WO2008000562A1

WO2008000562A1 - Detergent or treatment agent portion with a solubility and/or dispersibility gradient

Info

Publication number: WO2008000562A1
Application number: PCT/EP2007/054977
Authority: WO
Inventors: Frank Meier; Matthias Sunder; Dieter Nickel; Katja Peveling
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2006-06-27
Filing date: 2007-05-23
Publication date: 2008-01-03
Also published as: DE102006029838A1

Abstract

The invention relates to a dimensionally stable, single-piece detergent or treatment agent portion having a weight of at least 50g and a solubility and/or dispersibility gradient. Said portion enables a constant amount of an active substance to be released, even when the surface area of the detergent or treatment agent portion reduces.

Description

"Detergent or treating agent portion with solubility and / or dispersibility gradient"

The present invention relates to a dimensionally stable detergent or treating agent portion having a mass of at least 50 g, a process for producing this washing or treating agent portion, a kit comprising the washing or treating agent portion and a bag or container, a process for washing and / or treating of textiles in an automatic washing machine in which the washing or treating agent portion or kit is used, and the use of the washing or treating agent portion or automatic dosing kit in the drum of an automatic washing machine for textiles.

Detergents or treatment agents are available today for the consumer in a variety of forms. In addition to powders and granules, this offer also includes, for example, concentrates in the form of extruded or tableted compositions. These fixed, concentrated or compressed forms of supply are characterized by a reduced volume per dosing unit and thus reduce the costs for packaging and transport. In particular, the washing or treatment tablets additionally meet the consumer's desire for simplified dosage. The corresponding means are comprehensively described in the prior art. However, in addition to the advantages listed, compacted detergents or treatment agents also have a number of disadvantages. Especially tableted supply forms are characterized by their high compression often by a delayed disintegration and thus a delayed release of their ingredients. To solve this "conflict" between sufficient tablet hardness and short disintegration times, numerous technical solutions have been disclosed in the patent literature, reference being made by way of example to the use of so-called tablet disintegrants These disintegrants are added to the tablets in addition to the detergents or treatment-active substances Although they usually do not have washing or treatment-active properties themselves, they add to the complexity and cost of these agents.

As an alternative to the above-described particulate or compacted detergents or treatment agents, solid or liquid detergents or treatment agents which comprise a water-soluble or water-dispersible packaging have been increasingly described in recent years. have. These agents are characterized as the tablets by a simplified dosage, since they can be dosed together with the outer packaging in the washing machine, but on the other hand they also allow the preparation of liquid or powdered washing or treating agent, which compared to the compact data by a better Distinguish resolution and faster effectiveness.

The means mentioned so far have in common that the consumer must always dose the washing or treatment agent separately for each washing or treatment cycle. The tablets, powders, granules, liquids, gels and solid and liquid washing or treating agents repackaged in individual portions are completely consumed in the particular washing or treatment cycle selected.

In the prior art, however, medium portions are described which contain active ingredient for a variety of washing or treatment courses. In US 2002/0132752 A1 (Caruthers et al.) Such an agent is metered by means of a dispenser by metering a defined amount of water into the dispenser filled with the agent, dissolving a portion of the agent and thus providing a concentrated solution of the agent will be produced. This concentrated solution is then introduced into the cleaning device, for example the washing machine, and diluted with further water to a wash liquor which is contacted with the surfaces to be cleaned. A major disadvantage of this technique is that washing machines in which these agents are to be used, must have a separate Dispenser- device, which is not identical to the usual in Europe Einspülkammern.

This drawback does not apply to the solid detergent composition to be used several times, which is disclosed in the application WO 2005/077064 A2 (Ecosafe Technologies L.L.C.). This solid agent is used together with the laundry to be cleaned directly in the drum of the washing machine and releases active substance over several washes. According to the invention, the agent contains a homogeneous amount of cleaning agent, with the result that the agent has the same dissolving or dispersing properties from the "volume center" (in the middle of the room) to the "outer shell" of the detergent portion. However, since the portion of each portion with each wash peeled ingredients, the portion and thus the standing in contact with the water surface of the portion is smaller, with each wash less active material is released.

The object of the present invention was to overcome the disadvantages of the known detergents or treatment agents. In particular, a washing or treating agent should be provided, which can be dosed more easily and which - regardless of the size of the remaining portion of detergent or treating agent - releases substantially the same amount of ingredients in comparable washing or treating operations in an automatic washing machine for textiles.

It has now been found that this object can be achieved by a washing or treating agent portion which has a solubility and / or dispersibility gradient.

The present application is a dimensionally stable, one-piece washing or treating agent portion having a mass of at least 50 g, which has a solubility and / or dispersibility gradients.

It is preferable for the solubility and / or dispersibility gradient to be substantially from the center of the room to the surface of the washing or treating agent portion, ie "radially." It is preferred that the solubility and / or dispersibility of the washing or treating agent portion be radially in the direction Surface decreases.

In the context of the invention, the term "solubility or dispersibility gradient" is understood as meaning both continuously extending gradients and also those gradients whose progress has jumps, that is to say that the washing or treatment agent portion is in the form of several active-agent-containing phases or active substance-containing (shell) Layers is present and these phases or layers have a different solubility and / or dispersibility.

In one embodiment, the detergent or treating agent portion comprises pressed material having a radial density gradient. The density of the compressed material preferably increases radially toward the surface.

In a further embodiment, the washing or treatment agent portion is composed of several layers which have different solubilities and / or dispersing capabilities. The solubilities and / or dispersing capabilities of these layers preferably decrease radially towards the surface of the detergent or treating agent portion.

If a washing or treating agent portion according to the invention is used in an automatic washing machine for textiles, it is preferred that essentially the same amount of the washing or treating agent portion is always dissolved or dispersed during the first use of the portion and the further applications of this portion in comparable washing or treatment operations. Preferably, the deviation is at a Application detached or dispersed amount of washing or treatment agent portion of the average of the detached or dispersed substance amounts always less than 30 wt .-%, preferably less than 20 wt .-%, more preferably less than 10 wt .-% and in particular less than 5% by weight.

The washing or treating agent portion preferably has a mass of from 75 to 1500 g, preferably from 100 to 1000 g, particularly preferably from 200 to 850 g and in particular from 300 to 700 g. The washing or treating agent portion preferably has the form of a prism, preferably a cuboid or an ellipsoid, preferably a spheroid, in particular a flattened or prolapsed spheroid or a sphere. With particular preference, the shape of the washing or treating agent portion corresponds to a prolapsed spheroid having the geometric characteristics of a rugby ball. In a very preferred embodiment, the washing or treating agent portion is spherical and thus has the shape of a ball. The washing or treatment agent portion preferably releases over 2 to 60, more preferably over 4 to 50, and in particular more than 6 to 40 washing or treatment courses in an automatic washing machine for textiles active substance.

To the commercially available washing or treating agents in the form of powders, granules or tablets the requirement of rapid solubility / dispersibility or rapid disintegration is made. The active substances of these agents should be available as early as possible at the beginning of the washing or treatment cycle for which they were dosed individually. In the case of tablets, rapid disintegration is achieved, for example, by adding so-called tablet disintegrators. An opposite task arises with preferred washing or treatment agent portions: These should dissolve / disperse only so slowly that only the required amount of active substance is released per wash or treatment cycle.

The solubility / dispersibility is determined by knocking out a sample of defined mass from the detergent or treating agent portion of the invention or preparing a sample portion of the active-containing shell by compressing or casting the corresponding composition in a small mold and subjecting these samples to a standardized solubility test. For this purpose, a defined amount of city water of the specified water hardness and the respective temperature is placed in a beaker and kept in motion by means of a laboratory stirrer with stirring blades. The above-mentioned samples of defined amount are metered into the water and it is stirred for 300 seconds. Then the solution through a sieve (mesh size 200 .mu.m) is cast glass beaker and agitator blades are rinsed with a minimum of cold water over the sieve, the sieve dried in a drying oven at 40 ⁰ C to constant weight and by means of differential weighing the residue on the sieve. The amount of dissolved / dispersed substance is calculated from the difference between the amount of sample used and the residue. At least one double determination is carried out.

Among the ingredients of the water that interfere with the washing process are the elements calcium and magnesium. These alkaline earths determine the quality of the water for cleaning purposes. Calcium and magnesium ions form sparingly soluble salts with soap, the lime soap and magnesium soap. It is also possible with other anionic surfactants to form sparingly soluble compounds. Furthermore, sparingly soluble alkaline earth metal carbonates can deposit on the laundry and the heating rods of the washing machines. When washing alkaline earth ions are therefore generally undesirable. The sum of alkaline earths is recorded in terms of water hardness (total hardness). It is called water with a high content of calcium and magnesium ions as hard, such low content as soft. The figures are determined in terms of degrees of hardness. In the context of this text, the hardness of the water used is given in the unit German degree of hardness (° d) in use in Germany. In water of 1 ° d are 0.178 mmol / l Ca ²⁺ and Mg ²⁺ ions or water, which contains 1 mmol / l Ca ²⁺ and Mg ²⁺ ions, has a water hardness of 5.6 ° d , Also a disturbing effect when washing show iron and iron ions, which occur in low concentration in drinking and surface water. They form sparingly soluble salts in aqueous solution which can be identified by their yellow to brown color. The content of these salts in the city water used for the solubility test is preferably below 0.01 mg / 100 ml, in particular below 0.005 mg / 100 ml.

A reduced solubility / dispersibility compared to the laundry or treating agents which need to be dispensed separately per wash can be achieved in the detergent or treating agent portions of the present invention by compounding the washing or treating agent portion with a solubility control system. The system for controlling the solubility is preferably in homogeneous admixture with the detergent or treating agent composition and thus controls the solubility or the dispersibility of the respective washing or treatment agent phase or layer. In order to obtain a washing or treating agent portion with solubility or dispersibility gradients, the portion is preferably made up of several layers containing different systems for controlling the solubility and / or which are pressed to different extents, and which are preferably arranged in the portion in such a way in that the solubility / dispersibility of the individual layers decreases radially towards the surface.

