EP1904613B1 - Cleaning care product with improved emulsification properties - Google Patents

Abstract

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

Description

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

Cleaning or care products usually contain surfactants and have a wide range of uses and depending on a very different composition. After the pH, alkaline, neutral and acid cleaning or care products, according to the offer form liquid and solid cleaning or care products are distinguished. Especially for liquid cleaning or care products, the consumer expects that he can use the agents both in the undiluted and in the dilute aqueous state and in each case receives a satisfactory cleaning or care result.

Decisive for the cleaning or care effect are especially the surfactants and / or alkali carriers, which can be replaced by acids depending on the application, optionally also solvents such as glycol ethers and lower alcohols. In general, the formulations also contain builders, depending on the type, also bleaching agents, enzymes, as well as perfume oils and dyes. The cleaning success depends to a large extent on the - also geographically very different - type of soil and the properties of the surfaces to be cleaned.

Depending on the composition, cleaning or care products are used as general-purpose or special agents (car care products, oven cleaners, descaling agents, window cleaners, stain removers, floor care products, glass ceramic hob cleaners, stoves, leather care products, metal cleaners, furniture care products, pipe cleaners, sanitary cleaners, abrasives, carpet care products or toilet cleaners) assembled. Technical cleaning or care products are mainly used in the beverage, food, cosmetic and pharmaceutical industries, but also in the metal industry for metal degreasing. The product group also includes cleaning or care products for car washes, tank truck and aircraft cleaning or care products. The group of cleaning or care products includes, for example, the dishwashing detergents and agents for cleaning or care of washing machine or dishwasher interior.

Cleaning or care products have to cope with a variety of tasks in a variety of applications. In households, the removal of soiling such as fats and oils, food leftovers, limescale deposits, soap scraps or metal fittings as well as the corrosion protection of metal and glass are certainly in the foreground. Also in the industry, for example, the removal of fats and oils of interest.

Over the years, there have been numerous efforts to improve the cleaning or care performance of known cleaning or care products. Thus, the published patent application WO 2004/032886 A1 (Reckitt Benckiser ) Agents containing at least one surfactant and mandatory two organic acids with their salts and are suitable for cleaning surfaces. An improved cleaning performance is expected here from the combination of acids and salts. The advantages of a solvent mixture of a hydrophilic and a hydrophobic solvent in an acidic cleaning agent for hard surfaces is described in the document US 2002/187918 A1 (Reckitt Benckiser ). The solvent mixture is said to improve the solution of greasy soils. An increase in the cleaning performance due to an improved control of the area-covering application of the agent is disclosed in the published patent application US 200410186037 A1 (Cheung, Costa ). Here, insoluble, perceptible ingredients are incorporated into a hard surface cleaner which is intended to allow the end user to recognize where the agent was not or not applied in sufficient quantity. EP 1 308 499 discloses a surfactant blend with hydroxy mixed ethers and polymers.

Increasingly demanded by the end user cleaning or care products that perform without the action of mechanical energy such as rubbing and brushing optimal performance. Known examples are cleaning agent sprays for removing lime deposits on bathroom tiles or for degreasing metal objects such as extractor hoods.

Means that provide good cleaning or care results without significant mechanical treatment, offer in addition to the convenience for the user also the ability to clean surfaces whose mechanical treatment with the means is not or only to a small 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.

Even appliances such as washing machines or dishwashers, coffee machines or kettles are incomplete from the inside and only with great effort by mechanical action, for example, by a rag or a brush to clean, so that even for these applications cleaning or care products that perform well without significant mechanical treatment, are desired. In the case of washing machines and dishwashers, the effect of the cleaning or care products should be so great that not only the large surfaces the inside of the machine, which are exposed to the direct and intense operating pressure of the cleaning fleet and thus experience quite a mechanical load, but also angled areas, hose connections, door seals and all low-flow zones are optimally cleaned and / or maintained in these machines. The commercial alkaline or acidic dishwashing, cleaning or rinse aid are not or insufficiently suitable for cleaning the so-called "problem areas" of dishwashers or washing machines, as they are indeed metered into the cleaning or rinse cycle of the machine, but with the dirty areas either not at all or only briefly in contact. Even commercially available cleaners for hard surfaces are not suitable for this particular application because they generally contain strong foaming surfactants whose residues, for example in dishwashers, can lead to faults of many kinds and, moreover, can not cope with the requirements for cleaning and care properties.

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).

However, the previously mentioned agents, both the aforementioned cleaning or care products as well as the special agents "dishwashing detergents", have no satisfactory performance in the area of grease removal from surfaces. The effect of known cleaning or care medium is not sufficient to solve the Fettanschmutzungen in whole and also to keep a sufficient duration in dispersed form. As a result, it comes with manual cleaning to fat streaks on the already partially cleaned surfaces, since a separation of the cleaning liquor due to lack of emulsifying ability of the agent occurs. It deposits a thin film of grease on the cloth or on individual bristles of the brushes used. When machine cleaning or care of washing machines or dishwashers, the effect can be observed that during the rest periods of the liquor, that is, in the periods in which no circulation of 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, which does not dissolve or insufficiently in the further cleaning or care process and leads to an overall poor cleaning or care result. Furthermore, in washing machines or dishwashers, especially in dishwashers, the effect may arise that, during the cleaning with the agents described in the prior art, fat soils accumulate intensively in the areas which are exposed to only a small flow of water and there persistent incrustations and / or Oily streaks form, while on the large surfaces inside the machine interior quite a cleaning effect can be observed. Also, the formation of a greasy film on all surfaces of the machine interior using agents that have insufficient Fettemulgierfähigkeit is described. In the case of heavy contamination of the interior with greasy coverings is observed when using the known means that in addition to the problems described also inadequate cleaning of the large surfaces of the interior, which are exposed to the direct water pressure of the cleaning liquor is achieved and greater fat soiling the funds could not be dissolved or dissolved.

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

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

R¹ und R³

unabhängig voneinander für H oder einen linearen oder verzweigten, gesättigten oder ungesättigten, aliphatischen oder aromatischen Kohlenwasserstoffrest mit 1 bis 30 Kohlenstoffatomen steht, in welchem bis zu 6 Hydroxy- und/oder bis zu 3 Etherfunktionen enthalten sein können, 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-Butylrest steht, wobei jedes R² bei x ≥ 2 unterschiedlich sein kann und

x

für Werte größer 1 steht;

dargestellt werden können, sowie ein Verdickungsmittel umfasst und als 1 Gew.-%ige Lösung in Wasser (20°C) einen pH-Wert kleiner 6 aufweist.A first object of the present invention is a cleaning or care composition comprising a surfactant system comprising at least two nonionic surfactants A and B which have different chemical structures but both through the structure

R ¹ O- [CH ₂ CH (R ² ) O] _x -R ³

in which

R ¹ and R ³

independently of one another is H or a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 carbon atoms, in which up to 6 hydroxyl and / or up to 3 ether functions may be present, wherein 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-butyl radical, where each R ² may be different at x ≥ 2, and

x

stands for values greater than 1;

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

Cleaning or care compositions according to the invention, which comprise a combination of the two nonionic surfactants A and B and a thickening agent, show otherwise cleansed or care-containing preparations which instead of the nonionic surfactant A are used and / or the nonionic surfactant B nonionic surfactant (s) of other compound class (s) or only a nonionic surfactant of the above structure and a thickener or two different nonionic surfactants of the above structure, but containing no thickener, a significantly increased emulsifying for Fats and oils.

