DE102006009138A1 - Detergent for removing greasy or oily soil and cleaning and conditioning hard surface, e.g. washing machine or automatic dishwasher contains nonionic surfactant mixture of (poly)alkylene oxide mono- or di-ether and amine oxide - Google Patents

Abstract

Detergent contains (wt.%) (a) 0.1-4% nonionic surfactant (A) comprising a (poly)alkylene oxide mono- or di-ether and (b) 0.01-4% nonionic surfactant (B) selected from 8-22 carbon (C) amine oxides. Detergent contains (wt.%) (a) 0.1-4% nonionic surfactant (A), comprising a (poly)alkylene oxide mono- or di-ether of formula (I), and (b) 0.01-4% nonionic surfactant (B) selected from 8-22 carbon (C) amine oxides. R 1>O[CH 2CH(R 2>)O] xR 3> (I); R 1>, R 3>linear or branched, saturated or mono- or poly-unsaturated, (un)functionalized 2-26 C hydrocarbyl or, in one case only, H; R 2>H, Me, Et, n-Pr, i-Pr, n-Bu, 2-Bu or 2-methyl-2-butyl and may vary; x : 1-140 .

Description

The The invention relates to a washing or cleaning agent, in particular a cleaning agent for hard surfaces, which in comparison to known agents an increased emulsifying ability for fats and oils and the use of this agent for cleaning and care from hard surfaces like the interiors of washing machines and dishwashers.

cleaning or care products mostly contain surfactants and have a broad Field of application and dependent on it a very different composition. After the pH are alkaline, neutral and acid cleaning or care products, according to the offer form liquid and solid cleaning or care agents distinguished. specially of liquid Cleaning or care products, the consumer expects that he the means both undiluted as well as in the diluted one aqueous Condition can be used and in any case a satisfactory cleaning or care result receives.

authoritative for the Cleaning or care effect are especially the surfactants and / or Alkaline carriers, the depending on the application, can be replaced by acids, if necessary also solvents such as glycol ethers and lower alcohols. In general, in the Formulations about it addition, builders, depending on the type also bleach, enzymes, as well as perfume oils and dyes contain. The cleaning success depends to a great extent on the - also geographically very different - type of dirt and the properties of the surfaces to be cleaned.

ever By composition cleaning or care products are used as general purpose or as a special agent (Car Wash, Oven Cleaner, Descaling Agent, Window Cleaner, Stain removers, floor care products, Glass ceramic hob cleaner, stoves, leather care products, Metal cleaning agents, furniture care products, Pipe cleaners, sanitary cleaners, Abrasives, carpet care products or toilet cleaners). Technical cleaning or Care products are mainly used in the beverage, food, cosmetic and pharmaceutical industry, but also in the metal industry used for metal degreasing. The product group also includes cleaning or care products for Car washes, tank truck and aircraft cleaning or care products. For example, the group of cleaning or care products also the dishwashing detergent and means for cleaning or caring for washing machine or dishwasher interior spaces.

cleaning or care products have a variety of applications to handle a variety of tasks. In the household is certainly the removal of soiling such as fats and oils, leftovers, lime deposits, Soap residue or metal on the metal as well as the corrosion protection of metal and glass in the foreground. Also in the industry, for example the removal of fats and oils of interest.

in the Over the years, there have been numerous efforts in cleaning or cleaning To improve the care performance of known cleaning or care products. Thus, published patent application WO 2004/032886 A1 (Reckitt Benckiser) agents containing at least one surfactant and mandatory two organic acids containing their salts and suitable for cleaning surfaces are.

The Advantages of a solvent mixture from a hydrophilic and a hydrophobic solvent in an acidic Cleaning agent for hard surfaces is described in document US 2002/187918 A1 (Reckitt Benckiser). The solvent mixture should the solution improve from fatty soiling.

A increase the cleaning performance due to improved control of the nationwide application of the composition is disclosed in the publication US 2004/0186037 A1 (Cheung, Costa). Here become insoluble, perceptible by the eye Ingredients incorporated in a hard surface cleaner, which enable the end user should recognize, at which points the means do not or not was applied in sufficient quantity.

Increasingly be requested by the end user cleaning or care products, even without the action of mechanical energy such as rubbing and brushes to provide optimal services. Known examples are detergent sprays for the removal of limescale deposits on bathroom tiles or for degreasing metal objects such as Hoods.

Means that already without significant mechanical treatment good cleaning or care In addition to the convenience for the user, they also offer the possibility of cleaning surfaces whose mechanical treatment with the agent is not or only to a limited extent possible. Examples of mechanically poorly cleaned surfaces are corners and angled surfaces, the inner surface of pipes and funnels, sharp-edged or intertwined surfaces, meshes, hose connections, but also surfaces which, due to their nature, must not be subjected to mechanical stress.

Also equipment like washing machines or dishwashers, Coffee makers or kettles are incomplete and inside only with big ones Effort by mechanical action, for example by a rag or a brush to clean, so too for These applications include cleaning or care products that perform well even without significant mechanical treatment, are desirable. In the case of washing machines and dishwashers should have the effect the cleaning or Care products be so great that not only the big ones surfaces of the machine interior, the direct and intense operating pressure are exposed to the cleaning liquor and thus quite a mechanical Stress experienced, but also angled areas, hose connections, door seals and all low-flow Zones in these machines are optimally cleaned and / or maintained.

The commercial alkaline or acidic dishwashing, cleaning or rinse aid are suitable not or insufficiently for cleaning the so-called "problem areas" of dishwashing or also washing machines, as they may be in the cleaning or rinse cycle of the Machines are metered in, but with the dirty areas either not at all or only briefly in contact. Also commercially available cleaning agents for hard surfaces are for This particular application is not suitable as it is generally strong foaming Surfactants contain their residues, for example in dishwashers to disturbances diverse Kind of lead can and also the requirements for cleaning and care properties are not up to it.

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

The previously mentioned funds, both the aforementioned cleaning or care products as well as the special agent "cleaner for dishwashers ", but do not have any satisfactory performance in the area of grease removal from surfaces. The effect of known cleaning or care products is not enough out, the grease stains in whole to solve and also for to maintain a sufficient duration in dispersed form. As a result it comes with manual cleaning to fat streaks on the already partially cleaned surfaces, as a separation of the cleaning liquor due to lack of emulsifying ability the agent occurs. It superimposes a thin film of grease on the cloth or on individual bristles of the brushes used. At machine Cleaning or caring for washing machines or dishwashers may have the effect be observed during that the rest periods of the lye, that is in the times in which no upheaval the liquor takes place, a separation of the liquor into aqueous and oily phase takes place. The result is a fat edge in the lower machine interior, in the further cleaning or care process is not or insufficient triggers and to a total lack of cleaning or care result leads. Furthermore, in washing machines or dishwashers, especially in dishwashers The effect that occurs during cleaning with the agents described in the prior art intensify fatty soiling in the areas the only a small flow of water are exposed, collect and there persistent incrustations and / or oily streaks form while on the big one surfaces inside the machine interiors quite a cleaning effect can be observed. Also the education a greasy film on all surfaces of the machine interior when using agents that have insufficient fat emulsifying ability will be described. In case of heavy pollution of the interior with greasy coverings becomes when using the known means observed that in addition to the problems described additionally also an insufficient cleaning of the large surfaces of the interior, which the direct water pressure of the cleaning fleet are exposed achieved is going through and greater fat soiling the agent is not dissolved or dissolved could become.

task It was the object of the present invention to provide a washing or cleaning agent to provide that overcomes the above problems. In particular, this agent should have an increased emulsifying ability for fats and oils and thus have improved grease removal performance.

• a) 0,1 bis 4 Gew.-% eines nichtionischen Tensids (A) der allgemeinen Formel R¹O[CH₂CH(R²)O]_xR³, in welcher
• – R¹ und R³ unabhängig voneinander für H oder einen linearen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten, funktionalisierten oder nicht funktionalisierten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen stehen, wobei mindestens einer der Reste R¹ und R³ nicht für H steht;
• – R² für H oder einen Methyl-, Ethyl-, n-Propyl-, iso-Propyl, n-Butyl-, 2-Butyl- oder 2-Methyl-2-Butylrest steht;
• – x für Werte zwischen 1 und 140 steht, wobei jedes R² unterschiedlich sein kann; sowie
• b) 0,01 bis 4 Gew.-% eines nichtionischen Tensids (B) aus der Gruppe der C₈-C₂₂ Aminoxide enthält.

