Method for the preparation of viscosity modified dishwashing agents

Abstract

A method for producing a hand dishwashing composition comprising the steps of: providing at least one surfactant; providing at least one inorganic salt; providing organic solvent; and adjusting the pH of the composition to a value between 7 and 8.5, characterized in that the provision of the solvent takes place before the adjustment of the pH.

Description

[0001] Dishwashing liquids, especially liquid ones for manual dishwashing, are well-known. However, consumers often perceive low-viscosity dishwashing liquids as being of lower quality. Therefore, viscosity is an important quality criterion for dishwashing liquids. At the same time, modern dishwashing liquids should be produced in an environmentally friendly way while still providing the best possible cleaning performance. Another important requirement for dishwashing liquids is that they should be gentle on the skin.

[0002] Against this background, the demands placed on modern hand dishwashing detergent formulations are correspondingly high. In particular, adjusting the viscosity during the manufacturing process presents a challenge. Viscosity peaks in the formulations can make it difficult to achieve a homogeneous mixture of the components using stirring tools, thus making the processes more energy-intensive and time-consuming, or even impossible altogether.

[0003] Hand dishwashing liquids are listed in WO 2012 / 082096 A1, EP 1 111 031 A1,

[0004] Described in EP 0 476 212 A1, US 4 070 309 A and EP 3 670 637 A1.

[0005] Overall, there is a need for hand dishwashing detergents that meet the above-mentioned requirements.

[0006] The object underlying the present invention is therefore to provide a method for the production of hand dishwashing detergents that are perceived by the consumer as being of high quality, can be processed in an environmentally friendly manner and at the same time have good skin compatibility.

[0007] The problem is solved by a process for producing a hand dishwashing composition comprising the following steps: Providing at least one anionic surfactant; providing at least one inorganic salt; providing an organic solvent comprising ethanol and cumenesulfonate.

[0008] Adjusting the pH of the composition to a value between 7 and 8.5, characterized in that the solvent is provided before the pH is adjusted, the pH is adjusted after the solvent has been dosed, and no further organic solvent is added after the pH has been adjusted. The ratio of total surfactant content to solvent is between 4 and 6.

[0009] Furthermore, the composition includes an anionic surfactant.

[0010] It was surprisingly found that the process takes advantage of the good viscosity profile achieved through the interaction of inorganic salt and solvent at pH values ​​of about 7, with the essential point being that the pH value adjustment is carried out after dosing of the solvent.

[0011] According to a preferred embodiment, the viscosity of the composition is at least 1000 cps to 4000 cps.

[0012] According to a further preferred embodiment, the viscosity of the composition is at least 1500 cps to 2500 cps.

[0013] According to a further preferred embodiment, the viscosity of the composition is at least 1800 cps to 2200 cps.

[0014] The viscosity is determined using a Brookfield LVDV II+, spindle 31 at a temperature of 20°C, at 12 rpm.

[0015] According to a preferred embodiment, the method is described wherein the pH value of the composition is adjusted to a value between 7.5 and 8.5.

[0016] According to the invention, a method is described in which the entire organic solvent is provided before the pH is adjusted. After the pH is adjusted, preferably using an acid, no further organic solvent is added according to the invention. This embodiment has the advantage that the pH is adjusted with an optimized viscosity profile.

[0017] According to a particularly preferred embodiment, a method is described in which the inorganic salt is provided before the pH is adjusted. After the pH is adjusted, preferably using an acid, no further inorganic salt is added according to this embodiment. This embodiment has the advantage of preventing the adjusted pH of the composition from changing due to the addition of further salt.

[0018] According to a preferred embodiment, the process is described wherein the salt is an alkali halide and / or an alkaline earth halide, preferably sodium chloride.

[0019] According to a preferred embodiment, the process is described wherein the amount of inorganic salt is at least 2 wt.%, preferably at least 4 wt.%.

[0020] According to a preferred embodiment, the total amount of solvent is at least 1 wt.%, more preferably at least 2 wt.% and more preferably at least 2.5 wt.%.

