EP4098727B1 - Viscosity-modified washing up liquid - Google Patents

Description

Dishwashing detergents, in particular liquid dishwashing detergents for manual cleaning, of dishes are known. However, low-viscosity hand dishwashing compositions are perceived by consumers as being of lower quality. Viscosity is therefore an important quality criterion for hand dishwashing compositions. At the same time, modern hand dishwashing detergents should be produced in an environmentally friendly manner and at the same time have the best possible cleaning performance. Another special feature of hand dishwashing compositions is the requirement that they should be gentle on the skin.

Against this background, the demands placed on modern hand dishwashing compositions are correspondingly high. In particular, adjusting the viscosity in the manufacturing process represents a challenge. Viscosity peaks in the compositions can make it difficult to mix the components homogeneously using stirring tools, making the processes more energy-intensive and time-consuming or even completely impossible.

EP3670637 A1 discloses hand dishwashing detergent comprising at least one anionic surfactant and at least one amine oxide surfactant, wherein the amount of amine oxide surfactant is at least 20% by weight of the total amount of surfactant, and the composition has a viscosity factor of 0.1 to 50 mPas.

Overall, there is a need for hand dishwashing detergents that meet the above requirements.

The object on which the present invention is based is therefore to provide compositions which, on the one hand, are perceived by the consumer as being of high quality and which can also be processed in an environmentally friendly manner and at the same time have good skin compatibility.

• wenigstens ein Tensid,
• wobei die Zusammensetzung ferner umfasst
• wenigstens ein anorganisches Salz, wobei das Salz ein Alkalisalz und/oder ein Erdalkalisalz ist, sowie ein Lösungsmittel wobei das Lösungsmittel Ethanol und Cumolsulfonat umfasst, und wobei
• der pH Wert der Zusammensetzung wenigstens 7,5 beträgt und weniger als 8,5 und die Viskosität der Zusammensetzung 1000 cps bis 4000 cps beträgt.

This task is solved by a hand dishwashing composition comprising:

• at least one surfactant,
• wherein the composition further comprises
• at least one inorganic salt, the salt being an alkali metal salt and/or an alkaline earth metal salt, and a solvent, the solvent comprising ethanol and cumene sulfonate, and wherein
• the pH of the composition is at least 7.5 and less than 8.5 and the viscosity of the composition is 1000 cps to 4000 cps.

It was surprisingly found that the compositions according to the invention in particular have a good viscosity profile in the skin-friendly pH range of at least 7.5 to less than 8.5. In this context, a “good viscosity profile” means that the viscosity of the compositions is such that the consumer perceives the compositions as being of high quality and the viscosity is within the range The relevant pH range has a relatively small change depending on the pH value. It was identified that the viscosity range between 1000 cps and 4000 cps represents a particularly advantageous range in terms of finding a balance between good processability on the one hand and high-quality product properties on the other.

According to a further preferred embodiment, the viscosity of the composition is at least 1500 cps to 2500 cps.

According to a still further preferred embodiment, the viscosity of the composition is at least 1800 cps to 2200 cps.

The viscosity is determined using a Brookfield LVDV II+, spindle 31 at a temperature of 20 ° C, at 12 rpm.

According to a preferred embodiment, the hand dishwashing composition is described, wherein the salt is an alkali metal halide and/or an alkaline earth metal halide, preferably sodium chloride.

According to a preferred embodiment, the hand dishwashing composition is described, wherein the amount of inorganic salt is at least 2% by weight, preferably at least 4% by weight.

According to a preferred embodiment, the hand dishwashing composition is described, wherein the ratio of total surfactant content to solvent is less than 10, preferably between 4 and 6, more preferably 4 or 5.

According to a preferred embodiment, the hand dishwashing composition is described, wherein the hand dishwashing composition comprises at least one enzyme.

According to a preferred embodiment, the hand dishwashing composition is described, wherein the hand dishwashing composition comprises an anionic surfactant.

According to a preferred embodiment, the hand dishwashing composition is described, wherein the hand dishwashing composition comprises an amine oxide and/or a betaine surfactant.

