EP4574945A1 - Cleaning agent concentrate - Google Patents

Abstract

The present application relates to a cleaning agent concentrate which is liquid at 20 °C and which contains - based on the total weight of the concentrate -
(a) 38 to 65 wt% water,
(b) 0.55 to 0.95 wt% xanthan,
(c) 2.0 to 3.7 wt% non-ionic surfactants,
(d) 5.3 to 10.3 wt.% complexing agent from the group consisting of methylglycinediacetic acid (MGDA), glutamic acid diacetic acid (GLDA) and/or their salts, and
(e) at least one protease and/or at least one amylase.

Description

The present application relates to cleaning agent concentrates which are liquid at 20 °C and which contain - based on the total weight of the concentrate - 38 to 82 wt.% water (a), 0.55 to 0.95 wt.% xanthan (b), 2.0 to 3.7 wt.% non-ionic surfactants (c), complexing agents from the group consisting of methylglycinediacetic acid (MGDA), glutamic acid-diacetic acid (GLDA) and/or their salts (d) and at least one protease and/or at least one amylase (e).

Cleaning agents for hard surfaces, such as dishwashing detergents, are available to consumers in a wide variety of forms. In addition to traditional solid detergents, free-flowing and especially liquid to gel-like cleaning agents have recently gained increasing importance. Consumers particularly value their rapid solubility and the resulting rapid availability of the ingredients in the cleaning solution, especially during short-rinse cycles and at low temperatures.

In recent years, the topic of sustainability has also become increasingly important. While not wanting to forgo the convenience of modern dishwashers, users still want to reduce resource consumption when using appropriate dishwashing detergents, rely on products made from renewable raw materials, and also save on packaging material.

One option for more economical dosing is to use concentrates, which increase the active ingredient content and reduce the amount of aqueous carrier. Liquid dishwashing detergents in the form of concentrates are already known in the art.

For example, DE 10 2017 223 276 A1 Cleaning concentrates with a specific viscosity range that do not contain non-biodegradable polymers and are clear after dilution with water. The concentrates of the DE 10 2017 223 276 A1 are designed for hand cleaning and are not suitable for use in dishwashers due to their high content of foaming surfactants.

In WO 2016/041851 A1 Liquid dishwasher detergents thickened with the natural polymer xanthan gum were investigated. Packaging takes the form of a single-serve portion in a single-chamber foil pouch, so that the liquid dishwashing detergent itself does not need to be portioned, but can be used together with the foil packaging in the dishwasher. Possible disadvantages in flow behavior that could arise from thickening with xanthan gum are avoided in this packaging form by pre-portioning in the bag.

The object of the present application was to provide a liquid, automatic dishwashing detergent in the form of a concentrate that uses a biodegradable polymer for thickening, has a reduced water content, and possesses optimized rheological properties. The concentrate should not be packaged as a pouch, but rather be provided in a larger bottle from which the user can portion out the product themselves. To achieve this, the concentrate should have the optimal viscosity, not be too liquid, but still flow sufficiently quickly from the bottle in the form of a homogeneous gel. Above all, no inhomogeneities, lumpy components, or deposits of the thickener should form at the bottom of the bottle either immediately after production or during storage. On the other hand, the concentrate should not separate into different phases after extended storage periods. Finally, the flow behavior of the concentrate should change as little as possible depending on external influences such as temperature or the fill level of the bottle.

Surprisingly, it has now been shown that this task can be solved if the cleaning agent concentrate contains water, xanthan gum as a thickener, non-ionic surfactants, complexing agents and enzymes, whereby these components are used in certain quantities in relation to one another.

1. (a) 38 bis 82 Gew.-% Wasser,
2. (b) 0,55 bis 0,95 Gew.-% Xanthan,
3. (c) 2,0 bis 3,7 Gew.-% nichtionische Tenside,
4. (d) 5,3 bis 10,3 Gew.-% Komplexbildner aus der Gruppe aus Methylglycindiessigsäure (MGDA), Glutaminsäurediessigsäure (GLDA) und/oder deren Salzen, und
5. (e) mindestens eine Protease und/oder mindestens eine Amylase.

A first subject of the present application is a cleaning agent concentrate which is liquid at 20 °C and which contains - based on the total weight of the concentrate -

1. (a) 38 to 82 wt% water,
2. (b) 0.55 to 0.95 wt% xanthan,
3. (c) 2.0 to 3.7 wt% non-ionic surfactants,
4. (d) 5.3 to 10.3 wt.% complexing agent from the group consisting of methylglycinediacetic acid (MGDA), glutamic acid diacetic acid (GLDA) and/or their salts, and
5. (e) at least one protease and/or at least one amylase.

In the further description, the term "at least one" is synonymous with the term "one or more", and both terms can be used interchangeably.

"One or more," as used herein, refers to at least one and includes 1, 2, 3, 4, 5, 6, 7, 8, 9, or more of the named types. Similarly, "at least one," as used herein, refers to, but is not limited to, 1, 2, 3, 4, 5, 6, and more. With respect to an ingredient, it refers to the type of ingredient and not the absolute number of molecules. Thus, for example, "at least one surfactant" means at least one type of surfactant, i.e., it can mean one type of surfactant or a mixture of several different surfactants. Together with the weight information, the information refers to all compounds of the specified type contained in the composition/mixture, i.e. the composition does not contain any other compounds of this type beyond the specified amount of the corresponding compounds.

Cleaning agent concentrate

The detergent concentrates according to the invention are particularly suitable as dishwashing detergent compositions for automatic dishwashing. In one embodiment, the dishwashing detergent composition according to the invention is therefore an automatic dishwashing detergent composition.

1. (a) 38 bis 82 Gew.-% Wasser,
2. (b) 0,55 bis 0,95 Gew.-% Xanthan,
3. (c) 2,0 bis 3,7 Gew.-% nichtionische Tenside,
4. (d) 5,3 bis 10,3 Gew.-% Komplexbildner aus der Gruppe aus Methylglycindiessigsäure (MGDA), Glutaminsäurediessigsäure (GLDA) und/oder deren Salzen, und
5. (e) mindestens eine Protease und/oder mindestens eine Amylase.

In other words, the first subject matter of the invention is particularly preferably an automatic dishwashing detergent in concentrate form which is liquid at 20 °C and which - based on the total weight of the automatic dishwashing detergent - contains

1. (a) 38 to 82 wt% water,
2. (b) 0.55 to 0.95 wt% xanthan,
3. (c) 2.0 to 3.7 wt% non-ionic surfactants,
4. (d) 5.3 to 10.3 wt.% complexing agent from the group consisting of methylglycinediacetic acid (MGDA), glutamic acid diacetic acid (GLDA) and/or their salts, and
5. (e) at least one protease and/or at least one amylase.

The cleaning composition according to the invention is provided in the form of a liquid. The term "liquid," as used herein, includes liquids and gels. The term "liquid," as used herein, refers to dishwashing detergents or concentrates that are flowable and pourable at 20°C (1 bar).

A cleaning agent concentrate in the sense of the present application is understood to mean a liquid cleaning agent with a water content of 38 to 82 wt.%, preferably 45 to 80 wt.%, more preferably 55 to 79 wt.%, even more preferably 65 to 78 wt.% and particularly preferably 69 to 77 wt.%, wherein the amount of water is based on the total weight of the cleaning agent.

Water content (a)

As the first essential component (a), the concentrate or automatic dishwashing detergent according to the invention contains, based on its total weight, 38 to 82 wt.% water (a). Compared to known automatic dishwashing detergents that are not in concentrate form, the water content is reduced, which reduces the size of the packaging and thus saves material.

The work carried out in the course of this application has shown that, on the one hand, the complete dissolution of the xanthan (b) and all other components (c) to (e) can be ensured, but on the other hand separation of the concentrate into different phases can be avoided if the amounts of water (a) and xanthan (b) used are optimally coordinated. If the concentrate contains less than 38 wt.% water, there is a risk that the amount of xanthan used will not dissolve completely and will deposit in lumps at the bottom of the product. If more than 82 wt.% is used, the product is no longer a concentrate and can also separate during storage even if the xanthan is used in the amount (b).

