EP4098728A1 - Method for the preparation of viscosity modified dishwashing agents - Google Patents

Abstract

A method of making 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 providing the solvent before adjusting the pH value.

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 inferior 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 therefore correspondingly high. In particular, adjusting the viscosity in the manufacturing process poses 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 impossible.

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

The object on which the present invention is based is therefore to provide a process for the production of hand dishwashing detergents which 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.

• Bereitstellen wenigstens eines Tensides;
• Bereitstellen wenigstens ein anorganisches Salzes;
• Bereitstellen von organischem Lösungsmittel, und
• Einstellen des pH-Wertes der Zusammensetzung auf einen Wert zwischen 7 und 8,5, dadurch gekennzeichnet, dass
• das Bereitstellen des Lösungsmittels vor der Einstellung des pH-Wertes erfolgt.

The problem is solved by a method for producing a
Hand dishwashing composition comprising the steps:

• 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 solvent is provided before the pH is adjusted.

Surprisingly, it was found that the process utilizes the good viscosity profile which is achieved through the interaction of inorganic salt and solvent at pH values of around 7, it being essential that the pH value is adjusted after the solvent has been metered in.

In a preferred embodiment, the viscosity of the composition is at least 1000 cps to 4000 cps.
In a more preferred embodiment, the viscosity of the composition is at least 1500 cps to 2500 cps.
In an even more 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 method is described wherein the pH of the composition is adjusted to a value between 7.5 and 8.5.

According to a particularly preferred embodiment, a method is described in which all of the organic solvent is provided before the pH is adjusted. After the pH adjustment, which preferably takes place using an acid, no further organic solvent is added according to this embodiment. This embodiment has the advantage that the pH value is adjusted with an optimized viscosity profile.

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 adjustment, which preferably takes place using an acid, no further inorganic salt is added according to this embodiment. This embodiment has the advantage that the adjusted pH value of the composition is prevented from being changed by the addition of further salt.

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

According to a preferred embodiment, the method is described wherein the solvent comprises ethanol and/or cumene sulfonate.

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

According to a preferred embodiment the method is described wherein the composition comprises an anionic surfactant.

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

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

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

According to a preferred embodiment, the pH is adjusted to a value between 7 and 8.5 after providing at least one anionic surfactant. After adding the anionic surfactant, which has a basic effect, the pH is adjusted to a value between 7 and 8.5 by adding an acid, for example citric acid.
According to one embodiment, adjustment of the pH takes place after the inorganic salt is provided.

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

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

For example, the process step “providing organic solvent before adjusting the pH of the composition” would be to be interpreted as meaning that at least 50% by weight, more preferably at least 70% by weight, more preferably at least 90% by weight, of total amount of solvent before adjusting the pH.

According to a preferred embodiment a hand dishwashing composition is described wherein the level of amine oxides having a C16 or longer radical is less than 20%, more preferably less than 10%, based on the total weight of 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%, 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 amine oxide 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, the composition comprising an organic solvent, which is preferably ethanol and more preferably is present in an amount of at least 2% by weight.

According to a preferred embodiment, a manual dishwashing composition is described, the proportion of amine oxides having a C12 radical being 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 in which the proportion of amine oxides which have a C14 radical is between 20 and 35%, based on the total amount of amine oxide.

According to a preferred embodiment, a hand dishwashing composition is described in which the proportion of amine oxides which have only C10 or smaller radicals 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 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 the feeling of the skin or care for it.

In a further aspect, the present invention is also directed towards the use of the dishwashing 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 the context of components of the compounds described herein, this specification does not refer to the absolute amount of molecules, but 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 present, without giving any information about the amount of the individual compounds.

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

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

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

The expression "substantially free from" means that the compound in question can in principle be present, 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 from" of a specific 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 given in the format "in/from x to y" include the stated values. Where multiple preferred numeric ranges are given in this format, it is understood that any ranges resulting from the combination of the different endpoints are also included.

Information about 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 GPC using polystyrene standards.

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

When constituents of the present compositions 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 - sufficient for charge equalization - as the anion.

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 , preferably the substituent 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 a study of the following detailed description and claims. Any feature or embodiment from one aspect of the invention may be employed 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 should be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular the invention is not limited to these examples.

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

According to one embodiment, the composition has at least one alkyl benzene sulfonate, which preferably has one
C2-18 alkyl radical. It is particularly preferably cumene sulfonate. According to the invention, the term alkylbenzenesulfonate is understood to mean only a benzene ring which is substituted by an alkyl radical and also carries a sulfonate radical.

In preferred embodiments, the at least one alkyl benzene sulfonate is present in 0.5 to 50% by weight, preferably 0.5 to 30% by weight, particularly preferably 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 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 at 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 having the formula R1R2R3NO wherein each R1, R2 and R3 independently of the others is an optionally substituted, e.g. hydroxy-substituted, C1-C30 hydrocarbon chain is. Amine oxides used with particular preference 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. Exemplary 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 C12-16 amine oxides, particularly preferably from lower-chain C12-14 alkyl dimethyl amine oxides.