According to a preferred embodiment, the hand dishwashing composition is described, wherein the total amount of surfactant is at least 8% by weight, more preferably at least 12% by weight, more preferably at least 20% by weight.

According to a preferred embodiment, the hand dishwashing composition is described, wherein the hand dishwashing composition comprises at least one enzyme. According to a preferred embodiment, the hand dishwashing composition is described, wherein the hand dishwashing composition comprises an anionic surfactant. According to a preferred embodiment, the total amount of solvent is at least 1% by weight, more preferably at least 2% by weight and more preferably at least 2.5% by weight.

According to a further aspect, the use of the composition is for manual cleaning of dishes.

• Bereitstellen wenigstens eines Tensid,
• Bereitstellen wenigstens eines anorganischen Salzes, wobei das Salz ein Alkalisalz und/oder ein Erdalkalisalz ist,
• Bereitstellen von Lösungsmittel, und
• Einstellen des pH Wertes der Zusammensetzung in einem Bereich von wenigstens 7.

According to a further aspect, the preparation of the composition for manual dishwashing is described, comprising the steps:

• providing at least one surfactant,
• Providing at least one inorganic salt, the salt being an alkali metal salt and/or an alkaline earth metal salt,
• Providing solvent, and
• Adjusting the pH of the composition to a range of at least 7.

Preferably, the amount of total surfactant is at least 5% by weight, 10% by weight based on the total weight of the composition.

According to a preferred embodiment, a hand dishwashing composition is described, wherein the proportion of amine oxides having a C16 or longer residue is less than 20%, more preferably less than 10%, based on the total weight of the amine oxides in the composition.

According to a preferred embodiment, a hand dishwashing composition is described, wherein the anionic surfactant is present in an amount of at least 4% by weight, preferably at least 10% by weight, based on the total weight of the composition. According to a preferred embodiment, a hand dishwashing composition is described, wherein aminexoid is present in an amount of at least 4% by weight based on the total weight of the composition.

According to a preferred embodiment, a hand dishwashing composition is described, wherein betaine is present in an amount of at least 4% by weight based on the total weight of the composition.

According to a preferred embodiment, a hand dishwashing composition is described, wherein the composition comprises an organic solvent which is present in at least an amount of 2% by weight. According to a preferred embodiment, a hand dishwashing composition is described, wherein the proportion of amine oxides that have a C12 residue is between 50 and 85% based on the total amount of amine oxide, preferably between 60 and 85%. According to a preferred embodiment, a hand dishwashing composition is described, wherein the proportion of amine oxides which have a C14 residue is between 20 and 35% based on the total amount of amine oxide.

According to a preferred embodiment, a hand dishwashing composition is described, wherein the proportion of amine oxides which only have C10 or smaller residues is less than 5% based on the total amount of amine oxide.

According to a preferred embodiment, a hand dishwashing composition is described, wherein the surfactant system contains at least one anionic surfactant selected from ether sulfates, alkyl sulfates and mixtures thereof.

Hand dishwashing composition, wherein the dishwashing composition contains at least one additional ingredient selected from the group consisting of water, enzymes, organic solvents, enzymes, additives to improve drainage and drying behavior, to adjust the viscosity and / or for stabilization, UV stabilizers, perfume, pearlescent agents, Dyes, corrosion inhibitors, bitter substances, organic salts, disinfectants, structuring polymers, defoamers, encapsulated ingredients, pH adjusters and additives that improve or care for skin feel.

In a further aspect, the present invention is further directed to the use of the dishwashing detergent according to the invention for manually cleaning dishes.

"At least one" as used herein refers to 1 or more, for example 2, 3, 4, 5, 6, 7, 8, 9 or more. In connection with components of the compounds described herein, this information does not refer to the absolute amount of molecules, but rather to the type of component. “At least one surfactant” therefore means, for example, that only one type of surfactant compound or several different types of surfactant compounds can be included, without providing information about the amount of the individual compounds.