For this reason, it has been found to be particularly preferred if the automatic dishwashing detergent contains - based on its total weight - 45 to 80 wt.%, preferably 55 to 79 wt.%, more preferably 65 to 78 wt.% and particularly preferably 69 to 77 wt.% of water (a).

1. (a) 45 bis 80 Gew.-%, bevorzugt 55 bis 79 Gew.-%, weiter bevorzugt 65 bis 78 Gew.-% und besonders bevorzugt 69 bis 77 Gew.-% Wasser enthält.

In a particularly preferred embodiment, a concentrate according to the invention
characterized in that - based on the total weight of the concentrate -

1. (a) contains 45 to 80 wt.%, preferably 55 to 79 wt.%, more preferably 65 to 78 wt.% and particularly preferably 69 to 77 wt.% water.

Xanthan (b)

As a second essential component, the concentrate or automatic dishwashing detergent according to the invention contains - based on its total weight - 0.55 to 0.95 wt.% xanthan (b).

Xanthan gum is a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions. It has a molecular weight of 2 to 15 million Daltons. Xanthan gum is formed from a chain of β-1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate, and pyruvate, with the number of pyruvate units determining the viscosity of the xanthan gum. Xanthan gum can also be referred to as xanthan gum, E 414, or xanthan gum, and has the CAS number 11138-66-2.

Thickening with xanthan gum can improve the biodegradability of the concentrate. Preferably, the active ingredients of the compositions are biodegradable, resulting in a high percentage of biodegradability, preferably above 85% by weight of the composition. This means that 85% by weight of the components of the composition are biodegradable. Preferably, more than 90% by weight of the composition is biodegradable, and more preferably, more than 98% of the composition is biodegradable. The biodegradability of the components is defined according to OECD 301.

In the range of 0.55 to 0.95 wt.%, xanthan gum can be completely dissolved and is able to stabilize the liquid concentrate and minimize disintegration of the mixture. In particular, the sedimentation of all other components contained in the concentrate can also be reduced.

Particularly stable and homogeneous concentrates were obtained when the xanthan (b) - based on the total weight of the automatic dishwashing detergent or concentrate - was used in an amount range of 0.60 to 0.90 wt.%, preferably 0.65 to 0.90 wt.%, more preferably 0.70 to 0.90 and most preferably 0.80 to 0.90 wt.%.

The best results were obtained when the concentrate contained 0.80 to 0.90 wt.% xanthan. This most preferred embodiment allowed the amount of water to be reduced to a maximum while still allowing the xanthan to be completely dissolved and preventing sedimentation of all other components.

In a particularly preferred embodiment, a concentrate according to the invention is characterized in that it contains - based on the total weight of the concentrate -
(b) contains 0.60 to 0.90 wt.%, preferably 0.65 to 0.90 wt.%, more preferably 0.70 to 0.90 and most preferably 0.80 to 0.90 wt.% of xanthan.

Ratio of water (a) to xanthan (b)

As already described, it has proven essential to the invention to use both the water (a) and the xanthan (b) in certain quantities in the concentrate.

A homogeneous and stable concentrate was obtained especially when (a) and (b) were adjusted to their preferred or particularly preferred ranges and thus the weight ratio of (a) to (b) was also brought to the optimized values.

If the concentrate contains too little water compared to the amount of xanthan gum used, there is a risk that the xanthan gum used will not dissolve completely and will form lumps at the bottom of the product. If too much water (a) is used compared to the xanthan gum (b), the concentrate containing the other components (c) to (e) may separate during storage. For this reason, it is particularly preferred if water (a) and xanthan gum (b) are used in the concentrate in very specific weight ratios. The weight ratio of the amount of water (a) contained in the concentrate or in the automatic dishwashing detergent to the amount of xanthan gum (b), i.e. the weight ratio (a)/(b), is preferably in the range from 65 to 130, even more preferably in the range from 70 to 120, and most preferably in the range from 75 to 105.

In a particularly preferred embodiment, a concentrate according to the invention is characterized in that the weight ratio of the water (a) contained in the concentrate to xanthan (b), i.e. the weight ratio (a)/(b), is in the range from 60 to 140, preferably in the range from 65 to 130, more preferably in the range from 70 to 120 and most preferably in the range from 75 to 105.

For example, if 100 g of the concentrate according to the invention contains 72 g of water (a) and 0.8 g of xanthan (b), the weight ratio (a)/(b) is 90.

non-ionic surfactants (c)

As a third essential component (c), the concentrate according to the invention or the automatic dishwashing detergent contains - based on its total weight - 2.0 to 3.7 wt.% non-ionic surfactants.

All nonionic surfactants known to those skilled in the art can be used as nonionic surfactants. Low-foaming nonionic surfactants are preferably used, especially alkoxylated, especially ethoxylated, low-foaming nonionic surfactants such as alkyl glycosides, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, polyhydroxy fatty acid amides, or amine oxides. Particularly preferred nonionic surfactants are described in more detail below.

Preferred alcohol ethoxylates have a narrow range (NRE) distribution. In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohols with 14 EO, 25 EO, 30 EO, or 40 EO.

Particular preference is given to using ethoxylated nonionic surfactants obtained from _C6 - _C20 monohydroxyalkanols or _C6 - _C20 alkylphenols or _C16 - _C20 fatty alcohols and more than 12 mol, preferably more than 15 mol, and in particular more than 20 mol, of ethylene oxide per mole of alcohol. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C16-C20 alcohol), preferably from a C18 alcohol, and at least 12 mol, preferably at least 15 mol, and in particular at least 20 mol, of ethylene oxide. The so-called "narrow-range ethoxylates" are particularly preferred.

Preferred surfactants come from the group of alkoxylated non-ionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants). Such (PO/EO/PO) non-ionic surfactants are also characterized by good foam control.

In the context of the present invention, low-foam nonionic surfactants containing alternating ethylene oxide and alkylene oxide units have proven particularly preferred. Among these, surfactants with EO-AO-EO-AO blocks are preferred, wherein one to ten EO groups or AO groups are linked to one another before a block of the respective other group follows. Nonionic surfactants of the general formula

preferred are those in which R ¹ represents a straight-chain or branched, saturated or mono- or polyunsaturated functional C ₆ -C ₂₄ alkyl or alkenyl group; each R 2 and R 3 group is independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH(CH ₃ ) ₂ ; and the indices w, x, y and z independently represent integers from 1 to 6.

Preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide.

The above formula may vary depending on the alcohol's origin. When native sources are used, the ^R1 functional group has an even number of carbon atoms and is generally unbranched, with linear functional groups of native alcohols with 12 to 18 carbon atoms, such as coconut, palm, tallow, or oleyl alcohol, being preferred. Some examples of alcohols available from synthetic sources are Guerbet alcohols or functional groups that are methyl-branched or linear and 2-methyl-branched, as commonly found in the functional groups of oxo alcohols, in a mixture. Regardless of the type of alcohol used to produce the nonionic surfactants contained in the compositions, nonionic surfactants are preferred in which R ¹ represents a functional alkyl group having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15, in particular 9 to 11, carbon atoms in the above formula.

In addition to propylene oxide, butylene oxide is particularly suitable as an alkylene oxide unit present alternately with the ethylene oxide unit in the preferred nonionic surfactants. However, other alkylene oxides in which R ² and R ³ are independently selected from -CH ₂ CH ₂ CH ₃ and -CH(CH ₃ ) ₂ are also suitable. Preference is given to using nonionic surfactants of the above formula in which R ² and R ³ represent a -CH ₃ functional group; w and x are independently values of 3 or 4; and y and z are independently values of 1 or 2.

