WO2001029173A1 - Portion consisting of washing or cleaning agents which contain inert gas - Google Patents

Abstract

The invention relates to a portion consisting of washing or cleaning agents having at least one washing active preparation and one or more enclosures which enclose(s) at least one washing active preparation and which consist(s) of one or more water-soluble polymer materials. Said enclosure(s) is/are closed and contain(s) at least one anhydrous gas that does not react with the washing active preparation(s) or it/they contain(s) at least one substance which, when reacting with water or moisture, releases at least one gas that does not react with the washing active preparation(s) so that the total pressure inside the closed enclosure(s) is greater than the external pressure. The invention also relates to a corresponding method for protecting at least one washing active preparation in a portion consisting of washing and cleaning agents from disintegrating as a result of coming into contact with moisture or water.

Description

 Serving detergent or cleaning agent containing inert gas "

The present invention relates to a detergent or cleaning agent portion containing at least one inert gas. In particular, the invention relates to a detergent or cleaning agent portion with at least one detergent-active preparation and one or more enclosures completely or partially surrounding the at least one detergent-active preparation) or several water-soluble polymer materials (in which the enclosures) contain / contain at least one gas or comprise / comprise or enclose / enclose a substance which releases at least one inert gas on reaction with water

Detergents and cleaning agents and processes for their production have long been known and are extensively described in the prior art.Usually, detergents or cleaning agents are made available to the consumer in the form of spray-dried or granulated solid products or as liquid goods In accordance with the convenient dosage, in addition to the two classic variants mentioned, products in pre-portioned form have become established on the market and are also described in the prior art.There are descriptions of detergents or cleaning agents in the form of compressed molded articles, i.e. tablets, blocks, briquettes, rings and the like and portions of solid and / or liquid detergent or cleaning agent packed in bags

In the case of the single-dose quantities of detergents or cleaning agents that come onto the market packed in sachets, sachets made of water-soluble film have become established.This makes it unnecessary for the consumer to tear open the packaging.This makes it convenient for one to dose one Portion of the washing or cleaning cycle possible by inserting the bag directly into the washing machine or dishwasher, especially in its dispenser, or by throwing the bag into a certain amount of water, for example in a bucket, a bowl or in the hand wash or sink, the the pouch surrounding the detergent or cleaning agent portion dissolves without residue when a certain temperature is reached Detergents and cleaning agents packed in bags made of water-soluble film are also described in large numbers in the prior art.

For example, the older patent application DE 198 31 703 discloses a portioned washing or cleaning agent preparation in a bag made of water-soluble film, in particular a bag made of (optionally acetalized) polyvinyl alcohol (PVAL), in which at least 70% by weight of the particles of the washing or Detergent preparation have particle sizes> 800 μm.

Disadvantages with such detergent or cleaning agent preparations packaged in portions in water-soluble film, in particular in PVAL film, occurred because the films are permeable to moisture and water vapor. When the packaged preparations are stored in a moist environment, a moisture balance is established between the space surrounding the packaging and the space inside the packaging made of water-soluble film. The moisture that has penetrated into the interior of the packaging reacts with the components of the detergent preparation, thereby deactivating them or impairing their effectiveness. The inevitable consequence is a deterioration in the washing or cleaning result.

The object of the present invention was to overcome the disadvantages of the prior art. In particular, detergent or cleaning agent portions should be provided with an enclosure made of water-soluble film, the contents of which, i.e. their washing-active preparations, can be protected simply and reliably against ingress of water or moisture before the washing or cleaning cycle, so that the components of the washing-active Preparation (s) are not deactivated by reaction with water, but are actively available for the actual washing or cleaning cycle.

Surprisingly, it has been found that detergent or cleaning agent portions with superior storage stability can be obtained even in a moist environment if the packaging is conditioned in such a way that it contains a gas which does not react with the detergent preparations. The invention relates to a detergent or cleaning agent portion with at least one wash-active preparation and one or more enclosures (s) surrounding one or more water-soluble polymer material (s) surrounding the at least one wash-active preparation, in which the enclosure (s) is / are completed and contains at least one anhydrous gas which does not react with the wash-active preparation (s). It is preferred that the enclosure (s) contain the at least one anhydrous gas in an amount such that the total pressure within the enclosed enclosure (s) is above the external pressure. The enclosure (s) advantageously contain the at least one anhydrous gas in an amount such that the total pressure inside the enclosed enclosure (s) is at least 1 mbar above the external pressure, more preferably by at least 5 mbar, even more preferably by at least 10 mbar, particularly preferably in the range from 10 to 50 mbar.

The invention also relates to a detergent or cleaning agent portion with at least one wash-active preparation and one or more enclosures (s) surrounding the at least one wash-active preparation made of one or more water-soluble polymer material (s), in which the enclosure (s) ) is / are completed and contain at least one substance which, when reacted with water, releases at least one gas which does not react with the wash-active preparation (s) in an amount such that the total pressure within the closed enclosure (s) increases. The at least one substance advantageously releases the at least one gas in an amount such that the total pressure within the closed enclosure (s) increases by at least 1 mbar above the external pressure, preferably by at least 5 mbar, particularly preferably by a value in the range of 5 up to 50 mbar.

The invention further relates to a method for protecting at least one wash-active preparation in a casing consisting of at least one water-soluble polymer material from decomposition as a result of contact with moisture, in which the washing-active preparation (s) with at least one casing are made of a provides water-soluble polymer material, closes it around the wash-active preparation and applies an anhydrous gas which does not react with the wash-active preparation (s) to the closed enclosure. The process is advantageously carried out in such a way that the sealed enclosure is charged with the at least one water-free gas in an amount such that the total pressure within the sealed enclosure solution (s) above the external pressure, preferably that the total pressure within the closed enclosure (s) is at least 1 mbar above the external pressure, more preferably by at least 5 mbar, even more preferably by at least 10 mbar, particularly preferably in the range of 10 up to 50 mbar

The invention further relates to a method for protecting at least one wash-active preparation in an enclosure consisting of at least one water-soluble polymer material from decomposition as a result of contact with moisture, in which the wash-active preparation (s) with at least one enclosure are made from one provides water-soluble polymer material, introduces at least one substance into the enclosure which, when reacted with water, can release a gas which does not react with the washing-active preparation (s) in an amount such that the total pressure within the enclosed enclosures) increases, and that Water-soluble polymer material sealed around the wash-active preparation. A process is preferred in which at least one substance is introduced into the enclosure which, when reacted with water, can release at least one gas which does not react with the wash-active preparation (s) in an amount. that the total pressure within the closed scope solution (s) increases by at least 1 mbar above the external pressure, preferably by at least 5 mbar, particularly preferably by a value in the range from 5 to 50 mbar

The invention also relates to a washing method, in particular a method for machine washing, in which a detergent portion is placed in a washing machine according to the detailed description below and by adding water and adjusting the temperature to a value at which the enclosure (s) consists of at least one Water-soluble polymer material is released, which releases the wash-active preparation (s) into the wash liquor

The invention also relates to a cleaning method, in particular a method for machine-washing dishes, in which a portion of the cleaning agent is placed in a dishwasher according to the detailed description below and by adding water and adjusting the temperature to a value at which the surrounding area (s) are formed at least one water-soluble polymer material is released, which releases the washing actives into the cleaning liquor In the context of the present invention, the term “detergent or cleaning agent portion” means an amount of a detergent or cleaning agent which is sufficient for a washing or cleaning process taking place in an aqueous phase. This can be, for example, a machine washing or cleaning process as described with commercial washing machines or dishwashers is carried out according to the invention, however, this term also includes a hand wash cycle (for example carried out in a hand wash basin or in a bowl) or a dishwasher cycle carried out by hand or another washing or cleaning process. According to the invention, washing or cleaning are preferred Detergent portions used in machine washing or cleaning processes