Unless otherwise stated, all quantities given in connection with the dishwashing detergents described herein refer to % by weight based on the total weight of the dishwashing detergent. Furthermore, such quantities that relate to at least one component always refer to the total amount of this type of component contained in the dishwashing detergent, unless explicitly stated otherwise. This means that such quantities, for example in connection with “at least one surfactant”, refer to the total amount of surfactants contained in the dishwashing detergent, unless explicitly stated otherwise.

Numerical values stated herein without decimal places refer to the full stated value with one decimal place. For example, "99%" stands for "99.0%".

The expressions “approximately” “approx.” or "about", in connection with a numerical value, refers to a variance of ±10% based on the specified numerical value, preferably ±5%, particularly preferably ±1%.

The expression “essentially free of” means that the respective compound can in principle be included, but is then present in an amount that does not impair the function of the other components. In the context of the present invention, the property “substantially free of” a particular compound is therefore preferably a total weight of less than 0.1% by weight, more preferably less than 0.001% by weight, in particular free of this, based on the total weight of dishwashing detergent.

Numerical ranges specified in the format "in/from x to y" include the stated values. When multiple preferred numerical ranges are specified in this format, it is understood that any ranges resulting from the combination of the various endpoints will also be captured.

Information about the molecular weight refers to the weight-average molecular weight in g/mol, unless the number-average molecular weight is explicitly stated. Molecular weights are preferably determined by GPC using polystyrene standards.

In the context of the present invention, fatty acids or fatty alcohols or their derivatives - unless otherwise stated - represent branched or unbranched carboxylic acids or alcohols or their derivatives with preferably 6 to 22 carbon atoms. In particular, the oxo alcohols or their derivatives obtainable, for example, by ROELEN's oxo synthesis can also be used accordingly.

If components of the present agents are salts, they are preferably alkali metal or alkaline earth metal salts of the respective compounds, more preferably the alkali metal salts, in particular the sodium or potassium salts, most preferably sodium salts thereof. 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 as the anion - which is sufficient to balance the charge.

In the present invention, substituted radicals are preferably those radicals in which the substituent is selected from -F, -Cl, -Br, -OH, -OC1-4Alkyl, =O, -NH2, or -N(C1-4Alkyl)2 , the substituent preferably replaces one or more H atoms.

These and other aspects, features and advantages of the invention will become apparent to those skilled in the art from reading the following detailed description and claims. Any feature or embodiment from one aspect of the invention can be used in any other aspect of the invention. For example, described features or embodiments of the dishwashing detergents can also be applied to the claimed uses, and vice versa. Furthermore, it is to 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 dishwashing detergent according to the invention is preferably essentially free of cationic surfactants.

According to one embodiment, the composition has at least one alkyl benzene sulfonate, which preferably has a C2-18 alkyl radical. Cumenesulfonate is particularly preferred. According to the invention, the term alkylbenzenesulfonate refers only to a benzene ring substituted with an alkyl radical and which also carries a sulfonate radical.

In preferred embodiments, the at least one alkylbenzene sulfonate is contained in 0.5 to 50% by weight, preferably 0.5 to 30% by weight, particularly preferably in 0.5 to 5% by weight, based on the total weight of the dishwashing detergent.

The at least one fatty alcohol sulfate is preferably selected from C8-18 fatty alcohol sulfates. Particularly preferred fatty alcohol sulfates are derived from C12-18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol. Sodium lauryl sulfate is particularly preferred.

In preferred embodiments, the at least one fatty alcohol sulfate is contained in 0.5 to 45% by weight, preferably 0.5 to 40% by weight, more preferably in 3 to 15% by weight, based on the total weight of the dishwashing detergent.

