WO2003066797A1 - Cleaning paste - Google Patents

Abstract

A paste, comprising at least one hydrophobic component, is produced by mixing of the components and can be offered as a product with an application device and used as a stain removing agent for contaminated textiles or as a cleaning agent for hard surfaces or skin. For stain removal on textiles the paste is applied to the stain, optionally rubbed in, then, after a short period to take effect is optionally removed by rinsing with water and the textile piece subjected to washing.

Description

 , Cleaning paste "

The invention relates to a cleaning paste and the use of the paste for stain pretreatment and for cleaning hard surfaces and a method for stain removal. The invention further relates to a product containing a paste and a method for producing a paste.

Stain treatment, in particular sensitive textiles and textiles contaminated with oil or grease stains, is becoming increasingly important. It has been shown that stubborn stains containing grease and oil, particularly at low washing temperatures, are often insufficiently removed by the detergent used. In order to completely remove such stains, the use of non-polar solvents (cleaning gasoline, chlorinated hydrocarbons etc.) has proven itself in chemical cleaning.

For use in the home, there are cleaning sprays, which usually contain large amounts of solvents (e.g. hydrocarbons) for local stain pretreatment. However, the disadvantage of these products is the creation of ring-shaped edges which remain as a stain after washing. These are caused by the chromatography effect of the solvents, which transport the loosened dirt from the application point of the solvent to the outside and dry there. The aerosol sprays described above are mostly based on an anhydrous or low-water formulation, which also causes high raw material costs. The prior art also describes a large number of stain pretreatment agents which are present as microemulsions or as gels.

Microemulsions are thermodynamically stable mixtures of two immiscible liquids, usually water and a hydrocarbon (mixture), and surfactants as emulsifiers. A co-emulsifier may also be required to form a microemulsion. In contrast to macroemulsions, microemulsions only occur in a certain composition range of the multicomponent system and only exist in a defined temperature interval. The droplet size distribution in the emulsions is often used to differentiate between the two forms of emulsion. Macroemulsions generally have droplet sizes of at least 100 nm, while the microemulsions have droplet sizes below 50 nm. International application WO 97/23192 describes sugar surfactant-containing O / W microemulsions. These contain an oil phase based on mono- and / or diesters and / or fatty acid triglycerides, fatty acid N-alkylpolyhydroxyalkylamides and / or alkyl and / or alkenyl oligoglycosides as emulsifiers, and partial esters of fatty acids with polyols as co-emulsifiers. The microemulsions obtained are used in skin and body care products. However, use as a textile pretreatment agent or cleaning agent for hard surfaces is not described.

European application EP 0 801 130 describes microemulsions consisting of oil, water, surfactant and cosolvent. A surfactant system consisting of alkyl polyglycoside and optionally an anionic, nonionic or betaine auxiliary surfactant is used as the surfactant, an oligoester of short-chain, polybasic carbon or hydroxycarboxylic acids and the oils used in cosmetics, including paraffin oils, as an oil component. The use of these low-viscosity microemulsions for both skin cleaning and hard surface cleaning is described, but not as a stain pretreatment agent.

DE 196 12 811 shows that microemulsions are suitable as pretreatment agents for heavily oil and grease soiled textiles. Agents are described which contain a combination of nonionic surfactants from the group of ethoxylated fatty alcohols, water and one or more organic solvents from the group of aliphatic and aromatic hydrocarbons, preferably an n-paraffin mixture. Small amounts of a short-chain alcohol can also be present as a so-called cosurfactant. The stain pretreatment agent is primarily intended for use in commercial laundries; it is brought into contact with the entire wash liquor in large quantities and should be reusable several times.

WO 95/27034 also describes a microemulsion which contains a surfactant system composed of short-chain ethoxylated nonionic surfactants, a non-aqueous solvent and water. The composition should be used both for pretreatment of soiled textiles and for main wash.

The application EP 0 137 616 describes liquid detergents which contain customary washing-active substances and fat-dissolving solvents and as microemulsions be formulated. They are used primarily in textile washing, also as a pretreatment agent, whereby not only greasy dirt but also particulate contaminants are to be removed. Aliphatic or alicyclic (halogen) hydrocarbons are used as solvents here, especially paraffins and monoterpenes. Fatty acids and soaps serve, among other things, as stabilizers for the microemulsion. Anionic, nonionic, amphoteric and zwitterionic surfactants are suitable as washing-active substances, alkoxylated alcohols and alkylphenols being used as nonionic surfactants. Other uses of the agents described here are hard surface cleaners, carpet and all-purpose cleaners.

GB 2194547 describes stain pretreatment agents for textile washing, which can be microemulsions, solutions or gels. These contain C _{10- 8} -alkanes, ethoxylated fatty alcohols as nonionic surfactants, water and optionally also amine oxides or alkylphenol ethoxylates, C _10- 18 alcohols as cosurfactants, cosolvents and other auxiliaries. The agents described can also be used to clean hard surfaces, for example made of plastic, glass or metal, from grease and oil-containing contaminants.

Conventional spray pretreatment agents often contain large amounts of organic solvents, e.g. Benzine. This has the disadvantage that the contaminants to be removed are dissolved in the solvent by means of a chromatography effect and are transported to the outside from the application point of the solvent before the solvent evaporates, so that a wreath-like stain remains. Liquid detergents often run on the piece of textile to be cleaned, so that they often cannot optimally solve their cleaning task because of the short dwell time on the actual stain.

In the case of classic pretreatment agents based on organic solvents, deactivation of the detergent in the subsequent washing process can also be observed, since the surfactants present in the detergent are largely necessary for emulsifying the solvent.

When conventional ethoxylated nonionic surfactants are used as emulsifiers, microemulsions are often only stable over a narrow temperature range, so that temperature fluctuations which occur during storage or transport become cloudy or segregation of the product. The temperature dependence of the phase behavior of microemulsions can also lead to drastic changes in other properties, for example viscosity, in the course of the temperature, so that handling can be negatively influenced. From an ecological point of view, the fullest possible degradability of the surfactants used and the lowest possible content of organic solvents is desirable.

DE 44 14 815 A1 describes concentrated aqueous sugar surfactant pastes with a reduced tendency to crystallize. The pastes can be used as cleaning agents and have a content of 75 to 99% by weight of alkyl oligoglycosides and / or fatty acid-N-alkylpolyhydroxyalkylamides and 1 to 25% by weight of alkyl sulfates.

However, the pastes of the prior art have a significantly reduced cleaning performance, in particular with regard to oil and grease stains.

The present invention is therefore based on the object of providing a stain cleaning agent containing hydrophobic components which avoids the formation of rings during the stain treatment and also has a high cleaning performance. It was also the task to develop a water-based and therefore inexpensive formula.

Surprisingly, it has been found that hydrophobic components can be stably incorporated into pastes, as a result of which detergents which can be applied in a targeted manner and have a high cleaning performance are made available.