This object has been achieved by a washing or cleaning agent, which

• a) 0.1 to 4 wt .-% of a nonionic surfactant (A) of the general formula R ¹ O [CH ₂ CH (R ² ) O] _x R ³ , in which
• - R ¹ and R ^{3 are} independently H or a linear or branched, saturated or mono- or polyunsaturated, functionalized or non-functionalized hydrocarbon radical having 2 to 26 carbon atoms, wherein at least one of R ¹ and R ^{3 is} not H stands;
• R ^{2 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical;
• X represents values between 1 and 140, each R ^{2 being} different; such as
• b) 0.01 to 4 wt .-% of a nonionic surfactant (B) from the group of C ₈ -C ₂₂ amine oxides.

Cleaning according to the invention or care products that are a combination of the two nonionic Surfactants A and B, show opposite usual Agents which other surfactants or only one of the two surfactants included, a significantly increased emulsifying for fats and oils.

The inventive cleaning or care product is preferably used in the treatment hard surfaces and is in particular for the cleaning or care of washing machines or dishwashers, especially for dishwashers suitable.

The compositions of the invention contain as a first ingredient 0.1 to 4 wt .-% of a nonionic surfactant (A) of the general formula 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 mono- or polyunsaturated, functionalized or non-functionalized hydrocarbon radical having 2 to 26 carbon atoms, where at least one of the radicals 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-2-butyl radical; and x is between 1 and 140, wherein each R ² can be different.

As preferred surfactants (A) low-foaming nonionic surfactants are used. With particular preference, the detergents or cleaners contain nonionic surfactants from the group of alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Particular preference is therefore given to ethoxylated nonionic surfactants consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide. Of these, the so-called "narrow range ethoxylates" are particularly preferred.

Especially preferred are nonionic surfactants (A) which have a melting point above room temperature. Nonionic surfactant (s) (A) with a melting point above 20 ° C, preferably above 25 ° C, especially preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred.

Suitable nonionic surfactants (A) 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 for them to have a viscosity above 20 Pa · s, preferably above 35 Pa · s and in the air have particular above 40 Pa · s. Also, nonionic surfactants having waxy consistency at room temperature are preferred depending on their purpose.

nonionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO-Niotenside, are also with special Preference used.

The nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule. Preferably, such PO units make up to 25% by weight, especially preferably up to 20% by weight and in particular up to 15 wt .-% of the total molecular weight of the nonionic Surfactants. Particularly preferred nonionic surfactants are ethoxylated Monohydroxyalkanols or alkylphenols which additionally contain polyoxyethylene-polyoxypropylene Have block copolymer units. The alcohol or alkylphenol content such nonionic surfactant molecules makes preferably more than 30 wt .-%, more preferably more than 50 wt .-% and in particular more than 70 wt .-% of the total Molar mass of such nonionic surfactants. Preferred means are thereby characterized in that they are ethoxylated and propoxylated nonionic surfactants contain, in which the propylene oxide in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 Make up wt .-% of the total molecular weight of the nonionic surfactant.

Prefers Surfactants to be used come from the groups of the alkoxylated Nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control out.

In the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Nonionic surfactants 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 are preferred here in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 -alkyl or -alkenyl radical; 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 stand for integers from 1 to 6.

In particular, nonionic surfactants of the general formula R ¹ O [CH ₂ CH ₂ O] _w [CH ₂ CH (CH ₃ ) O] _x H are preferred, in which R ^{1 is} a straight-chain or branched, saturated or mono- or polysubstituted unsaturated C _6-24 alkyl or alkenyl radical, preferably represents a C ₁₂ -C ₁₄ alkyl radical and the indices w and x independently of one another are integers from 1 to 12, preferably from 1 to 7 and in particular from 2 to 5 ,

The preferred nonionic surfactants 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 may 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 being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions, preference is given to nonionic surfactants in which R ¹ in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or -CH (CH ₃ ) ₂ are suitable. Preference is given to using nonionic surfactants 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 are values of 1 or 2.

In summary, particularly preferred are nonionic surfactants which contain a C _9-15 alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, having from 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

• – R¹ für einen linearen oder verzweigten, aliphatischen Kohlenwasserstoffrest mit 4 bis 20 Kohlenstoffatomen, vorzugsweise mit 12 bis 20 Kohlenstoffatomen und insbesondere mit 12 bis 18 Kohlenstoffatomen steht;
• – R² für H oder einen Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, 2-Butyl- oder 2-Methyl-Butylrest, insbesondere für H oder einen Methyl-Rest steht, wobei jedes R² unterschiedlich sein kann; und
• – x für Werte zwischen 1 und 140, vorzugsweise zwischen 1 und 120 und insbesondere zwischen 1 und 90 steht.

Particularly preferred according to the invention are detergents or cleaners which comprise as nonionic surfactant (A) a surfactant of the general formula R ¹ O [CH ₂ CH (R ² ) O] _x H, in

• R ^{1 represents} a linear or branched aliphatic hydrocarbon radical having from 4 to 20 carbon atoms, preferably from 12 to 20 carbon atoms and especially from 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 H or a methyl radical, where each R ² may be different; and
• X represents values between 1 and 140, preferably between 1 and 120 and in particular between 1 and 90.

• – R¹ und R³ unabhängig voneinander für einen linearen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten, funktionalisierten oder nicht funktionalisierten Kohlenwasserstoffrest mit 2 bis 24 Kohlenstoffatomen stehen;
• – R² für H oder einen Methyl-, Ethyl-, n-Propyl-, iso-Propyl, n-Butyl-, 2-Butyl- oder 2-Methyl-2-Butylrest steht;
• – x für Werte zwischen 1 und 140, wobei jedes R² unterschiedlich sein kann;

According to the invention, washing or cleaning agents which comprise as nonionic surfactant (A) a surfactant of the general formula R ¹ O [CH ₂ CH (R ² ) O] _x CH ₂ CH (OH) R ³ are also preferred according to the invention

• - R ¹ and R ^{3 are} independently a linear or branched, saturated or mono- or polyunsaturated, functionalized or non-functionalized hydrocarbon radical having 2 to 24 carbon atoms;
• R ^{2 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical;
• X for values between 1 and 140, each R ^{2 being} different;

The group of these preferred surfactants (A) includes, for example, surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A''O) _y - (A ''' O) _z -R ² , in which R ¹ and R ² independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C _2-40 -alkyl or -alkenyl radical; A, A ', A''andA''' are independently of one another a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ - CH _{2 is} -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 24 carbon atoms, where x is between 1 and 24 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

Particularly preferred are surfactants 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 with 4 R ^{2 is} a linear or branched hydrocarbon radical having 2 to 24 carbon atoms or mixtures thereof and x is between 0.5 and 1.5 and y is at least 15.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the 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 is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 24 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 -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined 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 may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

• – R¹ und R³ unabhängig voneinander für einen linearen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten, funktionalisierten oder nicht funktionalisierten Kohlenwasserstoffrest mit 2 bis 24 Kohlenstoffatomen stehen;
• – R² für H oder einen Methyl-, Ethyl-, n-Propyl-, iso-Propyl, n-Butyl-, 2-Butyl- oder 2-Methyl-2-Butylrest steht;
• – x für Werte zwischen 1 und 140, wobei jedes R² unterschiedlich sein kann;

According to the invention, washing or cleaning agents which comprise as nonionic surfactant (A) a surfactant of the general formula R ¹ O [CH ₂ CH (R ² ) O] _x CH ₂ CH (OH) R ³ are also preferred according to the invention

• - R ¹ and R ^{3 are} independently a linear or branched, saturated or mono- or polyunsaturated, functionalized or non-functionalized hydrocarbon radical having 2 to 24 carbon atoms;
• R ^{2 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical;
• X for values between 1 and 140, each R ^{2 being} different;

Of the Weight fraction of the nonionic surfactant (A) is preferably between 0.1 and 3% by weight, preferably between 0.2 and 2.5% by weight and in particular between 0.4 and 2.0 wt .-%.

preferred inventive agent contain only a nonionic surfactant (A).

