DE102021106506A1 - Bad odor control in detergents - Google Patents

Abstract

The present invention relates to cleaning agents which contain at least one cyclodextrin. The invention also relates to the use of such agents for cleaning hard surfaces, a method for cleaning hard surfaces using such an agent and the use of such agents to reduce bad odors or prevent bad odors from occurring when cleaning hard surfaces.

Description

The present invention relates to cleaning agents which contain at least one cyclodextrin. The invention also relates to the use of such agents for cleaning hard surfaces, a method for cleaning hard surfaces using such an agent and the use of such agents to reduce bad odors and/or prevent bad odors from occurring when cleaning hard surfaces .

Commercially available cleaning agents are usually perfumed, since consumers want the product to have sufficient natural fragrance and to cover up “bad” secondary odours. Bad odors usually come from soiling on the surfaces to be cleaned themselves, but also from degradation and decomposition products from components of this soiling and from components contained in the respective cleaning agent formulation. For example, a cleaning utensil used for cleaning purposes in combination with the respective cleaning agent, such as a sponge or a cloth, develops an unpleasant odor profile over time, which can be attributed to residues of dirt but also cleaning agent remaining on it. Although the use of fragrances and fragrances, for example in the form of perfume compositions, including in encapsulated form, can help to a certain extent, bad odors and off-notes that occur can usually only be partially masked and accordingly cannot be completely neutralized. In addition, perfumes are comparatively high-priced cleaning agent components that are often difficult to formulate, and, last but not least, from a health perspective, an overdose of the same should generally be avoided.

There is consequently a continuing need for cleaning agents which reduce or even prevent the occurrence of bad odors and off-notes.

Surprisingly, it has now been found that cyclodextrins in commercially available cleaning agent formulations have a strong action against bad odors and thus lead to an improved olfactory impression both during and after use of the product in question.

A first object of the present invention is therefore a cleaning agent, characterized in that the agent contains at least one cyclodextrin in an amount of 0.01 to 30% by weight, based on the total weight of the cleaning agent.

In a further aspect, the invention also relates to the use of such a cleaning agent for cleaning hard surfaces.

Furthermore, the invention also relates to methods for cleaning hard surfaces, characterized in that a cleaning agent as described herein is used in at least one method step.

Finally, the present invention also relates to the use of a cleaning agent, as described herein, for reducing bad odors and/or for preventing the occurrence of bad odors when cleaning hard surfaces.

These and other aspects, features and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Each feature from one aspect of the invention can be used in any other aspect of the invention. Furthermore, it should be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular the invention is not limited to these examples.

The term “cleaning agent” means, in the context of the present invention, all conceivable types of cleaning agent that are used to clean hard surfaces, both concentrates and agents to be used undiluted, for use on a commercial scale, in the dishwasher or for manual cleaning. These include, for example, dishwashing detergents for automatic or manual dishwashing, or cleaners for hard surfaces such as metal, glass, porcelain, ceramics, tile, stone, painted surfaces, plastics, wood or leather, for which the term detergent is used, i.e. alongside manual and automatic dishwashing detergents e.g. scouring agents, glass cleaners, toilet air fresheners, etc.

"At least one" as used herein includes but is not limited to 1, 2, 3, 4, 5, 6 and more. With regard to an ingredient, the information refers to the type of ingredient and not to the absolute number of molecules. “At least one surfactant” thus means, for example, at least one type of surfactant, ie it can mean one type of surfactant or a mixture of several different surfactants. Together with weight information, the information relates to all compounds of the specified type that are contained in the composition/mixture, ie the composition does not contain any other compounds of this type beyond the specified amount of the corresponding compounds.

All percentages are % by weight unless otherwise indicated. Numeric ranges given in the format "from x to y" include the stated values. Where multiple preferred numeric ranges are given in this format, it is understood that any ranges resulting from the combination of the different endpoints are also included.

"About" or "about" as used herein in connection with a numerical value refers to the numerical value ±10%, preferably ±5%.

When reference is made herein to molar masses, this information always relates to the number-average molar mass M _n , unless explicitly stated otherwise. The number average molar mass can be determined, for example, by means of gel permeation chromatography (GPC) in accordance with DIN 55672-1:2007-08 with THF as the eluent. The mass-average molar mass M _w can also be determined by GPC, as described for M _n .

Whenever alkaline earth metals are mentioned below as counterions for monovalent anions, this means that the alkaline earth metal is of course only present in half the amount of substance - sufficient for charge equalization - as the anion.

"Liquid" as used in the context of the present invention means all flowable compositions (at 20°C, 1.013 bar), including gels and paste-like compositions, as well as non-Newtonian liquids that exhibit a yield point.

"Solid" as used herein in the context of the present invention means a powder, granule, extrudate or compact composition.

"Phosphate-free" and "phosphonate-free", as used herein, means that the composition in question is essentially free of phosphates or phosphonates, i.e. in particular phosphates or phosphonates in amounts less than 0.1% by weight, preferably less than 0 .01% by weight, based on the respective composition.

A composition according to the invention can be a one-component composition or a multi-component composition. In the context of the present invention, the term “one-component agent” refers to a cleaning agent which consists of only a single component. The term "multi-component agent", as used herein, on the other hand, designates a cleaning agent which is composed of at least two components. It is preferred that the individual components of a multi-component agent according to the invention are spatially separated from one another.

The term "spatially separated" in relation to the components of the composition, as used herein, means that the individual components cannot come into contact with each other prior to use of the composition. Usually, the agent is provided in a multi-chamber packaging, such as a bottle, tube or pouch, in particular a two-chamber bottle or a two-chamber pouch, with each individual component being located separately from the other component(s) in a separate chamber. The spatial separation of individual components of the agent makes it possible on the one hand to separate incompatible ingredients from one another and on the other hand to offer several different components of the agent in combination, which are used at different times.

In this context, the term "component" refers to a part of the cleaning agent that can be distinguished from another component of the agent, if applicable, on the basis of one or more characteristics, for example the type and/or amount of its ingredients, physical properties, external appearance, etc. For example, the cleaning agent described herein can be a liquid cleaning agent. This means, in the context of the present invention, that the means at least a liquid component as defined above, for example in the form of a gel or a paste. According to some embodiments of the invention, however, individual components of a cleaning agent according to the invention can also be in solid form, for example in the form of a powder, granules or extrudate. If an agent according to the invention comprises both liquid and solid components, it is preferred that the liquid component(s) is/are preferably spatially separated from the solid component(s), for example in a separate chamber of a multi-chamber pouch. In this context, however, solid phases such as encapsulated ingredients, such as encapsulated perfume and/or enzyme, but also "bacon" contained for decorative purposes, which in some embodiments are part of a liquid agent or a liquid component of the means described herein.

The detergent composition according to the invention is characterized in that it comprises at least one cyclodextrin. The amount of the at least one cyclodextrin is approximately 0.01% to 30% by weight, based on the total weight of the agent described herein. In various embodiments, the amount of cyclodextrin is approximately 0.01 to 25% by weight, preferably approximately 0.01 to 5% by weight, based on the total weight of the cleaning agent. The term "cyclodextrin" as used herein includes any of the known cyclodextrins, such as substituted and unsubstituted cyclodextrins, containing from about six to about twelve glucose units, and mixtures thereof. Suitable non-limiting examples of cyclodextrins according to the present invention can cyclodextrin selected from the group consisting of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, alkylated α-cyclodextrin, alkylated β-cyclodextrin, alkylated γ-cyclodextrin, hydroxyalkylated α-cyclodextrin , hydroxyalkylated β-cyclodextrin, hydroxyalkylated γ-cyclodextrin, methylated cyclodextrin, and mixtures thereof, wherein, in some embodiments, the at least one cyclodextrin is β-cyclodextrin, hydroxypropylated β-cyclodextrin, or methylated β-cyclodextrin, or mixtures thereof, preferably methylated β-cyclodextrin.

According to the invention, the at least one cyclodextrin, as defined above, is present in free form, i.e. non-complexed form, in the cleaning agent described herein. Without wanting to be bound to a specific theory, it is assumed that in this way intensive and bad-smelling compounds can be bound by the cyclodextrin contained in the agent, which is why the agents described herein have a strong effect against bad odors, such as are usually used in cleaning of dishes can occur. Onion, garlic and fish odors are non-limiting examples of bad odors which can occur when cleaning dishes but also other hard surfaces, for example hard surfaces in the kitchen such as fittings and sinks. Non-limiting examples of molecules which produce an olfactory impression, which is usually rated negatively, are amines, such as diethylamine and triethylamine; sulfides such as dimethyl sulfide and dimethyl trisulfide; thiols such as methyl mercaptan; and organic acids such as butyric acid, isovaleric acid and caproic acid. Thus, the use of cyclodextrins, as described above, can lead to an improved olfactory impression compared to the cleaning agents known in the prior art when using corresponding agents. In various embodiments, at least 60% of the cyclodextrin is in free form, preferably at least 65%, more preferably at least 70%, most preferably at least 80%, such as about 80, 81, 82, 83, 84, 85, 86, 87 , 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99 or 100%, in each case based on the total amount of cyclodextrin contained in the composition according to the invention.

In addition to the at least one cyclodextrin, as defined above, the cleaning agent according to the invention contains at least one cleaning-active component, which includes, for example, surfactants, enzymes and chelators. In various embodiments, an agent according to the invention contains in particular at least one surfactant and/or at least one enzyme. In various embodiments, an agent according to the invention contains at least one surfactant and at least one enzyme. In various other embodiments, an agent according to the invention contains at least one, preferably at least two surfactants and at least one, preferably at least two enzymes, for example at least one surfactant and at least two enzymes, such as at least one surfactant and at least three enzymes.

Surfactants useful in the context of the present invention are known in the art and include anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic, amphoteric surfactants, and mixtures thereof.

The group of suitable anionic surfactants includes fatty alcohol ether sulfates. Fatty alcohol ether sulfates enable a stable foam volume in the presence of dirt, in particular greasy soiling on the surfaces to be cleaned or in water. Fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols. The person skilled in the art generally understands alkoxylated alcohols to mean the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the context of the present invention preferably with longer-chain alcohols, i.e. with aliphatic straight-chain or mono- or poly-branched, acyclic or cyclic, saturated or mono- or poly- unsaturated, preferably straight-chain, acyclic, saturated alcohols having 6 to 22, preferably 8 to 18, in particular 10 to 16 and particularly preferably 12 to 14 carbon atoms. Depending on the reaction conditions, a complex mixture of addition products of different degrees of ethoxylation (n=1 to 30, preferably 1 to 20, in particular 1 to 10, particularly preferably 2 to 4) is generally formed from n moles of ethylene oxide and one mole of alcohol.

