EP1904613A1 - Cleaning care product with improved emulsification properties - Google Patents

Abstract

The invention relates to a cleaning care product containing a surfactant system with at least two non-ionic surfactants A and B, having different chemical structures from each other, both of which however can be represented by the following structure R<SUP>1</SUP>O-[CH<SUB>2</SUB>CH(R<SUP>2</SUP>)O]<SUB>X</SUB>-R<SUP>3</SUP>, where R<SUP>1</SUP> and R<SUP>3</SUP> independently = H or a linear or branched, saturated or unsaturated, aliphatic or aromatic 1-30C hydrocarbon which can contain up to 6 hydroxy and/or 3 ether functions, with the proviso that at least one of R<SUP>1</SUP> and R<SUP>3 </SUP>is not H, R<SUP>2</SUP> = H or methyl-, ethyl-, n-propyl-, iso-propyl-, n-butyl-, 2-butyl- or 2-methyl-butyl group, each R<SUP>2</SUP> with x = 2 can be different and x is greater than 1 and a thickening agent and has a pH of less than 6 as a 1 wt. % aqueous solution (20<SUP>?</SUP>C) which has an improved emulsifying capacity for fats and oils.

Description

 Cleaning and care products with improved emulsifying ability

The invention relates to a cleaning or care product, in particular a hard surface cleaner, which has a higher emulsifying ability for fats and oils compared to known agents, the use of this agent for cleaning and care of hard surfaces such as the interior of washing and Geschirrspülmaschinen and a method for cleaning and care of washing machines or dishwashers

Cleaning or care products usually contain surfactants and have a wide range of uses and depending on a very different composition on the pH alkaline, neutral and acidic cleaning or care products, according to the offer form liquid and solid cleaning or care products distinguished specifically by liquid Cleaning or care products, the consumer expects that he can use the funds in both undiluted and in the diluted wet state and in any case receives a satisfactory cleaning or care result

Decisive for the cleaning or care effect are especially the surfactants and / or alkali storage, which can be replaced by acids depending on the field of application, optionally also solvents such as glycol ethers and lower alcohols In general, in the formulations are also frits, depending on the type bleach , Enzymes, as well as Parfumole and dyes contain The cleaning success depends to a large extent on the - also geographically very different - dirt type and the properties of the surfaces to be cleaned from

Depending on the composition, cleaning or care products are used as general-purpose or special agents (car care products, oven cleaners, decalcifying agents, window cleaners, stain removers, floor care products, glass ceramic hob cleaners, stoves, leather care products, metal cleaners, furniture care products, pipe cleaners, sanitary cleaners, abrasives, carpet care products or toilet cleaners). ready-to-use Technical cleaning or care products are used primarily in the beverage, food, cosmetic and pharmaceutical industries, but also in the metal industry for metal degreasing. The product group also includes cleaning or care products for car washes, tank truck and aircraft cleaning or cleaning. Care products To the group of cleaning or care products pay, for example, the dishwashing detergent and means for cleaning or care of washing machine or Geschirrspülmaschinenmnenraumen Cleaning or care products have a variety of tasks to deal with in a wide variety of applications Households certainly focus on the removal of soiling such as fats and oils, leftovers, limescale deposits, soap residue or metal deposits as well as the corrosion protection of metal and glass For example, the removal of fats and oils is of interest

Over the years, there have been numerous attempts to improve the cleaning or care performance of known cleansing or care agents. Thus, WO 2004/032886 A1 (Reckitt Benckiser) discloses compositions containing at least one surfactant and necessarily two organic acids together with their salts The advantages of a solvent mixture of a hydrophilic and a hydrophobic solvent in an acid-containing hard surface cleaner are described in document US 2002/187918 A1 (Reckitt Benckiser) The solvent mixture is said to improve the solution of greasy soils. An increase in cleaning performance due to an improved control of the flat coverage of the agent is described in US 2004/0186037 A1 (Cheung, Costa). Insoluble, mi incorporated perceptible ingredients in a hard surface cleaner, which should enable the end user to recognize where the agent was not or not applied in sufficient quantity

Increasingly demanded by the end user cleaning or care products that provide optimal performance even without the action of mechanical energy such as rubbing and brushing Known examples are cleaning agent sprays for removing limescale on bathroom tiles or for degreasing metal objects such as cooker hoods means that already provide good cleaning or care results without significant mechanical treatment, in addition to the convenience for the user also offer the opportunity to clean surfaces whose mechanical treatment with the means not or only to a small extent possible Examples of mechanically poorly clean surfaces are corners and angled Surfaces, the inner surface of pipes and funnels, sharp-edged or intertwined surfaces, grids, hose connections, but also surfaces which, due to their nature, must not be subjected to mechanical stress

Even appliances such as washing machines or dishwashers, coffee machines or kettles are incomplete from the inside and only with great effort by mechanical action, for example, by a rag or a brush to clean, so that even for these applications cleaning or care products that perform well In the case of washing machines and dishwashers, the effect of the cleaning or care products should be so great that not only the large surfaces the inside of the machine, which are exposed to the direct and intense operating pressure of the cleaning fleet and thus experience quite a mechanical load, but also angled areas, hose connections, door seals and all low-flow zones are optimally cleaned and / or maintained in these machines.

The commercial alkaline or acidic dishwashing, cleaning or rinsing agents are not or insufficiently suitable for cleaning the so-called "problem areas" of dishwashers or washing machines, since they are metered into the cleaning or rinse cycle of the machines, but with the polluted areas either not at all or only for a short time in contact Also commercially available cleaners for hard surfaces are not suitable for this particular application, since they generally contain strong foaming surfactants whose residues can lead to disorders of various types, for example in dishwashers and also meets the requirements of Cleaning and care properties are not equal.

An attempt to circumvent the above-mentioned problems in the field of dishwashers are the cleaning and / or care products especially for dishwashers. Corresponding agents are described in the patents US 4,392,977 A (Henkel), EP 0 256 148 A1 (Joh. A Benckiser GmbH) and WO 94/07991 A1 (Henkel).

However, the abovementioned means, both the above-mentioned cleaning or care products and the special agents "dishwashing detergents", do not have a satisfactory performance in the area of the removal of grease from surfaces.The effect of known cleaning or care products is not sufficient, the fatty soils in their entirety As a result, manual cleaning leads to grease streaks on the already partially cleaned surfaces, since a separation of the cleaning liquor due to lack of emulsifying ability of the agent occurs In the case of automatic cleaning or care of washing machines or dishwashers, the effect can be observed that, during the rest periods of the liquor, that is to say in the periods in which no circulation of the liquor takes place, a separation of the liquor La uge takes place in aqueous and oily phase. The result is a fat edge in the lower machine interior, which does not dissolve or insufficiently in the further cleaning or care process and leads to an overall poor cleaning or care result. Furthermore, in washing machines or dishwashers, especially in dishwashers, the effect may arise that, during the cleaning with the agents described in the prior art, fat soils accumulate intensively in the areas which are exposed to only a small flow of water and there persistent incrustations and / or Oily streaks form, while on the large surfaces inside the machine interior quite a cleaning effect can be observed. Also, the formation of a greasy film on all surfaces of the machine interior using agents that have insufficient Fettemulgierfähigkeit is In the case of severe contamination of the interior with fatty deposits is observed when using the known means that in addition to the problems described in addition also insufficient cleaning of the large surfaces of the interior, which are exposed to the direct water pressure of the cleaning liquor is achieved and greater fat soiling could not be resolved or resolved by the means

The object of the present invention was to provide a remover or conditioner which overcomes the above-mentioned problems. In particular, this composition should have an increased emulsifying ability for fats and oils and thus an improved fat removal performance

Surprisingly, it has now been found that the above-mentioned problems using a combination of two different nonionic surfactants from the group of compounds represented by the general structure R ¹ O- [CH ₂ CH (R ² ) O] _X -R ³ and a Overcome thickener and achieved in comparison with Remigungs- or care products of the prior art significantly improved Emulgierkapazitat for fats and oils

A first object of the present invention is a remover or conditioner comprising a surfactant system comprising at least two nonionic surfactants A and B having different chemical structures but both through the structure

R ¹ O- [CH ₂ CH (R ² ) O] _X -R ³ in which

R ¹ and R ³ independently of one another are H or a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 carbon atoms, in which up to 6 hydroxyl and / or up to 3 ether functions may be present at least one of R ¹ and R ^{3 is} not H,

R ^{2 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl

Methyl-butyl radical, where each R ² can be different at x> 2 and x stands for values of 1,

can be represented and comprises a thickener and as a 1 wt -% solution in water (20 ⁰ C) has a pH of less than 6

Inventive Remigungs- or care products comprising a combination of the two nonionic surfactants A and B and a thickening agent, show to otherwise recipe-same Remigungs- or care products, which instead of the nonionic surfactant A and / or the nonionic surfactant B nιchtιonιsche (s) Tensιd (e) other Verbindungsklasse (s) or only a nonionic surfactant of the above structure and a thickener or two different nonionic surfactants of the above structure, but no thickener contain, a significantly increased emulsifying ability fats and oils

The erfmdungsgemaße cleaning or care agent is preferably used in the treatment of hard surfaces and is particularly suitable for the cleaning or care of washing or dishwashing machines, especially for dishwashers

As already stated, surprisingly, an increase in the emulsifying capacity is achieved by combining a thickening agent with two different nonionic surfactants of the above structure. Particularly good performance in the area of grease removal is achieved when using such cleaning or care agents in which the surfactant system comprises at least one nonionic surfactant A with an average molecular weight between 200 and 1200 g / mol, preferably between 300 and 1100 g / mol, more preferably between 400 and 1000 g / mol and in particular between 500 and 900 g / mol and at least one further nonionic surfactant B with an average molecular weight between 1000 and 2500 g / mol, preferably between 1100 and 2400 g / mol, preferably between 1200 and 2300 g / mol, more preferably between 1300 and 2200 and in particular between 1400 and 2100 g / mol

Accordingly, the surfactant system may consist of two surfactants having a different chemical structure but a comparable average molecular weight. Preferably, however, the average molecular weights of the nonionic surfactants A and B differ by at least 20 g / mol. The difference between the average molecular weights of the two nonionic surfactants is preferred A and B at least 100, preferably at least 200, preferably at least 300, more preferably at least 400, more preferably at least 500, most preferably at least 600 and in particular at least 700 g / mol

The sum of the proportions by weight of the two nonionic surfactants A and B, in particular of all nonionic surfactants present in the composition, in inventive compositions is preferably less than 10% by weight, more preferably less than 8% by weight, most preferably less than 6% by weight. , more preferably less than 4% by weight and in particular less than 3% by weight

Although it is possible to use the two nonionic surfactants A and B in the inventive agents in any ratio, the weight ratio between surfactant A and surfactant B is preferably between 10 1 and 1 1, preferably between 8.5 1 and 1, 25 1, more preferably between 7 1 and 1, 5 1, preferably between 5.5 1 and 1, 75 1 and in particular between 4 1 and 2 1 Preferably, the surfactant B is from 0.1 to 1, 7 wt .-%, preferably 0.2 to 1, 4 wt .-%, particularly preferably 0.3 to 1, 1 wt .-% and in particular to 0 , 4 to 0.8% by weight in the composition. The proportion of surfactant A in the composition according to the invention is preferably 0.6 to 5% by weight, preferably 0.8 to 4% by weight, more preferably 1 to 0 to 3% by weight and in particular 1.2 to 2 wt .-%.