[0021] According to a preferred embodiment, the method is described wherein the ratio of total surfactant content to solvent is less than 10, preferably between 4 and 6, and more preferably 4 or 5.

[0022] According to a preferred embodiment, the method is described wherein the composition comprises at least one enzyme.

[0023] According to a preferred embodiment, the method is described wherein the composition comprises an amine oxide and / or a betaine surfactant.

[0024] According to a preferred embodiment, the method is described wherein the total amount of surfactant is at least 5 wt.%, more preferably at least 12 wt.%, more preferably at least 20 wt.%.

[0025] According to the invention, organic solvent is provided before adjusting the pH of the composition to a value between 7 and 8.5.

[0026] According to a preferred embodiment, the pH value is adjusted to a value between 7 and 8.5 after the provision of at least one anionic surfactant. After the addition of the basic anionic surfactant, the pH value is adjusted to a value between 7 and 8.5 by adding an acid, for example citric acid.

[0027] According to one embodiment, the pH value is adjusted after the inorganic salt is provided.

[0028] According to an alternative embodiment, the pH value is adjusted before the at least one inorganic salt is provided.

[0029] If a sequence of process steps is specified in connection with the present invention, it is preferred with regard to the amount of component added in the specified process step that this amount comprises at least 50 wt.%, more preferably at least 70 wt.%, more preferably at least 90 wt.% of the total amount of component in the composition.

[0030] For example, the process step "providing organic solvent before adjusting the pH of the composition" could be interpreted as meaning that at least 50 wt.%, more preferably at least 70 wt.%, more preferably at least 90 wt.%, of the total amount of solvent is provided before adjusting the pH.

[0031] 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.

[0032] According to a preferred embodiment, a hand dishwashing composition is described, wherein the anionic surfactant is present in an amount of at least 4 wt.%, preferably at least 10 wt.%, based on the total weight of the composition.

[0033] According to a preferred embodiment, a hand dishwashing composition is described, wherein aminexoid is present in an amount of at least 4 wt.% based on the total weight of the composition.

[0034] According to a preferred embodiment, a hand dishwashing composition is described, wherein betaine is present in an amount of at least 4 wt.% based on the total weight of the composition.

[0035] According to a preferred embodiment, a hand dishwashing composition is described, wherein the composition comprises an organic solvent, which is preferably ethanol and is further preferably present in an amount of at least 2 wt.%.

[0036] According to a preferred embodiment, a hand dishwashing composition is described, wherein the proportion of amine oxides having a C12 residue is between 50 and 85% based on the total amount of amine oxide, preferably between 60 and 85%.

[0037] According to a preferred embodiment, a hand dishwashing composition is described wherein the proportion of amine oxides having a C14 residue is between 20 and 35% based on the total amount of amine oxide.

[0038] According to a preferred embodiment, a hand dishwashing composition is described wherein the proportion of amine oxides containing only C10 or smaller residues is less than 5% based on the total amount of amine oxide.

[0039] According to a preferred embodiment, a hand dishwashing composition is described, wherein the anionic surfactant is selected from ether sulfates, alkyl sulfates and mixtures.

[0040] 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 for improving drainage and drying behavior, for adjusting viscosity and / or for stabilization, UV stabilizers, perfume, pearlescent agents, dyes, corrosion inhibitors, bittering agents, organic salts, disinfectants, structuring polymers, defoamers, encapsulated ingredients, pH adjusters and skin-feeling or conditioning additives.

[0041] In a further aspect, the present invention relates to the use of the dishwashing detergent according to the invention for the manual cleaning of dishes.

[0042] "At least one," as used herein, refers to one or more, for example, two, three, four, five, six, seven, eight, nine, or more. In the context of constituents of the compounds described herein, this term refers not to the absolute quantity 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 may be present, without specifying the quantity of each individual compound.