A further embodiment of the alkoxylation consists in using mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Very particularly preferred for the purposes of the present invention are low-ethoxylated fatty alcohols having 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 2 EO such as Na-C ₁₂ -C ₁₄ fatty alcohols + 2 EO sulfate.

In some embodiments, the agent according to the invention contains one or more fatty alcohol ether sulfates, as defined above, preferably in an amount of 5 to 20% by weight, in particular 6 to 16% by weight, based in each case on the total weight of the agent.

The anionic surfactants which are preferably present in particular in hand dishwashing detergents include alkali metal salts of fatty alcohol sulfate. The agent according to the invention can preferably have 0.05 to 5% by weight, in particular 0.1 to 3% by weight, particularly preferably 0.3 to 1% by weight, of the alkali metal salt of a fatty alcohol sulfate, based on the total weight of the agent. This can be used as an additive that affects the foam volume. It has been shown that for water with a water hardness of 16 to 20° dH, i.e. hard water, a proportion of 0.05% by weight and in particular a proportion of 0.1% by weight is sufficient to to achieve only an insignificantly reduced foam volume compared to soft water. The harder the water, the higher the proportion of fatty alcohol sulfate should be. However, a proportion of more than 3% by weight, in particular more than 5% by weight, does not ensure any further stabilization of the foam, even in the case of very hard water with a water hardness of 20 to 32° dH. It has been shown that a proportion by weight of 0.3 to 1% by weight is sufficient to achieve the desired foam volume in both hard and very hard water with a water hardness of 16 to 32° dH, in particular 20 to 32° to get dH. A higher dosage of the alkali salt of the fatty alcohol sulfate would therefore only lead to an increase in costs, but not to a significantly larger foam volume.

According to the invention, the fatty alcohol sulfate preferably has 12 to 14 carbon atoms, in particular 13 carbon atoms. The alkali salt is preferably a sodium salt. In particular, the alkali metal salt of the fatty alcohol sulfate is sodium lauryl sulfate. This can be used in technical purity, so that in addition to a fatty alcohol sulfate with 13 carbon atoms, there is a mixture of alkyl chains with a chain length of preferably 12 to 14 carbon atoms. For example, a sodium lauryl sulfate sold under the trade name ^Texapon® LS35 by BASF can be used.

The anionic surfactants which are also preferably present, particularly in hand dishwashing detergents, also include alkyl sulfonates. The alkyl sulfonates (INCI: sulfonic acids) usually have an aliphatic straight-chain or mono- or polybranched, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably branched, acyclic, saturated alkyl radical with 6 to 22, preferably 9 to 20, in particular 11 to 18 and more preferably 14 to 17 carbon atoms.

Suitable alkyl sulfonates are therefore the saturated alkane sulfonates, unsaturated olefin sulfonates and - formally derived from the alkoxylated alcohols on which the alkyl ether sulfates are based - ether sulfonates, in which terminal ether sulfonates (n-ether sulfonates) with a sulfonate function attached to the polyether chain and internal ether sulfonates ( i-Ethersulfonates) with a sulfonate function linked to the alkyl radical. According to the invention, the alkanesulfonates, in particular alkanesulfonates with a branched, preferably secondary, alkyl radical, for example the secondary alkanesulfonate sec. Na-C ₁₃ -C ₁₇ alkanesulfonate (INCI: Sodium C _14-17 Alkyl Sec Sulfonate).

The detergent may also contain a linear alkyl benzene sulfonate or two or more linear alkyl benzene sulfonates as additional anionic surfactant(s). The cleaning agent according to the invention can contain these preferably in 0.1 to 20% by weight, in particular 1 to 10% by weight, particularly preferably 2 to 5% by weight, based on the total weight of the agent. In addition to a sulfonic acid or sulfonate group, linear alkylbenzenesulfonates usually also have an aliphatic straight-chain or mono- or polybranched, acyclic, saturated or mono- or polyunsaturated alkyl side chain with 6 to 22, preferably 8 to 20, in particular 10 to 16 and particularly preferably 12, on the benzene ring up to 14 carbon atoms. In preferred embodiments, these are the sodium salts of the linear alkyl benzene sulfonates.

Other possible anionic surfactants (anionic surfactants) that can be used are known to the person skilled in the art from the relevant prior art relating to detergents or cleaning agents. These include in particular aliphatic sulfates such as monoglyceride sulfates and ester sulfonates (sulfofatty acid esters), lignin sulfonates, fatty acid cyanamides, anionic sulfosuccinic acid surfactants, fatty acid isothionates, acylaminoalkane sulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates.

Other suitable anionic surfactants are also anionic gemini surfactants with a diphenyl oxide basic structure, 2 sulfonate groups and an alkyl radical on one or both benzene rings according to the formula (II): ^- O ₃ S (C ₆ H ₃ R) O (C ₆ H ₃ R')SO ₃ ^- , in which R is an alkyl group having, for example, 6, 10, 12 or 16 carbon atoms and R' is R or H (commercially available as Dowfax® Dry Hydrotrope Powder with C ₁₆ -alkyl group(s); INCI : sodium hexyl diphenyl ether sulfonate, disodium decyl phenyl ether disulfonate, disodium lauryl phenyl ether disulfonate, disodium cetyl phenyl ether disulfonate) and fluorinated anionic surfactants, particularly perfluorinated alkyl sulfonates such as ammonium C _9/10 perfluoroalkyl sulfonate (commercially available as Fluorad® FC 120) and perfluorooctane sulfonic acid potassium salt (commercially available as Fluorad® FC 95) , It being preferred that no fluorine compounds are contained in the agents according to the invention.

Particularly preferred further optionally present anionic surfactants are the anionic sulfosuccinic acid surfactants 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 the diamides of sulfosuccinic acid. 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, extremely preferably sodium salts.

In the sulfosuccinates, one or both carboxyl groups of the sulfosuccinic acid are preferably combined with one or two identical or different unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alcohols with 4 to 22, preferably 6 to 20, in particular 8 to 18, in particular preferably 10 to 16, most preferably 12 to 14 carbon atoms. They are particularly preferably esters of unbranched and/or saturated and/or acyclic and/or alkoxylated alcohols, in particular unbranched, saturated fatty alcohols and/or unbranched, saturated fatty alcohols alkoxylated with ethylene and/or propylene oxide, preferably ethylene oxide, with a degree of alkoxylation of 1 to 20, preferably 1 to 15, in particular 1 to 10, particularly preferably 1 to 6, extremely preferably 1 to 4. The monoesters are preferred over the diesters in the context of the present invention. A particularly preferred sulfosuccinate is sulfosuccinic acid lauryl polyglycol ester disodium salt (lauryl EO sulfosuccinate, di-Na salt; INCI: disodium laureth sulfosuccinate). In the sulfosuccinamates or sulfosuccinamides, one or both carboxyl groups of the sulfosuccinic acid preferably form with a primary or secondary amine that has one or two identical or different, unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alkyl radicals with 4 to 22, preferably A carboxylic acid amide carries 6 to 20, in particular 8 to 18, particularly preferably 10 to 16, extremely preferably 12 to 14 carbon atoms. Unbranched and/or saturated and/or acyclic alkyl radicals, in particular unbranched, saturated fatty alkyl radicals, are particularly preferred. Also suitable, for example, in the WO 2008/046778 A1 disclosed sulfosuccinamates and sulfosuccinamides, which are incorporated herein by reference. Yet another suitable sulfosuccinamate is disodium C _18-20 alkoxypropylene sulfosuccinamate.

Preferred anionic sulfosuccinic acid surfactants are imidosuccinate, mono-Na-sulfosuccinic acid di-isobutyl ester (commercially available as Monawet® MB 45), mono-Na-sulfosuccinic acid di-octyl ester (commercially available as Monawet® MO-84 R2W, Rewopol® SB DO 75 ), mono-Na-sulphobernstein acid di-tridecyl ester (commercially available as Monawet® MT 70), fatty alcohol polyglycol sulfosuccinate Na-NH ₄ salt (commercially available as sulfosuccinate S-2), di-Na-sulfosuccinic acid mono-C _12/14 -3EO ester ( commercially available as Texapon® SB-3), sodium sulfosuccinic acid diisooctyl ester (commercially available as Texin® DOS 75) and di-Na-sulfosuccinic acid mono-C _12/18 -ester (commercially available as Texin® 128-P), in particular the mono- Na-sulfosuccinic acid di-octyl ester. In a particular embodiment, the agent according to the invention contains one or more sulfosuccinates, sulfosuccinamates and/or sulfosuccinamides, preferably sulfosuccinates and/or sulfosuccinamates, in particular sulfosuccinates, as anionic sulfosuccinic acid surfactants, in an amount of usually 0.001 to 5% by weight, preferably 0.01 to 4 % by weight, in particular 0.1 to 3% by weight, particularly preferably 0.2 to 2% by weight, extremely preferably 0.5 to 1.5% by weight, for example 1% by weight.

The amphoteric surfactants (amphoteric surfactants, zwitterionic surfactants) that can be used according to the invention include betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amino acids and acylated amino acids or biosurfactants.

