EP1987119B1 - Washing or cleaning compositions - Google Patents

Abstract

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

Description

The invention relates to a washing or cleaning agent, in particular a hard surface cleaner, which in comparison to known agents has an increased emulsifying ability for fats and oils and the use of this agent for cleaning and care of hard surfaces such as the interiors of washing machines and 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 from liquid cleaning or care products, the consumer expects that he can use the agents both in the undiluted and in - 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 great extent on the - also geographically very different - type of dirt 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 cleaning agents, 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. The household is certainly the distance from

Contaminations such as fats and oils, food leftovers, lime deposits, soap scum or metal deposits as well as the corrosion protection of metal and glass in the foreground. Also in the industry, for example, the removal of fats and oils of interest.

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 which contain at least one surfactant and necessarily two organic acids together with their salts and are suitable for cleaning surfaces.

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 2004/0186037 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.

In US5364551 discloses reduced-mist oven cleaners containing polyvinyl alcohol, a mixture of strong acids, amine oxides, and nonionic surfactants having aromatic groups.

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 To clean by a rag or a brush, so that cleaning or care products that perform well without significant mechanical treatment, even for these applications 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 of the The inside of the machine, which is exposed to the direct and intensive operating pressure of the cleaning fleet and thus experiences 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 commercial cleaners for hard surfaces are not suitable for this particular application, since they generally contain strong foaming surfactants whose residues, for example, in dishwashers can lead to disorders of various kinds and also the requirements for cleaning and care properties are not equal.

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 products is not sufficient to completely solve the fat soils and also to keep in dispersed form for a sufficient duration. 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. In machine cleaning or care of washing machines or dishwashers, the effect can be observed that takes place 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. 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 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 having insufficient fat emulsifying ability will be 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 in addition also insufficient cleaning of the large surfaces of the interior, which are exposed to the direct water pressure of the cleaning liquor is achieved and greater fat soiling the funds could not be dissolved or dissolved.

The object of the present invention was to provide a washing or cleaning 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.

• a) 0,1 bis 4 Gew.-% eines nichtionischen Tensids (A) der allgemeinen Formel R¹O[CH₂CH(R²)O]_xR³, in welcher
  • R¹ und R³ unabhängig voneinander für H oder einen linearen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten, funktionalisierten oder nicht funktionalisierten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen stehen, wobei mindestens einer der Reste R¹ und R³ nicht für H steht;
  • R² für H oder einen Methyl-, Ethyl-, n-Propyl-, iso-Propyl, n-Butyl-, 2-Butyl- oder 2-Methyl-2-Butylrest steht;
  • x für Werte zwischen 1 und 140 steht, wobei jedes R² unterschiedlich sein kann;
• b) 0,02 bis 2 Gew.-% eines nichtionischen Tensids (B) aus der Gruppe der C₈-C₂₂ Aminoxide;
• c) 0,05 bis 1 Gew.-% natürliche oder vollsynthetische organische Verdickungsmittel; sowie
• d) 10 bis 90 Gew.% einer oder mehrerer anorganischer oder organischer Säure(n),

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

• a) 0.1 to 4 wt .-% of a nonionic surfactant (A) of the general formula R ¹ O [CH ₂ CH (R ² ) O] _x R ³ , in which
  • R ¹ and R ^{3 are} independently H or a linear or branched, saturated or mono- or polyunsaturated, functionalized or non-functionalized hydrocarbon radical having 2 to 26 carbon atoms, wherein at least one of R ¹ and R ^{3 is} not H ;
  • R ^{2 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical;
  • x is values between 1 and 140, where each R ² can be different;
• b) 0.02 to 2 wt .-% of a nonionic surfactant (B) from the group of C ₈ -C ₂₂ amine oxides;
• c) from 0.05% to 1% by weight of natural or fully synthetic organic thickening agents; such as
• d) 10 to 90% by weight of one or more inorganic or organic acid (s),

contains.

