DE102019207893A1 - Increase in solubility through a specific surfactant mixture - Google Patents

Abstract

The present invention relates to dishwashing detergents, preferably hand dishwashing detergents, containing a surfactant system, the surfactant system: (A) at least one alkylbenzenesulfonate; (B) at least one fatty alcohol sulfate; (C) at least one amine oxide; comprises or consists of, and (D) a salt of citric acid; provided that the following relationship is satisfied [(% by weight (A) x% by weight (B)) /% by weight (C)] +% by weight (D) = R, where R is a Number is from 5 to 120 and D is present in an amount of 0.05 to 5% by weight.

Description

1. (A) mindestens ein Alkylbenzolsulfonat;
2. (B) mindestens ein Fettalkoholsulfat; und
3. (C) mindestens ein Aminoxid; umfasst oder daraus besteht,
4. (D) ein Salz der Zitronensäure

mit der Maßgabe, dass folgende Beziehung erfüllt ist
(Gew.-% (A) x Gew.-%(B)) / Gew.-% (C) + Gew.-%(D) = R, wobei R eine Zahl von 5 bis 120 ist und
D in einer Menge von 0,05 bis 5 Gew.-% vorliegt.The present invention relates to dishwashing detergents containing a surfactant system, the surfactant system:

1. (A) at least one alkyl benzene sulfonate;
2. (B) at least one fatty alcohol sulfate; and
3. (C) at least one amine oxide; includes or consists of
4. (D) a salt of citric acid

with the proviso that the following relationship is fulfilled
(% By weight (A) x% by weight (B)) /% by weight (C) +% by weight (D) = R, where R is a number from 5 to 120 and
D is present in an amount from 0.05 to 5 percent by weight.

The present invention also relates to the use of the dishwashing detergent according to the invention for the manual cleaning of dishes.

The present invention also relates to the use of the surfactant system according to the invention in one for increasing the solubility of a dishwashing detergent.

Dishwashing detergents, in particular liquid dishwashing detergents for the manual cleaning of dishes, are known. In order to have suitable filling characteristics and to be able to be dosed appropriately by the consumer, liquid dishwashing detergents must have a specified flow behavior. Furthermore, the agents must be capable of dissolving a large number of components in a storage-stable manner. Solvents are usually added to this, but they are expensive and polluting. The object of the present invention was therefore to provide new dishwashing detergents with good solubility.

1. (A) mindestens ein Alkylbenzolsulfonat;
2. (B) mindestens ein Fettalkoholsulfat; und
3. (C) mindestens ein Aminoxid; umfasst oder daraus besteht,
4. (D) ein Salz der Zitronensäure

mit der Maßgabe, dass folgende Beziehung erfüllt ist
(Gew.-% (A) x Gew.-%(B)) / Gew.-% (C) + Gew.-%(D) = R, wobei R eine Zahl von 5 bis 120 ist und
D in einer Menge von 0,05 bis 5 Gew.-% vorliegt, gelöst. Es wurde überraschend gefunden, dass durch die Verwendung der drei spezifischen Tensidarten zusammen mit dem Salz der Zitronensäure gemäß der genannten Beziehung eine verbesserte Löslichkeit und ein verbessertes Fließverhalten erhalten wurde.This object was surprisingly achieved by the inventors of the present invention by providing a dishwashing detergent which contains a surfactant system

1. (A) at least one alkyl benzene sulfonate;
2. (B) at least one fatty alcohol sulfate; and
3. (C) at least one amine oxide; includes or consists of
4. (D) a salt of citric acid

with the proviso that the following relationship is fulfilled
(% By weight (A) x% by weight (B)) /% by weight (C) +% by weight (D) = R, where R is a number from 5 to 120 and
D is present in an amount of 0.05 to 5% by weight, dissolved. It was surprisingly found that the use of the three specific types of surfactant together with the salt of citric acid in accordance with the relationship mentioned resulted in improved solubility and improved flow behavior.

