EP4067468A1

EP4067468A1 - Dishwasher detergents comprising surfactants on magnesium carbonate carrier

Info

Publication number: EP4067468A1
Application number: EP21166655.7A
Authority: EP
Inventors: Hannah Benson; Gabi OHLENDORF
Original assignee: Clariant International Ltd
Current assignee: Clariant International Ltd
Priority date: 2021-04-01
Filing date: 2021-04-01
Publication date: 2022-10-05

Abstract

The invention concerns dishwasher detergents comprising
Z1) one or more surfactants on magnesium carbonate carrier;
Z2) one or more enzymes; and optionally
Z3) one or more glass corrosion inhibitors.

These dishwasher detergents display in particular an advantageous rinse performance and an advantageous drying performance.

Description

The present invention relates to dishwasher detergents comprising one or more surfactants on magnesium carbonate carrier Z1), one or more enzymes Z2), and optionally Z3) one or more glass corrosion inhibitors, to a method for cleaning dishware in dishwashers with aqueous alkaline compositions comprising a dishwasher detergent of the invention, and also to the use of the dishwasher detergents of the invention or the surfactants on magnesium carbonate carrier Z1) contained in these dishwasher detergents as rinse agents in machine dishwashing, for improving the wettability of dishware, for reducing the spotting and filming on dishware, for reducing, minimizing or preventing fatty residues in the machine department of an automatic dishwashing machine, for improving the rinse performance of a dishwasher detergent, or for improving the drying performance of a dishwasher detergent.
For the purposes of the present invention, the dishwasher detergents of the invention comprehend not only dishwasher detergents in the conventional sense but also rinse agents.
The requirements imposed on machine-washed dishware are nowadays very high, particularly by comparison with manual dishwashing. In addition to residue-free cleaning, the dishware after the complete cleaning program - generally consisting of a prewash cycle, a main wash cycle, followed by a rinse cycle with concluding drying phase, where the individual cycles are interrupted by intermediate cycles - is to be present in a streak-free and spot-free, flawlessly sparkling condition. Even in the case of the flawless elimination of food residues from the dishware, residues attributable to water hardness or other inorganic or organic salts, and spots which originate from dried-on water drops and water films, lead to the wash performance being rated not as flawless. For a long time, therefore, rinse aids have been successfully used for improved rinse performance in rinse agents and dishwasher detergents, in order to obtain spotless, streak-free, and residue-free dishware. In the case of rinse agents, the rinse aid is dispensed automatically from a metering tank into the interior of the dishwasher in the rinse cycle of the cleaning program. In products referred to as multifunctional combination products, the rinse aid is integrated into the dishwasher detergent itself.
Conventional rinse aids are liquid mixtures of low-foaming nonionic surfactants, organic acids such as, for example, citric acid, scale-inhibiting polymers, solvents such as, for example, ethanol, and other additives such as hydrotropes, thickeners and/or foam inhibitors.
The cleaning of dishware in dishwashers, particularly for domestic use, is continually subject to modifications and improvements. For example, new formats of multifunctional combination products ("all-in-one" metering systems) are continually being developed, such as single-phase or multiphase tablets, pouches, pods, and capsules ("caps"), or liquid formats such as multifunctional gels. Such multifunctional combination products require new rinse aid additives which are active against spotting and filming and which exhibit advantageous rinse performance and/or advantageous drying performance while they are present in the overall cleaning operation.
Surfactants have long been established in the prior art as active ingredients of detergents, especially of dishwasher detergents. In dishwasher detergents they are used in particular as rinse aid additives. In the prior art, both nonionic and anionic and also cationic or amphoteric surfactants have been described for these purposes.
Dishwasher detergents showing cleaning, rinse or drying performance already exist. However, in many dishwasher detergents of the prior art, there is still a need for improvement.
The object of the present invention was to provide dishwasher detergents which at least display an advantageous rinse performance and an advantageous drying performance.
Surprisingly it has been found that this object can be solved by means of dishwasher detergents comprising

Z1) one or more specific surfactants on magnesium carbonate carrier;
Z2) one or more enzymes; and optionally
Z3) one or more glass corrosion inhibitors.

Subject matter of the invention are therefore dishwasher detergents comprising

Z1) one or more specific surfactants on magnesium carbonate carrier and
Z2) one or more enzymes; and optionally
Z3) one or more glass corrosion inhibitors.

An aspect of the present invention relates to a dishwasher detergent comprising

Z1) one or more surfactants on magnesium carbonate carrier which are selected from the group consisting of fatty alcohol alkoxylates and end-capped fatty alcohol alkoxylates of the formula (XI)

RaO-(AO)x-Y (XI),

in which

Ra

is a linear or branched saturated alkyl group having 8 to 30 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 30 carbon atoms,

A

is selected from the group consisting of -C₂H₄- and -C₃H₆-,

X

is a number from 1 to 150,

Y

is a group -CH₂-CH(OH)-R_b, R_b is a linear or branched saturated alkyl group having 1 to 30 carbon atoms, and where the group -(AO)_x- comprises one or more -C₂H₄-O- groups and may additionally comprise one or more -C₃H₆-O- groups, and, when the group -(AO)_x- simultaneously comprises -C₂H₄-O- and -C₃H₆-O- groups, the -C₂H₄-O- and -C₃H₆-O- groups may be distributed over the -(AO)_x- group in any desired way, preferably in random, gradient-like or block-like manner and more preferably in block-like manner, and the molar amount of the -C₂H₄-O- groups in the group -(AO)_x- is preferably greater than the molar amount of the -C₃H₆-O- groups in the group -(AO)_x-;
Z2) one or more enzymes; and
Z3) one or more glass corrosion inhibitors.

Preferably, the dishwasher detergent comprises:

Z1) one or more surfactants on magnesium carbonate carrier which are selected from the group consisting of fatty alcohol alkoxylates and end-capped fatty alcohol alkoxylates of the formula (XI)

R_aO-(AO)_x-Y (XI),

in which

Ra

is a linear or branched saturated alkyl group having 8 to 30 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 30 carbon atoms,

A

is selected from the group consisting of -CH₂-CH₂- and -CH₂-CH(CH₃)-,

X

is a number from 1 to 150,

Y

is a group -CH₂-CH(OH)-R_b, R_b is a linear or branched saturated alkyl group having 1 to 30 carbon atoms, and where the group -(AO)_x- comprises one or more -C₂H₄-O- groups and may additionally comprise one or more -C₃H₆-O- groups, and, when the group -(AO)_x- simultaneously comprises -C₂H₄-O- and -C₃H₆-O- groups, the -C₂H₄-O- and -C₃H₆-O- groups may be distributed over the -(AO)_x- group in any desired way, preferably in random, gradient-like or block-like manner and more preferably in block-like manner, and the molar amount of the -C₂H₄-O- groups in the group -(AO)_x- is preferably greater than the molar amount of the -C₃H₆-O- groups in the group -(AO)_x-;
Z2) one or more enzymes; and
Z3) one or more glass corrosion inhibitors.

Carrier materials for surfactants are already known in the prior art.
It is well known that magnesium carbonate can be used in home care formulations. For example, US 4,303,542 refers to a powdered detergent suitable for use in home laundry machines.
EP 3 517 502 A1 describes a magnesium carbonate carrier material for the release of one or more active agent(s) in a home care formulation, a delivery system for the release of one or more active agent(s) in a home care formulation, a home care formulation comprising the delivery system for the release of one or more active agent(s), a method for preparing the delivery system for the release of one or more active agent(s) in a home care formulation as well as the use of the delivery system for the release of one or more active agent(s) in a home care formulation.
The poster "Disruptive carrier acts as sequestrant by enhancing performance and sustainability profile in ADW" (Ivanov and Keller, Sepawa Conference October 28-30, 2020), describes precipitated hydromagnesite as a material with high porosity which can release ingredients such as automatic dishwashing (ADW) surfactants and allows scavenging calcium ions and may reduce hardness of water.
An advantage of the present invention is that the dishwasher detergents of the invention can be prepared with high surfactant concentrations, in particular in solid automatic dishwashing product formats like tablets. The dishwasher detergents of the invention display, in addition to their cleaning performance, good dishware wettability, low spotting and filming on dishware, an advantageous rinse performance with no carrier residues, an advantageous drying performance, and less fatty residues, in particular in the machine department of automatic dishwashing machines and specifically on plastic parts of the machine department of the automatic dishwashing machines.
Surfactants are often wax-like or highly viscous and therefore their use in solid product formats, in particular in tablets, is limited up to a certain concentration. If the amount of wax-like or highly viscous surfactants is too high, the tablet itself tends to be sticky. Using surfactants on carrier material allows to incorporate more surfactants into the solid product formats, in particular into tablets, in comparison to the sole use of surfactants which are not present on a carrier. It is thereby possible to obtain non-sticky solid product formats with high surfactant amount. For example, in a solid product format the surfactants which are not present on a carrier could be used in their usual amounts and the total amount of the surfactants could be increased by additionally using surfactants on a carrier.
As used herein, -C₂H₄- preferably is a linear alkylene residue -CH₂-CH₂-. As used herein, -C₃H₆- may preferably be -CH₂-CH₂-CH₂- or -CH(CH₃)-CH₂- or -CH₂-CH(CH₃)-. Preferably and typically, -C₃H₆- is -CH₂-CH(CH₃)-. As used herein, -C₂H₄-O- preferably is a linear alkylene residue -CH₂-CH₂-O-. As used herein, -C₃H₆-O- may preferably be -CH₂-CH₂-CH₂-O- or -CH(CH₃)-CH₂-O- or -CH₂-CH(CH₃)-O-.
A further advantage of the invention is that the handling of surfactants on magnesium carbonate carrier is easier compared to the handling of highly viscous or wax-like surfactants.
The surfactants on magnesium carbonate carrier of component Z1) can be employed both in conventional and multifunctional combination products or can be employed with broad variability in the dishwasher detergents of the invention and develop their advantageous properties independently of their preparation form.
The surfactants on magnesium carbonate carrier of component Z1) do not contribute to increased foaming, and accordingly the dishwasher detergents of the invention are low-foaming detergents.
The dishwasher detergents of the invention are automatic dishwashing (detergent) compositions or automatic dishwashing (detergent) formulations.