[0043] Unless otherwise stated, all quantities specified in connection with the dishwashing detergents described herein refer to percentages by weight based on the total weight of the dishwashing detergent. Furthermore, any quantity specifications relating to at least one ingredient always refer to the total amount of that ingredient contained in the dishwashing detergent, unless explicitly stated otherwise. This means that, for example, quantities relating to "at least one surfactant" refer to the total amount of surfactants contained in the dishwashing detergent, unless explicitly stated otherwise.

[0044] Numerical values ​​given herein without decimal places refer to the full value given with one decimal place. For example, "99%" means "99.0%".

[0045] The expressions "approximately", "ca." or "about", in connection with a numerical value, refer to a variance of ±10% with respect to the stated numerical value, preferably ±5%, particularly preferably ±1%.

[0046] The expression "essentially free of" means that the respective compound may be present in principle, but only in an amount that does not impair the function of the other components. Within the scope of the present invention, therefore, the property "essentially free of" a particular compound is preferably considered to mean a total weight of less than 0.1% by weight, more preferably less than 0.001% by weight, and in particular, completely free of it, based on the total weight of the dishwashing detergent.

[0047] Numerical ranges specified in the format "in / from x to y" include the stated values. If multiple preferred numerical ranges are specified in this format, it is understood that all ranges resulting from the combination of the different endpoints are also included.

[0048] Molecular weight specifications refer to the weight-mean molecular weight in g / mol, unless the number-mean molecular weight is explicitly stated. Molecular weights are preferably determined by GPC using polystyrene standards.

[0049] Within the scope of the present invention, fatty acids or fatty alcohols or their derivatives – unless otherwise specified – represent branched or unbranched carboxylic acids or alcohols or their derivatives, preferably with 6 to 22 carbon atoms. In particular, oxo alcohols or their derivatives, obtainable, for example, by the Roelen oxo synthesis, can also be used accordingly.

[0050] If salts are components of the present composition, 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. Whenever alkaline earth metals are mentioned below as counterions for monovalent anions, this means that the alkaline earth metal is naturally present only in half the amount of substance – sufficient for charge balance – as the anion.

[0051] In the present invention, substituted residues are preferably residues in which the substituent is selected from -F, -Cl, -Br, -OH, -OC1-4Alkyl, =O, -NH2, or -N(C1-4Alkyl)2, preferably the substituent replacing one or more H atoms.

[0052] These and other aspects, features, and advantages of the invention will become apparent to the person skilled in the art upon studying 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 understood that the examples contained herein are intended to describe and illustrate the invention, but do not limit it, and in particular, the invention is not limited to these examples.

[0053] The dishwashing detergent according to the invention is preferably essentially free of cationic surfactants.

[0054] According to one embodiment, the composition comprises at least one alkylbenzenesulfonate, which preferably has a C2-18 alkyl group. Cumenesulfonate is particularly preferred. According to the invention, the term alkylbenzenesulfonate refers only to a benzene ring substituted with an alkyl group and furthermore bearing a sulfonate group.

[0055] In preferred embodiments, the at least one alkylbenzenesulfonate is contained in 0.5 to 50 wt. %, preferably 0.5 to 30 wt. %, and particularly preferably 0.5 to 5 wt. %, based on the total weight of the dishwashing detergent.

[0056] 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, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol. Sodium lauryl sulfate is particularly preferred.

[0057] In preferred embodiments, the at least one fatty alcohol sulfate is contained in 0.5 to 45 wt.%, preferably 0.5 to 40 wt.%, more preferably in 3 to 15 wt.%, based on the total weight of the dishwashing detergent.

[0058] In a preferred embodiment, the at least one amine oxide is a compound having the formula R1R2R3NO, wherein each R1, R2, and R3 is, independently of the others, an optionally substituted, for example, hydroxy-substituted, C1-C30 hydrocarbon chain. Particularly preferred amine oxides are those in which R1 is a C10-C16 alkyl and R2 and R3 are each independently C1-C4 alkyl, especially C10-C16 alkyldimethylamine oxides. Exemplary representatives of suitable amine oxides are N-cocosalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide. The at least one amine oxide is preferably selected from C12-16 amine oxides, particularly preferably from short-chain C12-14 alkyldimethylamine oxides.