Preferred nonionic surfactants within the scope of the invention are nonionic surfactants which have a melting point above room temperature. Nonionic surfactants having a melting point above 2O ⁰ C, preferably above 25 ° C, more preferably between 30 and 60 ° C and in particular between 40 and 50 ⁰ C, are especially preferred. Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Also, nonionic surfactants having waxy consistency at room temperature are preferred depending on their purpose.

In a preferred embodiment, the inventive composition contains a nonionic surfactant B having a melting point above 25 ° C, preferably above 3O ⁰ C, more preferably above 35 ⁰ C and in particular above 40 ⁰ C and an additional nonionic surfactant A with a melting point below 25 ⁰ C, preferably below 22.5 ⁰ C, more preferably below 2O ⁰ C and in particular below 17.5 ° C.

For combination with the thickening agents are within the scope of the present invention, all nonionic surfactants which can be represented by the formula ³ R ¹ O- [CH ₂ CH (R ²⁾ O] _X-R are suitable.

It is preferable that at least one and preferably both nonionic surfactants

A and B are alcohol alkoxylates, in particular fatty alcohol alkoxylates.

Both mixed alkoxylated fatty alcohol alkoxylates and fatty alcohol alkoxylates in which the radical R ^{2 is} not varied may be present in the compositions according to the invention.

Fettalkoholalkoxylate be by alkoxylation, ie reaction with ethylene oxide, propylene oxide or butylene oxide, etc., but preferably ethoxylation and / or propoxylation of primary long-chain fatty or oxo alcohols in the presence of basic or acidic catalysts at temperatures of 120-200 ⁰ C and pressures of 1-10 bar received. In the reaction of the alcohol with the alkylene oxide is formed in a polymerization reaction with the starter fatty alcohol, a polyglycol ether mixture of varying degrees alkoxylated homologues whose Distribution may vary depending on the catalyst and the amount of alkoxide between a Gauss and a non-selective Schulz-Flory curve. For example, in the presence of sodium hydroxide, a broad (narrow-ranked) homolog distribution is obtained using alkaline earth salts. As a result of the favored by acidic ethoxylation catalysts formation of 1, 4-dioxane as an undesirable by-product and because of the risk of corrosion on the steel of the reaction vessel are in the art preferably basic catalysts, for example sodium methoxide in methanol or potassium hydroxide in water used.

Addition products of from 1 to 40 mol, preferably from 5 to 30 mol, of ethylene oxide and / or propylene oxide onto monofunctional alcohols are preferably used in the cleansing or care compositions according to the invention. As monofunctional alcohols, the so-called fatty alcohols such as caproic, caprylic, lauryl, myristyl, cetyl and stearyl alcohols and their technical mixtures are suitable. Examples of monofunctional, branched alcohols are so-called oxo alcohols, which usually carry 2 to 4 methyl groups as branches and are prepared by the oxo process and so-called Guerbet alcohols which are branched in the 2-position with an alkyl group. Suitable Guerbet alcohols are 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol or 2-octyldodecanol. Among the suitable alcohols are coconut, palm, tallow and oleyl alcohol.

Preferably usable alkyl ethoxylates are the addition products of 2 to 15, preferably 2 to 10 moles of ethylene oxide (EO) and / or propylene oxide (PO) to fatty alcohols having 4 to 22, preferably 12 to 18 and in particular 12 to 14 carbon atoms in the alkyl radical. Suitable surfactants are, for example, C ₁₂ -i ₄ fatty alcohols having 1 to 10 EO, preferably C ₁₂ -i ₄ fatty alcohols containing 2, 3, 4, 6 or 7 EO, C1 _2-18 fatty alcohols containing 1 to 10 EO, preferably C1 ₂ -1 ₈ fatty alcohols with 2, 3, 4, 5, 8 or 9 EO,

C ₁₂ -i ₄ fatty alcohols with 1 to 8 EO and 1 to 8 PO, preferably C _12-14 fatty alcohols with 4 EO and 5 PO, with 6 EO and 4 PO, with 2 EO and 4 PO or with 5 EO and 4 PO , C _12-18 fatty alcohols containing 1 to 8 EO and 1 to 8 PO, preferably C ₁₂ . ₁₈ fatty alcohols with 2 EO and 4 PO and the adducts of isodecanol or C _9-11 (oxo) alcohol with 2.5 or 3, 5, 6, 7, 8, 10 or 11 EO.

Also particularly preferred are ethoxylated nonionic surfactants selected from C _6-20 monohydroxyalkanols or C _16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles, preferably more than 20 moles and especially more than 25 moles of ethylene oxide per mole of alcohol were used. A particularly preferred nonionic surfactant is selected from a straight-chain or branched, preferably a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 -AlkOhOl), preferably a mixture of C ₁₆ and C ₁₈ alcohol and at least 12 mol, preferably at least 15 Mol, preferably at least 20 mol and more preferably At least 25 moles and in particular 30 moles of ethylene oxide are obtained. Among the surfactants mentioned, the so-called "narrow-ranked ethoxylates" are particularly preferred

In a preferred embodiment of the present invention, the nonionic surfactants A and B independently of one another have the following structure

R ¹ O- [CH ₂ CH (R ² ) O] _X -H in which R ^{1 is} a linear or branched, aliphatic hydrocarbon radical having 4 to 20

Carbon atoms, preferably having 12 to 20 carbon atoms and in particular having 12 to 18 carbon atoms, R ^{2 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2 -Methyl-

Butyl radical, in particular an ethyl or propyl radical, wherein each R ² at x>

2 can be different and x stands for values greater than 1

As described above, each R ² in the above formula may be different if x> 2. Thus, the alkylene oxide unit in the square bracket may be varied. For example, when x is 3, the group R ^{3 may be} selected to be ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined together in any order, for example (EO) (PO) (EO), (EO) (EO) (PO), (EO) ( EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO) (PO) The value 3 for x has been chosen as an example and can be quite large where the variation width increases with increasing x values and includes, for example, a large number (EO) groups combined with a small number (PO) groups or vice versa

Preferably x has a value between 14 and 60, preferably between 18 and 52, more preferably between 22 and 46, and most preferably between 26 and 38, for the nonionic surfactant B. In this case, the radical R ^{2 can} vary, so that both ethoxy-, However, it is preferred that no variation of the radical R ² takes place and the nonionic surfactant B contains only ethylene oxide, propylene oxide or butylene oxide units. The surfactant B preferably contains B and / or butoxy units in the nonionic surfactant excluding ethylene oxide units

For the nonionic surfactant A, the value for x with less than 20, preferably less than 15 and in particular less than 10, is preferably smaller than in the surfactant A. Also for this surfactant, the variation of the radical R ^{2 can be} excluded so that the nonionic surfactant A is only ethylene oxide However, surfactant A preferably contains different radicals R ^2. Nonionic surfactant A in the context of the invention preferably comprises adducts of from 1 to 10 mol, preferably from 2 to 7 mol and in particular from 4 to 5 Mol of ethylene oxide and 1 to 10 mol of propylene oxide, preferably 2 to 6 mol and in particular 3 to 4 mol of propylene oxide to high molecular weight fatty alcohols into consideration The hydrocarbon radical of the surfactant A contains preferably 8 to 18, preferably 10 to 16 and in particular 16 to 14 carbon atoms

Preferably, a erfindungsgemaßes agent comprises a C ₁₂ -C ₄ -Alkylalkoholalkoxylat, which comprises both ethoxy and Propoxyemheiten, and a C ₁₆ -C ₁₈ -Alkylalkoholethoxylat

Further particularly preferred nonionic surfactants are the so-called mixed ethers, which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols, which are subsequently reacted with alkyl groups in the presence of bases and end-capped. Particularly suitable mixed ethers in the context of the present invention are those which are end-capped with a CrCβ-alkyl halide, in particular with a C ₁ -C ₄ -alkyl halide have been produced Particularly preferred are n-butyl and methyl, in particular n-butyl end-capped mixed ethers Typical examples of a mixed ether based on a C _12/18 - or C _{12 /} i ₄ - Alcohol radical to which 5 to 10 moles of ethylene oxide were added are C ₁₂ -i ₈ -fatty alcohols with 3, 4, 5, or 10 EO (each n-butyl endgruppenverschlossen), Ci ₂ - ₁₄ fatty alcohols with 9 or 10 EO (each n-butyl end-capped)

Furthermore, in the erfmdungsgemaßen means all known in the art Hydroxymischether, which can be represented by the formula R ¹ O- [CH ₂ CH (R ² ) O] _X -R ³ , can be used

Preferred in the present invention are hydroxy mixed ethers of the formula

R ^{1 is} -O- [CH ₂ CH (R ³ ) O] _X - [CH ₂ CH (OH)] - R ²

used in the

R ¹ and R ^{2 may be} different or the same, where

R ^{1 is} H or a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 carbon atoms,

R ^{2 is} H or a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 28 carbon atoms, which optionally up to 5

Contains hydroxy and / or up to 3 ether functions is,

R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-butyl radical, where each R ³ may be different at x> 2 and x stands for values of 1

Hydroxymix ethers of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² ,

in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y is a value of at least 15, are particularly preferred

Further preferably used hydroxy mixed ethers are the end-capped poly (oxyalkylιerten) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _J OR ² ,

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms for R ¹ or (30 - 1 - j - k) hydrocarbon radicals R ² , R ^{3 is} H or is a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5. When the value x> 2, each R ³ in the above formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH _{2] j} oR be ^{2 are} different R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, said radicals are particularly preferably having 8 to 18 carbon atoms for the group R ³ H, -CH ₃ or -CH ₂ CH ₃ particularly preferred Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15

As already described for the fatty alkoxylates, even in the above formula, each R ³ can be different if x> 2. Thus, the alkylene oxide unit can be varied in the square bracket. For example, if x is 3, the radical R ³ can be selected to be ethylene oxide To form (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined together in any order, for example (EO) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO) (PO) The value 3 for x has been selected here by way of example, and can be quite large, with the range of variation increasing with increasing x-values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa

Particularly preferred hydroxy mixed ethers of the above formula have values of k = 1 and j = 1, so that the above formula zu R ¹ O [CH ₂ CH (R ³ ) O] _X CH ₂ CH (OH) CH ₂ OR ²