Other preferably used non-ionic surfactants of the solid phase are non-ionic surfactants of the general formula

R ¹ O(AlkO) _xM (OAlk)yOR ² ,

in which R ¹ and R ² independently represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl function having 4 to 22 carbon atoms; Alk represents a branched or unbranched alkyl function having 2 to 4 carbon atoms; x and y independently represent values between 1 and 70; and M represents an alkyl function selected from the group consisting of CH ₂ , CHR ³ , CRR ³⁴ , CH2CHR ³ and CHR ³ CHR ⁴ , R ³ and R ⁴ which independently represent a branched or unbranched, saturated or unsaturated alkyl function having 1 to 18 carbon atoms.

In this case, non-ionic surfactants of the general formula

R ¹ -CH(OH)CH ₂ -O(CH ₂ CH ₂ O) _x CH ₂ CHR(OCH ₂ CH ₂ ) _y O-CH ₂ CH(OH)-R ²

in which R, R ¹ and R ² independently represent a functional alkyl group or a functional alkenyl group having 6 to 22 carbon atoms; x and y independently represent values between 1 and 40.

In this case, compounds of the general formula

R ¹ -CH(OH)CH ₂ -O(CH ₂ CH ₂ O) _x CH ₂ CHR(OCH ₂ CH ₂ ) _y O-CH ₂ CH(OH)-R ²

in which R represents a linear, saturated alkyl function having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently of one another represent values from 20 to 30. Such compounds can be obtained, for example, by reacting alkyldiols HO-CHR-CH ₂ -OH with ethylene oxide, followed by a reaction with an alkyl epoxide to close the free OH functions to form a dihydroxy ether.

• R¹ eine geradkettige oder verzweigte, gesättigte oder ein- oder mehrfach ungesättigte funktionelle C6-24-Alkyl- oder -Alkenylgruppe darstellt;
• R² steht für Wasserstoff oder eine lineare oder verzweigte funktionelle Kohlenwasserstoffgruppe mit 2 bis 26 Kohlenstoffatomen;
• A, A', A" und A‴ stehen unabhängig voneinander für eine funktionelle Gruppe aus der Gruppe -CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-, - CH₂-CH(CH₂-CH₃);
• w, x, y und z stehen für Werte zwischen 0,5 und 120, wobei x, y und/oder z auch 0 sein können.

In this case, preferred nonionic surfactants are those of the general formula R ¹ -CH(OH)CH ₂ O-(AO) _w -(AO) _x -(A"O) _y -(A‴O) _z -R ² , in which

• R ¹ represents a straight-chain or branched, saturated or mono- or polyunsaturated functional C6-24 alkyl or alkenyl group;
• R ² represents hydrogen or a linear or branched functional hydrocarbon group having 2 to 26 carbon atoms;
• A, A', A" and A‴ independently represent a functional group from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH(CH ₃ ), -CH ₂ -CH ₂ -CH 2 -CH ₂ , -CH _{2 -CH} (CH ₃ )-CH ₂ -, - CH ₂ -CH(CH ₂ -CH ₃ );
• w, x, y and z represent values between 0.5 and 120, where x, y and/or z can also be 0.

By adding the above-mentioned non-ionic surfactants of the general formula R ¹ -CH(OH) _CH2O -(AO) _w- (A'O) _x- (A "O) _y- (A‴O)zR ² , hereinafter also referred to as "hydroxy mixed ethers", the cleaning performance of preparations according to the invention can be significantly improved both in comparison to surfactant-free systems and in comparison to systems with alternative non-ionic surfactants, for example from the group of polyalkoxylated fatty substances.

By using these non-ionic surfactants, which have one or more free hydroxyl groups on one or both terminal alkyl functional groups, the stability of the enzymes contained in the cleaning agent preparations according to the invention can be significantly improved.

In particular, those end-capped poly(oxyalkylated) nonionic surfactants are preferred which correspond to the following formula,

R ¹ -O-(CH ₂ CH ₂ O)n-CH ₂ CH(OH)-R ²

in addition to a functional group R ¹ which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functions having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, also have a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon function R ² having 1 to 30 carbon atoms, where n represents values between 1 and 90, preferably values between 10 and 80 and in particular values between 20 and 60.

Particularly preferred surfactants are those of the above formula in which R ¹ is C ₇ to C ₁₃ , n is an integer from 16 to 28 and R ² is C ₈ to C ₁₂ .

Preferred surfactants are those of the formula R ¹ O[CH ₂ CH(CH ₃ )O] _x [CH ₂ CH ₂ O] _y CH ₂ CH(OH)R ² , in which R ¹ represents a linear or branched aliphatic hydrocarbon function having 4 to 18 carbon atoms or mixtures thereof, R ² represents a linear or branched hydrocarbon function having 2 to 26 carbon atoms or mixtures thereof, x represents values between 0.5 and 1.5 and y represents a value of at least 15. The group of these non-ionic surfactants includes, for example, the C2-26 fatty alcohol (PO) 1 (EO) 15-40 2-hydroxyalkyl ethers, in particular the C8-10 fatty alcohol (PO) 1 (EO) 22 2-hydroxydecyl ethers.

In particular, the end-capped poly(oxyalkylated) nonionic surfactants of the formula R ¹ O[CH ₂ CH ₂ O] _x [CH ₂ CH(R ³ )O] _y CH ₂ CH(OH)R ² are preferred, in which R ¹ and R ² independently represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon function having 2 to 26 carbon atoms, R ³ is independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH(CH ₃ ) ₂ , but preferably represents -CH ₃ , and x and y independently represent values between 1 and 32, with nonionic surfactants with R ³ = _-CH3 and with values for x from 15 to 32 and for y from 0.5 to 1.5 being particularly preferred.

Further non-ionic surfactants which can preferably be used are the end-capped poly(oxyalkylated) non-ionic surfactants of the formula R ¹ O[CH ₂ CH(R ³ )O] _x [CH ₂ ] _k CH(OH)[CH ₂ ] _j OR ² , in which R ¹ and R ² represent linear or branched, saturated or unsaturated, saturated or unsaturated, aliphatic or aromatic hydrocarbon functions having 1 to 30 carbon atoms, R ³ represents H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl function, x represents values between 1 and 30 and k and j represent values between 1 and 12, preferably between 1 and 5. If the value x > 2, each R ³ in the above formula R ¹ O[CH ₂ CH(R ³ )O] _x [CH ₂ ] _k CH(OH)[CH ₂ ] _j OR ² can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic functional hydrocarbon groups having 6 to 22 carbon atoms, with functional groups having 8 to 18 C atoms being particularly preferred. For the functional group R ³ , H, _- -CH ₃ or -CH ₂ CH ₃ are particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula can be different if x > 2. In this way, the alkylene oxide unit in square brackets can be varied. For example, if x is 3, the functional group R ³ can be chosen to form ethylene oxide (R ³ = H) or propylene oxide units (R ³ = _{CH 3} ), which can be linked together in any order, for example (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO)(PO). The value 3 for x was chosen here as an example and can certainly be larger, whereby the range of variation increases with the size of the values for x and, for example, a large number of (EO) groups are combined with a small number of (PO) groups, or vice versa.

• R¹ eine geradkettige oder verzweigte, gesättigte oder einfach oder mehrfach ungesättigte funktionelle C6-24-Alkyl- oder -Alkenylgruppe darstellt;
• R² steht für eine lineare oder verzweigte funktionelle Kohlenwasserstoffgruppe mit 2 bis 26 Kohlenstoffatomen;
• A eine funktionelle Gruppe aus der Gruppe CH2CH2, CH2CH2CH2, CH2CH(CH3), vorzugsweise CH2CH2, darstellt und
• w steht für Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40.