• (I): R¹-[CO-X-(CH₂)_n]_x-N⁺(R²)(R³)-(CH₂)_m-[CH(OH)-CH₂]_y-Y^- (I),

in der R¹ ein gesättigter oder ungesättigter C_6-22-Alkylrest, vorzugsweise C_8-18-Alkylrest, insbesondere ein gesättigter C_10-16-Alkylrest, beispielsweise ein gesättigter C_12-14-Alkylrest,
X NH, NR⁴ mit dem C_1-4-Alkylrest R⁴, O oder S,
n eine Zahl von 1 bis 10, vorzugsweise 2 bis 5, insbesondere 3,
x 0 oder 1, vorzugsweise 1,
R², R³ unabhängig voneinander ein C_1-4-Alkylrest, ggf. hydroxysubstituiert wie z B ein Hydroxyethylrest, insbesondere aber ein Methylrest,
m eine Zahl von 1 bis 4, insbesondere 1, 2 oder 3,
y 0 oder 1 und
Y COO, SO₃, OPO(OR⁵)O oder P(O)(OR⁵)O, wobei R⁵ ein Wasserstoffatom H oder ein C_1-4-Alkylrest ist, ist.Suitable betaines are the alkyl betaines, the alkylamidobetaines, the imidazolinium betaines, the sulfobetaines (INCI: sultaines) and the phosphobetaines and preferably satisfy the following formula

• (i): R ¹ -[CO-X-(CH ₂ ) _n ] _x -N ⁺ (R ² )(R ³ )-(CH ₂ ) _m -[CH(OH)-CH ₂ ] _y -Y ^- (I),

in which R ¹ is a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical,
X NH, NR ⁴ with the C _1-4 alkyl radical R ⁴ , O or S,
n is a number from 1 to 10, preferably from 2 to 5, in particular 3,
x is 0 or 1, preferably 1,
R ² , R ³ are independently a C _1-4 alkyl radical, optionally hydroxy-substituted such as a hydroxyethyl radical, but especially a methyl radical,
m is a number from 1 to 4, in particular 1, 2 or 3,
y 0 or 1 and
Y is COO, SO ₃ , OPO(OR ⁵ )O or P(O)(OR ⁵ )O, where R ⁵ is hydrogen, H or C _1-4 alkyl.

The alkyl and alkyl amido betaines, betaines of the formula I with a carboxylate group (Y ^- = COO ^- ), are also called carbobetaines.

Preferred betaines are the alkyl betaines of the formula (Ia), the alkylamidobetaines of the formula (Ib), the sulfobetaines of the formula (Ic) and the amidosulfobetaines of the formula (Id), R ¹ -N ⁺ (CH ₃ ) ₂ -CH ₂ COO ^- (Ia) R ¹ -CO-NH-(CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ COO ^- (Ib) R ¹ -N ⁺ (CH ₃ ) ₂ -CH ₂ CH(OH)CH ₂ SO ₃ ^- (Ic) R ¹ -CO-NH-(CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ CH(OH)CH ₂ SO ₃ ^- (Id) in which R ¹ has the same meaning as in formula (I) above.

Particularly preferred betaines are the carbobetaines, in particular the carbobetaines of the formula (Ia) and (Ib), most preferably the alkylamidobetaines of the formula (Ib).

Examples of suitable betaines and sulfobetaines are mandelamidopropyldimethyl glycine; 1-propanaminium, N-(carboxymethyl)-N,N-dimethyl-3-[(1-oxoapricot)amino]-, hydroxide, inner salts; 1-propanaminium, 3-amino-N-(carboxymethyl)-N,N-dimethyl, N-avocado oil acyl derivatives, inner salts; 1-Propanaminium, 3-amino-N-(carboxymethyl)-N,N-dimethyl-,N-babassu oil acyl derivatives, hydroxides, inner salts; 1-propanaminium, N-carboxymethyl-N,N-dimethyl-3-[(1-oxodocosanyl)amino]-, hydroxide, inner salt; (carboxylatomethyl)docosyldimethylammonium; methanaminium, 1-carboxy-N,N,N-trimethyl-, hydroxide inner salt; 1-propanaminium, 3-amino-N-(carboxymethyl)-N,N-dimethyl-canola oil acyl derivatives, inner salts; 2-[3-(octylamido)propyl]-N,N-dimethylammonioacetate and 2-[3-(decylamido)propyl]-N,N-dimethylammonioacetate; 1-propanaminium, 3-carboxy-2-hydroxy-N,N,N-trimethyl-, inner salt (R)-; (carboxylatomethyl)hexadecyldimethylammonium; 1-ethanaminium, N-(carboxymethyl)-N,N-dimethyl-2-[(1-oxococoalkyl)amino]-, hydroxides, inner salt; N-coco acyl derivatives of 3-amino-N-(carboxymethyl)-N,N-dimethyl-1-propanaminium; hydroxides, internal salts; 1-Propanaminium, N-(3-aminopropyl)-2-hydroxy-N,N-dimethyl-3-sulfo-,N-coco-acyl derivatives, hydroxides, inner salts; coco alkyldimethyl betaines; N-coco acyl derivatives of N,N-dimethyl-2-hydroxy-3-sulfo-1-propanamine; hydroxides, internal salts; N-(mixed coco acyl and 9-octadecenoyl) derivatives of N-carboxymethyl-N,N-dimethyl-3-amino-1-propanaminium; hydroxides, internal salts; N-coco acyl derivatives of N,N-dimethyl-3-sulfo-1-propanaminium; hydroxides, inner salts; (carboxymethyl)decyldimethylammonium hydroxide; 9-octadecene-1-aminium, N-(carboxymethyl)-N,N-bis(-2-hydroxyethyl)-, hydroxide, inner salt; Soybean Alkylaminium, N-carboxymethyl-N,N-bis(2-hydroxyethyl)-, hydroxides, inner salts; (carboxymethyl)bis(2-hydroxyethyl)octadecylammonium hydroxide; tallow alkylaminium, N-carboxymethyl-N,N-bis(2-hydroxyethyl)-, hydroxides, inner salt; (INCI: Dimethicone Propyl PG-Betaine), 1-propanaminium, 2-hydroxy-N,N-dimethyl-N-[3-[(1-oxo-13-docosenyl)amino]propyl]-3-sulfo-, hydroxide , inner salt; methanaminium, N-methyl-N-carboxymethyl-N-(hydrogenated tallow alkyl)-; 1-propanaminium, N-carboxymethyl-N,N-dimethyl-3-(1-oxoisooctadecylamino)- hydroxide inner salt; (carboxymethyl)dimethyl-3-[(1-oxododecyl)amino]propylammonium hydroxide; (carboxylatomethyl)dodecyldimethylammonium; dodecyl(2-hydroxy-3-sulfonatopropyl)dimethylammonium; dodecyldimethyl(3-sulfonatopropyl)ammonium; 1-propanaminium, 3-amino-N-(carboxymethyl)-N,N-dimethyl, N-milk fat acyl derivatives, inner salts; 1-Propanaminium, N,N-dimethyl-N-carboxymethyl-3-amino, N-mink oil acyl derivatives, hydroxides, inner salts; (carboxymethyl)dimethyl-3-[(1-oxotetradecyl)amino]propylammonium hydroxide; (carboxylatomethyl)dimethyltetradecylammonium; (Z)-(carboxymethyl)dimethyl-3-[(1-oxo-9-octadecenyl)amino]propylammonium hydroxide; (Z)-2-Hydroxy-3-sulfonatopropyldimethyl[3-[(1-oxo-9-octadecenyl)amino]propyl]ammonium; (carboxymethyl)dimethyloleylammonium hydroxide; 1-propanaminium, N-carboxymethyl-N,N-dimethyl-3-amino, N-olive acyl derivatives, hydroxides, inner salts; 1-propanaminium, N-carboxymethyl-N,N-dimethyl-3-amino,N-(palm oil acyl) derivatives, hydroxides, inner salts; 1-propanaminium, N-(carboxymethyl)-N,N-dimethyl-3-[(1-oxohexadecyl)amino]-, inner salt; 1-propanaminium, 3-carboxy-2-(1-oxohexadecyloxy)-N,N,N-trimethyl-, hydroxide inner salt; 1-propanaminium, N-carboxymethyl-N,N-dimethyl-3-amino, palm acyl derivatives, hydroxides, inner salts; poly(difluoromethylene), α-[2-(acetyloxy)-3-[(carboxymethyl)dimethylammonio]propyl]-ω-fluoro, inner salt; 1-Propanaminium, 3-amino-N-(carboxymethyl)-N,N-dimethyl-,N-castor oil acyl derivatives, hydroxides, inner salts; 1-propanaminium, N-carboxymethyl-N,N-dimethyl-3-amino, N-sesame oil acyl derivatives, hydroxides, inner salts; 1-propanaminium, 3-amino-N-carboxymethyl-N,N-dimethyl, N-soybean acyl derivatives, hydroxides, inner salts; (carboxymethyl)dimethyl-3-[(1-oxooctadecyl)amino]propylammonium hydroxide; (carboxylatomethyl)dimethyl(octadecyl)ammonium; 1-propanaminium, 3-amino-N-(carboxymethyl)-N,N-dimethyl, N-tallow acyl derivatives, hydroxides, inner salts; tallow amides, N-[3-(dimethylamino)propyl]-, alkylation products with sodium 3-chloro-2-hydroxypropanesulfonate; betaines, bis(hydroxyethyl)tallow alkyl; tallow alcohols; (Carboxymethyl)dimethyl[3-[(1-oxoundecenyl)amino]propyl]ammonium hydroxide and 1-propanaminium, N-carboxymethyl-N,N-dimethyl-3-amino, N-wheat germ acyl derivatives, hydroxides, inner salts . A preferred betaine is, for example, cocoamidopropyl betaine or betaine, which is commercially available from Evonik under the trade name Tego® Natural Betaine.

Useful amine oxides include alkyl amine oxides, particularly alkyl dimethyl amine oxides, alkyl amido amine oxides and alkoxyalkyl amine oxides.

Preferred amine oxides satisfy formula II or III,
R ⁶ R ⁷ R ⁸ N ^+- O ^- (II) or
R ⁶ -[CO-NH-(CH ₂ )w]zN ⁺ ( ^{R 7} )(RS )-O" (III) in the
R ⁶ is a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical, which in the alkylamidoamine oxides via a carbonylamidoalkylene group -CO -NH-(CH ₂ ) _z - and in the alkoxyalkylamine oxides via an oxaalkylene group -O-(CH ₂ )z- to the nitrogen atom N, where z is in each case a number from 1 to 10, preferably 2 to 5, in particular 3 , Where w is a number from 0 to 5, preferably 0 to 2, in particular 0 or 1, R ⁷ , R ⁸ are independently a C _1-4 alkyl radical, optionally hydroxy-substituted such. B. is a hydroxyethyl radical, in particular a methyl radical.