In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18 Particularly preferred are hydroxy mixed ethers in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15

Summarizing the latter statements, end-capped hydroxy mixed ethers of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² ,

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms for R ¹ or (30 - 1 - j - k) hydrocarbon radicals R ² , R ^{3 is} H or one Is methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl, x for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5, are preferred, wherein hydroxymix ethers of the type

R ¹ O [CH ₂ CH (R ³ ) O] _X CH ₂ CH (OH) CH ₂ OR ² ,

in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred

In the context of the present invention, particularly preferred hydroxy mixed ethers have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Preferred among these are hydroxy mixed ethers with EO-AO-EO-AO blocks, where in each case one to ten EO or AO groups are bonded to one another before one block follows from the other groups. Here are hydroxy mixed ethers of the general formula

R ¹ O [CH ₂ CH ₂ O] _w [CH ₂ CH (R ² ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (R ³ ) O] _z H

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl, each group R ² or R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w , x, y, z independently represent integers from 1 to 6 The preferred hydroxy mixed ethers of the above formula can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula can vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually unbranched, the linear radicals are selected from alcohols of natural origin having 12 to 18 carbon atoms, such as coconut, palm, tallow or oleyl alcohol, are preferably accessible from synthetic sources alcohols For example, the Guerbet alcohols or methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture, as they are usually present in oxoalcohol radicals Hydroxymix ethers are preferred regardless of the type of alcohol used to prepare the hydroxymethyl ether contained in the agents in which R ¹ in the above formula for an alkyl group of 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms

In addition to propylene oxide, in particular butylene oxide is also suitable as the alkylene oxide unit which is contained in the preferred hydroxy mixed ether in addition to the ethylene oxide unit. But also other alkylene oxides in which R ² or R ³ are selected independently from -CH ₂ CH ₂ -CH ₃ or CH (CH ₃ ) ₂ are suitable Preference is given to using hydroxy mixed ethers of the above formula in which R ² or R ^{3 is} a radical - CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another for values of 1 or 2 stand

In summary, especially hydroxy mixed ethers are preferred which have a C _{9 15} alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 Propylenoxidemheiten, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 Propylenoxidemheiten have These surfactants exhibit in wässπger solution, the required low viscosity and are inventively used with particular preference

Particularly preferred are hydroxy mixed ethers of the general formula

R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² ,

which in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, further a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having from 1 to 28 carbon atoms, preferably 2 to 22 carbon atoms, which is adjacent to a monohydroxylated intermediate group -CH ₂ CH (OH) - and in which x is between 1 and 90, preferably 40 and 80 and especially between 40 and 60 stands The corresponding end-capped hydroxy mixed ethers of the above formula can be obtained, for example, by reacting a terminal epoxide of the formula R ² CH (O) CH ₂ with an ethoxylated alcohol of the formula R ¹ O [CH ₂ CH ₂ O] _x-1 CH ₂ CH ₂ OH

Hydroxymix ethers of the general formula

R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² ,

in which R ¹ and R ² independently of one another represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ , but preferably represents -CH ₃ , and x and y independently of one another are values between 1 and 32 are preferred according to the invention, wherein hydroxy mixed ethers with values of x from 15 to 32 and y of 0.5 and 1.5 are most preferred

The C chain lengths given and ethoxy ether degrees or degrees of alkoxylation of the abovementioned hydroxy mixed ethers represent statistical mean values which may be a whole or a fractional number for a particular product. Because of the preparation processes, commercial products of the formulas mentioned are usually not made up of an individual member but of mixtures, thereby Mean values and, consequently, fractional numbers can result for both the C chain lengths and for the degrees of ethoxylation or alkoxylation

Also suitable in the context of the present invention are pure alkoxy block polymers, which are preferably composed of alternating ethylene oxide, propylene oxide and / or butylene oxide units. Alkoxy block polymers of the formulas HO- (EO) _x (PO) _y (EO) _z -H, HO are preferred - (PO) _x (EO) _y (PO) ₂ -H, HO- (EO) _x (PO) _y (PO) ₂ -H, HO- (EO) _x (EO) _y (PO) _z -H, HO- (EO) _x (BO) _y (EO) _z -H, HO- (BO) _x (EO) _y (BO) _z -H, HO- (EO) _x (BO) _y (BO) _z -H , HO- (EO) _x (EO) _y (BO) _z -H, HO- (BO) _x (PO) _y (BO) _z -H, HO- (PO) _x (BO) _x (PO) ₂ - H, HO- (BO) _x (PO) _y (PO) _z -H and HO- (BO) _x (BO) _y (PO) _z -H, in which the indices independently of one another have the values 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 to 100. The block polymers preferably have molecular weights between 100 and 15 000 g / mol, in particular from 900 to 4000 g / mol of suitable block polymers are, for example, the Pluronic® grades (BASF) Pluronic® PE 3100 and PE 4300

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

Further compulsory constituents of the compositions according to the invention are thickeners The field of application of thickeners, also called thickeners, is generally to increase the viscosity of liquids. The action of thickeners is based on various effects such as swelling, gelation, association of micelles, solvation, formation From network structures and / or hydrogen bonds and their interaction with each other, the molecular structure and relative molecular weight of the hydrocolloids determine the degree of thickening

Surprisingly, it has now been found that the combination of special surfactants and a thickening agent in a cleansing or care agent significantly increases the fat emulsifying capacity of this agent. All the thickeners known to those skilled in the art may be used in the compositions according to the invention, whereby it is also possible to use a combination of several thickeners is

In a preferred embodiment, the compositions according to the invention contain inorganic thickeners such as silicic acid, clays, phyllosilicates, preferably smectites, in particular montmorillonite or hektoπt, low molecular weight organic thickeners such as metal elves, hardened ricinusol, modified fatty derivatives or polyamides From the large group of organic fully synthetic thickeners in particular polyvinyl alcohols, polyacrylic and polymethacrylic acids and their salts, polyacrylamides, polyvinylpyrrolidone, polyethylene glycols, styrene-Maleinsaureanhydπd copolymers and their salts are used. Particularly preferred are the co- and terpolymers of acrylic and methacrylic acid

Associative thickeners differ from the modified natural products listed below and the organic fully synthetic thickeners in that in addition to hydrophilic groups, they also contain hydrophobic end or side groups in the molecule. Thus, associative thickeners become surfactant-type and capable of forming micelles It is noteworthy that associative thickeners differentiate finely divided dispersions more strongly than coarse grains because of their greater total surface area

hydrophobically modified polyacrylates containing nonionic hydrophilic and hydrophobic groups incorporated in an anionic acrylate thickener molecule by copolymerization,

hydrophobically modified cellulose ethers, prepared by reaction of hydroxyethylcellulose during the etherification or subsequently with long-chain alkyl epoxides or halides,

hydrophobically modified polyacrylamides prepared by copolymerization of acrylamide with alkyl-modified acrylamide and optionally acrylic acid, and

hydrophobically modified polyethers and associative polyurethane thickeners consisting of hydrophilic, relatively high molecular weight polyether segments linked via urethane groups, capped with at least two terminal, hydrophobic molecule groups

o f o o I o

, 11 M, Il II,

R is -NH-C- (O-CH ^ -CH ^ -fo-C-NH-Fr-NH-C- (O-CH ₂ -CHz) _x -TOC-NH-R ^{1 LJ} n

Preferred thickening agents come from the groups of organic natural thickeners such as starch, gelatin and casein and the modified natural products, in particular the polysaccharides Important representatives of the latter group are (hydroxy) ethylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, ethylhydroxyethylcellulose, succmoglycan, xanthan gum , Guar-flour, locust bean gum, tragacanth, as well as derivatives and mixtures of these thickeners

Preferably, the thickener contained in the agents of the invention is selected from polysaccharides, preferably from cellulose compounds, xanthan gum and guar gum, and from acrylate thickeners, urethane thickeners and clays

Particular preference is given to using compounds from the group of polysaccharides, especially the xanthan gum and derivatives thereof, as xanthan gum and thickener corresponding derivatives are available under the names Keltrol® RD (CP Kelco), Kelzan® S (CP Kelco), Kelzan® T (CP Kelco), Rhodopol® T (Rhodia) and Rhodigel® X747 (Rhone Poulenc)

In general, it is possible that in the inventive compositions one, two, three, four or even five different thickening center! The xanthan gum content preferably makes at least 20% by weight, preferably at least 40% by weight, preferably at least 60% by weight, particularly preferably at least 80% by weight and in particular at least 90% by weight, especially 99% by weight entire thickener contained in the agent from

With preference in the washing or cleaning agent, 0.05 to 1% by weight, preferably 0, 1 to 0.9% by weight, particularly preferably 0.15 to 0.8% by weight, preferably 0.2 to 0, 7% by weight, more preferably from 0.25 to 0.6% by weight, very particularly preferably from 0.3 to 0.5% by weight and in particular from 0.3 to 0.4% by weight of thickener

Further optimization of the fat emulsifying agent according to the invention can be achieved by the choice of suitable proportions between the nonionic surfactants A and B and the thickening agent. The weight ratio of surfactant A to thickening agent preferably has between 50 and 1. Preferably, this ratio is between 22 and 1 and 1 2, preferably between 18 1 and 1 1.5, more preferably between 14 1 and 1 1, preferably between 10 1 and 1, 5 1 and in particular between 6 1 and 2 1 The weight ratio between surfactant B and thickener is preferably between 40 1 and 1 30 This ratio preferably has between 10 1 and 1 8, preferably between 7.5 1 and 1 6, particularly preferably between 5 1 and 1 4 and in particular between 2.5 1 and 1 2

The improved Emulgierkapazitat erfindungsgemaßer means is observed in a broad pH range preferably has a 1 wt -% strength solution in water (2O ⁰ C) a pH of less than 5.5, preferably less than 5.0, more preferably less than 4, The undiluted liquid composition preferably has a pH of less than 6, preferably less than 5, more preferably less than 4, more preferably less than 3 and in particular less than 2.5

To ensure the acidic properties of the composition, it preferably contains an organic or inorganic acid. It is preferred that the detergent or cleaning agent is at least 10% by weight, preferably at least 13% by weight, more preferably at least 16% by weight, very particularly preferably at least 19% by weight and in particular at least 22% by weight, based on the total agent, of an inorganic or organic acid Suitable acids are organic mono- or polybasic optionally unsaturated by hydroxyl groups, optionally unsaturated carboxylic acids having 2 to 6 carbon atoms in the molecule Preferably, the acid has a dissociation constant less than 10 ⁶ Preferred aliphatic acids are formic acid, acetic acid, adipic acid, succinic acid, tartaric acid, malic acid, Glutaric acid, sorbic acid, maleic acid, malonic acid, lactic acid, glycolic acid, propionic acid, oxalic acid and especially citric acid From the group of aromatic carboxylic acids is preferably salicylic acid or benzoic acid are also suitable lactobionic acid and gluconic acid Preferred inorganic acids are boric acid, sulfamic acid, phosphoric acid, sulfuric acid, hydrochloric acid and Nitric acid Also suitable is cyanuric acid