The cleaning or care agent according to the invention is preferably used in the treatment of hard surfaces and is particularly suitable for the cleaning or care of washing machines or dishwashers, especially for dishwashers.

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

Accordingly, the surfactant system may consist of two surfactants with different chemical structure, but with comparable average molecular weight. However, the average molar masses of the nonionic surfactants A and B preferably deviate from one another by at least 20 g / mol. The difference between the average molar masses of the two nonionic surfactants A and B is preferably at least 100, preferably at least 200, preferably at least 300, preferably at least 400, more preferably at least 500, very preferably at least 600 and in particular at least 700 g / mol.

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

Although it is possible to use the two nonionic surfactants A and B in the inventive compositions in any ratio, the weight ratio between surfactant A and surfactant B is preferably between 10: 1 and 1: 1, preferably between 8.5: 1 and 1, 25: 1, more preferably between 7: 1 and 1.5: 1, preferably between 5.5: 1 and 1.75: 1 and in particular between 4: 1 and 2: 1.

Preferably, the surfactant B is from 0.1 to 1.7 wt .-%, preferably 0.2 to 1.4 wt .-%, particularly preferably 0.3 to 1.1 wt .-% and in particular to 0 , 4 to 0.8% by weight in the composition. The proportion of the surfactant A in the composition according to the invention is preferably 0.6 to 5 wt .-%, preferably 0.8 to 4 wt .-%, particularly preferably 1.0 to 3 wt .-% and in particular 1.2 to 2 wt .-%.

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

In a preferred embodiment, the agent according to the invention contains a nonionic surfactant B having a melting point above 25 ° C., preferably above 30 ° C., more preferably above 35 ° C. and especially above 4.0 ° C., and additionally a nonionic surfactant A having a melting point below 25 ° C, preferably below 22.5 ° C, more preferably below 20 ° C and especially below 17.5 ° C.

For the purposes of the present invention, all nonionic surfactants which can be represented by the formula R ¹ O- [CH ₂ CH (R ² ) ^O ] _x -R ³ are suitable for combination with the thickener.

Preferably at least one and preferably both nonionic surfactants A and B are alcohol alkoxylates, in particular fatty alcohol alkoxylates.

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

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

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

Preferably usable alkyl ethoxylates are the addition products of 2 to 15, preferably 2 to 10 moles of ethylene oxide (EO) and / or propylene oxide (PO) to fatty alcohols having 4 to 22, preferably 12 to 18 and in particular 12 to 14 carbon atoms in the alkyl radical. Suitable surfactants are, for example, C _12-14 fatty alcohols having 1 to 10 EO, preferably C _12-14 fatty alcohols having 2, 3 4, 6 or 7 EO, C _12-18 fatty alcohols having 1 to 10 EO, preferably C _12-18 fatty alcohols with 2, 3, 4, 5, 8 or 9 EO, C _12-14 fatty alcohols having 1 to 8 EO and 1 to 8 PO, preferably C _12-14 fatty alcohols with 4 EO and 5 PO, with 6 EO and 4 PO, with 2 EO and 4 PO or with 5 EO and 4 PO, C _12-18 fatty alcohols having 1 to 8 EO and 1 to 8 PO, preferably C _12-18 fatty alcohols with 2 EO and 4 PO and the adducts of isodecanol or C _{9 -11} (oxo) alcohol with 2.5 or 3, 5, 6, 7, 8, 10 or 11 EO.

Also with particular preference are ethoxylated nonionic surfactants selected from C _6-20 monohydroxyalkanols or C _16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles, preferably more than 20 moles and especially more than 25 moles of ethylene oxide per mole of alcohol were used. A particularly preferred nonionic surfactant is of a straight chain or branched, preferably a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), with preference for one. Mixture of C ₁₆ - and C ₁₈ -alcohol and at least 12 mol, preferably at least 15 mol, preferably at least 20 mol and more preferably recovered at least 25 moles and in particular 30 moles of ethylene oxide. Of the surfactants mentioned, the narrow range ethoxylates are particularly preferred.

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 einen Ethyl- oder Propyl-Rest steht, wobei jedes R² bei x ≥ 2 unterschiedlich sein kann und

x

für Werte größer 1 steht.

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

R ¹ O- [CH ₂ CH (R ² ) O] _x -H

in which

R ¹

is a linear or branched, aliphatic hydrocarbon radical having 4 to 20 carbon atoms, preferably having 12 to 20 carbon atoms and in particular having 12 to 18 carbon atoms,

R ²

is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-butyl radical, in particular an ethyl or propyl radical, where each R ² at x ≥ 2 may be different and

x

stands for values greater than 1.

As described above, each R ² in the above formula may be different if x ≥ 2. 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 ,

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

For the nonionic surfactant A, the value for x with less than 20, preferably less than 15 and in particular less than 10 is preferably smaller than in the surfactant A. Also for this surfactant, the variation of the radical R ^{2 can be} excluded, so that the nonionic surfactant A only Contains ethylene oxide, only propylene oxide or only butylene oxide units. Preferably, however, the surfactant A contains different radicals R ² . Preferred nonionic surfactant A in the context of the invention are adducts of from 1 to 10 mol, preferably from 2 to 7 mol and in particular from 4 to 5 Mole of ethylene oxide and 1 to 10 moles of propylene oxide, preferably 2 to 6 moles and especially 3 to 4 moles of propylene oxide to higher molecular weight fatty alcohols into consideration. The hydrocarbon radical of the surfactant A contains preferably 8 to 18, preferably 10 to 16 and in particular 12 to 14 carbon atoms.

Preferably, a composition according to the invention contains a C ₁₂ -C ₁₄ -alkyl alcohol alkoxylate which comprises both ethoxy and propoxy units, and a C ₁₆ -C ₁₈ -alkyl alcohol ethoxylate.

