EP2773736B1 - Structured detergent or cleaning agent having a flow limit ii - Google Patents

Description

The invention relates to a liquid washing or cleaning agent with yield point, containing anionic and nonionic surfactant. The invention also relates to the use of the washing or cleaning agent and a process for its preparation.

Stable suspension of solids in liquids is often problematic. In particular, when the solids differ in density from the liquid, they tend to sediment or float.

One method of suspending relatively large particles, such as visible capsules, is based on structured surfactant systems. The term "structured surfactant system" refers to aqueous systems which have surfactant structures that are larger than conventional spherical micelles and whose interaction confers thixotropic properties on the aqueous medium. These structures may be solid, mesophase, or liquid, and may be in the form of multilayer spherulites, rods, discs, or lamellae that are dispersed or emulsified discontinuously in the system, or which form weak network structures.

Three main types of suspending systems have been used in practice, all of which involve an L _α phase in which bilayers of surfactants with the hydrophobic part of the molecule on the inside and the hydrophilic part on the outside of the bilayer (or vice versa) are located. The bilayers lie side by side, for example in a parallel or concentric arrangement, sometimes separated by aqueous layers. L _α phases can usually be identified by their characteristic texture under the polarizing microscope and / or by X-ray diffraction.

Most surfactants form an L _α phase either at ambient or slightly higher temperatures when mixed with water in certain specific ratios. However, such L _α phases usually can not be used as structured suspending systems. Useful amounts of solids cause the systems to become non-pourable and smaller amounts of solids tend to sediment. Also, the concentrations at which L _α phases often occur are significantly higher than the usual and / or desired concentrations in liquid detergents and cleaners.

The main types of structured system used in practice are based on dispersed lamellar, spherulitic and attenuated lamellar phases.

Dispersed lamellar phases are two-phase systems in which the surfactant bilayers are arranged as parallel plates to form areas of La phases interspersed with an aqueous phase to form an opaque gel-like system.

Spherolitic phases include spherical bodies, commonly referred to in the art as spherulites, in which surfactant bilayers are arranged as concentric shells. The spherulites usually have a diameter in the range of 0.1 to 15 microns and are dispersed in an aqueous phase in the manner of a classical emulsion. The spherulites interact to form a structured system.

Many structured surfactant systems are dispersed between lamellar and spherulitic. The surfactant systems include both types of structures. Usually systems of a more spherulitic character are preferred because they lead to lower viscosities.

A third type of structured surfactant system comprises an extended L _α phase. It differs from the other two structural system types in that it is essentially a single phase and from conventional L _α phases in that it has a wider d-spacing.

Structured surfactant systems having dispersed lamellar or spherulitic phases are typically formed by the interaction of surfactants with dissolved electrolyte salts or bases. From the WO 2007/085410 A1 For example, structured hand dishwashing or scouring agents are known.

The pamphlets EP 452 106 A2 and US 5,952,285 A refer to flowable, concentrated and aqueous surfactant compositions with anionic surfactant, nonionic surfactant, co-surfactant and inorganic salt. It will be eg in EP 452 106 A2 Surfactant compositions containing alkyl ether sulfate and alkylbenzenesulfonate as anionic surfactant, alkylamine oxide as nonionic surfactant, lauryl ethoxylate with 3 units of ethylene oxide as co-surfactant and potassium carbonate as inorganic salt.

However, such structured surfactant systems often have no or no sufficiently high yield strengths and / or very high amounts of electrolyte. The latter leads to increased corrosion in the washing machines or detergents used in automatic washing machines or dishwashers.

It is therefore an object of the invention to provide a structured liquid washing or cleaning agent having a yield point, which is particularly suitable for use in automatic washing machines or dishwashers.

• 5 bis 20 Gew.-% anionisches Tensid ausgewählt aus der Gruppe bestehend aus Sulfonat-Tensiden, Sulfat-Tensiden und Mischungen daraus,
• 1 bis 15 Gew.-% nichtionisches Tensid ausgewählt aus der Gruppe bestehend aus alkoxylierten Fettalkoholen mit einem Alkoxylierungsgrad ≥ 4, alkoxylierten Fettsäurealkylestern, Fettsäureamiden, alkoxylierten Fettsäureamiden,

This object is achieved by a liquid washing or cleaning agent with yield point, containing

• From 5 to 20% by weight of anionic surfactant selected from the group consisting of sulphonate surfactants, sulphate surfactants and mixtures thereof,
• 1 to 15% by weight of nonionic surfactant selected from the group consisting of alkoxylated fatty alcohols having a degree of alkoxylation ≥ 4, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides,