In a preferred embodiment, the at least one amine oxide is a compound having the formula R1R2R3NO, where each R1, R2 and R3, independently of the others, is an optionally substituted, for example hydroxy-substituted, C1-C30 hydrocarbon chain. Particularly preferred amine oxides used are those in which R1 is C10-C16 alkyl and R2 and R3 are each independently C1-C4 alkyl, in particular C10-C16 alkyldimethylamine oxides. Examples of suitable amine oxides are N-cocoalkyl-N,N-dimethylamine oxide and N-tallow alkyl-N,N-dihydroxyethylamine oxide. The at least one amine oxide is preferably selected from C12-16 amine oxides, particularly preferably from low-chain C12-14 alkyldimethylamine oxides.

In preferred embodiments, the at least one amine oxide is contained in 0.1 to 20 wt.%, preferably 0.3 to 10 wt.%, more preferably 0.5 to 3 wt.%, based on the total weight of the dishwashing detergent .

If present, this is at least one further anionic, nonionic or zwitterionic surfactant, preferably in 0.1 to 45% by weight, preferably 0.5 to 40% by weight, more preferably in 1 to 25% by weight, based on the total weight of the dishwashing detergent included.

All anionic surfactants known for dishwashing detergents are suitable as further anionic surfactants.

Other suitable surfactants are, for example, alpha-olefin sulfonates. Preferred alpha-olefin sulfonates are selected from C10-20 alpha-olefin sulfonates, more preferably linear C10-20 alpha-olefin sulfonates. In particular it is selected from C12-14 alpha-olefin sulfonates; most preferably it is a linear C12-14 alpha-olefin sulfonate.

The at least one alpha-olefin sulfonate is preferably contained in 2.5 to 45% by weight, more preferably 3 to 30% by weight, particularly preferably in 5 to 25% by weight, based on the total weight of the dishwashing detergent.

A suitable alpha-olefin sulfonate is commercially available, for example, under the trade name Bio- ^Terge® AS-40 from Stephan.

In one embodiment, the at least one further anionic surfactant is selected from ether sulfates, alkyl sulfates and mixtures thereof.

Preferred ether sulfates are those of the formula (I)

R1-O-(AO)n-SO3- X+ (I).

In this formula (I), R1 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R1 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives having an even number of carbon atoms are preferred. Particularly preferred radicals R1 are derived from C12-C18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C10-C20 oxo alcohols.

X stands for a single-quality cation or the n-ten part of an N-quality cation, preferably the alkali metal ions and below Na+ or K+, where Na+ is extremely preferred. Further cations

AO represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group. The index n represents an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. Very particularly preferably n represents the numbers 2, 3, 4, 5, 6, 7 or 8.

Other suitable anionic surfactants are the alkyl sulfates, which are not derived from fatty alcohols, of the formula

R2-O-SO3-X+ (II).

In this formula (II), R2 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R2 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives having an even number of carbon atoms are preferred. They are particularly preferably derived from C10-20 oxo alcohols.

X stands for a single-quality cation or the n-ten part of an N-quality cation, preferably the alkali metal ions and below Na+ or K+, where Na+ is extremely preferred. Further cations

If present, the at least one further nonionic surfactant is 0.1 to 20 wt.%, preferably 0.5 to 10 wt.%, more preferably 1 to 8 wt.%, based on the total weight of the dishwashing detergent contain.

All nonionic surfactants known for dishwashing detergents are suitable as further nonionic surfactants.

In one embodiment, the at least one further nonionic surfactant is selected from alkoxylated fatty acid alkyl esters, polyhydroxy fatty acid amides, alkyl glycosides and alkoxylated alcohols and mixtures thereof.

Another class of preferably used nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

Other suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.

Also suitable are alkyl glycosides of the general formula RO (G) a glycose unit with 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

In one embodiment, the further nonionic surfactants are selected from the group of alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) or propylene oxide (PO) per mole of alcohol, in which the alcohol residue is linear or preferably in 2 position can be methyl-branched or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C12-14 alcohols with 3 EO or 4 EO, C8-11 alcohol with 7 EO, C13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-18 Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14 alcohol with 3 EO and C12-18 alcohol with 5 EO.

In various embodiments, the total amount of surfactants, i.e. the surfactant system, based on the weight of the agent, is 2.5 to 70% by weight, preferably 5 to 60% by weight, more preferably 6 to 50% by weight.