Further particularly preferred nonionic surfactants are the so-called mixed ethers, which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols, which are subsequently reacted with alkyl groups in the presence of bases and end-capped. Particularly suitable mixed ethers in the context of the present invention are those which have been prepared by end-capping with a C ₁ -C ₈ -alkyl halide, in particular with a C ₁ -C ₄ -alkyl halide. Particular preference is given to n-butyl and methyl, in particular n-butyl, end-capped mixed ethers. Typical examples of a mixed ether based on a C _12/18 or C _12/14 - alcohol residue to which 5 to 10 moles of ethylene oxide have been attached are C _12-18 fatty alcohols with 3, 4, 5 or 10 EO (in each case n-butyl end-capped), C _12-14 fatty alcohols with 9 or 10 EO (each n-butyl end-capped).

Furthermore, in the agents according to the invention all hydroxy mixed ethers known to those skilled in the art, which can be represented by the formula R ¹ O- (CH ₂ CH (R ² ) O] _x -R ³ , can be used.

• R¹ und R² unterschiedlich oder gleich sein können, wobei
• R¹ für H oder einen linearen oder verzweigten, gesättigten oder ungesättigten, aliphatischen oder aromatischen Kohlenwasserstoffrest mit 1 bis 30 Kohlenstoffatomen,
• R² für H oder einen linearen oder verzweigten, gesättigten oder ungesättigten, aliphatischen oder aromatischen Kohlenwasserstoffrest mit 1 bis 28 Kohlenstoffatomen, welcher optional bis zu 5 Hydroxy- und/oder bis zu 3 Etherfunktionen enthält, steht,
• R³ für H oder eine Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, 2-Butyl- oder 2-Methyl-Butylrest steht, wobei jedes R³ bei x ≥ 2 unterschiedlich sein kann und
• x für Werte größer 1 steht.

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

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

used in the

• R ¹ and R ^{2 may be} different or the same, where
• R ^{1 is} H or a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 carbon atoms,
• R ^{2 is} H or a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 28 carbon atoms, which optionally contains up to 5 hydroxyl and / or up to 3 ether functions,
• R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-butyl radical, where each R ³ may be different at x ≥ 2 and
• x stands for values greater than 1.

Hydroxymix ethers of the formula

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

in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15, are particularly preferred.

Further preferred hydroxy mixed ethers are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

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

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

As already described for the fatty alkoxylates, also in the above formula each R ³ can 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 may 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 The value 3 for x has been selected here by way of example and may well be greater, the range of variation increasing with increasing x values and, for example, a large number (EO) groups combined with a small number (PO). Includes groups, or vice versa.

Particularly preferred hydroxy mixed ethers of the above formula have values of k = 1 and j = 1, so that the above formula zu

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

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particular preference is given to hydroxy mixed ethers in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

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

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

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

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

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

Low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred hydroxy mixed ethers in the context of the present invention. Among these, in turn, hydroxy mixed ethers having EO-AO-EO-AO blocks are preferred, wherein one to ten EO or AO groups are bonded to each other before one block from the other groups follows. Here are hydroxy mixed ethers of the general formula

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

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical, each R ² or R ^{3 group is} independently selected from -CH ₃ , - CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently represent integers from 1 to 6.

The preferred hydroxy mixed ethers of the above formula can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula may vary depending on the origin of the alcohol. If natural sources are used, the radical R ^{1 has} an even number of carbon atoms and is unbranched, as a rule, the linear radicals of alcohols of native origin with 12 to 18 carbon atoms, for example coconut, palm, tallow fatty alcohol 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. Independently of the nature of the alcohol used to prepare the hydroxy mixed ethers used in the compositions, hydroxy mixed ethers are preferred 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 hydroxy mixed ether 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 hydroxy mixed ethers of the above formula in which R ² or R ^{3 is} a radical - CH ₃ , w and x are independently of one another values of 3 or 4 and y and z are independently of one another values of 1 or 2.

Hydroxy mixed ethers are summarize, particularly preferably having a C _9-15 alkyl group having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 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.

Particularly preferred are hydroxy mixed ethers of the general formula

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

which in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, further a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 28 carbon atoms, preferably 2 to 22 carbon atoms, which is adjacent to a monohydroxylated intermediate group -CH ₂ CH (OH) - and in which x is between 1 and 90, preferably 40 and 80 and especially between 40 and 40 and 60 stands.

The corresponding end-capped hydroxy mixed ethers of the above formula can be obtained, for example, by reacting a terminal epoxide of the formula R ² CH (O) CH ₂ with an ethoxylated alcohol of the formula R ¹ O [CH ₂ CH ₂ O] _x-1 CH ₂ CH ₂ OH ,

Hydroxymix ethers of the general formula

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

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

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned hydroxy mixed ethers represent statistical average values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.

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

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

Another mandatory ingredient of the compositions of the invention are thickeners.

The field of application of thickeners, also called thickeners, is generally to increase the viscosity of liquids. 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, the molecular structure and relative molecular weight of the hydrocolloids determine the degree of thickening.

Surprisingly, it has now been found that the combination of special surfactants and a thickening agent in a cleansing or care agent significantly increases the fat-lubricating ability of this agent. It can be used in the compositions according to the invention all known in the art thickeners, whereby the use of a combination of several thickeners is possible.

In a preferred embodiment, the compositions according to the invention contain inorganic thickeners such as silica, clays, phyllosilicates, preferably smectites, in particular montmorillonite or hectorite; low molecular weight organic thickeners such as metal soaps, hydrogenated castor oil, modified fatty derivatives or polyamides. Polyvinyl alcohols, polyacrylic and polymethacrylic acids and their salts, polyacrylamides, polyvinylpyrrolidone, polyethylene glycols, styrene-maleic anhydride copolymers and salts thereof are used in particular from the large group of organic fully synthetic thickeners. Particular preference is given to the copolymers 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 alkyl epoxides or halides;
  
• hydrophobically modified polyacrylamides prepared by copolymerizing 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 thickening agents come from the groups of organic natural thickening agents 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 gum, locust bean gum, tragacanth, as well as derivatives and mixtures of these thickeners.

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

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

In general, it is possible for one, two, three, four or even five different thickening agents to be present in the compositions according to the invention. Preferably, the xanthan gum content makes at least 20 wt .-%, preferably at least 40 wt .-%, preferably at least 60 wt .-%, particularly preferably at least 80 wt .-% and in particular at least 90 wt .-%, especially 99 wt .-% of the total thickener contained in the agent.

With preference in the washing or cleaning agent 0.05 to 1 wt .-%, preferably 0.1 to 0.9 wt .-%, particularly preferably 0.15 to 0.8 wt.%, Preferably 0.2 to 0, 7 wt .-%, preferably 0.25 to 0.6 wt .-%, very particularly preferably 0.3 to 0.5 wt .-% and in particular 0.3 to 0.4 wt .-% thickener.