The invention is therefore in a first embodiment, a paste containing at least one hydrophobic component.

Pastes are liquids with a doughy consistency. Pastes have a yield point and a high zero shear viscosity. Pastes preferred in the context of this invention meet the following conditions: 200 ml of the paste are placed in an open polyethylene cylinder with an inside diameter of 49 mm. One end of the cylinder has a bottom with a 5.8 mm diameter outlet centrally located in the bottom of the cylinder. It is within the scope of the invention Pastes are preferred if at 20 ° C within 5 seconds no more than 5 g of the paste run out of the cylinder through the outlet opening.

Contrary to expectations, it has surprisingly been found that the incorporation of hydrophobic components in liquid aqueous surfactant formulations can produce pastes which have the properties desired according to the invention. By incorporating the hydrophobic components, the viscosity of the formulations increases rapidly, so that pasty systems can be obtained in a simple manner. The hydrophobic components also enhance cleaning performance, especially with oil and grease stains.

The pastes according to the invention therefore contain at least one hydrophobic component as an essential component.

Hydrophobic components are understood to mean hydrophobic substances which are only sparingly soluble or not soluble in water. The hydrophobic components to be used according to the invention preferably have an HLB value (hydrophilic / lipophilic balance; Römpp Lexikon Chemie, 2nd version (electronic)) of less than 3.

All known oils, fats and waxes of mineral, animal, vegetable and synthetic origin are suitable as hydrophobic components. Because of their strong cleaning performance, preference is given to hydrophobic components which are selected from the group of paraffins or isoparaffins, preferably linear and / or branched and / or saturated and / or unsaturated C ₁₀ -C ₃₀ hydrocarbons, in particular C ₁₀ -C _2u - Hydrocarbons and any mixtures thereof. The hydrocarbons are advantageously in liquid form and can therefore be easily incorporated into the formulations for forming the paste according to the invention. Suitable hydrocarbons are primarily paraffins and isoparaffins such as isohexadecane or n-dodecane, but also others, for example triisobutene, pentapropylene or 1,3-di (2-ethylhexyl) cyclohexane.

Fatty acid esters with a total of 12 to 26 carbon atoms and any mixtures thereof are also suitable. Suitable fatty acid esters are, for example, substances such as methyl oleate, methyl palmitate, ethyl oleate, isopropyl myristate, n-hexyl laurate, n-butyl stearate, glycerol monooleate, glycerol monostearate and cetyl / stearyl isononanoate. In a preferred embodiment, isoparaffin mixtures are used as the hydrophobic component. For this purpose, for example, the under the trade names Cobersol ^® VP1 or Cobersol ^® B 105 (CBR) available C _16-2 o-isoparaffins or the Cι _2- ι isoparaffin mixture Isopar ^® M (Exxon Mobil) in question.

Other substances that can be used as hydrophobic components are dialkyl ethers with a total of 12-24 carbon atoms. Dialkyl ethers which are particularly suitable are, above all, the aliphatic dialkyl ethers, each having 6 to 10 carbon atoms per alkyl group. In addition, all other known oil components such as petroleum jelly, vegetable oils, synthetic triglycerides such as e.g. Glyceryl tricaprylate, but also fats and waxes and silicone oils can be contained in the pastes according to the invention. In a preferred embodiment of the invention, the pastes contain at least one hydrophobic component in an amount of up to 30% by weight, preferably up to less than 10% by weight, particularly preferably 0.5 to 9% by weight, in particular 1 5 to 8 wt .-%, each based on the entire paste.

In order to improve the cleaning performance, in a preferred embodiment the paste according to the invention can additionally contain surfactants, preferably selected from the groups of nonionic and / or anionic and / or amphoteric surfactants.

The total content of surfactants is preferably below 40% by weight, particularly preferably below 35% by weight, in each case based on the total paste.

Preferred nonionic surfactants are alkoxylated, advantageously ethoxylated and / or propoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) and / or 1 to 10 moles of propylene oxide (PO) per mole of alcohol used. Particularly preferred are C ₈ -C ₁₆ alcohol alkoxylates, advantageously ethoxylated and / or propoxylated C ₁₀ -C ₁₅ alcohol alkoxylates, in particular C ₁₂ -C ₁₄ alcohol alkoxylates, with a degree of ethoxylation between 2 and 10, preferably between 3 and 8, and / or a degree of propoxylation between 1 and 6, preferably between 1.5 and 5. The alcohol radical can preferably be methyl-branched linearly or particularly preferably in the 2-position or contain linear and methyl-branched radicals in the mixture, as is usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -alcohols with 3 EO or 4 EO, C ₉ -n alcohol with 7 EO, C ₁₃ .i5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ .ι ₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12- ι ₄ -Alcohol with 3 EO and C _12-18 - Alcohol with 5 EO. The degrees of ethoxylation and propoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates and propoxylates have a narrow homolog distribution (narrow range ethoxylates / propoxylates, NRE / NRP). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In a preferred embodiment, the pastes according to the invention additionally contain at least one nonionic surfactant, preferably a nonionic surfactant based on an alkoxylated fatty alcohol, particularly preferably an ethoxylated and / or propoxylated C ₁₀ -C ₂ o fatty alcohol, most preferably a C ₁₂ -C ₁₈ fatty alcohol with less than 10 ethoxylate groups and / or propoxylate groups, in particular a C ₁₂ -C ₁₈ fatty alcohol with less than or equal to 7 ethoxylate units.

End group-capped fatty alcohol alkoxylates in which the end groups are etherified with alkyl groups, preferably methyl or ethyl groups, are particularly preferred in the context of this invention. These nonionic surfactants are particularly suitable for bleach-containing formulations.

The content of nonionic surfactant based on an alkoxylated fatty alcohol is preferably below 35% by weight, preferably below 26% by weight, particularly preferably between 4 and 25% by weight, in particular between 15 and 25% by weight, each based on the entire paste.

Also suitable are alkoxylated amines, advantageously ethoxylated and / or propoxylated, in particular primary and secondary amines, preferably having 1 to 18 carbon atoms per alkyl chain and an average of 1 to 12 mol ethylene oxide (EO) and / or 1 to 10 mol propylene oxide (PO) per Mole of amine.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as they are for example in the Japanese patent application avoidance JP 58/217598 or which are preferably produced by the method described in the international patent application WO-A-90/13533.

So-called gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are generally separated from one another by a so-called “spacer”. This spacer is generally a carbon chain which should be long enough that the hydrophilic groups are sufficiently far apart that they can act independently of one another. Such surfactants are distinguished generally due to an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water, but in exceptional cases the term gemini surfactants means not only dimeric but also trimeric surfactants.

Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE-A-43 21 022 or dimer alcohol bis and trimeral alcohol tris sulfates and ether sulfates according to international patent application WO-A-96/23768. End group-capped dimeric and trimeric mixed ethers according to German patent application DE-A-195 13 391 are distinguished in particular by their bi- and multifunctionality. The end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes.

Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides, as described in international patent applications WO-A-95/1953, WO-A-95/19954 and WO-A-95/19955, can also be used.

Other suitable surfactants are polyhydroxy fatty acid amides of the following formula,

R ⁵

I R-CO-N- [Z] in the RCO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ⁵ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 up to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which are usually obtained by reductive amination of a reducing sugar can be obtained with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

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

R ⁶ -OR ⁷

R-CO-N- [Z] in the R for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ⁶ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ⁷ represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C ₁ -alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical, the alkyl chain of which has at least two hydroxyl groups is substituted, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Because of their good washing performance and their easy incorporation into the pastes according to the invention, in a preferred embodiment the pastes contain at least one alkyl glycoside as a nonionic surfactant, preferably in amounts of up to 20% by weight, particularly preferably between 1 and 15% by weight, in particular between 5 and 13% by weight.

Alkyl and alkenyl oligoglycosides are known nonionic surfactants which follow the formula (I), R ¹ O- [G] _p , in which R ^{1 is} an alkyl and / or alkenyl radical having 8 to 22 carbon atoms, G is a sugar radical 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP-A1-0 301 298 and WO 90/03977. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.

The index number p in the general formula (I) indicates the degree of oligomerization (DP degree), i.e. the distribution of mono- and oligoglycosides is on and stands for a number between 1 and 10. While p must always be an integer in a given compound and here can take on the values p = 1 to 6, the value p is for a certain alkyl - oligoglycoside is an average, which is usually a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.

The alkyl or alkenyl radical R ¹ can be derived from alcohols, preferably from those with a terminal hydroxyl group (primary alcohols) having 8 to 22, in particular 8 to 16, carbon atoms. Typical examples are caprylic alcohol, capric alcohol, undecyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, and mixtures thereof, for example, mixtures of them, beucyl alcohol such as Er, for example their mixtures the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides based on C ₁₂₁₆ - and C _8/10 - fatty alcohol cuts with a DP degree of 1 to 3, as they are available from the company Cognis, for example, under the trade name Plantacare ^® 1200 UP or Glucopon ^® 215 CSUP. These are often offered commercially as 50 percent solutions.

In addition, the pastes according to the invention can optionally contain amphoteric surfactants. In addition to numerous mono- to triple-alkylated amine oxides, such as, for example, N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, the betaines represent an important class.

Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation, of aminic compounds. The starting materials are preferably mixed with halocarboxylic acids or their salts, in particular especially condensed with sodium chloroacetate, forming one mole of salt per mole of betaine. The addition of unsaturated carboxylic acids, such as acrylic acid, is also possible. Regarding the nomenclature and in particular the distinction between betaines and "real" amphoteric surfactants, reference is made to the contribution by U.PIoog in Seifen-Öle-Fette-Wwachs, 108, 373 (1982). Further overviews on this topic can be found for example by A. O'Lennick et al. in HAPPI, Nov. 70 (1986), S. Holzman et al. in tens. Surf.Det. 1986, 23: 309, R.Bibo et al. in Soap Cosm.Chem.Speα, Apr. 46 (1990) and P.EIIis et al. in Euro Cosm. 1, 14 (1994). Examples of suitable betaines are the boxyalkylation products of secondary and in particular tertiary amines which follow the formula (I), R ²

R ¹ -N- (CH ₂ ) _n COOX (I)

in which R ¹ for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R ² for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ³ for alkyl radicals with 1 to 4 carbon atoms, n for numbers from 1 to 6 and X for a Alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexyl methylamine, amine-hexyldimethylamine, octyldimethylamine, decyldimethylamine, Dodecylmethyl-, dodecyldimethylamine, Dodecylethylmethylamin, C ristyldimethylamin _12/1 -Kokosalkyldimethylamin, mu-, cetyldimethylamine, stearyldimethylamine yldimethylamin, stearyl, olefinsulfonates, C _{16 /} ιβ- Tallow alkyl dimethylamine and their technical mixtures.

Carboxyalkylation products of amidoamines which follow the formula (II), R ^2, are also suitable

R ⁴ CO-NH- (CH ₂ ) _m -N- (CH ₂ ) _n COOX (II)

in which R ⁴ CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, m represents numbers from 1 to 3 and R ² , R ³ , n and X have the meanings given above. Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeosteal acid rinic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of C _{8 18} coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.

Furthermore, suitable starting materials for the betaines to be used in the context of the invention are also imidazolines which follow the formula (III)

in which R ^{5 is} an alkyl radical having 5 to 21 carbon atoms, R ^{6 is} a hydroxyl group, an OCOR ⁵ or NHCOR ⁵ radical and m is 2 or 3. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines, such as, for example, aminoethylethanolamine (AEEA) or diethylenetriamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines. Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C _{12 14} coconut fatty acid, which are subsequently betainized with sodium chloroacetate.

Furthermore, the pastes according to the invention can optionally contain one or more anionic surfactants.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates of the type obtained, for example, from C _12-18 monoolefins with an end or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

The alk (en) yl sulfates are the alkali and, in particular, the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from 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 this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-2 ι alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C _12-18 -Fatty alcohols with 1 to 4 EO are suitable. These so-called alkyl ether sulfates are particularly preferably used in the pastes according to the invention.

Other 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 especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8- ι ₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves. Here again are sulfosuccinates, the fatty alcohol residues of which are different from ethoxylated fatty alcohols with derive narrow homolog distribution, particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts. Another class of anionic surfactants is the class of ether carboxylic acids which can be obtained by reacting fatty alcohol ethoxylates with sodium chloroacetate in the presence of basic catalysts. They have the general formula: R ¹⁰ 0- (CH ₂ -CH ₂ -O) _p -CH ₂ - COOH with R ¹⁰ = Cι-Cι ₈ and p = 0.1 to 20. Ether carboxylic acids are insensitive to water hardness and have excellent surfactant properties , Production and application are, for example, in soaps, oils, fats, waxes 101, 37 (1975); 115, 235 (1989) and Tenside Deterg. 25, 308 (1988).

Suitable anionic surfactants are, for example, the partial esters of di- or polyhydroxyalkanes, mono- and disaccharides, polyethylene glycols with the ene adducts of maleic anhydride with at least monounsaturated carboxylic acids with a chain length of 10 to 25 carbon atoms with an acid number of 10 to 140, which are described in DE 38 08 114 A1 (Grillo-Werke) and EP 0 046 070 A (Grillo-Werke), to which reference is made in this regard and the two contents of which are hereby incorporated into this application.