Component Z1)

Preferably, one or more surfactants of formula (XI) comprised in a dishwasher detergent of the present invention, which are on a magnesium carbonate carrier, are selected from the group consisting of nonionic and cationic surfactants. Among the aforementioned nonionic and cationic surfactants, the nonionic surfactants are preferred.
Preferably, one or more surfactants comprised in a dishwasher detergent of the present invention, which are optionally on a magnesium carbonate carrier, are selected from the group consisting of fatty alcohol alkoxylates, end-capped fatty alcohol alkoxylates, ethyleneoxide-propyleneoxide-blockcopolymers, N-acylglucamines / N-acylglucamides, gylcerol triester alkoxylates, esterquats, and mixtures thereof.
Preferably, one or more surfactants comprised in a dishwasher detergent of the present invention, which are optionally on a magnesium carbonate carrier, are selected from the group consisting of end-capped fatty alcohol alkoxylates, preferably end-capped fatty alcohol ethoxylates, N-acylglucamines / N-acylglucamides, gylcerol triester alkoxylates, preferably glycerol triester ethoxylates, and mixtures thereof.
Examples of the alkyl and alkenyl groups R_a in the formula (XI) are, for example, the alkyl and alkenyl groups of the following alcohols R_a-OH: 1-octanol (caprylyl alcohol), 2-ethylhexanol, 1-nonanol (pelargon alcohol), 1-decanol (caprinyl alcohol), 1-undecanol, 1-dodecanol (lauryl alcohol), 1-tridecanol, isotridecanol, 1-tetradecanol (myristyl alcohol), 1-pentadecanol, 1-hexadecanol (cetyl alcohol), cis-9-hexadecen-1-ol (palmitoleyl alcohol), 1-heptadecanol, 1-octadecanol (stearyl alcohol), cetearyl alcohol, 16-methylheptadecan-1-ol (isostearyl alcohol), 9E-octadecen-1-ol (elaidyl alcohol), cis-9-octadecen-1-ol (oleyl alcohol), oleyl cetyl alcohol (i.e., a mixture of oleyl alcohol and cetyl alcohol), 9Z,12Z-octadecadien-1-ol (linoleyl alcohol), 9E,12E-octadecadien-1-ol (elaidolinoleyl alcohol), 9Z,12Z,15Z-octadecatrien-1-ol (linolenyl alcohol), 9E,12E,15E-octadecatrien-1-ol (elaidolinolenyl alcohol), 1-nonadecanol, 1-eicosanol (arachidyl alcohol), 1-heneicosanol, 1-docosanol (behenyl alcohol), cis-13-docosen-1-ol (erucyl alcohol), 1-tetracosanol (lignoceryl alcohol), 1-hexacosanol (ceryl alcohol), 1-octacosanol (montanyl alcohol), and 1-triacontanol (myricyl alcohol), or mixtures thereof.
R_a in formula (XI) is preferably a linear or branched saturated alkyl group having 8 to 22 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 22 carbon atoms, more preferably a linear or branched saturated alkyl group having 8 to 20 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 20 carbon atoms, and especially preferably a linear or branched saturated alkyl group having 8 to 18 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 18 carbon atoms.
Preferably the groups R_a in formula (XI) are saturated alkyl groups.
In formula (XI), x is preferably a number from 1 to 50, more preferably a number from 1 to 25, especially preferably a number from 5 to 25 and particularly preferably a number from 15 to 25.
Examples of the linear or branched saturated alkyl groups Y and R_b in the compounds of the formula (XI) include the examples specified above for the saturated alkyl group R_a in the compound of the formula (XI). Further examples are the alkyl groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl (2-pentyl), 3-pentyl, 2-methylbutyl, isopentyl (3-methylbutyl), 3-methylbut-2-yl, 2-methylbut-2-yl, neopentyl (2,2-dimethylpropyl), 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 2-ethyl-1-butyl, 1-heptyl, 2-heptyl, 3-heptyl, and 4-heptyl.
If Y in formula (XI) is a linear or branched saturated alkyl group, the saturated alkyl group in question preferably has 1 to 22 carbon atoms.
If Y in formula (XI) is the group -CH₂-CH(OH)-R_b, R_b preferably is a linear or branched saturated alkyl group having 8 to 22 and more preferably 8 to 20 carbon atoms.
In a particularly preferred embodiment of the invention, the group -(AO)_x- consists of one or more -C₂H₄-O- groups and contains no -C₃H₆-O- groups.
In another particularly preferred embodiment of the invention, the group -(AO)_x- comprises one or more -C₂H₄-O- groups and one or more -C₃H₆-O- groups. In this particularly preferred embodiment of the invention, the molar amount of the -C₃H₆-O- groups in the group -(AO)_x-, based on the total amount of -C₂H₄-O- and -C₃H₆-O- groups in the group -(AO)_x-, is preferably less than 50%, more preferably 45% or less than 45%, especially preferably 40% or less than 40%, and particularly preferably 33% or less than 33%.
In another particularly preferred embodiment of the invention, Y in formula (XI) is H. In this particularly preferred embodiment of the invention, the molar amount of the -C₃H₆-O- groups in the group -(AO)_x-, based on the total amount of -C₂H₄-O- and -C₃H₆-O- groups in the group -(AO)_x-, is preferably 20 to less than 50%, more preferably 33 to 45%, and especially preferably 33 to 40%.
If Y has a definition other than H, the molar amount of the -C₃H₆-O- groups in the group -(AO)_x-, based on the total amount of -C₂H₄-O- and -C₃H₆-O- groups in the group -(AO)_x-, is preferably 20% or less than 20% and more preferably 10% or less than 10%.
In another particularly preferred embodiment of the invention, Y in formula (XI) is a saturated alkyl group with 1 to 4 carbon atoms. In this particularly preferred embodiment the molar amount of the -C₃H₆-O- groups in the group -(AO)_x-, based on the total amount of -C₂H₄-O- and -C₃H₆-O- groups in the group -(AO)_x-, is preferably 20% or less than 20% and more preferably 10% or less than 10%.
In another particularly preferred embodiment of the invention, Y in formula (XI) is the group -CH₂-CH(OH)-R_b, in which R_b is a linear or branched saturated alkyl group having 8 to 22 and preferably 8 to 20 carbon atoms. In this particularly preferred embodiment of the invention the molar amount of the -C₃H₆-O- groups in the group -(AO)_x-, based on the total amount of -C₂H₄-O- and -C₃H₆-O- groups in the group -(AO)_x-, is preferably 20% or less than 20% and more preferably 10% or less than 10%. In this particularly preferred embodiment of the invention the group -(AO)_x- especially preferably consists of one or more -C₂H₄-O- groups and contains no -C₃H₆-O- groups.
In another particularly preferred embodiment of the invention, the group -(AO)_x- in formula (XI) comprises on molar average 8 -C₂H₄-O- groups and 4 -C₃H₆-O-groups and R_a is a linear or branched saturated alkyl group having 12 to 15 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 12 to 15 carbon atoms.
The variable "x" in the one or more compounds of the formula (XI) preferably represents molar averages, meaning that the dishwasher detergents of the invention may comprise a plurality of compounds of the formula (XI) having different degrees of alkoxylation.
Extraordinarily preferred are dishwasher detergents of the invention wherein at least one surfactant of the one or more surfactants, and preferably the one or more surfactants on magnesium carbonate carrier of component Z1) of the dishwasher detergents of the invention are selected from the group consisting of the end-capped fatty alcohol ethoxylates of the formula (XI-a)

R_aO-(AO)_x-Y (XI-a)

in which

Ra: is a linear or branched saturated alkyl group having 8 to 20 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 20 carbon atoms,
A: is -C₂H₄-,
x: is a number from 15 to 25,
Y: is -CH₂-CH(OH)-R_b, wherein R_b is a linear or branched saturated alkyl group having 8 to 22 and preferably 8 to 20 carbon atoms.