[0059] 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 in 0.5 to 3 wt.%, based on the total weight of the dishwashing detergent.

[0060] If present, it contains at least one further anionic, non-ionic or zwitterionic surfactant, preferably in 0.1 to 45 wt.%, more preferably 0.5 to 40 wt.%, more preferably in 1 to 25 wt.%, based on the total weight of the dishwashing detergent.

[0061] All anionic surfactants known for dishwashing detergents are also suitable.

[0062] Suitable additional surfactants include, for example, alpha-olefin sulfonates. Preferred alpha-olefin sulfonates are selected from C10-20 alpha-olefin sulfonates, more preferably from 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.

[0063] The at least one alpha-olefin sulfonate is preferably contained in 2.5 to 45 wt.%, more preferably 3 to 30 wt.%, and particularly preferably in 5 to 25 wt.%, based on the total weight of the dishwashing detergent.

[0064] A suitable alpha-olefin sulfonate is commercially available, for example, under the trade name Bio-Terge ®< AS-40 from the company Stephan.

[0065] In one embodiment, at least one further anionic surfactant is selected from ether sulfates, alkyl sulfates and mixtures thereof.

[0066] Preferred ether sulfates are those of formula (I) R1-O-(AO)n-SO3- X+ (I).

[0067] In this formula (I), R1 represents a linear or branched, substituted or unsubstituted alkyl group, preferably a linear, unsubstituted alkyl group, and particularly preferably a fatty alcohol group. Preferred R1 groups are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups and mixtures thereof, with those having an even number of carbon atoms being preferred. Particularly preferred R1 groups are derived from C12-C18 fatty alcohols, for example, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol, or from C10-C20 oxo alcohols.

[0068] X represents a monovalent cation or the nth part of an n-valent cation, preferably alkali metal ions, including Na+ or K+, with Na+ being highly preferred. Further cations X+ can be selected from NH4+, ½ Zn2+, ½ Mg2+, ½ Ca2+, ½ Mn2+, and mixtures thereof.

[0069] AO stands for an ethylene oxide (EO) or propylene oxide (PO) grouping, preferably for an ethylene oxide grouping. The index n stands for an integer from 1 to 50, preferably from 1 to 20, and particularly from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7, or 8.

[0070] Other suitable anionic surfactants are the alkyl sulfates, which are not derived from fatty alcohols, of the formula R2-O-SO3- X+ (II).

[0071] In this formula (II), R2 represents a linear or branched, substituted or unsubstituted alkyl group, preferably a linear, unsubstituted alkyl group, and particularly preferably a fatty alcohol group. Preferred R2 groups are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups and mixtures thereof, with those having an even number of carbon atoms being preferred. They are particularly preferably derived from C10-20 oxo alcohols.

[0072] X represents a monovalent cation or the nth part of an n-valent cation, preferably alkali metal ions, including Na+ or K+, with Na+ being highly preferred. Further cations X+ can be selected from NH4+, ½ Zn2+, ½ Mg2+, ½ Ca2+, ½ Mn2+, and mixtures thereof.

[0073] If present, at least one further non-ionic surfactant is included in 0.1 to 20 wt.%, preferably 0.5 to 10 wt.%, more preferably in 1 to 8 wt.%, based on the total weight of the dishwashing detergent.

[0074] All non-ionic surfactants known for use in dishwashing detergents are also suitable.

[0075] In one embodiment, the at least one further non-ionic surfactant is selected from alkoxylated fatty acid alkyl esters, polyhydroxy fatty acid amides, alkyl glycosides and alkoxylated alcohols and mixtures thereof.

[0076] Another class of preferably used non-ionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

[0077] Other suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.