The dishwashing detergent according to the present invention can also contain at least one additional ingredient selected from the group consisting of water, enzymes, additives to improve drainage and drying behavior, to adjust the viscosity and / or for stabilization, UV stabilizers, perfume, pearlescent agents, dyes , corrosion inhibitors, preservatives, bitter substances, organic salts, disinfectants, structuring polymers, defoamers, encapsulated ingredients, pH adjusters and additives that improve or care for skin feel.

In one embodiment, the dishwashing detergents according to the present invention are liquid and contain water as the main solvent, i.e. they are aqueous dishwashing detergents. The water content of the aqueous agent according to the invention is usually 15 to 90% by weight, preferably 20 to 60% by weight.

In addition, other organic solvents can be added to the dishwashing detergent. Suitable organic solvents include cumene sulfonate, mono- 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, glycerin, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, Ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl 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 solvents. Ethanol is particularly preferred. The organic solvent is preferably contained in 0.1 to 10% by weight, based on the total weight of the dishwashing detergent.

According to the invention, the solvent comprises cumene sulfonate and ethanol.

In various embodiments, the dishwashing detergents described herein may further contain at least one enzyme, preferably a protease. The proteases used are preferably alkaline serine proteases. They act as non-specific endopeptidases, that is, they hydrolyze any acid amide bonds that are inside peptides or proteins and thereby cause the breakdown of protein-containing soils on the items to be cleaned. Their pH optimum is usually in the significantly alkaline range.

• der Alkalischen Protease aus Bacillus amyloliquefaciens (BPN'),
• der Alkalischen Protease aus Bacillus licheniformis (Subtilisin Carlsberg),
• der Alkalischen Protease PB92,
• Subtilisin 147 und/oder 309 (Savinase)
• der Alkalischen Protease aus Bacillus lentus, vorzugsweise aus Bacillus lentus (DSM 5483),
• der Alkalischen Protease aus Bacillus alcalophilus (DSM 11233),
• der Alkalischen Protease aus Bacillus gibsonii (DSM 14391) oder einer hierzu mindestens zu 70% identischen Alkalischen Protease,
• der Alkalischen Protease aus Bacillus sp. (DSM 14390) oder einer hierzu mindestens zu 98,5% identischen Alkalischen Protease, und
• der Alkalischen Protease aus Bacillus sp. (DSM 14392) oder einer hierzu mindestens zu 98,1 % identischen Alkalischen Protease.

The proteases preferably used according to the invention are preferably a serine protease, in particular a subtilase, particularly preferably a subtilisin. The subtilisin can be a wild-type enzyme or a subtilisin variant, the wild-type enzyme or the starting enzyme of the variant preferably being selected from one of the following:

• the alkaline protease from Bacillus amyloliquefaciens (BPN'),
• the alkaline protease from Bacillus licheniformis (Subtilisin Carlsberg),
• the alkaline protease PB92,
• Subtilisin 147 and/or 309 (Savinase)
• the alkaline protease from Bacillus lentus, preferably from Bacillus lentus (DSM 5483),
• the alkaline protease from Bacillus alcalophilus (DSM 11233),
• the alkaline protease from Bacillus gibsonii (DSM 14391) or an alkaline protease that is at least 70% identical,
• the alkaline protease from Bacillus sp. (DSM 14390) or an alkaline protease that is at least 98.5% identical, and
• the alkaline protease from Bacillus sp. (DSM 14392) or an alkaline protease that is at least 98.1% identical.