Particularly preferred end-capped poly(oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, and therefore the previous formula is simplified to R ¹ O[CH ₂ CH(R ³ )O] _x CH ₂ CH(OH)CH ₂ OR ² . In the latter formula, R ¹ , R ² and R ³ are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred surfactants are those in which the functional groups R ¹ and R ² have 9 to 14 C atoms, R ³ stands for H and x assumes values from 6 to 15. Finally, the nonionic surfactants of the general formula R ¹ -CH(OH)CH2O-(AO)wR ² have proven to be particularly effective in which

• R ¹ represents a straight-chain or branched, saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl functional group;
• R ² represents a linear or branched functional hydrocarbon group having 2 to 26 carbon atoms;
• A represents a functional group from the group CH2CH2, CH2CH2CH2, CH2CH(CH3), preferably CH2CH2, and
• w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40.

The group of these non-ionic surfactants includes, for example, the C4-22 fatty alcohol (EO)10-80-2-hydroxyalkyl ethers, in particular the C8-12 fatty alcohol (EO)22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO)40-80-2-hydroxyalkyl ethers.

In various embodiments, the non-ionic surfactant is selected from non-ionic surfactants of the general formula R ¹ -O(CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which R ¹ and R ² independently represent an alkyl functional group or alkenyl functional group having 4 to 22 carbon atoms; R ³ and R ⁴ independently represent H or an alkyl functional group or alkenyl functional group having 1 to 18 carbon atoms and x and y independently represent values between 1 and 40.

In particular, compounds of the general formula R ¹ -O(CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² are preferred, in which R ³ and R ⁴ are H and the indices x and y independently assume values from 1 to 40, preferably from 1 to 15.

In particular, compounds of the general formula R ¹ -O(CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² are preferred, where the functional groups R ¹ and R ² independently represent saturated alkyl functional groups having 4 to 14 carbon atoms and the indices x and y independently assume values from 1 to 15 and in particular from 1 to 12.

In addition, compounds of the general formula R ¹ -O(CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² are preferred in which one of the functional groups R ¹ and R ² is branched.

Compounds of the general formula
R ¹ -O(CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , where the indices x and y, independently of one another, assume values from 8 to 12.

The stated carbon chain lengths and degrees of ethoxylation or alkoxylation of the nonionic surfactants represent statistical averages, which can be a whole number or a fraction for a specific product. Due to the manufacturing processes, the commercial products of the above-mentioned formulas generally do not consist of a single representative. but from mixtures, which is why average values and resulting fractions can result for both the C chain lengths and the degrees of ethoxylation and alkoxylation.

Of course, the above-mentioned non-ionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.

Nonionic surfactants with a melting point above room temperature are particularly preferred. Nonionic surfactants with a melting point above 20°C, preferably above 25°C, particularly preferably between 25 and 60°C, and in particular between 26.6 and 43.3°C are particularly preferred.

The nonionic surfactant, which is solid at room temperature, preferably has propylene oxide (PO) units in its molecule. Such PO units preferably make up to 25 wt.%, particularly preferably up to 20 wt.%, and especially up to 15 wt.% of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols that additionally contain polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol content of such nonionic surfactant molecules preferably makes up more than 30 wt.%, particularly preferably more than 50 wt.%, and especially more than 70 wt.% of the total molar mass of such nonionic surfactants. Preferred agents are characterized in that they contain ethoxylated and propoxylated non-ionic surfactants in which the propylene oxide units in the molecule make up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the non-ionic surfactant.

Whenever reference is made to molar masses, these figures always refer to the number-average molar mass _Mn , unless explicitly stated otherwise. The number-average molar mass can be determined, for example, by gel permeation chromatography (GPC) according to DIN 55672-1:2007-08 using THF as the eluent. The weight-average molar mass _Mw can also be determined by GPC as described for _Mn .

The use of the non-ionic surfactant(s) (c) in the amount range of 2.0 to 3.7 wt.% ensures the formulation of stable and homogeneous concentrates without sedimentation and without phase separation.

This was especially possible over longer storage periods and wider temperature ranges when the concentrate contained the non-ionic surfactant(s) (c) in a total amount of 2.2 to 3.6 wt.%, preferably 2.4 to 3.5 wt.%, more preferably from 2.6 to 3.4 wt.% and most preferably from 2.8 to 3.3 wt.%.

In a particularly preferred embodiment, a concentrate according to the invention is therefore characterized in that it contains - based on the total weight of the concentrate - 2.2 to 3.6 wt.%, preferably 2.4 to 3.5 wt.%, more preferably from 2.6 to 3.4 wt.% and very particularly preferably from 2.8 to 3.3 wt.% of non-ionic surfactants (c).

Complexing agent (d)

As a fourth component essential to the invention, the machine dishwashing detergent or concentrate according to the invention contains - based on its total weight - 5.3 to 10.3 wt.% of complexing agent (d) from the group consisting of methylglycinediacetic acid (MGDA), glutamic acid diacetic acid (GLDA) and/or their salts.

An explicitly particularly preferred complexing agent (d) is methylglycinediacetic acid (MGDA), which can alternatively be referred to as 2-methyl-2',2",2‴-nitrilotriacetic acid and is abbreviated as substance MGDA. MGDA has the CAS number 29578-05-0 and can be purchased commercially from various suppliers, for example, ABClabtory Scientific Co. Ltd, Chemieliva Pharmaceutical Co. Ltd, SIA "Chemspace," or Hong Kong Chemhere Co. Ltd. MGDA has the formula (Ia). The physiologically acceptable salts of MGDA are also according to the invention.

Well-suited salts of MGDA are, for example, the sodium, potassium, magnesium, calcium, zinc, or ammonium ion (NH ₄ ⁺ ) salts.

MGDA is particularly preferably used in the form of its trisodium salt in the concentrate.

The trisodium salt of MGDA has the CAS number 164462-16-2 and can be purchased, for example, from BASF under the trade name Neutrol MGDA.

The trisodium salt of MGDA is also commercially available under the trade name Trilon M. Trilon M raw materials are sold by BASF as liquid, powder, and granules.

wobei

• M1, M2 unabhängig voneinander für Natrium oder Kalium stehen, und
• M3, M4 unabhängig voneinander für Natrium oder Kalium stehen.

Another particularly suitable complexing agent is glutamic acid diacetic acid (GLDA). GLDA has the formula (Ib)

where

• M1, M2 independently represent sodium or potassium, and
• M3, M4 independently represent sodium or potassium.

An explicitly particularly preferred complexing agent (d) of this embodiment is tetrasodium N , N -bis(carboxylatomethyl)-L-glutamate. Tetrasodium N , N -bis(carboxylatomethyl)-L-glutamate falls under formula (Ib), where M1, M2, M3, and M4 represent a sodium cation.

Tetrasodium N , N -bis(carboxylatomethyl)-L-glutamate can alternatively be referred to as glutamic acid N , N -diacetic acid tetrasodium salt. The L-form is called L-tetrasodium N , N- bis(carboxylatomethyl)-L-glutamate or ( S )-glutamic acid N , N -diacetic acid tetrasodium salt, N , N- bis(carboxymethyl)-L-glutamic acid tetrasodium salt or GLDA-Na ₄ for short and has the CAS number 51981-21-6 The INCI name of this compound is TETRASODIUM GLUTAMATE DIACETATE.

Tetrasodium N,N-bis(carboxymethyl)-L-glutamate can be purchased from Aquapharm Chemicals, for example, under the trade name Aquacid 2015 EX.

Akzo Nobel sells N,N-bis(carboxymethyl) glutamic acid tetrasodium salt under the trade name Dissolvine GL PD S ( CAS number 51981-21-6 ) commercially distributed.

GLDA possesses a stereogenic center. Both the (S) and (R) forms (or both the L and D forms) are within the scope of the invention.

GLDA is particularly preferably used in the form of its tetrasodium salt in the concentrate.