Examples of suitable amine oxides are the following compounds: Amide, Mandel,N-[3-(dimethylamino)propyl]-,N-oxide; propane,1-dimethylamino-3-[(1-oxobabassu)amino]-,N-oxide; N,N-dimethyldocosylamine N-oxide; amides, coco,N-[3-(dimethylamino)propyl]; amines, coco-alkyldimethyl,N-oxide; morpholine, 4-coco-alkyl derivatives, 4-oxide; N,N-dimethyldecylamine,N-oxide; 1-tetradecanamine,2-decyl-N,N-dimethyl,N-oxide; 2,4-pyrimidinediamine,3-oxide; ethanol,2,2'-iminobis,N-[3-(C ₈ -C ₁₀ alkyloxy)propyl] derivatives, N-oxide; ethanol,2,2'-iminobis, N -[3-(C ₉ -C ₁₁ alkyloxy)propyl] derivatives, N -oxide; ethanol,2,2'-iminobis,N-[3-(C ₁₂ -C ₁₅ alkyloxy)propyl] derivatives, N-oxide; ethanol,2,2'-iminobis,N-coco-alkyl derivatives, N-oxide; dodecylamine, N,N-bis(2-hydroxyethyl)-,N-oxide; ethanol,2,2'-(octadecylimino)bis,N-oxide;ethanol,2,2'-iminobis,N-tallow alkyl derivatives te,N-oxide; amines, (hardened palm kernel oil alkyl)dimethyl,N-oxide; amines, (hydrogenated tallow alkyl)dimethyl, N-oxide; 1-propylamine,3-(C ₁₂ -C ₁₅ alkyloxy)-N-(2-hydroxyethyl)-N-(3-hydroxypropyl)-,N-oxide; isooctadecanamide, N -[3-(dimethylamino)propyl]-,N-oxide; isooctadecanamide, N -[3-(4-morpholinyl)propyl]-N-oxide; N -[3-(dimethylamino)propyl]dodecanamide N-oxide; dodecyldimethylamine oxide; 4-methylmorpholine-4-oxide monohydrate; milk fat amides, N-[3-(dimethyloxidoamino)propyl]; 1,3-propanediamine, N,N-dimethyl,N'-mink oil acyl derivatives, N-oxide; N -[3-(dimethylamino)propyl]myristamide N-oxide; N,N-dimethyltetradecylamine N-oxide; amines, N-(C ₁₄ -C ₁₆ -alkyl)-N,N-dimethyl, N-oxide; N -[3-(dimethylamino)propyl]-9-octadecenamide N-oxide; N,N-dimethyloleyl-N-oxide; olive oil amides, N-(3-dimethylaminopropyl)-,N-oxide; hexadecanamide, N -[(3-dimethylamino)propyl]-,N-oxide; hexadecyldimethylamine N-oxide; α-Hydro-ω-.ω'-[(dodecyloxidoimino)dipoly(oxy-1,2-ethanediyl), (average molar ratio 3 moles EO); phosphoric acid, monoesters with coco-alkylbis(2-hydroxyethyl)amine N-oxides, dipotassium salts; nitrilotris(methanephosphonic acid)-N-oxide, tripotassium salt; Sesame Oil Amide, N-(3-dimethylaminopropyl)-,N-oxide; Soyamides, N-[-3-(dimethylamino)propyl]-,N-oxide; N -[3-(dimethylamino)propyl]stearamide N-oxide; N,N-dimethyloctadecylamine N-oxide; tallow amides, N -[3-(dimethylamino)propyl]-,N-oxide; amine, tallow alkyldimethyl, N-oxide; 10-undecenamide, N-[3-(dimethylamino)propyl],N-oxide and wheat germ amides, N-(3-dimethylaminopropyl)-,N-oxide. A preferred amine oxide is, for example, cocamidopropylamine oxide (INCI: Cocoamidopropylamine oxide). The amine oxide is preferably selected from cocamidopropyl amine oxide, N-cocoalkyl-N,N-dimethyl amine oxide, N-tallow alkyl-N,N-dihydroxyethyl amine oxide, myristyl/cetyl dimethyl amine oxide or lauryl dimethyl amine oxide or mixtures thereof.

The alkylamidoalkylamines (INCI: Alkylamido Alkylamines) are amphoteric surfactants of the formula (III), R ⁹ -CO-NR ¹⁰ -(CH ₂ ) _i -N(R ¹¹ )-(CH ₂ CH ₂ O) _j (CH ₂ ) _k - [CH(OH)] _I -CH ₂ -Z-OM (III) in the
R ⁹ is a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical,
R ¹⁰ is hydrogen, H or C _1-4 alkyl, preferably H,
i is a number from 1 to 10, preferably 2 to 5, in particular 2 or 3,
R ¹¹ is a hydrogen atom H or CH ₂ COOM (M is defined as follows),
j is a number from 1 to 4, preferably 1 or 2, in particular 1,
k is a number from 0 to 4, preferably 0 or 1,
I 0 or 1, where k = 1 if I = 1,
Z is CO, SO ₂ , OPO(OR ¹² ), or P(O)(OR ¹² ), where R ¹² is C _1-4 alkyl or M (defined as follows) and M is hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, eg protonated mono-, di- or triethanolamine.

Preferred representatives satisfy the formulas IIIa to IIId, R ⁹ -CO-NH-(CH ₂ ) ₂ -N(R ¹¹ )-CH ₂ CH ₂ O-CH ₂ -COOM (IIIa) R ⁹ -CO-NH-(CH ₂ ) ₂ -N(R ¹¹ )-CH ₂ CH ₂ O-CH ₂ CH ₂ -COOM (IIIb) R ⁹ -CO-NH-(CH ₂ ) ₂ -N(R")-CH ₂ CH ₂ O-CH ₂ CH(OH)CH ₂ -SO ₃ M (IIIc) R ⁹ -CO-NH-(CH ₂ ) ₂ -N(R ¹¹ )-CH ₂ CH ₂ O-CH ₂ CH(OH)CH ₂ -OPO ₃ HM (IIId) in which R ¹¹ and M have the same meaning as in formula (III).

Examples of suitable alkylamidoalkylamines are, for example, those in WO 2008/046778 A1 disclosed, to which reference is explicitly made.

Likewise suitable amphoteric surfactants are in particular N-2-hydroxyethyl-N-carboxymethyl fatty acid amidoethylamine-Na (commercially available as Rewoteric® AMV) and N-caprylic/caprinamidoethyl-N-ethyl ether propionate-Na (commercially available as Rewoteric® AMVSF).

According to the invention preferred alkyl-substituted amino acids are monoalkyl-substituted amino acids according to formula (IV), R ¹³ -NH-CH(R ¹⁴ )-(CH ₂ ) _U -COOM' (IV)
in the
R ¹³ is a saturated or unsaturated C _6-22 alkyl group, preferably C _8-18 alkyl group, in particular a saturated C _10-16 alkyl group, for example a saturated C _12-14 alkyl group, R ¹⁴ is a hydrogen atom H or a C _{1 -4} -alkyl radical, preferably H,
u is a number from 0 to 4, preferably 0 or 1, in particular 1, and M 'is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, eg
protonated mono-, di- or triethanolamine, is,
alkyl-substituted imino acids according to formula (V), R ¹⁵ -N-[(CH2)V-COOM"] ₂ (V) in the
R ¹⁵ is a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical,
v is a number from 1 to 5, preferably 2 or 3, in particular 2, and
M" is hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine, where M" in the two carboxy groups can have the same or two different meanings, for example hydrogen and sodium or twice sodium , is,
and mono- or dialkyl-substituted natural amino acids according to formula (VI), R ¹⁶ -N(R ¹⁷ )-CH(R ¹⁸ )-COOM"' (VI)

in the
R ¹⁶ is a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical, R ¹⁷ is a hydrogen atom or a C _{1- 4} -alkyl radical, optionally hydroxy- or amine-substituted, for example a methyl, ethyl, hydroxyethyl or aminopropyl radical,
R ¹⁸ is the residue of one of the 20 natural α-amino acids H ₂ NCH(R ¹⁸ )COOH, and M'" is hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, eg protonated mono-, di- or triethanolamine.

Particularly preferred alkyl-substituted amino acids are the aminopropionates of the formula (IVa), R ¹³ -NH-CH ₂ CH ₂ COOM' (IVa)

in which R ¹³ and M' have the same meaning as in formula (IV).

Exemplary suitable alkyl-substituted amino acids are in WO 2008/046778 A1 disclosed, to which reference is explicitly made.

Acylated amino acids are amino acids, in particular the 20 natural α-amino acids which carry the acyl radical R ¹⁹ CO of a saturated or unsaturated fatty acid R ¹⁹ COOH on the amino nitrogen atom, where R ¹⁹ is a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl, especially saturated C _10-16 alkyl, for example saturated C _12-14 alkyl. The acylated amino acids can also be used as an alkali metal salt, alkaline earth metal salt or alkanolammonium salt, for example mono-, di- or triethanolammonium salt. Exemplary acylated amino acids are those summarized under Amino Acids according to INCI: acyl derivatives, eg sodium cocoylglutamate, lauroylglutamic acid, capryloylglycine or myristoylmethylalanine.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols preferably having 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, such as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear radicals from alcohols of natural 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 preferred. Preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO, 4 EO or 7 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants that contain EO and PO groups together in the molecule are also inventive appropriately usable. More preferably, the hard surface cleaner contains a C12-18 fatty alcohol with 7 EO or a C13-15 oxo alcohol with 7 EO as nonionic surfactant.

In combination with an amine oxide, these nonionic surfactants have good cleaning performance on hard surfaces soiled with grease, such as dishes, for example.

According to the invention, sugar surfactants also optionally contained in the cleaning agent are known surface-active compounds, which include, for example, the sugar surfactant classes of alkylglucose esters, aldobionamides, gluconamides (sugar acid amides), glyceramides, glycerol glycolipids, polyhydroxyfatty acid amide sugar surfactants (sugar amides) and alkylpolyglycosides. In the context of the teaching according to the invention, preferred sugar surfactants are the alkyl polyglycosides and the sugar amides and their derivatives, in particular their ethers and esters. The ethers are the products of the reaction of one or more, preferably one, sugar hydroxy group with a compound containing one or more hydroxy groups, for example C _1-22 alcohols or glycols such as ethylene and/or propylene glycol, the sugar hydroxy group also being polyethylene glycol and/or polypropylene glycol residues. The esters are the reaction products of one or more, preferably one, sugar hydroxy group with a carboxylic acid, especially a C _6-22 fatty acid.