In addition to an unbranched or branched, saturated or unsaturated, aliphatic or aromatic, acylclic or cyclic, optionally alkoxylated alkyl radical, preferred anionic surfactants have 4 to 28, preferably 6 to 20, in particular 8 to 18, particularly preferably 10 to 16, extremely preferably 12 to 14 carbon atoms, two or more anionic, in particular two, acid groups, preferably carboxylate, Sulfonate and / or sulfate groups, especially a carboxylate and a sulfate group. Examples of these compounds are the α-sulfofatty acid salts, the acylglutamates, the monoglyceride disulfates and the alkyl ethers of glycerol disulfate, and in particular the monoesterified sulfosuccinates described below.

Particularly preferred anionic surfactants are the sulfosuccinates, sulfosuccinamates and sulfosuccinamides, in particular sulfosuccinates and sulfosuccinamates, most preferably sulfosuccinates. The sulfosuccinates are the salts of the mono- and diesters of sulfosuccinic acid HOOCCH (SO ₃ H) CH ₂ COOH, while the sulfosuccinamates are the salts of the monoamides of sulfosuccinic acid and the sulfosuccinamides are the salts of Understands diamides of sulfosuccinic acid. A. Domsch and B. Irrgang in Anionic surfactants: organic chemistry (edited by HW Stäch; Surfactant science series; volume 56; ISBN 0-8247-9394-3; Marcel Dekker, Inc., New York provide a detailed description of these known anionic surfactants 1996, pp. 501-549).

The salts are preferably alkali metal salts, ammonium salts and mono-, di- or trialkanolammonium salts, for example mono-, di- or triethanolammonium salts, in particular lithium, sodium, potassium or ammonium salts, particularly preferably sodium or ammonium salts, most preferably sodium salts.

In the sulfosuccinates, one or both carboxyl groups of sulfosuccinic acid are preferably with one or two identical or different unbranched or branched, saturated or unsaturated, acylclic or cyclic, optionally alkoxylated alcohols with 4 to 22, preferably 6 to 20, in particular 8 to 18 , particularly preferably 10 to 16, most preferably 12 to 14 carbon atoms esterified. Particularly preferred are the esters of unbranched and / or saturated and / or acyclic and / - or alkoxylated alcohols, in particular unbranched, saturated fatty alcohols and / - or unbranched, saturated, with ethylene and / or propylene oxide, preferably ethylene oxide, alkoxylated fatty alcohols with a degree of alkoxylation from 1 to 20, preferably 1 to 15, in particular 1 to 10, particularly preferably 1 to 6, extremely preferably 1 to 4. In the context of the present invention, the monoesters are preferred over the diesters. A particularly preferred sulfosuccinate is sulfosuccinic acid, lauryl polyglycol ester di-sodium salt (lauryl-EO sulfosuccinate, di-Na salt; INCI Disodium Laureth sulfosuccinate), which, for example, as Tego ^® sulfosuccinate F 30 (Goldschmidt) with a sulfosuccinate content of 30 wt .-% is commercially available. In the sulfosuccinamates or sulfosuccinamides, one or both of the carboxyl groups of sulfosuccinic acid preferably form with a primary or secondary amine which contains one or two identical or different, unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alkyl radicals with 4 to 22, preferably 6 to 20, in particular 8 to 18, particularly preferably 10 to 16, most preferably 12 to 14 carbon atoms, a carboxamide. Unbranched and / or saturated and / or acyclic alkyl radicals, in particular unbranched, saturated fatty alkyl radicals, are particularly preferred.

Also suitable are, for example, the following sulfosuccinates and sulfosuccinamates designated according to INCI, which are described in more detail in the International Cosmetic Ingredient Dictionary and Handbook: ammonium dinonyl sulfosuccinate, ammonium lauryl sulfosuccinate, diammonium dimethicone copolyol sulfosuccinate, diammonium lauramido-MEA sulfosuccinate, sulfosuccinate, diammonium Diammonium Oleamido PEG-2 Sulfosuccinate, Diamyl Sodium Sulfosuccinate, Dicapryl Sodium Sulfosuccinate, Dicyclohexyl Sodium Sulfosuccinate, Diheptyl Sodium Sulfosuccinate, Dihexyl Sodium Sulfosuccinate, Diisobutyl Sodium Sulfosuccinate, Cisuccinate Sulfosuccinate, Dioctyl Sodium Disosamino -Sulfosuccinate, Disodium Cocamido PEG-3 Sulfosuccinate, Disodium Coco- Glucoside Sulfosuccinate, Disodium Cocoyl Butyl Gluceth-10 Sulfosuccinate, Disodium C12-15 Pareth Sulfosuccinate, Disodium Deceth-5 Sulfosuccinate, Disodium Deceth-6 Su lfosuccinate, Disodium Dihydroxyethyl Sulfosuccinylundecylenate, Disodium Dimethicone Copolyol Sulfosuccinate, Disodium Hydrogenated Cottonseed Glyceride Sulfosuccinate, Disodium Isodecyl Sulfosuccinate, Disodium Isostearamido MEA-Sulfosuccinate, Disodium Isostearamido MIPA-Sulfosuccinate Disodisulfinate Disodisulfinate Lauramido PEG-2 sulfosuccinate, disodium Lauramido PEG-5 sulfosuccinate, disodium Laureth-6 sulfosuccinate, disodium Laureth-9 sulfosuccinate, disodium Laureth-12 sulfosuccinate, disodium lauryl sulfosuccinate, disodium myristamido MEA sulfosuccinolate, disodium nonoxynoxyn , Disodium Oleamido MEA-Sulfosuccinate, Disodium Oleamido MIPA-Sulfosuccinate, Disodium Oleamido PEG-2 Sulfosuccinate, Disodium Oleth-3 Sulfosuccinate, Disodium Oleyl Sulfosuccinate, Disodium Palmitamido PEG-2 Sulfosuccinate, Disodium Palmitoleamido PEG-2 Sulfosuccinate PEG-2 Sulfosuccinate A-sulfosuccinate, disodium PEG-5 lauryl citrate sulfosuccinate, disodium PEG-8 palm glycerides sulfosuccinate, disodium ricinoleamido MEA sulfosuccinate, di- sodium Sitostereth-14 Sulfosuccinate, Disodium Stearamido MEA-Sulfosuccinate, Disodium Stearyl Sulfosuccinamate, Disodium Stearyl Sulfosuccinate, Disodium Tallamido MEA-Sulfosuccinate, Disodium Tallowamido MEA-Sulfosuccinate, Disodium Tallow Sulfosuccinamate, Disodium Tridecylenes Disodium Tridecylsulfate Sulfosuccinate, Disodium Wheat Germamido MEA-Sulfosuccinate, Disodium Wheat Germamido PEG-2 Sulfosuccinate, Di-TEA-Oleamido PEG-2 Sulfosuccinate, Ditridecyl Sodium Sulfosuccinate, Sodium Bisglycol Ricinosulfosuccinate, Sodium / MEA Diacidyl Starboxy- tetrasylate- tetrasyl- ethylsulfoxy- tetrasyl- ethyl sulfosylate- tetrasyl- ethyl sulfosylate- tetrasyl- ethyl sulfosylate- tetrasuccinate sulfosuccinamates. Yet another suitable sulfosuccinamate is -alkoxypropylene i8 disodium C _16.