In the context of the present invention, the term “portion of detergent or cleaning agent” is understood to mean a portion of a portion of washing or cleaning agent that is in a phase separated from other portions of washing or cleaning agent in spatial connection with other detergents or cleaning agents Partial portions of the same detergent or cleaning agent portion are present and are prepared by suitable measures so that they can be added to the liquor separately from other washing or cleaning agent partial portions of the same detergent or cleaning agent portion and, if appropriate, dissolved or suspended in them A detergent or cleaning agent portion can contain the same ingredients as another detergent or cleaning agent portion portion of the same detergent or cleaning agent portion, but preferably two detergent or cleaning agent portions of the same detergent or cleaning agent portion contain different contents toffe, in particular different washing-active preparations

According to the invention, the detergent or cleaning agent portions contain measured amounts of at least one detergent-active preparation, usually measured amounts of several detergent-active preparations. It is possible that the portions only contain detergent-active preparations of a certain composition. According to the invention, however, it is preferred that several, usually at least Two detergent-active preparations of different compositions are contained in the detergent or cleaning agent portions. The composition can differ in terms of the concentration of the individual components of the detergent-active preparation (quantitative) and / or with regard to the type of individual components of the detergent-active preparation (qualitative). be different. It is particularly preferred that the components are adapted in terms of type and concentration to the tasks which the detergent or cleaning agent portion portions have to fulfill in the washing or cleaning process. In the context of the present invention, the partial portions are preferably the first, second and, if appropriate, third or even higher (fourth, fifth, etc.) measured quantities of one or more detergent-active preparation (s) which are comprised of the same or different water-soluble materials and which form a detergent. or detergent portion are combined according to the invention.

In the context of the present invention, the term “wash-active preparation” or “rinse-active preparation” is understood to mean preparations of all conceivable substances which are relevant in connection with a washing or cleaning process Description of individual components explained in more detail, including active substances such as surfactants (anionic, nonionic, cationic and amphoteric surfactants), builder substances (inorganic and organic builder substances), bleaching agents (such as, for example, peroxo bleaching agents and chlorine bleaching agents), bleach activators, bleach stabilizers, Bleaching catalysts, enzymes, special polymers (eg those with cobuilder properties), graying inhibitors, dyes and fragrances (perfumes), without the term being restricted to these substance groups.

However, the term “wash-active preparations” or “rinse-active preparation” also includes washing aids and cleaning aids. Examples of these are optical brighteners, UV protection substances, so-called soil repellents, that is to say polymers which counteract re-soiling of fibers or hard surfaces Laundry treatment agents such as fabric softener or dishwashing detergent additives such as rinse aid are also considered to be detergent-active or dishwashing preparations.

According to the invention, the detergent or cleaning agent portion has at least one washing-active preparation. The number of detergent-active preparations is not limited and is largely dependent on the use of the detergent or cleaning agent portion. Several detergent preparations are usually contained in the detergent or cleaning agent portion according to the invention. The detergent and cleaning agent portions according to the invention contain one or more substances from the group of surfactants, surfactant compounds, builders, bleaching agents, lead activators, enzymes, foam inhibitors, dyes and fragrances and - in the event that the detergents or cleaning agents - Portions are at least partially in the form of shaped bodies - binding and disintegration aids. These classes of substances are described below

To develop the washing performance, the detergent and cleaning agent portions according to the invention can contain surface-active substances from the group of anionic, nonionic, zwitterionic or cationic surfactants, anionic surfactants being clearly preferred for economic reasons and because of their performance spectrum

The anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _{9 13} -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C ₂ . _18- Monoolefιnen with end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products obtained are also suitable alkane sulfonates obtained from C _{12 18} alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization the esters of 2-sulfofatty acids (ester sulfonates), for example the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable

Other suitable anionic surfactants are sulfonated fatty acid glycine nests. Fatty acid glycine nests are to be understood as meaning the mono-, di- and t-esters as well as their mixtures as they are produced by esterification of a monoglycene with 1 to 3 moles of fatty acid or in the transesterification of tnglycerides with 0. 3 to 2 moles of glycene are obtained. Preferred sulfonated fatty acid glycine nests are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, launic acid, palmitic acid, stearic acid or behenic acid

The alk (en) yl sulfates are the alkali and, in particular, the sodium salts of the sulfuric acid half-esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, methyl, cetyl or stearyl alcohol or C ₁₀ -C ₂₀ -Oxo alcohols and those Half-preferred secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials are the C ₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₅ alkyl sulfates and C ₄ -C ₁₅ alkyl sulfates are also preferred 2,3-alkyl sulfates, which are produced for example according to US Pat. Nos. 3,234,258 or 5,075,041 and as Shell's commercial products Oil Company under the name DAN ^® are suitable anionic surfactants

The sulfuric acid monoesters of the straight-chain or branched C _{7 21} alcohols ethoxy-containing 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C ₉ n alcohols with an average of 3.5 moles of ethylene oxide (EO) or C _{12 18} fatty alcohols 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight

Other suitable anionic surfactants are also the salts of alkyl sulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _{8 18} -fatty alcohol residues Mixtures of these particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). In turn, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred it is also possible to use alk (en) yl succinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof

Other suitable anionic surfactants are, in particular, soaps. Saturated fatty acid soaps, such as the salts of launic acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut oil, palm kernel oil or tallow fatty acid, are suitable The anionic surfactants, including the soaps, can 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 in the form of their sodium or potassium salts, in particular in the form of the sodium salts In a further embodiment of the invention, surfactants are used in the form of their magnesium salts

In the context of the present invention, detergent and cleaning agent portions are preferred which contain 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 15 to 25% by weight, of one or more anionic ten-s (s), included, each based on the detergent and cleaning agent portion

When selecting the anionic surfactants which are used in the detergent and cleaning agent portions according to the invention, there are no restrictions to be observed in terms of freedom from formulation. However, preferred washing and cleaning agent portions according to the invention have a soap content which is 0. 2% by weight, based on the total weight of the detergent and detergent portion, exceeds the preferred anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, preferred detergent and detergent portions being 2 to 20% by weight, preferably 2.5 to 15 % By weight and in particular 5 to 10% by weight of fatty alcohol sulfate (s), in each case based on the weight of the detergent and cleaning agent portion

The nonionic surfactants used are preferably alkoxy-hard, advantageously ethoxy-hard, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue is branched, preferably in the 2-position, methyl may or may contain linear and methyl-branched radicals in the mixture, such as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol , and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _{12 14} alcohols with 3 EO or 4 EO, C _{9 11} alcohol with 7 EO, C _{13 15} alcohols with 3 EO, 5 EO , 7 EO or 8 EO, C ₁₂ ι ₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, and mixtures of C _{12 1} alcohol with 3 EO and C _{12 18} alcohol with 5 EO The degrees of ethoxyherization shown are statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are taig fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxy, preferably ethoxy or ethoxy, and propoxy, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain , in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkypolyglycosides that can be used satisfy the general formula RO (G) ₂ , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, a phatic radical with 8 to 22, preferably 12 to 18 C atoms and G is the symbol which stands for a glycose unit with 5 or 6 C atoms, preferably for glucose, the degree of glycosidation z is between 1.0 and 4 .0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4