• – R¹ und R² unabhängig voneinander für einen Methyl-, Ethyl- oder Propoylrest stehen; und
• – R³ für einen linearen oder verzweigten Kohlenstoffrest mit 10 bis 22, vorzugsweise mit 12 bis 18 Kohlenstoffatomen steht

werden daher erfindungsgemäß bevorzugt.As a further constituent, the agents according to the invention contain nonionic surfactants (B) from the group of C ₈ -C ₂₂ amine oxides. Amine oxides having two short-chain alkyl radicals have proven to be particularly advantageous with respect to their emulsifying ability and fat-dissolving power. Detergents or cleaning agents, characterized in that the nonionic surfactant (B) comprises a surfactant of the general formula R ¹ R ² R ³ NO, in which

• - R ¹ and R ² independently of one another are a methyl, ethyl or propoyl radical; and
• - R ^{3 is} a linear or branched carbon radical having 10 to 22, preferably having 12 to 18 carbon atoms

are therefore preferred according to the invention.

Of the Weight fraction of the nonionic surfactant (B) is preferably between 0.01 and 3 wt .-%, preferably between 0.02 and 2% by weight and in particular between 0.05 and 1 Wt .-%.

Even though it possible is, the two nonionic surfactants (A) and (B) in the inventive compositions in any relationship have such agents with regard to their emulsifying ability and cleaning performance proved to be particularly advantageous in which the weight ratio the surfactants (A) and (B) between 30: 1 and 1: 1, preferably between 20: 1 and 2: 1 and in particular between 15: 1 and 4: 1.

The specified C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned Nonionic surfactants represent statistical averages that are suitable for a specific Product can be a whole or a fractional number. by virtue of the manufacturing process consist of commercial products of the formulas mentioned mostly not from an individual representative, but from mixtures, which is responsible for both the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation averages and resulting in fractional numbers.

The agents according to the invention can in addition to the described nonionic surfactants (A) and (B) further contain nonionic surfactants, wherein the weight fraction of the other nonionic surfactants can vary widely. Prefers is the proportion of additional however, less than 6% by weight, especially of nonionic surfactants used preferably below 4 wt .-%, preferably below 3 wt .-%, to preferably below 2 wt .-% and in particular below 1 wt .-%. Particular preference is given to such agents according to the invention, in which the weight fraction of nonionic surfactants (A) and (B), based on the total weight of all contained in the agent nonionic surfactants, at least 60% by weight, preferably at least 80 wt .-%, preferably at least 90 wt .-%, most preferably at least 95 wt .-% and in particular at least 98 wt .-% is. Especially preferred are those inventive agents whose nonionic Surfactants exclusively attributable to the nonionic surfactants of groups (A) and (B).

The Sum of the parts by weight of all non-ionic agents contained in the middle Surfactants is in agents according to the invention preferably between 0.2 and 10 wt .-%, more preferably between 0.2 and 8 wt .-%, most preferably between 0.2 and 6 wt .-% and in particular between 0.2 and 4 wt .-%.

From the group of other nonionic surfactants, the alkyl glycosides have proved to be detrimental to the inventive effect of the claimed detergents or cleaners. Preferred detergents or cleaners therefore contain less than 1% by weight, preferably less than 0.5% by weight. and especially no alkyl glycosides.

in der R für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgender Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.However, further suitable surfactants are polyhydroxy fatty acid amides of the formula

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

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula

R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 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 alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.

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

Compositions according to the invention can continue to contain a thickener. The scope of Thickening agents, also called thickeners, generally exist in it, the viscosity of liquids to increase. The effect of the thickener is based on various Effects such as swelling, gelation, association of micelles, Solvation, formation of network structures and / or hydrogen bonds and their interaction. In aqueous Systems determine the molecular structure and the relative molecular weight the hydrocolloids the degree of thickening.

Surprised has now been found that the combination of the nonionic Surfactants (A) and (B) and a thickening agent in a cleaning or conditioner the fat emulsifying ability of this agent clearly increases. It can in the inventive compositions all thickeners known to those skilled in the art are used, including the use of a combination of several thickeners possible is.

In a preferred embodiment contain the agents of the invention inorganic thickeners such as silica, clays, phyllosilicates, from this preferred smectites, in particular montmorillonite or hectorite; low molecular weight organic thickeners such as metal soaps, tempered castor oil, modified fat derivatives or polyamides. From the big group the organic fully synthetic thickener find particular Polyvinyl alcohols, polyacrylic and polymethacrylic and their salts, polyacrylamides, polyvinylpyrrolidone, polyethylene glycols, Styrene-maleic anhydride copolymers and their salts application. Particularly preferred are the co- and Terpolymers of acrylic and methacrylic acid.

• – hydrophob modifizierte Polyacrylate, die in einem anionaktiven Acrylat-Verdickermolekül durch Copolymerisation eingebaute nichtionogene hydrophile und hydrophobe Gruppen enthalten;
  
• – hydrophob modifizierte Celluloseether, hergestellt durch Reaktion von Hydroxyethylcellulose während der Veretherung od. nachträglich mit langkettigen Alkylepoxiden oder -halogeniden;
  
• – hydrophob modifizierte Polyacrylamide, hergestellt durch Copolymerisation von Acrylamid mit Alkyl-modifiziertem Acrylamid und gegebenenfalls Acrylsäure; und
• – hydrophob modifizierte Polyether und assoziative Polyurethan-Verdicker, bestehend aus über Urethan-Gruppen verknüpften hydrophilen, relativ hochmolekularen Polyether-Segmenten, verkappt mit mindestens zwei endständigen, hydrophoben Molekül-Gruppen.
  

Associative thickeners differ from the modified natural substances listed below and the organic fully synthetic thickeners in that they contain not only hydrophilic groups but also hydrophobic end or side groups in the molecule. This associative thickener surfactant character and are capable of forming micelles. Representatives of this group are preferably contained in the agents according to the invention. It is noteworthy that associative thickeners thicken finely divided dispersions more than coarse particles because of their larger total surface area. One differentiates

• Hydrophobically modified polyacrylates which contain nonionic hydrophilic and hydrophobic groups incorporated in an anionic acrylate thickener molecule by copolymerization;
  
• - hydrophobically modified cellulose ethers, prepared by reaction of hydroxyethyl cellulose during the etherification or subsequently with long-chain Alkylepoxiden 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.
  

preferred Thickeners come from the groups of organic natural Thickeners such as starch, Gelatin and casein and the modified natural substances, in particular the polysaccharides. Important representatives of the latter group are (hydroxy) ethylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, Hydroxypropylcellulose, hydroxymethylcellulose, ethylhydroxyethylcellulose, Succinoglycan, xanthan gum, guar flour, locust bean gum, tragacanth, as well as derivatives and mixtures of these thickeners.

Preferably is that in the inventive compositions contained thickeners 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 xanthan gum and derivatives thereof, as thickening agents. Xanthan Gum and corresponding derivatives are available under the name Keltrol ^® RD (CP Kelco), Kelzan ^® S (CP Kelco), Kelzan ^® T (CP Kelco), Rhodopol ^® T (Rhodia) and Rhodigel X747 ^® (Rhone Poulenc) available.

As a general rule Is it possible, that in the inventive compositions one, two, three, four or even five different thickening agents are included. The xanthan gum content preferably makes at least 20 wt .-%, preferably at least 40 wt .-%, preferably at least 60 wt .-%, more preferably at least 80 wt .-% and in particular at least 90% by weight, especially 99% by weight of the total contained in the composition Thickener out.

With Preference in the washing or cleaning agent 0.05 to 1 wt .-%, preferably 0.1 to 0.9% by weight, particularly preferably 0.15 to 0.8 wt .-%, preferably 0.2 to 0.7 Wt .-%, preferably 0.25 to 0.6 wt .-%, most preferably 0.3 to 0.5 wt .-% and in particular 0.3 to 0.4 wt .-% thickener contain.

A Further optimization of the fat emulsifying ability of agents according to the invention can by choosing appropriate proportions between the used nonionic surfactants A and B and the thickener achieved become. This is the weight ratio of surfactant (A) to thickener with preference between 50: 1 and 1:10. This is preferably relationship between 22: 1 and 1: 2, preferably between 18: 1 and 1: 1.5, especially preferably between 14: 1 and 1: 1, more preferably between 10: 1 and 1.5: 1 and especially between 6: 1 and 2: 1.