Cationic surfactants can also be contained in the pastes according to the invention.

Examples of such surfactants are quaternary ammonium compounds and cationic polymers, such as those used in hair care products and also in textile finishing agents.

Suitable examples are quaternary ammonium compounds of the formulas (I) and (II),

where in (I) R and R ^{1 are} an acyclic alkyl radical having 12 to 24 carbon atoms, R ^{2 is} a saturated CC ₄ alkyl or hydroxyalkyl radical, R ^{3 is} either R, R ¹ or R ² or is an aromatic radical , X ^" stands for either a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof. Examples of cationic compounds of the formula (I) are didecyldimethylammonium chloride, di-tallowdimethylammonium chloride or dihexadecylammonium chloride.

Compounds of formula (II) are so-called ester quats. Esterquats are characterized by excellent biodegradability. Here R ^{4 represents} an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds; R ⁵ represents H, OH or O (CO) R ⁷ , R ⁶ independently of R ^{5 represents} H, OH or O (CO) R ⁸ , where R ⁷ and R ⁸ each independently represent an aliphatic alkyl radical having 12 is up to 22 carbon atoms with 0, 1, 2 or 3 double bonds, m, n and p can each independently have the value 1, 2 or 3. X ^~ can be either a halide, methosulfate, methophosphate or phosphate ion, as well as mixtures of these. Compounds are preferred which contain the group O (CO) R ⁷ for R ⁵ and alkyl radicals having 16 to 18 carbon atoms for R ⁴ and R ⁷ . Compounds in which R ^{6 is} also OH are particularly preferred. Examples of compounds of the formula (II) are methyl N- (2-hydroxyethyl) -N, N-di (tallow acyl oxyethyl) ammonium methosulfate, bis (palmitoyl) ethyl hydroxyethyl methyl ammonium methosulfate or methyl-N, N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate. If quaternized compounds of the formula (II) are used which have unsaturated alkyl chains, preference is given to the acyl groups whose corresponding fatty acids have an iodine number between 5 and 80, preferably between 10 and 60 and in particular between 15 and 45 and which have a cis / trans isomer ratio (in% by weight) of greater than 30:70, preferably greater than 50:50 and in particular greater than 70:30. Commercial examples are the methylhydroxyalkyldialkoyloxyalkylammonium methosulfates sold by Stepan under the trademark Stepantex ^® or the products from Cognis known under Dehyquart ^® or the products from Goldschmidt-Witco known under Rewoquat ^® . Further preferred compounds are the diesterquats of the formula (III), which are available under the name Rewoquat® W 222 LM or CR 3099 and, in addition to the softness, also ensure stability and color protection.

R ²¹ and R ²² each independently represent an aliphatic radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.

In addition to the quaternary compounds described above, other known compounds can also be used, such as quaternary imidazolinium compounds of the formula (IV),

where R ^{9 is} H or a saturated alkyl radical with 1 to 4 carbon atoms, R ¹⁰ and R ¹¹ independently of one another each represent an aliphatic, saturated or unsaturated alkyl radical with 12 to 18 carbon atoms, R ⁰ alternatively also for O (CO) R ²⁰ , where R ^{20 is} an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, and Z is an NH group or oxygen and X ^{~ is} an anion. q can take integer values between 1 and 4.

Further suitable quaternary compounds are described by formula (V)

where R ¹² , R ¹³ and R ¹⁴ independently of one another represent a C 1-4 alkyl, alkenyl or hydroxyalkyl group, R ¹⁵ and R ¹⁶ each independently represent a Cs- ₂₈ alkyl group and r is a number between 0 and 5 is.

In addition to the compounds of the formulas (I) and (II), it is also possible to use short-chain, water-soluble, quaternary ammonium compounds, such as trihydroxyethylmethylammonium methosulfate or the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride.

Protonated alkylamine compounds which have a plasticizing effect and the non-quaternized, protonated precursors of the cationic emulsifiers are also suitable.

The quaternized protein hydrolyzates are further cationic compounds which can be used according to the invention.

Suitable cationic polymers include the polyquaternium polymers as described in the CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997), in particular the polyquaternium-6, polyquaterium-7-, also known as merquats. Polyquaternium 10 polymers (Ucare Polymer IR 400; Amerchol), polyquater nium-4 copolymers, such as graft copolymers with a cellulose skeleton and quaternary ammonium groups which are bonded via allyldimethylammonium chloride, cationic cellulose derivatives, such as cationic guar, such as guar-hydroxypropyltriammonium chloride, and similar quaternized guar derivatives (e.g. Cosmedia Guar, manufacturer: Cognis GmbH) ), cationic quaternary sugar derivatives (cationic alkyl polyglucosides), for example the commercial product Glucquat ^® 100, according to CTFA nomenclature a "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride", copolymers of PVP and dimethylaminomethacrylate, copolymers of vinylimidazole, and aminopyronolidone -polymers and copolymers.

Also employable polyquatemierte polymers (for example, Luviquat Care by BASF.), And cationic biopolymers based on chitin and derivatives thereof, for example, under the trade designation chitosan ^® (manufacturer: Cognis) polymer obtainable.

Also suitable are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Coming; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) Abil ^® -Quat 3270 and 3272 (manufacturer: Goldschmidt-Rewo; diquartary polydimethylsiloxanes, Quaternium-80), and silicone quat Rewoquat ^® SQ 1 (Tegopren ^® 6922 , Manufacturer: Goldschmidt-Rewo).

Compounds of the formula (VI) which can also be used are

the alkylamidoamines can be in their non-quaternized or, as shown, their quaternized form. R ¹⁷ can be an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds, s can assume values between 0 and 5. R ¹⁸ and R ¹⁹ each independently represent H, d-r alkyl or hydroxyalkyl. Preferred compounds are fatty acid amidoamines such as the stearylamidopropyldimethylamine available under the name Tego Amid ^® S 18 or the 3-tallowamidopropyl trimethylammonium methosulfate available under the name Stepantex ^® X 9124, which, in addition to having a good conditioning effect, are also characterized by color transfer inhibition distinguish themselves through their good biodegradability. Alkylated quaternary ammonium compounds, of which at least one alkyl chain is interrupted by an ester group and / or amido group, are particularly preferred, in particular N-methyl-N (2-hydroxyethyl) -N, N- (ditallcyloxyethyl) ammonium methosulfate and / or N-methyl -N (2-hydroxyethyl) -N, N- (palmitoyloxyethyl) ammonium methosulfate.