Inventive cleaning or care products show over conventional means a significantly increased emulsifying ability 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.

The compositions of the invention contain as a first ingredient 0.1 to 4 wt .-% of a nonionic surfactant (A) of the general formula R ¹ O [CH ₂ CH (R ² ) O] _x R ³ , in which R ¹ and R ³ independently of one another for H or a linear or branched, saturated or on or polyunsaturated, functionalized or non-functionalized hydrocarbon radical having 2 to 26 carbon atoms, wherein at least one of R ¹ and R ^{3 is} not H; R ^{2 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical and
x stands for values between 1 and 140, where each R ² can be different.

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

With particular preference, therefore, ethoxylated nonionic surfactant selected from C _6-20 monohydroxyalkanols or C _5-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole Alcohol was used. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide. Of these, the so-called "narrow range ethoxylates" are particularly preferred.

Particular preference is given to nonionic surfactants (A) which have a melting point above room temperature. Nonionic surfactant (s) (A) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, are particularly preferred.

Suitable nonionic surfactants (A) which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred 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.

Nonionic surfactants from the group of alkoxylated alcohols, more preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO-Niotenside, are also used with particular preference.

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

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

In the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here, preference is given to nonionic surfactants of the general formula R ¹ O [CH ₂ CH ₂ O] _w [CH ₂ CH (R ² ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (R ³ ) O] _z H in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 -alkyl or -alkenyl radical; each group R ² or R ^{3 is} independently selected from CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently of one another are integers from 1 to 6.

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

The preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula may vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions, preference is given to nonionic surfactants in which R ¹ in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.

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

In summary, particularly preferred are nonionic surfactants 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.

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

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

• R ^{1 represents} a linear or branched aliphatic hydrocarbon radical having from 4 to 20 carbon atoms, preferably from 12 to 20 carbon atoms and especially from 12 to 18 carbon atoms;
• R ^{2 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-butyl radical, in particular H or a methyl radical, each being R ² may be different; and
• x stands for values between 1 and 140, preferably between 1 and 120 and in particular between 1 and 90.

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

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

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

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

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

Particularly preferred are surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ^{2 is} a linear or branched one Hydrocarbon radical having 2 to 24 carbon atoms or mixtures thereof and x is between 0.5 and 1.5 and y is a value of at least 15.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 24 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

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

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

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

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

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

Preferred agents according to the invention contain only one nonionic surfactant (A).

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

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

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

are therefore preferred according to the invention.

The weight fraction of the nonionic surfactant (B) is between 0.02 and 2% by weight and in particular between 0.05 and 1% by weight.

Although it is possible to use the two nonionic surfactants (A) and (B) in any proportion in the compositions according to the invention, such agents have proved to be particularly advantageous in terms of emulsifiability and cleaning performance in which the weight ratio of the surfactants (A) and ( B) is between 30: 1 and 1: 1, preferably between 20: 1 and 2: 1 and in particular between 15: 1 and 4: 1.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean 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.

In addition to the described nonionic surfactants (A) and (B), the compositions according to the invention may contain further nonionic surfactants, it being possible for the proportion by weight of the further nonionic surfactants to vary within wide ranges. However, the proportion of additionally used nonionic surfactants is preferably below 6% by weight, more preferably below 4% by weight, preferably below 3% by weight, more preferably below 2% by weight and especially below 1% by weight. Particular preference is given to compositions according to the invention in which the weight fraction of nonionic surfactants (A) and (B), based on the total weight of all nonionic surfactants present in the composition, is at least 60% by weight, preferably at least 80% by weight, preferably at least 90 Wt .-%, most preferably at least 95 wt .-% and in particular at least 98 wt .-% is. Particular preference is given to agents according to the invention whose nonionic surfactants can be assigned exclusively to the nonionic surfactants of groups (A) and (B).