The inventive agents may simultaneously contain one, two, three, four, five or up to 12 different organic and / or inorganic acids (acid mixtures). Preferably, the cleaning or care agents contain less than 5, preferably less than 4, more preferably less as 3 and in particular only one acid

If the composition contains two or more acids, the proportion by weight of one of the acids, preferably of citric acid in the agent, is preferably at least 50% by weight, preferably at least 60% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight. %, more preferably at least 90% by weight and in particular at least 95% by weight, based on the acids present

No acids in the sense of the present invention are the builders. Also anionic surfactants as well as the anionic surfactants present in an agent in protonated form due to a low pH, ie the anionic surfactant acids, are not acids in the sense of the present invention

Within one, preferably all of the acid / salt pairs present in the middle, the proportion of the acid, based on the acid / salt pair, is preferably at least 10% by weight, preferably at least 25% by weight, particularly preferably at least 40% by weight preferably at least 55% by weight, preferably at least 60% by weight and in particular at least 85% by weight

With particular preference, the inventive cleaning or care agents additionally contain at least one surfactant from the group of anionic, cationic and amphoteric surfactants

The anionic surfactants used are used, for example of the type of sulfonate and sulfate surfactants of the sulfonate type are preferably C _{9 13} alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C _{12-i 8} -Monoolefιnen with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis Also suitable are alkanesulfonates which are obtained from C _12-18 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonylates Methyl esters of hydrogenated coconut, palm kernel or Taigfettsäuren suitable

Further suitable anionic surfactants are sulfonated fatty acid glycyl esters. Fatty acid glycylic esters are the mono-, di- and tri-esters and mixtures thereof, as in the preparation by esterification of a monoglycerine with 1 to 3 mol fatty acid or in the transesterification of triglycerides with 0.3 to Preferred sulfonated fatty acid glycyl esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic, caprylic, capnic, myristic, lauric, palmitic, stearic or behenic acid

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

Also the sulfuric acid monoesters of the straight-chain or branched C _7-21 -alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-1 ^ alcohols having on average 3.5 moles of ethylene oxide (EO) or C _12-18 . Fatty alcohols with 1 to 4 EO, are suitable They are used in the Remigungs- or care products due to their high foaming behavior only in relatively small amounts, for example in amounts of 1 to 5 wt -%

Further suitable anionic surfactants are also the salts of alkyl sulfosuccinic acid, which are also referred to as sulfosuccinates or sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 -fatty alcohol residues or mixtures These particularly preferred sulfosuccinates contain a fatty alcohol radical which is derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants. In turn, sulfosuccinates whose fatty alcohol radicals are derived from ethoxylated fatty alcohols with a narrow homolog distribution are 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 of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. 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 inventive agent preferably contains at least one surfactant selected from the group consisting of alkylphenoxybenzenedisulfonates, linear or branched alkylbenzenesulfonates, linear or branched alkylnaphthalene sulfonates, alkylsulfonates, olefinsulfonates, paraffin sulfonates, alkylarylsulfonates, soaps, alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alkylaryl polyether sulfates or monoglycerol sulfates.

In a particularly preferred embodiment, the agent comprises an alkylbenzenesulfonate, preferably an alkylbenzenesulfonate having an alkyl chain length of C ₂ -C ₂₀ , in particular cumene sulfonate.

The agent preferably contains an anionic surfactant which has hydrotropic properties.

If anionic surfactant (s), preferably anionic surfactant (s) having hydrotropic properties, are constituents of automatic dishwashing detergent, their content, based on the total weight of the compositions, is preferably between 2 and 10% by weight, preferably between 3 and 9% by weight. , most preferably between less than 4 and 8 wt .-% and in particular between 5 and 7 wt .-%. Automatic dishwashing detergents which contain only hydrotropic properties from the group of anionic surfactants are particularly preferred.

Instead of the surfactants mentioned or in conjunction with them, it is also possible to use cationic and / or amphoteric surfactants.

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

wherein each R ¹ group is independently selected from C _{1 6} alkyl, alkenyl or hydroxyalkyl groups, each group R ² is independently selected from C _{8 2} s-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 is

Betaines and / or amine oxides are preferably less than 10% by weight, preferably less than 8% by weight, particularly preferably less than 6% by weight, of the agents according to the invention being preferred for this purpose less than 4% by weight, with very particular preference less than 2% by weight, and in particular not at all

In the removers or care compositions according to the invention, the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. Agents which do not contain cationic and / or amphoteric surfactants are particularly preferred

The inventive agent can both be in solid form such as powders, pellets, tablets, capsules, beads and in the liquid form is the agent solid at room temperature, it is with advantage at temperatures below 90 ⁰ C., preferably below 80 ⁰ C, preferably below 70 ⁰ C, more preferably below 60 ⁰ C and in particular below 55 ⁰ C completely or partially flowable / liquid Under LIQUID is also gelformig and waxy understood "liquid" therefore refers to any condition that at 2O ⁰ C (fheßfahigen) by a fussigen aggregate state is characterized

Preferably, the agent is in the liquid state and has a viscosity above 50 mPas, preferably between 100 and 700 mPas, preferably between 200 and 600 mPas and in particular between 300 and 500 mPas

Suitable carriers of liquid agents are water, non-aqueous solvents and mixtures of these Suitable organic carriers are alcohols (methanol, ethanol, propanols, butanols, octanols, cyclohexanol), glycols (ethylene glycol, diethylene glycol), ethers and glycol ethers (diethyl ether, dibutyl ether, anisole, dioxane , Tetrahydrofuran, mono-, di-, tri-, polyethylene glycol ethers), ketones (acetone, butanone, cyclohexanone), esters (acetic acid esters, glycol esters), amides and other nitrogen compounds (dimethylformamide, pyridine, N-methylpyrrolidone, acetonitrile), sulfur -Venndungen (carbon disulfide, dimethyl sulfoxide, sulfolane), nitro compounds (nitrobenzene), halogenated hydrocarbons (dichloromethane, chloroform, carbon tetrachloride, tri-, tetrachloroethene, 1, 2-Dιchlorethan, chlorofluorocarbons), hydrocarbons (gasoline, petroleum ether, cyclohexane, methylcyclohexane, decalin , Terpene solvents, benzene, toluene, xylene) As already indicated, instead of pure solvents, they can also be used Such a solvent mixture is, for example, benzine, a mixture of various hydrocarbons suitable for dry-cleaning, preferably containing more than 60% by weight of C 12 to C 14 hydrocarbons, more preferably more than 80% by weight % and in particular above 90% by weight, in each case based on the total weight of the mixture, preferably with a boiling range of 81 to 110 ° C.

Water, alcohol or an alcohol / water mixture, preferably a water / alcohol mixture, is preferably used as the carrier in inventive compositions. Here, preference is given to using a polyhydric alcohol and in particular glycerin. Preferably, a water / glycerin mixture serves as a carrier

The ratio between alcohol and water in the carrier is preferably between 10 1 and 1 100, preferably between 1 1 and 1 90, more preferably between 1 5 and 1 80, very particularly preferably between 1 10 and 1 60 and in particular between 1 15 and 1 40

Depending on the intended use, the composition according to the invention may contain abrasive, undissolved and / or dispersed constituents, be cloudy or translucent or clear The inventive compositions described above preferably contain further cleaning-active and / or care-active substances, preferably from the group of frameworks, polymers, bleaching agents, bleach activators, enzymes, corrosion inhibitors, disintegration aids, fragrances and perfume carriers. These preferred ingredients are described in more detail below

In particular, zeolites, silicates, carbonates, organic co-builders and, where there are no ecological prejudices against their use, the phosphates also pay to the framework materials

Preference is given to using crystalline layered silicates of the general formula NaMSi _x O _{2x +} 1yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values x is 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 +} 1yH ₂ O are described, for example, by Claπant GmbH (Germany Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ × H ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ × H ₂ O), Magadnt), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ × H ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ × H ₂ O, makatite)

Particularly suitable for the purposes of the present invention are crystalline layer silicates of the formula NaMSi _x O _{2x +} IyH ₂ O, in which x is 2 In particular, both β- and δ-natural disilicates are Na ₂ Si ₂ O ₅ y H ₂ O. and furthermore especially Na-SKS-5 ((X-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ S ₂ O ₅ , Natrosiht), Na-SKS-9 (NaHSi ₂ O ₅ H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ 3H ₂ O, kanemite), Na-SKS-11 _(t-Na2 Sι ₂ 0 ₅₎ and Na-SKS-13 (NaHSi ₂ O _5), but especially Na-SKS-6 (5-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, preferably from 1.2 to 1.8 and in particular from 1.2 to 2.6, which are preferably loosely delayed and have secondary cleaning properties Loseverzogerung compared to conventional amorphous Natπumsilikaten can thereby be caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying In the context of this invention, the term "amorphous" understood that the silicates in X-ray extenuations do not provide sharp X-rays, such as they are typical of crystalline substances, but at most one or more maxima of the scattered X-radiation, which have a width of several degrees of the diffraction angle, cause

As an alternative or in combination with the abovementioned amorphous sodium silicates, it is possible to use X-ray silicates whose silicate particles produce blurred or even sharp diffraction maxima in electron diffraction phenomena. This is to be interpreted in such a way that the Products microcrystalline areas of large ten to a few hundred nm, with values up to max. 50 nm and in particular up to max. 20 nm being preferred. Such X-ray silicates also exhibit a loose delay compared to the conventional waterglass. Particular preference is given to compacted / compacted amorphous silicates, compounded amorphous Silicates and dried X-ray amorphous silicates

Of course, a use of the well-known phosphates as builders is possible, if such use should not be avoided for environmental reasons. Among the variety of commercially available phosphates Alkahmetallphosphate have with particular preference of pentasodium or Pentakaliumtnphosphat (sodium or Kaliumtπpolyphosphat) in the Detergents and cleaners industry the greatest importance

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

Technically particularly important phosphates are the pentasodium tπphosphate, Na ₅ P ₃ Oi ₀ (Natriumtπpolyphosphat) and the corresponding potassium salt Pentakaliumtnphosphat, K ₅ P ₃ Oi ₀ (Kaliumtπpolyphosphat) According to the invention preferably continue to use the Natriumkaliumtπpolyphosphate

Examples of alkali metal carriers are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, said alkahsilates, alkali metal alkoxides, and mixtures of the abovementioned substances. For the purposes of this invention, preference is given to using the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium mesic acid carbonate is a builder system containing a mixture of Tπpolyphosphat and Natnumcarbonat Also particularly preferred is a builder system comprising a mixture of tripolyphosphate and Natnumcarbonat and Natπumdisihkat