[0078] Also suitable are alkyl glycosides of the general formula RO(G)x, where R corresponds to a primary straight-chain or methyl-branched, in particular 2-position methyl-branched, aliphatic residue with 8 to 22, preferably 12 to 18 carbon atoms, and G is the symbol representing a glucose 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; preferably, x is between 1.2 and 1.4.

[0079] In one embodiment, the additional nonionic surfactants are selected from the group of alkoxylated alcohols. Preferably, alkoxylated, advantageously ethoxylated, and 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 are used as nonionic surfactants. The alcohol residue may be linear or, preferably, methyl-branched at the 2-position, or the mixture may contain both linear and methyl-branched residues, as is commonly found in oxo alcohol residues. However, alcohol ethoxylates with linear residues derived from 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 particularly preferred.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.

[0080] In various embodiments, the total amount of surfactants, i.e., of the surfactant system, based on the weight of the agent, is 2.5 to 70 wt.%, preferably 5 to 60 wt.%, more preferably 6 to 50 wt.%.

[0081] The dishwashing detergent according to the present invention may further contain at least one additional ingredient selected from the group consisting of water, organic solvents, enzymes, additives for improving drainage and drying properties, for adjusting viscosity and / or for stabilization, UV stabilizers, perfume, pearlescent agents, dyes, corrosion inhibitors, preservatives, bittering agents, organic salts, disinfectants, structuring polymers, defoamers, encapsulated ingredients, pH adjusters and skin-feeling or conditioning additives.

[0082] 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 typically 15 to 90 wt.%, preferably 20 to 60 wt.%.

[0083] Organic solvents can also be added to the dishwashing detergent. Suitable organic solvents include mono- or polyhydric alcohols, alkanolamines, or glycol ethers, provided they are miscible with water within the specified concentration range. Preferably, the solvents are selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerin, diglycyl, propyldiglycol, butyldiglycyl, 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. Preferably, the organic solvent is present in a concentration of 0.1 to 10% by weight, based on the total weight of the dishwashing detergent.

[0084] The dishwashing detergents described herein may, in various embodiments, further contain at least one enzyme, preferably a protease. The proteases used are preferably alkaline serine proteases. They act as non-specific endopeptidases, meaning they hydrolyze any amide bonds located within peptides or proteins, thereby breaking down protein-containing soiling on the items being cleaned. Their optimum pH is usually in the distinctly alkaline range.

[0085] The proteases preferably used according to the invention are preferably a serine protease, in particular a subtilase, and most preferably a subtilisin. The subtilisin can be a wild-type enzyme or a subtilisin variant, wherein the wild-type enzyme or the starting enzyme of the variant is preferably 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 at least 70% identical thereto, the alkaline protease from Bacillus sp. (DSM 14390) or an alkaline protease at least 98.5% identical thereto, and the alkaline protease from Bacillus sp. (DSM 14392) or an alkaline protease that is at least 98.1% identical to it.

[0086] Examples of proteases that can be used in the agents described herein are subtilisin 309 or functional fragments / variants thereof, and variants of alkaline protease from Bacillus lentus or variants thereof. subtilisin 309 is marketed under the trade name Savinase® 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 marketed under the name BLAP® are derived from alkaline protease from Bacillus lentus DSM 5483.Particularly preferred are protease variants which, compared to the BLAP wt (wild type) enzyme, have at least one mutation at R99 in the BLAP wt count, in particular R99E or R99D, with R99E being particularly preferred, and optionally also have at least one or two, preferably all three, of the amino acid substitutions S3T, V4I and V199I, with BLAP variants as described in SeqID No. 4 or 5 of WO 2014 / 177430 being particularly preferred.

[0087] In the dishwashing detergents described herein, the enzymes to be used may also be formulated together with accompanying substances, for example from fermentation. In liquid products, the enzymes are preferably used as liquid enzyme formulation(s).

[0088] Proteases are generally not supplied in the form of pure protein, but rather in the form of stabilized preparations that are suitable for storage and transport. These pre-prepared formulations include, for example, solid preparations obtained by granulation, extrusion, or lyophilization, or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with low water content, and / or containing stabilizers or other additives.