The sum of the weight fractions of all nonionic surfactants present in the composition is preferably between 0.2 and 10% by weight, more preferably between 0.2 and 8% by weight, very particularly preferably between 0.2 and 6% by weight in compositions according to the invention. -% and in particular between 0.2 and 4 wt .-%.

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

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

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

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C₁-₄-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula

R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, wherein C ₁ - ₄ alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.

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

Compositions according to the invention also contain a natural or fully synthetic organic thickener. 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 the nonionic surfactants (A) and (B) and a natural or fully synthetic organic thickener in a cleansing or care agent significantly increases the fat emulsifiability of this agent. It is possible to use in the compositions according to the invention all natural or fully synthetic organic thickeners known to the person skilled in the art, it also being possible to use a combination of several thickeners.

In a preferred embodiment, the agents according to the invention contain low molecular weight organic thickeners such as metal soaps, hydrogenated castor oil, modified fatty derivatives or else 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-grained ones 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. The xanthan gum content preferably makes at least 20% by weight, preferably at least 40% by weight, preferably at least 60% by weight, particularly preferably at least 80% by weight and in particular at least 90% by weight, especially 99% by weight. of the total thickener contained in the agent.

Natural or fully synthetic organic thickeners are in the detergent or cleaning agent in an amount of 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 .-%, more 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 .-% included.

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, more preferably between 5: 1 and 1: 4 and in particular between 2.5: 1 and 1: 2.

Inventive detergents or cleaning agents are further characterized in that they are between 10 and 90 wt .-%, preferably between 13 and 70 wt .-%, particularly preferably between 16 and 50 wt.%, Very particularly preferably between 19 and 40 wt. % and in particular between 22 and 30 wt .-% of one or more inorganic or organic acid (s).

The resulting acidic detergents or cleaners according to the invention are also suitable, in addition to the removal of greasy or oily contaminants, also for the removal of limescale and calcareous soils. Preferred detergents or cleaners are characterized in that a 1% strength by weight solution of the composition in water (20 ° C.) has a pH of less than 6.0, preferably less than 5.0, more preferably less than 4.5, very particularly preferably less than 4.0 and in particular less than 3.5. 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.

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, acetic, 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 or more organic and / or inorganic acids (acid mixtures). Preferably, the detergents or cleaners contain one or two acids.

Preferred washing or cleaning agents are characterized in that they contain citric acid and at least one further acid, wherein the weight fraction of citric acid in the acid mixture of two or more acids at least 50 wt .-%, preferably 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 .-%, based on the acids contained, is.

If the invention contains only one acid, this acid is preferably citric acid or acetic acid. The content of the agent in this one acid is then preferably between 15 and 60% by weight, particularly preferably between 18 and 50% by weight, very particularly preferably between 21 and 40% by weight and in particular between 24 and 30% by weight. ,

With particular preference, the inventive cleaning or care agents additionally contain at least one surfactant from the group of anionic, cationic and amphoteric surfactants. The 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. "Liquid" thus refers to any state which 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 more than 60% by weight, more preferably more than 80% by weight and in particular more than 90% by weight, of C12 to C14 hydrocarbons, in each case on the total weight of the mixture, preferably with a boiling range of 81 to 110 ° C.

The proportion by weight of the organic solvents in the total weight of compositions according to the invention is preferably between 0.1 and 7% by weight, preferably between 0.1 and 5% by weight and in particular between 0.1 and 3% by weight.

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

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, disintegration aids, fragrances and perfume carriers.

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

Recipe 1:

ingredient Weight fraction (wt .-%) Nonionic surfactant (A) 0.1 to 4.0 Nonionic surfactant (B) 0.01 to 2.0 Org. Acid 15 to 30 thickener 0.05 to 1.0 Org. Solvent 0.1 to 7.0 fragrances 0 to 0.5 Other ingredients 0 to 10 water rest

Recipe 2:

ingredient Weight fraction (wt .-%) Nonionic surfactant (A) 0.1 to 4.0 Nonionic surfactant (B) 0.01 to 2.0 citric acid 15 to 30 thickener 0.05 to 1.0 glycerin 0.1 to 7.0 fragrances 0 to 0.5 Other ingredients 0 to 10 water rest

Cleaning or care eyes, which have been prepared from water, the agent according to the invention and greasy impurities, separate due to the increased emulsifying capacity of the agent much later than corresponding alkalis, which were obtained using known means of the prior art, preferably no longer in several phases, ie 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%.