Examples of the alkyl and alkenyl groups R_a in the formula (XI-a) are, for example, the alkyl and alkenyl groups of the following alcohols R_a-OH: 1-octanol (caprylyl alcohol), 2-ethylhexanol, 1-nonanol (pelargon alcohol), 1-decanol (caprinyl alcohol), 1-undecanol, 1-dodecanol (lauryl alcohol), 1-tridecanol, isotridecanol, 1-tetradecanol (myristyl alcohol), 1-pentadecanol, 1-hexadecanol (cetyl alcohol), cis-9-hexadecen-1-ol (palmitoleyl alcohol), 1-heptadecanol, 1-octadecanol (stearyl alcohol), cetearyl alcohol, 16-methylheptadecan-1-ol (isostearyl alcohol), 9E-octadecen-1-ol (elaidyl alcohol), cis-9-octadecen-1-ol (oleyl alcohol), oleyl cetyl alcohol (i.e., a mixture of oleyl alcohol and cetyl alcohol), 9Z,12Z-octadecadien-1-ol (linoleyl alcohol), 9E,12E-octadecadien-1-ol (elaidolinoleyl alcohol), 9Z,12Z,15Z-octadecatrien-1-ol (linolenyl alcohol), 9E,12E,15E-octadecatrien-1-ol (elaidolinolenyl alcohol), 1-nonadecanol, and 1-eicosanol (arachidyl alcohol), or mixtures thereof.
R_a in formula (XI-a) is preferably a linear or branched saturated alkyl group having 8 to 18 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 18 carbon atoms.
Preferably the groups R_a in formula (XI-a) are saturated alkyl groups.
In formula (XI-a), x is preferably a number from 16 to 24 and more preferably from 19 to 23.
Examples of the linear or branched saturated alkyl groups R_b in the compounds of the formula (XI-a) include the examples specified above for the saturated alkyl group R_a in the compound of the formula (XI-a). Further examples are the alkyl groups heneicosyl and behenyl.
The variable "x" in the one or more compounds of the formula (XI-a) preferably represents molar averages, meaning that the dishwasher detergents of the invention may comprise a plurality of compounds of the formula (XI-a) having different degrees of alkoxylation.
It will be understood that furthermore, combinations of surfactants can be used.
Further preferred are dishwasher detergents of the invention wherein at least one surfactant of the one or more surfactants, and preferably the one or more surfactants on magnesium carbonate carrier of component Z1) are selected from the group consisting of zwitterionic surfactants and anionic surfactants.
Preferred are dishwasher detergents of the invention, wherein component Z1) comprises the one or more surfactants in an amount ranging from 10 to 300 wt.-%, preferably from 40 to 250 wt.-%, more preferably from 50 to 200 wt.-%, especially preferably from 60 to 170 wt.-%, and particularly preferably from 70 to 150 wt.-%, based on the total weight of the magnesium carbonate carrier.
The dishwasher detergents of the invention preferably comprise the one or more surfactants on magnesium carbonate carrier of component Z1) in amounts from 0.5 to 30 wt.-% and more preferably in amounts from 3 to 25 wt.-%, based in each case on the total weight of the dishwasher detergent of the invention.
As used herein, the term "the one or more surfactants on magnesium carbonate carrier" may be understood as the combination of the magnesium carbonate carrier with the one or more surfactants thereon, i.e., as component Z1) as a whole. Accordingly, in other words, in a preferred embodiment of the present invention, the dishwasher detergents of the invention comprise component Z1) in amounts from 0.5 to 30 wt.-% and more preferably in amounts from 3 to 25 wt.-%, based in each case on the total weight of the dishwasher detergent of the invention.
The carrier material of component Z1) of the dishwasher detergent of the invention consists of magnesium carbonate, preferably having a specific surface area of ≥ 25 m²/g, measured using nitrogen and the BET method according to ISO 9277:2010.
It is appreciated that the term "magnesium carbonate" refers to a material that comprises at least 80 wt.-% magnesium carbonate, e.g. at least 85 wt.-%, preferably between 85 and 100 wt.-%, more preferably between 90 and 99.95 wt.-%, based on the total dry weight of the material. Thus, it is to be noted that the magnesium carbonate may further comprise impurities typically associated with the type of material used. For example, the magnesium carbonate may further comprise impurities such as magnesium hydroxide, calcium hydroxide, calcium carbonate and mixtures thereof. However, such impurities are present in amounts of less than 20 wt.-%, preferably less than 15 wt.-% and more preferably from 0.05 to 10 wt.-%, based on the total dry weight of the material.
The magnesium carbonate can be a naturally occurring or synthetic magnesium carbonate. For example, the magnesium carbonate encompasses naturally occurring or synthetic magnesium carbonate selected from the group comprising magnesite (MgCO₃), hydromagnesite (Mg₅(CO₃)₄(OH)₂ · 4H₂O), artinite (Mg2(CO3)(OH)2 · 3H₂O), dypingite (Mg₅(CO₃)₄(OH)₂ · 5H₂O), giorgiosite (Mg₅(CO₃)₄(OH)₂ · 5H₂O), pokrovskite (Mg₂(CO₃)(OH)₂ · 0.5H₂O), barringtonite (MgCO₃ · 2H₂O, lansfordite (MgCO₃ · 5H₂O), nesquehonite (MgCO₃ · 3H₂O) and mixtures thereof.
Preferably, the magnesium carbonate encompasses synthetic magnesium carbonate selected from the group comprising magnesite (MgCO₃), hydromagnesite (Mg₅(CO₃)₄(OH)₂ · 4H₂O), artinite (Mg2(CO3)(OH)2 · 3H₂O), dypingite (Mg₅(CO₃)₄(OH)₂ · 5H₂O), giorgiosite (Mg₅(CO₃)₄(OH)₂ · 5H₂O), pokrovskite (Mg₂(CO₃)(OH)₂ · 0.5H₂O), barringtonite (MgCO₃ 2H₂O, lansfordite (MgCO₃ · 5H₂O), nesquehonite (MgCO₃ · 3H₂O) and mixtures thereof. For example, the magnesium carbonate comprises the synthetic magnesium carbonate selected from the group comprising magnesite (MgCO₃), hydromagnesite (Mg₅(CO₃)₄(OH)₂ · 4H₂O), artinite (Mg2(CO3)(OH)2 · 3H₂O), dypingite (Mg₅(CO₃)₄(OH)₂ · 5H₂O), giorgiosite (Mg₅(CO₃)₄(OH)₂ · 5H₂O), pokrovskite (Mg₂(CO₃)(OH)₂ · 0.5H₂O), barringtonite (MgCO₃ · 2H₂O, lansfordite (MgCO₃ · 5H₂O), nesquehonite (MgCO₃ · 3H₂O) and mixtures thereof in an amount of at least 80 wt.-%, preferably at least 85 wt.-%, more preferably between 85 and 100 wt.-%, and especially preferably between 90 and 99.95 wt.-%, based on the total dry weight of the material.
In one embodiment, the magnesium carbonate comprises synthetic hydromagnesite (Mg₅(CO₃)₄(OH)₂ · 4H₂O). Preferably, the magnesium carbonate comprises synthetic hydromagnesite (Mg₅(CO₃)₄(OH)₂ · 4H₂O) in an amount of at least 80 wt.-%, more preferably at least 85 wt.-%, especially preferably between 85 and 100 wt.-%, and particularly preferably between 90 and 99.95 wt.-%, based on the total dry weight of the material.
A carrier material having a specific surface area of ≥ 25 m²/g, measured using nitrogen and the BET method according to ISO 9277:2010 has a high loading capacity for surfactant(s) together with a high release efficiency when loaded with surfactant(s). Accordingly, such carrier material is specifically suitable as delivery system for the release of one or more surfactants in dishwasher detergents of the invention.
It is thus one specific requirement of the present invention that the magnesium carbonate has a specific surface area of ≥ 25 m²/g, measured using nitrogen and the BET method according to ISO 9277:2010. It is preferred that the magnesium carbonate has a specific surface area in the range from 25 to 150 m²/g, more preferably from 35 to 120 m²/g, and especially preferably from 35 to 100 m²/g, measured using nitrogen and the BET method according to ISO 9277:2010.
Furthermore, it is specifically advantageous if the magnesium carbonate has a high intra-particle intruded specific pore volume. For example, it is preferred that the magnesium carbonate has an intra-particle intruded specific pore volume in the range from 0.9 to 2.3 cm³/g, calculated from mercury intrusion porosimetry. In one embodiment, the magnesium carbonate has an intra-particle intruded specific pore volume in the range from 1.1 to 2.1 cm³/g, and most preferably from 1.2 to 2.0 cm³/g, calculated from mercury intrusion porosimetry.
According to one embodiment of the present invention, the magnesium carbonate has

a) a specific surface area of ≥ 25 m²/g, preferably in the range from 25 to 150 m²/g, more preferably from 35 to 120 m²/g, and especially preferably from 35 to 100 m²/g, measured using nitrogen and the BET method according to ISO 9277:2010, and
b) an intra-particle intruded specific pore volume in the range from 0.9 to 2.3 cm³/g, preferably from 1.1 to 2.1 cm³/g, and more preferably from 1.2 to 2.0 cm³/g, calculated from mercury porosimetry measurement.

Preferably, the magnesium carbonate has a specific surface area in the range from 35 to 100 m²/g, measured using nitrogen and the BET method according to ISO 9277:2010, and an intra-particle intruded specific pore volume in the range from 1.2 to 2.0 cm³/g, calculated from mercury porosimetry measurement.
The magnesium carbonate is in the form of a particulate material and may have a particle size distribution as conventionally employed for the material(s) involved in the type of product to be produced. In general, it is preferred that the magnesium carbonate has a d₅₀(vol) in the range from 1 to 75 µm, as determined by laser diffraction. For example, the magnesium carbonate has a d₅₀(vol) in the range from 1.2 to 50 µm, more preferably from 1.5 to 30 µm, especially preferably from 1.7 to 15 µm and particularly preferably from 1.9 to 10 µm, as determined by laser diffraction.
Additionally, or alternatively, the magnesium carbonate has a d₉₈(vol) in the range from 2 to 150 µm, as determined by laser diffraction. For example, the magnesium carbonate has a d₉₈(vol) in the range from 4 to 100 µm, more preferably from 6 to 80 µm, especially preferably from 8 to 60 µm and particularly preferably from 10 to 40 µm, as determined by laser diffraction.
Thus, the magnesium carbonate preferably has a

a) a d₅₀(vol) in the range from 1 to 75 µm, preferably from 1.2 to 50 µm, more preferably from 1.5 to 30 µm, especially preferably from 1.7 to 15 µm and particularly preferably from 1.9 to 10 µm, as determined by laser diffraction, and
b) a d₉₈(vol) in the range from 2 to 150 µm, preferably from 4 to 100 µm, more preferably from 6 to 80 µm, especially preferably from 8 to 60 µm and particularly preferably from 10 to 40 µm, as determined by laser diffraction.

In one embodiment, the magnesium carbonate has a d₅₀(vol) in the range from 1.9 to 10 µm, as determined by laser diffraction, and a d₉₈(vol) in the range from 10 to 40 µm, as determined by laser diffraction.
In order to obtain a carrier material having a high loading capacity together with a high release efficiency when loaded with active agent(s), it is especially preferred that the magnesium carbonate has

a) a specific surface area of 25 m²/g, preferably in the range from 25 to 150 m²/g, more preferably from 35 to 120 m²/g, and especially preferably from 35 to 100 m²/g, measured using nitrogen and the BET method according to ISO 9277:2010, and
b) an intra-particle intruded specific pore volume in the range from 0.9 to 2.3 cm³/g, preferably from 1.1 to 2.1 cm³/g, and more preferably from 1.2 to 2.0 cm³/g, calculated from mercury porosimetry measurement, and
c) a d₅₀(vol) in the range from 1 to 75 µm, preferably from 1.2 to 50 µm, more preferably from 1.5 to 30 µm, especially preferably from 1.7 to 15 µm and particularly preferably from 1.9 to 10 µm, as determined by laser diffraction, and/or
d) a d₉₈(vol) in the range from 2 to 150 µm, preferably from 4 to 100 µm, more preferably from 6 to 80 µm, even more preferably from 8 to 60 µm and most preferably from 10 to 40 µm, as determined by laser diffraction.

Preferably, the magnesium carbonate has

a) a specific surface area of 25 m²/g, preferably in the range from 25 to 150 m²/g, more preferably from 35 to 120 m²/g, and especially preferably from 35 to 100 m²/g, measured using nitrogen and the BET method according to ISO 9277:2010, and
b) an intra-particle intruded specific pore volume in the range from 0.9 to 2.3 cm³/g, preferably from 1.1 to 2.1 cm³/g, and more preferably from 1.2 to 2.0 cm³/g, calculated from mercury porosimetry measurement, and
c) a d₅₀(vol) in the range from 1 to 75 µm, preferably from 1.2 to 50 µm, more preferably from 1.5 to 30 µm, especially preferably from 1.7 to 15 µm and particularly preferably from 1.9 to 10 µm, as determined by laser diffraction, and
d) a d₉₈(vol) in the range from 2 to 150 µm, preferably from 4 to 100 µm, more preferably from 6 to 80 µm, especially preferably from 8 to 60 µm and particularly preferably from 10 to 40 µm, as determined by laser diffraction.

In one embodiment, the magnesium carbonate has

a) a specific surface area in the range from 35 to 100 m²/g, measured using nitrogen and the BET method according to ISO 9277:2010, and
b) an intra-particle intruded specific pore volume in the range from 1.2 to 2.0 cm³/g, calculated from mercury porosimetry measurement, and
c) a d₅₀(vol) in the range from 1.9 to 10 µm, as determined by laser diffraction, and
d) a d₉₈(vol) in the range from 10 to 40 µm, as determined by laser diffraction.