[0089] Alternatively, the enzymes can be encapsulated for both 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, such as those in which the enzymes are enclosed as if in a solidified gel, or in core-shell type capsules in which an enzyme-containing core is coated with a protective layer impermeable to water, air, and / or chemicals. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be applied in superimposed layers. Such capsules are produced using methods known per se, for example, by shake or roll granulation or in fluid-bed processes. Advantageously, such granules are low in dust, for example, by applying polymeric film formers, and are shelf-stable due to the coating.

[0090] Furthermore, it is possible to combine two or more enzymes so that a single granule has multiple enzyme activities.

[0091] 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.

[0092] The dishwashing detergent according to the invention particularly preferably further contains at least one amylase.

[0093] The amylase(s) is / are preferably α-amylase. The hemicellulase is preferably β-glucanase, pectinase, pullulanase, and / or 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. All of the aforementioned enzymes can be configured as described above for the proteases.

[0094] In dishwashing liquids according to the invention, which in one embodiment are in predominantly liquid, pasty or gel form, the at least one enzyme, preferably the at least one protease and / or at least one amylase, is contained in an amount of 0.01 - 1.6 wt.%, preferably 0.05 - 1.2 wt.% based on the total weight of the dishwashing liquid.

[0095] In various embodiments, the enzyme(s) can be preformulated with enzyme stabilizers in an enzyme composition. The enzyme protein typically constitutes only a fraction of the total weight of the enzyme preparation. Preferred 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 especially between 0.8 and 10 wt.% of the enzyme protein. In such compositions, an enzyme stabilizer can be present in an amount of 0.05–35 wt.%, preferably 0.05–10 wt.%, based on the total weight of the enzyme composition. This enzyme composition can then be used in dishwashing detergents according to the invention in amounts that lead to the final concentrations in the dishwashing detergent specified above. Suitable enzyme stabilizers are known in the prior art.In various embodiments, the agent according to the invention can accordingly additionally comprise one or more enzyme stabilizers.

[0096] Protein concentration can be determined using established methods, such as the BCA method (bicinchoninic acid; 2,2'-bicinolyl-4,4'-dicarboxylic acid) or the biuret method. The determination of the active protein concentration is carried out by titration of the active sites using a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonylfluoride (PMSF)) and determination of the residual activity (see M. Bender et al., J. Am. Chem. Soc. 88, 24 (1966), pp. 5890-5913).

[0097] To further improve the flow and / or drying behavior, the agent according to the invention can contain one or more additives from the group of polymers and builder substances (builders), typically in an amount of 0.001 to 5 wt.%, preferably 0.01 to 4 wt.%, in particular 0.1 to 3 wt.%, especially preferably 0.2 to 2 wt.%, most preferably 0.5 to 1.5 wt.%, for example 1 wt.%.

[0098] Polymeric thickening agents within the meaning of the present invention are the polycarboxylates acting as polyelectrolytes, 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 conventional thickening polymers.

[0099] Suitable polysaccharides or heteropolysaccharides include polysaccharide gums, such as gum arabic, agar, alginates, carrageenan and its salts, guar, guaranine, tragacanth, gellan gum, ramsan, dextran, or xanthan gum and their derivatives, e.g., propoxylated guar gum, 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. Examples include starches of various origins and starch derivatives, e.g., hydroxyethyl starch, starch phosphate esters, or starch acetates, or carboxymethylcellulose or its sodium salt, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, or hydroxyethylmethylcellulose, or cellulose acetate.

[0100] Acrylic acid polymers suitable as polymeric thickening agents include, for example, high molecular weight homopolymers of acrylic acid (INCI Carbomer) cross-linked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers.

[0101] Particularly suitable polymeric thickening agents include 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 C14 alkanols (INCI Acrylates Copolymer), which include, for example, 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) cross-linked high-molecular-weight acrylic acid copolymers, which include, for example, the copolymers of C10-30 alkyl acrylates with one or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters, preferably formed with C14 alkanols (INCI Acrylates / C10-30 Alkyl Acrylate Crosspolymer).