1. (A) mindestens ein Alkylbenzolsulfonat;
2. (B) mindestens ein Fettalkoholsulfat; und
3. (C) mindestens ein Aminoxid; umfasst oder daraus besteht,
4. (D) ein Salz der Zitronensäure

mit der Maßgabe, dass folgende Beziehung erfüllt ist
(Gew.-% (A) x Gew.-%(B)) / Gew.-% (C) + Gew.-%(D) = R, wobei R eine Zahl von 5 bis 120 ist und
D in einer Menge von 0,05 bis 5 Gew.-% vorliegt.In a first aspect, the present invention is therefore directed to a dishwashing detergent containing a surfactant system, the surfactant system:

1. (A) at least one alkyl benzene sulfonate;
2. (B) at least one fatty alcohol sulfate; and
3. (C) at least one amine oxide; includes or consists of
4. (D) a salt of citric acid

with the proviso that the following relationship is fulfilled
(% By weight (A) x% by weight (B)) /% by weight (C) +% by weight (D) = R, where R is a number from 5 to 120 and
D is present in an amount from 0.05 to 5 percent by weight.

In a further aspect, the present invention is also directed to the use of the dishwasher detergent according to the invention for the manual cleaning of 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 constituents of the compounds described herein, this indication does not refer to the absolute amount of molecules, but to the type of constituent. “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 specifying the amount of the individual compounds.

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

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

The expressions “approximately” “approximately” or “approximately” in connection with a numerical value relates 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 “essentially free from” a certain 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.

Numeric ranges given in the format “in / from x to y” include the stated values. If several preferred numerical ranges are given in this format, it is understood that all ranges resulting from the combination of the various endpoints are also recorded.

Information on the molecular weight relates to the weight average molecular weight in g / mol, unless the number average molecular weight is explicitly mentioned. Molecular weights are preferably determined by means of 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, or their derivatives 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 in the following as counterions for monovalent anions, this means that the alkaline earth metal is of course only present in half the amount of substance - sufficient to balance the charge - as the anion.

In the present invention, substituted radicals are preferably those radicals in which the substituent is selected from -F, -Cl, -Br, -OH, -OC _1-4 alkyl, = O, -NH ₂ , or -N (C _{1 -4} alkyl) ₂ , the substituent preferably replacing 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 a study of the following detailed description and claims. Each feature or each 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 goes without saying 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.

1. (A) mindestens ein Alkylbenzolsulfonat;
2. (B) mindestens ein Fettalkoholsulfat; und
3. (C) mindestens ein Aminoxid; umfasst oder daraus besteht,
4. (D) ein Salz der Zitronensäure

mit der Maßgabe, dass folgende Beziehung erfüllt ist
(Gew.-% (A) x Gew.-%(B)) / Gew.-% (C) + Gew.-%(D) = R, wobei R eine Zahl von 5 bis 120 ist und
D in einer Menge von 0,05 bis 5 Gew.-% vorliegt.The dishwashing detergent according to the invention contains a surfactant system which comprises:

1. (A) at least one alkyl benzene sulfonate;
2. (B) at least one fatty alcohol sulfate; and
3. (C) at least one amine oxide; includes or consists of
4. (D) a salt of citric acid

with the proviso that the following relationship is fulfilled
(% By weight (A) x% by weight (B)) /% by weight (C) +% by weight (D) = R, where R is a number from 5 to 120 and
D is present in an amount from 0.05 to 5 percent by weight.

The dishwashing detergent according to the invention is preferably essentially free from cationic surfactants.

In preferred embodiments, the salt of citric acid is “trisodium citrate dihydrate”.