It is one requirement that the carrier material consists of magnesium carbonate. That is to say, the carrier material contains the magnesium carbonate in an amount of at least 96.0 wt.-%, preferably between 96.0 and 100 wt.-%, more preferably between 99.0 and 99.99 wt.-%, and especially preferably between 99.3 and 99.8 wt.-%, based on the total dry weight of the carrier material.
In one embodiment, the magnesium carbonate contains up to 15 000 ppm Ca²⁺ ions. For example, the magnesium carbonate contains up to 10 000 ppm, more preferably up to 5 000 ppm and especially preferably up to 2 000 ppm Ca²⁺ ions. Depending on the magnesium carbonate, the magnesium carbonate preferably has a residual total moisture content of from 0.01 to 20 wt.-%, more preferably from 0.01 to 15 wt.-%, especially preferably from 0.02 to 12 wt.-% and particularly preferably from 0.04 to 10 wt.-%, based on the total dry weight of the magnesium carbonate. It is appreciated that the total moisture content includes crystal water as well as free water.

Delivery system

Component Z1) of the dishwasher detergents of the invention is a delivery system for the release of one or more surfactants in the dishwasher detergents of the invention, i.e. in automatic dishwashing formulations. It is required that the delivery system comprises the carrier material as defined herein, i.e. the magnesium carbonate carrier, and one or more surfactant(s) which is/are loaded on the carrier material.
With regard to the definition of the carrier material and preferred embodiments thereof, reference is made to the statements provided above when discussing the technical details of the carrier material of the present invention.
The delivery system for the release of one or more surfactant(s) in an automatic dishwashing formulation of the invention thus comprises

a) a carrier material consisting of magnesium carbonate having a specific surface area of ≥ 25 m²/g, measured using nitrogen and the BET method according to ISO 9277:2010, and
b) the one or more surfactant(s) which is/are loaded on the carrier material.

Thus, one requirement of the present invention is that one or more surfactant(s) is/are loaded on the carrier material.
The one or more surfactant(s) can be one kind of surfactant. Alternatively, the one or more surfactant(s) can be a mixture of two or more kinds of surfactants.
The one or more surfactant(s) is/are loaded on the carrier material as defined herein. The loading is preferably an adsorption onto the surface of the carrier material, be it the outer or the inner surface of the material or an absorption into the carrier material, which is possible due to its porosity.
In this respect, it is believed that because of the advantageous high specific surface area in combination with a high intra-particle intruded specific pore volume of the magnesium carbonate, this material is a superior carrier material to release previously loaded surfactant(s) over time relative to common carrier materials having lower specific surface areas and/or intra-particle intruded specific pore volume.
Thus, it is appreciated that the one or more surfactant(s) is/are adsorbed onto and/or adsorbed and/or absorbed into the carrier material.
As already mentioned, the delivery system comprises the carrier material as defined herein and one or more surfactant(s) which is/are loaded on the carrier material.
The amount of the one or more surfactant(s) which is/are loaded on the carrier material depends on the surfactant(s) and the intended use. Generally, the delivery system comprises the one or more surfactant(s) in an amount ranging from 10 to 300 wt.-%, based on the total weight of the carrier material.
For example, the delivery system comprises the one or more surfactant(s) in an amount preferably ranging from 40 to 250 wt.-%, more preferably from 50 to 200 wt.-%, especially preferably from 60 to 170 wt.-% and particularly preferably from 70 to 150 wt.-%, based on the total weight of the carrier material.
The delivery system can be provided in any form that is conventionally employed for the material(s) involved in the type of product to be produced. It is appreciated that the carrier material is in the form of a particulate material. The term "particulate" in the meaning of the present application refers to a material which is composed of a plurality of particles.
Thus, the delivery system is preferably in the form of a powder, a tablet, a pellet, or granules. More preferably, the delivery system is in the form of a powder. Such forms and methods for their preparation are well known in the art and do not need to be described in more detail in the present application.
The method for preparing a delivery system for the release of one or more surfactant(s) in a dishwasher detergent of the invention comprises the steps of

a) providing magnesium carbonate having a specific surface area of ≥ 25 m²/g, measured using nitrogen and the BET method according to ISO 9277:2010,
b) providing one or more surfactant(s) in the form of a liquid or dissolved in a solvent, and
c) contacting the magnesium carbonate of step a) with the one or more surfactant(s) of step b).

With regard to the definition of the delivery system, the magnesium carbonate and preferred embodiments thereof, reference is made to the statements provided above when discussing the technical details of the carrier material and the delivery system of the present invention.
The magnesium carbonate may be provided in any suitable liquid or dry form in step a). For example, the magnesium carbonate may be in form of a powder and/or a suspension. The suspension can be obtained by mixing the magnesium carbonate with a solvent, preferably water. The magnesium carbonate to be mixed with a solvent, and preferably water, may be provided in any form, for example, as suspension, slurry, dispersion, paste, powder, a moist filter cake or in pressed or granulated form.
In order to obtain a high loading of the one or more surfactant(s) on the carrier material, it is advantageous to provide the magnesium carbonate as concentrated as possible, i.e. the water content should be as low as possible. Thus, the magnesium carbonate is preferably provided in dry from, i.e. as a powder.
In case the magnesium carbonate is provided in dry form, the moisture content of the magnesium carbonate can be between 0.01 and 20 wt.-%, based on the total weight of the magnesium carbonate. The moisture content of the magnesium carbonate can be, for example, in the range from 0.01 to 15 wt.-%, based on the total weight of the magnesium carbonate, preferably in the range from 0.02 to 12 wt.-%, and more preferably in the range from 0.04 to 10 wt.-%.
According to step b) of the present method, the one or more surfactant(s) is/are provided in the form of a liquid or dissolved in a solvent.
That is to say, in one embodiment the one or more surfactant(s) is/are in the form of a liquid. The term "liquid" with regard to the one or more surfactant(s) refers to non-gaseous fluid surfactant(s), which is/are readily flowable at the pressure conditions and temperature of use, i.e. the pressure and temperature at which the method, preferably method step c), is carried out.
Thus, it is appreciated that the one or more surfactant(s) can be liquid in a temperature range from 5 to 200°C, preferably from 10 to 120°C and more preferably from 10 to 100°C. For example, the one or more surfactant(s) can be liquid in a temperature range from 5 to 200°C, preferably from 10 to 120°C and more preferably from 10 to 100°C at ambient pressure conditions, i.e. at atmospheric pressure. Alternatively, the one or more surfactant(s) can be liquid in a temperature range from 5 to 200°C, preferably from 10 to 120°C and more preferably from 10 to 100°C at reduced pressure conditions, e.g. a pressure of from 100 to 700 mbar.
Alternatively, the one or more surfactant(s) is/are dissolved in a solvent. That is to say, the one or more surfactant(s) and the solvent form a system in which no discrete solid particles are observed in the solvent and thus form a "solution".
In one embodiment of the present invention, the solvent is selected from the group comprising water, methanol, ethanol, n-butanol, isopropanol, n-propanol, acetone, dimethylsulphoxide, dimethylformamide, tetrahydrofurane, vegetable oils and the derivatives thereof, animal oils and the derivatives thereof, molten fats and waxes, and mixtures thereof. Preferably, the solvent is selected from water, alkanes, esters, ethers, alcohols, such as ethanol, ethylene glycol and glycerol, and/or ketones, such as acetone. More preferably, the solvent is water.
The contacting of the magnesium carbonate of step a) with the one or more surfactant(s) of step b) may be carried out in any manner known by the skilled person. The contacting is preferably carried out under mixing. The mixing may be carried out under conventional mixing conditions. The skilled person will adapt these mixing conditions (such as the configuration of mixing pallets and mixing speed) according to his process equipment. It is appreciated that any mixing method which would be suitable to form the delivery system may be used.
It is appreciated that the magnesium carbonate of step a) is loaded with the one or more surfactant(s) of step b) by contacting step c) to form the delivery system.
The loading may be achieved by adding the one or more surfactant(s) to the dry magnesium carbonate.
According to the present invention, the magnesium carbonate is defined to be loaded, if the specific surface area is at least partially covered and/or the intra-particle pore volume of same is at least partially filled by the one or more surfactant(s), and if present, the solvent in which the one or more surfactant(s) is/are dissolved. For example, the magnesium carbonate is loaded, if the specific surface area is at least partially covered and/or the intra-particle pore volume of same is at least partially filled preferably by at least 10 wt.-%, more preferably at least 40 wt.-%, especially preferably at least 50 wt.-%, particularly preferably at least 60 wt.-%, and exceptionally preferably at least 70 wt.-%, based on the total weight of the magnesium carbonate, with the one or more surfactant(s), and if present, the solvent in which the one or more surfactant(s) is/are dissolved. Preferably, the magnesium carbonate is loaded, if the specific surface area is at least partially covered and/or the intra-particle pore volume of same is at least partially filled by 10 to 300 wt.-%, more preferably from 40 to 250 wt.-%, especially preferably from 50 to 200 wt.-%, particularly preferably from 60 to 170 wt.-%, and exceptionally preferably from 70 to 150 wt.-%, based on the total weight of the magnesium carbonate, with the one or more surfactant(s), and if present, the solvent in which the one or more surfactant(s) is/are dissolved.
It is appreciated that method step c) can be carried out over a broad temperature and/or pressure range, provided that the one or more surfactant(s) is/are in liquid form. For example, method step c) is carried out in a temperature range from 5 to 200°C, preferably from 10 to 120°C and more preferably from 10 to 100°C at ambient pressure conditions, i.e. at atmospheric pressure. Alternatively, method step c) is carried out in a temperature range from 5 to 200°C, preferably from 10 to 120°C and more preferably from 10 to 100°C at reduced pressure conditions, e.g. a pressure of from 100 to 700 mbar.
In one embodiment, method step c) is carried out at ambient temperature and pressure conditions, e.g., at room temperature, such as from about 5 to 35°C, preferably from 10 to 30°C and more preferably from 15 to 25°C, and at atmospheric pressure. This embodiment preferably applies in case the one or more surfactant(s) is/are liquid at room temperature or are dissolved in a solvent.
In case the one or more surfactant(s) is/are dissolved in a solvent, the solvent is preferably removed after method step c), e.g. by evaporation. In this embodiment, the method thus preferably comprises a further step of separating the prepared delivery system from the excess solvent.
The solvent is preferably removed by means of separating the solvent from the loaded magnesium carbonate. This is preferably achieved by drying by means selected from the group comprising drying in a rotational oven, jet-drying, fluidized bed drying, freeze drying, flash drying, spray drying and temperature-controlled high or low shear mixer.
The delivery system according to the present invention may thus be produced by a method comprising the following steps:

a) providing magnesium carbonate having a specific surface area of ≥ 25 m²/g, measured using nitrogen and the BET method according to ISO 9277:2010,
b) providing one or more surfactant(s) dissolved in a solvent,
c) contacting the magnesium carbonate of step a) with the one or more surfactant(s) of step b), and d) separating the delivery system formed in step c) from the excess solvent.