The weight ratio between surfactant (B) and thickener is preferably between 40: 1 and 1:30. With preference, this ratio is between 10: 1 and 1: 8, preferably between 7.5: 1 and 1: 6, more preferably between 5: 1 and 1: 4, and more preferably between 2.5: 1 and 1: 2.

preferred Detergents or cleaning agents are characterized in that they are between 10 and 90 wt .-%, preferably between 13 and 70 wt .-%, especially preferably between 16 and 50 wt .-%, most preferably between 19 and 40 wt .-% and in particular between 22 and 30 wt .-% of one or more inorganic or organic acid (s) contain.

The resulting acidic according to the invention or detergents are suitable in addition to the elimination of grease or oily ones Contamination also continues to remove limescale and calcareous soils. Preferred detergents or cleaners are characterized in that a 1% by weight solution of the agent in water (20 ° C) a pH of less than 6.0, preferably less than 5.0, more preferably less than 4.5, most preferably less than 4.0, and in particular smaller than 3.5. The undiluted liquid agent is preferred 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 on.

Suitable acids are organic mono- or polybasic, optionally substituted 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 used. Also suitable are lactobionic acid and gluconic acid. preferred inorganic acids are boric acid, sulfamic, Phosphoric acid, Sulfuric acid, hydrochloric acid and nitric acid. Also suitable is cyanuric acid.

The inventive means can one, two, three, four or more organic and / or inorganic acids (Acid mixtures) contain. Preferably, the washing or cleaning agents contain a or two acids.

preferred Detergents or cleaning agents are characterized in that they include citric acid and at least another acid wherein the proportion by weight of citric acid in the Acid mixture two or more acids at least 50% by weight, preferably at least 60% by weight, preferred at least 70% by weight, particularly preferably at least 80% by weight, preferably at least 90% by weight and in particular at least 95 wt .-%, based on the acids contained, is.

Contain the invention only an acid, so it is with this acid preferably citric acid or acetic acid. The content of the agent in this one acid is then preferably between 15 and 60 wt .-%, particularly preferably between 18 and 50 wt .-%, most preferably between 21 and 40 wt .-% and in particular between 24 and 30% by weight.

With particular advantage include the inventive cleaning or Care products additionally at least one surfactant from the group of anionic, cationic and amphoteric surfactants.

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

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

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

The sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 . Fatty alcohols with 1 to 4 EO are suitable. They are used in the cleaning 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 alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols represent. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

When other anionic surfactants are especially soaps into consideration. Suitable are saturated fatty acid soaps, like the salts of lauric acid, myristic, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow derived soap mixtures. The anionic surfactants including Soaps can in the form of their sodium, potassium or ammonium salts and as soluble salts organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.

With The agents according to the invention preferably contain at least one anionic agent Surfactant from the group of Alkylphenoxybenzoldisulfonate, linear or branched alkylbenzenesulfonates, linear or branched Alkylnaphthalenesulfonates, alkylsulfonates, olefin-sulfonates, paraffin-sulfonates, Alkylarylsulfonates, soaps, alkyl sulfates, alkyl ether sulfates, alkylamido ether 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.

With Preference contains the agent is an anionic surfactant having hydrotropic properties has (hydrotrope).

Is / are Anionic surfactant (s), preferably anionic surfactant (s) having hydrotropic properties Component of automatic dishwashing detergent, its content is based on the total weight of the means, preferably between 2 and 10% by weight, preferably between 3 and 9% by weight, very particularly preferably between less than 4 and 8 wt .-% and in particular between 5 and 7 wt .-%. Machine dishwashing detergents, which are from the group the anionic surfactants contain only those which have hydrotropic properties are particularly preferred.

At Place of said surfactants or in conjunction with them may also cationic and / or amphoteric surfactants are used.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.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 R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

Out The group of amphoteric surfactants are in particular the betaines to call. Betaines and / or amine oxides are in the agents according to the invention preferably less than 10% by weight, preferably less than 8% by weight, more preferably less than 6% by weight, more preferably less as 4 wt .-%, most preferably less than 2 wt .-% and especially not included.

In the cleaning or care products the content of cationic and / or amphoteric surfactants 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 means can be used both in solid form such as powders, pellets, Tablets, capsules, beads as well as in liquid form. is the agent solidifies at room temperature, so it is preferred at temperatures below 90 ° C, preferably below 80 ° C, preferably below 70 ° C, more preferably below 60 ° C and in particular below 55 ° C Completely or partially fluid / liquid.

Under liquid also becomes gel here Understood. "Liquid" thus indicates every condition at 20 ° C through a liquid (flowable) state of aggregation is marked.

Prefers the agent lies in the liquid Condition and has a viscosity above 50 mPas, preferably between 100 and 700 mPas, preferably between 200 and 600 mPas and especially between 300 and 500 mPas.

Suitable carriers of liquid agents are water, nonaqueous 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 compounds (carbon disulfide, dimethyl sulfoxide, sulfolane), nitro compounds (Nitrobenzene), halogenated hydrocarbons (dichloromethane, chloroform, carbon tetrachloride, tri-, tetrachloroethene, 1,2-dichloroethane, chlorofluorocarbons), hydrocarbons (benzene, petroleum ether, cyclohexane, methylcyclohexane, decalin, terpene solvent, benzene, toluene, xylenes). As already indicated, instead of the pure solvents, their mixtures, which advantageously combine, for example, the dissolution properties of various solvents, can also be used. Such a solvent mixture is, for example, benzine, a mixture of various hydrocarbons suitable for dry cleaning, preferably containing C12 to C14 hydrocarbons above 60% by weight, more preferably above 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.

Of the Weight fraction of organic solvents on the total weight of compositions according to the invention is preferably between 0.1 and 7% by weight, preferably between 0.1 and 5 wt .-% and in particular between 0, 1 and 3 wt .-%.

preferred Detergents or cleaning agents are characterized in that they relate on the total weight of the washing or cleaning agent, between 10 and 95 wt .-%, preferably between 20 and 80 wt .-%, preferably between 30 and 80% by weight and in particular between 40 and 70% by weight a liquid carrier have, wherein this carrier preferably selected is from the group which, in addition to water, still comprises the alcohols, being a water / alcohol mixture and in particular a water / glycerol mixture particularly preferred.

The relationship 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, most preferably between 1:10 and 1:60 and especially between 1:15 and 1:40.

The inventive agent can depending on the application abrasive, undissolved and / or dispersed ingredients included, cloudy or translucent or clear.

The previously described inventive compositions preferably contain further cleaning-active and / or care-active substances, preferably from the group of builders, Polymers, bleaches, bleach activators, enzymes, corrosion inhibitors, Disintegration aids, fragrances and perfume carriers. These preferred ingredients will get closer in the episode described.

To the builders counting in particular the zeolites, silicates, carbonates, organic cobuilders and where no ecological Prejudices against their use exist - even the phosphates.

Preference is given to using crystalline layer-form silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, in which M represents sodium or hydrogen, x 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 layer-form silicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O are for example sold by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ S ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .xH ₂ O, Makatite).

Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O, in which x is 2. In particular, both β- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ .yH ₂ O and furthermore especially Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O _5, natrosilite), 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- Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ).

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

alternative or in combination with the aforementioned amorphous sodium silicates become X-ray amorphous Silicate used, the silicate particles in electron diffraction experiments provide blurred or even sharp diffraction maxima. This is to interpret that the products microcrystalline areas the size ten up to several hundred nm, with values up to max. 50 nm and especially up to max. 20 nm are preferred. Such X-ray amorphous Silicates also have a dissolution delay over the conventional ones water glasses on. Particularly preferred are compacted / compacted amorphous Silicates, compounded amorphous silicates and overdried X-ray amorphous Silicates.

Of course it is also a use of the well-known phosphates as builders possible, if such use is not avoided for environmental reasons should be. Among the variety of commercially available Phosphates have the alkali metal phosphates, with particular preference of Pentasodium or pentakalium triphosphate (sodium or potassium tripolyphosphate) in the washing and cleaning industry the greatest importance.

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

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

Further builders are the alkali carriers. As alkali carrier For example, alkali metal hydroxides, alkali metal carbonates, Alkali metal bicarbonates, alkali metal sesquicarbonates, the mentioned alkali metal silicates, alkali metal silicates, and mixtures of aforementioned substances, wherein for the purposes of this invention preferably the Alkali carbonates, especially sodium carbonate, sodium bicarbonate or sodium sesquicarbonate. Especially preferred is a builder system containing a mixture of tripolyphosphate and Sodium. Also particularly preferred is a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.