Examples of the proteases that can be used in the agents described herein are subtilisin 309 or functional fragments/variants thereof and variants of the alkaline protease from Bacillus lentus or variants thereof. Subtilisin 309 is sold under the trade name Savinase ^® by the Distributed by Novozymes A/S, Bagsvaerd, Denmark. Optimized enzyme variants of subtilisin 309 from Bacillus lentus are available from Novozymes under the trade names ^Blaze® and ^Ovozyme® , which represent a preferred embodiment of the invention. For example, the protease variants known as BLAP ^® are derived from the alkaline protease from Bacillus lentus DSM 5483. Particular preference is given here to those protease variants which, compared to the BLAP wt (wild-type) enzyme, in the count according to BLAP wt, have at least one mutation at R99, in particular R99E or R99D, particularly preferred is R99E, and optionally additionally at least one or two , preferably all three of the amino acid substitutions S3T, V4I and V199I, particularly preferred are the BLAP variants as in SeqlD No 4 or 5 of WO 2014/177430 are described.

In the dishwashing detergents described here, the enzymes to be used can also be formulated together with accompanying substances, for example from fermentation. In liquid agents, the enzymes are preferably used as enzyme liquid formulation(s).

The proteases are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations. These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and/or mixed with stabilizers or other auxiliaries.

Alternatively, the enzymes can be encapsulated for both the solid and liquid dosage forms, 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 are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is covered with a water-, air- and/or chemical-impermeable protective layer. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers. Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes. Such granules are advantageously low-dust, for example by applying polymeric film formers, and are storage-stable due to the coating.

Furthermore, it is possible to assemble two or more enzymes together so that a single granulate has several enzyme activities.

Dishwashing detergents according to the invention can alternatively or in addition to the at least one protease contain one or more further enzymes, in particular from the following group: amylases, hemicellulases, cellulases, lipases and oxidoreductases.

The dishwashing detergent according to the invention particularly preferably also contains at least one amylase.

The amylase(s) is preferably an α-amylase. The hemicellulase is preferably a β-glucanase, a pectinase, a pullulanase and/or a mannanase. The cellulase is preferably a cellulase mixture or a single-component cellulase, preferably or predominantly an endoglucanase and/or a cellobiohydrolase. The oxidoreductase is preferably an oxidase, in particular a choline oxidase, or a perhydrolase. The enzymes mentioned can all be formulated as described above for the proteases.

In dishwashing detergents according to the invention, the at least one enzyme, preferably the at least one protease and/or at least one amylase, is present in an amount of 0.01 - 1.6% by weight, preferably 0.05 - 1.2% by weight on the total weight of the dishwashing detergent contained in it.

In various embodiments, the enzyme(s) may be preformulated with enzyme stabilizers in an enzyme composition. The enzyme protein usually only forms a fraction of the total weight of the enzyme preparation. Enzyme preparations used with preference contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0.8 and 10% by weight. % of enzyme protein. In such compositions, an enzyme stabilizer may be included in an amount of 0.05-35% by weight, preferably 0.05-10% by weight, based on the total weight, in the enzyme composition. This enzyme composition can then be used in dishwashing detergents according to the invention in amounts which lead to the final concentrations in the dishwashing detergent specified above. Suitable enzyme stabilizers are known in the art. In various embodiments, the agent according to the invention can accordingly additionally have one or more enzyme stabilizers.

The protein concentration can be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method. In this regard, the active protein concentration is determined by titrating the active protein Centers using a suitable irreversible inhibitor (for proteases, for example phenylmethylsulfonyl fluoride (PMSF)) and determining the residual activity (cf. M. Bender et al., J. Am. Chem. Soc. 88, 24 (1966), pp. 5890-5913 ).

To further improve the drainage and/or drying behavior, the agent according to the invention can contain one or more additives from the group of polymers and builders, usually in an amount of 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, most preferably 0.5 to 1.5% by weight, for example 1% by weight.

Polymeric thickeners in the context of the present invention are the polycarboxylates, which act as polyelectrolytes and have a thickening effect, 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 common thickening polymers.

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

Acrylic acid polymers suitable as polymeric thickeners are, for example, high molecular weight homopolymers of acrylic acid (INCI carbomer) crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers.