• 0,5 bis 10 Gew.-% eines anorganischen Salzes und
• 0,5 bis 5 Gew.-% eines Co-Tensids ausgewählt aus der Gruppe bestehend aus alkoxylierten C₈-C₁₈-Fettalkoholen mit einem Alkoxylierungsgrad ≤ 3, aliphatischen C₆-C₁₄-Alkoholen, aromatischen C₆-C₁₄-Alkoholen, aliphatischen C₆-C₁₂-Dialkoholen, Monoglyceride von C₁₂-C₁₈-Fettsäuren, Monoglycerinether von C₈-C₁₈-Fettalkoholen und Mischungen daraus

wobei als nichtonisches Tensid mindestens eine Verbindung enthalten ist, die ausgewählt wird aus alkoxylierten Fettalkoholen mit einem Alkoxylierungsgrad ≥ 4, und
wobei als besagtes Co-Tensid mindestens eine Verbindung enthalten ist, die ausgewählt wird aus der Gruppe bestehend aus alkoxylierten C₁₂-C₁₈-Fettalkoholen mit einem Alkoxylierungsgrad ≤ 3, aliphatischen C₆-C₁₄-Alkoholen und Mischungen daraus.Polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof,

• 0.5 to 10 wt .-% of an inorganic salt and
• 0.5 to 5 wt .-% of a co-surfactant selected from the group consisting of alkoxylated C ₈ -C ₁₈ fatty alcohols having a degree of alkoxylation ≤ 3, C ₆ -C ₁₄ aliphatic alcohols, aromatic C ₆ -C ₁₄ alcohols aliphatic C ₆ -C ₁₂ dialcohols, monoglycerides of C ₁₂ -C ₁₈ fatty acids, diglycerol ethers of C ₈ -C ₁₈ fatty alcohols and mixtures thereof

wherein as non-ionic surfactant at least one compound is selected, which is selected from alkoxylated fatty alcohols having a degree of alkoxylation ≥ 4, and
wherein as said cosurfactant at least one compound is selected which is selected from the group consisting of alkoxylated C ₁₂ -C ₁₈ fatty alcohols having a degree of alkoxylation ≤ 3, C ₆ -C ₁₄ aliphatic alcohols and mixtures thereof.

It has surprisingly been found that by adding selected amounts of an inorganic salt and a specific cosurfactant to a liquid washing or cleaning agent with a specific surfactant system comprising selected anionic and nonionic surfactants, an internally structured detergent or cleaning agent with yield point is obtained. This washing or cleaning agent is able to disperse particles stably without the addition of a polymeric thickener. The ability to dispense with polymeric thickeners, not only has the advantage that the funds can be made easier and cheaper, but also unwanted side effects of a polymeric thickener, such as graying in the treatment of textiles can be avoided. Accordingly, in a preferred embodiment, the detergent or cleaning agent is free of polymeric thickener. Furthermore, the washing or cleaning agent is stable even without the addition of another polymeric stabilizer or dispersant. In addition, the detergents or cleaning agents can be used without problems in machine washing or cleaning agents, since their content of inorganic salt is significantly reduced compared to detergents or cleaners known in the prior art.
It is preferred that the anionic surfactant is selected from the group consisting of C _9-13 alkyl benzene sulfonates, olefin sulfonates, C _12-18 alkanesulfonates, ester sulfonates, alk (en) yl sulfates, fatty alcohol ether sulfates, and mixtures thereof.
It has been found that these sulfonate and sulfate surfactants are particularly suitable for the preparation of stable liquid washing detergents with yield point. Liquid washing or cleaning compositions which comprise as anionic surfactant C _9-13- alkylbenzenesulfonates and fatty alcohol ether sulfates have particularly good dispersing properties.
It is preferable that the inorganic salt is selected from the group consisting of sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, calcium chloride, magnesium chloride and mixtures thereof, since these salts are very soluble in water.
Further, it is preferable that the co-surfactant is an alkoxylation degree ≦ 3.

In a particularly preferred embodiment, the washing or cleaning agent additionally contains dispersed particles. The dispersed particles may comprise capsules, abrasives and / or insoluble constituents of the washing or cleaning agent. Capsules are preferred dispersed particles, since with their help sensitive, chemically or physically incompatible and volatile components (= active ingredients) of the liquid detergent or cleaning agent can be trapped stable storage and transport.

In a preferred embodiment of the invention, the washing or cleaning agent contains at least one enzyme. The use of enzymes in detergents has been known and standard for many years.

However, since the protease itself and other enzymes are proteins, the protease in liquid detergents tends to self-degrade or degrade other enzymes. For this reason, stabilization of enzymes is required, especially in liquid systems. In the prior art, this is usually done by the inhibition of the protease, in which the active center is reversibly blocked. Such stabilization is usually achieved by borax, boric acids, boronic acids or their salts or esters and / or by the use of polyols. Surprisingly, it has now been found that the liquid structured detergents or cleaners can be used to increase the stability of enzymes. It has been found that the use of conventional enzyme stabilizers can be reduced, and even that the use of conventional enzyme stabilizers can be dispensed with altogether.

In a preferred embodiment of the invention, therefore, liquid structured and enzyme-containing washing or cleaning agents are free from borax, boric acids, boronic acids or their salts or esters. These include, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid (4-FPBA) or the salts or esters of the abovementioned compounds.