[0102] The content of polymeric thickening agent is usually no more than 8 wt.%, preferably between 0.1 and 7 wt.%, particularly preferably between 0.5 and 6 wt.%, especially between 1 and 5 wt.% and most preferably between 1.5 and 4 wt.%, for example between 2 and 2.5 wt.%, based on the total weight of the dishwashing detergent.

[0103] To stabilize the composition according to the invention, particularly at high surfactant content, one or more dicarboxylic acids and / or their salts can be added, especially a composition of sodium salts of adipic, succinic, and glutaric acid, such as that available under the trade name Sokalan® DSC. Advantageously, these are used in amounts of 0.1 to 8 wt.%, preferably 0.5 to 7 wt.%, particularly 1.3 to 6 wt.%, and most preferably 2 to 4 wt.%, based on the total weight of the dishwashing detergent.

[0104] However, if their use can be dispensed with, the agent according to the invention is preferably free of dicarboxylic acid (salts).

[0105] In addition, one or more other auxiliary and additive substances – particularly common in hand dishwashing detergents – may be present, especially UV stabilizers, perfume, opacifying agents (INCI: Opacifying Agents; for example, glycol distearate, e.g., Cutina® AGS from Cognis, or mixtures containing it, e.g., Euperlane® from Cognis), dyes, corrosion inhibitors, preservatives (e.g., the technical compound 2-bromo-2-nitropropane-1,3-diol (CAS 52-51-7), also known as Bronopol, which is commercially available from Boots as Myacide® BT or Boots Bronopol BT), or Acticide MBR 1 or Acticide CMB 2, organic salts, disinfectants, pH adjusters, and skin-feeling or skin-conditioning additives (e.g.,dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D, panthenol, sericerin, collagen partial hydrolysate, various vegetable protein partial hydrolysates, protein hydrolysate 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, glycerin, urea, quaternized hydroxyethylcellulose), in quantities of usually not more than 8% by weight, based on the total weight of the dishwashing detergent.

[0106] Na-xylenesulfonate can be used as an additive.

[0107] 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, wherein - particularly if hand compatibility is desired - a range of 4 to 9.

[0108] To adjust and / or stabilize the pH value, the composition according to the invention can contain one or more buffering agents (INCI buffering agents), typically in amounts of 0.001 to 5 wt.%, preferably 0.005 to 3 wt.%, particularly 0.01 to 2 wt.%, most preferably 0.05 to 1 wt.%, and most preferably 0.1 to 0.5 wt.%, for example 0.2 wt.%. Buffering agents that are also complexing agents or even chelating agents (INCI chelating agents) are preferred. Particularly preferred buffering agents are citric acid or citrates, especially sodium and potassium citrates, for example trisodium citrate dihydrate and tripotassium citrate dihydrate. Example compositions:

[0109] The example compositions shown in Table 1 were prepared based on a base formulation comprising 6.4 wt% anionic surfactant and 1.6% amine oxide surfactant. The total amount of surfactant is therefore 8 wt%. The formulation also contained smaller amounts of fragrances and dyes, as well as protease and amylase enzymes. Table 1 Example Reference sign EtOH CS AM / LMges 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

[0110] All values ​​are given as wt.% in relation to the total composition.

[0111] The compositions are additively derived from the values ​​in Table 1 and the base formulation. According to Table 1, the solvent comprises ethanol and cumenesulfonate, CS₂. The table also specifies the ratio of the total amount of surfactant to the total amount of solvent. The viscosity curves are shown in Figure 1 shown.

[0112] The example formulations E1 to E5 according to the invention show that the compositions exhibit a particularly good viscosity profile in the skin-friendly pH range of at least 7. The viscosities of the compositions are such that the compositions are perceived by the consumer as being of high quality, and the viscosity within the relevant pH range exhibits a relatively small / stable change depending on the pH value. Homogeneous mixing of the components using stirring tools was sufficiently successful.