The system for controlling the solubility of the washing or treating agent portion is preferably in an amount of at least 5 wt .-%, preferably of at least 10 wt .-%, particularly preferably from at least 15 wt .-%, most preferably in an amount of 20 to 65 wt .-% and in particular in an amount of 25 to 60 wt .-%. The system for controlling the solubility preferably comprises at least one component which has a softening temperature between 35 and 200 ^° C., preferably between 45 and 150 ^° C. Alternatively, or in addition to the system to control the solubility preferably comprises a component which possibilities at 15 ° C and 50 ⁰ C significantly different solubility / dispersibilities in water (see above Illustrated solubility) has. Preferably dissolve / disperse from this component in 15 ° C warm water (city water, 16 ° d) at most 20 wt .-%, preferably at most 10 wt .-% and in particular at most 5 wt .-% of the mass, which is otherwise identical conditions of the component in 50 ⁰ C warm water (city water, 16 ° d) dissolves / dispersed.

In principle, all compounds which have a suitable solubility / dispersion profile can be present in the system for controlling the solubility. Particularly suitable are compounds from the group of polymers, which can also be used in combination with one another.

Suitable polymers are a) water-soluble nonionic polymers from the group of a1) polyvinylpyrrolidones, a2) vinylpyrrolidone / vinyl ester copolymers, a3) cellulose ethers

b) water-soluble amphoteric polymers from the group of b1) alkylacrylamide / acrylic acid copolymers b2) alkylacrylamide / methacrylic acid copolymers b3) alkylacrylamide / methylmethacrylic acid copolymers b4) alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b6) alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid

Copolymers b7) alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate

Copolymers b8) Copolymers of b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids bδiii) optionally further ionic or nonionic monomers c) water-soluble zwitterionic polymers from the group of d) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their

Alkali and ammonium salts c2) Acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts c3) Methacroylethylbetain / methacrylate copolymers

d) water-soluble anionic polymers from the group of d1) vinyl acetate / crotonic acid copolymers d2) vinylpyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers d4) graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or im Mixture copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one nonionic type monomer, d5ii) at least one ionic type monomer, dδiii) from polyethylene glycol and d5iv) a crosslinked d6) copolymers obtained by copolymerization of at least one monomer of each of the following three groups: d6i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, d6ii) unsaturated carboxylic acids, dθiii) esters of long chain Carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched Cs-is-alcohol d7) terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester d8) tetra- and pentapolymers d8i) crotonic acid or allyloxyacetic acid d8ii) vinyl acetate or vinyl propionate dδiii) branched allyl or methallyl esters d8iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters d9) crotonic acid copolymers with one or more monomers from the

Group ethylene, vinylbenzene, vinylmethyl ether, acrylamide and their water-soluble salts d10) terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic α-branched monocarboxylic acid

e) water-soluble cationic polymers from the group of e1) quaternized cellulose derivatives e2) polysiloxanes with quaternary groups e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid e5) Copolymers of vinylpyrrolidone with quaternized derivatives of the dialkylaminoacrylate and methacrylate e6) vinylpyrrolidone-methoimidazolinium chloride copolymers e7) quaternized polyvinyl alcohol e8) polymers indicated under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

In a preferred process variant, the solubility control system comprises one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof and their mixtures.

In the present invention, it is preferable that the solubility controlling system at least partially comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, more preferably 81 to 89 mol%, and especially 82 to 88 mol%. Preference is given to using polyvinyl alcohols of a specific molecular weight range, it being preferred according to the invention for the solubility control system to comprise a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 1,000 to 90,000 gmol ^-1 , particularly preferably 12,000 ^{"gmol 1} and in particular from 13000 to ^70000" to 80,000 gmol ^1. The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.

The water solubility of PVAL can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization). As particularly preferred and due to their Polyvinyl alcohols which have been acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven particularly advantageous. To use extremely advantageous are the reaction products of PVAL and starch.

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

PVP are prepared by radical polymerization of 1-vinylpyrrolidone. Commercially available PVP have molecular weights in the range of about 2,500 to 750,000 g / mol and are 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 J _n -OH

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

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

Preferred as a component of the solubility control system are materials comprising a polymer selected from the group consisting of starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose, and mixtures thereof. Starch is a homoglycan, wherein the glucose units are linked α-glycosidically. Starch is composed of two components of different molecular weight; from about 20 to 30% straight-chain amylose (MW about 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (MW about 300,000 to 2,000,000). In addition, small amounts of lipids, phosphoric acid and cations are still included. Whereas the amylose forms long, helical, entangled chains with about 300 to 1,200 glucose molecules as a result of the 1,4-position bond, the amylopectin branch branches off into a branch-like structure after an average of 25 glucose building blocks by 1,6-binding with about 1,500 to 12,000 molecules of glucose. In addition to pure starch, starch derivatives which are obtainable from starch by polymer-analogous reactions are also suitable. Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, starches in which the hydroxy groups have been replaced by functional groups that are not bonded via an oxygen atom can also be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino starches.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ Os) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5,000 glucose units and therefore have average molecular weights of 50,000 to 500,000.

Further suitable as a component of the system for controlling the solubility are fusible substances from the group of fats and / or triglycerides and / or fatty acids and / or fatty alcohols and / or waxes and / or paraffins.

Fat (s) or triglyceride (s) is the name for compounds of glycerol in which the three hydroxy groups of glycerol are esterified by carboxylic acids. The naturally occurring fats are triglycerides, which usually contain different fatty acids in the same glycerol molecule. By saponification of the fats and subsequent esterification or reaction with acyl chlorides, however, synthetic triglycerides in which only one fatty acid is bound are also available (for example tripalmitin, triolein or tristearin). Natural and / or synthetic fats and / or mixtures of the two are preferred as a component of the solubility control system.

As fatty acids in the present application aliphatic saturated or unsaturated, carboxylic acids with branched or unbranched carbon chain called. For the production of fatty acids, a variety of manufacturing methods exist. While the lower fatty acids are mostly oxidative processes starting from alcohols and / or aldehydes As well as aliphatic or acyclic hydrocarbons based, the higher homologs most often still today most accessible by saponification of natural fats. With advances in transgenic plants, there are now almost limitless possibilities for varying the fatty acid spectrum in the storage fats of oil plants. Preferred fatty acids in the context of the present invention have a melting point which permits processing of these fats in a casting process. In this case, fatty acids have proved to be particularly advantageous, which have a melting point above 25 ° C. Preferred components of the solubility control system are therefore capric acid and / or undecanoic acid and / or lauric acid and / or tridecanoic acid and / or myristic acid and / or pentadecanoic acid and / or palmitic acid and / or margaric acid and / or stearic acid and / or nonadecanoic acid and / or Arachinic acid and / or erucic acid and / or elaeosteraric acid. But also fatty acids with a melting point below 25 ° C can be used.

Fatty alcohol is a collective name for the linear, saturated or unsaturated primary alcohols having 6 to 22 carbon atoms obtainable by reduction of the triglycerides, fatty acids or fatty acid esters. The fatty alcohols may be saturated or unsaturated depending on the method of preparation. Myristyl alcohol and / or 1-pentadecanol and / or cetyl alcohol and / or 1-heptadecanl and / or stearyl alcohol and / or erucyl alcohol and / or 1-nonadecanol and / or arachidyl alcohol and / or 1-heneicosanol and / or behenyl alcohol and / or Erucyl alcohol and / or brassidyl alcohol are preferred components of the solubility control system.

It has also proved to be advantageous if the system for controlling the solubility in the washing or treating agent portions according to the invention contains waxes. Preferred waxes have a melting range of between about 35 ° C and about 75 ° C. That is, in the present case, the melting range occurs within the specified temperature interval and does not indicate the width of the melting range. Waxes with such a melting range are dimensionally stable at room temperature, but melt at typical automatic washing machine temperatures of 30 ⁰ C to 90 ⁰ C and are therefore more easily water-dispersible at these temperatures.

"Waxing" is understood to mean a series of naturally or artificially produced substances which generally melt above 40 ^° C. without decomposition and are already relatively low-viscous and non-stringy just above the melting point. They have a strong temperature-dependent consistency and solubility. According to their origin, the waxes are divided into three groups, the natural waxes, chemically modified waxes and the synthetic waxes.

The natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, Japan wax, Espartograswachs, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, spermaceti, lanolin (wool wax), or crepe fat, mineral waxes such as ceresin or ozokerite (groundwax), or petrochemical waxes such as petrolatum, paraffin waxes or microwaxes.

The chemically modified waxes include, for example, hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes are generally understood as meaning polyalkylene waxes or polyalkylene glycol waxes. It is also possible to use as meltable or softenable substances for the compositions which cure by cooling, and compounds of other substance classes which fulfill the stated requirements with regard to the softening point. Suitable synthetic compounds, for example, higher esters of phthalic acid, in particular dicyclohexyl have hexyl phthalate, commercially available under the name Unimoll 66 ^® (Bayer AG) is available, proven. Also suitable are synthetic waxes made of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ^® ETLP (Condea) is available. Conversely, synthetic or partially synthetic esters of lower alcohols can be used with fatty acids from natural sources. This class of substances includes, for example, ^Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate. Shellac, for example shellac KPS-Dreiring-SP (Kalkhoff GmbH) can also be used.

Likewise to the waxes in the context of the present invention, for example, the so-called wax alcohols are calculated. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols having generally about 22 to 40 carbon atoms. The wax alcohols are, for example, in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating of the present invention the solid particles coated can optionally also contain wool wax alcohols which are understood to be understood triterpenoid and steroid alcohols, for example lanolin, available, for example, under the trade designation Argowax ^® (Pamentier & Co).

In another preferred embodiment, the solubility control system includes paraffin wax (paraffins). Preferably, at least 50% by weight of the system is for control the solubility of paraffin wax. Particularly suitable are paraffin wax contents (based on the total weight of the system for controlling the solubility) of about 60 wt .-%, about 70 wt .-% or about 80 wt .-%, with even higher levels of, for example, more than 90 wt. % are particularly preferred. In a particular embodiment of the invention, the entire system for controlling solubility is paraffin wax.

In the context of the present invention, paraffin waxes have the advantage over the other natural waxes mentioned that they do not undergo hydrolysis in an alkaline environment (as is to be expected, for example, with wax esters), since paraffin wax contains no hydrolyzable groups.

Paraffin waxes consist mainly of alkanes as well as low levels of iso- and cycloalkanes. Preferably, the content of the paraffin wax used at ambient temperature (usually about 10 to about 30 ⁰ C) solid alkanes, isoalkanes and cycloalkanes as high as possible. The more solid wax constituents in a wax at room temperature, the more useful it is within the scope of the present invention.