In preferred embodiments, the salt of citric acid is contained in the agent in an amount of 0.02% by weight to 4% by weight, in particular 0.1% by weight to 3% by weight, in particular 0.3% by weight % to 1% by weight.

wobei R' und R" unabhängig voneinander H oder einen, bevorzugt linearen, C_2-18 Alkylrest darstellen, wobei mindesten ein Rest nicht H ist. Erfindungsgemäß verstehen sich unter dem Merkmal Alkylbenzolsulfonat lediglich mit einem Alkylrest substituierte Benzolring der ferner einen Sulfonatrest trägt.The at least one alkylbenzenesulfonate is preferably selected from compounds of the formula A-1

where R 'and R "independently represent H or a, preferably linear, C _2-18 alkyl radical, at least one radical not being H. According to the invention, the feature alkylbenzenesulfonate means only benzene ring substituted with an alkyl radical which also bears a sulfonate radical.

In preferred embodiments, the at least one alkylbenzenesulfonate is in 2.5 to 50% by weight, preferably 2.5 to 50% by weight, in particular 3 to 40% by weight, especially preferably 5 to 30% by weight, based on the total weight of the dishwashing detergent.

The at least one fatty alcohol sulfate is preferably selected from C _8-18 fatty alcohol sulfates, particularly preferred fatty alcohol sulfates are derived from C _12-18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol. In particular, sodium lauryl sulfate is preferred.

In preferred embodiments, the at least one fatty alcohol sulfate is present in 0.5 to 45% by weight, preferably 0.5 to 40% by weight, more preferably 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 which has the formula R ¹ R ² R ³ NO, where each R ¹ , R ² and R ³ independently of the others is an optionally substituted, for example hydroxy-substituted, C ₁ - C _{30 is} hydrocarbon chain. Particularly preferably used amine oxides are those in which R ^{1 is} C ₁₂ -C ₁₈ alkyl and R ² and R ^{3 are} each independently C ₁ -C ₄ alkyl, in particular C ₁₂ -C ₁₈ alkyldimethylamine oxides. Exemplary representatives of suitable amine oxides are N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide. The at least one amine oxide is preferably selected from C _12-18 amine oxides, particularly preferably from C _12-18 alkyldimethylamine oxides, and most preferably it is C ₁₂ alkyldimethylamine oxide.

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

The surfactant system can also contain further anionic, nonionic or zwitterionic surfactants which differ from (A) to (C).

If present, the 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.

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

Suitable further surfactants are, for example, alpha-olefin sulfonates. Preferred alpha olefin sulfonates are selected from C _10-20 alpha olefin sulfonates, more preferably from linear C _10-20 alpha olefin sulfonates. In particular, it is selected from C _12-14 alpha olefin sulfonates; most preferably it is a linear C _12-14 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 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) R ¹ -O- (AO) _n -SO ₃ ^- X ⁺ (I).

In this formula (I), R ^{1 represents} a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ¹ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C- Atoms are preferred. Particularly preferred radicals R ¹ are derived from C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C ₁₀ -C ₂₀ oxo alcohols.

X stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na ⁺ or K ⁺ , Na ^{+ being} extremely preferred. Further cations X ⁺ can be selected from NH4 ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ , and mixtures thereof.

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

mit k = 11 bis 19, n = 2, 3, 4, 5, 6, 7 oder 8. Besonders bevorzugte Vertreter sind Na-C_12-14 Fettalkoholethersulfate mit 2 EO (k = 11-13, n = 2 in Formel 1-1).Fatty alcohol ether sulfates of the formula 1-1 are likewise preferred

with k = 11 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Particularly preferred representatives are Na-C _12-14 fatty alcohol _ether sulfates with 2 EO (k = 11-13, n = 2 in formula 1 -1).

Further suitable anionic surfactants are the alkyl sulfates, which are not derived from fatty alcohols, of the formula R'-O-SO ₃ ^- X ⁺ (II).

In this formula (II), R ^{2 represents} a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ² are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C- Atoms are preferred. They are particularly preferably derived from C _10-20 oxo alcohols.

X stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na + or K +, Na + being extremely preferred. Further cations X ⁺ can be selected from NH ₄ ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ , and mixtures thereof.

If present, the at least one further nonionic surfactant is 0.1 to 20% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 8% by weight, 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 nonionic surfactants used with preference are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

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

Also suitable are alkyl glycosides of the general formula RO (G) x in which R corresponds to a primary straight-chain or methyl-branched, in particular methyl-branched in the 2-position, aliphatic radical with 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol for a glycose unit with 5 or 6 carbon atoms, preferably for 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, especially 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 radical is linear or preferably in 2 -Position can be methyl-branched or can contain linear and methyl-branched radicals in the mixture, as they are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _8-11 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 5 EO.

In various embodiments, the total amount of surfactants, i. of the surfactant system, based on the weight of the agent, 2.5 to 70% by weight, preferably 5 to 50% by weight, even more preferably 7 to 40% 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, organic solvents, enzymes, additives to improve the 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 the skin.

In one embodiment, the dishwashing detergents according to the present invention are liquid and contain water as the main solvent, i. 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 various embodiments, the water content is more than 5% by weight, preferably more than 15% by weight and particularly preferably more than 20% by weight, based in each case on the total amount of dishwashing detergent.

Organic solvents can also be added to the dishwashing detergent. Suitable organic 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, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol ether, butyl glycol propyl ether, ethylene glycol 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, methoxy triglycol, ethoxy triglycol, butoxy triglycol, 1-butoxyethoxy-2-propanol, propylene-butoxyethoxy-2-propanol, propylene-butoxy-3-butyl ether, and mixtures of these n-butoxyethoxy-2-propanol, 3-butyl-3-butylether, propylene-propylene, propylene-octanol, propylene-octanol, 3-butyl ether, di-propylene-butyl-3-ether, propylene-octanolether, propylene-octanolether, di-propylene-butyl-3-ether, propylene glycol monomethyl ether, Solvent. In particular, ethanol is preferred. The organic solvent is preferably contained in 0.1 to 10% by weight, based on the total weight of the dishwashing detergent.

In various embodiments, the dishwashing detergents described herein can also contain at least one enzyme, preferably a protease. The proteases used are preferably alkaline serine proteases. They act as unspecific endopeptidases, that is, they hydrolyze any acid amide bonds that are inside peptides or proteins and thereby break down protein-containing soiling on the items to be cleaned. Their pH optimum is usually in the clearly 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 to this,
• - the alkaline protease from Bacillus sp. (DSM 14390) or an alkaline protease that is at least 98.5% identical to this, and
• - the alkaline protease from Bacillus sp. (DSM 14392) or an alkaline protease that is at least 98.1% identical to this.

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 Novozymes A / S, Bagsvaerd, Denmark. Optimized enzyme variants of the subtilisin 309 from Bacillus lentus are available from the Novozymes company under the trade names Blaze® and Ovozyme®, which represent a preferred embodiment of the invention. From the alkaline protease from Bacillus lentus DSM 5483, for example, the protease variants sold under the name BLAP® are derived. In particular, those protease variants are preferred 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 R99E is preferred, and optionally also has at least one or two, preferably all three of the amino acid substitutions S3T, V4I and V199I, particularly preferred are the BLAP variants as described in SeqlD No 4 or 5 of the WO 2014/177430 are described.

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

As a rule, the proteases are 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 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 are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaches 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. Such granules are advantageously low in dust, for example due to the application of polymeric film formers, and due to the coating are stable in storage.

Furthermore, it is possible to pack 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 one-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 packaged as described above for the proteases.

In dishwashing detergents according to the invention, which in one embodiment are predominantly liquid, pasty or gel form, the at least one enzyme, preferably the at least one protease and / or at least one amylase, is in an amount of 0.01-1.6% by weight, preferably 0.05-1.2% by weight based on the total weight of the dishwashing detergent.