A known from the literature stabilizer for enzymes in liquid detergents or cleaning agents are polyols, especially glycerol and 1,2-propylene glycol. Surprisingly, it has been found that such polyols in the liquid structured detergents or cleaners are not required for the stabilization of enzymes. In a further preferred embodiment of the invention, therefore, the liquid washing or cleaning agents according to the invention are free of glycerol and 1,2-propylene glycol.

In a further preferred embodiment of the invention, liquid structured and enzyme-containing detergents or cleaners have neither polymeric thickeners nor borax, boric acids, boronic acids or their salts or esters.

In a further preferred embodiment of the invention, liquid structured and enzyme-containing detergents or cleaners have neither glycerol and / or 1,2-propylene glycol nor borax, boric acids, boronic acids or their salts or esters.
In a further preferred embodiment of the invention, liquid structured and enzyme-containing detergents or cleaners neither glycerol and / or 1,2-propylene glycol nor polymeric thickeners nor borax, boric acids, boronic acids or their salts or esters.
Furthermore, the invention relates to the use of the washing or cleaning agent according to the invention for washing and / or cleaning textile fabrics or hard surfaces.

• 5 bis 20 Gew.-% anionisches Tensid ausgewählt aus der Gruppe bestehend aus Sulfonat-Tensiden, Sulfat-Tensiden und Mischungen daraus,
• 1 bis 15 Gew.-% nichtionisches Tensid ausgewählt aus der Gruppe bestehend aus alkoxylierten Fettalkoholen mit einem Alkoxylierungsgrad ≥ 4, alkoxylierten Fettsäurealkylestern, Fettsäureamiden, alkoxylierten Fettsäureamiden, Polyhydroxyfettsäureamiden, Alkylphenolpolyglycolethern, Aminoxiden, Alkylpolyglucosiden und Mischungen daraus,

wobei als nichtonisches Tensid mindestens eine Verbindung enthalten ist, die ausgewählt wird aus alkoxylierten Fettalkoholen mit einem Alkoxylierungsgrad ≥ 4, und
wobei das Co-Tensid ausgewählt ist aus der Gruppe bestehend aus alkoxylierten C₈-C₁₈-Fettalkoholen mit einem Alkoxylierungsgrad ≤ 3, aliphatischen C₆-C₁₄-Alkoholen, und Mischungen daraus.
In einem weiteren Aspekt betrifft die Erfindung ein Verfahren zur Herstellung eines flüssigen Wasch- oder Reinigungsmittels mit Fließgrenze, enthaltend

• 5 bis 20 Gew.-% anionisches Tensid ausgewählt aus der Gruppe bestehend aus Sulfonat-Tensiden, Sulfat-Tensiden und Mischungen daraus und
• 1 bis 15 Gew.-% nichtionisches Tensid ausgewählt aus der Gruppe bestehend aus alkoxylierten Fettalkoholen mit einem Alkoxylierungsgrad ≥ 4, alkoxylierten Fettsäurealkylestern, Fettsäureamiden, alkoxylierten Fettsäureamiden, Polyhydroxyfettsäureamiden, Alkylphenolpolyglycolethern, Aminoxiden, Alkylpolyglucosiden und Mischungen daraus, wobei als nichtonisches Tensid mindestens eine Verbindung enthalten ist, die ausgewählt wird aus alkoxylierten Fettalkoholen mit einem Alkoxylierungsgrad ≥ 4, und

bei dem dem flüssigen Wasch- oder Reinigungsmittel 0,5 bis 10 Gew.-% eines anorganischen Salzes und 0,5 bis 5 Gew.-% eines Co-Tensids, welches ausgewählt ist aus der Gruppe bestehend aus alkoxylierten C₈-C₁₈-Fettalkoholen mit einem Alkoxylierungsgrad ≤ 3, aliphatischen C₆-C₁₄-Alkoholen, aromatischen C₆-C₁₄-Alkoholen, aliphatischen C₆-C₁₂-Dialkoholen, Monoglyceride von C₁₂-C₁₈-Fettsäuren, Monoglycerinether von C₈-C₁₈-Fettalkoholen und Mischungen daraus, zugesetzt werden, wobei als besagtes Co-Tensid mindestens eine Verbindung zugesetzt wird, die ausgewählt wird aus der Gruppe bestehend aus alkoxylierten C₁₂-C₁₈-Fettalkoholen mit einem Alkoxylierungsgrad ≤ 3, aliphatischen C₆-C₁₄-Alkoholen und Mischungen daraus.The invention also encompasses the use of a combination of 0.5 to 10% by weight of an inorganic salt and 0.5 to 5% by weight of a cosurfactant for producing a flow limit in a liquid detergent or cleaning composition containing

• From 5 to 20% by weight of anionic surfactant selected from the group consisting of sulphonate surfactants, sulphate surfactants and mixtures thereof,
• 1 to 15% by weight of nonionic surfactant selected from the group consisting of alkoxylated fatty alcohols having a degree of alkoxylation ≥ 4, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof,

wherein as non-ionic surfactant at least one compound is selected, which is selected from alkoxylated fatty alcohols having a degree of alkoxylation ≥ 4, and
wherein the co-surfactant is selected from the group consisting of alkoxylated C ₈ -C ₁₈ fatty alcohols having a degree of alkoxylation ≤ 3, aliphatic C ₆ -C ₁₄ alcohols, and mixtures thereof.
In a further aspect, the invention relates to a process for the preparation of a liquid washing or cleaning agent having yield stress, comprising