Particularly preferred salts of the complexing agents (d) are their alkali metal salts, in particular the trisodium salt of methylglycinediacetic acid (MGDA) or the tetrasodium salt of glutamatediacetic acid (GLDA). Especially when the concentrate contains the complexing agent(s) MGDA and/or GLDA in the form of the trisodium or tetrasodium salts, the ionic strength in the concentrate is increased.

It is known from the literature that monovalent and divalent cations can strongly influence the viscoelastic properties of aqueous xanthan gum solutions. Depending on the concentration of the ions present, the viscosity can decrease due to charge shielding and electrostatic repulsion between ionized groups.

The addition of monovalent ions to an aqueous xanthan gum solution can exert a significant influence on the molecular properties of xanthan gum. For example, the presence of ionic charges can cause the side chains of xanthan gum to collapse toward the polymer backbone. In this context, it has proven particularly important to adjust the amount of complexes in salt form (d) to the amounts of water (a) and xanthan (b) present.

It has been found that the viscosity could be adjusted well to the desired range and did not change adversely during storage, in particular when the concentrate contained the complexing agent(s) (d), in particular the salts of methylglycinediacetic acid (MGDA) and/or glutamic acid diacetic acid (GLDA), in a quantity range of 5.3 to 10.3 wt.%.

The complexing agent(s), in particular the sodium salts of MGDA and/or GLDA, are very particularly preferably contained in the concentrate in an amount range from 5.8 to 9.7% by weight, preferably 6.4 to 9.5% by weight, more preferably from 7.0 to 9.3% by weight, even more preferably from 7.6 to 9.1% by weight and very particularly preferably from 8.0 to 9.0% by weight.

In a particularly preferred embodiment, a concentrate according to the invention is characterized in that it contains - based on the total weight of the concentrate - 5.8 to 9.7 wt.%, preferably 6.4 to 9.5 wt.%, more preferably from 7.0 to 9.3, even more preferably from 7.6 to 9.1 wt.% and most preferably from 8.0 to 9.0 wt.% of complexing agent (d) from the group consisting of methylglycinediacetic acid (MGDA), glutamic acid diacetic acid (GLDA) and/or salts thereof.

In an explicitly particularly preferred embodiment, a concentrate according to the invention is characterized in that it contains - based on the total weight of the concentrate - 5.8 to 9.7 wt.%, preferably 6.4 to 9.5 wt.%, more preferably from 7.0 to 9.3, even more preferably from 7.6 to 9.1 wt.% and most preferably from 8.0 to 9.0 wt.% of complexing agent (d) from the group consisting of methylglycinediacetic acid trisodium salt and glutamic acid diacetic acid tetrasodium salt.

Citric acid and/or citrates

In addition to the complexing agent(s) (d), the cleaning agent concentrate according to the invention particularly preferably contains citric acid and/or citric acid salts. A particularly suitable citric acid salt is sodium citrate, in particular trisodium citrate, anhydrous trisodium citrate, or trisodium citrate dihydrate.

Combinations of citric acid or its salts with methylglycinediacetic acid (MGDA) or its salts are also preferred. The combination of the trisodium salt of methylglycinediacetic acid (MGDA) and trisodium citrate is particularly preferred.

In a particularly preferred embodiment, a cleaning agent concentrate according to the invention is characterized in that it contains - based on the total weight of the concentrate - 5.7 to 10.5 wt.%, preferably 6.3 to 10.1 wt.%, more preferably 7.3 to 9.7 wt.% and most preferably 8.3 to 9.4 wt.% of citric acid and/or its salts.

In a particularly preferred embodiment, a cleaning agent concentrate according to the invention is characterized in that it contains - based on the total weight of the concentrate - 5.7 to 10.5 wt.%, preferably 6.3 to 10.1 wt.%, more preferably 7.3 to 9.7 wt.% and most preferably 8.3 to 9.4 wt.% sodium citrate.

Enzymes (e)

The concentrate or dishwasher detergent according to the invention contains at least one protease and/or at least one amylase (e).

Enzymes are added to enhance cleaning performance or to ensure the same cleaning performance under milder conditions (e.g., at lower temperatures). The enzymes can be used in free form or in chemically or physically immobilized form on a carrier or in encapsulated form.

Cleaning agents according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-6 wt.% to 5 wt.%, based on active protein. The protein concentration can be determined using known methods, e.g., the BCA method or the biuret method.

Among the proteases, the subtilisin-type proteases are preferred. Examples of these are the Subtilisins BPN' and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, the subtilisin DY, as well as the enzymes thermitase, proteinase K and the proteases TW3 and TW7, which belong to the subtilases but no longer to the subtilisins in the narrower sense.

Examples of amylases that can be used according to the invention are α-amylases from Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger, and A. oryzae, as well as further developments of the aforementioned amylases that have been improved for use in cleaning agents. Particularly noteworthy in this context are the α-amylases from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Cleaning-active proteases and amylases are generally not supplied in the form of pure proteins, but rather in stabilized, storable, and transportable preparations. These finished preparations include, for example, solid preparations obtained by granulation, extrusion, or freeze-drying, or, particularly in the case of liquid or gel-like products, solutions of the enzymes, preferably maximally concentrated, low in water, and/or supplemented with stabilizers or other excipients.

Alternatively, the enzymes can also be encapsulated, e.g., by spray-drying or extrusion of the enzyme solution together with a preferably natural polymer, or in the form of capsules, e.g., those in which the enzymes are enclosed in a solid gel, or in core-shell capsules, in which an enzyme-containing core is coated with a water-, air-, and/or chemical-impermeable protective layer. In the case of cover layers, other active ingredients such as stabilizers, emulsifiers, pigments, or dyes can also be applied. Such capsules are applied using conventional methods, for example, by shaking or rolling granulation or in a fluidized-bed process. Such granules are advantageously low in dust, e.g., through the use of polymeric film formers, and are storage-stable due to the coating.

As can be seen from the foregoing, the enzyme protein makes up only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations used according to the invention contain between 1 and 40 wt.%, preferably between 2 and 30 wt.%, particularly preferably between 3 and 25 wt.% of the enzyme protein. Particularly preferred cleaning agents are those which, based on their total weight, contain 0.1 to 12 wt.%, preferably 0.2 to 10 wt.%, and especially 0.5 to 8 wt.% of the respective enzyme preparations.

If the dishwashing detergent formulations contain enzymes, they preferably contain them in Amounts of 0.001 to 3.0% of active enzyme protein, based on the weight of the total composition. The percentage of enzymes is calculated based on the mass of active enzyme protein per weight of the total composition.

In a preferred embodiment, the automatic dishwashing detergent formulation is characterized in that the composition comprises amylases in an amount of 0.05 to 20 mg of active enzyme protein per gram of the total composition, preferably 0.10 to 10 mg of active enzyme protein per gram of the total composition, most preferably 0.15 to 2 mg of active enzyme protein per gram of the total composition.

In a preferred embodiment, the dishwashing detergent formulation is further characterized in that the composition comprises proteases in an amount of 0.1 to 50 mg of active enzyme protein per gram of the total composition, preferably 0.2 to 25 mg of active enzyme protein per gram of the total composition, 0.5 to 10 mg of active enzyme protein per gram of the total composition.

According to the invention, amylases and proteases (e) are preferably used.

Formulations according to the invention may contain one or more enzyme stabilizers. Enzyme stabilizers serve to protect enzymes – especially during storage – from damage such as inactivation, denaturation, or decomposition, e.g., due to physical influences, oxidation, or proteolytic cleavage.

Examples of enzyme stabilizers are reversible protease inhibitors, e.g., benzamidine hydrochloride, borax, boric acid, boronic acids, or their salts or esters, including, in particular, derivatives with aromatic groups, e.g., ortho-, meta-, or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or esters of the aforementioned compounds. Peptide aldehydes, i.e., oligopeptides with a reduced carbon terminus, particularly those consisting of 2 to 50 monomers, are also used for this purpose. Peptide reversible protease inhibitors include, among others, ovomucoid and leupeptin. Specific, reversible peptide inhibitors for the protease subtilisin, as well as fusion proteins of proteases and specific peptide inhibitors, are also suitable for this purpose. Other examples of enzyme stabilizers include amino alcohols such as mono-, di-, triethanolamine, and propanolamine, and their mixtures, aliphatic mono- and dicarboxylic acids, and even C12 carboxylic acids such as succinic acid. Terminally capped fatty acid amide alkoxylates are also suitable as enzyme stabilizers. Calcium chloride is also a good stabilizer for proteases.