In various embodiments, the enzyme (s) can be pre-formulated with enzyme stabilizers in an enzyme composition. The enzyme protein usually only forms a fraction of the total weight of the enzyme preparation. Preferably used enzyme preparations contain between 0.1 and 40 wt .-%, preferably between 0.2 and 30 wt .-%, particularly preferably between 0.4 and 20 wt .-% and in particular between 0.8 and 10 wt .-% % of the enzyme protein. In such compositions, an enzyme stabilizer can be included in the enzyme composition in an amount of 0.05-35% by weight, preferably 0.05-10% by weight, based on the total weight. This enzyme composition can then be used in dishwashing detergents according to the invention, specifically in amounts which lead to the final concentrations specified above in the dishwashing detergent. Suitable enzyme stabilizers are known in the prior 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 with the aid of known methods, for example the BCA method (bicinchoninic acid; 2,2'-bichinolyl-4,4'-dicarboxylic acid) or the biuret method. The active protein concentration is determined in this regard by titrating the active 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, extremely preferably 0.5 to 1.5% by weight, for example 1% by weight.

Polymeric thickeners for the purposes of the present invention are the polycarboxylates that act as polyelectrolytes, preferably homopolymers and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, in particular heteropolysaccharides, and other customary thickening polymers.

Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, e.g. 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, 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 C _1-4 alkanols (INCI Acrylates Copolymers), to which such as 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); (ii) crosslinked high molecular weight acrylic acid copolymers, including the copolymers of C _10-30 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 C _1-4 - Alkanols formed, include esters (INCI Acrylates / C10-30 Alkyl Acrylate 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 extremely 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 with a high surfactant content, one or more dicarboxylic acids and / or their salts can also be added, in particular a composition of sodium salts of adipic, succinic and glutaric acid, such as those sold under the trade name Sokalan ^® DSC is available. They are 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.

In addition, possible to use one or more further - especially in hand dishwashing detergents - conventional auxiliaries and additives, in particular UV stabilizers, perfumes, pearlescent agents (INCI opacifying agents, for example glycol distearate, for example Cutina ^® AGS from Cognis, or mixtures comprising, for example. the Euperlane ^® from. Cognis), dyes, corrosion inhibitors, preservatives (for example, the technical also known as Bronopol 2-bromo-2-nitropropane-1,3-diol (CAS 52-51-7), for example, as Myacide BT ^® or commercially available as Boots Bronopol BT from Boots) or Acticide MBR 1 or Acticide CMB 2, organic salts, disinfectants, pH regulators and additives that improve 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 lecithin, soybean oil, etc., plant extracts such as aloe vera, azulene, witch hazel extracts, algae extracts, etc., allantoin, AHA Complexes, glycerine, urea, quaternized hydroxyethyl cellulose), in amounts of usually not more than 8% by weight, based on the total weight of the dishwashing detergent.

Na xylene sulfonate can be present in the composition as a viscosity-regulating additive.

The pH of the agent according to the invention can be adjusted by means of customary pH regulators, for example acids such as mineral acids or citric acid and / or alkalis such as sodium or potassium hydroxide, with a range from 4 to 9, preferably 5 to 8.5, in particular 5.5 to 8, is preferred.

In one embodiment, the dishwashing detergent according to the invention also contains sodium hydroxide, preferably in 0.1 to 2.9 or 5% by weight, based on the total weight of the dishwashing detergent.

To adjust and / or stabilize the pH, 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 0.1 to 2% by weight, particularly preferably 0.05 to 1% by weight, extremely preferably 0.1 to 0.5% by weight, for example 0.2% by weight. Preference is given to buffer substances that are also complexing agents or even chelating agents (chelators, INCI chelating agents). Particularly preferred buffer substances are citric acid or the citrates, in particular the sodium and potassium citrates, for example trisodium citrate · 2H ₂ O and tripotassium citrate · H ₂ O.