Further optimization of the fat emulsifying ability of agents according to the invention can be achieved by the choice of suitable proportions between the nonionic surfactants A and B used and the thickener. For this purpose, the weight ratio of surfactant A to thickener is preferably between 50: 1 and 1:10. This ratio is preferably between 22: 1 and 1: 2, preferably between 18: 1 and 1: 1.5, more preferably between 14: 1 and 1: 1, more preferably between 10: 1 and 1.5: 1, and in particular between 6: 1 and 2: 1.

The weight ratio between surfactant B and thickener is preferably between 40: 1 and 1:30. This ratio is preferably between 10: 1 and 1: 8, preferably between 7.5: 1 and 1: 6, particularly preferably between 5: 1 and 1: 4 and in particular between 2.5: 1 and 1: 2.

The improved emulsifying capacity of agents according to the invention can be observed in a wide pH range. Preferably, a 1 wt .-% solution in water (20 ° C) has a pH of less than 5.5, preferably less than 5.0, more preferably less than 4.5, most preferably less than 4.0 and in particular less than 3 , 5 on. The undiluted liquid composition preferably has a pH of less than 6, preferably less than 5, more preferably less than 4, more preferably less than 3 and in particular less than 2.5.

To ensure the acidic properties of the agent, it preferably contains an organic or inorganic acid. In this case, it is preferred that the washing or cleaning agent at least 10 wt .-%, preferably at least 13 wt .-%, more preferably at least 16 wt .-%, most preferably at least 19 wt .-% and in particular at least 22 wt .-%, based on the total agent, of an inorganic or organic acid.

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, succinic, tartaric, malic, glutaric, sorbic, maleic, malonic, lactic, glycolic, propionic, oxalic and especially citric acid. Salicylic acid or benzoic acid is preferably used from the group of aromatic carboxylic acids. Also suitable are lactobionic acid and gluconic acid. Preferred inorganic acids are boric acid, sulfamic acid, phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid. Also suitable is cyanuric acid.

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

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

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

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

With particular preference, the inventive cleaning or care agents additionally contain 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 the sulfonation obtained. 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 are synthetic, petrochemical. Basis produced straight-chain alkyl radical containing an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. 2,3-alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable Anionteriside.

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

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

The inventive agent preferably contains at least one surfactant selected from the group consisting of alkylphenoxybenzenedisulfonates, linear or branched alkylbenzenesulfonates, linear or branched alkylnaphthalene sulfonates, alkylsulfonates, olefinsulfonates, paraffin sulfonates, alkylarylsulfonates, soaps, alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alkylaryl polyether sulfates or monoglycerol sulfates.

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

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

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

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

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.

From the group of amphoteric surfactants are in particular the betaines mentioned. Betaines and / or amine oxides in the compositions according to the invention are preferably less than 10% by weight, preferably less than 8% by weight, more preferably less than 6% by weight, more preferably less than 4% by weight, completely more preferably less than 2% by weight, and especially not at all.

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

The inventive agent may be in solid form such as powders, pellets, tablets, capsules, pearls, as well as in liquid form. If the agent is solid at room temperature, it is preferably completely or partially flowable / liquid at temperatures below 90 ° C., preferably below 80 ° C., preferably below 70 ° C., more preferably below 60 ° C. and in particular below 55 ° C.

Under liquid is understood here also gel and waxy. "liquid" thus refers to any state that is characterized at 20 ° C by a fluid (flowable) state of matter.

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

Suitable carriers of liquid agents are water, 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.

It is preferred to use water, alcohol or an alcohol / water mixture, preferably a water / alcohol mixture, as the carrier in inventive compositions. In this case, a polyhydric alcohol and in particular glycerol is preferably used. Preferably, a water / glycerol mixture serves as a carrier.

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

Depending on the intended use, the composition according to the invention may contain abrasive, undissolved and / or dispersed constituents, be cloudy or translucent or clear.

The agents according to the invention described above preferably comprise further cleaning-active and / or care-active substances, preferably from the group of builders, polymers, bleaches, bleach activators, enzymes. Corrosion inhibitors, disintegrants, fragrances and perfume carriers. These preferred ingredients will be described in more detail below.

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

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

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, those of polycarboxylic acids being those Carboxylic acids are understood to carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

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

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

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

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

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer. Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ..

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

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

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

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

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

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

Suitable nonionic surfactants which can be used in addition to the nonionic surfactants described above are, for example, alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, especially methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18 C And G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

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

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 are customary can be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

In general, in the invention. In addition to nonionic polymers, it is also possible to use cationic, anionic and amphoteric polymers.

According to the invention, preference is given to using polymers which contain diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units.

The aforementioned amphoteric polymers have not only cationic groups but also anionic groups or monomer units.

Preference is given to amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers methacrylamidoalkyl-trialkylammonium chloride and dimethyl (diallyl) ammonium chloride.

Particularly preferred amphoteric polymers are from the group of the Methacrylamidoalkyl-trialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers and their alkali metal and ammonium salts.

Particular preference is given to amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium

Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference.

Particularly preferred as sulfonic acid-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other 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.

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

Suitable further ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds. Preferably, the content of the used. Polymers of these other ionic or nonionic monomers less than 20 wt .-%, 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.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.

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

In the case of terpolymers, particular preference is given to those which contain from 20 to 85% by weight of monomer from group i). From 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight 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- yielding peracidic salts or peracids, such as perbenzoates. Peroxophthalates. Diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

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

These bleach activators are preferably used in amounts of up to 10% by weight, in particular from 0.1% by weight to 8% by weight, especially from 2 to 8% by weight and more preferably from 2 to 6% by weight, based in each case on the total weight of bleach activator-containing agents.

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

Bleach-enhancing transition metal complexes, in particular 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 are preferably used.

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

In a preferred embodiment, the composition contains 0.6 to 5.0 wt .-%, preferably 0.8 to 4 wt .-% of a C ₁₂ -C ₁₈ alkyl alcohol alkoxylate, preferably a C ₁₂ -C ₁₄ alkyl alcohol alkoxylate having an average molecular weight of about 500 - 900 g / mol, 0.1 to 1.7 wt .-%, preferably 0.2 to 1.4% by weight of a C ₁₂ -C ₁₈ -alkyl alcohol alkoxylate, preferably a C ₁₆ -C ₁₈ -alkyl alcohol alkoxylate having an average molar mass of 1400-2100 g / mol, 0.05 to 1% by weight, preferably 0, 1 to 0.9 wt .-% of a thickener, preferably a thickener from the group of polysaccharides and in particular xanthan gum and at least 10 wt .-%, preferably at least 13 wt .-% of an inorganic or organic acid, preferably citric acid, and preferably also 2 to 10 wt .-% cumene sulfonate.