However, particularly suitable polymeric thickeners are the following acrylic acid copolymers: (i) copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters, preferably formed with C1 4 alkanols (INCI Acrylates Copolymer), which include the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate ( CAS 25035 69 2) or from butyl acrylate and methyl methacrylate ( CAS 25852 37 3 ) belong; (ii) crosslinked high molecular weight acrylic acid copolymers, which include, for example, the copolymers of C10 30 alkyl acrylates crosslinked with an allyl ether of sucrose or pentaerythritol with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably formed with C1 4 alkanols, esters (INCI Acrylates/C10-30 Alkyl Acrylates Crosspolymer).

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, based on the total weight of the dishwashing detergent.

To stabilize the agent according to the invention, especially when there is a high surfactant content, one or more dicarboxylic acids and/or their salts can be added, in particular a composition of Na salts of adipic, succinic and glutaric acid, such as those available under the trade name ^Sokalan® DSC is. It is advantageously used in amounts of 0.1 to 8% by weight, preferably 0.5 to 7% by weight, in particular 1.3 to 6% by weight and particularly preferably 2 to 4% by weight, based on the total weight of the dishwashing detergent.

However, if their use can be dispensed with, the agent according to the invention is preferably free of dicarboxylic acid (salts).

In addition, one or more other - especially in hand dishwashing detergents - common auxiliaries and additives, in particular UV stabilizers, perfume, pearlescent agents (INCI opacifying agents; for example glycol distearate, for example Cutina ^® AGS from Cognis, or mixtures containing this, for example Euperlane ^® from Cognis), dyes, corrosion inhibitors, preservatives (e.g. the technical 2-bromo-2-nitropropane-1,3-diol, also known as bronopol ( CAS 52-51-7 ), which is commercially available, for example, as Myacide ^® BT or as Boots Bronopol BT from Boots) or Acticide MBR 1 or Acticide CMB 2, organic salts, disinfectants, pH adjusters and additives that improve skin feel or care for the skin (e.g. dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D panthenol, sericerin, collagen partial hydrolyzate, various vegetable protein partial hydrolysates, protein hydrolyzate fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such as e.g. lecithin, soybean oil, etc., plant extracts such as aloe vera, azulene, witch hazel extracts, algae extracts, etc., allantoin, AHA complexes, glycerin, urea, quaternized hydroxyethyl cellulose), in amounts usually not more than 8% by weight based on the total weight of the dishwashing detergent.

Na-xylenesulfonate can be used as an additive.

The pH value of the agent according to the invention can be adjusted using conventional pH regulators, for example acids such as mineral acids or citric acid and/or alkalis such as sodium or potassium hydroxide, with a range of 4 to 9 - particularly if hand tolerance is desired.

To adjust and/or stabilize the pH value, the agent according to the invention can contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight, preferably 0.005 to 3% by weight, in particular 0 .01 to 2% by weight, particularly preferably 0.05 to 1% by weight, most preferably 0.1 to 0.5% by weight, for example 0.2% by weight. Buffer substances that are also 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 2 H2O and tripotassium citrate H2O.

Example compositions:

The example compositions shown in Table 1 were provided using a basic formulation comprising 6.4% by weight anionic surfactant and 1.6% amine oxide surfactant. The total amount of surfactant is therefore 8% by weight. The recipe also contained smaller amounts of fragrances and dyes as well as protease and amylase enzymes. Table 1 Example Reference symbols EtOH C.S AM / LM _total NaCl C1 10 0 0.6 13 4.4 E1 50 1.5 0.6 4 6.7 E2 30 0.75 0.6 6 5.27 E3 40 1,125 0.6 5 6 E4 80 1.5 0.6 4 7.65 E5 70 1.5 0.6 4 7.2

All information is given as% by weight in relation to the overall composition. The compositions result from the values in Table 1 and the basic recipe. According to Table 1, the solvent includes ethanol and cumene sulfonate, CS. The table also shows the ratio of the total amount of surfactant to the total amount of solvent. The viscosity curves are in Figure 1 shown.

The example recipes E1 to E5 according to the invention show that the compositions according to the invention in particular have a good viscosity profile in the skin-friendly pH range of at least 7. The viscosities of the compositions are such that the consumer perceives the compositions to be of high quality and the viscosity within the relevant pH range has a relatively small/stable change depending on the pH value. The homogeneous mixing of the components using stirring tools was possible sufficiently well.