Due to the unusually good emulsifying ability of the agents according to the invention, they are suitable, as mentioned at the beginning, in particular for the removal of greasy or oily stains. Another object of the present application is therefore the use of a washing or cleaning agent according to the invention for the removal of greasy or oily stains.

An additional subject 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 for cleaning the interior of dishwashers.

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 that the consumer applies the agent directly from a storage bottle or a storage package on the surface to be cleaned. However, at least for cleaning and / or caring for dishwashers or dishwashers, it is preferred that the consumer introduce the agent into the machine in a prefabricated dosing unit, such as a tablet, a pouch with a solid or liquid filling or a small bottle, without risking it to be exposed to skin contact with the agent.

This dosing unit comprises, especially when using liquid agents for cleaning the interiors of washing machines or dishwashers between 100 to 400 ml, preferably between 200 to 300 ml. Depending on the application, it may also be advantageous to provide smaller dosing units, so that the consumer lower May use amounts or depending on the state of the surface, the average amount by simultaneous use of 2, 3, 4, 5 or 6 dosing units can vary.

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 to remove the closure part, for example, 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 machine interior. 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, more 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.

Examples:

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

a) recipes

Recipe ingredient Recipe 1 Recipe 2 Recipe 3 nonionic surfactant (A) 1.5 1.5 1.5 nonionic surfactant (B) 30% - 0.6 0.4 nonionic surfactant (C) 0.6 - - Citric acid 1H ₂ O 25.0 25.0 25.0 Glycerin 86% 2.5 2.5 2.5 C ₃ -alkylbenzenesulfonate 40% 6.0 6.0 6.0 Perfume 0.2 0.2 0.2 thickener 0.35 0.35 0.35 Sodium hydroxide 50% 2.44 2.44 2.44 water rest rest rest nonionic surfactant (A): C ₁₂ -C ₁₄ fatty alcohol · 5 EO · 4 PO
nonionic surfactant (B): C ₁₂ -C ₁₄ dimethylamine oxide
nonionic surfactant (C): C ₁₆ -C ₁₈ fatty alcohol · 30 EO

b) Pump Simulation Test

This test 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 2.5 mL of the formulation with 47.5 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 1 minute 1 mL 0.5 mL 0.5 mL 3 minutes 5mL 1.5 2mL 5 minutes 8 mL 3mL 5mL

It can be seen from the measurement results that the formulations 2 and 3 according to the invention have a significantly improved emulsifying ability compared to the comparative example, despite the small total amounts of nonionic surfactants. At the same time, these formulations also significantly improve performance when removing soiling containing grease or oil. This is especially true for the cleaning of hard surfaces.

Claims (15)

1. A washing or cleaning agent, comprising

   a) 0.1 to 4 wt % of a non-ionic surfactant (A) of the general Formula R¹O[CH₂CH(R²)O]_xR³, in which

   - R¹ and R³ independently of one another stand for a linear or branched, saturated or mono or polyunsaturated, functionalised or unfunctionalised hydrocarbon group containing 2 to 26 carbon atoms, wherein at least one of the groups R¹ and R³ does not stand for H;

   - R² stands for H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl group;

   - x stands for values between 1 and 140, wherein each R² can be different;

   b) 0.02 to 2 wt % of a non-ionic surfactant (B) from the group of the C₈-C₂₂ amine oxides;

   c) 0.05 to 1 wt % of a natural or totally synthetic organic thickener;

   d) 10 to 90 wt % of one or more inorganic or organic acid(s).
2. Washing or cleaning agent according to claim 1, characterised in that the weight fraction of the non-ionic surfactant (A) is between 0.1 and 3 wt %, preferably between 0.2 and 2.5 wt % and particularly between 0.4 and 2.0 wt %.
3. Washing or cleaning agent according to one of the previous claims, characterised in that the non-ionic surfactant (A) includes a surfactant of the general Formula R¹O[CH₂CH(R²)O]_xH, in which