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

If present, the at least one further anionic, nonionic or zwitterionic surfactant is preferably at 0.1 to 45% by weight, preferably 0.5 to 40% by weight, more preferably at 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.

Other suitable surfactants are, 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.

The at least one alpha-olefin sulfonate is preferably present in an amount of 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 additional 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 is 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 with 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 monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and including Na+ or K+, with Na+ being extremely preferred. Further cations X+ can be selected from NH4+, ½ Zn2+, ½ Mg2+, ½ Ca2+, ½ Mn2+, and mixtures thereof.

AO stands for an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably for an ethylene oxide moiety. The index n is an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. n is very particularly preferably 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 is 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 with an even number of carbon atoms are preferred. More preferably they are derived from C10-20 oxo alcohols.

X stands for a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and including Na+ or K+, with Na+ being extremely preferred. Further cations X+ can be selected from NH4+, ½ Zn2+, ½ Mg2+, ½ Ca2+, ½ Mn2+, and mixtures thereof.

If present, the at least one other nonionic surfactant is at from 0.1% to 20%, preferably from 0.5% to 10%, more preferably from 1% to 8% by weight based on the total weight of the dishwashing composition 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 having 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) x in which R is a primary straight-chain or methyl-branched, in particular methyl-branched in the 2-position, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol for 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; x is preferably from 1.2 to 1.4.

In one embodiment, the other nonionic surfactants are selected from the group of alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols preferably having 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) or propylene oxide (PO) per mole of alcohol, in which the alcohol radical is linear or preferably in the 2nd -position can be methyl-branched or can contain linear and methyl-branched radicals in the mixture, such as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear radicals from alcohols of natural origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are 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 3 EO, 5 EO or 7 EO alcohols 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 the surfactants, i.e. the surfactant system, based on the weight of the composition is from 2.5 to 70% by weight, preferably from 5 to 60% by weight, more preferably from 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, organic solvents, enzymes, additives to improve drainage and drying behavior, to adjust viscosity and/or for stabilization, UV stabilizers, perfume, Pearlizing agents, dyes, corrosion inhibitors, preservatives, bitter substances, organic salts, disinfectants, structuring polymers, defoamers, encapsulated ingredients, pH adjusters and additives that improve the feeling of the skin or care for it.

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 composition according to the invention is usually 15 to 90% by weight, preferably 20 to 60% by weight.

In addition, organic solvents can 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, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, Diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures of these Solvent. In particular, ethanol is preferred. Preferably, the organic solvent is 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 non-specific endopeptidases, which means that they hydrolyze any acid amide bonds that are inside peptides or proteins, thereby breaking down protein-containing soiling on the items to be cleaned. Their optimum pH 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, with 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 thereto,
• of the alkaline protease from Bacillus sp. (DSM 14390) or an alkaline protease which is at least 98.5% identical thereto, and
• of the alkaline protease from Bacillus sp. (DSM 14392) or an alkaline protease which is at least 98.1% identical thereto.

Examples of the proteases that can be used in the compositions described herein are Subtilisin 309 or functional fragments/variants thereof and Bacillus lentus alkaline protease variants or variants thereof. Subtilisin 309 is marketed under the trade name ^Savinase® by Novozymes A/S, Bagsvaerd, Denmark. Optimized enzyme variants of the subtilisin 309 from Bacillus lentus are available under the trade names ^Blaze® and ^Ovozyme® from the company Novozymes, which represent a preferred embodiment of the invention. For example, the protease variants listed under the name ^BLAP® are derived from the alkaline protease from Bacillus lentus DSM 5483. Preference is given here in particular to those protease variants which, compared to the BLAP wt (wild-type) enzyme, counted according to BLAP wt, have at least one mutation on R99, in particular R99E or R99D, R99E being particularly preferred, and optionally at least one or two in addition , preferably all three of the amino acid substitutions S3T, V4I and V1991, particularly preferred are the BLAP variants, as in SeqID No. 4 or 5 of WO 2014/177430 are described.

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

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

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

Furthermore, it is possible to formulate 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 formulated as described above for the proteases.

In dishwashing detergents according to the invention, which in one embodiment are in predominantly liquid, paste-like 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, contained in the latter.

In various embodiments, the enzyme(s) may be pre-formulated with enzyme stabilizers in an enzyme composition. The enzyme protein usually makes up only 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%, preferably 0.05-10% by weight based on the total weight of the enzyme composition. This enzyme composition can then be used in dishwashing detergents according to the invention, specifically in amounts which lead to the final concentrations in the dishwashing detergent indicated 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 via a titration of the active centers using a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)) and determination of the residual activity (cf. M. Bender et al., J. Am. Chem. Soc. 88, 24 (1966), pp. 5890-5913 ).

To further improve the sagging 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.