The method may further comprise an optional step e) of granulating the mixture obtained in step c) or optional step d) for obtaining tablets, pellets or granules of the desired form and size.
The granulation equipment may be selected from the conventionally used ones for granulation purposes. Thus, the granulation device may be selected from the group comprising Eirich mixers, fluidized bed dryers/granulators, plate granulators, table granulators, drum granulators, disc granulators, dish granulators, ploughshare mixer, vertical or horizontal mixers, high or low shear mixer, high speed blenders, roller compactor and rapid mixer granulators.
It might be noted that there may be differences as regards the granule sizes or granule size distributions to be achieved depending on the method used.
For example, the use of a fluidized bed mixer for granulation appears to provide a more uniform granule size distribution than the Lödige mixer, whereas the Lödige mixer gives a wider size distribution. Thus, multiple size ranges may be provided.
In one embodiment, the method for preparing a delivery system for the release of one or more surfactant(s) in an automatic dishwashing formulation of the invention comprises the steps of

a) providing magnesium carbonate having a specific surface area of ≥ 25 m²/g, measured using nitrogen and the BET method according to ISO 9277:2010,
b) providing one or more surfactant(s) in the form of a liquid or dissolved in a solvent,
c) contacting the magnesium carbonate of step a) with the one or more surfactant(s) of step b),
d) optionally separating the delivery system formed in step c) from the excess solvent, and
e) granulating the delivery system formed in step c) or optional step d) for obtaining tablets, pellets or granules.

It is appreciated that the carrier material has a high loading capacity for surfactant(s) together with a high release efficiency when loaded with surfactant(s).
It is appreciated that the delivery system provides a release efficiency for the one or surfactant(s) represented by the following formula (I) $release efficiency = 100 * \frac{m (surfactant released)}{m (surfactant loaded)}$
of ≥ 50%.
Preferably, the delivery system provides a release efficiency for the one or more surfactant (s) represented by the formula (I) of ≥ 72%, and more preferably ≥ 80%.
It is preferred that the release efficiency is attained within a time period of 15 min, preferably within 5 min and more preferably within 1 min.

Particle size distribution

Volume determined median particle size d₅₀(vol) and the volume determined top cut particle size d₉₈(vol) is evaluated using a Malvern Mastersizer 3000 Laser Diffraction System (Malvern Instruments Pic., Great Britain) equipped with a Hydro LV system. The d₅₀(vol) or d₉₈(vol) value indicates a diameter value such that 50% or 98% by volume, respectively, of the particles have a diameter of less than this value. The powders are suspended in 0.1 wt.-% Na₄O₇P₂ solution. 10 mL of 0.1 wt.-% Na₄O₇P₂ is added to the Hydro LV tank, then the sample slurry is introduced until an obscuration between 10-20% is achieved and the system is ultrasonicated at the 40% setting for 1 min. Measurements are conducted with red and blue light for 10 s each. For the analysis of the raw data, the models for non-spherical particle sizes with the Fraunhofer assumption is utilized, and a particle refractive index of 1.57, a density of 2.70 g/cm³, and an absorption index of 0.005 is assumed. The methods and instruments are known to the skilled person and are commonly used to determine particle size distributions of fillers and pigments.

Specific surface area (SSA)

The specific surface area is measured via the BET method according to ISO 9277:201 using nitrogen as adsorbing gas on a Micromeritics ASAP 2460 instrument from Micromeritics. The samples are pretreated in vacuum (10^-5 bar) by heating at 100°C for a period of 120 min prior to measurement.

Intra-particle intruded specific pore volume (in cm³/g)

The specific pore volume is measured using a mercury intrusion porosimetry measurement using a Micromeritics Autopore V 9620 mercury porosimeter having a maximum applied pressure of mercury 414 MPa (60 000 psi), equivalent to a Laplace throat diameter of 0.004 µm (∼ nm). The equilibration time used at each pressure step is 20 seconds. The sample material is sealed in a 3 cm³ chamber powder penetrometer for analysis. The data are corrected for mercury compression, penetrometer expansion and sample material compression using the software Pore-Camp (Gane, P.A.C., Kettle, J.P., Matthews, G.P. and Ridgway, C.J., "Void Space Structure of Compressible Polymer Spheres and Consolidated Calcium Carbonate Paper-Coating Formulations", Industrial and Engineering Chemistry Research, 35(5), 1996, p1753-1764.).
The total pore volume seen in the cumulative intrusion data can be separated into two regions with the intrusion data from 208 µm down to about 1 - 4 µm showing the coarse packing of the sample between any agglomerate structures contributing strongly. Below these diameters lies the fine inter-particle packing of the particles themselves. If they also have intra-particle pores, then this region appears bi-modal, and by taking the specific pore volume intruded by mercury into pores finer than the modal turning point, i.e. finer than the bi-modal point of inflection, the specific intra-particle pore volume is defined. The sum of these three regions gives the total overall pore volume of the powder, but depends strongly on the original sample compaction/settling of the powder at the coarse pore end of the distribution.
By taking the first derivative of the cumulative intrusion curve the pore size distributions based on equivalent Laplace diameter, inevitably including pore-shielding, are revealed. The differential curves clearly show the coarse agglomerate pore structure region, the inter-particle pore region and the intra-particle pore region, if present. Knowing the intra-particle pore diameter range it is possible to subtract the remainder inter-particle and inter-agglomerate pore volume from the total pore volume to deliver the desired pore volume of the internal pores alone in terms of the pore volume per unit mass (specific pore volume). The same principle of subtraction, of course, applies for isolating any of the other pore size regions of interest.

Chemical oxygen demand analysis

For chemical oxygen demand (COD) analysis, suspensions are filtered (Chromafil^® Xtra RC-20/25 syringe filter) and adequately diluted for the analysis. Active concentrations are determined using a cell test (according to ISO 15705; Spectroquant^® for non-Merck photometers; 0-1500 mg L^-1) in an Aqualytics COD250 varia photometer. For each sample, 5 readings are taken and the result averaged. The concentration of the samples is calculated based on a calibration curve with previously prepared standard solutions.

Loading of the carrier materials

For loading experiments, 10 g of the carrier material is weighed into a beaker and mechanically stirred. Then, the desired amount of surfactant solution is added dropwise using a pipette. Solid surfactants are dissolved in water at a suitable concentration before the loading procedure. The nominal loading of surfactant is calculated according to equation (I). $Loading [%] = \frac{mass of surfactant [g]}{mass of powder [g]} \cdot 100$

Component Z2)

Preferably, the one or more enzymes of component Z2) of the dishwasher detergents of the invention are selected from the group consisting of proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases, oxidoreductases, and mixtures thereof. These enzymes are typically of natural origin. Improved variants based on the natural molecules are obtainable for use in dishwasher detergents and accordingly are preferred.
Among the proteases, preference is given to those of the subtilisin type. Examples of such are the subtilisins BPN' and Carlsberg and also the further-developed forms thereof, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY, and subtilases.
Examples of amylases which can be used in accordance with the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae, and also the further-developed forms of the aforesaid amylases that have been improved for use in dishwasher detergents. Further deserving of emphasis for this purpose are the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
Other enzymes which can be used in accordance with the invention are lipases or cutinases, particularly on the basis of their triglyceride-cleaving activities, but also for generating peracids in situ from suitable precursors. They include, for example, the lipases obtainable originally from Humicola lanuginosa (Thermomyces lanuginosus) and/or further developments thereof, particularly those with the amino acid replacement D96L. Further of possible use, for example, are the cutinases isolated originally from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, and/or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocma and Fusarium solanii.
It is possible, furthermore, to use enzymes referred to collectively as hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectinesterases, pectate lyases, xyloglucanases (= xylanases), pullulanases, and β-glucanases.
To increase the bleaching activity, it is possible in accordance with the invention to use oxidoreductases, examples being oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, or bromo-peroxidases, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases). Added advantageously, additionally, are preferably organic, more preferably aromatic, compounds which interact with the enzymes in order to boost the activity of the oxidoreductases in question (enhancers) or in order to ensure electron flow (mediators) when there are sharp differences in redox potentials between the oxidizing enzymes and the soiling.
The enzymes can be used in any form established according to the prior art. These forms include, for example, the solid preparations obtained by granulation, extrusion or lyophilization, or else - particularly in the case of liquid or gel compositions - solutions of the enzymes, advantageously in very highly concentrated form, of low water content and/or with stabilizers added.
Alternatively, the enzymes, for both the solid and the liquid presentation forms, may be encapsulated, by spray drying or extrusion of the enzyme solution, for example, together with a preferably natural polymer, or in the form of capsules, examples being those wherein the enzymes are included as in a solidified gel, or in those of the core-shell type, for which an enzyme-containing core is coated with a protective layer which is impermeable to water, air and/or chemicals. In added-on layers there may additionally be further active ingredients applied, examples being stabilizers, emulsifiers, pigments, bleaches or dyes. Capsules of these kinds are applied by techniques that are known per se, as for example by agitated granulation or roll granulation or in fluid-bed operations. Advantageously, such granules, as a result of application of polymeric film-formers, for example, are low in dust and stable in storage by virtue of the coating.
It is possible, furthermore, to formulate two or more enzymes together, so that a single type of granule contains a plurality of enzymes.
Dishwasher detergents of the invention comprise the one or more enzymes of component Z2) preferably in amounts from 1 x 10^-6 to 5 wt.-%, more preferably in amounts from 1 x 10^-5 to 3 wt.-%, and especially preferably in amounts from 1 x 10^-4 to 2 wt.-%, based in each case on the total weight of the dishwasher detergents of the invention. The amount of the one or more enzymes of component Z2) of the dishwasher detergents of the invention is also based on active protein. The protein concentration may be determined by known techniques, such as by the BCA method or the biuret method, for example.