Particular examples of organic cobuilders include 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 framework substances are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids being such For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, ammocarboxylic acids, nitrilotriacetic acid (NTA) _1, if such use is not objectionable for ecological reasons, As well as their builder action, the free acids also typically have the property of an acid component and thus also serve to establish a lower and milder pH of detergents or cleaners. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures are particularly suitable to name from these

As scaffolds further polymeric polycarboxylates are suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70000 g / mol

In the context 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 gel permeation chromatography (GPC) using a UV detector. The measurement was carried out against an external polyacrylic acid standard which gives realistic molecular weight values owing to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data in which polystyrenesulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this specification

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

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and 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 are particularly suitable 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. The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution

To improve water-immunity, 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 containing as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or the monomers of the 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 Substances are particularly preferred 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 prepared from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid

Other 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, the hydrolysis products have average molecular weights in the range from 400 to 500000 g / mol. 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 customary measure of the reducing action of a polysaccharide in comparison with dextrose, Usable are both Maltodextnne with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide to the carboxylic acid function

Oxydisuccinates and other derivatives of disuccinates, preferably Ethylendiammdisuccinat are further suitable cobuilders Ethylenediamine-N, N ^'- disuccinate (EDDS) is preferably in the form its sodium or magnesium salts thereof are furthermore preferred in this context, glycerin and Glycerintnsuccinate Further 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 which are capable of forming complexes with alkaline earth metals can be used as scaffolds

However, the agents according to the invention preferably contain methylglycinediacetic acid (MGDA), ethylenediaminetetraacetic acid (EDTA) and / or nitroglioacetic acid (NTA), their salts and mixtures of the acids and / or salts

In addition to the nonionic surfactants already mentioned, it is possible to use further nonionic surfactants known to the person skilled in the art. However, the proportion of nonionic surfactants additionally used is below 10% by weight, more preferably below 8% by weight, preferably below 6% by weight, more preferably below 4 % By weight and in particular below 2% by weight. With particular preference, no nonionic surfactants which can not be represented by the formula R ¹ O- [CH ₂ CH (R ² ) O], rR ³ are used

Suitable nonionic surfactants which can be used in addition to the nonionic surfactants described above are, for example, alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, especially methyl-branched, aliphatic radical having 8 to 22, preferably 12 to Corresponds to 18 C 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 an arbitrary number between 1 and 10, preferably x is 1, 2 to 1, 4

The agents according to the invention preferably contain less than 2.5% by weight, preferably less than 1.5% by weight, more preferably less than 0.5% by weight and in particular no amine oxide

However, further suitable surfactants are polyhydroxy fatty acid amides of the formula

wherein R is an aliphatic acyl group having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms, and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups The polyhydroxy fatty acid amides are known substances which are customary can 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 Fettsaurechloπd

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 oxy-alkyl radical having 1 to 8 carbon atoms, with C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxy-, preferably ethoxylated or propoxylated Derivatives of this residue

[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 prepared by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst be converted into the desired polyhydroxy fatty acid amides

In general, cationic, anionic and amphoteric polymers can also be used in the inventive compositions in addition to nonionic polymers

"Cationic polymers" in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain. Particularly preferred cationic polymers are derived from the groups of the quaternized cellulose Derivatives of quaternary group polysiloxanes, cationic guar derivatives, dimethyldiallylammonium polymeric salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, copolymers of vinylpyrrolidone with quaternized derivatives of dialkylammoacrylate and methacrylate, vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers listed under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 For the purposes of the present invention, "amphoteric polymers" further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.

Suitable polymers are characterized in that they contain a polymer a) which has monomer units of the formula R ¹ R ² C =CR ³ R ⁴ , in which each radical R ¹ , R ² , R ³ , R ^{4 is} selected independently of one another Hydrogen, derivatized hydroxy, C _1-30 linear or branched alkyl groups, aryl, aryl substituted C _1-30 linear or branched alkyl groups, polyalkoxylated alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least an amino group having a positive charge in the partial range of the pH range of 2 to 11, or salts thereof, with the proviso that at least one radical R ¹ , R ² , R ³ , R ^{4 is} a heteroatomic organic group having at least one positive charge without charged nitrogen, at least one quaternized nitrogen atom or at least one amino group having a positive charge.

Suitable cationic or amphoteric polymers contain as monomer unit a compound of the general formula

in which R ¹ and R ⁴ are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ^{3 are} independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3. X represents a counterion, preferably a counterion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R ¹ and R ⁴ in the above formula are selected from -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 , and - (CH ₂ CH ₂ -O) _n H. Very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ¹ and R ^{4 are} H, R ² and R ^{3 are} methyl and x and y are each 1. The corresponding monomer unit of the formula

H ₂ C = C H- (CH ₂ JN (CH ₃ ) ₂ - (CH ₂ ) -CH = CH ₂

in the case of X = chloride, they are also referred to as DADMAC (diallyldimethylammonium chloride).

Further particularly preferred cationic or amphoteric polymers contain a monomer unit of the general formula

X ^"in which R ^1, R ^2, R ^3, R ⁴ and R ^{5 are} independently a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from - 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 , and - (CH ₂ CH ₂ -O) _{n is} H and x is an integer between 1 and 6.

For the purposes of the present application, very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ^{1 is} H and R ² , R ³ , R ⁴ and R ^{5 are} methyl and x is 3. The corresponding monomer units of the formula

H ₂ C = C (CH ₃ ) -C (O) -NH- (CH 2) _X -N ⁺ (CH ₃ ) 3

X ^"

in the case of X = chloride also referred to as MAPTAC (Methyacrylamidopropyl trimethylammonium chloride).

According to the invention, preference is given to using polymers which contain diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units. The above-mentioned amphoteric polymers have not only cationic groups but also anionic groups or monomer units. Such anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched , saturated or unsaturated sulfates or the linear or branched, saturated or unsaturated sulfonates Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid , maleic acid, fumaric acid, cinnamic acid and its derivatives, the allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acid

Preferred usable amphoteric polymers come from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the

Alkylacrylamιd / methacrylic acid / Alkylamιnoalkyl (meth) acrylic acid copolymers, the

Alkylacrylamιd / Methylmethacrylsaure / Alkylamιnoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / Alkylammoethylmethacrylat / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically deπvatisierten unsaturated carboxylic acids and optionally other ionic or nonionic monomers

Preferred zwitterionic polymers are selected from the group of acrylamidoalkyltπalkylammoniumchlorid / acrylic acid copolymers and their alkali metal and ammonium salts, the Acrylamidoalkyltπalkylammoniumchlorid / methacrylic acid copolymers and their alkali metal and ammonium salts and Methacroylethylbetain / methacrylate copolymers

Also preferred are amphoteric polymers, which in addition to one or more anionic monomers as cationic monomers Methacrylamidoalkyl-tnalkylammoniumchlorid and Dιmethyl (dιallyl) ammonιumchloπd include

Particularly preferred amphoteric polymers are from the group of methacrylamidoalkyl- tπalkylammonιumchlorιd / Dιmethyl (dιallyl) ammonιumchlorιd / acrylic acid copolymers, the Methacryl- amιdoalkyltrιalkylammonιumchloπd / Dιmethyl (dιallyl) ammonιumchloπd / methacrylic acid copolymers and the Methacrylamidoalkyltπalkylammoniumchloπd / DimethyKdiallyOammoniumchlorid / alkyl

(meth) acrylic acid copolymers and their alkali metal and ammonium salts

Particular preference is given to amphoteric polymers from the group of

Methacrylamιdopropyltπmethylammoniumchloπd / Dιmethyl (dιallyl) ammonιumchloπd / Acrylsaure-

Copolymers comprising methacrylamidopropyltrimethylammonium chloride / dimethy-kiallylammonium chloride / acrylic acid copolymers and methacrylamidopropylmethylammonium Chlorιd / Dιmethyl (dιallyl) Ammonιumchlorιd / alkyl (meth) acrylic acid copolymers and their Alkah- and ammonium salts

In a particularly preferred embodiment of the present invention, the polymers are present in prefabricated form. For the preparation of the polymers, the encapsulation of the polymers by means of water-soluble or water-dispersible substances is suitable here

Coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers, the encapsulation of the polymers by means of water-insoluble, fusible

Coating composition, preferably by means of water-insoluble coating agent from the

Group of waxes or paraffins with a melting point above 30 ⁰ C, the cogranulation of the polymers with inert Tragermateπalien, preferably with

Tragermateπalien from the group of washing or cleaning-active substances, particularly preferably from the group of builders (scaffolds) or cobuilders

Examples of polymers effective as a softener are the sulfonic acid group-containing polymers which are used with particular preference

Copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionogenic or nonionogenic monomers are particularly preferably usable as sulfonic acid-containing polymers

In the context of the present invention are unsaturated carboxylic acids of the formula as a monomer

R ¹ (R ² ) C = C (R ³ ) COOH

in which R ¹ to R ^3, independently of one another, are -H, -CH ₃ , a straight-chain or branched, saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms

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

In the sulfonic acid group-containing monomers are those of the formula R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

in which R ⁵ to R ⁷ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group , which is selected from - (CH ₂ ) _n - with n = O to 4, -COO- (CH ₂ K- with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and C (O) -NH-CH (CH ₂ CH ₃ ) -

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

HO ₃ SX (R ⁶⁾ C = C (R ⁷⁾ -X-SO ₃ H

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = O to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, Methacrylamιdo-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of said acids

In particular, ethylenically unsaturated compounds are suitable as further ionic or nonionogenic monomers. The content of the polymers used in these other ionic or nonionic monomers is less than 20% by weight, based on the polymer. Polymers to be used particularly preferably consist only of monomers of the formula R. ¹ (R ² ) C = C (R ³ ) COOH and monomers of the formula R ⁵ (R ⁶ ) C = C (R ⁷ ) -

X-SO ₃ H

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

Further particularly preferred copolymers consist of i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid ii) one or more sulfonic acid group-containing monomers of the formulas:

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CHa) -X-SO ₃ H

HO ₃ SX (R ⁶⁾ C = C (R ⁷⁾ -X-SO ₃ H

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ J ₂ and X is an optional spacer group which is selected from - (CH ₂ V with n = O to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C ( O) -NH-CH (CH ₂ CH ₃ ) - iii) optionally further ionogenic or non-ionogenic monomers.