Also preferred is an agent which comprises from 0.6% to 5.0%, preferably from 0.8% to 4%, by weight of a C ₁₂ -C ₁₈ alkyl alcohol, preferably a C ₁₂ -C ₁₄ alkyl alcohol, both is ethoxylated and propoxylated and preferably contains 2 to 7 moles, in particular 4 to 5 moles of ethylene oxide and 2 to 7 moles of propylene oxide, in particular 3 to 4 moles of propylene oxide, 0.1 to 1.7 wt .-%, preferably 0.2 to 1.4 wt .-% of a C ₁₂ -C ₁₈ alkyl alcohol alkoxylate, preferably a C ₁₆ -C ₁₈ -Alkytalkoholalkoxylats containing no propylene oxide units and at least 15, preferably at least 25 ethylene oxide units, 0.05 to 1 wt .-%, preferably 0.1 to 0.9 wt .-% of a thickener, preferably a thickener from the group of polysaccharides and in particular xanthan gum, at least 10 wt .-%, preferably at least 13 wt .-% of an inorganic or organic acid, preferably citric acid, and preferably contains glycerol.

The compositions of further preferred agents according to the invention are given in the table below. Here the abbreviation M means average molecular weight. In acid mixtures of these example formulations, the proportion of citric acid, based on the acid mixture, is at least 50% by weight, preferably at least 80% by weight. The ratio of water to glycerol is between 1: 1 and 1:90, preferably between 1:10 and 1:60. Preferably, the agent additionally contains a surfactant having hydrotropic properties, preferably cumene sulfonate, basic components such as alkali metal caustic solutions and / or perfume. The stated percentages by weight are based on the total agent. 0.6-5.0% by weight of surfactant A 0.1-1.7% by weight of surfactant B 0.05-1.0% by weight of thickener minute 10% by weight of acid 20-80% by weight carrier C _12-14 fatty alcohol 1-7 EO 1-7 PO - 40 EO C _16-18 fatty alcohol 20 Xanthan gum citric acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl- 40 EO group capped C _16-18 fatty alcohol 20 Xanthan gum citric acid water C _12-14 fatty alcohol C _16-18 fatty alcohol 20 xanthan citric acid water Hydroxymix ether M = 450-1000 g / mol - 40 EO Gum EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol 20 - 40 EO Xanthan gum citric acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol 20-40 EO butyl-group capped Xanthan gum citric acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped C _16-18 fatty alcohol 20 40 EO butyl group capped Xanthan gum citric acid water C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol 20-40 EO butyl-group capped Xanthan gum citric acid water EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol 20-40 EO butyl-group capped Xanthan gum citric acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol Xanthan gum citric acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol Xanthan gum citric acid water C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol Xanthan gum citric acid water EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol Xanthan gum citric acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO EO-PO block polymer M = 1000-2500 g / mol Xanthan gum citric acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped EO-PO block polymer M = 1000-2500 g / mol Xanthan gum citric acid water C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol EO-PO block polymer M = 1000-2500 g / mol Xanthan gum citric acid water EO-PO block polymer M = 450-1000 g / mol EO-PO block polymer M = 1000-2500 g / mol Xanthan gum citric acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol 20 - 40 EO polyacrylate citric acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO group-capped C _16-18 fatty alcohol 20 butyl- 40 EO polyacrylate citric acid water C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol 20 - 40 EO polyacrylate citric acid water EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol 20 - 40 EO polyacrylate citric acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol 20-40 EO butyl-group capped polyacrylate citric acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped C _16-18 fatty alcohol 20 40 EO butyl group capped polyacrylate citric acid water C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-16 fatty alcohol 20-40 EO butyl group capped polyacrylate citric acid water EO-PO block polymer M = 450-1000 g / mol - C _16-18 fatty alcohol 20 40 EO butyl group capped polyacrylate citric acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol polyacrylate citric acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol polyacrylate citric acid water C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol polyacrylate citric acid water EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol polyacrylate citric acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO EO-PO block polymer M = 1000-2500 g / mol polyacrylate citric acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped EO-PO block polymer M = 1000-2500 g / mol polyacrylate citric acid water C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol EO-PO block polymer M = 1000-2500 g / mol polyacrylate citric acid water EO-PO block polymer M = 450-1000 g / mol EO-PO block polymer M = 1000-2500 g / mol polyacrylate Citric acid, water C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol 20 - 40 EO Xanthan gum Citric acid / formic acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO group-capped C _16-18 fatty alcohol 20 butyl- 40 EO Xanthan gum Citric acid / formic acid water C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol 20 - 40 EO Xanthan gum Citric acid / formic acid water EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol 20 - 40 EO Xanthan gum Citric acid / formic acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol 20-40 EO butyl-group capped Xanthan gum Citric acid / formic acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl - group capped C _16-18 fatty alcohol 20 40 EO butyl group capped Xanthan gum Citric acid / formic acid water C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol 20-40 EO butyl-group capped Xanthan gum Citric acid / formic acid water EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol 20-40 EO butyl-group capped Xanthan gum Citric acid / formic acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol Xanthan gum Citric acid / formic acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol Xanthan gum Citric acid / formic acid water C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol Xanthan gum Citric acid / formic acid water EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol Xanthan gum Citric acid / formic acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO EO-PO block polymer M = 1000-2500 g / mol Xanthan gum Citric acid / formic acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped EO-PO block polymer M = 1000-2500 g / mol Xanthan gum Citric acid / formic acid water C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol EO-PO block polymer M = 1000-2500 g / mol Xanthan gum Citric acid / formic acid water EO-PO block polymer M = 450-1000 g / mol EO-PO block polymer M = 1000-2500 g / mol Xanthan gum Citric acid / formic acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol 20 - 40 EO polyacrylate Citric acid / formic acid water C _12-14 fatty alcohol, 1-7 EO 1-7 PO butyl- 40 EO group capped C _16-18 fatty alcohol 20 polyacrylate Citric acid / formic acid water C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol 20 - 40 EO polyacrylate Citric acid / formic acid water EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol 20 - 40 EO polyacrylate Citric acid / formic acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol 20-40 EO butyl-group capped polyacrylate Citric acid / formic acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped C _16-18 fatty alcohol 20 40 EO butyl group capped polyacrylate Citric acid / formic acid water C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol 20-40 EO butyl group capped polyacrylate Citric acid / formic acid water EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol 20-40 EO butyl-group capped polyacrylate Citric acid / formic acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol polyacrylate Citric acid / formic acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol polyacrylate Citric acid / formic acid water C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol polyacrylate Citric acid / formic acid water EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol polyacrylate Citric acid / formic acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO EO-PO block polymer M = 1000-2500 g / mol polyacrylate Citric acid / formic acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped EO-PO block polymer M = 1000-2500 g / mol polyacrylate Citric acid / formic acid water C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol EO-PO block polymer M = 1000-2500 g / mol polyacrylate Citric acid / formic acid water EO-PO block polymer M = 450-1000 g / mol EO-PO block polymer M = 1000-2500 g / mol polyacrylate Citric acid / formic acid water C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol 20 - 40 EO Xanthan gum citric acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO group-capped C _16-18 fatty alcohol 20 butyl- 40 EO Xanthan gum citric acid Water / glycerol C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol 20 - 40 EO Xanthan gum citric acid Water / glycerol EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol 20 - 40 EO Xanthan gum citric acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol 20-40 EO butyl-group capped Xanthan gum citric acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped C _16-18 fatty alcohol 20 40 EO butyl group capped Xanthan gum citric acid Water / glycerol C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol 20-40 EO butyl-group capped Xanthan gum citric acid Water / glycerol EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol 20-40 EO butyl-group capped Xanthan gum citric acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol Xanthan gum citric acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped C _16-18 . Fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol Xanthan gum citric acid Water / glycerol C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol Xanthan gum citric acid Water / glycerol EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol Xanthan gum citric acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO EO-PO block polymer M = 1000-2500 g / mol Xanthan gum citric acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped EO-PO block polymer M = 1000-2500 g / mol Xanthan gum citric acid Water / glycerol C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol EO-PO block polymer M = 1000-2500 g / mol Xanthan gum citric acid Water / glycerol EO-PO block polymer M = 450-1000 g / mol EO-PO block polymer M = 1000-2500 g / mol Xanthan gum citric acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol 20 -40 EO polyacrylate citric acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped C _16-18 fatty alcohol 20 40 EO polyacrylate citric acid Water / glycerol C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol 20 - 40 EO polyacrylate citric acid Water / glycerol EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol 20 - 40 EO polyacrylate citric acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol 20-40 EO butyl-group capped polyacrylate citric acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped C _16-18 fatty alcohol 20 40 EO butyl group capped polyacrylate citric acid Water / glycerol C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol 20-40 EO butyl-group capped polyacrylate citric acid Water / glycerol EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol 20-40 EO butyl-group capped polyacrylate citric acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol polyacrylate citric acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol polyacrylate citric acid Water / glycerol C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol polyacrylate citric acid Water / glycerol EO-PO block polymer M = 450 = 1000 g / mol C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol polyacrylate citric acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO EO-PO block polymer M = 1000-2500 g / mol polyacrylate citric acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped EO-PO block polymer M = 1000-2500 g / mol polyacrylate citric acid Water / glycerol C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol EO-PO block polymer M = 1000-2500 g / mol polyacrylate Citric acid, Water / glycerol EO-PO block polymer M = 450-1000 g / mol EO-PO block polymer M = 1000-2500 g / mol polyacrylate citric acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol 20 - 40 EO Xanthan gum Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO group-capped C _16-18 fatty alcohol 20 butyl- 40 EO Xanthan gum Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol 20 - 40 EO Xanthan gum Citric acid / formic acid Water / glycerol EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol 20 - 40 EO Xanthan gum Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol 20-40 EO butyl-group capped Xanthan gum Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped C _16-18 fatty alcohol 20 40 EO butyl group capped Xanthan gum Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol 20-40 EO butyl-group capped Xanthan gum Citric acid / formic acid Water / glycerol EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol 20-40 EO butyl-group capped Xanthan gum Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol Xanthan gum Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol Xanthan gum Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol Xanthan gum Citric acid / formic acid Water / glycerol EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol Xanthan gum Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO EO-PO block polymer M = 1000-2500 g / mol Xanthan gum Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped EO-PO block polymer M = 1000-2500 g / mol Xanthan gum Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol EO-PO block polymer M = 1000-2500 g / mol Xanthan gum Citric acid / formic acid Water / glycerol EO-PO block polymer M = 450-1000 g / mol EO-PO block polymer M = 1000-2500 g / mol Xanthan gum Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol 20 - 40 EO polyacrylate Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO group-capped C _16-18 fatty alcohol 20 butyl- 40 EO polyacrylate Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol 20 - 40 EO polyacrylate Citric acid / formic acid Water / glycerol EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol 20 -40 EO polyacrylate Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol 20-40 EO butyl-group capped polyacrylate Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped C _16-18 fatty alcohol 20 40 EO butyl group capped polyacrylate Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol 20-40 EO butyl-group capped polyacrylate Citric acid / formic acid Water / glycerol EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol 20-40 EO butyl-group capped polyacrylate Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol polyacrylate Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol polyacrylate Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol polyacrylate Citric acid / formic acid Water / glycerol EO-PO block polymer M = 450-1000 g / mol C _16-18 fatty alcohol hydroxy mixed ether M = 1000-2500 g / mol polyacrylate Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO EO-PO block polymer M = 1000-2500 g / mol polyacrylate Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol 1-7 EO 1-7 PO butyl-group capped EO-PO block polymer M = 1000-2500 g / mol polyacrylate Citric acid / formic acid Water / glycerol C _12-14 fatty alcohol hydroxy mixed ether M = 450-1000 g / mol EO-PO blockpotmer M = 1000-2500 g / mol polyacrylate Citric acid / formic acid Water / glycerol EO-PO block polymer M = 450-1000 g / mol EO-PO block polymer M = 1000-2500 g / mol polyacrylate Citric acid / formic acid Water / glycerol