Glass corrosion inhibitors (Component Z3)

Glass corrosion inhibitors may be ingredients of the dishwasher detergents of the present invention. Glass corrosion inhibitors may prevent the appearance of clouding, streaks and scratches, but may also prevent the surface of machine-cleaned glassware becoming iridescent.
A glass corrosion inhibitor may be any glass corrosion inhibitor known in the art. Preferred glass corrosion inhibitors may include one or more salts selected from the group consisting of magnesium (which different from the magnesium carbonate carrier of component Z1), cobalt, bismuth, and zinc, and also complexes of one or more of magnesium (which different from the magnesium carbonate carrier of component Z1), cobalt, bismuth, and/or zinc.
Thus, in a preferred embodiment, the one or more glass corrosion inhibitors of component Z3) are selected from the group consisting of, preferably water-soluble, salts or complexes of one or more cations selected from the group consisting of zinc, magnesium, cobalt, bismuth, and combinations of two or more thereof.
In a further preferred embodiment, the one or more glass corrosion inhibitors of component Z3) are, preferably water-soluble, salts comprising one or more anions selected from the group consisting of sulfate, nitrate, acetate, oxide, sulfate, phosphate, halide, carbonate or carboxylate salt.
For instance, the one or more glass corrosion inhibitors may be selected from the group consisting of zinc sulfate, zinc nitrate, zinc acetate, zinc phosphate, zinc a zinc halide (e.g., zinc chloride), zinc carbonate, magnesium sulfate, magnesium nitrate, magnesium acetate, magnesium phosphate, magnesium, a magnesium halide (e.g., magnesium chloride), magnesium carbonate, cobalt sulfate, cobalt nitrate, cobalt acetate, cobalt phosphate, cobalt, a cobalt halide (e.g., cobalt chloride), cobalt carbonate, bismuth sulfate, bismuth nitrate, bismuth acetate, bismuth phosphate, bismuth, a bismuth halide (e.g., bismuth chloride), bismuth carbonate, and combinations of two or more thereof or complexes comprising one or more of these salts.
Preferably, the dishwasher detergent according to the present invention comprises component Z3) in an amount from 0.01 to 10 wt.-%, more preferably in an amount from 0.1 to 5 wt.-%, even more preferably in an amount from 0.2 to 4 wt.-%, and especially preferably in an amount from 0.4 to 3 wt.-%, from 0.5 to 2 wt.-% or from 0.2 to 1 wt.-%, based in each case on the total weight of the dishwasher detergent.
The dishwasher detergents of the invention may optionally additionally comprise one or more further substances. With particular preference, these further substances optionally present in the dishwasher detergents of the invention are selected from the components Z4), Z5), Z6), Z7), and/or Z8):

Z4) a bleaching system,
Z5) one or more surfactants other than those of component Z1),
Z6) one or more further additives, preferably selected from the group consisting of builders, complexing agents, water, organic solvents, thickeners, foam inhibitors, color particles, silver protectants, agents for preventing tarnishing of silver, metal corrosion inhibitors, dyes, fillers, microbicides, hydrotropes, antioxidants, enzyme stabilizers, fragrances, solubilizers, carrier materials, processing assistants, pigments, and pH modifiers,
Z7) one or more tableting aids, preferably selected from polyethylene glycol, polysaccharides, and derivatives thereof, and/or
Z8) one or more polymers other that component Z7).

In a preferred embodiment, the one or more surfactants other than those of component Z1) of component Z5) are selected from the group consisting of fatty alcohol alkoxylates, end-capped fatty alcohol alkoxylates, ethyleneoxide-propylenoxide-blockcopolymers, N-acylglucamines, N-acylglucamides, gylcerol triester alkoxylates, esterquats, and mixtures thereof, preferably wherein the one or more surfactants of component Z5) are on the magnesium carbonate carrier,
The pH of the dishwasher detergents of the invention at 20°C is preferably from 8 to 14, more preferably from 9 to 11.5, and especially preferably from 9.5 to 11.5, measured as a 10 wt.-% solution of the solid or liquid dishwasher detergent of the invention in water.
The above-mentioned stated substances and other preferred ingredients of the dishwasher detergents of the invention are described in more detail below.

Bleaching system (Component Z4)

The dishwasher detergents of the invention may also comprise a bleaching system.
The bleaching system of the dishwasher detergents of the invention comprises preferably one or more substances from the group consisting of bleaches, bleach activators, and bleaching catalysts.
As bleaches, the dishwasher detergents of the invention may comprise an oxygen bleach. Among these oxygen bleaches, which in water yield H₂O₂, particular importance is possessed by sodium percarbonate, sodium perborate tetrahydrate, and sodium perborate monohydrate. Examples of other useful bleaches are peroxypyrophosphates, citrate perhydrates, and also H₂O₂-donating peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. Organic bleaches can also be used. Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide. Further typical organic bleaches are the peroxy acids, such as alkylperoxy acids and the arylperoxy acids.
The dishwasher detergents of the invention preferably comprise one or more bleaches from the group consisting of oxygen bleaches, peroxypyrophosphates, citrate perhydrates, H₂O₂-donating peracid salts or peracids, and organic bleaches.
With particular preference the dishwasher detergents of the invention comprise 1.0 to 20 wt.-%, preferably 4.0 to 18 wt.-%, and more preferably 8 to 15 wt.-%, of an oxygen bleach, preferably sodium carbonate, based in each case on the total weight of the dishwasher detergent of the invention.
In order to achieve an improved bleaching effect when cleaning at temperatures of around 60°C and below, the dishwasher detergents of the invention may additionally comprise one or more bleach activators. The bleach activator or bleach activators are preferably selected from the group consisting of compounds which under perhydrolysis conditions furnish aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, more preferably 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and/or N-acyl groups with the stated number of carbon atoms, and/or optionally substituted benzoyl groups. Preferred are polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.
Bleach activators, especially TAED, are used preferably in amounts of up to 10 wt.-%, more preferably in amounts of 0.1 to 8 wt.-%, especially preferably in amounts of 2 to 8 wt.-%, and particularly preferably in amounts of 2 to 6 wt.-%, based in each case on the total weight of the bleach activator-containing dishwasher detergent of the invention.
Further to the conventional bleach activators or in their place, use may also be made of what are called bleaching catalysts. These compounds are bleach-boosting transition metal salts or transition metal complexes such as, for example, Mn-, Fe-, Co-, Ru- or Mo-salen complexes or -carbonyl complexes. Also possible for use as bleaching catalysts are Mn, Fe, Co, Ru, Mo, Ti, V, and Cu complexes with nitrogen-containing tripod ligands, and also Co-, Fe-, Cu-, and Ru-amine complexes.
Particular preference is given to using complexes of manganese in the II, III, IV or V oxidation state, preferably containing one or more macrocyclic ligands with N, NR, PR, O and/or S donor functions. Preferred ligands are those having nitrogen donor functions. It is particularly preferred in that case to use bleaching catalyst(s) comprising as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me/Me-TACN) and/or 2-methyl-1,4,7-triazacyclononane (Me/TACN). Examples of suitable manganese complexes are [Mn^III ₂(µ-O)₁(µ-OAc)₂(TACN)₂](CIO₄)₂, [Mn^IIIMn^IV(µ-O)₂(µ-OAc)₁(TACN)₂](BPh₄)₂, [Mn^IV ₄(µ-O)₆(TACN)₄](CIO₄)₄, [Mn^III ₂(µ-O)₁(µ-OAc)₂(Me-TACN)₂](CIO₄)₂, [Mn^IIIMn^IV(µ-O)₁(µ-OAc)₂(Me-TACN)₂](CIO₄)₃, [Mn^IV2(µ-O)₃(Me-TACN)₂](PF₆)₂, and [Mn^IV2(µ-O)₃(Me/Me-TACN)₂](PF₆)₂(OAc=OC(O)CH₃).
In another preferred embodiment of the invention, the dishwasher detergents of the invention comprise one or more bleaching catalysts from the group of the bleach-boosting transition metal salts and transition metal complexes, preferably from the group of the manganese complexes with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN) and 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me₄-TACN), since by means of these bleaching catalysts it is possible to pose significant improvements in the cleaning outcome.
The bleaching system preferably comprises one or more bleaches and one or more substances from the group of the bleach activators and bleaching catalysts. With particular preference the bleaching system comprises one or more bleaches, one or more bleach activators, and one or more bleaching catalysts.
The dishwasher detergents of the invention comprise the bleaching system of component Z4) preferably in amounts of 1 to 40 wt.-%, more preferably in amounts of 0.5 to 30 wt.-%, and especially preferably in amounts of 3 to 25 wt.-%, based in each case on the total weight of the dishwasher detergent of the invention.

Surfactants others that those of component Z1) (Component Z5)

Preferred dishwasher detergents of the invention further comprise one or more surfactants of component Z5), the group of the surfactants including the nonionic, the anionic, the cationic, and the amphoteric surfactants. In a preferred embodiment these surfactants of component Z5) are not present on a carrier material and in this preferred embodiment the surfactants themselves may be optionally the same as those used in component Z1). In another preferred embodiment, the surfactants of component Z5) can be on magnesium carbonate carrier and in this other preferred embodiment the surfactants themselves are different from those used in component Z1).
Preferably at least one surfactant of the one or more surfactants, and more preferably the one or more surfactants of component Z5) of the dishwasher detergents of the invention are selected from the group consisting of the nonionic surfactants and more preferably of the low-foaming nonionic surfactants. Nonionic surfactants which can be used in the context of the present invention are all nonionic surfactants known to the skilled person.
More preferably at least one surfactant of the one or more surfactants, and even more preferably the one or more surfactants of component Z5) of the dishwasher detergents of the invention are selected from the group of nonionic surfactants consisting of fatty alcohol alkoxylates, endgroup-capped fatty alcohol alkoxylates, preferably end-capped fatty alcohol ethoxylates, e.g. epoxy-capped poly(alkoxylated) fatty alcohols, preferably epoxy-capped poly(ethoxylated) fatty alcohols, ethyleneoxide-propyleneoxide-blockcopolymers, N-acylglucamines / N-acylglucamides, glycerol triester alkoxylates, preferably glycerol triester ethoxylates, and mixtures thereof.
Especially preferred are dishwasher detergents of the invention wherein at least one surfactant of the one or more surfactants, and preferably the one or more surfactants of component Z5) of the dishwasher detergents of the invention are selected from the group consisting of the fatty alcohol alkoxylates and end-capped fatty alcohol alkoxylates of the formula (XI-b)

RaO-(AO)x-Y (XI-b),

in which

Ra: is a linear or branched saturated alkyl group having 8 to 30 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 30 carbon atoms,
A: is selected from the group consisting of -C₂H₄- and -C₃H₆-,
x: is a number from 1 to 150,
Y: is a group -CH₂-CH(OH)-R_b, R_b is a linear or branched saturated alkyl group having 1 to 30 carbon atoms, and where the group -(AO)_x- comprises one or more -C₂H₄-O- groups and may additionally comprise one or more -C₃H₆-O- groups, and, when the group -(AO)_x- simultaneously comprises -C₂H₄-O- and -C₃H₆-O- groups, the -C₂H₄-O- and -C₃H₆-O- groups may be distributed over the -(AO)_x- group in any desired way, preferably in random, gradient-like or block-like manner and more preferably in block-like manner, and the molar amount of the -C₂H₄-O- groups in the group -(AO)_x- is preferably greater than the molar amount of the -C₃H₆-O- groups in the group -(AO)_x-.