Linear alkyl polygiucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used

The detergent and cleaning agent portions according to the invention can preferably contain alkyl polyglycosides, the contents of the detergent and cleaning agent portions of APG being greater than 0.2% by weight, based on the total shaped body, being preferred. Particularly preferred detergent and cleaning agent portions contain APG in amounts of 0.2 to 10% by weight, preferably in amounts of 0.2 to 5% by weight and in particular in amounts

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dιhydroxyethylamιnoxιd, and the fatty Acid alkanolamides may be suitable. The amount of these nonionic surfactants is preferably no more than that of the ethoxy-modified fatty alcohols, in particular not more than half of them

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

R ¹

I R-CO-N- [Z] (I)

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

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

R ¹ -OR

R-CO-N- [Z] (II)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cychly alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cychschen alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, d ^ -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted by at least two hydroxyl groups, or alkoxy radicals, preferably ethoxy radicals or propoxy radicals Derivatives of this rest

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

Furthermore, it may be preferred to use cationic surfactants in addition to anionic and nonionic surfactants. They are preferably used as washing performance boosters, only small amounts of cationic surfactants being required. If cationic surfactants are used, they are preferably in amounts of 0 in the compositions , 01 to 10% by weight, in particular 0.1 to 3.0% by weight

In the cases in which the detergent and cleaning agent portions according to the invention are detergents, these usually contain one or more surfactants) ^{| n} total amounts of 5 to 50% by weight, preferably in amounts of 10 to 35% by weight , With partial portions of the detergent portions according to the invention, surfactants can be present in larger or smaller amounts. In other words, the amount of surfactant is not the same in all partial portions, rather partial portions with a relatively larger and partial portions with a relatively smaller surfactant content can be provided

In the cases in which the detergent and cleaning agent portions according to the invention are cleaning agents, in particular dishwashing agents, they usually contain one or more surfactants in total amounts of 0.1 to 10% by weight, preferably in amounts from 0.5 to 5% by weight, with partial portions of the cleaning agent portions according to the invention containing surfactants in larger or smaller amounts. In other words, the amount of surfactant is not the same in all partial portions even with detergents or dishwashing agents, rather partial portions can with relatively larger and partial portions with a relatively smaller surfactant content. In addition to the washing-active substances, builders are the most important ingredients of detergents and cleaning agents. The detergent and cleaning agent portions according to the invention may contain builders usually used in detergents and cleaning agents, in particular zeolites, sihcates . Carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also phosphates Suitable crystalline, layered sodium silicates have the general formula NaM

Sι _x O _{2x +} ι yH ₂ O, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are such crystalline layered silicates Described in the European patent application EP-A-0 164 514 Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disihcates are Na ₂ Si ₂ O. ₅ yH ₂ O is preferred, wherein β-Natπumdisihcat can be obtained, for example, by the method described in international patent application WO-A-91/08171

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

An optionally used finely crystalline, synthetic and bound water-containing zeo th is preferably Zeohth A and / or P. Zeohth MAP (eg commercial product Doucil A24 from Crosfield) is particularly preferred as the P-type zeo th However, Zeohth X and mixtures of A, X and / or P are also commercially available and can preferably be used in the context of the present invention, for example a co-crystallate of Zeohth X and Zeohth A (about 80% by weight Zeohth X), which is from is sold by CONDEA Augusta S p A under the brand name VEGOBOND AX ^® and through the formula

n Na ₂ O (1-n) K ₂ O AI ₂ O ₃ (2 - 2.5) SiO ₂ (3.5 - 5.5) H ₂ O n = 0 90 - 1 00

Suitable zeolites have an average particle size of less than 10 μm (volume distribution, Coulter Counter measurement method) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water

It is of course also possible to use the generally known phosphates as builders in detergents, provided that such use should not be avoided for ecological reasons. The sodium salts of the orthophosphates, the pyrophosphates and in particular the polyphosphates are particularly suitable

Usable organic scent substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function. Aminocarboxylic acids, nitro solder acetic acid (NTA), provided that their use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acid and mixtures of these, including the acids themselves can be used In addition to their builder effect, the acids typically also have the property of an acid component and thus also serve to set a lower and milder pH value for detergent and cleaning agent portions, in particular according to the invention In this context, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these are to be mentioned Polymeric polycarboxylates are also suitable as builders. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol

In the context of the present invention, the molar masses given for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were basically determined by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external poly acrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers.This information differs significantly from the molecular weight data for which polystyrene sulfonic acids are used as standard.The molecular weights measured against polystyrene acid are generally significantly higher than those in the context of the present invention specified molecular weights

Suitable polymers are in particular polyacrylates, which preferably have a molar mass of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates from this group, the molar masses of 2,000 to 10,000 g / mol, particularly preferably of, can be preferred 3,000 to 5,000 g / mol

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid or of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable Molar mass, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol

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

To improve the solubility in water, the polymers can also contain allyl sulfonic acids, such as, for example, in EP-B 0 727 448, allyloxybenzenesulfonic acid and methyl sulfonic acid as a monomer In particular, biodegradable polymers of more than two different monomer units are preferred, for example those which, according to DE-A 43 00 772, as monomers, salts of acrylic acid and maleic acid, and vinyl alcohol or vinyl alcohol derivatives, or according to DE-C 42 21 381 Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives

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

Likewise, preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A 195 40 086 that they are used in addition to co-builders - Properties also have a bleach-stabilizing effect

Further suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A 0 280 223. Preferred polyacetals are derived from dialdehydes such as glyoxal , Glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid

Other suitable organic builder substances are dextrins, for example ohgomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. Preferably, the products are hydrolysis products with average molecular weights in the range from 400 up to 500,000 g / mol A polysacchand with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing effect of a polysacchand in comparison to dextrose, which has a DE of 100 usable are both maltodextnne with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins higher molar masses in the range from 2,000 to 30,000 g / mol A preferred dextrin is described in British patent application 94 19 091

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 to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known in particular from European patent applications EP-A 0 232 202, EP-A 0 427 349, EP-A 0 472 042 and EP-A 0 542 496 as well as from international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95 / 07303, WO 95/12619 and WO 95/20608 known Also suitable is an oxidized Ohgosaccha d according to German patent application DE-A 196 00 018. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable co-builders. Ethylenediamine-N, N'-disuccinate (EDDS), the synthesis of which is described, for example, in US Pat. No. 3,158,615, is preferred in the form of its sodium - or magnesium salts are furthermore preferred in this connection, too. Glycene disuccinates and glycine nesuccinates, as described, for example, in US Pat. Nos. 4,524,009 and 4,639,325, in European patent application EP-A 0 150 930 and in Japanese patent application JP- A 93 / 339,896 are described. Suitable amounts are 3 to 15% by weight in formulations containing zeolites and / or silicates.

Further usable organic co-builders are, for example, acetyheric hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and at most two acid groups. Such co-builders are described, for example, in international patent application WO 95 / 20029

Another class of substances with co-builder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroalkane phosphonates, 1-hydroxyethane-1,1-phosphonate (HEDP) is of particular importance as a co-builder. It is preferred used as the sodium salt, the dinate salt reacting neutral and the tetranate salt reacting alkaline (pH = 9) Aminoalkane phosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably used in the form of the neutral-reacting sodium salts, for example as the hexasodium salt of EDTMP or as the hepta- and octasodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, in particular if the detergent or cleaning agent portions according to the invention also contain bleach, it may be preferred to use aminoalkane phosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as co-builders.