• 5 to 20 wt .-% of anionic surfactant selected from the group consisting of sulfonate surfactants, sulfate surfactants and mixtures thereof and
• 1 to 15 wt .-% of nonionic surfactant selected from the group consisting of alkoxylated fatty alcohols having a degree of alkoxylation ≥ 4, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, Polyhydroxyfettsäureamiden, Alkylphenolpolyglycolethern, amine oxides, alkyl polyglucosides and mixtures thereof, wherein at least one compound as a non-ionic surfactant is selected from alkoxylated fatty alcohols having a degree of alkoxylation ≥ 4, and

in which the liquid washing or cleaning agent contains 0.5 to 10% by weight of an inorganic salt and 0.5 to 5% by weight of a cosurfactant which is selected from the group consisting of alkoxylated C ₈ -C ₁₈ - fatty alcohols having a degree of alkoxylation ≤ 3, aliphatic C ₆ -C ₁₄ alcohols, aromatic C ₆ -C ₁₄ alcohols, aliphatic C ₆ -C ₁₂ dialcohols, monoglycerides of C ₁₂ -C ₁₈ fatty acids, monoglycerol ethers of C ₈ -C ₁₈ fatty alcohols and mixtures thereof, wherein as said cosurfactant at least one compound selected from the group consisting of alkoxylated C ₁₂ -C _{18 is added} Fatty alcohols having a degree of alkoxylation ≦ 3, C ₆ -C ₁₄ aliphatic alcohols and mixtures thereof.

In the following, the invention will be described in more detail, inter alia, by way of examples. Unless indicated otherwise, all amounts in% by weight of active ingredient, based on the total washing or cleaning agent, are indicated throughout the application.

The liquid washing or cleaning agent contains an anionic surfactant, a nonionic surfactant, an inorganic salt and a co-surfactant.

As anionic surfactant sulfonates and / or sulfates are used. The content of anionic surfactant is 5 to 20 wt .-% and preferably 8 to 15 wt .-%, each based on the total washing or cleaning agent.

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

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₆ alkyl sulfates are preferred. 2,3-alkyl sulfates are also suitable anionic surfactants.

Also, fatty alcohol ether sulfates, such as the sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _{12 -18} fatty alcohols with 1 to 4 EO are suitable.

It is preferred that the liquid detergent or cleaning agent contains a mixture of sulfonate and sulfate surfactants. In a particularly preferred embodiment, the liquid washing or cleaning agent C contains _9-13- alkylbenzenesulfonates and fatty alcohol ether sulfates as anionic surfactant. The ratio of the sulfate surfactants to sulfonate surfactants is preferably in the range of 3: 1 to 1: 3, and more preferably in the range of 3: 1 to 1: 1. In a special In a preferred embodiment, the liquid washing or cleaning agent contains fatty alcohol ether sulfates and C _9-13 -alkylbenzenesulfonates in the ratio 2: 1.

In addition to the anionic surfactant, the liquid washing or cleaning agent may also contain soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.

The anionic surfactants and the soaps may be in the form of their sodium, potassium or magnesium or ammonium salts. Preferably, the anionic surfactants are in the form of their sodium salts. Further preferred counterions for the anionic surfactants are also the protonated forms of choline, triethylamine, monoethanolamine or methylethylamine.

The amount of soap in the liquid washing or cleaning agent is preferably up to 5% by weight and more preferably up to 2% by weight, based on the total amount of detergent or cleaning agent.

The washing or cleaning agent contains not only the anionic surfactant but also nonionic surfactant. The nonionic surfactant includes alkoxylated fatty alcohols having a degree of alkoxylation ≥ 4, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof.

The nonionic surfactant used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 4 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical may 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 having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 5 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 4 EO or 7 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 5 EO, 7 EO or 8 EO, C _12-18 Alcohols with 5 EO or 7 EO and mixtures of these. The degrees of ethoxylation given represent statistical means which, for a particular product, may be 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. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Also suitable are also a mixture of a (more) branched ethoxylated fatty alcohol and a unbranched ethoxylated fatty alcohol, such as a mixture of a C _16-18 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO. With particular preference, the washing, cleaning, after-treatment or washing assistant contains a C _12-18 fatty alcohol with 7 EO or a C _13-15 oxo alcohol with 7 EO as nonionic surfactant.

The content of nonionic surfactant is 1 to 15 wt .-% and preferably 2 to 10 wt .-%, each based on the total washing or cleaning agent.

The total amount of anionic and nonionic surfactant in the liquid washing or cleaning agent is up to 35 wt .-%, preferably up to 15 wt .-%, based on the total liquid detergent or cleaning agent.