Particularly preferred sugar amides satisfy the formula R'C(O)N(R")[Z], in which R' is a linear or branched, saturated or unsaturated acyl radical, preferably a linear unsaturated acyl radical, having 5 to 21, preferably 5 to 17, in particular 7 to 15, particularly preferably 7 to 13 carbon atoms, R" is a linear or branched, saturated or unsaturated alkyl radical, preferably a linear unsaturated alkyl radical, having 6 to 22, preferably 6 to 18, in particular 8 to 16, particularly preferably 8 to 14 carbon atoms, a C _1-5 alkyl radical, in particular a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or n-pentyl radical, or hydrogen and Z is a sugar radical , ie a monosaccharide residue. Particularly preferred sugar amides are the amides of glucose, the glucamides, for example lauroyl-methyl-glucamide.

The alkyl polyglycosides (APG) are particularly preferred sugar surfactants within the scope of the teaching according to the invention and preferably satisfy the general formula R'O(AO) ₃ [G] _x , in which R' represents a linear or branched, saturated or unsaturated alkyl radical with 6 to 22 , preferably 6 to 18, in particular 8 to 16, particularly preferably 8 to 14 carbon atoms, [G] for a glycosidically linked sugar radical and x for a number from 1 to 10 and AO for an alkyleneoxy group, for example an ethyleneoxy or propyleneoxy group, and a stand for the average degree of alkoxylation from 0 to 20. The group (AO) ₃ can also contain different alkyleneoxy units, for example ethyleneoxy or propyleneoxy units, in which case a is the average overall degree of alkoxylation, ie the sum of the degree of ethoxylation and degree of propoxylation. Unless stated otherwise in more detail below, the alkyl radicals R′ of the APG are linear unsaturated radicals having the specified number of carbon atoms.

APG are nonionic surfactants and are known substances that can be obtained by the relevant methods of preparative organic chemistry. The index number x indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While x in a given compound must always be an integer and here in particular the values x = 1 to 6, the value x for a specific alkyl glycoside is an analytically calculated value that is usually a fractional number. Alkyl glycosides with an average degree of oligomerization x of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to alkyl glycosides whose degree of oligomerization is less than 1.7 and in particular is between 1.2 and 1.6. Xylose is preferably used as the glycosidic sugar, but glucose is used in particular. The alkyl or alkenyl radical R' can be derived from primary alcohols having 8 to 18, preferably 8 to 14, carbon atoms. Typical examples are caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and the technical mixtures thereof obtained, for example, in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from ROELEN's oxosynthesis.

However, the alkyl or alkenyl radical R′ is preferably derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol. Mention should also be made of elaidyl alcohol, petrolemyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical mixtures thereof.

Particularly preferred APG are not alkoxylated (a = 0) and satisfy the formula RO[G] _x , in which R as before represents a linear or branched, saturated or unsaturated alkyl radical having 4 to 22 carbon atoms, [G] represents a glycosidically linked sugar radical, preferably a glucose residue, and x is a number from 1 to 10, preferably from 1.1 to 3, in particular from 1.2 to 1.6. Correspondingly preferred alkyl polyglycosides are, for example, C _8-10 - and a C _12-14 -alkyl polyglucoside with a DP degree of 1.4 or 1.5, in particular C _8-10 -alkyl-1,5-glucoside and C _12-14 -alkyl-1,4-glucoside.

Other suitable nonionic surfactants are in particular C ₁₀ -dimethylamine oxide (commercially available as Ammonyx® DO), C _10-14 -fatty alcohol + 1,2PO+6,4EO (commercially available as Dehydol® 980), C _12/14 -fatty alcohol + 6EO (commercially available as Dehydol® LS6), C ₈ fatty alcohol+1,2PO+9EO (commercially available as Dehydol® O10), C _16/20 Guerbet alcohol+8EO, n-butyl capped (commercially available as Dehypon® G2084) , Mixture of several n-butyl-capped nonionic surfactants and C _8/10 -APG (commercially available as Dehypon® Ke 2555), C _8/10 -fatty alcohol+1PO+22EO-(2-hydroxydecyl)-ether (commercially available as Dehypon ® Ke 3447), C _12/14 fatty alcohol+5EO+4PO (commercially available as Dehypon® LS 54 G), C _12/14 fatty alcohol+5EO+3PO, methyl-capped (commercially available as Dehypon® LS 531), C _{12 /14} fatty alcohol+10EO, n-butyl capped (commercially available as Dehypon® LS 104 L), C ₁₁ -oxo alcohol+8EO (commercially available as Genapol® UD 088), C ₁₃ -oxo alcohol +8EO (commercially available as Genapol® X 089), C _13/15 fatty alcohol EO adduct, n-butyl capped (commercially available as Plurafac® LF 221) and alkoxylated fatty alcohol (commercially available as Tegotens® EC11).

The agent according to the invention can additionally contain one or more cationic surfactants (cationic surfactants; INCI: Quaternary Ammonium Compounds). Preferred cationic surfactants are the quaternary surface-active compounds, in particular with an ammonium, sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. By using quaternary surface-active compounds with an antimicrobial effect, the agent can be designed with an antimicrobial effect or its antimicrobial effect, which may already be present due to other ingredients, can be improved.

Particularly preferred cationic surfactants are the quaternary ammonium compounds (QAV, INCI: Quaternary Ammonium Compounds) of the general formula (R')(R")(R"')(R' ^V )N ⁺ X", where R' to R ' ^v Identical or different C _1-22 -alkyl radicals, C _7-28 -aralkyl radicals or heterocyclic radicals, where two or, in the case of an aromatic bond as in pyridine, even three radicals together with the nitrogen atom form the heterocycle, for example a pyridinium or imidazolinium compound, form, represent and X ^- are halide ions, sulfate ions, hydroxide ions or similar anions.For an optimal antimicrobial effect, at least one of the radicals preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.QAC are obtained by reacting tertiary amines with alkylating agents such as methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide The alkylation of tertiary amines with a long alkyl radical and two methyl groups ge is particularly easy, and the quaternization of tertiary amines with two long residues and one methyl group can also be carried out under mild conditions using methyl chloride. Amines that have three long alkyl groups or hydroxy-substituted alkyl groups are not very reactive and are preferably quaternized with dimethyl sulfate.

Examples of suitable QAC are benzalkonium chloride (N-alkyl-N,N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkon B (m,p-dichlorobenzyl-dimethyl-C ₁₂ alkylammonium chloride, CAS No. 58390-78-6) , benzoxonium chloride (benzyl-dodecyl-bis-(2-hydroxyethyl)-ammonium chloride), cetrimonium bromide (N-hexadecyl-N,N-trimethyl-ammonium bromide, CAS No. 57-09-0), benzetonium chloride (N,N-dimethyl- N-[2-[2-[p-(1,1,3,3-tetramethylbutyl)phenoxy]ethoxy]ethyl]-benzylammonium chloride, CAS No. 121-54-0), dialkyldimethylammonium chloride such as di-n-decyldimethylammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyl-dimethyl-ammonium chloride, 1-cetylpyridinium chloride (CAS No. 123-03-5) and thiazoline iodide (CAS No. 15764- 48-1) and mixtures thereof. Preferred QAVs are the benzalkonium chlorides with C _8-18 -alkyl radicals, in particular C ₁₂ - ₁₄ -alkyl-benzyldimethylammonium chloride. A particularly preferred QAC is coconut pentaethoxymethyl ammonium methosulfate (INCI: PEG-5 Cocomonium Methosulfate, commercially available as Rewoquat® CPEM).

Other suitable cationic surfactants are, in particular, cationic surfactants that are compatible with anionic surfactants, such as quaternary ammonium compounds, for example coconut pentaethoxymethylammonium methosulfate (INCI: PEG-5 Cocomonium Methosulfate, commercially available as Rewoquat® CPEM).

In order to avoid possible incompatibilities of the cationic surfactants with the anionic surfactants preferably present, as far as possible anionic surfactant-compatible and/or as few cationic surfactants as possible are used cal surfactant used or dispensed entirely with cationic surfactants in a particular embodiment of the invention.

The total surfactant content of the cleaning agent according to the invention is preferably about 4 to about 65% by weight, preferably about 6 to about 35% by weight, based in each case on the total weight of the agent.

Enzymes suitable in the context of the present invention include all those enzymes which are suitable for use in a detergent formulation according to the invention and which are commonly used in detergents and are accordingly known in the art.

Such an enzyme may be a hydrolytic enzyme or other enzyme at a concentration appropriate for the effectiveness of the particular composition.

All enzymes which can develop a catalytic activity in the agent according to the invention can preferably be used in this context, in particular an amylase, lipase, cutinase, protease, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, xyloglucanase, β-glucosidase, pectinase, Carrageenase, perhydrolase, oxidase, or oxidoreductase, and mixtures thereof.

One or more enzymes are advantageously contained in the agent in an amount of 1 x 10-8 to 5% by weight based on active protein, in particular in an amount of 1 x 10-7 to 3% by weight, from 0 .00001 to 1% by weight, from 0.00005 to 0.5% by weight, from 0.0001 to 0.1% by weight and particularly preferably from 0.0001 to 0.05% by weight, each based on the total weight of the agent and related to active protein.

The protein concentration can be determined using known methods, e.g. the BCA method (bicinchoninic acid; 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the Biuret method (Gornall et al., 1948, J. Biol. Chem., 177:751-766). In this regard, the active protein concentration can be determined by titrating the active centers using a suitable irreversible inhibitor and determining the residual activity (Bender et al., 1966, J. Am. Chem. Soc. 88(24):5890-5913).

The enzymes used particularly preferably show synergistic cleaning performance against certain types of soiling or stains, i.e. the enzymes contained in the agent composition support each other in their cleaning performance. Such a synergism is very particularly preferred between a protease and another enzyme of an agent according to the invention, including in particular between a protease and an amylase and/or a lipase and/or a mannanase and/or a cellulase and/or a pectinase. Synergistic effects can occur not only between different enzymes, but also between one or more enzymes and other ingredients of the agent according to the invention.

The enzymes to be used in the context of the present invention can, for example, originally come from microorganisms, such as the genera Bacillus, Streptomyces, Humicola or Pseudomonas, and/or can be produced by suitable microorganisms using biotechnological methods known per se, for example by transgenic expression hosts, e.g. the genera Escherichia , Bacillus or by filamentous fungi.

It is emphasized that technical enzyme preparations of the respective enzyme can also be involved, i.e. accompanying substances can be present. Therefore, the enzymes can be packaged and used together with accompanying substances, for example from fermentation or with other stabilizers.