Preferred components for the system for controlling the solubility are also polyalkylene glycols, preferably polyethylene glycols and polypropylene glycols. Polymers of ethylene glycol, those of the general formula

H- (O-CH ₂ -CH ₂ ) _n -OH

satisfy, where n can assume values between 1 (ethylene glycol) and several thousand. Technically common is the specification of the average relative molecular weight following the indication "PEG", so that "PEG 200" characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210. The average relative molecular weight of the polyalkylene glycol (s) used is preferably between 200 and 36,000, preferably between 200 and 14,000 and particularly preferably between 300 and 12,000.

Polypropylene glycols (abbreviated PPG) are polymers of propylene glycol which are of the general formula

H- (O-CH-CH ₂ ) _n -OH

CH ₃ satisfy, where n can assume values between 1 (propylene glycol) and several thousand. Of particular technical importance here are di-, tri- and tetrapropylene glycol, ie the representatives with n = 2, 3 and 4 in the above formula.

Particular preference is given to using systems for controlling the solubility which comprise a nonionic polymer, preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol, where the weight fraction of the poly (ethylene) glycol in the total weight of the solubility control system is preferably between 10 and 90% by weight, more preferably between 30 and 80% by weight and in particular between 50 and 70% by weight. Particularly preferred are systems for controlling the solubility which are more than 92% by weight, preferably more than 94% by weight, more preferably more than 96% by weight, very preferably more than 98% by weight and in particular 100% % By weight of poly (alkylene) glycol, preferably poly (ethylene) glycol and / or poly (propylene) glycol, but in particular poly (ethylene) glycol. Systems for controlling the solubility, which in addition to poly (ethylene) glycol also contain poly (propylene) glycol, preferably have a ratio of the weight fractions of poly (ethylene) glycol to poly (propylene) glycol between 40: 1 and 1: 2, preferably between 20: 1 and 1: 1, more preferably between 10: 1 and 1, 5: 1 and in particular between 7: 1 and 2: 1.

Other preferred components of the solubility control system are the nonionic surfactants which are used alone, but more preferably in combination with a nonionic polymer. Detailed information on the usable nonionic surfactants can be found in the context of the description of washing or treatment-active substances.

Another class of compounds that is preferred for use in the solubility control system are the sugars, sugar acids, and sugar alcohols.

The monosaccharides, disaccharides and oligosaccharides and derivatives and mixtures thereof are preferably used. Particularly preferably glucose, fructose, ribonucleic se, maltose, lactose, sucrose, maltodextrin and isomalt are ^® and mixtures of two, three, four or more mono- and / or di-saccharides and / or derivatives of mono- and / or di-saccharides ,

The sugar acids can be used alone or in combination with other substances such as the above-mentioned sugars as part of a preferred liquid release agent. Preferred sugar acids are gluconic acid, galactonic acid, mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid, and 2-deoxyribonic acid and derivatives thereof. Preferably in mixture with these sugar acids, derivatives of the sugar acids, sugars and / or sugar derivatives or alone are used compounds from the group of the sugar alcohols, preferably mannitol, sorbitol, xylitol, dulcitol and arabitol.

Suitable polyhydric alcohols as components of the solubility control system are compounds having at least two hydroxyl groups. The physical state of these compounds at room temperature (20 ⁰ C) is fixed. Particularly suitable polyhydric alcohols are, for example, trimethylolpropane, pentaerythritol and the "sugar alcohols", ie the polyhydroxy compounds formed from monosaccharides by reduction of the carbonyl group. One differentiates in these according to the number of hydroxyl groups contained in the molecule Tetrite, Pentite, Hexite, etc. In the context of the present invention particularly suitable sugar alcohols are, for. B. Threit u. Erythritol, adonite (ribitol), arabitol (formerly: lyxite) and xylitol, dulcitol (galactitol), mannitol and sorbitol (glucitol), the latter also being referred to as sorbitol.

Another preferred class of material that can be used as a component of the solubility control system is water-soluble polyurethanes. Polyurethanes are polyadducts of at least two different monomer types, a di- or polyisocyanate (A) and a compound (B) having at least 2 active hydrogen atoms per molecule.

The polyurethanes used as solution or suspension or dispersion are obtained from reaction mixtures in which at least one diisocyanate and at least one polyethylene glycol and / or at least one polypropylene glycol are present.

In addition, the reaction mixtures may contain further polyisocyanates. A content of the reaction mixtures - and thus of the polyurethanes - on other diols, triols, diamines, triamines, polyetherols and polyesterols is possible. The compounds having more than 2 active hydrogen atoms are usually used only in small amounts in combination with a large excess of compounds having 2 active hydrogen atoms. The polyurethanes contain diisocyanates as monomer unit. The diisocyanates used are predominantly hexamethylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 4,4'-methylenedi (phenyl isocyanate) and in particular isophorone diisocyanate. The polyurethanes furthermore contain diols as the monomer component, these diols originating at least partially from the group of the polyethylene glycols and / or the polypropylene glycols. In preferred embodiments of the present invention, the polyurethanes have molecular weights of from 5,000 to 150,000 gmol ^-1 , preferably from 10,000 to 100,000 gmol ^-1, and more preferably from 20,000 to 50,000 gmol ^-1 . In summary, the layers within the detergent or treating agent portion comprise pressed material and / or a system for controlling the solubility of the respective layer. The system for controlling the solubility preferably comprises one or more components from the group of polyethylene glycols, polypropylene glycols, polybutyrates, polyhydric alcohols, sugars, polyurethanes, natural waxes, chemically modified waxes, synthetic waxes, wax alcohols, wax esters, paraffins, polyvinyl alcohols, polyacrylic acids and their derivatives, gelatin and celluloses. Particularly preferred are solubility control systems comprising paraffins and / or polyethylene glycols. Also suitable components of a system for controlling the solubility of the washing or treating agent portions according to the invention are amorphous silica and potassium silicate.

Layers of the detergent or treating agent portion containing a system for controlling the solubility of the respective layer are preferably obtained by lowering the temperature, incorporating water of hydration or other solvent components, reacting components contained in the fluid masses, modification conversions, evaporating water or other solvent components, condensation , Irradiated or solidified by pressing.

Particularly preferred detergent or treating agent portions comprise multiple layers containing as systems for controlling the solubility of the respective layer polyethylene glycol of different average molecular mass and / or paraffins of different average molecular mass. In this case, the layers are preferably arranged such that the solubility and / or dispersibility of the washing or treatment agent portion decreases radially in the direction of the surface.

In one embodiment with a plurality of active substance-containing layers, the washing or treating agent portion according to the invention has at least two, preferably between 3 and 20 and in particular 4 to 15 layers which, when used in an automatic washing machine, are dissolved / dispersed essentially successively, from outside to inside become. It is particularly preferred if, per washing or treatment cycle, at most one, preferably one of the layers of the washing or treating agent is consumed.

In a preferred embodiment, the individual layers of the detergent or treating agent portion contain substantially the same detergent or treating agent composition except for the solubility control system. If a layer of the portion is always dissolved / dispersed in several washing or treatment courses, the same active ingredients are preferably always released in the same quantitative ratio and preferably in a comparable amount. However, it can also be provided that the individual layers differ in composition. It is preferred, for example, that the layers have different colors, so that the consumer can understand the layer degradation on the basis of the color change of the washing or treatment agent portion. Also preferred is the packaging of the individual layers with different perfumes, which causes the textiles washed or treated in separate washing or treatment courses to have a different fragrance.

In a preferred embodiment, the washing or treating agent portion according to the invention comprises a base detergent for white and / or colored textiles, delicate textiles and / or wool.

Basic detergents for white textiles or colored textiles are known to consumers in Europe under the term heavy duty detergent or color washing medium. Basic laundry detergents for wool are commercially available under the term wool detergents. In the context of these remarks, the term "basic detergents for delicate textiles" is intended to encompass all substances which are suitable for washing and treating special textiles Examples of such basic detergents are light detergents, curtain detergents, black textile detergents, white textile detergents , which should not be brought into contact with heavy-duty detergents, detergents for synthetic textiles etc. Suitable ingredients of basic detergents are listed later.

With particular preference comprises a washing or treatment agent portion according to the invention

5 to 15 wt .-%, preferably 7 to 13 wt .-% anionic surfactant, 0.5 to 7 wt .-%, preferably 1 to 5 wt .-% of nonionic surfactant, 12 to 45 wt .-%, preferably 15 to 40 Wt .-% builder including cobuilder, 0 to 0.6 wt .-%, preferably 0.05 to 0.3 wt .-% enzymes, optionally bleach activator and / or optical brighteners and

30 to 70 wt .-%, preferably 35 to 65 wt .-% of a system for controlling the solubility.

If the washing or treating agent portion comprises a base wash, the portion preferably has a mass of from 150 to 1000 g, preferably from 250 to 900 g, more preferably from 300 to 800 g and in particular from 350 to 700 g. With particular preference, the washing or treatment composition comprising a base detergent for white and / or colored textiles, sensitive textiles and / or wool contains significant amounts of surfactant, for example at least 6% by weight, preferably at least 9% by weight anionic surfactant. Includes a washing or treating agent portion of one of the above-mentioned base detergents, so this preferably over 2 to 40, preferably over 4 to 30 and especially about 6 to 20 washing or treatment courses in an automatic washing machine for textiles free active. In the context of the present text, the term "wash cycle" is understood to mean any wash program that can be set in an automatic washing machine, such as, for example, kitchen linen, coloreds, delicates, handwashes, wool washing programs at different temperatures. The term treatment includes those programs of an automatic washing machine whose main focus is not on the cleaning of textiles, but their equipment and treatment. Examples of treatment courses are starches, rinsing, dyeing, soaking, etc .. Washing or treatment operations each include the actual washing or treatment cycles and rinsing cycles. Per wash or treatment, preferably 40 to 150 g, preferably 50 to 140 g, more preferably in particular 60 to 130 g and in particular 70 to 120 g of the base detergent-containing detergent or treatment agent portion dissolved / dispersed.