Another essential constituent of the washing or cleaning agent according to the invention is the inorganic salt. This is, depending on the surfactant system used in an amount of 0.5 to 10 wt .-%, preferably in an amount of 1 to 8 wt .-% and most preferably 2 to 5 wt .-%, each based on the total Detergents or cleaning agents used.

Preferred inorganic salts include sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, calcium chloride, magnesium chloride, and mixtures thereof. Particularly stable washing or cleaning agents are obtained when using sodium chloride or mixtures of sodium chloride and potassium sulfate.

The addition of the inorganic salt promotes the formation of lamellar structures. In addition, the inorganic salt has an influence on the viscosity of the washing or cleaning agent and with the aid of the inorganic salt, the viscosity can be adjusted so that the detergent or cleaning agent is easy to dose and a container with the detergent or cleaning a good residual emptying having.

The washing or cleaning agent according to the invention necessarily contains a co-surfactant which is selected from the group consisting of alkoxylated C ₈ -C ₁₈ fatty alcohols having a degree of alkoxylation ≦ 3, aliphatic C ₆ -C ₁₄ -alcohols, aromatic C ₆ -C ₁₄ Alcohols, aliphatic C ₆ -C ₁₂ dialcohols, monoglycerides of C ₁₂ -C ₁₈ fatty acids, monoglycerol ethers of C ₈ -C ₁₈ fatty alcohols and mixtures thereof. This co-surfactant is used in an amount of 0.5 to 5 wt .-%, preferably in an amount of 1 to 4.5 wt .-% and most preferably 2 to 4 wt .-%, each based on the total Detergents or cleaning agents used.

Co-surfactants according to this application are amphiphilic molecules with a small, hydrophilic head group. In a binary system with water, these cosurfactants are only weak or even not soluble. Accordingly, they do not form micelles there either. In the presence of the claimed anionic and nonionic surfactants, the co-surfactants are incorporated into their associates and thereby change the morphology of these associates. The spherical micelles become rod-shaped and / or disc-shaped micelles. At a sufficiently high total surfactant content, the desired formation of lamellar phases or structures occurs.
Thus, the inorganic salt and the co-surfactant contribute to the formation of the lamellar phases or structures. By adding the inorganic salt and the co-surfactant to the selected surfactant system, an internally structured liquid detergent or cleaning agent with very good dispersing properties. The liquid washing or cleaning agent obtained is extremely stable and shows no phase separation and / or precipitation of the anionic and / or nonionic surfactants.
Suitable alkoxylated C ₁₂ -C ₁₈ fatty alcohols having a degree of alkoxylation ≦ 3 include, for example, iC ₁₃ H ₂₇ O (CH ₂ CH ₂ O) ₂ H, iC ₁₃ H ₂₇ O (CH ₂ CH ₂ O) ₃ H, C _12-14 -Alcohol with 2 EO, C _12-14 -alcohol with 3 EO, C _13-15 -alcohol with 3 EO, C _12-18 -alcohols with 2 EO and C _12-18 -alcohols with 3 EO.
Other suitable cosurfactants are 1-hexanol, 1-heptanol, 1-octanol, 1,2-octanediol, stearic monoglycerol and mixtures thereof.

Fragrance alcohols such as geraniol are also suitable as co-surfactants.
Preferred cosurfactants are C ₁₂ -C ₁₈ fatty alcohols having a degree of alkoxylation ≦ 3. These cosurfactants are incorporated particularly well into the associates of the anionic and nonionic surfactant.
It may be preferred that the washing or cleaning agent additionally contains a C ₁₂ -C ₁₈ fatty acid. C ₁₂ -C ₁₈ fatty acids can have a positive influence on the formation of lamellar structures or phases and in particular support their formation.
It may be particularly preferred that the washing or cleaning agent contains the neutralized and unneutralized form of a C ₁₂ -C ₁₈ fatty acid. This is particularly advantageous in the case of detergents or cleaning agents containing fatty acid soaps, since the content of unneutralized fatty acid can be adjusted very simply via the pH, for example by adding pH regulators. Suitable C ₁₂ -C ₁₈ fatty acids include lauric, myristic, palmitic, stearic, (hydrogenated) erucic acid, behenic coconut fatty acid, palm kernel fatty acid, olive oil fatty acid and / or tallow fatty acid.