As a rule, the enzymes are not provided in the form of the pure protein, but rather in the form of stabilized preparations that can be stored and transported. These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like preparations, solutions of the enzymes, advantageously as concentrated as possible, low in water and/or mixed with stabilizers or other auxiliaries.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes have solidified gel encapsulated or of the core-shell type in which an enzyme-containing core is coated with a water, air and/or chemical impermeable protective layer. Additional active substances, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can also be applied in superimposed layers. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example due to the application of polymeric film formers, produce little dust and are stable in storage due to the coating.

Furthermore, it is particularly possible to package two or more enzymes together, so that a single granulate has a number of enzyme activities, as explained above.

An enzyme-containing formulation as described above contains at least one enzyme as defined above, usually in an amount of 0.1 to 50% by weight, preferably 0.1 to 20% by weight, based on the total weight of the formulation .

In liquid formulations, the enzymes are preferably used as enzyme liquid formulation(s). In various embodiments, such a liquid enzyme-containing formulation contains at least one organic solvent, preferably selected from alcohols, particularly preferably polyhydric alcohols that are liquid under standard conditions (20° C., 1013 mbar), in particular glycerol, 1,2-propanediol and sorbitol, and mixtures thereof . When included, the amount is preferably from 0.1% to 99.9%, more preferably from 10% to 90% by weight based on the total weight of the enzyme-containing formulation.

In various embodiments, the pH of an enzyme-containing composition is in the range of 5 to 9, preferably in the range of 5.5 to 8.5, more preferably in the range of 6.5 to 8.0, most preferably in the range of 7.0 to 7.5.

A broad spectrum of activity can be achieved, for example, by combining different enzymes with one another in such a way that there is enzymatic activity against a large number of different types of soiling, for example against grass stains, greasy and starchy soiling.

The agents according to the invention can contain other ingredients, for example at least one other component, preferably at least two other components, which further improve the performance and/or aesthetic properties of the agent. These include, for example, in particular additives to improve the sagging and drying behavior, to adjust the viscosity and/or for stabilization, as well as other auxiliaries and additives customary in cleaning agents, such as chelators, UV stabilizers, fragrances (perfume), dyes, pearlescent agents, corrosion inhibitors , preservatives, bitter substances, organic salts, disinfectants, (structuring) polymers, defoamers, encapsulated ingredients (e.g. encapsulated perfume), pH adjusters and additives that improve the feeling of the skin or care for it.

The amount of suitable components in compositions according to the invention depends on the respective intended use of the composition and the trained specialist is generally familiar with suitable dosages of these components or is able to find correspondingly suitable quantity information in the literature. In various embodiments, the amount of such further additives is up to about 40% by weight, in particular up to about 30% by weight, preferably up to about 25% by weight, more preferably up to about 20% by weight, in each case on the total weight of the cleaning agent.

Examples of additives and additives suitable in the context of the present invention are listed below.

Substances that are also used as ingredients in cosmetic products are referred to below, where appropriate, in accordance with the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds carry an INCI designation in English. In the following, the German translation is given as far as possible and, if necessary, the English name in brackets. The INCI designation can be found in the "International Cosmetic Ingredient Dictionary and Handbook, 7th Edition (1997)" published by The Cosmetic, Toiletry and Fragrance Association (CTFA), Washington D.C. (USA) is published. The indication CAS means that the following sequence of numbers is a designation of the Chemical Abstracts Service.

In some embodiments, an agent according to the invention contains at least one water-soluble and/or water-insoluble, organic and/or inorganic builder (builder).

The builders that can generally be used include, in particular, the aminocarboxylic acids and their salts, zeolites, silicates, carbonates, organic (co)builders and—where there are no ecological prejudices against their use—also the phosphates. According to preferred embodiments, however, the agents according to the invention are phosphate-free.

For example, crystalline layered silicates of the general formula NaMSi _x O _2x+1 · y H ₂ O can be used, where M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particular preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layered silicates of the formula NaMSi _x O _2x+1 · y H ₂ O are marketed, for example, by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₆ .xH ₂ O, kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS -3 (Na ₂ Si ₈ O ₁₇ x H ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ x H ₂ O, makatite). Crystalline phyllosilicates of the formula NaMSi _x O _2x+1 .yH ₂ O, in which x is 2, are particularly suitable for the purposes of the present invention. In particular, both β- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ · y H ₂ O and, above all, Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , Natrosilit), Na-SKS-9 (NaHSi ₂ O ₅ H ₂ O), Na-SKS-10 (NaHSi ₂ O ₆ 3H ₂ O, kanemite), Na-SKS-11 (t -Na ₂ Si ₂ O ₆ ) and Na-SKS-13 (NaHSi ₂ O ₆ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ) is preferred.

Amorphous sodium silicates with an Na ₂ O:SiO ₂ modulus of 1:2 to 1:3.3, preferably of 1:2 to 1:2.8 and in particular of 1:2 to 1:2.6, can also be used are preferably delayed in dissolution and have secondary washing properties. The delay in dissolving compared to conventional amorphous sodium silicates can have been brought about in various ways, for example by surface treatment, compounding, compacting/densification or by overdrying. In the context of this invention, the term "amorphous" is understood to mean 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 , cause.

In the context of the present invention, it is preferred that these silicate(s), preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, are present in the agents in amounts of 1 to 40% by weight, preferably 2 to 35% by weight. -% each based on the weight of the agent are included.

The agents can also contain, in particular, phosphonates as a further builder. A hydroxyalkane and/or aminoalkane phosphonate is preferably used as the phosphonate compound. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. The detergents preferably contain phosphonates in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.5 to 8% by weight, based in each case on the total weight of the dishwashing detergent.

Other builders are the alkali carriers. Examples of alkali carriers are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, the alkali metal silicates mentioned, alkali metal metasilicates and mixtures of the aforementioned substances, with preference being given to using the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, for the purposes of this invention. Due to their low chemical compatibility with some other ingredients of detergents and cleaning agents compared to other builder substances, the optional alkali metal hydroxides are preferably only used in small amounts, preferably in amounts below 10% by weight, more preferably below 6% by weight below 4% by weight and in particular below 2% by weight, based in each case on the total weight of the agent. Agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides are particularly preferred.

Particular preference is given to using carbonate(s) and/or bicarbonate(s), preferably alkali metal carbonate(s), particularly preferably sodium carbonate, in amounts of from 2 to 50% by weight, preferably from 5 to 40% by weight and in particular from 7.5 to 30% by weight, in each case based on the weight of the composition. Agents are particularly preferred which, based on the weight of the agent, contain less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and in particular less contain carbonate(s) and/or bicarbonate(s), preferably alkali metal carbonate(s), particularly preferably sodium carbonate, as 9% by weight.

Organic builders which should be mentioned in particular are polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and the phosphonates already mentioned above as builders. These substance classes are described below.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of the free acid and/or their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder effect, the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH. Particular mention should be made here of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these.

The use of citric acid and/or citrates in these agents has proven to be particularly advantageous for the cleaning and rinsing performance of the agents described herein. Automatic dishwashing detergents are therefore preferred, characterized in that the automatic dishwashing detergent contains citric acid or a salt of citric acid.

Another important class of phosphate-free builders are aminocarboxylic acids and/or their salts. Particularly preferred representatives of this class are methylglycine diacetic acid (MGDA) or its salts and glutamic diacetic acid (GLDA) or its salts or ethylenediamine diacetic acid or its salts (EDDS). Also suitable are iminodisuccinic acid (IDS) and iminodiacetic acid (IDA). The content of these aminocarboxylic acids or their salts can be, for example, between 0.1 and 30% by weight, preferably between 1 and 25% by weight and in particular between 5 and 20% by weight. Aminocarboxylic acids and their salts can be used together with the aforementioned builders.

In various embodiments, the at least one builder is selected from the group consisting of methylglycine diacetic acid (MGDA), glutamic diacetic acid (GLDA), and 1-hydroxyethane-1,1-diphosphonate (HEDP).

In some embodiments, agents according to the invention or individual components of an agent according to the invention can contain water as the main solvent, i.e. it is an aqueous agent or an aqueous component. The water content of an aqueous agent or an aqueous component is usually 15 to 70% by weight, preferably 20 to 60% by weight. In various embodiments, the water content is more than 5% by weight, preferably more than 15% by weight and particularly preferably more than 50% by weight, based in each case on the total amount of the aqueous agent or the aqueous component.

In addition, non-aqueous solvents can be added. Suitable non-aqueous solvents include monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range. The solvents are preferably 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 of these Solvent.

The one or more non-aqueous solvent(s) is/are usually in an amount of 0.1 to 60% by weight, preferably 5 to 60% by weight, more preferably 10-30% by weight, based on the total weight of the aqueous Contained by means or the aqueous component.

In general, the pH of the agents according to the invention can be adjusted using customary pH regulators. In various embodiments, the pH of agents according to the invention is in a range from 6.5 to 12, preferably 7.0 to 11.5, preferably greater than 7, in particular 7.5 to 10.5. As a pH adjuster acids and/or alkalis, preferably alkalis, are used. Suitable acids are, in particular, organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid.

In addition, however, the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used. Suitable bases come from the group of alkali metal and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide is preferred. The alkali source described above is particularly preferably used to adjust the pH. Even if volatile alkali, for example in the form of ammonia and/or alkanolamines, which can contain up to 9 carbon atoms in the molecule, can be used to adjust the pH, the alkanolamine can here be selected from the group consisting of mono -, Di-, triethanol- and -propanolamine and mixtures thereof, such volatile alkali sources, in particular ethanolamines, are preferably avoided. In various embodiments, the agents according to the invention therefore contain less than 1.75% by weight of alkanolamine, in particular monoethanolamine, and they are very particularly preferably free of it.

To adjust and/or stabilize the pH, an agent according to the invention can also contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight. Buffer substances which are at the same time complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate H ₂ O and tripotassium citrate H ₂ O.