A preferred subject matter of the present invention is a dimensionally stable, one-part washing or treating agent portion having a mass of at least 50 g, comprising a base detergent for white and / or colored textiles, sensitive textiles and / or wool, which enzyme and / or substantial amounts of surfactant, preferably at least 6 wt .-% surfactant and having a solubility and / or dispersibility gradients.

In a further, likewise preferred embodiment, the detergent or treatment agent portion comprises an additional component for a base detergent for white and / or colored textiles, sensitive textiles and / or wool, preferably a bleach, enzyme or finishing component for textiles, antimicrobial agents and / or nonionic surfactants, enzymes and mixtures of these components.

The term "finishing components for textiles" includes those components which are applied to the fibers of the textiles and thus bring about a change in the properties of the textile surfaces Examples of suitable finishing components are fabric softening compounds such as cationic surfactants, clays, cationic polymers and polysiloxanes Soil repellent polymers, preferably from the group of terephthalic compounds, which are particularly preferably sulfonated, repellents or impregnating agents, antistatic agents, optical brighteners, UV protectants, skin care components and compounds such as silicone derivatives, which are an improvement The textiles finishing components also include fragrance compositions, crease inhibitors, grayness inhibitors, shrinkage inhibitors, etc., as well as perfume compositions, wrinkle retardants, graying inhibitors, anti-wetting properties of the treated textiles, and ease of ironing the treated textiles der, fluorescers and color transfer inhibitors. A washing or treating agent portion according to the invention comprising an additional component for a base detergent preferably has a mass of from 65 to 1000 g, preferably from 75 to 800 g, more preferably from 85 to 600 g and in particular from 95 to 500 g. With particular preference contains a washing or treating agent portion which comprises an additional component for a washing or treating agent, at least 20 wt .-%, preferably at least 30 wt .-% and in particular at least 40 wt .-% bleaching agent, at least 0.5 wt .-%, preferably at least 1, 5 wt .-% and in particular at least 2.5 wt .-% enzyme, at least 20 wt .-%, preferably at least 30 wt .-% and in particular at least 40 wt .-% of a plasticizer and / or at least 1, 5 wt .-%, preferably at least 3 wt .-%, particularly preferably at least 4.5 wt .-% and in particular at least 10 wt .-% of at least one soil repellent polymer, which preferably terephthalate groups and sulfonate groups. If the washing or treating agent portion comprises an additional component, it preferably releases active substance in an automatic washing machine for from 5 to 60, preferably from 10 to 50 and in particular from 15 to 40 washing or treatment courses. 1 to 60 g, preferably 1, 5 to 55 g and in particular 2 to 50 g of the additional component-containing washing or treatment agent portion are dissolved / dispersed per wash or treatment cycle.

Another preferred subject matter of the present invention is a dimensionally stable, one-part washing or treating agent portion having a mass of at least 50 g, comprising an additional component for a washing or treating agent, preferably a bleaching, enzyme and / or finishing component for textiles and at least 6 wt % Surfactant and a solubility or dispersibility gradient.

If the detergent or treating agent portion contains equipment components as defined above, then it may be preferred that the active ingredients should be released primarily in the rinse cycles of a laundry or treat cycle. The solubility / dispersibility of such agents is preferably controlled via the pH and / or ionic strength of the use liquor by means of a (physico) chemical switch so that the detergent or treating agent portion comprising the equipment component and the (physicochemical switch in the Cycles in which no or little washing or treating agents are dissolved in the water, ie in the rinsing cycles, dissolves / dispersed, however, in the cycles in which washing or treating agent is dissolved in a significant amount in the water, not or only to a small extent part dissolves / dispersed. with preference dissolved / dispersed by the active- material coating layer containing an inventive washing or treatment agent portion, which has a gear component, in a 0.1 M sodium hydroxide (NaOH + city water 16 ° d, 20 ⁰ C) and / or 1 M saline (saline + city water 16 ° d, 20 °) less than 30% by weight, preferably less than 25% by weight. , preferably less than 20 wt .-% and in particular less than 15 wt .-% of the mass, which under otherwise identical conditions by the coating layer containing the active ingredient in water (city water 16 ° d, 20 ⁰ C, without further additives) dissolved / dispersed.

Preferably, the (physico-) chemical switch comprises one or more component (s) undergoing a change in the physical and / or chemical properties of a change in the electrolyte concentration (the ionic strength) in the washing, treatment or rinsing liquor , Alternatively or in addition, the (physicochemical) chemical switch may include one or more components that change when the H ⁺ ion concentration (pH) in the wash, treatment or rinse liquor is changed the physical and / or chemical properties learns / experienced.

The (physico-) chemical switch causes the washing or treating agent in water, which has a high pH and / or a high ionic strength, a lower solubility / dispersibility, as in water, which has a lower pH Value and / or a lower ionic strength. With particular preference, the (physico-) chemical switch itself has washing, treatment or rinse-active properties. The (physicochemical switch preferably contains one or more substances from the group comprising (acidic) cellulose derivatives, in particular cellulose acetate phthalate, hydroxypropylmethylcellulose, hydroxypropylmethylcellulose acetate succinate, methylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, methylhydroxyethylcellulose, carboxymethylcellulose with different degrees of substitution, (acidic) poly (meth) ) acrylates, in particular methacrylic acid-methacrylate copolymer, methacrylic acid-ethyl acrylate copolymer, (acidic) polymers based on vinyl alcohol, in particular polyvinyl acetate phthalate, polyvinylpyrrolidones, polystyrene sulfonate, shellac, proteins, basic polymers and / or copolymers, in particular amino groups or aminoalkyl groups, imino groups and / or pyridine groups-containing basic polymers and / or copolymers and in particular aminoalkyl-methacrylate copolymer, particularly preferably the switch comprises cellulose derivatives, in particular methylcellu loosely, hydroxyethylcellulose, hydroxypropylcellulose, methylhydroxyethylcellulose, carboxymethylcellulose with various degrees of substitution; Polyvinyl alcohols having various degrees of saponification and molecular weights; Polyelectrolytes, e.g. Polyacrylates and particularly preferably polystyrenesulfonate, basic polymers and / or copolymers, in particular those the amino groups or aminoalkyl groups, imino, amido or pyridine wear, with particular preference aminoalkyl methacrylate copolymer or N-oxidized polyvinylpyridine.

Preferred constituents of the washing or treating agent portion are builders, nonionic surfactants, anionic surfactants, polymers, complexing agents, bleaching agents, bleach activators, bleach catalysts, enzymes, fragrances, dyes, pH adjusters, foam inhibitors, anti-settling agents or soil repellent polymers, grayness inhibitors, fabric softeners - Components, repellents or impregnating agents and antistatic agents, silicones, UV protection substances and optical brighteners. These are described below.

The builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.

With preferred crystalline layered silicates of general formula NaMSi _x O _{2x + I} ^■ y H ₂ O are used, wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, wherein particularly preferred Values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layered silicates of the formula NaMSi _x O _{2x + 1} ^■ y H ₂ O are sold for example by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ ^.xH ₂ O, kenyaite), Na-SKS-2 (Na ₂ Sh ₄ O ₂₉ ^.xH ₂ O, magadiite), Na-SKS -3 (Na ₂ Si ₈ Oi ₇ ^.xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ ^.xH ₂ O, makatite).

Particularly suitable for the purposes of the present invention are crystalline layer silicates with the formula NaMSi _x O _{2x + 1} ^■ y H ₂ O, in which x stands for 2 h. In particular, both .beta.- and δ-sodium Na ₂ Si ₂ O ₅ ^■ y H ₂ O, and further in particular Na-SKS-5 ((X-Na ₂ Si ₂ O _5), Na SKS-7 (B- Na ₂ Si ₂ O _5, natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ ^■ H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ ^■ 3 H ₂ O, kanemite), Na-SKS-11 (T-Na ₂ Si ₂ 0 ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (6-Na ₂ Si ₂ O ₅ ) is preferred.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "a-morph" is understood to mean that the silicates in X-ray diffraction experiments do not give sharp X-ray reflections typical of crystalline substances, but at most one or more maxima of the scattered X-rays having a width of several degrees of the diffraction angle.

Alternatively or in combination with the abovementioned amorphous sodium silicates, X-ray amorphous silicates are used whose silicate particles produce blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such X-ray amorphous silicates, also have a dissolution delay compared to the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

Of course, it is also possible to use the generally known phosphates as builders, if such an application should not be avoided for ecological reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with particular preference of pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are the most important in the detergent and cleaner industry.

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

Technically particularly important phosphates are the pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ Oi ₀ (potassium tripolyphosphate). The sodium potassium tripolyphosphates are also preferably used according to the invention.

Further builders are the alkali carriers. Examples of alkali carriers are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the alkali metal silicates, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention. Particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate. Also particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.

Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s).

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates. These classes of substances are described below. Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

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

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and 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. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol. To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,

Further preferred copolymers are those which have as their monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glycolysis, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers 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, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE of between 3 and 20 and dry glucose syrups with a DE of between 20 and 37 and also so-called yellow dextrins and white dextrins with relatively high molecular weights in the range from 2000 to 30 000 g / mol are useful.

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.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine succinate, are other suitable co-builders. Ethylenediamine-N, ^{N'-disuccinate} (EDDS) is preferably used in form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates.

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

In addition, all compounds capable of forming complexes with alkaline earth ions can be used as builders.

The washing or treating agent portion preferably comprises surfactants from the group of nonionic surfactants, anionic surfactants, amphoteric surfactants and / or zwitterionic surfactants, preferably nonionic and / or anionic surfactants. The washing or treating agent portion preferably contains at least 6% by weight of surfactant, more preferably at least 8% by weight of surfactant, most preferably at least 10% by weight and in particular at least 12% by weight of surfactant.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, washing or treating agents contain nonionic surfactants from the group of alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol residue is linear or preferably methyl-branched in the 2-position may be or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, Taigfetto- or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -i ₄ -alcohols with 3 EO or 4 EO, C ₉ . n-Alcohol with 7 EO, Ci _3- i ₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci ₂ -i ₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures from C ₁₂ -i ₄ -alcohol with 3 EO and C ₁₂ _ ₁₈ -alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). Alternatively or in addition to these nonionic surfactants fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially methyl-branched in the 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1, 2 to 1, 4.

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

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

Further suitable surfactants are polyhydroxy fatty acid amides of the formula

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

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

R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having from 1 to 8 carbon atoms, where C | _4- alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.