Cleaning or care eyes, which consist of water, the agent of the invention and fatty. Contaminants have been prepared, due to the increased emulsifying capacity of the composition, separate much later than corresponding alkalis obtained using known means of the prior art, preferably no longer into multiple phases, i. in an aqueous and / or organic phase, on. A quantification of the emulsifying ability of the agents is possible by means of standardized phase separation tests. Suitable shake and pump simulation tests are described in detail in the examples.

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

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

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

For cleaning and / or care of dishwasher interiors, the agent is preferably introduced into the cutlery basket or directly into one of the baskets or the machine interior (interior floor). In washing machines, the compositions according to the invention are used either by introduction into the dosing drawer or into the washing drum.

Furthermore, it is possible for the consumer to apply the agent directly from a supply bottle or a storage package to the surface to be cleaned. At least for cleaning and / or Care of washing machines or dishwashers, however, it is preferred that the consumer brings the agent in a prefabricated dosage unit, such as a tablet a pouch with a solid or liquid filling or a small bottle in the machine without the risk of skin contact with the agent exposed to become.

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

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

Preferably, the inventive agent is released at the beginning of the consumer started washing or cleaning program of the washing machine or dishwasher in the machine interior. This can be achieved by completely or partially dissolving or dispersing the packaging or by melting individual or all packaging parts at temperatures of preferably less than 60 ° C., more preferably less than 50 ° C. and in particular less than 40 ° C.