Examples of the alkyl and alkenyl groups R_a in the formula (XI-b) are, for example, the alkyl and alkenyl groups of the following alcohols R_a-OH: 1-octanol (caprylyl alcohol), 2-ethylhexanol, 1-nonanol (pelargon alcohol), 1-decanol (caprinyl alcohol), 1-undecanol, 1-dodecanol (lauryl alcohol), 1-tridecanol, isotridecanol, 1-tetradecanol (myristyl alcohol), 1-pentadecanol, 1-hexadecanol (cetyl alcohol), cis-9-hexadecen-1-ol (palmitoleyl alcohol), 1-heptadecanol, 1-octadecanol (stearyl alcohol), cetearyl alcohol, 16-methylheptadecan-1-ol (isostearyl alcohol), 9E-octadecen-1-ol (elaidyl alcohol), cis-9-octadecen-1-ol (oleyl alcohol), oleyl cetyl alcohol (i.e., a mixture of oleyl alcohol and cetyl alcohol), 9Z,12Z-octadecadien-1-ol (linoleyl alcohol), 9E,12E-octadecadien-1-ol (elaidolinoleyl alcohol), 9Z,12Z,15Z-octadecatrien-1-ol (linolenyl alcohol), 9E,12E,15E-octadecatrien-1-ol (elaidolinolenyl alcohol), 1-nonadecanol, 1-eicosanol (arachidyl alcohol), 1-heneicosanol, 1-docosanol (behenyl alcohol), cis-13-docosen-1-ol (erucyl alcohol), 1-tetracosanol (lignoceryl alcohol), 1-hexacosanol (ceryl alcohol), 1-octacosanol (montanyl alcohol), and 1-triacontanol (myricyl alcohol), or mixtures thereof.
R_a in formula (XI-b) is preferably a linear or branched saturated alkyl group having 8 to 22 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 22 carbon atoms, more preferably a linear or branched saturated alkyl group having 8 to 20 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 20 carbon atoms, and especially preferably a linear or branched saturated alkyl group having 8 to 18 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 18 carbon atoms.
Preferably the groups R_a in formula (XI-b) are saturated alkyl groups.
In formula (XI-b), x is preferably a number from 1 to 50, more preferably a number from 1 to 25, especially preferably a number from 5 to 25 and particularly preferably a number from 15 to 25.
Examples of the linear or branched saturated alkyl groups Y and R_b in the compounds of the formula (XI-b) include the examples specified above for the saturated alkyl group R_a in the compound of the formula (XI-b). Further examples are the alkyl groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl (2-pentyl), 3-pentyl, 2-methylbutyl, isopentyl (3-methylbutyl), 3-methylbut-2-yl, 2-methylbut-2-yl, neopentyl (2,2-dimethylpropyl), 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 2-ethyl-1-butyl, 1-heptyl, 2-heptyl, 3-heptyl, and 4-heptyl.
If Y in formula (XI-b) is a linear or branched saturated alkyl group, the saturated alkyl group in question preferably has 1 to 22 carbon atoms.
If Y in formula (XI-b) is the group -CH₂-CH(OH)-R_b, R_b preferably is a linear or branched saturated alkyl group having 8 to 22 and more preferably 8 to 20 carbon atoms.
In one particularly preferred embodiment of the invention, the group -(AO)_x- consists of one or more -C₂H₄-O- groups and contains no -C₃H₆-O- groups.
In another particularly preferred embodiment of the invention, the group -(AO)_x- comprises one or more -C₂H₄-O- groups and one or more -C₃H₆-O- groups. In this particularly preferred embodiment of the invention, the molar amount of the -C₃H₆-O- groups in the group -(AO)_x-, based on the total amount of -C₂H₄-O- and -C₃H₆-O- groups in the group -(AO)_x-, is preferably less than 50%, more preferably 45% or less than 45%, especially preferably 40% or less than 40%, and particularly preferably 33% or less than 33%.
In another particularly preferred embodiment of the invention, Y in formula (XI-b) is H. In this particularly preferred embodiment of the invention, the molar amount of the -C₃H₆-O- groups in the group -(AO)_x-, based on the total amount of -C₂H₄-O- and -C₃H₆-O- groups in the group -(AO)_x-, is preferably 20 to less than 50%, more preferably 33 to 45%, and especially preferably 33 to 40%.
If Y has a definition other than H, the molar amount of the -C₃H₆-O- groups in the group -(AO)_x-, based on the total amount of -C₂H₄-O- and -C₃H₆-O- groups in the group -(AO)_x-, is preferably 20% or less than 20% and more preferably 10% or less than 10%.
In another particularly preferred embodiment of the invention, Y in formula (XI-b) is a saturated alkyl group with 1 to 4 carbon atoms. In this particularly preferred embodiment the molar amount of the -C₃H₆-O- groups in the group -(AO)_x-, based on the total amount of -C₂H₄-O- and -C₃H₆-O- groups in the group -(AO)_x-, is preferably 20% or less than 20% and more preferably 10% or less than 10%.
In another particularly preferred embodiment of the invention, Y in formula (XI-b) is the group -CH₂-CH(OH)-R_b, in which R_b is a linear or branched saturated alkyl group having 8 to 22 and preferably 8 to 20 carbon atoms. In this particularly preferred embodiment of the invention the molar amount of the -C₃H₆-O- groups in the group -(AO)_x-, based on the total amount of -C₂H₄-O- and -C₃H₆-O- groups in the group -(AO)_x-, is preferably 20% or less than 20% and more preferably 10% or less than 10%. In this particularly preferred embodiment of the invention the group -(AO)_x- especially preferably consists of one or more -C₂H₄-O- groups and contains no -C₃H₆-O- groups.
In another particularly preferred embodiment of the invention, the group -(AO)_x- in formula (XI-b) comprises on molar average 8 -C₂H₄-O- groups and 4 -C₃H₆-O-groups and R_a is a linear or branched saturated alkyl group having 12 to 15 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 12 to 15 carbon atoms.
The one or more nonionic surfactants of component Z5) of the dishwasher detergents of the invention have with particular preference a cloud point of 40 to 60°C.
The variable "x" in the one or more compounds of the formula (XI-b) preferably represents molar averages, meaning that the dishwasher detergents of the invention may comprise a plurality of compounds of the formula (XI-b) having different degrees of alkoxylation.
Extraordinarily preferred are dishwasher detergents of the invention wherein at least one surfactant of the one or more surfactants, and preferably the one or more surfactants of component Z5) of the dishwasher detergents of the invention are selected from the group consisting of the end-capped fatty alcohol ethoxylates of the formula (XI-c)

R_aO-(AO)_x-Y (XI-c)

in which

Examples of the alkyl and alkenyl groups R_a in the formula (XI-c) are, for example, the alkyl and alkenyl groups of the following alcohols R_a-OH: 1-octanol (caprylyl alcohol), 2-ethylhexanol, 1-nonanol (pelargon alcohol), 1-decanol (caprinyl alcohol), 1-undecanol, 1-dodecanol (lauryl alcohol), 1-tridecanol, isotridecanol, 1-tetradecanol (myristyl alcohol), 1-pentadecanol, 1-hexadecanol (cetyl alcohol), cis-9-hexadecen-1-ol (palmitoleyl alcohol), 1-heptadecanol, 1-octadecanol (stearyl alcohol), cetearyl alcohol, 16-methylheptadecan-1-ol (isostearyl alcohol), 9E-octadecen-1-ol (elaidyl alcohol), cis-9-octadecen-1-ol (oleyl alcohol), oleyl cetyl alcohol (i.e., a mixture of oleyl alcohol and cetyl alcohol), 9Z,12Z-octadecadien-1-ol (linoleyl alcohol), 9E,12E-octadecadien-1-ol (elaidolinoleyl alcohol), 9Z,12Z,15Z-octadecatrien-1-ol (linolenyl alcohol), 9E,12E,15E-octadecatrien-1-ol (elaidolinolenyl alcohol), 1-nonadecanol, and 1-eicosanol (arachidyl alcohol), or mixtures thereof.
R_a in formula (XI-c) is preferably a linear or branched saturated alkyl group having 8 to 18 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 18 carbon atoms.
Preferably the groups R_a in formula (XI-c) are saturated alkyl groups.
In formula (XI-c), x is preferably a number from 16 to 24 and more preferably from 19 to 23.
Examples of the linear or branched saturated alkyl groups R_b in the compounds of the formula (XI-c) include the examples specified above for the saturated alkyl group R_a in the compound of the formula (XI-c). Further examples are the alkyl groups heneicosyl and behenyl.
The variable "x" in the one or more compounds of the formula (XI-c) preferably represents molar averages, meaning that the dishwasher detergents of the invention may comprise a plurality of compounds of the formula (XI-c) having different degrees of alkoxylation.
In a preferred embodiment, the dishwasher detergent of the invention further comprises one or more further surfactants as component Z5), which optionally may also be on a magnesium carbonate carrier (optionally the magnesium carbonate carrier of component Z1)).
Such optional further surfactants are preferably selected from the group consisting of the N-acylglucamides, which are also known as N-1-deoxysorbityl-fatty acid amides or glucamides, of the formula (XII)
in which

Rb: is a linear or branched saturated alkyl group having 11 to 21 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 11 to 21 carbon atoms, and
Rc: is hydrogen or a linear or branched saturated alkyl group having 1 to 4 carbon atoms and preferably a methyl or an ethyl group.