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

With particular preference further combinations of one or more Taigfettalkoholen be used with 20 to 30 EO and silicone defoamers.

Nonionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO / AO / EO nonionic surfactants, or the PO / AO / PO nonionic surfactants, especially the PO / EO / PO nonionic surfactants are particularly preferred. Such PO / EO / PO nonionic surfactants are characterized by good foam control.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. Suitable surfactants of the sulfonate type are preferably C ₉ -i ₃ -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and also disulfonates, as are known for example from C 1 _{_2-18} monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates, which are obtained from C _12-i ₈ alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. Likewise suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

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

Also, the sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 moles of ethylene oxide. ₂ i-alcohols, such as 2-methyl-branched Cg.-π-alcohols having on average 3.5 mol of ethylene oxide (EO) or Ci ₂ _i ₈ -Fettalkohole with 1 to 4 EO, are suitable.

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

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel 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, in particular in the form of the sodium salts.

The group of polymers includes, in particular, the washing or treatment-active polymers and / or polymers which act as softeners. In general, cationic, anionic and amphoteric polymers can be used in detergents or treatment agents in addition to nonionic polymers.

"Cationic polymers" in the meaning of the present invention are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, the Vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

For the purposes of the present invention, "amphoteric polymers" also have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may, for example, be carboxylic acids, sulfonic acids or phosphonic acids.

The bleaching agents are a particularly preferred washing or treatment-active substance. Among the compounds used as bleaching agents in water H ₂ O ₂ compounds, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate hydrate have special meaning. Other useful bleaching agents are, for example, peroxypyrrophosphates, citrate perhydrates and H ₂ O ₂ -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, a- also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperacycaproic acid [Phthaliminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonylamidoperoperadipic acid and N-nonenylamidopersuccinates and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl- di (6-aminopercaproic acid).

As a bleaching agent and chlorine or bromine releasing substances can be used. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

Bleach activators are used in detergents or treating agents, for example, to achieve an improved bleaching effect at temperatures of 60 ^° C. and below. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2, 5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium acetonitrile methylsulfate (MMA) and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl capro lactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used. Further bleach activators which are preferably used in the context of the present invention are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula

Ri R2 N _(CH2) -CN X ^"

R3

in which R ¹ is -H, -CH _3, a C ₂ - ₂₄ alkyl or alkenyl group, a substituted C _{_2-24} -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or Alkenylarylrest with a C-ι_ ₂₄ alkyl group, or represents a substituted alkyl or Alkenylarylrest with a Ci_ ₂₄ alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH _3, -CH ₂ - CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH _3, -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion, preferably from the group chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate.

Particular preference is given to compounds of the formulas (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH (CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , or (HO-CH ₂ - CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^' , wherein from the group of these substances, in turn, the cationic nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^' , in which X ^'is an anion selected from the group consisting of chloride, bromide, iodide, Hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate is particularly preferred.

In addition to, or in place of, the conventional bleach activators, so-called bleach catalysts can also be used. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

Bleach-enhancing transition metal complexes, in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate are used in conventional amounts. It is particularly preferred to use complexes of manganese in the oxidation state II, IM, IV or IV, which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN ), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1,4,7-triazacyclononane (Me / TACN). Suitable manganese complexes are, for example, [Mn ¹ " ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (CIO ₄ ) 2, [Mn" ¹ Mn ^lv (μ-O) ₂ (μ-)

OAc) ₁ (TACN) ₂ ] (BPh ₄ ^, [Mn ^IV ₄ (μ-O) ₆ (TACN) ₄ ] (Clθ ₄ ) ₄ , [Mn ^I " ₂ (μ-O) ₁ (μ-OAc) ₂ (Me-TACN) ₂ ] (CIO ₄ ) ₂ , [[MMnn "" ^II MMnn ^llvv ((μμ-OO)) ₁₁ ((μμ-OOAAcc)) ₂₂ ((MMee-TTAACCNN)) ₂₂ ] ] ((CCIIOO ₄₄₎₎ ₃₃ ,, [[IMn ^'v ₂ (μ-O) ₃ (Me-TACN) _2] (PF ₆₎ ₂ and [Mn ^ιv ₂ (μ- O) ₃ (Me / Me TACN) ₂ ] (PF ₆ ) ₂ (OAc = OC (O) CH ₃ ).

Enzymes can be used to increase the washing performance of detergents or treatment agents. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or treatment agents, which are preferably used accordingly.

Among the proteases, those of the subtilisin type are preferable. Examples are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the subtilases, but not the subtilisins in the enzymes, thermase, proteinase K and the proteases TW3 and TW7.

Examples of usable amylases are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae, as well as the further developments of the aforementioned amylases which are improved for use in detergents or treating agents. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

It is also possible to use lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanu- ginosus) or further developed, in particular those with the amino acid exchange D96L. Furthermore, for example, the cutinases can be used, originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.

Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

Particular preference is given to using perhydrolases in the compositions according to the invention.

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

The enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, additional active ingredients, for example stabilizers, emulsifiers, pigments, bleach or dyes may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating. Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities.

A protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Washing or treating agents may contain stabilizers for this purpose.

As perfume oils or perfumes, within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon types are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.

In order to be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note", "middle note" or "body note" ) and "base note" (end note or dry out). Since odor perception is also largely due to odor intensity, the top note of a perfume does not consist solely of volatile compounds, while the base note is largely made up of less volatile, i. adherent fragrances. For example, in the composition of perfumes, more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly. In the subsequent classification of the fragrances in "more volatile" or "adherent" fragrances so nothing about the olfactory impression and whether the corresponding fragrance is perceived as a head or middle note, nothing said.

The fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance. As such carrier materials, for example cyclodextrins have been proven, wherein The cyclodextrin-perfume complexes can additionally be coated with other excipients.

When choosing the colorant, it must be taken into account that the colorants have a high storage stability and insensitivity to light as well as not too high an affinity for textile surfaces and, in particular, for synthetic fibers. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the washing or treating agents varies. In the case of readily water-soluble colorants, colorant concentrations in the range of a few 10 ^-2 to 10 ³ % by weight are typically selected. In the due to their brilliance, particularly preferred, but are less readily water-soluble pigment dyestuffs, however, the appropriate concentration of the colorant is in washing or treatment agents, typically a few 10 ^{~ 3} to 10 ^{~ 4} wt .-%.

Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe.

In order to bring the pH of detergents or treatment agents into the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited. Usually, the amount of these adjusting agents does not exceed 1% by weight of the total formulation.

Suitable foam inhibitors are, inter alia, soaps, oils, fats, paraffins or silicone oils, which may optionally be applied to support materials. Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the abovementioned materials. Agents preferred in the context of the present invention comprise paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are constructed according to the scheme (R ₂ SiO) _x and are also referred to as silicone oils. These silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids having a molecular weight between 1,000 and 150,000 and viscosities between 10 and 1,000,000 mPa.s. Suitable anti-redeposition agents, which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether and the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful. Also usable as graying inhibitors are cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof.

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

To combat microorganisms antimicrobial agents can also be used in the portion of a washing or treatment agent portion, which is not intended to care for the automatic washing machine. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungicides and fungicides, etc. Suitable antimicrobial agents are preferably selected from the groups of the alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides , Phenols, phenol derivatives, diphenyls, diphenylalkanes, urea Substance derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1, 2-dibromo-2,4-dicyanobutane, iodo-2 propynyl-butyl-carbamate, iodine, iodophores, peroxo compounds, halogen compounds and any mixtures of the above.

In a preferred embodiment, the antimicrobial active ingredient is selected from ethanol, n-propanol, isopropanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, benzoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N-methylmorpholine-acetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 4,4'-dichloro-2'-hydroxydiphenyl ether (dichlosan) , 2,4,4'-trichloro-2'-hydroxydiphenyl ether (trichloro), chlorhexidine, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) -urea, N, N '- (1, 10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4-chlorophenyl) -3,12-diimino-2,4,11, 13-tetraaza-tetradecandiimidamide, glucoprotamines, antimicrobial surface-active quaternary compounds, guanidines including the bi- and polyguanidines, halogenated xylene and cresol derivatives such as p-chloromethacresol or p-chloro-meta-xylene, amphoteric and natural antimicrobial agents pflan Of origin (for example, from spices or herbs), animal and microbial origin, more preferably at least one antimicrobial surface active quaternary compound, a natural antimicrobial agent of plant origin and / or a natural antimicrobial agent of animal origin, most preferably at least one natural antimicrobial Substance of vegetable origin from the group comprising caffeine, theobromine and theophylline and essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial agent of animal origin selected from the group comprising enzymes such as milk proteins, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface-active quaternary compound having an ammonium, sulfonium, phosphonium, iodonium or arsonium group, peroxo compounds and chlorine compounds. Also substances of microbial origin, so-called bacteriocins, can be used.

Quaternary ammonium compounds (QAV) suitable as antimicrobial agents have the general formula (R ¹ ) (R ² ) (R ³ ) (R ⁴ ) N ⁺ X ^" , in which R ¹ to R ^{4 are the} same or different C ₁ - C ₂₂ -Alkyl radicals, C ₇ -C ₂₈ -aralkyl radicals or heterocyclic radicals, where two or, in the case of an aromatic incorporation such as in pyridine, even three radicals together with the nitrogen atom form the heterocycle, for example a pyridinium or imidazolinium compound, and X ^- > halide ions, For optimal antimicrobial activity, at least one of the radicals preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms. QACs can be prepared by reacting tertiary amines with alkylating agents, such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide. The alkylation of tertiary amines with a long alkyl radical and two methyl groups is particularly easy, the quaternization of tertiary amines with two long radicals and one methyl group can be carried out with the aid of methyl chloride under mild conditions. Amines having three long alkyl radicals or hydroxy-substituted alkyl radicals are less reactive and are preferably quaternized with dimethyl sulfate.