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

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

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

The maximum liquor temperature is preferably greater than 30 ° C, preferably greater than 35 ° C. more preferably greater than 40 ° C, preferably greater than 45 ° C, most preferably greater than 50 ° C and in particular 60 ° C to 70 ° C.

When using the inventive means for cleaning and / or care of washing machines also maximum liquor temperatures of up to 95 ° C can be selected.

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

Examples

• Rezeptur 1: Vollrezeptur
• Rezeptur 2: ohne Verdickungsmittel
• Rezeptur 3: ohne Tensid B
• Rezeptur 4: ohne Tenside A und B

Rezepturbestandteil Rezeptur 1 Rezeptur 2 Rezeptur 3 Rezeptur 4 nichtionisches Tensid A 1,5 1,5 1,5 0,0 nichtionisches Tensid B 0,6 0,6 0,0 0,0 Zitronensäure 1 H₂O 25,0 25,0 25,0 25,0 Glycerin 86%ig 2,5 2,5 2,5 2,5 C₃-Alkylbenzolsulfonat 40%ig 6,0 6,0 6,0 6,0 Parfüm 0.2 0,2 0,2 0,2 Verdicker 0,35 0,0 0,35 0,35 Natronlauge 50%ig 2,44 2,44 2,44 2,44 Wasser 61,41 61,76 62,01 63,51 nichtionisches Tensid A: C₁₂-C₁₄-Fettalkohol · 5 EO 4 PO (mittleres Molgewicht ca. 650 g/mol) nichtionisches Tensid B: C₁₆-C₁₈-Fettalkohol · 30 EO (mittleres Molgewicht ca. 1500 g/mol) The emulsifiability of the following four formulations was determined by a shake test and by a pump simulation test:

• Recipe 1: full recipe
• Formulation 2: without thickener
• Formulation 3: without surfactant B
• Formulation 4: without surfactants A and B

Recipe ingredient Recipe 1 Recipe 2 Recipe 3 Recipe 4 nonionic surfactant A 1.5 1.5 1.5 0.0 nonionic surfactant B 0.6 0.6 0.0 0.0 Citric acid 1H ₂ O 25.0 25.0 25.0 25.0 Glycerin 86% 2.5 2.5 2.5 2.5 C ₃ -alkylbenzenesulfonate 40% 6.0 6.0 6.0 6.0 Perfume 0.2 0.2 0.2 0.2 thickener 0.35 0.0 0.35 0.35 Sodium hydroxide 50% 2.44 2.44 2.44 2.44 water 61.41 61.76 62,01 63.51 nonionic surfactant A: C ₁₂ -C ₁₄ fatty alcohol 5 EO 4 PO (average molecular weight about 650 g / mol) nonionic surfactant B: C ₁₆ -C ₁₈ fatty alcohol 30 EO (average molecular weight about 1500 g / mol)

a) Shake test

Dilute 10 mL of the product with 40 mL of distilled water, place in a 100 mL graduated cylinder and add 50 mL of olive oil (Bertolli Extra Vergine). The measuring cylinder is shaken by hand in a defined manner for 20 seconds.

After adjustment of the shaking motion, a phase separation takes place and it settles on the cylinder bottom an aqueous. Phase off. The volume of this newly forming phase is measured in milliliters as a function of time. Phase separation after Recipe 1 Recipe 2 Recipe 3 Recipe 4 1 minute 0 mL 12 mL 2 mL 20 mL 5 minutes 3 mL 35 mL 10 mL 50 mL

b) Pump Simulation Test

This test is used to simulate the short-term energy input through a circulation pump in a household dishwasher. The energy for making the emulsion is introduced into the system at 800 rpm using a four-blade 30 mm diameter stirrer (IKA RW 20). To do this, dilute 10 mL of the product with 40 mL of distilled water, place in a beaker and add 50 mL of olive oil (Bertolli Extra Vergine). The stirrer is switched on for 30 seconds. Immediately afterwards, the sample is transferred to a 100 mL graduated cylinder. There, a phase separation takes place in which settles an aqueous phase at the bottom of the cylinder. The volume of this newly forming phase is measured in milliliters as a function of time. Phase separation after Recipe 1 Recipe 2 Recipe 3 Recipe 4 1 minute 0 mL 10 mL 1 mL 12 mL 5 minutes 2 mL 31 mL 5 mL 40 mL

Conclusion of the experiments

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

Claims (23)

1. A cleaning or maintenance agent comprising

   - a surfactant system comprising at least two nonionic surfactants A and B, which have chemical structures which differ from one another but both of which may be represented by the structure
   
           R¹O-[CH₂CH(R²)O]_x-R³
   
   in which

   R¹ and R³ mutually independently denote H or a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residue with 1 to 30 carbon atoms, in which up to 6 hydroxy and/or up to 3 ether functions may be present, wherein at least one of the residues R¹ and R³ does not denote H,

   R² denotes H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methylbutyl residue, wherein, where x ≥ 2, each R² may be different and

   x denotes values greater than 1,

   and

   - a thickener,

   wherein a 1 wt.% solution of the agent in water (20°C) exhibits a pH value of less than 6.
2. An agent according to claim 1, characterised in that the surfactant system comprises at least one nonionic surfactant A with an average molar mass of between 200 and 1200 g/mol, preferably of between 300 and 1100 g/mol, particularly preferably of between 400 and 1000 g/mol and in particular of between 500 and 900 g/mol and at least one further nonionic surfactant B with an average molar mass of between 1000 and 2500 g/mol, preferentially of between 1100 and 2400 g/mol, preferably of between 1200 and 2300 g/mol, particularly preferably of between 1300 and 2200 and in particular of between 1400 and 2100 g/mol.
3. An agent according to either of claim 1 or claim 2, characterised in that the difference in the average molar masses of the two nonionic surfactants A and B amounts to at least 100, preferentially to at least 200, preferably to at least 300, more preferably to at least 400, particularly preferably to at least 500, very particularly preferably to at least 600 and in particular to at least 700 g/mol.
4. An agent according to any one of claims 1 to 3, characterised in that the ratio by weight between surfactant A and surfactant B is between 10:1 and 1:1, preferentially between 8.5:1 and 1.25:1, particularly preferably between 7:1 and 1.5:1, more preferably between 5.5:1 and 1.75:1 and in particular between 4:1 and 2:1.
5. An agent according to any one of claims 1 to 4, characterised in that surfactant B is present in the agent in amount of 0.1 to 1.7 wt.%, preferably of 0.2 to 1.4 wt.%, particularly preferably of 0.3 to 1.1 wt.% and in particular of 0.4 to 0.8 wt.%.
6. An agent according to any one of claims 1 to 5, characterised in that surfactant A is present in the agent in an amount of 0.6 to 5 wt.%, preferably of 0.8 to 4 wt.%, particularly preferably of 1.0 to 3 wt.% and in particular of 1.2 to 2 wt.%.
7. An agent according to any one of claims 1 to 6, characterised in that the nonionic surfactants A and B exhibit the following structure
   