When Organic co-builders are in particular polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) as well as phosphonates. These classes of substances are hereafter described.

useful organic builders For example, they are in the form of the free acid and / or their sodium salts usable polycarboxylic acids, where among polycarboxylic acids such carboxylic acids be understood that carry more than one acid function. For example these are citric acid, Adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such an application for ecological reasons not is objectionable, as well as mixtures of these. Own the free acids In addition to their builder effect typically also the property of a acidifying and thus serve to set a lower and milder one pH of wash or detergents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.

When builders are further polymeric polycarboxylates suitable, these are for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight from 500 to 70000 g / mol.

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

suitable Polymers are in particular polyacrylates, which preferably have a molecular mass of 2000 to 20,000 g / mol. Because of their superior solubility can from this group again the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and more preferably from 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their molecular weight relative to free acids is generally 2000 to 70000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol. The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.

to Improvement of water solubility can the polymers also include allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as Contain monomer.

Especially Biodegradable polymers of more than two are also preferred various monomer units, for example, those as monomers Salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers Salts of acrylic acid and 2-alkylallyl sulfonic acid and sugar derivatives.

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

As well are as further preferred builders polymeric aminodicarboxylic acids whose Salts or their precursors to call. Particular preference is given to polyaspartic acids or their salts.

Further Suitable builders are polyacetals, which by reaction of dialdehydes with polyol carboxylic acids containing 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained. preferred Polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic receive.

Further suitable organic builders are dextrins, for example Oligomers or polymers of carbohydrates by partial Hydrolysis of starches can be obtained. The hydrolysis can be carried out according to usual, for example acidic or enzyme-catalyzed processes. Preferably These are hydrolysis products with average molecular weights in the range from 400 to 500,000 g / mol. It is a polysaccharide with a Dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 preferred where DE is a common one Measure of the reducing Effect of a polysaccharide compared to dextrose, which DE of 100 is. Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrup with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher Molar masses in the range of 2000 to 30,000 g / mol.

at the oxidized derivatives of such dextrins are their reaction products with oxidants, which are able are at least one alcohol function of the saccharide ring to the carboxylic acid function to oxidize.

Also Oxydisuccinates and other derivatives of disuccinates, preferably Ethylenediamine disuccinate are other suitable cobuilders. there becomes ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates.

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

Furthermore can all compounds that are capable of complexes with alkaline earth ions train as builders be used.

Prefers contain the agents of the invention but methylglycinediacetic acid (MGDA), ethylenediaminetetraacetic acid (EDTA) and / or nitrilotriacetic acid (NTA), their salts and mixtures of the acids and / or salts.

As a general rule are in the inventive compositions in addition to nonionic polymers also cationic, anionic and Amphoteric polymers can be used.

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

"Amphoteric Poylmere "in the sense of the present invention have besides a positively charged group in the polymer chain also negatively charged groups or On monomer units.

at These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic act.

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 group, C _1-30 linear or branched alkyl groups, aryl, aryl substituted C _1-30 linear or branched alkyl groups, polyalkoyxylierte 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 N atom or at least one amino group having a positive charge.

bei der R¹ und R⁴ unabhängig voneinander für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen steht; R² und R³ unabhängig voneinander für eine Alkyl-, Hydroxyalkyl-, oder Aminoalkylgruppe stehen, in denen der Alkylrest linear oder verzweigt ist und zwischen 1 und 6 Kohlenstoffatomen aufweist, wobei es sich vorzugsweise um eine Methylgruppe handelt; x und y unabhängig voneinander für ganze Zahlen zwischen 1 und 3 stehen. X repräsentiert ein Gegenion, vorzugsweise ein Gegenion aus der Gruppe Chlorid, Bromid, Iodid, Sulfat, Hydrogensulfat, Methosulfat, Laurylsulfat, Dodecylbenzolsulfonat, p-Toluolsulfonat (Tosylat), Cumolsulfonat, Xylolsulfonat, Phosphat, Citrat, Formiat, Acetat oder deren Mischungen.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 from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, lauryl sulfate, 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.

werden im Falle von X^– = Chlorid auch als DADMAC (Diallyldimethylammonium-Chlorid) bezeichnet.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

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

in der R¹, R², R³, R⁴ und R⁵ unabhängig voneinander für einen linearen oder verzweigten, gesättigten oder ungesättigen Alkyl-, oder Hydroxyalkylrest mit 1 bis 6 Kohlenstoffatomen, vorzugsweise für einen linearen oder verzweigten Alkylrest ausgewählt aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, und -(CH₂CH₂-O)_nH steht und x für eine ganze Zahl zwischen 1 und 6 steht.Further particularly preferred cationic or amphoteric polymers contain a monomer unit of the general formula

in which R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a linear or branched, saturated or un saturated 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 H and x is an integer between 1 and 6.

werden im Falle von X^– = Chlorid auch als MAPTAC (Methyacrylamidopropyl-trimethylammonium-Chlorid) bezeichnet.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

in the case of X ^- = chloride, also referred to as MAPTAC (methylacrylamidopropyltrimethylammonium chloride).

According to the invention preferred Polymers are used which are diallyldimethylammonium salts as monomer units and / or acrylamidopropyltrimethylammonium salts.

The previously mentioned Amphoteric polymers have not only cationic groups, but also anionic groups or monomer units. Such anionic For example, monomer units are from the linear group or branched, saturated or unsaturated Carboxylates, linear or branched, saturated or unsaturated Phosphonates, which are linear or branched, saturated or unsaturated Sulfates or the linear or branched, saturated or unsaturated Sulfonates. Preferred monomer units are the acrylic acid, the (Meth) acrylic acid, the (dimethyl) acrylic acid, the (ethyl) acrylic acid, the cyanoacrylic acid, the vinylessing acid, the allylacetic acid, the crotonic acid, the maleic acid, the fumaric acid, the cinnamic acid and their derivatives, the allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallyl or the allylphosphonic acids.

preferred usable amphoteric polymers are from the group of alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers, and the copolymers of unsaturated Carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Prefers usable zwitterionic polymers are from the group of Acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their Alkali and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the Methacroylethylbetain / methacrylate copolymers.

Prefers are further amphoteric polymers, which in addition to one or more anionic monomers as cationic monomers Methacrylamidoalkyl-trialkylammonium chloride and dimethyl (diallyl) ammonium chloride.

Especially preferred amphoteric polymers are from the group of the Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers as well as their alkali and ammonium salts.

Especially amphoteric polymers from the group of methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers are preferred and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers as well as their alkali and ammonium salts.

• – die Verkapselung der Polymere mittels wasserlöslicher oder wasserdispergierbarer Beschichtungsmittel, vorzugsweise mittels wasserlöslicher oder wasserdispergierbarer natürlicher oder synthetischer Polymere;
• – die Verkapselung der Polymere mittels wasserunlöslicher, schmelzbarer Beschichtungsmittel, vorzugsweise mittels wasserunlöslicher Beschichtungsmittel aus der Gruppe der Wachse oder Paraffine mit einem Schmelzpunkt oberhalb 30°C;
• – die Cogranulation der Polymere mit inerten Trägermaterialien, vorzugsweise mit Trägermaterialien aus der Gruppe der wasch- oder reinigungsaktiven Substanzen, besonders bevorzugt aus der Gruppe der Builder (Gerüststoffe) oder Cobuilder.

In a particularly preferred embodiment of the present invention, the polymers are present in prefabricated form. For the preparation of the polymers is suitable inter alia

• The encapsulation of the polymers by means of water-soluble or water-dispersible 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 compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C;
• - The cogranulation of the polymers with inert support materials, preferably with support materials from the group of washing or cleaning-active substances, particularly preferably from the group of builders (builders) or cobuilders.

When softeners effective polymers are, for example, the sulfonic acid-containing Polymers which are used with particular preference.

Especially preferably as sulfonic acid-containing Polymers can be used are copolymers of unsaturated carboxylic acids containing sulfonic acid groups Monomers and optionally further ionic or nonionic Monomers.

In the context of the present invention are as unsaturated monomer carboxylic acids of the formula 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-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 = 0 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 = 0 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 ) -.

Especially preferred sulfonic acid group-containing Monomers 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, 3-methacrylamido-2-hydroxy propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, Sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts the acids mentioned.

Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds. The content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer. Particularly preferred polymers to be used 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.

• i) ungesättigten Carbonsäuren der Formel R¹(R²)C=C(R³)COOH in der R¹ bis R³ unabhängig voneinander für -H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,
• ii) Sulfonsäuregruppen-haltigen Monomeren der Formel R⁵(R⁶)C=C(R⁷)-X-SO₃H in der R⁵ bis R⁷ unabhängig voneinander für -H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
• iii) gegebenenfalls weiteren ionogenen oder nichtionogenen Monomeren besonders bevorzugt.

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, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or for -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 are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ in which R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optionally present spacer group which is selected from - (CH ₂ ) _n - where n = 0 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 ionic or nonionic monomers are particularly preferred.

• i) einer oder mehreren ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln: H₂C=CH-X-SO₃H H₂C=C(CH₃)-X-SO₃H HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H, in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
• iii) gegebenenfalls weiteren ionogenen oder nichtionogenen Monomeren.

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 (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 optionally present spacer group is selected from - (CH ₂ ) _n - with n = 0 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 nonionic monomers.

The Copolymers can the monomers from groups i) and ii) and optionally iii) contained in varying amounts, all representatives from the group i) with all Representatives from group ii) and all representatives from the group Group iii) can be combined. Particularly preferred polymers have certain structural units on, 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 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 ) - 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.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. When the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise 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 - 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 O- (CH ₂ ) - where n = 0 to 4, -O- (C ₆ H ₄ ) -, -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , are preferred.

Acrylic acid and / or methacrylic acid 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 - [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). One arrives in this way According to the invention preferred copolymers, the structural units of the formula - [HCOOH-CHCOOH] _m - [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 - [HCOOCH-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 2,000 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.

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-CHCOOH] _m - [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 2,000 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 (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred.

In the polymers can the sulfonic acid groups wholly or partly in neutralized form, i. that the acidic acid atom of the sulfonic acid group in some or all of them Sulfonic acid groups against Metal ions, preferably alkali metal ions and in particular against Sodium ions, can be replaced. The use of partial or fully neutralized sulfonic acid group-containing Copolymer is preferred according to the invention.

The Monomer distribution of the copolymers preferably used according to the invention is for copolymers containing only monomers from groups i) and ii), preferably in each case from 5 to 95% by weight of i) or ii), particularly preferably 50 to 90% by weight of monomer from group i) and 10 to 50% by weight Monomer from group ii), in each case based on the polymer.

at Terpolymers are particularly preferred which contain from 20 to 85% by weight. Monomer from group i), 10 to 60 wt .-% monomer from the group ii) and 5 to 30 wt .-% of monomer from group iii).

The molar mass 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 end use. Preferred washing or cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

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

Farther can Also bleach from the group of organic bleach used become. Typical organic bleaches are the diacyl peroxides, such as. Dibenzoyl. Other typical organic bleaches are the peroxyacids, Examples being the alkyl peroxyacids and the aryl peroxyacids become. Preferred representatives are (a) the peroxybenzoic acid and their ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and Magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, like peroxylauric acid, Peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaliminoperoxyhexanoic acid (PAP)], o-Carboxybenzamidoperoxycapronsäure, N-nonylamidoperadipic acid and N-Nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic, such as 1,12-diperoxy carboxylic acid, 1,9-diperoxyazelaic acid, Diperocysebacinsäure, diperoxybrassylic, the diperoxyphthalic acids, 2-Decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronate).

When Bleach can Chlorine or bromine releasing substances are used. Among the suitable chlorine or bromine releasing materials come for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Bleach activators are used in detergents or cleaning agents, for example, to improve cleaning at temperatures of 60 ° C and below To achieve bleaching effect. As bleach activators, compounds, which under perhydrolysis aliphatic peroxycarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, are used. Suitable substances are the O- and / or N-acyl groups of the mentioned C atom number and / or optionally substituted benzoyl groups wear. Preference is given to polyacylated alkylenediamines, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methylsulfate (MMA) and acetylated sorbitol and mannitol or their Mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), Pentaacetylfruktose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also used preferably used. Also combinations of conventional bleach activators can be used.

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 especially preferably 2 to 6 wt .-%, each based on the total weight the bleach activator-containing agent used.

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_2-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_2-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O_n)H mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist.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 radical, 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 C _2-24 alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C _2-24 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.

in der R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt sind aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, wobei R⁴ zusätzlich auch -H sein kann und X ein Anion ist, wobei vorzugsweise R⁵ = R⁶ = -CH₃ und insbesondere R⁴ = R⁵ = R⁶ = -CH₃ gilt und Verbindungen der Formeln (CH₃)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH(CH₃))₃N⁽⁺⁾CH₂-CN X^–, oder (HO-CH₂-CH₂)₃N⁽⁺⁾CH₂-CN X^– besonders bevorzugt sind, wobei aus der Gruppe dieser Substanzen wiederum das kationische Nitril der Formel (CH₃)₃N⁽⁺⁾CH₂-CN X^–, in welcher X^– für ein Anion steht, das aus der Gruppe Chlorid, Bromid, Iodid, Hydrogensulfat, Methosulfat, p-Toluolsulfonat (Tosylat) oder Xylolsulfonat ausgewählt ist, besonders bevorzugt wird.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 ^{- represents} an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is particularly preferred.

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

Bleach-enhancing transition metal complexes, in particular with 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 the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate preferably used.

to Increase of the cleaning performance of the agents according to the invention are enzymes used. These include in particular proteases, Amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof.

Under Proteases are preferred to those of the subtilisin type. Examples therefor are the subtilisins BPN 'and Carlsberg and its advanced forms, the protease PB92, subtilisins 147 and 309, the Bacillus alkaline protease lentus, subtilisin DY and the subtilases, but not anymore the enzymes subtilisins in the strict sense, thermitase, Proteinase K and the proteases TW3 and TW7.

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

Usable according to the invention are still lipases or cutinases, especially because of their Triglyceride-splitting activities, but also to in situ peracids from suitable precursors produce. These include for example, the original one from Humicola lanuginosa (Thermomyces lanuginosus) available, respectively further developed lipases, in particular those with the amino acid exchange D96L. Furthermore, for example, the cutinases can be used, the original from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose starting enzymes originally from Pseudomonas mendocina and Fusarium solanii have been isolated.

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

to increase the bleaching effect oxidoreductases according to the invention, for example, oxidases, oxygenases, catalases, peroxidases, such as Halo, chloro, bromo, lignin, glucose or manganese peroxidases, Dioxygenases or laccases (phenol oxidases, polyphenol oxidases) used become. Advantageously, organic, particularly preferably aromatic, interacting with the enzymes Compounds added to the activity of the respective oxidoreductases to reinforce (Enhancer) or at very different redox potentials between the oxidizing enzymes and the soiling the electron flow to ensure (Mediators).

The Enzymes can used in any form established in the prior art become. These include for example, by granulation, extrusion or lyophilization obtained solid preparations or, especially in liquid or gelatinous Means, solutions the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers.

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

Farther Is it possible, to assemble two or more enzymes together, making one individual granules has several enzyme activities.

One Protein and / or enzyme may be particularly harmful during storage against damage such as inactivation, denaturation or decay, for example through physical influences, Oxidation or proteolytic cleavage are protected. In microbial Obtaining the proteins and / or enzymes is inhibiting the Proteolysis particularly preferred, especially if the means Contain proteases. Detergents or cleaners can contain stabilizers for this purpose; the provision of such funds represents a preferred embodiment of the present invention.

corrosion inhibitors serve the protection of the machine, being in the range of the machine dishwashing especially silver protectants have a special meaning. usable are the known substances of the prior art. Generally can especially silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, Alkylaminotriazole and the transition metal salts or complexes are used. Particularly preferable to use are benzotriazole and / or alkylaminotriazole. According to the invention preferred are 3-amino-5-alkyl-1,2,4-triazoles or their physiologically acceptable Salts used.

preferred acids for the Salt formation are hydrochloric acid, Sulfuric acid, Phosphoric acid, Carbonic acid, sulphurous Acid, organic carboxylic acids such as acetic, glycolic, citric and succinic acid. Very effective are 5-pentyl, 5-heptyl, 5-nonyl, 5-undecyl, 5-isononyl, 5-versatic-10-alkyl-3-amino-1,2,4-triazoles as well as mixtures of these substances.

you In addition, cleaning agent formulations often contain active chlorine Means that can significantly reduce the corrosion of the silver surface. In Chlorine-free cleaners are especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds used. Also salt- and complex-like inorganic compounds, such as salts of Metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Prefers here are the transition metal salts, the selected are from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds for preventing the Corrosion on the items to be washed be used.