In addition to the surfactant and builder components mentioned, the washing or cleaning agents according to the invention can contain further ingredients from the group of bleaching agents, bleach activators, enzymes, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, which are common in washing or cleaning agents , Color transfer inhibitors and corrosion inhibitors included.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecotacic acid. If cleaning or bleaching preparations for machine dishwashing are produced, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate; (b) the aliphatic or substituted aliphatic peroxy acids, such as Peroxylaunnsaure, Peroxysteannsaure, ε-Phthahmidoperoxy-capronsaure [Phthaloiminoperoxyhexansureure (PAP)], o-Carboxybenzamido-peroxycapronsaure, N-Nonenylamido-peradipinsaure and N-Nonenylamidopersuccinate, and (a) carboxamate and, (a) carbonic acid 12-peroxydonate, and (a) carboxamate and, (a) carbonic acid 12-peroxydonate, and (a) carbonic acid 12-peroxydonate, and (a) carboxamate and, (a) carboxylic acid 12-peroxyacidate, and (c), 1-carbonic acid peracidate, and (c), 1-carbonic acid peracidate, and, (a) carbonic acid peracidate, and, (a) carbonic acid-1, and a) carbonic acid-12-peroxyacidate, and (c), 1-carboxylic acid peracidic acid, and (a) carbonic acid, and pericarboxylic acid 12%, , 1, 9-Dιperoxyazelaιnsaure, Dipero- cysebacinsaure, Diperoxybrassylsure, the Diperoxyphthalsauren, 2-Decyldιperoxybutan- 1, 4-Dιsaure, N, N-Terephthaloyl-dι (6-amιnopercapronsaue) can be used

Chlorine or bromine-releasing substances can also be used as bleaching agents in compositions for machine dishwashing. Among the suitable chlorine or bromine-releasing materials are, for example, heterocyclic N-bromine and N-chloramides, for example tnchloroisocyanuric acid, trichloroisocyanuric acid

Dibromo isocyanuric acid and / or dichlonsocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium are also suitable. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin, are also suitable

In order to achieve an improved bleaching effect when washing or cleaning at temperatures of 60 ° C. and below, bleach activators can be incorporated into the detergent and cleaning agent portions. Bleach activators can be compounds which contain periphocarboxylic acids with preferably 1 to 10 carbon atoms under perhydrolysis conditions, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid, can be used. Substances which carry O- and / or N-acyl groups of the stated number of carbon atoms and / or optionally substituted benzoyl groups are preferred. Multiple are preferred acy erte alkylenediamines, especially tetraacetylethylenediamine (TAED), acyherte triazindenvate, especially 1, 5-dιacetyl-2,4-dιoxohexahydro-1, 3,5-trιazιn (DADHT), acyherte glycolunle, especially tetraacetylglycol), N-TAGU Acyhmide, especially N-Nonanoylsuccinimid (NOSI), acyherte Phenolsulfonate, in particular n-Nonanoyl- or Isononanoyloxybenzo Isulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acyherte polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dιhydrofuran

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the detergent and cleaning agent portions. These substances are bleach-strengthening transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo Salene complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing Tnpod ligands as well as Co, Fe, Cu and Ru. Amine complexes can be used as bleaching catalysts

Enzymes from the class of proteases, lipases, amylases, cellulases or their mixtures are particularly suitable. Bacterial strains or fungi, such as Bacillus subti s, Bacillus hcheniformis and Streptomyces griseus, are particularly suitable. Proteases of the subtihsin type and are preferred in particular proteases obtained from Bacillus lentus are used. Enzyme mixtures, for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but especially cellulase -containing mixtures of particular interest Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carrier substances and / or embedded in shell substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules in the invention Appropriate compositions can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight

According to the prior art, enzymes are primarily added to a detergent preparation, in particular to a dishwashing detergent which is intended for the main wash cycle. The disadvantage here was that the optimum effect of the enzymes used restricted the choice of temperature and also problems with the stability of the enzymes in the strongly alkaline Milieu occurred With the detergent or cleaning agent portions according to the invention, it is possible to use enzymes also in the pre-wash cycle and thus to use the pre-wash cycle in addition to the main wash cycle for enzyme action on soiling of the ware

According to the invention, it is therefore particularly preferred to add enzymes to the washing-active preparation or partial portion of a detergent portion and then - more preferably - to include such a preparation with a material that is already water-soluble at low temperature, for example in order to prevent the enzyme-containing preparation from losing its effectiveness Protect environmental conditions The enzymes are furthermore preferably optimized for use under the conditions of the fast-moving cycle, for example in cold water The detergent portions according to the invention can be advantageous if the enzyme preparations are in liquid form, as are partially available commercially, because then a quick effect can be expected that already occurs in the (relatively short and cold water) pre-wash cycle even if - as usual - the enzymes are used in solid form and they are provided with a cover made of a water-soluble material that is already soluble in cold water, the enzymes can develop their effect before the main wash or main wash cycle. Advantage of using a cover made of water-soluble material , in particular from cold water-free chemical material, that the enzyme (s) in cold water quickly comes into effect after dissolving the enclosure. This allows their duration of action to be extended, which benefits the washing or rinsing result

According to a particularly preferred embodiment, the detergent or cleaning agent portions according to the invention also contain further additives, as are known from the prior art as additives for washing or cleaning agent preparations. These can be either one or more, if necessary, all of them - Portions (detergent-active preparations) of the detergent or cleaning agent portions according to the invention are added or - as described in the copending patent application No. 199 29 098 9 entitled "Active ingredient portion pack" - into the water-soluble materials comprising the detergent preparations, ie for example, can be incorporated into the water-soluble films, but also into the capsules or coatings according to the invention

A preferred group of additives used according to the invention are optical brighteners. The optical brighteners customary in detergents can be used here. These are added as an aqueous solution or as a solution in an organic solvent to the polymer solution which is converted into the film, or are added to a partial portion (detergent active Preparation) of a washing or cleaning agent added in solid or liquid form. Examples of optical brighteners are derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Examples of suitable salts are 4,4'-Bιs (2-anιhno-4-morpholιno1, 3.5 -tπazιnyl-6-amιno) stιlben-2,2'-disulfonic acid or compounds of the same structure which carry a diethanol-amino group, a methylamino group, an anhno group or a 2-methoxyethylamino group instead of the morphohno group Furthermore, brighteners of the type of the substituted diphenylstyryl can be in the partial portions (Washing-active preparations) of the detergent or cleaning agent portions according to the invention may be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyls Mixtures of the aforementioned brighteners can also be used

Another preferred group of additives according to the invention are UV protection substances. These are substances which are released in the washing liquor during the washing process or during the subsequent soft rinsing process and which accumulate on the fiber, in order then to have a UV protection effect The products from Ciba Speciahty Chemicals, which are commercially available under the name Tinosorb, are suitable

Other conceivable additives which are preferred in special embodiments are surfactants, which in particular can influence the solubility of the water-soluble film, but can also control its wettability and the foaming when dissolved, as well as inhibitors of foam, but also bitter substances, which inadvertently swallow such packaging or parts can prevent such packaging from children

Another preferred group of additives according to the invention are dyes, in particular water-soluble or water-dispersible dyes. Dyes are preferred here, as are usually used to improve the visual appearance of products in detergents and cleaning agents. The selection of such dyes is not difficult for the person skilled in the art, especially since such conventional dyes have a high storage stability and insensitivity to the other ingredients of the wash-active preparations and to light and have no pronounced substantivity to textile fibers so as not to dye them. The dyes according to the invention are in the detergent or cleaning agent portions in amounts of less than 0.01 % By weight