           R¹O-[CH₂CH(R²)O]_x-H
   
   in which

   R¹ denotes a linear or branched, aliphatic hydrocarbon residue with 4 to 20 carbon atoms, preferentially with 12 to 20 carbon atoms and in particular with 12 to 18 carbon atoms,

   R² denotes H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methylbutyl residue, in particular an ethyl or propyl residue, wherein, where x ≥ 2, each R² may be different and

   x denotes values greater than 1.
8. An agent according to claim 7, characterised in that the surfactant system contains a C₁₂-C₁₄ alkyl alcohol alkoxylate which comprises both ethoxy and propoxy units, and a C₁₆-C₁₈ alkyl alcohol ethoxylate.
9. An agent according to any one of claims 1 to 8, characterised in that the thickener is selected from polysaccharides, preferentially from cellulose compounds, xanthan gum and guar gum, and from acrylate thickeners, urethane thickeners and clays.
10. An agent according to any one of claims 1 to 9, characterised in that it contains at least 10 wt.%, preferably at least 13 wt.%, particularly preferably at least 16 wt.%, very particularly preferably at least 19 wt.% and in particular at least 22 wt.% of an inorganic or organic acid.
11. An agent according to any one of claims 1 to 10, characterised in that the organic or inorganic acid is selected from the acids:

    formic acid, acetic acid, adipic acid, succinic acid, tartaric acid, malic acid, glutaric acid, sorbic acid, maleic acid, malonic acid, lactic acid, glycolic acid, propionic acid, oxalic acid, citric acid, salicylic acid, benzoic acid, lactobionic acid, gluconic acid, boric acid, sulfamic acid, phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, cyanuric acid or mixtures of these acids.
12. An agent according to claim 11, characterised in that two or more acids are present in the agent and the proportion by weight of citric acid in this mixture of two or more acids constitutes at least 50 wt.%, preferentially at least 60 wt.%, preferably at least 70 wt.%, particularly preferably at least 80 wt.%, more preferably at least 90 wt.% and in particular at least 95 wt.%, relative to the acids present.
13. An agent according to any one of claims 1 to 12, characterised in that the agent additionally contains at least one surfactant from the group of anionic, cationic and amphoteric surfactants.
14. An agent according to claim 13, characterised in that it contains an anionic surfactant which exhibits hydrotropic properties.
15. An agent according to claim 13 or claim 14, characterised in that the agent contains at least one surfactant from the group of alkyl phenoxybenzene disulfonates, linear or branched alkylbenzene sulfonates, linear or branched alkylnaphthalene sulfonates, alkyl sulfonates, olefin sulfonates, paraffin sulfonates, alkylaryl sulfonates, soaps, alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglycerol sulfates, preferentially alkylbenzene sulfonates.
16. An agent according to any one of claims 1 to 15, characterised in that water, alcohol or an alcohol/water mixture, preferably a water/alcohol mixture and in particular a water/glycerol mixture is used as carrier.
17. An agent according to claim 16, characterised in that the ratio between alcohol and water in the carrier is between 10:1 and 1:100, preferably between 1:1 and 1:90, particularly preferably between 1:5 and 1:80, very particularly preferably between 1:10 and 1:60 and in particular between 1:15 and 1:40.
18. An agent according to any one of claims 1 to 17, characterised in that the agent exhibits a viscosity of above 50 mPa.s, preferentially of between 100 and 700 mPa·s, preferably of between 200 and 600 mPa·s and in particular of between 300 and 500 mPa·s.
19. An agent according to any one of claims 1 to 18, characterised in that, in a pump simulation test, the agent exhibits within 1 minute a phase separation of less than 15%, preferably of less than 10%, particularly preferably of less than 5%, very particularly preferably of less than 2.5%, more preferably of less than 1.0% and in particular of less than 0.2% or within 5 minutes of less than 40%, preferably of less than 30%, particularly preferably of less than 20%, very particularly preferably of less than 10%, more preferably of less than 5% and in particular of less than 2.5%.
20. An agent according to any one of claims 1 to 19, characterised in that it contains 0.6 to 5.0 wt.%, preferentially 0.8 to 4 wt.% of a C₁₂-C₁₈ alkyl alcohol alkoxylate, preferentially of a C₁₂-C₁₄ alkyl alcohol alkoxylate with an average molar mass of 500-900 g/mol, 0.1 to 1.7 wt.%, preferentially 0.2 to 1.4 wt.% of a C₁₂-C₁₈ alkyl alcohol alkoxylate, preferentially of a C₁₆-C₁₈ alkyl alcohol alkoxylate with an average molar mass of 1400-2100 g/mol, 0.05 to 1 wt.%, preferentially 0.1 to 0.9 wt.% of a thickener, preferentially of a thickener from the group of polysaccharides and in particular xanthan gum and at least 10 wt.%, preferentially at least 13 wt.% of an inorganic or organic acid, preferably citric acid, and preferably additionally 2 to 10 wt.% of cumenesulfonate.
21. An agent according to any one of claims 1 to 20, characterised in that it contains 0.6 to 5.0 wt.%, preferentially 0.8 to 4 wt.% of a C₁₂-C₁₈ alkyl alcohol, preferentially of a C₁₂-C₁₄ alkyl alcohol which is both ethoxylated and propoxylated and preferably contains 2 to 7 mol, in particular 4 to 5 mol of ethylene oxide and 2 to 7 mol of propylene oxide, in particular 3 to 4 mol of propylene oxide, 0.1 to 1.7 wt.%, preferentially 0.2 to 1.4 wt.% of a C₁₂-C₁₈ alkyl alcohol alkoxylate, preferentially of a C₁₆-C₁₈ alkyl alcohol alkoxylate which contains no propylene oxide units and at least 15, preferentially at least 25 ethylene oxide units, 0.05 to 1 wt.%, preferentially 0.1 to 0.9 wt.% of a thickener, preferentially of a thickener from the group of polysaccharides and in particular xanthan gum, at least 10 wt.%, preferentially at least 13 wt.% of an inorganic or organic acid, preferentially citric acid, and preferably glycerol.
22. Use of the agent according to any one of claims 1-21 for the cleaning and maintenance of hard surfaces, preferentially of washing or dishwashing machines, in particular of dishwashing machines.
23. A method for the cleaning and maintenance of a washing or dishwashing machine, preferentially of a dishwashing machine, characterised in that the agent according to any one of claims 1 to 21 is placed in the unloaded machine and then the washing or cleaning program is started.