The copolymers may contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from group i) being combined with all representatives from group ii) and all representatives from group iii) Particularly preferred polymers have certain structural units which are described below

For example, copolymers which are structural units of the formula are preferred

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with π = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CHa) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred

These polymers are prepared by Copolymeπsation of acrylic acid with a Sulfonsäuregruppen- containing Acrylsauredeπvat Copolymeπsiert the Sulfonsauregruppen-containing Acrylsauredenvat with methacrylic acid, one arrives at another polymer whose use is also preferred The corresponding copolymers contain the structural units of the formula

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

each of m and p is an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals containing from 1 to 24 carbon atoms, wherein O- (CH ₂ ) n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ J ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, are preferred

Acrylic acid and / or ⁽ vinylacetamide) can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, copolymers which are structural units of the formula ## STR5 ##

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) -, are particularly preferred, just as preferred as copolymers, the structural units of the formula - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred.

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred copolymers, the structural units of the formula

- [HOOCCH-CHCOOHIn ₁ - [CH ₂ -CHC (O) -Y-SO ₃ H] _P -

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred. Also preferred according to the invention are copolymers which contain structural units of the formula

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p -

in which m and p are each an integer between 1 and 2, and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CHa) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In summary, such copolymers are preferred according to the invention, the structural units of the formulas

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p -

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p -

- [HOOCCH-CHCOOHIm- [CH ₂ -CHC (O) -Y-SO ₃ H] _P -

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CHa) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred

In the polymers, the sulfonic acid groups may be completely or partially in neutralized form, ie that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and especially sodium ions. The use of partially or fully neutralized sulfonic acid group-containing copolymers is erfmdungsgemaß prefers

The monomer distribution of the copolymers preferably used according to the invention is in the case of copolymers which contain only monomers from groups (I) and (I), preferably in each case from 5 to 95% by weight or preferably from 50 to 90% by weight of monomer from the group ι) and 10 to 50% by weight of monomer from the group ιι), each based on the polymer

In the case of terpolymers, particular preference is given to those containing from 20 to 85% by weight of monomer from the group I), from 10 to 60% by weight of monomer from the group I) and from 5 to 30% by weight of monomer from the group III)

The molecular weight of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use. Preferred detergents or cleaners are characterized in that the copolymers have molecular weights of 2,000 to 200,000 gmol ¹ , preferably 4,000 to 25,000 gmol ¹ and in particular from 5000 to 15,000 gmol ^'1 have

The bleaching agents are a cleaning-active substance used with particular preference. Among the compounds which serve as bleaching agents in water H ₂ O ₂ , sodium percarbonate, sodium borate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaches which can be used are, for example, peroxypyrophosphates, citrate perhydrate and H ₂ O ₂ -producing peracid Salts or peracids, such as perbenzoates, peroxophthalates, diperazelamic acid, phthaloiminoperacid or diperdodecanedioic acid bleaches can also be used from the group of organic bleaches. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are the peroxyacids Preferred are (a) the peroxybenzoic acid and its ring-substituted derivatives such as alkylperoxybenzoic acids, but also (B) the aliphatic or substituted aliphatic peroxyacids, such as peroxylic acid, peroxy acid, ε-phthalimidoperoxycaproic acid

Carboxybenzamidoperoxycaproic acid, N-Nonenylamidoperadipinsäure and N-

Nonenylamidopersuccinate, and (c) ahphatische and arahphatische peroxydicarboxylic acids, such as 1, 12-Dιperoxycarbonsäure, 1, 9-Dιperoxyazelaιnsaure, Diperocysebacinsaure,

Diperoxybrassylic acid, the diperoxyphthalic acids, 2-Decyldιperoxybutan-1, 4-diacid, N ₁ N-terephthaloyl-dι (6-amιnopercapronsaue)

Chlorine or bromine-releasing substances can also be used as the bleaching agent. Suitable chlorine-containing or bromine-releasing materials include, for example, heterocyclic N-bromo- and N-chloramides, for example, t-chloroisocyanuric acid, tribromoisuricacid, dibromoisocyanuric acid and / or dichloic acid (DICA) and / or salts thereof Cations such as potassium and sodium into consideration Hydantoinverbindungen, such as 1, 3-Dιchlor-5,5-dιmethylhydanthoιn are also suitable

Bleach activators are used in washing or cleaning agents, for example, in order to achieve cleaning at temperatures of 60 ⁰ C and below, an improved bleaching effect The bleach activators used may be compounds which form aliphatic perhydrolysis Peroxocarbonsauren preferably having 1 to 10 carbon atoms, in particular 2 to 4 C Suitable are substances which carry O- and / or N-acyl groups of said carbon atom number and / or optionally substituted benzoyl groups. Preferred are polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated Tnazinderivate, in particular 1, 5-Dιacetyl-2,4-dιoxohexahydro-1, 3,5-tπazιn (DADHT) ₁ acylated Glycolunle, in particular Tetraacetylglykoluπl (TAGU), N-Acylιmιde, in particular N-Nonanoylsuccιnιmιd (NOSI), acylated phenolsulfonates , in particular n-nonanoyl or Isononanoyloxybenzolsulfonat (n- or iso-NOBS), Carbonsaureanhydnde, in particular Phthalsaureanhydπd, acylated polyhydric alcohols, especially Tnacetin, ethylene glycol diacetate and 2,5-Dιacetoxy-2,5-dιhydrofuran, n-methyl-morpholinium acetonitnl-methyl sulfate (MMA) and acetylated sorbitol and mannitol or their Mixtures (SORMAN), acylated sugar derivatives, in particular pentaacety iglucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylιertes glucamine and gluconolactone, and / or N-acylιerte lactams, for example N-benzoylcaprolactam Hydrophilic substituted acylacetals and acyl lactams are also Preference is also given to using combinations of conventional bleach activators These bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight, based in each case on the total weight of bleach activator-containing agents.

Further bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula

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

Particularly preferred is a cationic nitrile of the formula

in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ - CH ₃ , -CH (CH ₃ ) -CH ₃ , wherein R ⁴ additionally also -H may be and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ( CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^' , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X- are particularly preferred, wherein from the group of these substances 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, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is particularly preferred. In addition to the conventional bleach activators or in their place also so-called bleach catalysts can be used These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing Tπpod ligands and Co, Fe, Cu and Ru amine complexes can 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 manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammine) Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are preferably used

Enzymes can be used to increase the cleaning performance of the agents according to the invention. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof

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 are no longer, however, preferred among the proteases Enzymes Thermitase, Proteinase K, and Proteases TW3 and TW7, which can be classified as subtilisins in the narrower sense

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, B amyloliquefaciens, β-stearothermophilus, Aspergillus niger and A oryzae and the further developments of the abovementioned amylases which are improved for use in detergents and cleaners - Amylase from Bacillus sp A 7-7 (DSM 12368) and the Cyclodextπn glucanotransferase (CGTase) from ß agaradherens (DSM 9948)

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceπd-cleaving activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanugmosa (Thermomyces lanuginosus) or further developed, in particular those with the Amino acid exchange D96L Furthermore, for example, the cutinases can be used, which were originally isolated from Fusaπum solam pisi and Humicola insolens are still lipases, or cutinases whose Initial enzymes were originally isolated from Pseudomonas mendocina and Fusanum solanu

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

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 advantageously be used according to the invention to increase the bleaching effect additionally preferably organic, particularly preferably aromatic, interacting with the enzymes compounds added to enhance the activity of the respective oxidoreductases (enhancer) or to ensure at very different redox potentials between the oxidizing enzymes and the stains electron flow (mediators)

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 gelated agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers added

Alternatively, the enzymes can 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 superposed layers may additionally contain other active ingredients, such as stabilizers, emulsifiers, pigments, bleaches or dyes Capsules of this kind are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, granules of this type, for example by application of polymeric film formers, are low in dust and storage-stable due to the charge

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, especially during storage, be protected against damage such as, for example, inactivation, denaturation or decomposition, for example by physical influences, Oxidation or proteolytic cleavage Protected microbial recovery of the proteins and / or enzymes inhibition of proteolysis is particularly preferred, especially if the agents contain proteases detergents or cleaning agents may contain stabilizers for this purpose, the provision of such means is a preferred embodiment of the present invention

Corrosion inhibitors are used to protect the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. The silver-protecting agents selected from the group of tnazoles, benzotnazoles, bisbenzotriazoles, aminotnazoles, .alpha Particularly preferably to be used are Benzotπazol and / or Alkylaminotπazol According to the invention preferably 3-Amιno-5-alkyl-1, 2,4-trιazole or their physiologically acceptable salts are used

Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric and succinic acids. Very particularly effective are 5-pentyl, 5-heptyl, 5-nonyl, 5 Undecyl-, 5-isononyl-, 5-Versatιc-10-Saurealkyl-3-amιno-1, 2,4-tπazole and mixtures of these substances

Chlorine-free detergents also contain oxygen- and nitrogen-containing organic redox-active compounds, such as dihydric and trihydric phenols, for example hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, Phloroglucin, pyrogallol or derivatives of these compounds used also salt and complex inorganic compounds, such as salts of metals Mn, Ti, Zr, Hf, V, Co and Ce are often used Here, preference is given to the transition metal salts, which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate be used to prevent corrosion on Spulgut

Instead of or in addition to the silver protectants described above, for example the benzotnazoles, redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group consisting of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium. Salts and / or complexes, wherein the metals are preferably present in one of the oxidation states II, III, IV, V or VI The metal salts or metal complexes used should be at least partially soluble in water. The counterions suitable for salt formation comprise all conventional mono-, di-, or tri-negatively charged inorganic anions, for example oxide, sulfate, nitrate, fluoride, but also organic anions such as stearate

Particularly preferred metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) -citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [I -Hydroxyethane-1, 1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ , and mixtures thereof, such that the metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) -citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) _{3 are used} with particular preference

The inorganic redox-active substances, in particular metal salts or metal complexes, are preferably coated, ie completely coated with a water-tight material which is readily soluble in the cleaning temperatures, in order to prevent their premature decomposition or oxidation during storage. Preferred coating materials which are prepared by known processes, for example melt-coating processes according to Sandwik from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candelilla wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids

The metal salts and / or metal complexes mentioned are contained in cleaning agents, preferably in an amount of 0.05 to 6% by weight, preferably 0.2 to 2.5% by weight, in each case based on the total agent

The compositions according to the invention can be formulated in liquid or solid form, for example in the form of tablets. In order to facilitate the disintegration of preformed shaped bodies, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these compositions in order to shorten the disintegration tents Understood excipients that provide for the rapid disintegration of tablets in water or other media and for the drafty release of the active ingredients

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

Cellulosic disintegrants are used as preferred disintegrants. Pure cellulose has the gross formal composition (C ₆ H ₁₀ Os) _n and formally represents a beta-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses in this case from about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulosic disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses comprise For example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as cellulose-based disintegrating agents but are used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50 % By weight, more preferably below 20% by weight, based on the cellulose-based disintegrating agent It is particularly preferable to use cellulose-based disintegrating agent as pure cellulose which is free of cellulose derivatives

The cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted before admixing. The particle sizes of such disintegrating agents are generally above 200 .mu.m, preferably at least 90% by weight 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm

As a further disintegrating agent based on cellulose or as a component of this component, microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses. but leave the crystalline areas (about 70%) without damage. Subsequent deaggregation of the microfine celluloses resulting from the hydrolysis yields the microcrystalline celluloses which have particle sizes of about 5 μm and can be compacted, for example, into granules having an average particle size of 200 μm The gas-evolving effervescent system may consist of a single substance which releases a gas on contact with water. Among these compounds is in particular the magnesium peroxide, which releases oxygen upon contact with water However, gas-releasing effervescent system in turn of at least two components that react with each other to form gas While here a variety of systems is thinkable and ausfuhrbar that release, for example, nitrogen, oxygen or hydrogen, the used in the detergents and cleaners effervescent system is based both economic and can also be selected based on ecological considerations Preferred effervescent systems consist of Alkahmetallcarbonat and / or - bicarbonate and an Acidifizierungsmittel which is suitable from the Alk Alimetallsalzen in wassπger solution to release carbon dioxide

For example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts are preferably used. However, organic acidifiers are preferably used, citric acid being a particularly preferred acidifier. Acidifying agents in the effervescent system are preferably selected from the group of organic acids Di-, tri- and ethoxylic acids or mixtures

For the purposes of the present invention, perfume oils or perfumes may be selected from the group consisting of synthetic esters, ethers, aldehydes, ketones, alcohols and hydrocarbons. 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 those obtainable from vegetable sources, such as pine, citrus, jasmine, patchouly, rose or ylang-ylang oil

In order to be perceptible, a perfume must be volatile, in addition to the nature of the functional groups and the structure of the chemical compound and the molecular weight plays an important role So most perfumes have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and more represent an exception Due to the different odor of odoriferous substances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note", "middle note" or "middle note" Since the perception of odors is based to a large extent on the odor intensity, the top note of a perfume or fragrance is not only from volatile compounds while the base note for the most part from less volatile, ie adherent Fragrances exists in the composition of perfumes For example, it is easier for volatile fragrances to be bound to specific fixatives, which prevents them from evaporating too quickly. The subsequent classification of the fragrances into "light volatile" or "firmly adhering" fragrances therefore depends on the odor impression and whether the corresponding fragrance is used as head or head Heart note is perceived, nothing stated

The fragrances can be processed directly, but it may also be advantageous to apply the fragrances on carriers that provide a slower release of fragrance for long-lasting fragrance as such Tragermateπalien example cyclodextrins have preserved, the Cyclodextπn-perfume complexes additionally with other excipients can be coated

Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the compositions and to light and no pronounced substantivity to the substrates to be treated with the dye-containing agents, such as textiles, glass, ceramics or plastic dishes do not stain them

When choosing the colorant, it must be taken into account that the colorants have a high storage stability and insensitivity to light. At the same time, it must be considered when choosing suitable colorants that colorants have different stabilities to oxidation. In general, water-insoluble colorants are more stable to oxidation than Water-soluble colorants Depending on the degree of dissociation and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. For water-soluble colorants, it is typical to use colorant concentrations in the range from a few 10 ² to 10 ^-3 % by weight their brilliance, particularly preferred, but are less readily water-soluble pigment dyes is the appropriate concentration of the color agent in washing or cleaning agents, however, typically a few 10 ^'3 to 10 ^"4 wt -%

Colorants are preferred which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proven 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 nitrosofarbenes

In a preferred embodiment the composition contains 0.6 to 5.0 wt -%, preferably 0.8 to 4 wt -% of a C ₁₂ -C ₁₈ -Alkylalkoholalkoxylats, a C ₂ -C ₁₄ preferably -Alkylalkoholalkoxylats having an average molecular weight of about 500-900 g / mol, 0.1 to 1.7% by weight, preferably 0.2 to 1, 4 wt -% of a C ₁₂ -C ₁₈ -Alkylalkoholalkoxylats, preferably a Ci ₆ -C ₈ - Alkylalkoholalkoxylats having an average Momasse 1400-2100 g / mol, 0.05 to 1 wt -%, preferably 0.1 to 0.9% by weight of a thickener, preferably a thickener from the group of polysaccharides and in particular xanthan gum and at least 10% by weight, preferably at least 13% by weight of an inorganic or organic acid, preferably citric acid, and preferably also 2 to 10% by weight -% cumene sulfonate

Also preferred is an agent which is from 0.6 to 5.0% by weight, preferably 0.8 to 4% by weight of a C ₁₂ -C ₁₈ alkyl alcohol, preferably a C ₁₂ -C 14 alkyl alcohol, which is both ethoxylated and is propoxylated and preferably 2 to 7 moles, in particular 4 to 5 moles of ethylene oxide and 2 to 7 moles of propylene oxide, in particular 3 to 4 moles of propylene oxide, 0, 1 to 1.7% by weight, preferably 0.2 to 1, 4 wt -% of a C ₁₂ -C ₁₈ -Alkylalkoholalkoxylats, a Ci ₆ is preferably - C ₁₈ -Alkylalkoholalkoxylats which no propylene oxide units and at least 15, preferably at least 25 ethylene oxide containing 0.05 to 1 wt -%, preferably 0 1 to 0, 9% by weight of a thickening agent, preferably of a thickener from the group of polysaccharides and in particular xanthan gum, at least 10% by weight, preferably at least 13% by weight of an inorganic or organic acid, preferably citric acid, and preferably glycerol

The compositions of further preferred agents according to the invention are given in the following table. Here, the abbreviation M means average molar mass. In acid mixtures of these example formulations, the proportion of citric acid, based on the acid mixture, is at least 50% by weight, preferably at least 80% by weight Glyceπn amounts to between 1 1 and 1 90, preferably between 1 10 and 1 60. Preferably, the agent additionally contains a surfactant having hydrotropic properties, preferably cumene sulfonate, basic components such as alkali metal caustic solutions and / or perfume. The stated percentages by weight are based on the total agent

0.6 - 5 0% by weight 0 1 - 1, 7% by weight 0.05 - 1, 0 min 10% by weight - 20 - 80% by weight

Tensic J A Surfactant B% by weight Acid Carrier

thickener

Ci ₂ 14 Fatty Alcohol 1- C1 ₆ -18 Fatty Alcohol 20 Xanthan Lemonic Acid Water

7 EO 1-7 PO - 40 EO Gum

Ci ₂ -14 fatty alcohol 1- C ₁₆ -I ₈ fatty alcohol 20 Xanthan Lemonic acid Water

7 EO 1-7 PO butyl- 40 EO Gum group locked

Ci ₂ - ₁ 4 Fatty Alcohol Ci _{6 IB} Fatty Alcohol 20 Xanthan Lemonic Acid Water

Remaining or care eyes, which have been prepared from water, the agent according to the invention and fatty impurities, separate due to the increased Emulgierkapazitat the agent much later than corresponding alkalis, which were obtained using known means of the prior art, preferably no longer in A plurality of phases, ι e in a wassπge and / or an organic phase, on A quantification of the emulsifying ability of the means is possible using standardized phase separation tests Suitable spill and pump simulation tests are described in detail in the examples

Preferably, an alkali containing the inventive agent, a standardized fatty or oily component and water in specified amounts in a pump simulation test within 1 minute shows a phase separation of less than 15%, preferably less than 10%, more preferably less than 5%, most preferably less than 2.5%, more preferably less than 1.0% and more preferably less than 0.2%, or less than 40%, preferably less than 30%, more preferably less than 40%, within 5 minutes less than 20%, more preferably less than 10%, more preferably less than 5%, and most preferably less than 2.5%

Another object of the present invention is the use of the inventive agent for cleaning and care of hard surfaces, preferably of washing machines or dishwashers, in particular dishwashers

Third subject of the present invention is a method for cleaning and care of a washing machine or dishwasher, preferably a dishwasher, in which the inventive agent is introduced into the unloaded machine and then the washing or cleaning program is started

For cleaning and / or care of dishwashing machine interior spaces, the agent is preferably introduced into the cutlery basket or directly into one of the crockery racks or the machine interior (interior bottom floor). In washing machines, the agents according to the invention are used either by being introduced into the dosing drawer or into the washing drum

Furthermore, it is possible that the consumer applies the agent directly from a storage bottle or a storage package on the surface to be cleaned at least for cleaning and / or Care of dishwashers, however, it is preferred that the consumer introduce the agent into the machine in a prefabricated dosage unit, such as a tablet, a pouch with a solid or liquid filling or a small bottle, without risking skin contact with the agent to become

This dosing unit preferably comprises 100 to 400 ml, preferably 200 to 300 ml or 100 to 400 g, preferably 200 to 300 g

Depending on the field of application, it may be preferable to provide smaller dosing units, so that the consumer can use smaller amounts or, depending on the condition of the surface, the average amount can vary by simultaneously using 2, 3, 4, 5 or 6 dosing units

The inventive agent is preferably released into the machine cavity at the beginning of the washing or cleaning program of the washing or dishwashing machine started by the consumer. This can be achieved by completely or partially dissolving or dispersing the packaging or else by melting individual or all packaging sites at temperatures of preferably less than 60 ° C, more preferably less than 50 ⁰ C and in particular less than 4O ⁰ C are possible

Furthermore, it is possible for the consumer, for example, to remove the closure part from a dosing unit such as a bottle filled with a solidified melt, wax or gel and then introduce the dosing unit into the interior of the machine with the opening downwards warm liquor reduces and thus allows a drafty release of the liquid agent by flowing out of the packaging

Preferably at least 80% by weight, preferably at least 90% by weight and in particular at least 95% by weight of the agent used in a package within 15, preferably within 12, preferably within 9, more preferably within 6 and in particular within Released 5 minutes after reaching the maximum liquor temperature in the washing machine or dishwasher interior

In a particularly preferred embodiment, the agent has such a low viscosity that it flows out immediately after removal of the closure with a suitable inclination of the container and is thus available during the entire cleaning or care process

The maximum liquor temperature is preferably greater than 30 ⁰ C, preferably greater than 35 ⁰ C, more preferably greater than 40 ⁰ C, preferably greater than 45 ⁰ C, most preferably greater than 50 ⁰ C and in particular 6O ⁰ C to 70 ° C When using the inventive means for cleaning and / or care of washing machines also maximum liquor temperatures of up to 95 ° C can be selected.