Polymers suitable as additives are in particular maleic acid-acrylic acid copolymer Na salt (for example the commercially available Sokalan® CP 5 from BASF, Ludwigshafen (Germany)), modified polyacrylic acid Na salt (for example the commercially available Sokalan® CP 10 of BASF, Ludwigshafen (Germany)), modified polycarboxylate sodium salt (for example the commercially available Sokalan® HP 25 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example the commercially available Silwet® L-77 from the company BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example the commercially available Silwet® L-7608 from BASF, Ludwigshafen (Germany)) and polyethersiloxanes (copolymers of polymethylsiloxanes with ethylene oxide/propylene oxide segments (polyether blocks)), preferably water-soluble linear ones Polyethersiloxanes with terminal polyether blocks like the commercially available compounds Tegopren® 5840, Tegopren® 5843, Tegopren® 5847, Tegopren® 5851, Tegopren® 5863 or Tegopren® 5878 from Evonik, Essen (Germany). In a particular embodiment of the invention, the polymers mentioned are omitted.

Polymer thickeners, which can also be contained in the cleaning agent, are the polyelectrolytes, which have a thickening effect, polycarboxylates, preferably homo- and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, in particular heteropolysaccharides, as well as other customary thickening agents polymers.

Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacant, gellan, ramsan, dextran or xanthan and their derivatives, for example propoxylated guar, and their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, can be used as an alternative, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl -, Hydroxypropylmethyl- or Hydroxyethyl-methylcellulose or cellulose acetate.

A preferred polymeric thickening agent is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2-15×10 ⁶ and is available, for example, from Kelco under the trade name Keltrol®. for example as a cream-colored powder Keltrol® T (Transparent) or as white granules Keltrol® RD (Readily Dispersable).

Acrylic acid polymers suitable as polymeric thickeners are, for example, high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI: carbomer), which are also referred to as carboxyvinyl polymers will. Such polyacrylic acids are available, inter alia, from BFGoodrich under the trade name Carbopol®, for example Carbopol® 940 (molecular weight M _w approx. 4,000,000 g/mol), Carbopol® 941 (molecular weight M _w approx. 1,250,000 g/mol) or Carbopol® 934 (molecular weight M _w approx. 3,000,000 g/mol).

However, particularly suitable polymeric thickeners are the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters, preferably formed with C _1-4 alkanols (INCI: acrylates copolymer). which include the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and which, for example, from Rohm & Haas under the trade names Aculyn® and Acusol® are available, for example the anionic non-associative polymers Aculyn® 33 (crosslinked), Acusol® 810 and Acusol® 830 (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, which include, for example, the copolymers crosslinked with an allyl ether of sucrose or pentaerythritol of C _10-30 -alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with C _1-4 -Alkanols formed, esters (INCI Acrylates/C _10-30 Alkyl Acrylate Crosspolymer) belong and which are available, for example, from BFGoodrich under the trade name Carbopol®, for example the hydrophobic Carbopol® ETD2623 and Carbopol® 1382 (INCI: Acrylates/C ₁₀ - ₃₀ alkyl acrylate crosspolymer) and Carbopol® AQUA 30 (formerly Carbopol® EX 473).

The content of polymeric thickener is usually not more than 8% by weight, preferably between 0.1 and 7% by weight, particularly preferably between 0.5 and 6% by weight, in particular between 1 and 5% by weight and most preferably between 1.5 and 4% by weight, for example between 2 and 2.5% by weight. In various embodiments of the invention, the cleaning agent is free of polymeric thickeners.

The agent according to the invention can contain one or more water-soluble salts to reduce the viscosity. These can be inorganic and/or organic salts; in a preferred embodiment, the agent contains at least one inorganic salt.

Inorganic salts that can be used according to the invention are preferably selected from the group consisting of colorless, water-soluble halides, sulfates, sulfites, carbonates, hydrogen carbonates, nitrates, nitrites, phosphates and/or oxides of alkali metals, alkaline earth metals, aluminum and/or transition metals; ammonium salts can also be used. Halides and sulfates of the alkali metals are particularly preferred; the inorganic salt is therefore preferably selected from the group consisting of sodium chloride, potassium chloride, sodium sulfate, potassium sulfate and mixtures thereof. Sodium chloride is particularly preferred.

In preferred embodiments, the cleaning agents according to the invention are free of phosphates and/or phosphonates.

The organic salts that can be used according to the invention are, in particular, colorless, water-soluble alkali metal, alkaline earth metal, ammonium, aluminum and/or transition metal salts of carboxylic acids, including dicarboxylic acids. The salts are preferably selected from the group consisting of formate, acetate, propionate, citrate, malate, maleate, tartrate, succinate, malonate, oxalate, lactate, fumarate, adipate, succinate, glutarate, methylglycine diacetic acid trisodium salt and mixtures thereof.

In various embodiments, the viscosity of a liquid agent according to the invention is preferably above 230 mPa*s-1 (Brookfield instrument LVDV II+, spindle 31, 30 rpm, 20° C.), in particular between 240 mPa*s-1 and 1000 mPa*s-1, preferably between 250 mPa*s-1 and 1000 mPa*s-1 and between 250 mPa*s-1 and 350 mPa*s-1.

Other additives customary in cleaning agents include, above all, UV stabilizers, perfume, pearlescent agents (INCI: Opacifying Agents; for example glycol distearate, for example the commercially available Cutina® AGS from Cognis, or mixtures containing it, for example the commercially available Euperlane® from Cognis), dyes, corrosion inhibitors, preservatives (e.g. the technical 2-bromo-2-nitropropane-1,3-diol (CAS 52-51-7), also known as Bronopol), which is available, for example, as Myacide® BT or Boots Bronopol BT from commercially available from Boots), disinfectants, pH adjusters, in particular NaOH, KOH and buffer substances, as well as skin-feel-improving or caring additives (e.g. dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D-panthenol , sericerin, collagen partial hydroly sat, various vegetable protein partial hydrolyzates, protein hydrolyzate fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such as lecithin, soybean oil, etc., plant extracts such as aloe vera, azulene, witch hazel extracts, algae extracts, etc., allantoin, AHA complexes). The additives mentioned above can be present in cleaning agents according to the invention in amounts of up to 10% by weight, usually not more than 5% by weight.

In a preferred embodiment, the agent according to the invention contains at least one perfume and/or at least one fragrance. All perfumes and/or fragrances known to the person skilled in the art can be used, with the proviso that they essentially do not adversely affect the properties of the agent.

It may be desirable to keep the active ingredients that have a positive effect on skin feel or else other sensitive active ingredients, such as perfumes, spatially separate from the actual agent until use. An elegant method for incorporating such sensitive, chemically or physically incompatible or volatile ingredients is the use of microcapsules in which these ingredients are enclosed in a stable manner for storage and transport and from which they are mechanically, chemically, thermally or enzymatically released for or during use . In a preferred embodiment, therefore, one or more of the active ingredients and/or perfumes and/or fragrances which have a positive effect on the feel of the skin are incorporated wholly or partially into microcapsules.

Microcapsules are finely dispersed liquid or solid phases coated with film-forming polymers, during the production of which the polymers are deposited on the material (active ingredient) to be coated after emulsification and coacervation or interfacial polymerization. Here, the active ingredient is encased in a shell-like manner by a solid membrane (microcapsule in the narrower sense) or enclosed by a matrix (microsphere or sphere). In the following, the term microcapsule is used in the general sense for both variants. Such capsules are usually microscopically small (< 50 µm) and are sometimes also referred to as nanocapsules or nanospheres, they can be dried like powder. However, larger capsules or beads (>0.5 mm) that are visible to the naked eye and filled with active ingredients can also be produced. When incorporated into the agent according to the invention, these offer an additional optical attraction if the capsules are distributed in the agent in a stable suspension, which can be achieved by selecting suitable surfactants and thickening agents and setting a suitable viscosity.

All surfactant-stable capsules and capsule materials or spheres and sphere materials available on the market can be used as microcapsules, such as the commercially available Primasphere® (chitosan and agar or carboxymethylcellulose) and Primasponge® (alginate, chitosan, agar) from BASF, Hallcrest Microcapsules ® (gelatin, gum arabic) from Hallcrest, Inc. (US), Coletica Thalaspheres® (maritime collagen) from Coletica (FR), Lipotec Millicapseln® (alginic acid, agar-agar) from Lipotec S.A. (ES), Induchem Unispheres® (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose) and Unicerin® C30 (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose) from Induchem AG (CH), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids) and Softspheres@ (modified Agar-Agar) from Kobo (US) and Kuhs Probiol Nanospheres (phospholipids) from Kuhs (DE) and others. The microcapsules can have any shape within the production-related scope, but they are preferably egg-shaped or ellipsoidal in shape or, in particular, approximately spherical. Depending on the active ingredient and application, the diameter along its greatest spatial extent can be on average between 100 nm (not visually recognizable as a capsule) and 10 mm. The preferred mean diameter is in the range between 0.1 mm and 7 mm, microcapsules with a mean diameter between 0.4 mm and 5 mm being particularly preferred. Dyes, color pigments or pearlescent components can also be added to improve the appearance.

The active substance can be released from the microcapsules mechanically either by crushing the microcapsules during the cleaning process or by breaking them open using a suitable metering device. Other possibilities are the release of the active substance by changing the temperature (putting it into warm washing up liquid), by shifting the pH value, changing the electrolyte content, etc.

If microcapsules are used, their content is usually from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, in particular from 0.2 to 3% by weight and extremely preferably from 0.3 to 2% by weight -%, in each case based on the total weight of the agent, it being possible for the agent according to the invention to contain exclusively microcapsules of the same type or mixtures of microcapsules of different types.

In some embodiments, a cleaning agent according to the invention is in the form of a cleaning agent concentrate. Detergent and cleaning agent concentrates are known in the prior art and expressly fall under the subject matter of the present invention. Suitable concentrates can in particular be in the form of a gel-like or pasty formulation, preferably with a low water content or essentially anhydrous.

The cleaning agents described herein can, in various embodiments, be prepackaged to form dosing units. These dosing units preferably include the amount of cleaning-active substances required for one cleaning cycle. In some embodiments, suitable dosage units have a weight between 12 and 30 g, for example. The volume of the aforementioned dosing units and their three-dimensional shape are particularly preferably selected in such a way that the prefabricated units can be dosed via the dosing chamber of a washing machine or dishwasher. The volume of the dosage unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.

The cleaning agents, in particular the prefabricated dosing units, can have a water-soluble coating. In some embodiments, a composition as described herein is in the form of a unit dose as previously described. In preferred embodiments of this type, such an agent is present, in particular, encased by a water-soluble film.

The water-soluble cover is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures. The cover can be formed from one or from two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if any, can be the same or different. Films are particularly preferred which can be glued and/or sealed to form packaging such as tubes or pillows after they have been filled with an agent. In various embodiments, the foils are in the form of multi-chamber pouches.