Calcium chloride

With regard to the rheological properties of the concentrate, it has also proven to be particularly It was found to be advantageous if the concentrate contained calcium chloride to stabilize the protease (e).

Similar to monovalent salts, divalent salts such as magnesium chloride or calcium chloride in water can reduce the electrostatic repulsion between the charged groups of xanthan gum, which can ultimately lead to a reduction in the viscosity of the concentrate. For this reason, calcium chloride is also preferably used in the concentrate in certain quantity ranges. Particularly suitable amounts of calcium chloride are 0.23 to 0.60 wt.%, preferably 0.26 to 0.55 wt.%, more preferably 0.27 to 0.45 wt.%, particularly preferably 0.29 to 0.36 wt.%, and particularly preferably 0.31 to 0.40 wt.%, whereby these amounts are based on the total weight of the concentrate.

In a particularly preferred embodiment, a concentrate according to the invention is characterized in that it contains - based on the total weight of the concentrate - 0.23 to 0.60 wt.%, preferably 0.26 to 0.55 wt.%, more preferably 0.27 to 0.45 wt.% and particularly preferably 0.29 to 0.36 wt.% calcium chloride.

phosphate-free and bleach-free concentrate

The concentrate according to the invention is particularly preferably substantially phosphate-free. "Phosphate-free" here means that the cleaning agent is substantially free of phosphate (including orthophosphate, polyphosphate, and/or pyrophosphate), in particular with phosphates in an amount of less than 0.1% by weight, preferably less than 0.01% by weight, based on the total weight of the composition.

The expression "essentially free of" means that the respective compound may in principle be present, but is then present in an amount that does not impair the function of the other components. Therefore, within the context of the present invention, the property "essentially free of" a particular compound is preferably understood to mean a total weight of less than 0.1 wt.%, more preferably less than 0.001 wt.%, in particular free of the compound, based on the total weight of the composition.

In a particularly preferred embodiment, a concentrate according to the invention is characterized in that it is substantially free of phosphates.

The cleaning composition according to the invention is essentially free of bleaching agents. Within the scope of the invention, this means that the compositions contain less than 0.1% by weight of percarbonate salts, alkali hypochlorite, hydrogen peroxide, and their precursors, based on the total weight of the composition. Preferably, the compositions contain less than 0.01% by weight, more preferably less than 0.001% by weight, of these components. based on the total weight of the composition.

"Bleach-free" here means that the cleaning agent is substantially free of active ingredients capable of releasing bleaching agents, particularly peroxide-containing compounds, hypohalogenated compounds, or H2O2, into the wash liquor in an automatic dishwasher. In a preferred embodiment, "bleach-free" means that the composition contains bleaching compounds (compounds that release bleaching agents) in an amount of less than 0.1% by weight, preferably less than 0.01% by weight, based on the total weight of the composition.

In a particularly preferred embodiment, a concentrate according to the invention is characterized in that it is substantially free of bleaching agents.

Sulfo polymers

Even though the concentrate according to the invention is preferably largely biodegradable, it may contain at least one sulfopolymer to improve the dispersing properties.

For example, a copolymeric polysulfonate, such as a hydrophobically modified copolymeric polysulfonate, can be used as a sulfopolymer. Such copolymers can have two, three, four, or more different monomer units.

Copolymeric polysulfonates may contain, in addition to monomer(s) containing sulfonic acid groups, at least one monomer from the group of unsaturated carboxylic acids.

As unsaturated carboxylic acid(s) it is/are particularly preferred to use unsaturated carboxylic acids of the formula R ¹ (R ² )C=C(R ³ )COOH, in which R ¹ to R ³ independently of one another represent -H, -CH3, a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH2, -OH or -COOH as defined above or represent -COOH or -COOR ⁴ , where R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid, or mixtures thereof. Unsaturated dicarboxylic acids can, of course, also be used.

Among the monomers containing sulfonic acid groups, those of the formula

R ⁵ (R ⁶ )C=C(R ⁷ )-X-SO _3H |

preferred, in which R ⁵ to R ⁷ independently of one another represent -H, -CH3, a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH2, -OH or -COOH or -COOH or -COOR ⁴ , where R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group selected from -(CH2)n- where n = 0 to 4, -COO-(CH2)k- where k = 1 to 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2- and -C(O)-NH-CH(CH3)-CH2-.

Preferred monomers are those of the formulas

H2C=CH-X- _SO3H

H2C=C( _CH3 )-X- _SO3H

HO ₃ SX-(R ⁶ )C=C(R ⁷ )-X-SO ₃ H,

in which R ⁶ and R ⁷ are independently selected from -H, -CH3, -CH2CH3, -CH2CH2CH3 and -CH(CH3)2 and X represents an optionally present spacer group selected from -(CH2)n- with n = 0 to 4, -COO-(CH2)k- with k = 1 to 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2- and -C(O)-NH-CH(CH3)-CH2-.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their water-soluble salts.

In a particularly preferred embodiment, these are the sulfopolymers, which are copolymers, terpolymers) of acrylic acid and acrylamidopropanesulfonic acid (as monomers) with optionally other monomers, in particular as described above. Such polymers are available, for example, under the trade names Acusol ^590® or Acusol® ⁵⁸⁸ from Dow Chemical.

Also very suitable is Acusol 902 N (acrylic acid sodium salt polymer, terminated with sodium sulfonate, CAS No. 68479-09-4), which is available commercially from Dow Chemical.

In the polymers, the sulfonic acid groups may be present in completely or partially neutralized form, i.e. the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.

The monomer distribution of the preferably used copolymers is preferably 5 to 95% by weight in each case for copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90% by weight and the proportion of the monomer containing carboxylic acid groups is 10 to 50% by weight, the monomers being preferably selected from those mentioned above.

The molecular weight of the preferably used sulfo copolymers can be varied to adapt the properties of the polymers to the desired application. Preferred liquid dishwashing detergents are characterized by the copolymers having molecular weights of 2,000 to 200,000 gmol ^-1 , preferably of 4,000 to 25,000 gmol- ¹ , and in particular of 5,000 to 15,000 gmol- ¹ .

The sulfopolymer(s) are also preferably present in the concentrate in certain amounts. It has proven particularly preferred if the cleaning agent concentrate or dishwasher detergent according to the invention contains—based on its total weight—2.0 to 3.7 wt.%, preferably 2.3 to 3.7 wt.%, more preferably 2.6 to 3.5 wt.%, and particularly preferably 2.9 to 3.3 wt.% of sulfopolymer(s).

In a particularly preferred embodiment, a cleaning agent concentrate according to the invention is characterized in that it contains - based on the total weight of the concentrate - 2.0 to 3.7 wt.%, preferably 2.3 to 3.7 wt.%, more preferably 2.6 to 3.5 wt.% and particularly preferably 2.9 to 3.3 wt.% of sulfopolymer(s).

other optional ingredients in the concentrate

In addition, the cleaning agent concentrate or dishwasher detergent according to the invention can optionally also contain one or more further ingredients, which can be selected, for example, from the group of builders, builders, pH adjusters, cationic Polymers, anionic homo- or copolymers of (meth)acrylic acid, corrosion inhibitors, fragrances, foam inhibitors, dyes and antimicrobial agents.

In a particularly preferred embodiment, a cleaning agent concentrate according to the invention is characterized in that it additionally contains one or more substances selected from the group consisting of builders, builders, pH adjusters, cationic polymers, amphoteric polymers, corrosion inhibitors, fragrances, foam inhibitors, dyes and antimicrobial agents.