The determination of the content of the non-neutralized fatty acid content in a liquid detergent or cleaning agent containing fatty acids can be carried out experimentally (for example by means of titration) or with knowledge of the pKa value of the fatty acid used using the Henderson-Hasselbalch equation.
Alternatively, the fatty acid soap may be derived from a different fatty acid than the C ₁₂ -C ₁₈ fatty acid used to further aid in the formation of lamellar structures or phases.
In addition to the anionic surfactant, the nonionic surfactant, the inorganic salt and the co-surfactant, the washing or cleaning agent may contain further ingredients which further improve the performance and / or aesthetic properties of the washing or cleaning agent. In the context of the present invention, the washing or cleaning agent preferably additionally contains one or more substances from the group of builders, bleaches, enzymes, electrolytes, nonaqueous solvents, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, antiredeposition agents, Graying inhibitors, anti-shrinkage agents, anti-wrinkling agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, plasticizing components and UV absorbers.
In a preferred embodiment, the washing or cleaning agent is free of polymeric thickener.
Suitable builders which may be present in the washing or cleaning agent are in particular silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
Organic builders which may be present in the washing or cleaning agent are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA) and derivatives thereof and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

As builders further polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 600 to 750,000 g / mol.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,000 to 5,000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. To improve the water solubility, the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

However, preference is given to using soluble builders, such as, for example, citric acid, or acrylic polymers having a molar mass of from 1,000 to 5,000 g / mol in the liquid detergents or cleaners.

In a particularly preferred embodiment, the liquid washing or cleaning agent contains an enzyme or a mixture of enzymes. The most important detergent enzyme is protease. Apart from proteases, however, especially those of the class of the hydrolases such as the (poly) esterases, lipases, amylases, glycosyl hydrolases, hemicellulases, cutinases, β-glucanases, oxidases, peroxidases, mannanases, perhydrolases, oxireductases and / or laccases are suitable.

The amount of enzyme or of the enzymes is from 0.01 to 10 wt .-%, preferably 0.12 to about 3 wt .-%, based on the total detergent or cleaning agent. The enzymes are preferably used as enzyme liquid formulation (s).

Without wishing to be limited to this theory, it is assumed that the macroscopic single phase through the lamellar phase has a microcompartmentalization. It is thought that the enzyme molecules are trapped between the lamellae and the mobility of the enzymes is restricted accordingly. As a result, they can not diffuse to each other and can not inactivate each other, even if they are not inhibited. In a very particularly preferred embodiment of the invention, the repetition length of the lamellar phase (periodicity) is between 10 and 20 nm, preferably 11 to 16 nm and with even greater preference 12 to 14 nm. Such repetition lengths can be calculated, for example, from small-angle X-ray scattering measurements (SAXS).

The detergents or cleaners are liquid and contain water as the main solvent. It is preferred that the washing or cleaning agent more than 5 wt .-%, preferably more than 15 wt .-% and particularly preferably more than 25 wt .-%, each based on the total amount of detergent or cleaning agent, water contains.

In addition, nonaqueous solvents can be added to the washing or cleaning agent. Suitable non-aqueous solvents include mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the specified concentration range. Preferably, the solvents are selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, 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 ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures thereof Solvent. However, it is preferred that the washing or cleaning agent contains an alcohol, in particular ethanol and / or glycerol, in amounts between 0.5 and 5 wt .-%, based on the total washing or cleaning agent.

In addition to these constituents, a washing or cleaning agent may contain dispersed particles whose diameter along their greatest spatial extent is preferably 1 to 1000 μm.

For the purposes of the present invention, particles may be capsules, abrasives as well as powders, granules or compounds of compounds which are insoluble in the washing or cleaning agent, with capsules being preferred.

The term "capsule" on the one hand understood aggregates with a core-shell structure and on the other hand aggregates with a matrix. Core-shell capsules contain at least one solid or liquid core which is enclosed by at least one continuous shell, in particular a shell of polymer (s).

Inside the capsules, sensitive, chemically or physically incompatible as well as volatile components (= active ingredients) of the liquid washing or cleaning agent can be enclosed stable in storage and transport. The capsules may include, for example, optical brighteners, surfactants, complexing agents, bleaches, bleach activators, dyes and fragrances, antioxidants, builders, enzymes, enzyme stabilizers, antimicrobial agents, graying inhibitors, anti redeposition agents, pH adjusters, electrolytes, detergency boosters, vitamins, proteins , Foam inhibitors and UV absorbers are located. The fillings of the capsules may be solids or liquids in the form of solutions or emulsions or suspensions.

The capsules may have any shape in the production-related framework, but they are preferably approximately spherical. Their diameter along their largest spatial extent can be between 1 μm and 1000 μm, depending on the components contained in their interior and the application.

Alternatively, it is also possible to use particles which have no core-shell structure but in which the active substance is distributed in a matrix of a matrix-forming material. Such particles are also referred to as "speckles".

The matrix formation in these materials takes place for example via gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions and is well known in the art as well as the production of particles with these matrix-forming materials. An exemplary matrix-forming material is alginate. For the preparation Alginatbasierter speckles is an aqueous alginate solution which also contains the entrapped active ingredient or active ingredients to be entrapped, and then dripped ²⁺ or Al ³⁺ ions cured precipitation bath containing Ca in a. Alternatively, other, matrix-forming materials can be used instead of alginate.

The particles can be stably dispersed in the liquid detergents or cleaners. Stable means that the detergents or cleaning agents are stable at room temperature for a period of at least 4 weeks, and preferably for at least 6 weeks, without the particles in the medium creaming or sedimenting.

The release of the active ingredients from the capsules is usually carried out by destruction of the shell or the matrix due to mechanical, thermal, chemical or enzymatic action.