Instead of from or in addition to the silver protectants described above, for example the Benzotriazoles, can redox-active substances are used. These substances are preferably inorganic redox-active substances from the group manganese, titanium, zirconium, hafnium, vanadium, cobalt and Cerium salts and / or complexes, the metals preferably in one of the oxidation states II, III, IV, V or VI.

The used metal salts or metal complexes should at least partially soluble in water be. The counterions suitable for salt formation include all common ones mono-, di- or tri-negatively charged inorganic anions, e.g. Oxide, sulphate, 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) - [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 , 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, i. completely with a waterproof, but easily soluble at the cleaning temperatures Material coated, to their premature decomposition or oxidation during storage too prevent. Preferred coating materials which, according to known methods, such as Sandwik's melt coating process from the food industry, are applied are paraffins, microwaxes, waxes of natural origin like carnauba wax, candellila wax, beeswax, higher melting Alcohols such as hexadecanol, soaps or fatty acids.

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

The agents according to the invention can in liquid or solid form, for example in the form of tablets become. It is to facilitate the disintegration of prefabricated moldings possible, Disintegration aids, so-called disintegrants, in to incorporate these agents to reduce disintegration times. Under Tablet disintegrants or disintegrators are adjuvants understood that for the rapid disintegration of tablets in water or other media and for the speedy Release of the active ingredients.

These Substances that are also referred to as "explosives" due to their effect increase when water enters their volume, on the one hand increasing the intrinsic volume (swelling), on the other hand also about the Release of gases can create a pressure on the tablet can disintegrate into smaller particles. Well-known Disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can 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 derivatives.

Preferred disintegrating agents are cellulosic disintegrating agents. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.

The Cellulose used as disintegration aid is preferably not used in finely divided form, but before mixing transferred to the premixes to be compressed in a coarser form, for example, granulated or compacted. The particle sizes of such Disintegrating agents are usually above 200 microns, preferably at least 90 wt .-% between 300 and 1600 microns and in particular at least 90 wt .-% between 400 and 1200 microns.

When another disintegrating agent based on cellulose or as an ingredient This component can be used microcrystalline cellulose. This microcrystalline cellulose is made by partial hydrolysis of Celluloses obtained under such conditions, only the amorphous ones Areas (about 30% of the total cellulose mass) of the celluloses attack and completely dissolve, the crystalline areas (about 70%) but leave undamaged. A subsequent disaggregation of the resulting from the hydrolysis microfine celluloses provide the microcrystalline celluloses, the primary particle sizes of approx. 5 μm and compactable, for example, to granules having an average particle size of 200 microns are.

Furthermore, according to the invention, gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries. The gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water. Among these compounds, mention should be made in particular of magnesium peroxide, which liberates oxygen on contact with water. Usually, however, the gas-releasing effervescent system in turn consists of at least two constituents which react with one another to form gas. While a variety of systems are conceivable and executable here, which release, for example, nitrogen, oxygen or hydrogen, the bubble system used in detergents and cleaners can be selected both on the basis of economic and environmental considerations. Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable from the alkali metal salts in aqueous solution Koh lendioxid.

When Acidifying agents consisting of the alkali salts in aqueous solution Carbon dioxide release, for example, boric acid as well Alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, preference is given used organic Acidifizierungsmittel, wherein the citric acid a particularly preferred acidifying agent. Preferred are Acidifier in effervescent system from the group of organic Di-, tri- and oligocarboxylic acids or mixtures.

When Perfume oils or Fragrances can in the context of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, Ketones, alcohols and hydrocarbons are used. Prefers However, mixtures of different fragrances are used, the together create an appealing scent. Such perfume oils can also natural Contain fragrance mixtures, as they are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.

Around to be perceptible, a fragrance must be volatile, being next to the Nature of the functional groups and the structure of the chemical Compound also plays a role in the molecular weight. So own most fragrances have molecular weights up to about 200 daltons, while molar masses from 300 daltons and above constitute an exception. Due to the different volatility changed by fragrances the smell of a compound of several fragrances perfumes or perfume during Evaporation, whereby the odor impressions in "top note", "middle note" (middle note or body) and "base note" (end note or dry divided out). Because the smell perception to a large extent too on the smell intensity is based, the top note of a perfume or fragrance is not alone from volatile Connections while the base note for the most part from less volatile, i.e. adherent fragrances. When composing perfumes can be easier volatile For example, fragrances can be bound to specific fixatives. which prevents it from evaporating too quickly. At the following Classification of the fragrances in "lighter volatile or "adherent" fragrances So over the smell impression and about it, whether the corresponding perfume perceived as a head or middle note nothing is said.

The Fragrances can can be processed directly, but it can also be beneficial to the Fragrances on carrier The slow release of fragrance for long-lasting Provide scent. As such carrier materials For example, cyclodextrins have proven useful, with the cyclodextrin-perfume complexes additionally still can be coated with other excipients.

preferred Dyes whose selection does not present any difficulty to the skilled person have a high storage stability and insensitivity to the rest Ingredients of the agents and against light and no pronounced substantivity to the with the dye-containing agents to be treated substrates such as for example textiles, glass, ceramics or plastic dishes, so as not to 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 should also be taken into account 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 solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, colorant concentrations in the range of a few 10 ^-2 to 10 ^-3 % by weight are typically selected. By contrast, in the case of the particularly preferred, but less readily water-soluble, pigment dyes due to their brilliance, the suitable concentration of the colorant in detergents or cleaners is typically about 10 ^-3 to 10 ^-4 % by weight.

It become colorants preferably, which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be beneficial proved, colorants to be used in water or at room temperature in liquid organic Substances are soluble. Suitable are, for example, anionic colorants, e.g. anionic Nitroso.

Rezeptur 2:

To illustrate the present invention, the following non-limiting recipe examples are intended to serve as liquid agents according to the invention: Recipe 1:

Recipe 2:

cleaning or care eyes, which from water, the agent according to the invention and fatty contaminants have been separated due to the increased emulsifying the remedy much later as appropriate lyes, which are known using the means of Prior art were obtained, preferably not more in several phases, i.e. in an aqueous and / or organic Phase, up. A quantification of the emulsifying ability of the funds is based on standardized phase separation tests possible. Suitable shaking and Pump simulation tests are described in detail in the examples.

Preferably shows a lye containing the inventive agent, a standardized greasy or oily Component and water in specified amounts in a 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%, more preferred less than 1.0% and in particular less than 0.2% or within 5 minutes of less than 40%, preferably less than 30%, more preferably less than 20%, most preferably less than 10%, more preferably less than 5%, and in particular less than 2.5%.

by virtue of the unusual good emulsifying ability agent according to the invention, These are, as mentioned above, in particular for the elimination greasy or oily Soils. Another subject of the present application is therefore the use of a washing or cleaning agent according to the invention for the removal of grease or oil Soils.

One additional The present invention is the use of the agent according to the invention for cleaning and care of hard surfaces, preferably washing or dishwashers, in particular for cleaning the interiors of dishwashers.

to Cleaning and / or care of dishwasher interiors will be the agent preferably in the cutlery basket or directly in one the baskets introduced or the machine interior (interior floor). In Washing machines come the agents according to the invention either by introducing in the dosing drawer or in the washing drum used.

Farther Is it possible, that the consumer gets the remedy directly from a storage bottle or a supply package on the surface to be cleaned. At least for cleaning and / or care of washing machines or dishwashers However, it is preferable for the consumer to use the product in one prefabricated dosage unit, about a tablet with a pouch solid or liquid filling or a small bottle into the machine without doing so to be exposed to the risk of skin contact with the agent.

These Dosing unit comprises, in particular when using liquid means for the Cleaning the interiors from washing machines or dishwashers between 100 to 400 ml, preferably between 200 to 300 ml. Depending on the application but it may also be advantageous to provide smaller dosing units, so that the consumer can use smaller quantities or in dependence the state of the surface the Medium amount by simultaneous use of 2, 3, 4, 5 or 6 Dosage units may vary.