Particularly suitable builders and/or cobuilders that can be used are water-soluble or water-insoluble substances whose primary function is to bind calcium and magnesium ions. The terms "builder" and "cobuilder" according to the invention do not include citric acid, methylglycinediacetic acid (MGDA), glutamic acid diacetic acid (GLDA), and/or their salts. Builders and/or cobuilders can be low-molecular-weight carboxylic acids and their salts, such as alkali metal malonates, fatty acid sulfonates, gluconic acids, oxadiacetates, carboxymethyloxysuccinates, tartrate monoacetate, tartrate diacetate, and α-hydroxypropionic acid.

Other builders that can be used in conjunction with the dishwashing detergent formulations according to the invention are carbonates and hydrocarbons, of which the alkali salts, in particular sodium salts, are preferred.

Homo- or copolymers of acrylic acid or methacrylic acid can be used. Suitable comonomers include, in particular, monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, as well as their anhydrides, such as maleic anhydride. Comonomers containing sulfonic acid groups, such as 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid, and vinylsulfonic acid, are also suitable. Hydrophobic comonomers are also suitable, such as isobutene, diisobutene, styrene, and alpha-olefins with 10 or more carbon atoms. Hydrophilic monomers containing hydroxyl groups or alkylene oxide groups can also be used as comonomers.

Examples include allyl alcohol and isoprenol, as well as their alkoxylates and methoxypolyethylene glycol (meth)acrylate. Graft polymers based on degraded starch and the above-mentioned monomers, such as (meth)acrylic acid, maleic acid, fumaric acid, and 2-acrylamido-2-methylpropanesulfonic acid, can also be used as cobuilders.

The detergent formulations contemplated here may contain one or more surfactants other than the surfactants of group (c), selected from the group consisting of anionic surfactants, cationic, zwitterionic, and amphoteric surfactants. Combinations of the above-mentioned surfactant types are also conceivable.

To prevent glass corrosion, which manifests itself as cloudiness, iridescence, streaks, and lines on the glass, glass corrosion inhibitors are preferably used. Preferred glass corrosion inhibitors include magnesium, zinc, and bismuth salts and complexes, as well as polyethyleneimine.

Silver preservatives from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used as corrosion inhibitors, provided they are ecologically compatible.

Other examples of enzyme stabilizers include sodium sulfite, reducing sugars, and potassium sulfate. Another example of a suitable enzyme stabilizer is sorbitol.

Organic solvents may also be present, but are preferably limited to an amount of up to 30% by weight, based on the weight of the composition. Particularly preferred organic solvents are propanediol, glycerin, and/or sorbitol. These amounts of organic solvents contribute to the flowability and stabilization of the active ingredients.

In a preferred embodiment of the present invention, the dishwashing detergent composition contains one or more organic solvents selected from the group consisting of sorbitol, glycerin, and/or propanediol. The composition preferably contains 1 to 25% by weight, preferably 2 to 12% by weight of the total composition, of the group consisting of sorbitol, glycerin, and/or propanediol.

The dishwashing detergent formulation according to the invention is preferably characterized in that the composition has a pH of 7.0 to 11.5 at 20°C. The pH is measured in the product itself. A suitable measuring device is, for example, a conventional pH electrode.

The group of polymers includes, in particular, cleaning-active polymers, such as rinse aid polymers and/or polymers that act as water softeners. In general, cationic, anionic, and amphoteric polymers can be used in liquid dishwashing detergents in addition to non-ionic polymers.

"Cationic polymers" in the sense of the present invention are polymers that carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl)ammonium groups or other positively charged groups present in the polymer chain. Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, polymeric dimethyldiallylammonium salts, and their Copolymers with esters and amides of acrylic acid and methacrylic acid, copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, vinylpyrrolidone-methoimidazolinium chloride copolymers, quaternized polyvinyl alcohols or the polymers specified under the INCi names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

"Amphoteric polymers" within the meaning of the present invention contain, in addition to a positively charged group in the polymer chain, negatively charged groups or monomer units. These groups can be, for example, carboxylic acids, sulfonic acids, or phosphonic acids.

Preferred amphoteric polymers that can be used come from the group of alkylacrylamide/acrylic acid copolymers, alkylacrylamide/methacrylic acid copolymers, alkylacrylamide/methylmethacrylic acid copolymers, alkylacrylamide/acrylic acid/alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/methacrylic acid/alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/methylmethacrylic acid/alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/alkylmethacrylate/alkylaminoethylmethacrylic copolymers and copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or non-ionic monomers.

Preferred zwitterionic polymers come from the group of acrylamidoalkyltrialkylammonium chloride/acrylic acid copolymers and their alkali and ammonium salts, acrylamidoalkyltrialkylammonium chloride/methacrylic acid copolymers and their alkali and ammonium salts and methacroylethylbetaine/methacrylate copolymers.

Glass corrosion inhibitors prevent the occurrence of clouding, streaks, and scratches, as well as iridescence on the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts, as well as magnesium and zinc complexes. In the context of the present invention, the zinc salt content in liquid dishwashing detergents is preferably between 0.1 and 5 wt.%, more preferably between 0.2 and 4 wt.%, and in particular between 0.4 and 3 wt.%, or the zinc content in oxidized form (calculated as Zn ² + ) is between 0.01 and 1 wt.%, preferably between 0.02 and 0.5 wt.%, and in particular between 0.04 and 0.2 wt.%, in each case based on the total weight of the agent containing the glass corrosion inhibitor.

Within the scope of the present invention, individual fragrance compounds, e.g. synthetic products of the ester, ether, aldehyde, Ketones, alcohols, and hydrocarbons are used. However, mixtures of different fragrances are preferred, which together create an appealing scent. Such perfume oils can also contain natural fragrance mixtures, such as those available from plant sources, such as pine, citrus, jasmine, patchouli, rose, or ylang-ylang oil.

The liquid dishwashing detergent may contain at least one alcohol, particularly a polyhydric alcohol. Such polyhydric alcohols can allow the incorporation of other ingredients into a liquid dishwashing detergent formulation with a small amount of water, particularly when the amount of water is limited to 20% by weight.

The polyhydric alcohol is preferably selected from glycerin, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propanediol, and mixtures thereof. Another suitable alcohol that also possesses antimicrobial properties is phenoxyethanol.

Viscosity of the cleaning agent concentrate

By using the previously described components (a) to (e) in their defined quantity ranges, a cleaning agent concentrate was developed that, despite a reduction in its water content, could be stably adjusted to the desired viscosity range and was present in a particularly homogeneous form without the occurrence of phase separation or sedimentation. Portioning and homogenization were particularly easy when the concentrate had a viscosity of 2000 to 6000 mPas, preferably 2200 to 5500 mPas, more preferably 2400 to 5000 mPas, even more preferably 2600 to 4500 mPas, and most preferably 3000 to 4000 mPas (measured with a Brookfield LVDV II+ viscometer at 20 °C, spindle no. 31, 6 revolutions per minute).

In a further very particularly preferred embodiment, the cleaning agent concentrate according to the invention is therefore characterized in that it has a viscosity of 2000 to 6000 mPas, preferably of 2200 to 5500 mPas, more preferably of 2400 to 5000 mPas, even more preferably of 2600 to 4500 mPas and very particularly preferably of 3000 to 4000 mPas (measured with a Brookfield LVDV II+ viscometer at 20 °C, spindle no. 31, 6 revolutions per minute).

use

The present application further relates to the use of a detergent concentrate, which is liquid at 20°C, for cleaning dishes. The compositions are preferably used in dishwashers and/or automatic dishwashers. For the purposes of the present invention, "dishes" include plates, cups, cutlery, glasses, Storage containers, cooking utensils (cookware) and the like.

A further subject matter of the present application is the use of a detergent concentrate, as disclosed in detail in the description of the first subject matter of the invention, for machine dishwashing.