In a preferred embodiment, the liquid detergents or cleaners contain capsules in which one or more fragrances are contained.

Alternatively, the particles may comprise abrasives such as plastic or calcium carbonate beads as well as powders, granules or compounds of compounds insoluble in the detergent or cleaning agent.

In a preferred embodiment of the invention, the liquid washing or cleaning agent contains identical or different particles in amounts of 0.05 to 10 wt .-%, in particular 0.1 to 8 wt .-% and most preferably 0.2 to 5 wt. -%.

The washing or cleaning agent can be used for washing and / or cleaning fabrics or hard surfaces.

The preparation of the washing or cleaning agent by means of conventional and known methods and methods. Thus, for example, the constituents of the washing or cleaning agents can be mixed in stirred tanks, initially water is introduced. Then the nonaqueous solvents and surfactants, including the cosurfactant, are added. Subsequently, if present, the fatty acid is added and the saponification of the fatty acid moiety and the neutralization of the anionic surfactants are used, which are used in the acid form. Then the other ingredients, preferably in portions, are added. The inorganic salt may be added as a solid or in the form of a concentrated solution at various times in the manufacturing process.

The flow limits of the detergents or cleaning agents were measured using a rotary rheometer from TA-Instruments, type AR G2. This is a so-called shear stress controlled rheometer.

To measure a yield point with a shear stress controlled rheometer various methods are described in the literature, which are known in the art.

The flow limits in the context of the present invention were determined as follows at 23 ° C.
The samples were loaded in the rheometer with a time-increasing shear stress s (t). For example, the shear stress can be increased in the course of 10 minutes from the smallest possible value (eg 2 mPa) to eg 10 Pa. As a function of this shear stress, the deformation y of the sample is measured. The deformation is plotted against the shear stress in a log-log plot. If the examined sample has a yield point, clearly two areas can be distinguished in this plot. Below a certain shear stress, one finds a purely elastic deformation. The slope of the curve γ (σ) (log-log plot) in this area is one. Above this shear stress, the flow range begins and the slope of the curve is suddenly higher. The shear stress at which the bending of the curve takes place, ie the transition from the elastic to a plastic deformation, marks the yield stress. A convenient determination of the break point is possible by applying tangents to the two curve parts. Samples without yield point do not show a characteristic kink in the function γ (σ).

Table 1 below shows the compositions of three inventive detergents or cleaners E1 to E3 and the composition of a comparative example V1 (All amounts are in wt .-% active, based on the total washing or cleaning agent, indicated). Table 1: Wt .-% ingredients V1 E1 E2 E3 C ₁₂ -C ₁₈ ROH with 7 EO 2 2 2 4 Na lauryl ether sulfate (2 EO) 8th 8th 8th 8th C ₁₂ -C ₁₈ fatty acid 1 1 1 1 linear C _9-13 -alkylbenzenesulfonic acid, sodium salt 4 4 4 4 Phosphonic acid, Na salt 0.8 0.8 0.8 0.8 Optical brightener 0.1 0.1 0.1 0.1 Silicone antifoam 0.02 0.02 0.02 0.02 citric acid 2.5 2.5 2.5 2.5 boric acid 1.1 1.1 1.1 1.0 ethanol 3 3 3 3 Enzymes (Cellulase, Amylase & Protease) 1.8 1.8 1.8 1.8 Perfume 0.2 0.2 - 0.2 Perfume capsules (∅ = 15 μm) - - 0.2 - dye 0.0001 0.0001 0.0001 0.0001 NaCl 3 3 3 5 iC ₁₃ ROH with 3 EO - 4 4 - hexanol - - - 2 water Ad 100 Ad 100 Ad 100 Ad 100 NaOH (50%) At pH 7 At pH 7 At pH 7 At pH 8.4 yield - + + +

The three detergents E1 to E3 were stable at room temperature for 6 weeks. In particular washing or cleaning agent E2 showed no significant creaming and / or sedimentation of the dispersed capsules.

Comparative Example C1 clearly shows that the use of inorganic salt alone does not lead to a liquid washing or cleaning agent having a yield point. In the comparative example, although the inorganic salt is present in the claimed amount range, but since the co-surfactant is missing, the resulting detergent or cleaning agent has no yield point. In addition, the washing or cleaning agent V1 separates into two phases.