In a preferred embodiment, the pastes according to the invention additionally contain an emulsifier, preferably selected from the group of polar organic solvents, in particular from the group of alcohols, glycols and glycol ethers.

Emulsifiers which can be used in the pastes according to the invention come, for example, from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers. The solvents are preferably selected from water-soluble monohydric or polyhydric alcohols having 1 to 8 carbon atoms, e.g. B. methanol, ethanol, n- or i-propanol, butanols, n-hexanol, n-octanol, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether , Ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, butoxy propoxy propanol (BPP), dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl -, or -ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents. Monohydric alcohols are preferably used, particularly preferably ethanol in amounts of 0 to 30% by weight, preferably 0 to 14.5%, and / or n-hexanol / n-octanol in amounts of 0-10%, preferably 0-5%.

In order to achieve inexpensive formulations which are as low in solvents as possible, it has proven to be advantageous if the water content is above 20% by weight, preferably above 50% by weight, in each case based on the total paste.

The pastes can optionally contain bleaching agents. Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaching agents that can be used are, for example, peroxopyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as persulfates or wise persulfuric acid. The urea peroxohydrate percarbamide can also be used, which can be described by the formula H ₂ N-CO-NH ₂ Η ₂ O ₂ . In particular, when the pastes are used for cleaning hard surfaces, for example in automatic dishwashing, they can, if desired, also contain bleaches from the group of organic bleaches, although their use is also possible in principle for agents for textile washing. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are peroxybenzoic acid and its ring-substituted derivatives, such as alkyl peroxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, the aliphatic or substituted aliphatic peroxyacids, such as peroxlauric acid, peroxystearic acid, ε-phthalimidoperoxycaproidoxy, hexthalene, phthaloxy, phthalate o-Carboxybenzamidoperoxycapronsäure, N-Nonenylami- doperadipinsäure and N-nonenylamidopersuccinates, and aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, DIPE roxysebacinsäure, diperoxybrassylic acid, diperoxyphthalic acids, the 2-Decyldiperoxybu- tan-1 4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid) can be used.

The bleaching agents are preferably coated to protect them against premature decomposition. The incorporation of hydrogen peroxide and / or phthalimidoperoxicaproic acid has proven to be particularly advantageous in aqueous pasty systems.

The builder and / or pH regulators which may be present in the pastes according to the invention are preferably those which are selected from the group of organic di-, tri- or polycarboxylic acids and their salts, in particular citric acid and / or sodium citrate.

Other suitable builders are crystalline, layered sodium silicates which have the general formula NaMSi _x O _{2x +} ι 'H ₂ O, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are. Such crystalline layered silicates are described, for example, in European patent application EP-A 0 164514. Preferred crystalline phyllosilicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ß- and δ-sodium disilicate

Na ₂ Si ₂ O ₅ yH ₂ O is preferred, with β-sodium disilicate for example by the process can be obtained, which is described in the international patent application WO-A 91/08171.

Amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Aügusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ O '(1-n) K ₂ 0 ^■ Al ₂ 0 ₃ ^■ (2 - 2.5) SiO ₂ ^■ (3.5 - 5.5) H ₂ O can be described. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C-fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course, it is also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

Other suitable builders are, for example, citric acid, alkali metal citrates, gluconates, nitrilotriacetates, carbonates and bicarbonates, in particular sodium citrate, gluconate and nitrilotriacetate as well as sodium and potassium carbonate and bicarbonate, and mixtures thereof. These also include the salts of glutaric acid, succinic acid, adipic acid, tartaric acid and benzene hexacarboxylic acid as well as phosphonates and phosphates, for example sodium hexametaphosphate. The paste can contain builders in amounts, based on the composition, of 0 to 30% by weight.

The pastes according to the invention preferably have a transparent appearance and, at 20 ° C., have a viscosity of above 10,000 mPas, preferably above 15,000 mPas and in particular above 20,000 mPas (measured with a Brookfield RVT viscometer, 20 revolutions per minute, spindle 6) ,

The pastes can also all other thickeners commonly used in detergents and cleaning agents, for example organic natural thickeners (agar-agar, carrageenan, xanthan gum and its derivatives, tragacanth, acacia, alginates, pectins, polyoses, guar flour, locust bean gum flour, starch , Dextrins, gelatin, casein), organic modified natural substances (carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and the like, core meal ether), organic fully synthetic thickeners (polyacrylic and polymethacrylic compounds, Contain vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides) and inorganic thickeners (polysilicic acids, clay minerals such as montmorillonites, zeolites, silicas). However Glycerinmonoester are preferably of fatty acids, more preferably glycerol monooleate, which is offered under the trade name ^® Monomuls 90-O18 by the company Cognis, for example, glycerol monostearate, for example that available from Cognis Cutina GMS ^®, and mixtures thereof.

In addition to the previously mentioned components, other auxiliaries may also be present in the paste according to the invention. For example, enzymes, perfumes / fragrances, dyes, defoamers, bleach activators, electrolytes, pH regulators, complexing agents, fluorescent agents, dyes, graying inhibitors, anti-crease agents, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids, UV absorbers, optical absorbers , Anti-redeposition agents, viscosity regulators, pearlescent agents, color transfer inhibitors, anti-shrink agents, corrosion inhibitors, preservatives, phobing and impregnating agents.

In a particular embodiment of the invention, the paste contains one or more optionally stabilized enzymes.

The paste according to the invention can contain one or more different amylolytic enzymes, in particular α-amylases. Sen Examples of commercially available amylases are BAN ^®, Termamyl ^®, Purastar ^{®, ®} LT-amylase, Maxamyl ^®, Duramyl ^® and / or Purafect ^® OxAm.

In particular on chemically diverse soiling, it can be advantageous to use several different washing and / or cleaning-active enzymes. These include, for example, proteases, but also lipases, cutinases, esterases, pullulanases, celluloses, hemicellulases and / or xylanases, and mixtures thereof. Proteases, lipases, β-glucanases and / or cellulases are particularly preferred. Additional enzymes extend the cleaning performance of the corresponding agents by their specific enzymatic performance. These include, for example, oxidoreductases or peroxidases as components of enzymatic bleaching systems, for example laccases (WO 00/39306), β-glucanases (WO 99/06515 and WO 99/06516) or pectin-dissolving enzymes (WO 00/42145), which in particular are used in special detergents. Examples of commercially available enzymes for use in the inventive paste are proteases such as subtilisin BPN ^', Properase ^®, alkaline protease from Bacillus lentus, Optimase ^®, Opticlean ^®, Maxatase ^®, Maxacal ^®, Maxapem ^®, Alcalase ^®, Esperase ^®, Savinase ^® , Durazym ^® , Everlase ^® and / or Purafect ^® G or Purafect ^® OxP and lipases such as Lipolase ^® , Lipomax ^® , Lumafast ^® and / or Lipozym ^® . The protease activity in such agents can be determined by the method described in Tenside, Vol. 7 (1970), pp. 125-132. Accordingly, it is given in PE (protease units). The protease activity of preferred agents can be up to 1,500,000 protease units per gram of preparation (PE, determined by the method described in Tenside, Vol. 7 (1970), pp. 125-132).