The comparison formulation C1, however, showed an unsuitable viscosity profile. High viscosity values could be achieved. In contrast to the example recipes according to the invention, however, these were not sufficiently constant/stable depending on the pH value. The manufacturing process of such a composition is made considerably more difficult or even impossible due to the viscosity peaks, since sufficient mixing of the composition using stirring tools is prevented.

Overall, the composition E2 has a slight peak in viscosity. The ratio of total surfactant content to solvent is 6. Therefore, according to a preferred embodiment, a ratio of total surfactant content to solvent is described which is less than 10, in particular 4 and 5, as is the case in examples E1, E3, E4, and E5 is.

Furthermore, example compositions with a higher total surfactant content were provided. The corresponding example compositions shown in Table 2 were provided using a basic recipe comprising 16% by weight anionic surfactant and 4% amine oxide surfactant. The total amount of surfactant is therefore 20% by weight. The recipe also contained smaller amounts of fragrances and dyes as well as protease and amylase enzymes. Table 2 Example Reference symbols EtOH C.S AM / LM _total NaCl C2 110 1 1 10 1,875 E6 150 3.9 1 4 4.9

All information is given as% by weight in relation to the overall composition. The compositions result from the values in Table 2 and the basic recipe. According to Table 2, the solvent includes ethanol and cumene sulfonate, CS. The table also shows the ratio of the total amount of surfactant to the total amount of solvent. The viscosity curves are in Figure 2 shown.

The comparison formulation C2 showed an even more pronounced viscosity peak than in the compositions with lower total surfactant amounts C1. The problem already presented applies particularly to higher total surfactant contents.

The composition E6 according to the invention is characterized by a particularly stable viscosity profile. Compared to the recipes E1 to E5 with a lower total surfactant content, even better stabilization of the viscosity is achieved.

In conclusion, it should be noted that the advantageous stabilization of the viscosity curve occurs particularly at higher total surfactant amounts of at least 12% by weight. Here the ratio of total surfactant content to solvent is also preferably less than 10, in particular between 4 and 6, more preferably 4 or 5.

Claims (10)

1. Hand dishwashing composition comprising:

   at least one surfactant,

   characterized in that the composition further comprises

   at least one inorganic salt, wherein the salt is an alkali metal salt and/or an alkaline earth metal salt, solvent, and wherein the viscosity of the composition is 1000 cps to 4000 cps, and

   wherein the pH of the composition is at least 7.5 and less than 8.5, and wherein the solvent comprises ethanol and cumene sulfonate.
2. Hand dishwashing composition according to claim 1, wherein the viscosity of the composition is 1500 cps to 3500 cps, preferably 1500 to 3000 cps.
3. Hand dishwashing composition according to any one of the preceding claims, wherein the salt is an alkali metal halide and/or an alkaline earth metal halide, preferably potassium chloride and/or sodium chloride.
4. Hand dishwashing composition according to any one of the preceding claims, wherein the amount of inorganic salt is at least 2% by weight, preferably at least 4% by weight.
5. Hand dishwashing composition according to any one of the preceding claims, wherein the ratio of total surfactant content to solvent is less than 10, preferably between 4 and 6, more preferably 4 or 5.
6. A hand dishwashing composition according to any one of the preceding claims, wherein the hand dishwashing composition comprises at least one enzyme.
7. A hand dishwashing composition according to any one of the preceding claims, wherein the hand dishwashing composition comprises an anionic surfactant.
8. Hand dishwashing composition according to any one of the preceding claims, wherein
   the hand dishwashing composition comprises an amine oxide and/or a betaine surfactant.
9. Hand dishwashing composition according to any one of the preceding claims, wherein the total amount of surfactant is at least 12% by weight, preferably at least 20% by weight.
10. Use of a composition according to any one of the preceding claims for the manual cleaning of dishes.

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