Suitable QAVs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B (m, p-dichlorobenzyl-dimethyl-C 12 -alkylammonium chloride, CAS No. 58390-78-6), benzoxonium chloride (benzyldodecylbis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethylammonium bromide, CAS No. 57 -09-0), benzetonium chloride (N, N-dimethyl-N- [2- [2- [p- (1,1,3,3-tetramethylbutyl) -phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS no. 121-54-0), dialkyl dimethyl ammonium chlorides such as di-n-decyl dimethyl ammonium chloride (CAS No. 7173-51-5-5), didecyl dimethyl ammonium bromide (CAS No. 2390-68-3), dioctyl dimethyl ammonium chloride, 1-cetyl pyridinium chloride (CAS No. 123-03-5) and thiazoline iodide (CAS No. 15764-48-1) and mixtures thereof. Particularly preferred QACs are the benzalkonium chlorides having C ₈ -C ₁₈ -alkyl radicals, in particular C 1 -C 4 -alkylbenzyldimethylammonium chloride.

Further suitable antimicrobial agents are bleaching compounds. These have already been described in advance.

In a particularly preferred embodiment, the washing or treatment agent portion comprises a machine care worker. Preferably, the machine operator comprises care components and / or antimicrobial agents. The term antimicrobial agents are understood here as meaning both those substances which kill microorganisms, for example bactericides and fungicides, ie also those which inhibit only the vegetation of the microorganisms, for example bacteriostats and fungistatics. With particular preference, the machine care provider contains a combination of at least one care component and at least one antimicrobial component.

"Nursing component" in the sense of the present invention means that this component has water-softening and / or scale-dissolving properties and / or maintains metal, for example stainless steel, and / or rubber, for example gaskets and hoses, for example solvents such as isopropanol or ethanol for the removal of greasy soils, nonionic or anionic surfactants already mentioned, complexing agents such as thiourea and sodium thiosulfate and silicone compounds and fine polishing bodies and the components known to those skilled in the art by the term "silver corrosion inhibitors".

Suitable water softeners are all substances known from the prior art which are capable of complexing Ca ions. Descaler are substances that are capable of dissolving limescale deposits and preferably to keep them in solution.

To prevent undesirable changes to the washing or treating agents and / or the treated fabrics caused by oxygen and other oxidative processes, the compositions may contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

Furthermore, it is possible to use UV protective substances which are applied to the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds which are active by radiationless deactivation and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the endogenous urocanic acid.

As cationic active substances, for example, cationic compounds of the following formulas can be used:

Ri

Ri-N- (CH ₂₎ _n -T-R 2 (CH ₂₎ _n -T-R2

Ri I ₊

Ri-N- (CH ₂ ) -C C H ₂ I ^v 'II Ri TT

I i

R2 R2 R1 R3-N- (CH ₂₎ -T-R2

R4

wherein each R ¹ group is independently selected from Ci _-6 alkyl, alkenyl or

hydroxyalkyl; each group R is independently selected from C ₈ . ₂₈ alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, - O-CO- or -CO-O- and n is an integer from 0 to 5.

Textile softening compounds can be used to care for the textiles and to improve the textile properties such as a softer feel and reduced electrostatic charge (increased wearing comfort) The active ingredients of these formulations are quaternary ammonium compounds having two hydrophobic radicals, such as the disteraryldimethylammonium chloride, however because of its insufficient biodegradability, it is increasingly being replaced by quaternary ammonium compounds which contain ester groups as biodegradation breakpoints in their hydrophobic residues Such esterquats having improved biodegradability are obtainable, for example, by mixing mixtures of methyldiethanolamine and / or triethanolamine with fatty acids esterified and the reaction products are then quaternized in a manner known per se with alkylating agents, dimethylolethyleneurea being also suitable as a finish ,

Phobic and impregnation processes are used to furnish textiles with substances that prevent the deposition of dirt or facilitate its leaching ability. Preferred repellents and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum and zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or polymerizable compounds coupled with perfluorinated acyl or sulfonyl radical. The penetration of the impregnating agent in the form of solutions or emulsions of the active substances in question can be facilitated by adding wetting agents which reduce the surface tension. A further field of application of repellents and impregnating agents is the water-repellent finish of textiles, in which, in contrast to waterproofing, the fabric pores are not closed, thus the fabric remains breathable (hydrophobing). The hydrophobizing agents used for hydrophobizing coat the textiles with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups. Suitable water repellents are, for example, paraffins, waxes, metal soaps, etc. with additions of aluminum or zirconium salts, quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, silicones, organotin compounds and glutaraldehyde and perfluorinated Links. The hydrophobized materials do not feel greasy; nevertheless, similar to greasy substances, water droplets emit from them without moistening. For example, silicone-impregnated textiles have a soft feel and are water and dirt repellent; Stains from ink, wine, fruit juices and the like are easier to remove.

Increased comfort may result from the additional use of antistatic agents. Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges. External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are likewise suitable as antistatics for textiles or as an additive to detergents or treatment agents, wherein a softening effect is additionally achieved.

Silicone derivatives can be used to improve the water absorbency, rewettability of the treated fabrics, and ease of ironing the treated fabrics. These additionally improve the rinsing out of detergents or treatment agents by their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. Further preferred silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which comprise, for example, polyethylene glycols and the polyalkylene oxide-modified dimethylpolysiloxanes.

Finally, it is also possible to use UV protective substances which are applied to the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds which are active by radiationless deactivation and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the endogenous urocanic acid.

Optical brighteners (so-called "whiteners") may be added to the washing or treating agents to eliminate graying and yellowing of the treated fabrics. These fabrics impinge on the fiber and cause whitening and bleaching by transforming invisible ultraviolet radiation into visible longer wavelength light, emitting the ultraviolet light absorbed from the sunlight as faint bluish fluorescence, and pure with the yellowness of the grayed or yellowed wash White results. Suitable compounds for example, originate from the substance classes of the 4,4 ^{^{'diamino-2,2-stilbenedisulfonic}} acids (flavonic), ^{4,4'-biphenylene} -Distyryl, liferone Methylumbel-, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, Benzoxazole, Benzisoxazol- and benzimidazole systems and substituted by heterocycles pyrene derivatives.

Compared to the known powders, granules, tablets and portioned liquids or gels, which are consumed in a single washing or treatment course and which already release all active ingredients at the beginning of a washing or treatment program, the washing or treatment agent portions according to the invention show a higher performance ,

As the innermost layer, preferably as core, a washing or treating agent portion according to the invention preferably contains pressed material, which preferably has substantially the same washing or treating agent composition as the other layers.

However, it can also be provided that the detergent or treatment agent portion comprises a core which differs in composition from the composition of the remaining detergent or treatment agent portion. In this case, the core preferably comprises a machine care worker, which preferably comprises a combination of at least one care component and at least one antimicrobial component.

For example, sterilization of the automatic washing machine can be counteracted and / or the interior of the automatic washing machine can be maintained by releasing a disinfecting / nourishing substance after a number (n) of washing or treatment cycles in a further (n + 1st) washing or treatment cycle , This is achieved by a particularly preferred embodiment of the present invention, in which the washing or treatment agent portion contains a active substance-containing core comprising a machine guard, which only comes into contact after dissolving the active substance-containing coating layer with the environment. It may be preferred that the core contains other washing or treatment-active substances in addition to the machine care worker, so that even in the last washing or treatment cycle with the washing or treatment agent portion according to the invention, in which the machine guard is released, textiles can be washed and / or treated.

Alternatively or in combination, the machine care agent may also be contained in a washing or treating agent phase outside the invention and thus released before dissolving / dispersing the washing or treating agent. In this way, the automatic washing machine is maintained / disinfected in the first washing or treatment cycle, which is carried out with the washing or treatment agent portion according to the invention. The washing or treating agent for the textiles is preferably released only in the washing or treatment courses following this first washing or treatment course. However, it can also be provided that the active-material-containing coating layer contains a washing or treating agent and additionally a machine guard so that even in the first washing or treatment cycle in which the washing or treating agent portion according to the invention is used, textiles are washed and / or or can be treated.

Preferably, the active substance-containing core of the washing or Behandlungsmittelportion comprises a machine care worker who comes into contact after dissolving the active substance-containing shell layer with the environment and which preferably water-softening substances and / or E-delstahlpfleger and / or care agents for elastic parts and / or agents from the Group of substances that kill microorganisms or inhibit their vegetation. Suitable nourishing and antimicrobial components have already been mentioned.

The separation of different fragrance compositions and the controlled resolution maximum one, preferably exactly one active substance-containing layer and thus the targeted release of a defined amount of active material can be achieved, for example, that exist between the individual active substance-containing layers barrier layers, preferably a deviating from the active substance-containing layers solubility - or have dispersing behavior.

Suitable materials for these barrier layers have already been listed under the terms "solubility control system" and "(physicochemical) chemical switch". To avoid repetition, please refer to the corresponding text passages.

Depending on the intended use, barrier layers which dissolve / disperse predominantly in heated water and thus in the actual washing or treatment cycle are preferred, as well as those which are predominantly in the rinsing cycle, owing to the lower ionic strength and / or the lower pH Value can be dissolved / dispersed. Barrier layers containing a (physico-) chemical switch are preferably used in washing or treating agent portions according to the invention which have a plurality of active substance-containing layers whose active substances are to be released in a washing or treatment cycle carried out with heated water and which has a system for controlling the Contain solubility as defined above. Examples of suitable active substances are the substances mentioned in advance under the term "basic detergents" or also bleaching or enzyme components.

Barrier layers having a (physico-) chemical switch allow an active-material-containing layer applied outside the barrier layer to be dissolved / dispersed and thus consumed in a washing cycle treated with heated water, due to the barrier layer during the washing or treatment cycle However, the increased ionic strength and / or the increased pH remains intact. In this case, the barrier layer dissolves / disperses in the subsequent rinsing cycle, in which the ionic strength and / or the pH drops, or disperses, thus allowing contact of the active substance-containing layer below the barrier layer with the water. If this layer in turn has a higher solubility / dispersibility in a washing or treatment cycle than in a rinsing cycle, the active substance contained in this layer will not be released until the next washing or treatment cycle.

Barrier layers which have a temperature-dependent solubility / dispersibility are preferably used in washing or treating agent portions according to the invention which have a plurality of active substance-containing layers but whose active substances are to be released in the rinse and which preferably contain a (physico-) chemical switch. Examples of suitable active substances are the substances mentioned in advance under the term "equipment components".