Prefers the inventive step is the beginning of the consumer started Washing or cleaning program of the washing machine or dishwasher released into the machine interior. This can be done by complete or partial dissolution or dispersing the packaging or by melting individual or all packaging parts at temperatures of preferably smaller 60 ° C, especially preferably less than 50 ° C and in particular less than 40 ° C possible become.

Farther Is it possible, that the consumer, for example, from one with a frozen one Melt, a wax or gel filled dosing unit such as a Bottle the closure part removed and then the dosing with the opening down into the machine interior brings. Preferably, the viscosity reduces the agent through the warm wash and allows so a swift one Release of the liquid By means of flowing out from the packaging.

Prefers be at least 80 wt .-%, preferably at least 90 wt .-% and in particular at least 95 wt .-% of the used in a package Means preferred within 15, preferably within 12 within 9, more preferably within 6 and in particular within 5 minutes after reaching the maximum liquor temperature in the washing machine or dishwasher interior released.

In a particularly preferred embodiment the agent has such a low viscosity that it is directly after Removal of the closure flows at a suitable inclination of the container and thus during the entire cleaning or care process is available.

The maximum liquor temperature is preferably greater than 30 ° C, preferably greater than 35 ° C, especially preferably greater than 40 ° C, to preferably greater than 45 ° C, whole particularly preferably greater than 50 ° C and especially 60 ° C up to 70 ° C.

at Use of the inventive agent for cleaning and / or care of washing machines can In addition, maximum liquor temperatures of up to 95 ° C can be selected.

Examples:

• nichtionisches Tensid (A): C₁₂-C₁₄-Fettalkohol·5 EO·4 PO
• nichtionisches Tensid (B): C₁₂-C₁₄-Dimethylaminoxid
• nichtionisches Tensid (C): C₁₆-C₁₈-Fettalkohol·30 EO

The emulsifying ability of the following three formulations was determined by a pump simulation test: a) recipes

• nonionic surfactant (A): C ₁₂ -C ₁₄ fatty alcohol · 5 EO · 4 PO
• nonionic surfactant (B): C ₁₂ -C ₁₄ dimethylamine oxide
• nonionic surfactant (C): C ₁₆ -C ₁₈ fatty alcohol · 30 EO

b) Pump Simulation Test

This Test serves the adjustment of the short-term energy input by a circulation pump in a household dishwasher. The energy for making the emulsion is made using a four-leaf stirrer (IKA RW 20) with 30 mm diameter at 800 U / min introduced into the system. To do this, add 2.5 mL of the recipe with 47.5 mL of distilled water diluted put into a beaker and add 50 mL of olive oil (Bertolli Extra Vergine) added. The stirrer is for 30 seconds on. Immediately afterwards the sample will be transferred to a 100 mL graduated cylinder. There is a phase separation instead, in which an aqueous phase settles on the cylinder bottom. The volume this newly forming phase becomes dependent in milliliters measured by time.

The Measurement results can be seen that the formulations of the invention 2 and 3 despite low total amounts of nonionic surfactants over the Comparative example a significantly improved emulsifying ability exhibit. These formulas also show at the same time in the elimination greasy or oily Soiling significantly improved performance. This is especially true for the Cleaning hard surfaces.

Claims (15)

Detergents or cleaning compositions containing a) from 0.1 to 4% by weight of a nonionic surfactant (A) of the general formula R ¹ O [CH ₂ CH (R ² ) O] _x R ³ , in which - R ¹ and R ³ independently of one another are or a linear or branched, saturated or mono- or polyunsaturated, functionalized or non-functionalized hydrocarbon radical having 2 to 26 carbon atoms, where at least one of the radicals 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-2-butyl radical; X represents values between 1 and 140, each R ^{2 being} different; b) 0.01 to 4 wt .-% of a nonionic surfactant (B) from the group of C ₈ -C ₂₂ amine oxides. Washing or cleaning agent according to claim 1, characterized characterized in that Weight fraction of nonionic surfactant (A) between 0.1 and 3 Wt .-%, preferably between 0.2 and 2.5 wt .-% and in particular between 0.4 and 2.0 wt .-% is. Detergent or cleaner according to one of the preceding claims, characterized in that the nonionic surfactant (A) comprises a surfactant of the general formula R ¹ O [CH ₂ CH (R ² ) O] _x H in which - R ^{1 represents} a linear or branched, aliphatic hydrocarbon radical having 4 to 20 carbon atoms, preferably having 12 to 20 carbon atoms and especially 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 H or a methyl radical, where each R ² may be different; and x represents values between 1 and 140, preferably between 1 and 120 and in particular between 1 and 90. Detergent or cleaner according to one of the preceding claims, characterized in that the nonionic surfactant (A) is a surfactant of the general formula R ¹ O [CH ₂ CH (R ² ) O] _x CH ₂ CH (OH) R ³ in which R ¹ and R ^{3 are} independently a linear or branched, saturated or mono- or polyunsaturated, functionalized or non-functionalized hydrocarbon radical having 2 to 24 carbon atoms; R ^{2 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical; X for values between 1 and 140, each R ^{2 being} different; Washing or cleaning agent according to one of the previous Claims, characterized in that the weight fraction of the nonionic surfactant (B) is between 0.01 and 3% by weight, preferably between 0.02 and 2% by weight and in particular between 0.05 and 1 Wt .-% is. Detergent or cleaner according to one of the preceding claims, characterized in that the nonionic surfactant (B) comprises a surfactant of the general formula R ¹ R ² R ³ NO in which - R ¹ and R ² independently of one another are methyl, ethyl - or propoyl are; and R ^{3 is} a linear or branched carbon radical having 10 to 22, preferably 12 to 18 carbon atoms. Washing or cleaning agent according to one of the previous Claims, characterized in that the weight ratio of Surfactants (A) and (B) between 30: 1 and 1: 1, preferably between 20: 1 and 2: 1 and in particular between 15: 1 and 4: 1. Washing or cleaning agent according to one of the previous Claims, characterized in that it is between 10 and 90 wt .-%, preferably between 13 and 70 wt .-%, especially preferably between 16 and 50 wt .-%, most preferably between 19 and 40 wt .-% and in particular between 22 and 30 wt .-% of a or more inorganic or organic acid (s). Washing or cleaning agent according to one of the previous Claims, characterized in that it is a or more organic or inorganic acid (s) is selected from the acids formic acid, Acetic acid, adipic acid, Succinic acid, Tartaric, malic, glutaric, sorbic, maleic, malonic, lactic, glycolic, propionic, oxalic, citric, salicylic, benzoic, lactobionic, gluconic, boric, sulfamic, phosphoric, sulfuric, hydrochloric, nitric, cyanuric acids. Washing or cleaning agent according to one of the previous Claims, characterized in that it citric acid and at least one other acid contains and the weight proportion of citric acid in the acid mixture from two or more acids at least 50% by weight, preferably at least 60% by weight, preferred at least 70% by weight, particularly preferably at least 80% by weight, preferably at least 90% by weight and in particular at least 95 wt .-%, based on the acids contained, is. Washing or cleaning agent according to one of the previous Claims, characterized in that a 1% by weight solution of the agent in water (20 ° C) has a pH of less than 6, preferably between 3 and 6 having. Washing or cleaning agent according to one of the previous Claims, characterized in that it an anionic surfactant from the group of the Alkylphenoxybenzoldisulfonate, linear or branched alkylbenzenesulfonates, linear or branched Alkylnaphthalenesulfonates, alkylsulfonates, olefin-sulfonates, paraffin-sulfonates, Alkylarylsulfonates, soaps, alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, Alkylarylpolyethersulfate, Monoglycerinsulfate, preferably the Contains alkylbenzenesulfonates. Washing or cleaning agent according to one of the previous Claims, characterized in that it based on the total weight of the washing or cleaning agent, between 10 and 95% by weight, preferably between 20 and 80% by weight, preferably between 30 and 80% by weight and in particular between 40 and 70% by weight of a liquid carrier having, wherein this carrier preferably selected is from the group which, in addition to water, still comprises the alcohols, being a water / alcohol mixture and in particular a water / glycerol mixture particularly preferred. Use of a washing or cleaning agent after one of the preceding claims for the removal of grease or oil Soils. Use of the agent according to one of the previous claims for cleaning and care of hard surfaces, preferably washing or dishwashers, in particular for cleaning the interiors of dishwashers.