These optionally additionally used enzymes can, as described for example in European patent EP 0 564 476 or in international patent applications WO 94/23005, be adsorbed on carriers and / or be embedded in coating substances in order to protect them against premature inactivation. They are contained in detergents preferably in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight, particular preference being given to enzymes stabilized against oxidative degradation, such as, for example, from international patent applications WO 94/18314 known to be used.

The paste can contain enzymes in amounts of 0 to 3% by weight.

The paste according to the invention can also contain dyes. All dyes commonly used in detergents and cleaning agents are suitable. The paste can contain dyes in amounts of 0 to 0.5% by weight

Perfumes or fragrances can also be contained in the paste according to the invention. All substances normally used as such in washing and cleaning agents can be used here, preferably perfume oils in amounts of 0 to 20% by weight, particularly preferably 0-10% by weight.

In a second embodiment, the invention relates to the use of the paste according to the invention for cleaning textiles, in particular for textile pretreatment. The paste according to the invention is particularly well suited for the targeted pretreatment of stains on various textiles. Thus, items of clothing and textile articles made of nonwovens, felt, woven or knitted natural and chemical fibers such as cotton, wool, silk, linen, artificial silk, e.g. viscose, polyamide, polyacrylic, polyester, polyvinyl chloride, elastane and all other commonly used fibers as well as any Mixtures of these are brought into contact with the paste according to the invention at contaminated locations. The paste according to the invention is particularly suitable for removing greasy and oily stains. However, the paste can also be used for pretreating textile goods with different types of stains, which is further promoted by the addition of some of the auxiliaries mentioned above, for example the enzymes.

In a third embodiment, the subject matter of the invention is a product containing a paste according to the invention and an application device.

All containers for the pastes are to be understood as application devices which, by virtue of their nature, serve to simply and precisely apply their contents to the area to be treated, which are thus aligned in such a way that portioned application of the paste is made possible. The application device is preferably designed as a tube or as a roller-type metering dispenser in which the paste is located. The container material of the application device, which is in direct contact with the paste, advantageously consists of an easily deformable material. Reversibly deformable bottles, tubes and rollers make it easier to push the paste out of the application device. The container material of the application device, which is in direct contact with the paste, is advantageously selected from the group of polymers which substantially prevent diffusion of hydrophobic components, in particular hydrocarbons, preferably selected from the group of polyethylenes, polypropylenes and multilayer plastics. LDPE (low density polyethylene) and laminate plastics, which are provided with barrier layers for hydrophobic components, have proven to be particularly suitable. In a preferred embodiment, the product according to the invention additionally has a device for grinding the paste at the outlet opening of the application device. A brush and / or a sponge is particularly preferably attached to the application device. In a fourth embodiment, the subject of the invention is a method for removing stains on textiles using a paste according to the invention.

The paste is applied by applying it to the stain, preferably with the aid of one of the application devices mentioned above, and preferably for about 10 minutes. The paste is particularly preferably rubbed on the stain and / or dabbed. Then it is either rinsed out with clear water or the exquisite piece is sent to a subsequent textile washing process or dry cleaning process.

The paste is particularly preferably applied from a tube to the stain to be treated. Further preferred forms, which come into question depending on the application device, provide for application by rolling up, dabbing on with a sponge or an absorbent cloth or rubbing in or brushing with corresponding cloths or brushes.

The paste can of course also be used in a washing machine than for textile washing. However, the paste according to the invention is preferably used in a hand washing process. For this purpose, the textiles to be cleaned are placed in a container and then the paste and water are added. After the exposure time, the textiles can preferably be rinsed with water.

In a fifth embodiment, the subject of the invention is the use of the paste according to the invention as a cleaning agent for hard surfaces or skin.

For the purposes of this invention, hard surfaces are all plastic, glass, ceramic or metal surfaces customary in the household, for example kitchen surfaces, stoves, bathroom surfaces, floor tiles, laminate floors or dishes. Due to its high fat-dissolving power, the paste is particularly suitable for cleaning kitchen stoves and kitchen surfaces. The paste is however also suitable for cleaning ^"of the skin, such as for cleaning oil-soiled hands.

In a sixth embodiment, the subject of the invention is a method for producing the paste according to the invention. The individual ingredients are mixed neither at room temperature or, if appropriate, at a higher temperature, for example stirred at 40-70 ° C.

However, it has proven to be advantageous to additionally incorporate a degassing step of the paste when producing the paste. For this purpose, in a preferred embodiment, the air-containing paste is liquefied by heating and passed through a degassing room. By degassing the pastes according to the invention, the transparency is increased and also ensures an adequate filling guarantee, that is to say the degree of filling of a product filled with the paste does not change over the course of time due to a slow escape of gases.

However, the problem of removing gases from the pastes according to the invention can also be solved by operating the production of the paste in a continuously running system (continuous system). The initially thin and therefore gas-free or low-gas individual components or premixes of the paste are fed to a continuously running tubular reactor via various filling stations and mixed with the help of mixing devices implemented within this system. Since the system is always filled, the pastes obtained in this way are extremely low in gas.

The pastes according to the invention are notable for better cleaning performance and, owing to their transparency occurring in preferred embodiments, for increased consumer acceptance thanks to improved aesthetics. Due to the pasty consistency, the agent can be applied in a targeted manner and thus adheres excellently to the stain, so that it can develop its full cleaning effect longer at the desired location, and there is also no unwanted ring formation or only to a reduced extent.

Examples

Table 1 shows recipes for pastes according to the invention. The information is given in percent by weight, based in each case on the entire paste.

Table 1 :

The viscosities (in mPas) were determined at 20 ° C. using a Brookfield RVT viscometer with 20 rpm / spindle 7.

Raw materials:

Cobersol B105 C16-20 Isoparffine from CBR

Glucopon 600 CSUP C12-16-alkyl-1, 4-glucoside, DP = 1, 4 from Cognis Hostapur SAS 60 sec. Alkane sulfonate from Clariant Isopar M C12-14 isoparaffins from Exxon Mobil Lutensol A05 C13-15 oxo alcohol + 5EO from BASF Texapon LS 35 C12-14 fatty alcohol sulfate from Cognis Texapon SPN 70 C12-14 fatty alcohol ether sulfate 1, 3-EO from Cognis

The pastes according to the invention all have excellent cleaning performance both in washing processes and in pretreatment. Table 2 shows formulations 8 to 10 of pastes according to the invention and a comparison formulation V. The data are given in percent by weight, in each case based on the total paste.