Another class of additives which can be added to the detergent or cleaning agent portions according to the invention are polymers. Among these polymers are polymers which, on washing or cleaning or rinsing, have cobuilder properties, for example polyacrylic acids, also modified Polyacrylic acids or corresponding copolymers Another group of polymers are polyvinyl pyrrod and other graying inhibitors, such as copolymers of polyvinyl pyrrodon, Cellulose ethers and the like According to a further embodiment of the invention, so-called soil repellents are also suitable as polymers, as are known to those skilled in the detergent and cleaning agent and are described in detail below

Another group of additives are bleaching catalysts, in particular bleaching catalysts for machine dishwashing detergents or detergents. Complexes of manganese and cobalt are used here, in particular with ligands containing nitrogen

Another preferred group of additives in the sense of the invention are silver protection agents. These are a large number of mostly cych organic compounds which are also familiar to the person skilled in the art and which help to prevent tarnishing of silver-containing objects during the cleaning process Tπazoles, Benzotnazole and their complexes with metals such as Mn, Co, Zn, Fe, Mo, W or Cu

As further additives according to the invention, the detergent or cleaning agent portions can also contain so-called soil repellents, that is to say polymers which build up on fibers or hard surfaces (for example on porcelain and glass) which have a positive effect on the oil and fat washability from textiles and thus one Counteracting re-soiling in a targeted manner This effect is particularly evident if a textile or a hard object (porcelain, glass) is soiled that has already been washed several times beforehand with a washing or cleaning agent according to the invention which contains this oil- and fat-dissolving component the preferred oil- and fat-free components are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropoxy groups of 1 to 15% by weight, based in each case on the nonionic cellulose ethers, as well as those known from the prior art Polymers of phthalic acid and / or terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. The sulfonated derivatives of phthalic and terephthalic acid polymers are particularly preferred All of these additives are added to the detergent or cleaning agent portions according to the invention in amounts of up to at most 30% by weight, preferably 2 to 20% by weight. As already mentioned, the addition can also be made to a material of a water-soluble enclosure, the one or the other The washing action (s) comprises (s) In order to maintain the balance of the recipe, it is therefore possible for the person skilled in the art to either increase the weight of the plastic material for the enclosure, in order to achieve the depot effect of the invention to exploit or to keep at least some of the additives mentioned in the rest of the active detergent preparation. However, this is less preferred

Fragrances are added to the detergent and cleaning agent portions according to the invention in order to improve the overall aesthetic impression of the products and, in addition to the technical performance (fabric softening result), to provide the consumer with a sensorially typical and distinctive product. Individual perfume compounds can be used as perfumes or fragrances are, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon fragrance compounds of the ester type are, for example, benzyl acetate, phenoxy thyrobutyrate, pt-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl-carbinyl acetate, phthal nylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl sahyl cylate The ethers include, for example, benzyl ethyl ether. The aldehydes include linear alkanals with 8 to 18 carbon atoms, citral aldehyde, citral aldehyde Cyclamenaldehyde, Hydroxycitronellal, Lileal and Bourgeonal

The ketones include the lonones, α-isomethyhonone, and methyl cedryl ketone. The alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons are mainly terpenes such as limonene and pmen. Mixtures of different fragrances are preferably used are coordinated with one another in such a way that they together produce an appealing fragrance. Such perfumes can also contain natural fragrance mixtures as are available from plant sources. Examples are pine, citrus, jasmine, patchouli, rose or ylang-ylang. Also suitable are nutmeg, sageiol, chamomile oil, clove oil, messol, mint, cinnamon leafol, lindenblutenol, juniper berryol, vetiverol, ohbanumol, gal- banumol and labdanumol as well as orange blutenol, nero oil, orange peel oil and sandalwood oil

The fragrance content usually lies in the range up to 2% by weight of the total detergent or cleaning agent portion

The fragrances can be incorporated directly into the wash-active preparations, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the wash and ensure a long-lasting fragrance for the textiles due to a slower release of the fragrance Cyclodextrins preserved The cyclodextine-perfume complexes can additionally be coated with other auxiliaries

In principle, the perfumes and fragrances can be contained in each of the partial portions (washing-active preparations) of the detergent or cleaning agent portions according to the invention. However, it is particularly preferred that they are contained in a detergent in a partial detergent provided for the post-wash cycle or fabric softener cycle. Portion or in a detergent, especially in a dishwashing detergent, in a portion of detergent portion intended for rinse or rinse aid, especially portion of detergent portion. According to the invention, therefore, you only have to use one of the conditions (especially the Temperature) of the post-wash cycle or rinse cycle water-soluble material, water-insoluble under the conditions (in particular at the temperature) of the preceding wash cycles or rinse cycles, in particular of a corresponding film or capsule. According to the invention, this is for example with a bag consisting of several chambers s foils of different water solubility possible

In the detergent or cleaning agent portions according to the invention, the at least one (or more) wash-active preparation (s) is completely or partially surrounded by one or more enclosures. According to the invention, an enclosure can be present that completely or at least one wash-active preparation partially includes, or there may be several enclosures that completely or partially comprise the same or different detergent-active preparations. It is possible for the detergent or cleaning agent portion to contain one enclosure or one or more water-soluble ones -

Polymer material (ιen) contains or that several enclosures are included. In the context of the present invention, the presence of an enclosure is preferred, which has advantages in the choice of materials and also in view of the requirement that the water-soluble polymer material be residue-free in the washing or The enclosure (s) can be made from a single water-soluble polymer material or can be made from several different polymer materials. In view of the present task, the use of several different polymer materials can be particularly preferred according to the invention, whereupon will be discussed in more detail below

According to a preferred embodiment of the invention, the water-soluble polymer material that partially or completely surrounds the at least one washing-active preparation is a water-soluble packaging. This is understood to mean a flat-shaped part that partially or completely surrounds at least one washing-active preparation. The exact form of such packaging is not critical and can be largely adapted to the conditions of use There are, for example, various shapes (such as tubes, cushions, cylinders, bottles, disks or the like) processed plastic foils or plates, capsules and other conceivable shapes in question. According to the invention, foils are particularly preferred, for example can be glued and / or sealed to packaging such as hoses, pillows or the like after they have been provided with partial portions of the detergent or cleaning agent portions according to the invention or with the detergent or cleaning agent portfolio according to the invention themselves have been filled

According to the invention, plastic foal packaging made of water-soluble polymer materials is further preferred according to the invention due to the properties which can be adapted to the desired physical conditions

In principle, all polymer materials can be considered as water-soluble polymer materials which, under the given conditions (temperature, pH value, concentration of detergent components), can be completely dissolved in the aqueous phase. The polymer materials can particularly preferably be removed from the groups ) Belong to polyvinyl alcohol, polyvinylpyrrohdon, polyethylene oxide, gelatin, cellulose and their derivatives and mixtures of the materials mentioned Polyvinyl alcohols (PVAL for short) are polymers of the general structure

[-CH ₂ -CH (OH) -] "

those in small quantities also structural units of the type

[-CH ₂ -CH (OH) -CH (OH) -CH ₂ -]

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

Commercial PVAL (eg Mowiol ^® types from Hoechst) are commercially available as white-yellowish powders or granules with degrees of polymerization in the range from approximately 500 to 2500 (corresponding to molar masses from approximately 20,000 to 100,000 g / mol) and have different degrees of hydrolysis from 75 to 99 mol% or from 85 to 92 mol% or from 87 to 89 mol%. They are therefore partially saponified polyvinyl acetates with a residual acetyl group content of approx. 1 to 25 mol% or 8 to 15 mol% or 11 to 13 mol%.