   - R¹ stands for a linear or branched, aliphatic hydrocarbon group containing 4 to 20 carbon atoms, preferably containing 12 to 20 carbon atoms and in particular containing 12 to 18 carbon atoms;

   - R² stands for H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl group, in particular for H or a methyl group, wherein each R² can be different; and

   - x stands for values between 1 and 140, preferably 1 and 120 and in particular 1 and 90.
4. Washing or cleaning agent according to one of the previous claims, characterised in that the non-ionic surfactant (A) includes a surfactant of the general Formula R¹O[CH₂CH(R²)O]_xCH₂CH(OH)R³, in which

   - R¹ and R³ independently of one another stand for a linear or branched, saturated or a mono or polyunsaturated, functionalised or unfunctionalised hydrocarbon group containing 2 to 24 carbon atoms;

   - R² stands for H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl group;

   - x stands for values between 1 and 140, wherein each R² can be different.
5. Washing or cleaning agent according to one of the previous claims, characterised in that the weight fraction of the non-ionic surfactant (B) is between 0.05 and 1 wt %.
6. Washing or cleaning agent according to one of the previous claims, characterised in that the non-ionic surfactant (B) includes a surfactant of the general Formula R¹R²R³N-O, in which

   - R¹ and R² independently of one another stand for a methyl, ethyl or propyl group; and

   - R³ stands for a branched carbon group containing 10 to 22, preferably 12 to 18 carbon atoms.
7. Washing or cleaning agent according to one of the previous claims, characterised in that the weight ratio of the surfactants (A) and (B) is between 30:1 and 1:1, preferably between 20:1 and 2:1 and in particular between 15:1 and 4:1.
8. Washing or cleaning agent according to one of the previous claims, characterised in that it comprises between 13 and 70 wt %, particularly preferably between 16 and 50 wt %, quite particularly preferably between 19 and 40 wt % and in particular between 22 and 30 wt % of one or more inorganic or organic acid(s).
9. Washing or cleaning agent according to one of the previous claims, characterised in that it comprises one or more organic or inorganic acid(s) 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, sulfaminic acid, phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, cyanuric acid.
10. Washing or cleaning agent according to one of the previous claims, characterised in that it comprises citric acid as well as at least one additional acid and that the weight fraction of the citric acid in the acid mixture of two or more acids is at least 50 wt %, advantageously 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 comprised acids.
11. Washing or cleaning agent according to one of the previous claims, characterised in that a 1 wt % concentrated solution of the agent in water (20 °C) exhibits a pH value below 6, preferably between 3 and 6.
12. Washing or cleaning agent according to one of the previous claims, characterised in that it comprises an anionic surfactant from the group of the alkylphenoxybenzene 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, monoglycerine sulfates, preferably from the alkylbenzene sulfonates.
13. Washing or cleaning agent according to one of the previous claims, characterised in that it possesses, relative to the total weight of the washing or cleaning agent, between 10 and 95 wt %, advantageously between 20 and 80 wt %, preferably between 30 and 80 wt % and in particular between 40 and 70 wt % of a liquid carrier, wherein said carrier is preferably selected from the group that besides water additionally includes the alcohols, wherein a water/alcohol mixture and in particular a water/glycerine mixture are particularly preferred.
14. Use of a washing or cleaning agent according to one of the previous claims for eliminating stains that contain fat or oil.
15. Use of a washing or cleaning agent according to one of the previous claims for cleaning and caring for hard surfaces, preferably of washing machines or automatic dishwashers, in particular for cleaning the interiors of automatic dishwashers.