Crevices having a solubility control system which provides a significantly higher temperature solubility / dispersibility enable an active-substance containing layer applied outside the barrier layer to be in a rinse cycle, that of cold water preferably at low ionic strength and / or low pH is carried out, dissolved / dispersed and thus consumed, the barrier layer remains intact during the Spülzyklus- ses due to the low temperature. In this case, the barrier layer dissolves / disperses in the subsequent washing or treatment cycle, which is carried out with heated water, and thus enables the contact of the active substance-containing layer located below the barrier layer with the water. If this layer again has a higher solubility / dispersibility in a rinsing cycle than in a washing or treatment cycle, then the active substance contained in this layer will not be released until the next rinsing cycle. If, in this embodiment, the barrier layer only performs insulating tasks, then the washing or treating agent portion according to the invention releases active substance only in the rinsing cycles. Preferably, the barrier layer contains a base detergent which is dissolved / dispersed together with the insulating barrier material. Thus, during the washing or treatment cycles which are carried out with heated water, this washing or treating agent portion according to the invention releases base detergent (or also an additional component for a base detergent) and, in the rinsing cycles, an equipment component for textiles.

The barrier layers preferably contain polymeric compounds, preferably polycarbonates and in particular (modified) polyacrylates.

The barrier layers preferably have a thickness of at most 1, 0 mm, more preferably of at most 0.7 mm and in particular of not more than 0.4 mm.

In a preferred embodiment, there is a barrier layer between the active substance-containing core and the adjacent layer which has a lower water solubility / water dispersibility than further barrier layers which are located in the washing or treatment agent portion. The water solubility / water dispersibility of the barrier layers can be controlled, for example, by the degree of crosslinking of the polymers used as the barrier layer component, the choice of substituents of the polymer backbone, and the molecular weight of the polymers. The barrier layer located between the active substance-containing core and the adjacent coating layer preferably dissolves / disperses only in an aqueous medium, if this has a temperature of at least 30 ^° C., preferably at least 40 ^° C., more preferably at least 50 ^° C., more preferably at least 60 ^° C and in particular of at least 90 ⁰ C. Alternatively or in addition, it may be provided that the barrier layer located between the active substance-containing core and the adjacent enveloping layer can / must be removed manually.

Due to an increased ease of use, it is preferred if the barrier layer between the active substance-containing core and the adjacent active substance-containing layer is colored and thus has an indicator effect. In this way, the consumer can recognize when the active substance-containing layers of the washing or treatment agent portion according to the invention are consumed and thus the active substance-containing core - preferably for the care of the automatic washing machine - used and a corresponding washing or treatment program of the automatic washing machine can be selected.

Furthermore, it is preferred that in the washing or treatment agent portion according to the invention at least one strip, wedge and / or other volume (one or more further Preferably radially through the portion - but preferably not through the optionally contained core - and its composition is in at least one component or the concentration of at least one component of the composition (s) of the active agent containing core and / or the remaining washing or treatment agent portion, ie the active substance-containing layer.

It is particularly preferred that the washing or treatment agent according to the invention substantially in the form of a prism, preferably a cuboid or ellipsoid, preferably a spheroid, in particular a flattened or prolapsed spheroid or a sphere and the further (n) phase ( n), preferably in the form of a cylinder, cuboid, cone, pyramid, ellipsoid or irregular volume in the washing or treating agent portion, the further phase (s) preferably extending radially in the washing or treating agent portion / extend. With preference, the further phase (s) extends / extend essentially from the center of the washing or treatment agent portion to the surface of the washing or treatment agent portion, wherein the tip of the respective spatial form (cone, pyramid) is preferably substantially in the center of the washing or treatment agent portion is located. The further phase (s) are preferably solid or highly viscous and thus dimensionally stable.

In a preferred embodiment, the further phase (s) and the remaining washing or treating agent portion have comparable dissolving / dispersing properties. In this way, the active ingredients of the cladding layer (s) and the other (s) phases in the same cycle, so preferably released either in the washing or treatment cycle or in the rinse cycle. An example of a corresponding washing or treating agent portion according to the invention is a portion which comprises in one or more active substance-containing coating layer (s) a base detergent for white and / or colored textiles, sensitive textiles and / or wool and which additionally has at least one volume, which is preferably in the form of a cone extending from the center of the detergent or treating agent portion to the surface thereof and comprising an additive component for a washing or treating agent, preferably a bleach, enzyme or softening composition for textiles. Also preferred is a detergent or treating agent portion which comprises an enzyme-containing, but substantially bleach-free, composition in the active substance-containing coating layer (s) and which additionally contains at least one volume in which a substantially enzyme-free bleaching composition is contained vice versa. Likewise preferred is a washing or treating agent portion which, within the coating layer (s), contains a base detergent, in a volume which preferably extends in the form of a cone from the middle of the washing or treating agent portion to the surface thereof, a bleaching composition. and another volume, which also preferably extends radially in the portion, containing an enzyme composition.

An advantage of these embodiments is the ability to separate incompatible ingredients that are to be released at the same time, for example, the separation of bleach and enzyme or bleach and dyes and / or fragrances and other sensitive components.

In another preferred embodiment, the further phase (s) and the active ingredient-containing shell layer (s) have opposite dissolving / dispersing properties, so that the active substance-containing shell layer (s) is dissolved / dispersed in the washing or treatment cycle while the other phase (s) release active in the rinse cycle or vice versa. An example of a corresponding washing or treating agent portion according to the invention is a portion which comprises in one or more active substance-containing coating layer (s) a base detergent for white and / or colored textiles, sensitive textiles and / or wool and which additionally has at least one volume, which is preferably in the form of a cone extending from the center of the detergent or treating agent portion to the surface thereof and an equipment component, preferably a plasticizer compound, soil repellent polymers, repellents or impregnating agents, antistatic agents, optical brighteners, compounds which improve the water absorbency, the Renewability of the treated textiles and the ease of Bügeins serve the treated textiles and / or fragrances. Also preferred is a washing or treating agent portion which comprises an enzyme-containing, but substantially bleach-free composition in the active substance-containing coating layer (s) and which additionally contains at least one volume in which an equipment component is contained or vice versa.

An example of a detergent or treating agent portion of the present invention is a portion comprising a active agent-containing core containing a machine care agent and comprising 4 further coating layers arranged to decrease the solubility / dispersibility of the coating layers towards the surface of the portion ,

The cladding layers in this embodiment each comprise 65% by weight of a washing or treatment active composition

From 8 to 13% by weight of anionic surfactant,

1 to 5% by weight of nonionic surfactant,

25 to 40% by weight of builders, up to 10% by weight of neutral salts, up to 5% by weight of water,

0.05 to 0.2 wt .-% enzymes as well as other small components contains. This composition is present in homogeneous blend with 35% by weight of different solubility control systems. The first, ie innermost shell layer comprises 35% by weight PEG 4000, the second layer following the first shell layer comprises 35% by weight PEG 12000, the third layer following the second shell layer comprises 35% by weight of one 1: 2.5 mixture of paraffin (melting range 42-44 ° C) and PEG 12000 and the outer shell layer comprises 35 wt .-% paraffin (melting range 42-44 ° C).

A further subject of the present invention is a process for producing a washing or treating agent portion according to the invention, comprising the following steps: a) providing a core, preferably by means of melt casting, tableting or extrusion; b) wrapping the core with 1 to 59, preferably 3 to 49 and in particular 5 to 39 layers, the layers preferably by hardening of flowable masses due to temperature reduction, incorporation of water of hydration or other solvent components, reaction of components contained in the flowable materials, modification conversions , Evaporation of water or other solvent components, condensation, irradiation or by compression in such an order that the detergent or treating agent portion has a solubility and / or dispersibility gradient, preferably the solubility and / or dispersibility of the individual layers and the core decreases radially towards the surface of the washing or treatment agent portion.

Preferably, a step c) is carried out between step a) and step b) and / or between several steps b) in which a barrier layer is obtained by melt solidification, incorporation of water of hydration or other solvent components, reaction of components contained in the barrier material, modification conversions, Evaporation of water or other solvent components, condensation, irradiation or by pressing on the respective outer layer of the agent is applied.

The structure of the layers of a washing or treating agent portion can be carried out, for example, by immersing the core in a melt, solution or dispersion comprising the constituents of the washing or treating agent composition or its precursor constituents. Furthermore, it is possible to fix the core in a mold, preferably in the middle of the mold, and to pour the flowable components or precursor constituents of the laundry or treating agent composition into the mold, so that the core is completely enclosed by the cast-in material. Curing of the cast-in material preferably takes place for the portion according to the invention Drying, ie evaporation of water or other solvents, incorporation of water of hydration or melt solidification due to temperature reduction instead. Another possibility for enveloping the active substance-containing core is spraying the core with a sprayable preparation comprising the constituents or precursor constituents of the washing or treating agent composition.

It is also possible in the case of immersion and spraying in / with a liquid to viscous preparation comprising the (precursor) components of the cladding layer (s) dusting (sprinkling, rolling, inflation) of the not completely solidified portions with particulate components.

The present invention also relates to a kit comprising a washing or treating agent portion according to the invention and a bag of water-permeable material or a rigid at least in areas container with one or more opening (s), through which liquids, but not the washing or treatment agent portion in undissolved , non-dispersed and non-pulverized form, can enter and exit.

According to the invention, the bag or the container is at least partially permeable to water, so that when the kit is used in an automatic washing machine, water, aqueous solutions and dispersions of the washing or treatment agent active substances can enter and leave through these openings. With preference, the diameter of the openings for water / wash liquor is between 0.1 and 1 cm, in particular 0.2 and 0.5 cm, so that the exchange of dissolved and / or dispersed components of the washing or treatment agent portion done, but not the Treatment agent portion in undissolved, non-dispersed, not pulverized form from the envelope or the bag can escape. Preferably, the material of the bag is elastic and adapts to the decreasing size of the washing or treating agent portion with the number of washing or treatment courses.

The bag or container prevents direct contact of the washing or treating agent portion with the textile during the washing or treatment process as well as in the period between completion of the washing or treatment process and removal of the washed or treated textiles from the automatic washing machine by the consumer. Further, the bag or container controls the dissolution / dispersion of the detergent or treating agent portion because the surface of the detergent or treating agent portion contacts less water / wash liquor due to limited fluid passage through the bag / container material than does the direct use of the wash - or treatment agent portion in the washing drum of an automatic washing machine would be the case. An additional protection of the washing or treatment agent portion from the mechanical influences A washing or treatment cycle is achieved by the introduction of cushioning material, preferably of water-permeable foam or fleece. With particular preference, the kit comprises a bag which contains an inner and an outer layer of a net-like material and an intermediate layer of a cushioning material, preferably foam, and is preferably elastic.