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

Examples of suitable water-soluble PVAL films are the PVAL films available from Syntana Handelsgesellschaft E. Harke GmbH & Co. under the name "SOLUBLON ^® ". Their solubility in water can be adjusted to the degree, and films of this product series are available, which are soluble in the aqueous phase in all temperature ranges relevant to the application. Polyvinylpyrrohones, abbreviated as PVP, can be described by the following general formula

PVP are produced by radical polymerization of 1-vinyl pyrrolidon Commercial PVP have molar masses in the range from about 2500 to 750 000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions

Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula

H- [O-CH ₂ -CH ₂ ] _n -OH

which are technically produced by base-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small water-containing systems with ethylene glycol as the starting molecule.They have molar masses in the range from approx. 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of approx. 5 to> 100,000 Polyethylene oxides have an extremely low concentration of reactive hydroxyl end groups and show only weak glycol properties

Gelatin is a polypeptide (molecular weight approx. 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of the gelatin largely corresponds to that of the collagen, from which it was obtained, and varies depending on its provenance. The use of gelatin as a water-soluble Hullmatenal is extremely widespread, especially in pharmacy in the form of hard or soft gelatin capsules. Gelatin is found in the form of foils because of their compared to the above mentioned polymers high price only little use

Also preferred in the context of the present invention are detergent and cleaning agent portions whose packaging is made of water-soluble film from at least one polymer the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof

Starch is a homoglycan, whereby the glucose units are linked α-glycosidically. Starch is made up of two components of different molecular weights from approx. 20 to 30% straight-chain amylose (MW approx. 50,000 to 150,000) and 70 to 80% branched-chain amylopectin ( MG approx. 300,000 to 2,000,000) In addition, small amounts of lipids, phosphoric acid and cations are contained. While the amylose forms long, helical, intertwined chains with about 300 to 1200 glucose molecules due to the binding in the 1,4 position, branches the chain in the case of amylopectin after an average of 25 glucose units by means of a 1,6-bond to form an astahnhchen structure with about 1,500 to 12,000 molecules of glucose. In addition to pure starch, the detergent and detergent portions for the preparation of water-soluble contents are also within the scope of the present invention Starch derivatives obtainable from starch by polymer-analogous reactions include such chemically modified starches Products from esterifications or etherifications, for example, in which hydroxyl hydrogen atoms have been substituted, but also starches, in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom, can be used as starch derivatives in the group the starch derivatives include, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starters and amino starches

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approx. 500 to 5000 glucose - Units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications, in which hydroxyl hydrogen atoms have been substituted But celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkahcelluloses, Carboxymethylcellulo se (CMC), cellulose esters and ethers as well as amino celluloses Preferred enclosures made of water-soluble film consist of a polymer with a molecular weight of between 5000 and 500,000 Daltons, preferably between 7500 and 250,000 Daltons and in particular between 10,000 and 100,000 Daltons. The water-soluble film which forms the casing preferably has a thickness of 1 to 150 μm, preferably from 2 to 100 μm, particularly preferably from 5 to 75 μm and in particular from 10 to 50 μm

These water-soluble films can be produced by various manufacturing processes. Blowing, calendering and casting processes are to be mentioned here in principle. In a preferred process, the films are blown from a melt with air through a blowing mandrel to form a tube. In the calendering process, this also One of the preferred manufacturing processes used is that the raw materials plasticized by suitable additives are used to form the films. In this case, it may be necessary, in particular, to connect drying to the evaporations. In the casting process, which is also one of the preferred manufacturing processes, an aqueous polymer preparation is applied to a heatable drying roller, after the evaporation of the water is optionally cooled and the film is removed as a film. If necessary, this film is additionally powdered before or during the removal

According to the invention, it is preferred that the one or more enclosures is / are completed. This has the advantage that the active detergent preparations are optimally protected against environmental influences, in particular against moisture Develop further that the detergent or cleaning agent portions to protect the contents of the enclosure (s) from moisture contain at least one gas. According to the invention, two embodiments can be realized

Thus, it corresponds to a preferred embodiment of the invention that the enclosure (s) is / are closed and contains / contain at least one water-free gas which does not react with the wash-active preparation (s), more preferably in an amount that the Total pressure within the closed enclosure (s) is above the external pressure, even more preferably at least 1 mbar above the external pressure. Particularly preferred embodiments of the detergent or cleaning agent Portions according to the invention contain at least one anhydrous gas which does not react with the wash-active preparations in such an amount that the total pressure within the closed enclosure (s) is at least 5 mbar, more preferably at least 10 mbar, very particularly preferably in Range from 10 mbar to 50 mbar. Particularly in the case of the preferred embodiments with a total pressure within the enclosure (s) that is well above the external pressure, access to moisture or water to the interior of the enclosure can surprisingly be reduced or even reliably prevented in connection with the In the present invention, "external pressure" is understood to mean the pressure that prevails on the surrounding side of the enclosure (s) and acts on the exterior of the enclosure (s), specifically at the time of filling the (if necessary, the washing act (s) or spulaktιve (n ) Preparations) already containing) with the respective least ens a water-free gas

According to the invention, the enclosure (s) can either contain an anhydrous gas or can contain several anhydrous gases. In practice, it is preferred to apply a gas to the enclosure (s) due to the associated lower costs The present invention understood that the gas (s) are carefully dried before use in the detergent or cleaning agent portions according to the invention and therefore contain no or almost no water when used, a water content approaching zero being preferred. The drying process can by any route known to the person skilled in the art for this purpose, the aim is that the gases contain as little water as possible which could react with the components in the detergent or cleaning agent portions and thus become more sensitive to moisture or water to a deterioration in the quality of such Components could run Preferred Washing or Re Detergent portions according to the invention comprise as gas (s) at least one anhydrous gas which is selected from the group N ₂ , noble gas (s), C0 ₂ , N ₂ 0, O ₂ , H ₂ , air, gaseous hydrocarbons, entirely especially N ₂ , which is available cheaply everywhere and can be completely "dried" by methods known per se. The gases mentioned are advantageously inert to the components of the detergent-active preparation and are therefore sometimes referred to as "inert gases" in the context of the present invention According to a further, likewise preferred embodiment of the detergent or cleaning agent portion according to the invention, the enclosure (s) is / are closed and contain at least one substance which, when reacted with water, contains a gas which does not react with the washing-active preparation (s) in one Quantity releases that the total pressure within the closed enclosure (s) increases. Those detergent or cleaning agent portions in which the at least one substance contained in the enclosure (s) is at least one gas in reaction with water are particularly advantageous releases a quantity such that the total pressure within the closed enclosure (s) increases by at least 1 mbar above the external pressure, preferably by at least 5 mbar, particularly preferably by a value in the range from 5 to 50 mbar. This embodiment is of particular advantage in that their manufacture compared to the embodiment in which the gas in the closed enclosure g is contained, is greatly simplified, since only the at least one substance that generates at least one gas when in contact with moisture / water in the closed enclosure must be added. Any moisture that has penetrated into the enclosure is immediately capable of reacting with water Substance absorbed and converted and is therefore no longer available for a deterioration in the quality of the components of the detergent preparation. Mixed forms of detergent or detergent preparation are also conceivable, in which both (at least) one anhydrous gas is in the sealed enclosure from the start as well as a substance capable of reacting with water is contained. With this embodiment, the deterioration of the components of the washing-active preparation (s) can be prevented in a particularly good and efficient manner by ingress of moisture or water