Polymer thickeners in the sense of the present invention are the polyelectrolytes having a thickening effect polycarboxylates, preferably homo and copolymers of acrylic acid, especially acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, especially 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 gum, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, for example propoxylated guar, as well as their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, can be used as an alternative, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl-, 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 crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI Carbomer), which are also referred to as carboxyvinyl polymers.

However, particularly suitable polymeric thickeners are the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters, preferably formed with C1-4 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 ) 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 consisting of acrylic acid, methacrylic acid and their simple esters, preferably formed with C1-4 alkanols ( 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 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 composition.

One or more dicarboxylic acids and/or their salts can be added to stabilize the agent according to the invention, particularly with a high surfactant content, particularly a composition of sodium 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 from dicarboxylic acid (salts).

In addition, one or more other - especially in hand dishwashing detergents - usual auxiliaries and additives, in particular UV stabilizers, perfume, pearlescent agents (INCI opacifying agents; for example glycol distearate, e.g. Cutina ^® AGS from Cognis, or mixtures containing this, e.g the 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 the feel of the skin 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 hydrolyzates, protein hydrolyzate fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such as eg lecithin, soybean oil, etc., plant extracts such as eg aloe vera, azulene, witch hazel extracts, algae extracts, etc., allantoin, AHA complexes, glycerol, urea, quaternized hydroxyethyl cellulose) in amounts usually not exceeding 8% by weight based on the total weight of the dishwashing detergent.

Na xylene sulfonate can be used as an additive.

The pH 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 hydroxide or potassium hydroxide, with a range of 4 to 9 being possible, particularly if hand tolerance is desired.

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 0.01 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. Buffer substances which are at the same time complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate·2H2O and tripotassium citrate·H2O.

example compositions:

The example compositions shown in Table 1 were provided from a base 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 formulation also contained smaller amounts of fragrances and colorings as well as protease and amylase enzymes. Table 1 example Reference sign EtOH CS AM / LMtotal 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 data are given as % by weight based on the total 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 formulations E1 to E5 according to the invention show that the compositions according to the invention have in particular a 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 exhibits a relatively small/stable change as a function of the pH value within the relevant pH range. The homogeneous mixing of the components by means of stirring tools was sufficiently well possible.

The comparison formulation C1, on the other hand, showed an unsuitable viscosity profile. It is true that high viscosity values could be achieved. In contrast to the example formulations according to the invention, however, these were not sufficiently constant/stable as a function of the pH. The production process of such a composition is made considerably more difficult or even impossible because of the viscosity peaks, since adequate mixing of the composition using stirring tools is prevented. So the pH value is adjusted at an early stage, in particular before the solvent is added, there is a risk that the composition can no longer be mixed and the energy input increases significantly. Adjusting the pH value before adding inorganic salt and before adding solvent would be possible in view of the low viscosity at this point in time, but is unsuitable since the pH value changes significantly as a result of the addition of the salt.

The composition E2 has a slight viscosity peak 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 is.

Surprisingly, it has now been found that the process utilizes the good viscosity profile which is achieved through the interaction of inorganic salt and solvent at pH values of around 7, it being essential that the pH value is adjusted after the solvent has been metered in.

Also provided were example compositions at higher total surfactant levels. The respective example compositions shown in Table 2 were provided from a base formulation comprising 16% by weight anionic surfactant and 4% amine oxide surfactant. The total amount of surfactant is therefore 20% by weight. The formulation also contained smaller amounts of fragrances and colorings as well as protease and amylase enzymes. Table 2 example Reference sign EtOH CS AM / LMtotal NaCl C2 110 1 1 10 1,875 E6 150 3.9 1 4 4.9

All data are given as % by weight based on the total 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 amounts of surfactants C1. The problems already presented apply particularly to higher total surfactant contents.
The composition E6 according to the invention is characterized by a particularly stable viscosity profile. In comparison to the formulations E1 to E5 with a lower total surfactant content, even better stabilization of the viscosity is achieved.

In conclusion, it can therefore be stated that the advantageous stabilization of the viscosity curve takes place in particular at higher total amounts of surfactants 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.

It therefore follows that the process step sequence according to the invention, to the effect that the pH value is adjusted 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 (11)

A method of making 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 solvent is provided before the pH is adjusted. A method according to claim 1, wherein the pH of the composition is adjusted to a value between 7.5 and 8.5. Process according to any 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. Process 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. Process 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. A method according to any one of the preceding claims, wherein the solvent comprises ethanol and/or cumene sulphonate. A method according to any one of the preceding claims, wherein the composition comprises at least one enzyme. A method according to any one of the preceding claims, wherein the composition comprises at least one anionic surfactant. Method according to any one of the preceding claims, wherein
the composition comprises at least one amine oxide and/or one betaine surfactant. Method according to any one of the preceding claims, wherein
the inorganic salt is provided before the pH is adjusted. Process according to any one of the preceding claims, wherein the total amount of surfactant is at least 5% by weight, preferably at least 12% by weight, more preferably at least 20% by weight.

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