Table 2

The viscosities (in mPas) were determined at 20 ° C. using a Brookfield RVT viscometer at 20 rpm / spindle 7, at Rez. V using spindle 2.

With the formulas 10 and V, a comparative washing test was carried out in the rental washing machine type W 918 to prove the effect of the gasoline.

Pretreatment of 10 x 10 cm cotton lobes that are completely contaminated with artificial soiling. A round stain area with a diameter of 4 cm is pretreated with the two test substances.

The exposure time of both formulations is 10 minutes, application of 1 g formulation per stain, the paste being rubbed lightly with the finger. The lobes are then subjected to a washing process under the following conditions: 40 ° C., 2.5 kg laundry load, 16 ° dH water hardness, 17 liters of washing solution, detergent: 50g Spee universal detergent powder,

The experiments were repeated 5 times for each artificial soiling and then the color value Y was determined (color value Y at 420 nm). The mean values were calculated for each soiling and each formulation. The lower the color value, the more contaminated the textile.

There were significant advantages for the pastes according to the invention, for example on the following soiling:

WFK 10 C = pigment / wool fat recipe 10: Y = 71, 2 recipe.

V: Y = 68.2

WFK 10GM = used mineral oil recipe. 10: Y = 72.5 recipe

V: Y = 68.7

EMPA carbon black / mineral oil recipe. 10: Y = 45.3 recipe

V: Y = 42.8

Claims

claims

1. Paste containing at least one hydrophobic component.

2. Paste according to claim 1, characterized in that the hydrophobic component (s) has an HLB value of less than 3 (have).

3. Paste according to one of claims 1 or 2, characterized in that the hydrophobic component (s) is / are selected from the group of paraffins or isoparaffins, preferably linear and / or branched and / or saturated and / or unsaturated Cιo- C ₃₀ -hydrocarbons, in particular C ₁₀ -C ₂₀ -hydrocarbons and any mixtures thereof.

4. Paste according to one of claims 1 to 3, characterized in that the hydrophobic component (s) in an amount of up to 30 wt .-%, preferably up to less than 10 wt .-%, particularly preferably 0.5 to 9% by weight, in particular from 1.5 to 8% by weight, in each case based on the total paste, is present.

5. Paste according to one of claims 1 to 4, characterized in that it contains surfactants, preferably selected from the groups of nonionic and / or anionic and / or amphoteric surfactants.

6. Paste according to claim 5, characterized in that the total content of surfactants is below 40% by weight, preferably below 35% by weight, in each case based on the total paste.

7. Paste according to claim 5 and 6, characterized in that it contains at least one nonionic surfactant, preferably a nonionic surfactant based on an alkoxylated fatty alcohol, particularly preferably an ethoxylated and / or propoxylated C ₀ -C ₂₀ fatty alcohol, most preferably a C _12th -C ₁₈ fatty alcohol with less than 10 ethoxylate groups and / or propoxylate groups, in particular a C ₁₂ -C ₁₈ fatty alcohol with less than or equal to 7 ethoxylate units.

8. Paste according to claim 7, characterized in that the content of nonionic surfactant based on an alkoxylated fatty alcohol is below 35% by weight, preferably below 26% by weight, particularly preferably between 4 and 25% by weight, in particular between 15 and 25% by weight, based in each case on the total paste.

9. Paste according to claim 5 to 7, characterized in that it is a nonionic surfactant, an alkyl glycoside, preferably in amounts up to 20 wt .-%, particularly preferably between 1 and 15 wt .-%, in particular between 5 and 13 wt .-% , contains.

10. Paste according to one of claims 5 to 9, characterized in that it contains anionic surfactants, in particular alkyl sulfates and / or alkyl ether sulfates.

11. Paste according to one of claims 1 to 10, characterized in that it additionally has an emulsifier, preferably selected from the group of polar organic solvents, in particular from the group of alcohols, glycols and glycol ethers.

12. Paste according to one of claims 1 to 11, characterized in that the water content is above 20% by weight, preferably above 50% by weight, in each case based on the total paste.

13. Paste according to one of claims 1 to 12, characterized in that it additionally contains a bleaching agent, preferably hydrogen peroxide and / or phthalimidoperoxy-caproic acid and / or coated bleaching agents.

14. Paste according to one of claims 1 to 13, characterized in that it additionally contains a builder and / or a pH regulator, preferably selected from the group of organic di-, tri- or polycarboxylic acids and their salts, in particular citric acid and / or Contains sodium citrate.

15. Paste according to one of claims 1 to 14, characterized in that it is transparent.

16. Paste according to one of claims 1 to 15, characterized in that it has a viscosity of above 10,000 mPas at 20 ° C, preferably above 15,000 mPas and in particular above 20,000 mPas (measured with a Brookfield RVT viscometer, 20 revolutions per Minute, spindle 6).

17. Use of a paste according to one of the preceding claims for textile cleaning, in particular for pretreating stains on textiles.

18. Use of a paste according to one of claims 1 to 16 as a cleaning agent for hard surfaces.

19. A method for removing stains on textiles, in which a paste according to one of claims 1 to 16 is applied to the stain and, if appropriate, triturated and / or dabbed.

20. A method for removing stains on textiles according to claim 19, characterized in that the paste is rinsed out with water after a short exposure time.

21. The method according to any one of claims 19 and 20 for removing grease and oil stains on textiles.

22. The method according to any one of claims 19 to 21, in which the piece of textile treated with paste is subsequently fed to a textile washing process.

23. The method according to any one of claims 19 to 22, in which the textile piece treated with the paste is subsequently fed to a textile dry cleaning process.

24. Product containing a paste according to one of claims 1 to 16 and an application device.

25. Product according to claim 24, wherein the application device is aligned such that a portioned application of the paste is made possible.

26. Product according to one of claims 24 and 25, characterized in that the application device is designed as a tube or a roller-type dispenser in which the paste is located.

27. Product according to one of claims 24 to 26, characterized in that the container material of the application device, which is in direct contact with the paste, consists of an easily deformable material.

28. Product according to one of claims 24 to 27, characterized in that the container material of the application device, which is in direct contact with the paste, is selected from the group of polymers which substantially prevent the diffusion of hydrocarbons, preferably selected from the group of polyethylenes, polypropylenes and multilayer plastics.

29. Product according to one of claims 24 to 28, characterized in that a device for rubbing in the paste, preferably a brush and / or a sponge, is additionally attached to the outlet opening of the application device.

30. A method for producing a paste according to any one of claims 1 to 16, characterized in that the individual components are mixed together.

31. The method according to claim 30, characterized in that the production takes place in a continuous process with at least one dosing station.

32. The method according to any one of claims 30 or 31, characterized in that an additional degassing step is implemented.