The bag or container preferably has a device that allows the closure of the enclosure. Preference is given to devices in which a tape or a cord is passed through a channel along the upper edge of the bag, which can be pulled together and verschnürrt or clamped together.

A method for washing and / or treating textiles in an automatic washing machine in which a washing or treating agent portion according to the invention or a kit according to the invention is introduced into the drum of the washing machine and a washing or treatment program of the washing machine is started is a further subject matter of the present invention Invention.

Preferably, the washing or treating agent portion according to the invention or the kit according to the invention in the washing machine drum exposes the water to from 2 to 60, preferably from 4 to 50 and in particular from 6 to 40 washing or treatment cycles, the active substance-containing phases of the washing agent dissolving and / or disperse and the active substance contained is released.

If the washing or treating agent portion comprises a base detergent for white and / or colored textiles, delicate textiles and / or wool, then the portion, preferably in the form of the described kit, preferably the water is from 2 to 40, preferably 4 to 30 and in particular 6 to 20 washing or treatment courses suspended and / or is used in addition to an additive component for a base detergent, such as an enzyme, bleach or equipment component as defined above in an automatic washing machine for textiles. If the washing or treating agent portion contains an additional component for a basic detergent, then the portion, preferably in the form of the described kit, is preferably exposed to the water from 5 to 60, preferably from 10 to 50, and in particular from 15 to 40, washing or treatment courses and / or additionally to a basic detergent for white and / or colored textiles, delicate textiles and / or wool used in an automatic washing machine for textiles.

After substantially complete dissolution and / or dispersion of the portion of washing or treating agent, the optionally contained ak- tivstoffhaltige core dissolved and / or dispersed and preferably disinfected and / or maintained the automatic washing machine with the liberated active ingredients. Particularly good cleaning and / or care results are obtained when the core in a washing or treatment cycle without textiles at least 18 ° C, preferably at least 30 ⁰ C, more preferably at least 40 ⁰ C, preferably at least 50 ⁰ C, very particularly preferably at least 60 ⁰ C and in particular at 90 ⁰ C is dissolved or dispersed. The active agent-containing core preferentially dissolves / disperses only after a barrier layer has been dissolved and / or dispersed or removed manually between the active-containing core and the adjacent coating layer.

Another object of the present invention is the use of a washing or treating agent portion according to the invention or a kit according to the invention for automatic dosing in the drum of an automatic washing machine for textiles. Preferably, a washing agent or treating agent portion according to the invention or the kit according to the invention is used in 2 to 60, preferably 4 to 50 and in particular more than 6 to 40 washing or treatment courses.

In a preferred embodiment of this invention, a dimensionally stable one-piece washing or treating agent portion having a mass of at least 50 g, comprising a base detergent for white and / or colored textiles, delicate textiles and / or wool, as well as a fully enclosed active substance-containing core, at least in one component or the concentration of at least one constituent of the composition of the active substance-containing cladding layer, wherein the washing or treating agent portion has a radially extending solubility or dispersibility gradients, used alone or together with an additional component for a base detergent in an automatic washing machine and there for washing and / or treating textiles. Preferably, the active substance-containing core contained in the washing or treating agent portion according to the invention is used for caring and / or disinfecting the automatic washing machine following the washing or treatment cycles in which the active substance-containing coating layer dissolves or disperses. The washing or treating agent portion of the invention is - preferably enclosed by a bag - metered directly into the drum of the washing machine and left there for 2 to 40 washing or treatment courses. The additional component for the basic detergent can be dosed via the dispenser or also directly into the drum of the automatic washing machine. Preferably, the additional component for the base detergent is also in the form of a dimensionally stable, one-piece treatment agent portion having a mass of at least 50 g, which provides active ingredient for 5 to 60 washing or treatment courses and which preferably also has a radially extending solubility or dispersibility gradients.

In a further embodiment of the present invention, a dimensionally stable one-piece washing or treating agent portion having a mass of at least 50 g, comprising an additional component for a washing or treating agent, preferably an enzyme, bleaching or finishing component, and a fully enclosed active substance-containing core, which differs at least in one constituent or in the concentration of at least one constituent from the composition of the active substance-containing enveloping layer, wherein the washing or treating agent portion has a radially extending solubility or dispersibility gradient, alone or together with a base detergent for white and / or colored textiles , delicate textiles and / or wool used in an automatic washing machine and used there for washing and / or treating textiles. Preferably, the active substance-containing core contained in the washing or treating agent portion according to the invention is used for caring and / or disinfecting the automatic washing machine following the washing or treatment cycles in which the active substance-containing coating layer dissolves or disperses. The washing or treating agent portion according to the invention is - preferably enclosed by a bag - dosed directly into the drum of the washing machine and left there for 5 to 60 washing or treatment courses. The basic detergent can be dosed via the dispenser or also directly into the drum of the automatic washing machine. Preferably, the base detergent is also in the form of a dimensionally stable, one-part treatment agent portion having a mass of at least 50 g, which provides active ingredient for 2 to 40 washing or treatment courses and which preferably also has a radially extending solubility or dispersibility gradients.

It is preferred to use a washing or treating agent portion according to the invention comprising a base detergent in an automatic washing machine for washing and / or treating textiles. Depending on requirements, washing or treating agent portions according to the invention comprising bleach, enzyme and / or equipment components are metered into the washing or treating agent portion comprising the base washing agent, so that these portions are used together for washing and / or treating textiles in an automatic washing machine. It may be preferred to use at least two, preferably all, portions of the invention used in a bag or a container or to use each portion of the invention individually in a container or bag. However, due to possible incompatibilities of the ingredients of the detergent or treating agent portions or affecting the solubility or dispersion behavior, it is preferred to use the detergent or treating agent portions individually in a bag or container in the drum of an automatic washing machine.

Claims

claims:

1. dimensionally stable, one-piece detergent or treatment agent portion having a mass of at least 50 g, characterized in that it has a solubility and / or dispersibility gradients.

2. Washing or treating agent portion according to claim 1, characterized in that the solubility and / or dispersibility gradient extends substantially from the center of the room to the surface of the washing or treatment agent portion (radial).

3. washing or treating agent portion according to any one of claims 1 or 2, characterized in that the solubility and / or the dispersibility of the washing or treatment agent portion decreases radially towards the surface.

4. washing or treatment agent portion according to one of claims 1 to 3, characterized in that it comprises compressed material having a radial density gradient, wherein the density of the compressed material preferably increases radially toward the surface.

5. washing or treating agent portion according to one of claims 1 to 4, characterized in that it is composed of several layers having different solubilities and / or dispersing capabilities, wherein the solubilities and / or dispersing these layers preferably radially towards the surface of the washing - or treatment agent portion decrease.

6. washing or treating agent portion according to claim 5, characterized in that the layers comprise pressed material within the washing or treatment agent portion and / or contain a system for controlling the solubility of the respective layer, which comprises one or more components from the group of polye ethylene glycols, polypropylene glycols, polybutyrates, polyhydric alcohols, sugars, polyurethanes, natural waxes, chemically modified waxes, synthetic waxes, wax alcohols, wax esters, paraffins, polyvinyl alcohols, polyacrylic acids and their derivatives, gelatin and celluloses.

7. washing or treating agent portion according to one of claims 1 to 6, characterized in that it comprises a plurality of layers which as systems for controlling the solubility of the respective layer of polyethylene glycol different mean Molecular mass and / or paraffins of different average molecular mass, wherein the layers are preferably arranged such that the solubility and / or dispersibility of the washing or Behandlungsmittelportion decreases radially towards the surface.

8. washing or treating agent portion according to one of claims 1 to 7, characterized in that it has a mass of 75 to 1500 g, preferably from 100 to 1000 g, more preferably from 200 to 850 g and in particular from 300 to 700 g.

9. washing or treating agent portion according to one of claims 1 to 8, characterized in that it comprises a base detergent for white and / or colored textiles, delicate textiles and / or wool and / or an additional component for a base detergent for white and / or colored Textiles, delicate textiles and / or wool, preferably a bleaching, enzyme or finishing component for textiles, antimicrobial agents and / or nonionic surfactants, enzymes and mixtures of these components.

10. A process for producing a washing or treating agent portion according to any one of claims 1 to 9, characterized by the following steps a) providing a core, preferably by means of melt casting, tableting or extrusion; b) wrapping the core with 1 to 59, preferably 3 to 49 and in particular 5 to 39 layers, the layers preferably by hardening of flowable masses due to temperature reduction, incorporation of water of hydration or other solvent components, reaction of components contained in the flowable materials, modification conversions , Evaporation of water or other solvent components, condensation, irradiation or by compression in such an order that the detergent or treating agent portion has a solubility and / or dispersibility gradient, preferably the solubility and / or dispersibility of the individual layers and of the core decreases radially towards the surface of the detergent or treating agent portion.

1 comprising 1. A kit comprising a washing or treating agent portion according to any one of claims 1 to 9 and a bag of water-permeable material or a rigid at least in areas container with one or more openings (s) through which liquids, but not the detergent portion in undissolved, non-dispersed and non-pulverized form, can enter and exit.

12. Kit according to claim 1 1, characterized in that the bag or container comprises a device which allows the closing of the bag or container and / or a cushioning material, preferably water-permeable foam comprises.

13. A method for washing and / or treating textiles in an automatic washing machine, characterized in that one introduces a washing or treating agent portion according to any one of claims 1 to 9 or a kit according to any one of claims 1 1 or 12 in the drum of the washing machine and exposing the water from 2 to 60, preferably from 4 to 50, and in particular from 6 to 40, washing or treatment cycles, whereby the washing or cleaning agent portion is dissolved and / or dispersed and the active substance contained is liberated.

14. Use of a washing or treating agent portion according to any one of claims 1 to 9 or a kit according to any one of claims 11 or 12 for automatic dosing in the drum of an automatic washing machine for textiles.

15. Use according to claim 14, characterized in that a washing or treating agent portion according to one of claims 1 to 9 or a kit according to one of claims 11 or 12 in 2 to 60, preferably 4 to 50 and in particular about 6 to 40 washing or Treatment courses is used.