[0113] In contrast, the comparison formulation C1 exhibited an unsuitable viscosity profile. While high viscosity values ​​could be achieved, these were not sufficiently constant / stable with respect to pH, unlike the example formulations according to the invention. The manufacturing process of such a composition is considerably hampered, if not rendered entirely impossible, due to the viscosity peaks, as adequate mixing of the composition by means of stirring tools is prevented. Therefore, if the pH is adjusted too early, particularly before the addition of the solvent, there is a risk that the composition will no longer be mixable and the energy input will increase significantly.While adjusting the pH value before adding inorganic salt and before adding solvent would be possible due to the low viscosity at that time, it is unsuitable because the pH value changes significantly with the addition of the salt.

[0114] Composition E2 exhibits a slight peak in viscosity overall. 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 to 5, as is the case in Examples E1, E3, E4, and E5.

[0115] It has now been surprisingly discovered that the process takes advantage of the good viscosity profile achieved through the interaction of inorganic salt and solvent at pH values ​​of approximately 7, whereby it is essential that the pH value adjustment is carried out after dosing of the solvent.

[0116] Furthermore, example formulations with a higher total surfactant content were provided. The corresponding example formulations, shown in Table 2, were prepared based on a basic formulation comprising 16 wt% anionic surfactant and 4% amine oxide surfactant. The total amount of surfactant is therefore 20 wt%. The formulation also contained smaller amounts of fragrances and dyes, as well as protease and amylase enzymes. Table 2 Example Reference sign EtOH CS AM / LMges NaCl C2 110 1 1 10 1,875 E6 150 3,9 1 4 4,9

[0117] All values ​​are given as wt.% in relation to the total composition.

[0118] The compositions are additively derived from the values ​​in Table 2 and the basic formulation. According to Table 2, the solvent comprises ethanol and cumenesulfonate, CS₂. The table also specifies the ratio of the total amount of surfactant to the total amount of solvent. The viscosity curves are shown in Figure 2 shown.

[0119] The comparison formulation C2 showed an even more pronounced viscosity peak than in the formulations with lower total surfactant amounts C1. The problem already described therefore applies particularly to higher total surfactant contents.

[0120] The composition E6 according to the invention is characterized by a particularly stable viscosity profile. Compared to formulations E1 to E5 with a lower total surfactant content, even better viscosity stabilization is achieved.

[0121] In conclusion, it can be stated that the advantageous stabilization of the viscosity curve occurs particularly at higher total surfactant concentrations of at least 12 wt%. Here, the ratio of total surfactant content to solvent is between 4 and 6, preferably 4 or 5.

[0122] Therefore, it follows that the process sequence according to the invention, in that the pH value adjustment is carried out after dosing of the solvent, makes even better use of the increased interaction of inorganic salt and solvent in the case of higher total surfactant concentrations.

Claims

1. A method for preparing a hand dishwashing composition comprising the steps of: providing at least one anionic surfactant; providing at least one inorganic salt; providing an organic solvent, wherein the solvent comprises ethanol and cumene sulfonate; and adjusting the pH of the composition to a value between 7 and 8.5, characterized in that the provision of the solvent takes place before the adjustment of the pH value, in such a way that the pH value adjustment takes place after dosing of the solvent, whereby no further organic solvent is added after the pH value adjustment, the ratio of total surfactant content to solvent being between 4 and 6.

2. Method according to claim 1, wherein the pH value of the composition is adjusted to a value between 7.5 and 8.5.

3. Method according to one of the preceding claims, wherein the salt is an alkali metal halide and / or an alkaline earth metal halide, preferably sodium chloride or potassium chloride.

4. Method according to one of the preceding claims, wherein the composition comprises at least one enzyme.

5. Method according to one of the preceding claims, wherein the composition comprises at least one amine oxide and / or a betaine surfactant.

6. Method according to one of the preceding claims, wherein the inorganic salt is provided before the pH value is adjusted.

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