To illustrate the present invention, the following non-limiting examples are intended to serve:

Examples

The emulsifiability of the following four formulations was determined by a shake test and by a pump simulation test:

Formulation 1: full formulation Formulation 2: without thickener Formulation 3: without surfactant B Formulation 4: without surfactants A and B

nonionic surfactant A: C ₁₂ -C ₁₄ fatty alcohol ^• 5 EO ^• 4 PO (average molecular weight about 650 g / mol) nonionic surfactant B: C ₁₆ -C ₈ fatty alcohol ^■ 30 EO (average molecular weight about 1500 g / mol )

a) Shake test

Dilute 10 mL of the product with 40 mL of distilled water, place in a 100 mL graduated cylinder and add 50 mL of olive oil (Bertolli Extra Vergine). The measuring cylinder is with the

Hand shaken in a defined manner for 20 seconds.

After adjustment of the shaking motion, a phase separation takes place and it settles on

Cylinder bottom from an aqueous phase. The volume of this newly forming phase is in

Milliliters measured as a function of time.

b) Pump Simulation Test

This test is used to simulate the short-term energy input through a circulation pump in a household dishwasher. The energy for making the emulsion is introduced into the system at 800 rpm using a four-blade 30 mm diameter stirrer (IKA RW 20). To do this, dilute 10 mL of the product with 40 mL of distilled water, place in a beaker and add 50 mL of olive oil (Bertolli Extra Vergine). The stirrer is switched on for 30 seconds. Immediately afterwards, the sample is transferred to a 100 mL graduated cylinder. There, a phase separation takes place in which settles an aqueous phase at the bottom of the cylinder. The volume of this newly forming phase is measured in milliliters as a function of time.

Phase separation according to recipe 1 Formulation 2 Formulation 3 Formulation 4

1 minute O mL 1O mL 1 mL 12 mL

5 minutes 2 mL 31 mL 5 mL 4 O mL

Conclusion of the experiments

As can be concluded from the comparison of the volumes of the newly forming aqueous phases, the full formulation (formulation 1) shows the best emulsion stability and thus the agent used the highest emulsifying ability. Formulations without thickener (formulation 2) or without surfactant system (formulation 4) coagulate very quickly. The incorporation of the thickener causes a significant improvement in the emulsion stability (Comparison of Recipes 1 and 2). The addition of surfactant B improves the stability of the emulsion again (Comparison of Recipes 1 and 3). Only the combination of surfactant A, surfactant B and the thickener leads to the best performance. A system without surfactants only with thickening agent separates in the fastest time and thus has the lowest emulsifying capacity (formula 4).

Claims

claims:

1. cleaning or care products, comprising

a surfactant system comprising at least two nonionic surfactants A and B which have different chemical structures but both through the structure

R ¹ O- [CH ₂ CH (R ² ) O] _X -R ³ in which

R ¹ and R ³ independently of one another are H or a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 carbon atoms, in which up to 6 hydroxyl and / or up to 3 ether functions can be contained, wherein at least one of the radicals R ¹ and R ³ does not stand for H,

R ^{2 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-butyl radical, where each R ² may be different at x> 2 and x is values greater than 1;

can be represented as well

a thickening agent, wherein a 1 wt .-% solution of the composition in water (2O ⁰ C) has a pH of less than 6.

2. Composition according to claim 1, characterized in that the surfactant system at least one nonionic surfactant A having an average molecular weight between 200 and 1200 g / mol, preferably between 300 and 1 100 g / mol, more preferably between 400 and 1000 g / mol and in particular between 500 and 900 g / mol and at least one further nonionic surfactant B having an average molar mass between 1000 and 2500 g / mol, preferably between 1100 and 2400 g / mol, preferably between 1200 and 2300 g / mol, particularly preferably between 1300 and 2200 and especially between 1400 and 2100 g / mol.

3. Composition according to one of claims 1 or 2, characterized in that the difference in the average molecular weights of the two nonionic surfactants A and B at least 100, preferably at least 200, preferably at least 300, preferably to at least 400, more preferably at least 500, most preferably at least 600 and in particular at least 700 g / mol amounts

Composition according to one of claims 1 to 3, characterized in that the weight ratio between surfactant A and surfactant B between 10 1 and 1 1, preferably between 8.5 1 and 1, 25 1, more preferably between 7 1 and 1, 1 , to preferably between 5.5 1 and 1, 75 1 and in particular between 4 1 and 2 1 hegt

Agent according to one of claims 1 to 4, characterized in that the surfactant B at 0.1 to 1, 7 wt -%, preferably 0.2 to 1, 4 wt -%, particularly preferably 0.3 to 1, 1% by weight and especially 0.4 to 0.8% by weight is contained in the composition

Agent according to one of claims 1 to 5, characterized in that the surfactant A to 0.6 to 5 wt -%, preferably 0.8 to 4 wt -%, more preferably from 1, 0 to 3 wt -% and in particular from 1.2 to 2% by weight is contained in the composition

Agent according to one of claims 1 to 6, characterized in that the nonionic surfactants A and B have the following structure

R ¹ O- [CH ₂ CH (R ² ) O] _X -H in which R ^{1 is} a linear or branched, aliphatic hydrocarbon radical having 4 to 20

Carbon atoms, preferably having 12 to 20 carbon atoms and in particular having 12 to 18 carbon atoms, R ^{2 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2 -Methyl-

Butyl radical, in particular an ethyl or propyl radical, wherein each R ² at x>

2 can be different and x stands for values of 1

Composition according to Claim 7, characterized in that the surfactant system comprises a C ₁₂ -C ₁₄ -alkyl alcohol alkoxylate which comprises both ethoxy and propoxy units and a C ₁₆ -C ₁₈ -alkyl alcohol ethoxylate

Agent according to one of claims 1 to 8, characterized in that the thickener is selected from polysaccharides, preferably from cellulose compounds, xanthan gum and guar gum, and from acrylate thickeners, urethane thickeners and clays Agent according to one of claims 1 to 9, characterized in that it contains at least 10% by weight, preferably at least 13% by weight, more preferably at least 16% by weight, most preferably at least 19% by weight and in particular at least 22% by weight an inorganic or organic acid

Agent according to one of claims 1 to 10, characterized in that the organic or inorganic acid is selected from the acids

Formic acid, acetic acid, adipic acid, succinic acid, tartaric acid, malic acid, glutaric acid, sorbic acid, maleic acid, malonic acid, lactic acid, glycolic acid, propionic acid, oxalic acid, citric acid, sahcylic acid, benzoic acid, lactobionic acid, gluconic acid, boric acid, sulfamic acid, phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, Cyanuric acid or mixtures of these acids

Composition according to Claim 11, characterized in that two or more acids are present in the composition and the proportion by weight of citric acid in this mixture of two or more acids is at least 50% by weight, preferably at least 60% by weight, preferably at least 70% by weight. , particularly preferably at least 80% by weight, more preferably at least 90% by weight and in particular at least 95% by weight, based on the acids contained

Agent according to one of claims 1 to 12, characterized in that the agent additionally contains at least one surfactant from the group of anionic, cationic and amphoteric surfactants

Composition according to claim 13, characterized in that it contains an anionic surfactant which has hydrotropic properties

Composition according to claim 13 or 14, characterized in that the agent comprises at least one surfactant from the group of Alkylphenoxybenzoldisulfonate, linear or branched Alkylbeπzolsulfonate, linear or branched Alkylnaphtalinsulfonate, alkyl sulfonates, Olefinsulfonate, Paraffmsulfonate, Alkylarylsulfonate, soaps, alkyl sulfates, alkyl ether sulfates, Alkylamidoethersulfate, Alkylarylpolyethersulfate Monoglycensulfates, preferably containing the alkylbenzenesulfonates

Agent according to one of claims 1 to 15, characterized in that as a carrier water, alcohol or an alcohol / water mixture, preferably a water / alcohol mixture and in particular a water / Glyceπn mixture is used Composition according to claim 16, characterized in that the ratio between alcohol and water in the carrier between 10 1 and 1 100, preferably between 1 1 and 1 90, more preferably between 1 5 and 1 80, most preferably between 1 10 and 1 60 and in particular between 1 15 and 1 40

Agent according to one of claims 1 to 17, characterized in that the agent has a viscosity above 50 mPas, preferably between 100 and 700 mPas, preferably between 200 and 600 mPas and in particular between 300 and 500 mPas

Composition according to one of claims 1 to 18, characterized in that the means in the pump simulation test within 1 minute, a phase separation of less than 15%, preferably less than 10%, more preferably less than 5%, most preferably less than 2.5%, preferably less than 1, 0% and in particular less than 0.2% or within 5 minutes less than 40%, preferably less than 30%, more preferably less than 20%, whole more preferably less than 10%, more preferably less than 5%, and most preferably less than 2.5%

Composition according to one of claims 1 to 19, characterized in that it is 0.6 to 5.0% by weight, preferably 0.8 to 4% by weight of a C ₁₂ -C ₁₈ alkyl alcohol alkoxylate, preferably a C ₁₂ -C ₁₄ -Alkylalkoholalkoxylats having an average molecular weight of 500 - 900 g / mol, 0.1 to 1, 7 weight -%, preferably 0.2 to 1, 4 wt -% of a C ₁₂ -C ₁₈ - Alkylalkoholalkoxylats, preferably a Ci ₆ - C ₁₈ -alkyl alcohol alkoxylate having an average molecular weight of 1400-2100 g / mol, 0.05-1% by weight, preferably 0.1-0.9% by weight of a thickener, preferably a thickener from the group of polysaccharides and in particular xanthan Gum and at least 10% by weight, preferably at least 13% by weight of an inorganic or organic acid, preferably citric acid, and preferably also contains 2 to 10% by weight of cumene sulfonate

Agent according to one of claims 1 to 20, characterized in that it contains 0.6 to 5.0% by weight, preferably 0.8 to 4% by weight of a C ₁₂ -C ₁₈ -alkyl alcohol, preferably a C ₁₂ -C ₁₄ -Alkyl alcohol which is both ethoxylated and propoxylated and preferably contains 2 to 7 moles, in particular 4 to 5 moles of ethylene oxide and 2 to 7 moles of propylene oxide, in particular 3 to 4 moles of propylene oxide, 0.1 to 1.7% by weight, preferably 0.2 to 1, 4 wt -% of a C ₁₂ -C ₁₈ -Alkylalkoholalkoxylats, preferably a C ₁₆ -C ₁₈ - Alkylalkoholalkoxylats which no Propylenoxidemheiten and at least 15, preferably at least 25 ethylene oxide containing 0.05 to 1 wt -% , preferably 0.1 to 0.9% by weight of a thickening agent, preferably one Thickening agent from the group of polysaccharides and in particular xanthan gum, at least 10 wt .-%, preferably at least 13 wt .-% of an inorganic or organic acid, preferably citric acid, and preferably contains glycerol.

22. Use of the agent according to one of claims 1 - 21 for cleaning and care of hard surfaces, preferably of washing machines or dishwashers, in particular of dishwashers.

23. A method for cleaning and care of a washing machine or dishwasher, preferably a dishwasher, characterized in that the agent is introduced according to one of claims 1 to 21 in the unloaded machine and then the washing or cleaning program is started.