According to a preferred embodiment of the invention, the substance which releases a gas with water is a constituent part of the wash-active preparation and is - even more preferably - a hygroscopic substance which is contracted with the components of the wash-active preparations). en) Moisture or water, when this access to the inside of the enclosure, is immediately absorbed with the formation of a gas which increases the internal pressure inside the enclosure to a value above atmospheric pressure and thus surprisingly the access of further moisture or further water difficult or impossible Examples of such substances are, without being understood as limiting, substances which are selected from the group consisting of bound hydrogen peroxide-containing substances, substances containing -OO groups, substances containing OCO groups, hydrides and carbides, more preferably a substance, which is selected from the group of percarbonates (particularly preferably sodium percarbonate), persulfates, perborates, peracids, M _A M _B H ₄ , where M _{A is} an alkali metal (particularly preferably Li or Na) (for example LιAIH ₄ , NaBH ₄ , NaAIH ₄ ) and M _{B is} B or Al, or M ' ₂ C ₂ or M "C ₂ , where M ^{1 is} a monovalent metal and M" is a divalent metal (e.g. CaC ₂ )

According to the invention, detergent or cleaning agent portions are preferred in which the water-free gas contained in the enclosure (s), with which the enclosure (s) are directly applied, is selected from the group N ₂ , noble gas (s), CO ₂ , HO, O ₂ , H ₂ , air, gaseous hydrocarbons or mixtures thereof. Preferred gas - or at least one of the preferred gases used - is N ₂ , because of the fact that nitrogen is available cheaply everywhere and works well with conventional ones Agents can be dried or stored dry

Also preferred according to the invention are those detergent or cleaning agent portions in which the at least one gas formed within the enclosure by the substance reactive with water or moisture is selected from the group CO ₂ , N ₂ , H ₂ , 0 ₂ , gaseous Hydrocarbons such as, in particular, methane, ethane, propane or a mixture of several of the gases mentioned. The gases mentioned are advantageously inert to the components of the detergent-active preparation and are therefore sometimes referred to as “inert gases” in the context of the present invention

Surprisingly, it was found in the context of the present invention that when the at least one anhydrous gas filled in the enclosure or the at least one gas formed from the moisture or water reactive substance builds up a pressure above atmospheric pressure within the at least one enclosure , the (further) access of water or moisture is made difficult or almost impossible due to the water-soluble polymer material of the enclosure. The mechanism for this is not yet clear, but it is observed in the result that the shelf life of the detergents or cleaning agents Servings according to the invention comparable portions of the prior art significantly improved even in a humid environment

The invention also relates to a method for protecting at least one washing-active preparation in an enclosure consisting of at least one water-soluble polymer material from decomposition as a result of contact with moisture or undesired access to water. This can be moisture, for example, as is the case when storing or storing laundry - or cleaning agent portions occur, e.g. in the washroom or laundry room, in the kitchen or during transport or storage between manufacturer and consumer

In order to protect the wash-active preparations from the ingress of moisture or water, the invention proposes two variants of the method. In both variants, the wash-active (s) or spulact-active (s) preparation (s) are provided with at least one enclosure made of a water-soluble polymer. Material In both cases, in the last step, this is also sealed around the at least one wash-active or spool-active preparation, for example by sealing, gluing, fusing, clamping or a combination of the said steps of sealing or by any person skilled in the art in the field of washing detergents. or detergent portions known procedure Particularly preferred are methods of sealing, fusing or gluing, water-soluble adhesives being particularly preferably used in the case of the latter procedure. In the case of using capsules as a casing for the washing act (s) or spulaktve (n) tub Under certain circumstances, simply plugging the two capsule halves together is sufficient as a closure, and in a manner known to the person skilled in the art, a plug closure of the capsule parts can also be used, which is counteracted by a projection / groove system on the two capsule parts unintentional opening is secured

The two embodiments of the method according to the invention now differ in that in one case the enclosure (s) filled with the wash-active preparation (s) and then closed are made of water-soluble polymer material with at least one with the wash-active preparation (s) ) non-reacting water-free gas can be applied. One gas or several gases can be used. pressure or overpressure occur. The at least one anhydrous gas is particularly preferably applied to the enclosure (s) in an amount of the at least one anhydrous gas which is so large that the total pressure within the enclosed enclosure (s) increases. that the total pressure within the closed enclosure (s) is at least 1 mbar above the external pressure, more preferably by at least 5 mbar, particularly preferably by at least 10 mbar and most preferably at a pressure in the range from 10 mbar to 50 mbar above that External pressure is present, that is to say above the pressure which acts from the outside on the enclosure (s) made of the at least one waterless polymer material which surrounds / surrounds the detergent or cleaning agent portion according to the invention. This embodiment allows access of moisture or water in the interior of the enclosure and thus contact of moisture or water with the wascha Make effective preparation (s) effectively difficult or even prevent

In this variant of the method according to the invention, the gas is particularly preferably selected from the group N ₂ , one or more noble gases, CO ₂ , N ₂ 0, 0 ₂ , H ₂ , air, gaseous hydrocarbons and mixtures of the gases mentioned. N _{2 is} used with particular advantage

In the other case of the method according to the invention, at least one substance is introduced into the enclosure which, when reacted with moisture or water, can release at least one gas which does not react with the wash-active substance (s). In this case, too, the reaction should preferably be used The amount of gas released must be so great that the pressure within the (later) closed enclosure rises, particularly preferably so far that it rises by at least 1 mbar, even more preferably by at least 5 mbar and most preferably by 5 to 50 mbar above the external pressure Then the water-soluble polymer material is sealed around the wash-active preparation

In particularly preferred embodiments of the method according to the invention, the substance (s) reacting with moisture or water can either be incorporated into the washing agent (s) or spulacting agent (s), that is to say carefully in the mixture (s) ( en) the components of the detergent preparations are distributed, which can be done in the usual ways of mixing and according to the invention in particular which is preferred, or the substance (s) reacting with moisture or water can be introduced into the enclosure (s) in addition to the components of the wash-active or rinse-active preparations. Both alternatives of this process step lead to a reliable absorption of moisture or water that has penetrated into the interior of the enclosure and therefore contribute to effectively preventing an interaction of the moisture or water with the component (s) of the detergent preparation.

It is further preferred in the stated method according to the invention to incorporate a hygroscopic substance into the washing-active preparation (s) or to add a hygroscopic substance to the preparations. According to the invention, it is particularly preferred to use at least one substance (or also a plurality of substances) which is / are selected from the group consisting of bound hydrogen peroxide-containing substances, substances containing -OO groups, substances containing OCO groups, hydrides and carbides, more preferably a substance , which is selected from the group of percarbonates (particularly preferably sodium percarbonate), persulfates, perborates, peracids, M _A M _B H ₄ , where M _{A is} an alkali metal (particularly preferably Li or Na) and M _{B is} B or Al , for example LiAIH ₄ , NaBH ₄ or NaAIH, or M ' ₂ C ₂ or M "C ₂ , in which M ^{1 is} a monovalent metal and M" is a divalent metal, for example CaC ₂ , but this should not be understood as a limitation is.

In this variant of the method, those substances which are introduced into the enclosure (s) and which can release at least one gas which is selected from the group CO ₂ , N when reacted with water or moisture are used with further advantage ₂ , H ₂ , O ₂ , gaseous hydrocarbons such as methane, ethane, propane and mixtures of the gases mentioned. If one or more of these gases is present, it can surprisingly be prevented that further moisture or water penetrates into the enclosure (s) and this leads to a deterioration in the quality of one or more components of the wash-active or rinse-active preparation (s) of the invention Serving detergent or cleaning agent portions.