Claims (15)

1. A liquid washing or cleaning agent having a yield point, containing

   - 5 to 20 wt.% of anionic surfactant selected from the group consisting of sulfonate surfactants, sulfate surfactants and mixtures thereof,

   - 1 to 15 wt.% of non-ionic surfactant, selected from the group consisting of alkoxylated fatty alcohols having a degree of alkoxylation of ≥ 4, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof,

   - 0.5 to 10 wt.% of an inorganic salt and

   - 0.5 to 5 wt.% of a co-surfactant selected from the group consisting of alkoxylated C₈-C₁₈ fatty alcohols having a degree of alkoxylation of ≤ 3, aliphatic C₆-C₁₄ alcohols, aromatic C₆-C₁₄ alcohols, aliphatic C₆-C₁₂ dialcohols, monoglycerides of C₁₂-C₁₈ fatty acids, monoglycerol ethers of C₈-C₁₈ fatty alcohols and mixtures thereof,

   wherein at least one compound selected from alkoxylated fatty alcohols having a degree of alkoxylation of ≥ 4 is contained as a non-ionic surfactant, and
   wherein at least one compound selected from the group consisting of alkoxylated C₁₂-C₁₈ fatty alcohols having a degree of alkoxylation of ≤ 3, aliphatic C₆-C₁₄ alcohols and mixtures thereof is contained as said co-surfactant.
2. The liquid washing or cleaning agent according to claim 1, characterized in that the anionic surfactant is selected from the group consisting of C_9-13 alkylbenzene sulfonates, olefin sulfonates, C_12-18 alkane sulfonates, ester sulfonates, alk(en)yl sulfates, fatty alcohol ether sulfates and mixtures thereof.
3. The liquid washing or cleaning agent according to claim 2, characterized in that the anionic surfactant comprises C_9-13 alkylbenzene sulfonates and fatty alcohol ether sulfates.
4. The liquid washing or cleaning agent according to one of claims 1 to 3, characterized in that the inorganic salt is selected from the group consisting of sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, calcium carbonate, magnesium chloride and mixtures thereof.
5. The liquid washing or cleaning agent according to one of claims 1 to 4, characterized in that the co-surfactant is a C₁₂-C₁₈ fatty alcohol having a degree of alkoxylation of ≤ 3.
6. The liquid washing or cleaning agent according to one of claims 1 to 5, characterized in that the liquid washing or cleaning agent contains dispersed particles.
7. The liquid washing or cleaning agent according to claim 6, characterized in that the dispersed particles are capsules, abrasive substances and/or insoluble components of the washing or cleaning agent.
8. The liquid washing or cleaning agent according to one of claims 1 to 7, characterized in that the washing or cleaning agent is free of thickeners.
9. The liquid washing or cleaning agent according to one of claims 1 to 8, characterized in that the washing or cleaning agent additionally contains a C₁₂-C₁₈ fatty acid.
10. The liquid washing or cleaning agent according to one of claims 1 to 9, characterized in that it contains at least one enzyme.
11. The liquid washing or cleaning agent according to one of claims 1 to 10, characterized in that it is free of borax, boric acids or salts or esters thereof.
12. The liquid washing or cleaning agent according to one of claims 1 to 11, characterized in that it does not contain glycerol and/or 1,2 propylene glycol.
13. The use of the washing or cleaning agent according to one of claims 1 to 12 for washing and/or cleaning textile fabrics or hard surfaces.
14. The use of a combination of 0.5 to 10 wt.% of an inorganic salt and 0.5 to 5wt.% of a co-surfactant for generating a yield point in a liquid washing or cleaning agent, containing

    - 5 to 20 wt.% of anionic surfactant selected from the group consisting of sulfonate surfactants, sulfate surfactants and mixtures thereof,

    - 1 to 15 wt.% of non-ionic surfactant, selected from the group consisting of alkoxylated fatty alcohols having a degree of alkoxylation of ≥ 4, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof,

    wherein at least one compound selected from alkoxylated fatty alcohols having a degree of alkoxylation of ≥ 4 is contained as a non-ionic surfactant and wherein the co-surfactant is selected from the group consisting of alkoxylated C₁₂-C₁₈ fatty alcohols having a degree of alkoxylation of ≤ 3, aliphatic C₆-C₁₄ alcohols and mixtures thereof.
15. A method for preparing a liquid washing or cleaning agent having a yield point, containing

    - 5 to 20 wt.% of anionic surfactant selected from the group consisting of sulfonate surfactants, sulfate surfactants and mixtures thereof and

    - 1 to 15 wt.% of non-ionic surfactant is selected from the group consisting of alkoxylated fatty alcohols having a degree of alkoxylation of ≥ 4, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl poly glucosides and mixtures thereof, wherein at least one compound selected from alkoxylated fatty alcohols having a degree of alkoxylation of ≥ 4 is contained as a non-ionic surfactant, and

    in which 0.5 to 10 wt.% of an inorganic salt and 0.5 to 5 wt.% of a co-surfactant selected from the group consisting of alkoxylated C₈-C₁₈ fatty alcohols having a degree of alkoxylation of ≤ 3, aliphatic C₆-C₁₄ alcohols, aromatic C₆-C₁₄ alcohols, aliphatic C₆-C₁₂ dialcohols, monoglycerides of C₁₂-C₁₈ fatty acids, monoglycerol ethers of C₈-C₁₈ fatty alcohols and mixtures thereof are added to the liquid washing or cleaning agent, wherein at least one compound selected from the group consisting of alkoxylated C₁₂-C₁₈ fatty alcohols having a degree of alkoxylation of ≤ 3, aliphatic C₆-C₁₄ alcohols and mixtures thereof is added as said co-surfactant.