one or more other active washing preparations is/are released into the 25 wash liquor by further additions) of water and adjustment of the temperature to one or more other temperature values) above the first temperature value and optionally above other previous temperature values.
Accordingly, the washing or cleaning process seeks to achieve optimal conditioning of the washing/cleaning liquor through the release of corresponding detergent/cleaner portions into the liquor under conditions, primarily and hence preferably under temperature conditions, which enable the properties of the active washing preparation released to be optimally developed, i.e. in particular at the staggered (first, second and optionally higher) temperatures of the particular washing or cleaning steps.
The present invention therefore provides detergent/cleaner portions and wrappers ~;uitable for accommodating them which, even in the wrappers, contain at least one component which is present in one of the active washing preparations of the detergent/cleaner portions and/or even in at least one active washing preparation of the detergent portions contain at least one component which is present in a water-soluble polymer material forming the wrapper. Not only ideal packaging or wrapping/coating materials for active washing preparations, but also practical detergent/cleaner portions convenient to dose by the consumer with improved properties in relation to the prior art are obtained in this way.

Claims

1. A detergent/cleaner composition in the form of a portion, for placing in a washing/dishwashing machine for a program taking place in an aqueous phase, comprising at least one measured quantity of at least one active washing preparation and at least one water-soluble polymer material surrounding the measured quantity of at least one active washing preparation, one or more components of at least one of the active washing preparations also being present in the water-soluble polymer material.

2. A detergent/cleaner composition in the form of a portion, for placing in a washing/dishwashing machine for a program taking place in an aqueous phase, comprising at least one measured quantity of at least one active washing preparation and at least one water-soluble polymer material surrounding the measured quantity of at least one active washing preparation, one or more components of the water-soluble polymer material also being present in at least one of the active washing preparations.

3. A portion, for placing in a washing/dishwashing machine for a program taking place in an aqueous phase, comprising at least one measured quantity of at least one active washing preparation and at least one water-soluble polymer material surrounding the measured quantity of at least one active washing preparation, one or more components of at least one of the active washing preparations also being present in the water-soluble polymer material and one or more components of the water-soluble polymer material also being present in at least one of the active washing preparations.

4. A portion as claimed in any of claims 1 to 3, wherein the components of at least one of the active washing preparations also present in the water-soluble polymer material is selected from the group of substances which are liquid or paste- to wax-like at room temperature, optionally after addition of small quantities of water.

5. A portion as claimed in claim 4, wherein the components are selected from the group consisting of alkoxylated fatty alcohols containing 8 to 20 carbon atoms and 3 to 80 alkoxy groups, preferably ethoxy groups, in the molecule, alkoxylated C8-20 fatty acid alkyl esters containing 1 to 8 carbon atoms in the alkyl chain and 3 to 80 and in the molecule, C9-13 alkyl sulfonates, cumeme sulfonate, C12-18 fatty alcohol sulfates and salts of C8-20 fatty acids.

6. A portion as claimed in claim 5, wherein the alkyl esters contain up to 20 alkoxy groups in the molecule.

7. A portion as claimed in claim 6, wherein the alkyl esters contain ethoxy groups in the molecule.

8. A portion as claimed in claim 2 or 3, wherein the components of the water-soluble polymer material also present in at least one active washing preparation are selected from hydrophilic plasticizers.

9. A portion as claimed in claim 8, wherein the components are selected from the group of polyols containing 1 to 20 carbon atoms and 2 to 6 hydroxy groups, polyalkylene glycols containing 2 to 4 carbon atoms in the alkylene group and structural-analog amines containing -NH- groups instead of the -O- groups in the molecule.

10. A portion as claimed in claim 9, wherein the components are polyethylene glycols and polypropylene glycols or structural-analog amines.

11. A portion as claimed in claim 10, wherein the polyethylene glycols and polypropylene glycols have molecular weights in the range from 200 to

12,000.
12. A portion as claimed in claim 10, wherein the structural-analog amines molecular weights of <1,500.