The agent according to the invention can be used for the manual cleaning of dishes.

The dishwashing detergent is produced using customary and known methods and processes.

Examples

component E1 V1 Tri-sodium citrate dihydrate 0.5 0 Propanediol 1,2 1 1 Alkvlbenzenesulfonic acid 21.1 21.1 Ethanol 3 3 Amine oxide (Ammonyx LO) 2.3 2.3 Fatty alcohol sulfate (STEPANOL WA-EXTRA HP) 11.3 11.3 Fragrances, dyes, preservatives <2 <3 Water, demineralized rest rest

All data are given in% by weight based on the total weight of the composition and represent the content of active substance.

In the case of E1, the batch was easily stirrable and homogeneous even after the addition of the fatty alcohol sulfate (STEPANOL WA-EXTRA HP), which dissolved quickly and easily.

In the case of V1, the batch was very difficult to stir after the addition of SLS.

QUOTES INCLUDED IN THE DESCRIPTION

This list of the documents listed 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 2014/177430 [0057]

Non-patent literature cited

• M. Bender et al., J. Am. Chem. Soc. 88, 24 (1966), pp. 5890-5913 [0067]

Claims (8)

Dishwashing detergents, preferably hand dishwashing detergents, containing a surfactant system, the surfactant system: (A) at least one alkyl benzene sulfonate; (B) at least one fatty alcohol sulfate; and (C) at least one amine oxide; includes or consists of (D) a salt of citric acid provided that the following relationship is satisfied [(% By weight (A) x% by weight (B)) /% by weight (C)] +% by weight (D) = R, where R is a number from 5 to 120 and D in is present in an amount from 0.05 to 5 percent by weight. Dishwashing detergent according to Claim 1 , wherein the at least one alkylbenzenesulfonate (i) is selected from compounds of the formula A-1

where R 'and R''independently of one another represent H or a preferably linear C _2-18 alkyl radical, at least one radical not being H; and / or (ii) in 2.5 to 50% by weight, preferably 3 to 40% by weight, particularly preferably 5 to 30% by weight, based on the total weight of the dishwashing detergent. Dishwashing detergent according to one of the preceding claims, wherein the at least one fatty alcohol sulfate (i) in 0.5 to 45 wt .-%, preferably 0.5 to 40 wt .-%, more preferably in 3 to 15 wt .-%, based on is included in the total weight of the dishwashing detergent; and / or (ii) is selected from C _8-18 fatty alcohol sulfates, particularly preferred fatty alcohol sulfates are derived from C _12-18 fatty alcohols, more preferably from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, most preferably sodium lauryl sulfate . Dishwashing detergent according to one of the preceding claims, wherein the at least one amine oxide (i) in 0.1 to 20% by weight, preferably 0.3 to 10% by weight, more preferably in 0.5 to 3% by weight, based on total weight of dishwashing detergent; and / or (ii) is selected from C _12-18 amine oxides, preferably from C _12-18 alkyldimethylamine oxides, in particular it is C ₁₂ alkyldimethylamine oxide. The dishwashing detergent according to one of the preceding claims, characterized in that the surfactant system is based on the total weight of the dishwashing detergent in an amount of 2.5 to 70% by weight, preferably 5 to 50% by weight, more preferably 7 to 40% by weight. -%, is included. The dishwashing detergent according to one of the preceding claims, characterized in that the surfactant system contains at least one further surfactant selected from ether sulfates, alkyl sulfates, linear alpha-olefin sulfonates and mixtures thereof. The dishwashing detergent according to one of the preceding claims, characterized in that the dishwashing detergent has at least one additional ingredient selected from the group consisting of water, organic solvents, enzymes, additives to improve the drainage and drying behavior, to adjust the viscosity and / or to stabilize, 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 the skin. Use of the surfactant system according to one of the preceding claims to increase the solubility of the dishwashing detergent.