Process for automatic dishwashing

The present invention further relates to a method for cleaning dishes, preferably in an automatic dishwasher, characterized in that at least one cleaning agent concentrate according to the invention, as disclosed in detail in the description of the first subject matter of the invention, is used in at least one method step. In particular, the present invention relates to a method for cleaning dishes in an automatic dishwasher, in which the agent is introduced into the interior of an automatic dishwasher during the execution of a washing program, before the start of the main wash cycle, or during the course of the main wash cycle. The agent can be dispensed or introduced into the interior of the dishwasher manually, but preferably the agent is dispensed from the dosing chamber into the interior of the dishwasher. Dosing is carried out by the user, who pours the concentrate from a storage bottle or container designed for multiple use into this dosing chamber.

A further subject matter of the present application is a method for automatic dishwashing, in which a liquid detergent concentrate, as disclosed in detail in the description of the first subject matter of the invention, is dosed from a storage container suitable for multiple use, preferably a storage bottle, into the device of a dishwasher provided for this purpose.

In various embodiments of the disclosure, the (washing) temperature in such dishwashing methods is preferably 50°C or less, more preferably 45°C or less, even more preferably 40°C or less.

For the description of the use and method according to the invention, what has been said about the cleaning agent concentrate according to the invention applies mutatis mutandis.

Examples:

Compositions 1 to 4 were prepared using the components summarized in Table 1, the amounts of active ingredients in wt% referring to the total weight of the composition, unless otherwise stated. Table 1: component 1 (wt%) Comparison 2 (wt%) 3 (wt%) 4 (wt%) Comparison dye 0.01 0.01 0.01 0.01 Xanthan 0.52 0.75 0.87 1.05 anionic dispersing polymer (sulfopolymer) 1.92 2.75 3.21 3.85 Calcium chloride 0.21 0.29 0.34 0.41 MGDA trisodium salt, (methylglycinediacetic acid, trisodium salt) 5.20 7.43 8.67 10.40 Sodium citrate dihydrate 5.50 7.86 9.17 11.00 Phenoxyethanol 0.50 0.71 0.83 1.00 low-foaming non-ionic surfactant (hydroxy mixed ether) 1.90 2.71 3.17 3.80 cationic rinse aid polymer 0.10 0.15 0.17 0.20 Formic acid 0.86 1.22 1.43 1.71 Amylase (relative to the amount of active protein) 0.02 0.02 0.02 0.02 Protease (relative to the amount of active protein) 0.2 0.2 0.2 0.2 Water to 100 to 100 to 100 to 100 Water content 83% by weight 76 wt.% 72 wt.% 66 wt.% Weight ratio water (a) / xanthan (b) 160 101 83 63

The pH of the undiluted liquid concentrates was adjusted to a value of 7.8 (at 20 °C) by adding formic acid.

100 g of the concentrate was filled into a glass jar with a screw cap and stored at room temperature for 4 weeks. After this storage period, the stability of the formulations was visually assessed.

The composition of Example 1 is homogeneous and stable, but does not constitute a concentrate within the meaning of the present application.

The compositions of Examples 2 and 3 are concentrates that remained stable, flowable, and homogeneous even after a storage period of 4 weeks. Example composition 3 could be concentrated the most, but was still stable and homogeneous.

The composition of Example 4 is a concentrate. After a storage period of 4 weeks, lumpy deposits were visible at the bottom of the glass container. This composition proved to be unstable.

Claims (15)

Cleaning agent concentrate which is liquid at 20 °C and which contains - based on the total weight of the concentrate - (a) 38 to 82 wt% water, (b) 0.55 to 0.95 wt% xanthan, (c) 2.0 to 3.7 wt% non-ionic surfactants, (d) 5.3 to 10.3 wt.% complexing agent from the group consisting of methylglycinediacetic acid (MGDA), glutamic acid diacetic acid (GLDA) and/or their salts, and (e) at least one protease and/or at least one amylase. Cleaning agent concentrate according to claim 1, characterized in that it contains - based on the total weight of the concentrate - (a) contains 45 to 80 wt.%, preferably 55 to 79 wt.%, more preferably 65 to 78 wt.% and particularly preferably 69 to 77 wt.% water. Cleaning agent concentrate according to one of claims 1 to 2, characterized in that it contains - based on the total weight of the concentrate - (b) 0.60 to 0.90 wt.%, preferably 0.65 to 0.90 wt.%, more preferably 0.70 to 0.90 and most preferably 0.80 to 0.90 wt.% xanthan. Cleaning agent concentrate according to one of claims 1 to 3, characterized in that the weight ratio of the water (a) contained in the concentrate to xanthan (b), ie the weight ratio (a)/(b), is in the range from 60 to 140, preferably in the range from 65 to 130, more preferably in the range from 70 to 120 and most preferably in the range from 75 to 105. Cleaning agent concentrate according to one of claims 1 to 4, characterized in that it contains - based on the total weight of the concentrate - 2.2 to 3.6 wt.%, preferably 2.4 to 3.5 wt.%, more preferably from 2.6 to 3.4 wt.% and very particularly preferably from 2.8 to 3.3 wt.% of non-ionic surfactants (c). Cleaning agent concentrate according to one of claims 1 to 5, characterized in that it contains - based on the total weight of the concentrate - 5.8 to 9.7 wt.%, preferably 6.4 to 9.5 wt.%, more preferably from 7.0 to 9.3, even more preferably from 7.6 to 9.1 wt.% and very particularly preferably from 8.0 to 9.0 wt.% of complexing agent (d) from the group consisting of methylglycinediacetic acid (MGDA), glutamic acid diacetic acid (GLDA) and/or salts thereof. Cleaning agent concentrate according to one of claims 1 to 6, characterized in that it contains - based on the total weight of the concentrate - 5.7 to 10.5 wt.%, preferably 6.3 to 10.1 wt.%, more preferably 7.3 to 9.7 wt.% and most preferably 8.3 to 9.4 wt.% of citric acid and/or its salts. Cleaning agent concentrate according to one of claims 1 to 7, characterized in that it contains - based on the total weight of the concentrate - 0.23 to 0.60 wt.%, preferably 0.26 to 0.55 wt.%, more preferably 0.27 to 0.45 wt.% and particularly preferably 0.29 to 0.36 wt.% calcium chloride. Cleaning agent concentrate according to one of claims 1 to 8, characterized in that it is substantially free of phosphates. Detergent concentrate according to one of claims 1 to 9, characterized in that it is substantially free of bleaching agents. Cleaning agent concentrate according to one of claims 1 to 10, characterized in that it contains - based on the total weight of the concentrate - 2.0 to 3.7 wt.%, preferably 2.3 to 3.7 wt.%, more preferably 2.6 to 3.5 wt.% and particularly preferably 2.9 to 3.3 wt.% of sulfopolymer(s). Cleaning agent concentrate according to one of claims 1 to 11, characterized in that it additionally contains one or more substances selected from the group consisting of builders, structural agents, pH adjusters, cationic polymers, anionic homo- or copolymers of (meth)acrylic acid, corrosion inhibitors, fragrances, foam inhibitors, dyes and antimicrobial agents. Cleaning agent concentrate according to one of claims 1 to 12, characterized in that it has a viscosity of 2000 to 6000 mPas, preferably of 2200 to 5500 mPas, more preferably of 2400 to 5000 mPas, even more preferably of 2600 to 4500 mPas and most preferably of 3000 to 4000 mPas (measured with a Brookfield LVDV II+ viscometer at 20 °C, spindle no. 31, 6 revolutions per minute). Use of a detergent concentrate according to one of claims 1 to 13 for machine dishwashing. Method for automatic dishwashing, in which a liquid detergent concentrate according to one of claims 1 to 13 is dispensed from a storage container suitable for multiple use, preferably a storage bottle, into the container provided for this purpose. device of a dishwasher.