It is preferred that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings that contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with sufficiently high water solubility, especially cold water solubility.

Suitable water-soluble films for producing the water-soluble casing are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 to 1,000,000 gmol ^-1 , preferably from 20,000 to 500,000 gmol ^-1 , particularly preferably from 30,000 to 100,000 gmol ^-1 and in particular from 40,000 to 80,000 gmol ^-1 .

Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are correspondingly produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol %, preferably 80 to 90 mol %, particularly preferably 81 to 89 mol % and in particular 82 to 88 mol %.

A polymer selected from the group comprising (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers can also be added to a polyvinyl alcohol-containing film material suitable for producing the water-soluble covering be. A preferred additional polymer are polylactic acids.

In addition to vinyl alcohol, preferred polyvinyl alcohol copolymers include dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.

Polyvinyl alcohol copolymers which are also preferred include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.

It can be preferred that the film material contains further additives. The film material can contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof. Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, anti-blocking agents, anti-adhesive agents or mixtures thereof.

Suitable water-soluble films for use in the water-soluble wrappers of the water-soluble packages of the invention are films sold by MonoSol LLC, for example, under the designation M8630, C8400 or M8900. Other suitable films include films with the designation Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or films VF-HP from Kuraray.

In various embodiments, the cleaning agent according to the invention is in particular a dishwashing detergent, particularly preferably a hand dishwashing detergent.

The invention also relates to the use of the compositions according to the invention for cleaning hard surfaces, as defined herein.

A further subject matter of the invention is a method for cleaning hard surfaces, which is characterized in that an agent according to the invention is used in at least one method step.

The cleaning agent can be applied undiluted or as an aqueous dilution either directly or, for example, by means of a cloth, a sponge or a brush to the surface to be cleaned, optionally left to act and then removed again with water. The agent according to the present invention is used for cleaning surfaces, preferably hard surfaces, in particular crockery, cutlery and cooking utensils.

A further object of the present invention is accordingly also methods for manual cleaning of surfaces, preferably hard surfaces, in particular crockery, cutlery and cooking utensils, in which an agent according to the invention is used in at least one method step.

In principle, such manual methods are also contemplated in which the packaging or dosage form of a cleaning agent according to the invention, for example in the form of a concentrate, is selected in such a way that skin contact during use can be largely avoided. A form of administration that is advantageous in this respect can include, for example, the application of the agent from a tube, in which case the tube opening can also optionally be provided with an attachment facilitating the application of the agent to the surface to be cleaned or treated, for example in the form of a brush or lamella. Skin contact can also be largely avoided if an agent according to the invention is pre-portioned in a water-soluble coating and is used, for example, to produce an aqueous dilution of the agent for use in cleaning methods according to the invention.

In a further aspect, the present invention also relates to the use of a cleaning agent, as described herein, for reducing bad odors and/or preventing the occurrence of bad odors when cleaning hard surfaces, in particular for reducing bad odors that occur over time and/or for avoiding the the occurrence of bad odors over time when cleaning hard surfaces. As used herein, the expression "time-related occurrence of bad odors" refers to the occurrence of bad odors that do not occur immediately when cleaning hard surfaces, but only develop over time and can emanate, for example, from cleaning aids such as sponges, brushes, cloths or the like, which are used during cleaning and have residual moisture and also residues of cleaning agents and soiling, which have thus been at least partially removed from the surfaces. Correspondingly, the cleaning agent according to the invention develops advantageous effects even after the actual application.
In a further aspect, the present invention therefore also relates to the use of a cleaning agent, as described herein, for reducing bad odors and/or preventing the occurrence of bad odors after cleaning hard surfaces.

In the context of the present invention, non-limiting examples of hard surfaces are crockery, cutlery and cooking utensils such as pots and pans, kitchen surfaces such as sinks and fittings, and bathroom surfaces such as sinks, toilets and showers and fittings, and hard floor and wall coverings such as tiles.

All facts, objects and embodiments that are described for means according to the invention are also applicable to this subject of the invention. Therefore, at this point, reference is expressly made to the disclosure at the appropriate point, with the indication that this disclosure also applies to the above methods according to the invention.

The invention is illustrated below using examples, but is not limited to these.

examples

Example 1: Bad odor assessment

Based on a standardized mixture of real substances, which simulates the dirt in a rinsing process for hand dishwashing detergent, tests were carried out in a sponge application form that contained the mixture of real substances for the bad odor test. One sponge was used per experiment and tested as described below.

mixture of real substances

50% by weight liquid ballast dirt
6.67% by weight onions (fresh)
3.33% by weight garlic (fresh)
23.33% by weight anchovy paste (manufacturer: Dittmann)
16.67% by weight Harz cheese (manufacturer: Loose)

ballast dirt

71.14% by weight tap water
5.08% by weight UHT milk 1.5% fat
2.54% by weight of tomato ketchup (manufacturer: Kühne)
2.54% by weight mustard (Lion mustard extra)
2.54% by weight gravy (manufacturer: Knorr)
0.51% by weight potato starch (manufacturer: Emsland)
0.41% by weight benzoic acid
10.16% by weight of margarine (manufacturer: Risso)
5.08% by weight egg yolk (Wiesenhof Eifix)

A bad odor profile was created by the residues of the test dirt of the real substance mixture and the residual moisture in the sponge. The sponges used in the rinsing process were placed in a test container with a volume of 27 l which had an opening (approx. 10×20 cm) in order to allow an olfactory control of the atmosphere in it and thus of the malodor profile emanating from the sponges. Ten olfactory-trained persons assessed the dishwashing sponges used after one day (Table 1) and after two days (Table 2) by smelling them. The intensity of the malodor was rated on a scale from 1 to 10 (1=no longer perceptible; 10=extreme, strong). Table 1 sample malodour intensity Hand dishwashing liquid* 5 Hand dishwashing liquid + 0.1% by weight cyclodextrin 1** 2 Hand dishwashing liquid + 0.1% by weight cyclodextrin 2*** 3
*Pril Kraft Gel Ultra Plus
*methylated beta-cyclodextrin
**Hydroxypropylated beta-cyclodextrin Table 2 sample malodour intensity hand dishwashing detergent 7 Hand dishwashing liquid + 0.1% by weight cyclodextrin 1** 2 Hand dishwashing liquid + 0.1% by weight cyclodextrin 2*** 4
*Pril Kraft Gel Ultra Plus
**methylated beta-cyclodextrin
***Hydroxypropylated beta-cyclodextrin

Example 2: Hand dishwashing detergent formulations (quantities in wt. %)

Table 3 ingredients Formulation 1 Formulation 2 Formulation 3 Formulation 4 water, demin. to 100 to 100 to 100 to 100 anionic surfactant 4-25 4-35 4-32 8-30 Nonionic surfactant 1 -6.5 - 0.1-8 - amphoteric surfactant 1.5-10 1 - 10 - - enzyme 1 0-0.6 0-0.6 0-0.6 0-0.6 enzyme 2 0-0.6 0-0.6 0-0.6 0-0.6 solvent 0.5-10 0.5-10 0.5 - 10 0.5-10 thickener * * * * Citric Acid / Sodium Hydroxide ** ** ** ** preservatives 0.1 -1 0.1-1 0.1-1 0.1-1 Perfume 0.1-0.5 0.1-0.5 0.1-0.5 0.1-0.5 dye 0.00001 -0.2 0.00001 -0.2 0.00001 -0.2 0.00001 -0.2
*Adjust to a viscosity of 1000 - 7000 mPas·s
**Adjust to pH 4 - 9

QUOTES INCLUDED IN DESCRIPTION

This list of documents cited by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent Literature Cited

• WO 2008/046778 A1 [0037, 0050, 0056]

Claims (12)

Cleaning agent, characterized in that the agent contains at least one cyclodextrin in an amount of 0.01 to 30% by weight, based on the total weight of the cleaning agent. The detergent according to claim 1 , characterized in that it further contains at least one surfactant and/or at least one enzyme, preferably at least one surfactant and at least one enzyme. The detergent according to claim 1 or claim 2 , characterized in that the cyclodextrin is contained in an amount of 0.01 to 25% by weight, more preferably in an amount of 0.01 to 5% by weight, in each case based on the total weight of the composition. The cleaning agent according to one of Claims 1 until 3 , characterized in that the cyclodextrin is selected from the group consisting of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, alkylated α-cyclodextrin, alkylated β-cyclodextrin, alkylated γ-cyclodextrin, hydroxyalkylated α-cyclodextrin, hydroxyalkylated β-cyclodextrin , hydroxyalkylated γ-cyclodextrin, methylated cyclodextrin, and mixtures thereof. The cleaning agent according to one of Claims 1 until 4 , characterized in that the cyclodextrin is selected from β-cyclodextrin, hydroxypropylated β-cyclodextrin, methylated β-cyclodextrin and mixtures thereof. The cleaning agent according to one of Claims 1 until 5 , characterized in that the cyclodextrin is methylated β-cyclodextrin or hydroxypropylated β-cyclodextrin or a mixture thereof. The cleaning agent according to one of Claims 1 until 6 , characterized in that the cyclodextrin is methylated β-cyclodextrin. The cleaning agent according to one of Claims 1 until 7 , characterized in that the agent contains at least one further component, preferably at least two further components, selected from the group consisting of additives to improve the flow and drying behavior, to adjust the viscosity and/or for stabilization, chelating agents, UV stabilizers, fragrances ( perfume), dyes, pearlescent agents, corrosion inhibitors, preservatives, bitter substances, organic salts, disinfectants, (structuring) polymers, defoamers, encapsulated ingredients (e.g. encapsulated perfume), pH adjusters and additives that improve the feeling of the skin or care for it. The liquid detergent or cleaning agent according to one of Claims 1 until 8th , characterized in that the agent - is in the form of a detergent concentrate; and/or - is in the form of a unit dose, preferably wrapped in a water-soluble film; and/or - is phosphate-free. Use of the washing or cleaning agent according to one of Claims 1 until 9 for cleaning hard surfaces. Method for cleaning hard surfaces, characterized in that in at least one method step a cleaning agent according to one of Claims 1 until 9 is applied. Use of a cleaning agent according to one of Claims 1 until 9 to reduce malodors and/or to prevent the occurrence of malodors when cleaning hard surfaces.