13. A portion as claimed in claim 1 or 3, wherein the components of at least one of the active washing preparations also present in the water-soluble polymer material are selected from perfumes and perfume preparations.

14. A portion as claimed in claim 13, wherein the components are selected from synthetic perfume compounds of the ester, ether, alcohol or hydrocarbon type and/or mixtures thereof and natural perfume mixtures obtainable from vegetable sources.

15. A portion as claimed in any of claims 1 to 14, wherein the components are present in the at least one water-soluble polymer material and in the at least one active washing preparation in a concentration corresponding to the equilibrium state, based on the total weight of the particular phase.

16. A portion as claimed in claim 15, wherein concentration is 0.5 to 50% by weight.

17. A portion as claimed in claim 15, wherein the concentration is 1 to 30% by weight.

18. The portion as claimed in claim 15, wherein the concentration is 3 to 25% by weight.

19. A portion as claimed in any of claims 1 to 18, wherein the components are present in the at least one water-soluble polymer material and in the at least one active washing preparation in a concentration above or below the concentration corresponding to the equilibrium state and the concentration corresponding to the equilibrium state is established in a controlled time, based on the total weight of the particular phase.

20. A portion as claimed in any of claims 1 to 19, wherein the water-soluble polymer material is selected from the group consisting of (optionally acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatine, starch, cellulose and their derivatives and mixtures thereof.

21. A portion as claimed in any of claims 1 to 20, wherein the water-soluble polymer material is present in the form of films, capsules or coatings.

22. A portion as claimed in any of claims 1 to 21 additionally comprising a wrapper which is less permeable to water vapor and/or to the components than the polymer material.

23. A portion as claimed in claim 22, wherein the wrapper has a water vapor transmission rate of ~ 10 g/m2 per day at 23°C/85% relative air humidity.

24. A portion as claimed in claim 23, wherein the water vapor transmission rate is < 5 gg/m2 per day as measured to DIN EN 53 122.

25. A portion as claimed in claim 23, wherein there is no measurable water vapor transmission rate as measured to DIN EN 53 122.

26. A portion as claimed in claim 24 or 25, wherein the wrapper is reclosable.

27. A process for the production of a detergent/cleaner portion for placing in a washing/dishwashing machine for a program taking place in an aqueous phase, comprising at least one measured quantity of at least one active washing preparation and at least one water-soluble polymer material surrounding the measured quantity of the at least one active washing preparation, the process comprising the steps of preparing the at least one measured quantity of the at least one active washing preparation;
preparing the at least one water-soluble polymer material, comprising one or more components of the at least one of the active washing preparations;
and/or preparing the at least one water-soluble polymer material, the at least one measured quantity of at least one active washing preparation containing one or more components of the water-soluble polymer material;
and enveloping at least one measured quantity of at least one active washing preparation in the at least one water-soluble polymer material.

28. A machine washing process, comprising placing a detergent portion claimed in any of claims 1 to 26 in a washing machine; releasing at least one active washing preparation into wash liquor by addition of water and adjustment of the temperature to a first temperature value at which at least one water-soluble polymer material surrounding a measured quantity of the active washing preparation of the detergent portion dissolves; and optionally releasing one or more other active washing into the wash liquor by further additions of water and adjustment of the temperature to one or more other temperature values above the first temperature value and optionally above other previous temperature values.

29. A machine dishwashing process, comprising placing a detergent portion claimed in any of claims 1 to 26 in a dishwashing machine;
releasing at least one active washing preparation into the wash liquor by addition of water and adjustment of the temperature to a first temperature value at which at least one water-soluble polymer material surrounding a measured quantity of the active washing preparation of the detergent portion dissolves; and optionally releasing one or more other active washing preparations into the wash liquor by further additions of water and adjustment of the temperature to one or more other temperature values above the first temperature value and optionally above other previous temperature values.