The invention also relates to a washing method, in particular a method for machine washing, in which a detergent portion according to the detailed description above is placed in a washing machine and by adding water and adjusting the temperature to a value at which the enclosure (s) detaches from at least one water-soluble polymer material and releases the wash-active preparation (s) into the wash liquor.

Finally, the invention also relates to a cleaning method, in particular a method for machine washing dishes, in which a portion of the cleaning agent according to the detailed description above is placed in a dishwasher and by adding water and adjusting the temperature to a value at which the dimensions) dissolves at least one water-soluble polymer material, which releases the washing-active preparation (s) into the cleaning liquor.

Claims

PATENT CLAIMS

1. Detergent or cleaning agent portion with at least one detergent-active preparation and one or more enclosures (s) surrounding the at least one detergent-active preparation made of one or more water-soluble polymer material (s), in which the enclosure (s) is / are completed and contains at least one anhydrous gas which does not react with the wash-active preparation (s).

2. Detergent or detergent portion according to claim 1, wherein the enclosure (s) contains the at least one anhydrous gas in an amount such that the total pressure within the closed enclosure (s) is above the external pressure, preferably that the total pressure within the closed enclosure (s) is at least 1 mbar above the external pressure, more preferably by at least 5 mbar, even more preferably by at least 10 mbar, particularly preferably in the range from 10 to 50 mbar.

3. Detergent or cleaning agent portion according to claim 1 or claim 2, wherein the at least one anhydrous gas is selected from the group N ₂ , noble gases, CO ₂ , N ₂ O, O ₂ , H ₂ , air, gaseous hydrocarbons, preferred wherein the gas is N ₂ .

4. Detergent or cleaning agent portion with at least one wash-active preparation and one or more enclosures (s) surrounding the at least one wash-active preparation made of one or more water-soluble polymer material (s), in which the enclosure (s) is / are completed and contain at least one substance which, when reacted with water, releases at least one gas which does not react with the wash-active preparation (s) in an amount such that the total pressure within the closed enclosure (s) increases.

5. A detergent or detergent portion according to claim 4, wherein the at least one substance contained in the enclosure (s) releases the at least one gas in reaction with water in an amount such that the total pressure within the closed enclosure (s) by at least 1 mbar rises above the external pressure, preferably by at least 5 mbar, particularly preferably by a value in the range from 5 to 50 mbar.

A detergent or detergent portion according to claim 4 or claim 5, wherein the water-releasing substance is part of the active detergent preparation

A detergent or detergent portion according to any one of claims 4 to 6, wherein the water-releasing substance is a hygroscopic substance, preferably a substance selected from the group consisting of hydrogen peroxide-containing substances, substances containing -OO groups Substances containing OCO groups, hydrides and carbides, more preferably a substance which is selected from the group percarbonates (particularly preferably sodium percarbonate), persulfates, perborates, peracids, M _A M _B H ₄ , where M _{A is} for a Alkahmetall (particularly preferably for Li or Na) and M _{B stands} for B or Al, or M ' ₂ C ₂ or M "C ₂ , where M ^{1 stands} for a monovalent metal and M" stands for a divalent metal

Detergent or detergent portion according to any one of claims 4 to 7, wherein the at least one gas is selected from CO ₂ , N ₂ , O ₂ , H ₂ , gaseous hydrocarbons (in particular methane, ethane, propane) or a mixture of several of the above

Portion of detergent or cleaning agent according to one of claims 1 to 8, wherein the enclosure (s) consists of one or more water-soluble polymer material (s) in the form of films or capsules

A detergent or detergent portion according to any one of claims 1 to 9, wherein the films or capsules are those made from (optionally containing residual acetate groups) polyvinyl alcohol, polyvinylpyrrodon, polyalkylene glycol, gelatin, starch, cellulose or their derivatives or mixtures thereof, preferably those made from polyvinyl alcohol , more preferably films made of polyvinyl alcohol, even more preferably those made of polyvinyl alcohol with a degree of saponification of 75 to 99%, most preferably with a degree of saponification of 85 to 92%

Process for protecting at least one washing-active preparation in a containment consisting of at least one water-soluble polymer material from decomposition. as a result of contact with moisture, in which the wash-active preparation (s) are provided with at least one enclosure made of a water-soluble polymer material, the latter is sealed around the wash-active preparation and the sealed enclosure with at least one with the wash-active preparation (s) non-reacting water-free gas.

12. The method of claim 11, wherein the sealed enclosure is charged with the at least one anhydrous gas in an amount such that the total pressure within the enclosed enclosure (s) is above the external pressure, preferably that the total pressure within the enclosed enclosure (s) is at least 1 mbar above the external pressure, more preferably by at least 5 mbar, even more preferably by at least 10 mbar, particularly preferably in the range from 10 to 50 mbar.

13. The method according to claim 11 or claim 12, wherein the at least one gas is selected from the group N ₂ , noble gases, CO ₂ , N ₂ O, O ₂ , H ₂ , air, gaseous hydrocarbons preferably wherein the gas is N ₂ .

14. A method for protecting at least one wash-active preparation in a casing consisting of at least one water-soluble polymer material from decomposition due to contact with moisture, in which the wash-active preparations are provided with at least one casing made of a water-soluble polymer material the enclosure introduces at least one substance which, when reacted with water, can release at least one gas which does not react with the wash-active preparation (s) in an amount such that the total pressure within the enclosed enclosure (s) increases, and the water-soluble polymer material seals the active washing preparation.

15. The method according to claim 14, wherein at least one substance is introduced into the enclosure which, when reacted with water, can release at least one gas which does not react with the washing-active preparations in an amount such that the total pressure within the closed enclosure (s) increases by at least 1 mbar above the external pressure, preferably by at least 5 mbar, particularly preferably by a value in the range from 5 to 50 mbar.

16. The method according to claim 14 and claim 15, wherein the water-releasing substance at least one substance is incorporated into the detergent preparation.

17. The method according to any one of claims 14 to 16, wherein the hygroscopic substance used as water-releasing substance is a hygroscopic substance, preferably a substance selected from the group consisting of bound hydrogen peroxide-containing substances, -OO- substances, OCO- Group-containing substances, hydrides and carbides, more preferably a substance which is selected from the group percarbonates (particularly preferably sodium percarbonate), persulfates, perborates, peracids, M _A M _B H ₄ , where M _{A is} an alkali metal (particularly preferably for Li or Na) and M _{B is} B or Al, or M ' ₂ C ₂ or M ⁿ C ₂ , where M ^{1 is} a monovalent metal and M "is a divalent metal.

18. The method according to any one of claims 14 to 17, wherein the at least one gas is selected from CO ₂ , N ₂ , O ₂ , H ₂ , gaseous hydrocarbons (in particular methane, ethane, propane) or a mixture of several of the gases mentioned.

19. Washing method, in particular method for machine washing, in which a detergent portion according to one of claims 1 to 10 is placed in a washing machine and by adding water and adjusting the temperature to a value at which the enclosure (s) consists of at least one water-soluble Polymer material dissolves, which releases the wash-active preparation (s) into the wash liquor.

20. Cleaning method, in particular method for machine washing dishes, wherein a detergent portion according to one of claims 1 to 10 is placed in a dishwasher and by adding water and adjusting the temperature to a value at which the enclosure (s) consists of at least dissolves a water-soluble polymer material, which releases the wash-active preparation (s) into the cleaning liquor.