In the one or more N-acylglucamides of the formula (XII), Rc is more preferably a methyl group.
In the one or more N-acylglucamides of the formula (XII), Rb is preferably a linear or branched saturated alkyl group having 11 to 17 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 11 to 17 carbon atoms.
In the one or more N-acylglucamides of the formula (XII), Rb is more preferably a linear or branched saturated alkyl group having 15 to 17 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 15 to 17 carbon atoms.
In one particularly preferred embodiment of the invention, 50 wt.-% or more, preferably 60 to 99 wt.-%, and more preferably 70 to 98 wt.-%, of the groups Rb in the one or more N-acylglucamides of the formula (XII) are linear or branched saturated alkyl groups having 17 carbon atoms.
In a further particularly preferred embodiment of the invention, 0.1 to 50 wt.-%, preferably 0.5 to 40 wt.-%, and more preferably 1.0 to 30 wt.-% of the groups Rb in the one or more N-acylglucamides of the formula (XII) are linear or branched saturated alkyl groups having 15 carbon atoms.
In a further particularly preferred embodiment of the invention, 50 wt.-% or more of the groups Rb in the one or more N-acylglucamides of the formula (XII) are linear or branched unsaturated alkenyl groups having one or more double bonds.
In one exceptionally preferred embodiment of the invention, 50 wt.-% or more, preferably 80 wt.-% or more and more preferably 90 wt.-% or more of the groups Rb in the one or more N-acylglucamides of the formula (XII) are linear or branched unsaturated alkenyl groups having one or more double bonds and 17 carbon atoms.
In the one or more N-acylglucamides of the formula (XII), Rb preferably is a linear group.
In another particularly preferred embodiment of the invention, RbCO in the one or more N-acylglucamides of the formula (XII) derives from lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid or linolenic acid, preferably from stearic acid, oleic acid, linoleic acid or linolenic acid, more preferably from oleic acid, linoleic acid or linolenic acid, and especially preferably from oleic acid.
Further surfactants which may optionally be comprised in a dishwasher detergent of the present invention as component Z5) (optionally also on a magnesium carbonate carrier such as, e.g., that of component Z1)) may preferably be selected from the group consisting of the glycerol triester ethoxylates of formula (I)
wherein R¹, R² and R³ are equal or different and are independently selected from linear or branched saturated alkyl groups having 7 to 25 carbon atoms or linear or branched unsaturated alkenyl groups having one or more double bonds and 7 to 25 carbon atoms;
m, n and o are equal or different and are each independently a number from 1 to 200, preferably from 1 to 80, more preferably from 2 to 70, with the proviso that the number-average of the sum of m + n + o is greater than 5, preferably from 20 to 70, more preferably from 30 to 60.
Particularly preferred are dishwasher detergents of the invention, wherein at least one surfactant of the one or more surfactants, and preferably the one or more surfactants of component Z5) of the dishwasher detergents of the invention are selected from the group consisting of the glycerol triester ethoxylates of formula (I)
prepared from ethylene oxide and one or more triglycerides of formula (II)
in the presence of a calcium catalyst (C), wherein
R¹, R² and R³ in formulae (I) and (II) are equal or different and are independently selected from linear or branched saturated alkyl groups having 7 to 25 carbon atoms or linear or branched unsaturated alkenyl groups having one or more double bonds and 7 to 25 carbon atoms;
m, n and o in formula (I) are equal or different and are each independently a number from 1 to 200, preferably from 1 to 80, more preferably from 2 to 70, with the proviso that the number-average of the sum of m + n + o is greater than 5, preferably from 20 to 70, more preferably from 30 to 60; and
the calcium catalyst (C) is a catalyst obtainable by a reaction involving

(A) calcium hydroxide and
(B) a carboxylic acid comprising 3 to 40 carbon atoms,

The variables "m", "n" and "o" in the one or more compounds of the formula (I) preferably represent molar averages, meaning that the dishwasher detergents of the invention may comprise a plurality of compounds of the formula (I) having different degrees of ethoxylation.
Further surfactants which may optionally be comprised in a dishwasher detergent of the present invention as component Z5) (optionally also on a magnesium carbonate carrier such as, e.g., that of component Z1)) may preferably be selected from the group consisting of the surfactants of formulae (VII), (VIII) and/or (IX)

wherein
each R¹⁰ group is independently selected from linear or branched, preferably linear, saturated alkyl groups having 1 to 6 carbon atoms, linear or branched, preferably linear, unsaturated alkenyl groups having one or more double bonds and 2 to 6 carbon atoms, and linear or branched, preferably linear, saturated hydroxyalkyl groups having 1 to 6 carbon atoms;
each R¹¹ group is independently selected from linear or branched saturated alkyl groups having 8 to 28 carbon atoms, linear or branched unsaturated alkenyl groups having one or more double bonds and 8 to 28 carbon atoms;
R¹² is the same as R¹⁰ or (CH₂)_n-T-R¹¹;
R¹³ is the same as R¹⁰, R¹¹ or (CH₂)_n-T-R¹¹;
T is selected from -CH₂-, -O-CO- or -CO-O-;
q is an integer from 0 to 5;
n is an integer from 0 to 5;
X is an inorganic or organic anion having the charge b-;
b is a number from 1 to 4; and
c is a number having a value of 1/b.
Further surfactants which may optionally be comprised in a dishwasher detergent of the present invention as component Z5) (optionally also on a magnesium carbonate carrier such as, e.g., that of component Z1)) may preferably be selected from the group consisting of the compounds of formula (X)
wherein

R14: is a linear or branched, preferably linear, saturated alkyl group having from 1 to 6 carbon atoms;
R15, R16 and R17: are equal or different and are independently selected from the group consisting of hydrogen, linear or branched saturated alkyl groups having from 1 to 18 carbon atoms, linear or branched unsaturated alkenyl groups having one or more double bonds and from 2 to 18 carbon atoms, and -CO-R¹⁸;
R18: is a linear or branched saturated alkyl group having 7 to 19 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 7 to 19 carbon atoms;
r, s and t: are equal or different and are independently a number from 0 to 50;
X: is an inorganic or organic anion having the charge b-;
b: is a number from 1 to 4; and
c: is a number having a value of 1/b;

¹⁵

¹⁶

¹⁷

¹⁸

¹⁵

¹⁶

¹⁷

Particularly preferred are dishwasher detergents of the invention, wherein at least one surfactant of the one or more surfactants, and preferably the one or more surfactants of component Z5) of the dishwasher detergents of the invention are selected from the group consisting of the compounds formula (X), wherein

R14: is methyl,
R15, R16 and R17: are equal or different and are independently selected from the group consisting of hydrogen and -CO-R¹⁸; and R¹⁸ is a linear or branched saturated alkyl group having 7 to 19 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 7 to 19 carbon atoms; with the proviso that at least two of the groups R¹⁵, R¹⁶ and R¹⁷ are -CO-R¹⁸ which form an ester moiety with the oxygen atom of an ethoxy group;
r, s and t: are equal or different and are independently a number from 1 to 30; the sum of r + s + t is a number from 3 to 70;
X: is an inorganic or organic anion having the charge b-;
b: is 1, and
c: is 1.

The variables "r", "s" and "t" in the one or more compounds of the formula (X) preferably represent molar averages, meaning that the dishwasher detergents of the invention may comprise a plurality of compounds of the formula (X) having different degrees of ethoxylation.
Further preferred are dishwasher detergents of the invention wherein at least one surfactant of the one or more surfactants, and preferably the one or more surfactants of the component Z5) of the dishwasher detergents of the invention are selected from the group consisting of zwitterionic surfactants and anionic surfactants.
The zwitterionic surfactants are preferably selected from the group consisting of C₈ to C₁₈ (preferably C₁₂ to C₁₈) amine oxides, sulfobetaines and hydroxylbetaines, such as N-alkyl-N,N-dimethylamino-1-propanesulfonate, where the alkyl group may be C₉ to C₁₈, preferably C₁₀ to C₁₄.
The anionic surfactants are preferably selected from alkyl ethoxysulfates having a degree of ethoxylation of more than 3, more preferably 4 to 10, and especially preferably 6 to 8, and a chain length in the range from C₈ to C₁₆ and preferably C₁₁ to C₁₅. Also, branched alkyl carboxylates are preferred if the branching occurs in the middle and the average overall chain length is 10 to 18 and preferably 12 to 16 in the case of a side-chain length of 2 to 4 carbon atoms. One example thereof is 2-butyloctanoic acid. The anionic surfactant is commonly of a type having good solubility in the presence of calcium. Anionic surfactants of this kind are further represented by sulfobetaines, alkyl (polyethoxy)sulfates (AES), short-chain C₆-C₁₀ alkyl sulfates and alkylsulfonates. It has emerged that straight-chain fatty acids are ineffective because of their sensitivity toward calcium.
The dishwasher detergents of the invention comprise the one or more surfactants of component Z5) preferably in amounts of 0 to 15 wt.-%, more preferably in amounts of 0 to 10 wt.-%, especially preferably in amounts of 0.5 to 7 wt.-% and particularly preferably in amounts of 3 to 7 wt.-%, based in each case on the total weight of the dishwasher detergent of the invention.

Additives (Component Z6)

The dishwasher detergents of the invention may comprise further ingredients which are commonly used in dishwasher detergents. In a further preferred embodiment of the invention, the dishwasher detergents of the invention comprise one or more substances selected from the group consisting of complexing agents, water, organic solvents, thickeners, foam inhibitors, color particles, silver protectants, agents for preventing the tarnishing of silver, dyes, fillers, microbicides, hydrotropes, antioxidants, enzyme stabilizers, fragrances, solubilizers, carrier materials, processing assistants, pigments, and pH modifiers.

Builders

The dishwasher detergents of the invention may also comprise one or more builders.
The builders and also other constituents which may be used in the dishwasher detergents of the invention are described for example in US 2010/0160204 A1 and EP 1 757 676 A1 .
The dishwasher detergents of the invention preferably comprise one or more builders of the group consisting of carbonates, hydrogencarbonates, organic builders, preferably citrate, methylglycinediacetic acid (MGDA), silicates, phosphates, phosphonates, and alkali metal hydroxides.
Preferred is the use of carbonate(s) and/or hydrogencarbonate(s), preferably alkali metal carbonate(s), more preferably sodium carbonate. These compounds are used preferably in amounts of 2 to 50 wt.-%, more preferably of 10 to 30 wt.-%, and especially preferably of 10 to 25 wt.-%, based on the total weight of the dishwasher detergent of the invention.
The organic builders include polycarboxylates, polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, and dextrins.
Useful organic builders include the polycarboxylic acids, which can be used in the form of the free acid and/or the sodium salts thereof, with polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, and nitrilotriacetic acid (NTA), and also mixtures thereof. The free acids typically also possess the property of an acidifying component, as well as their builder effect, and hence also serve to establish a lower and milder pH for the dishwasher detergents of the invention. Preferred in this context are citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, tartaric acid, and any desired mixtures thereof.
Examples of customary aminocarboxylic acids which are preferred in the context of the present invention are ethylenediaminetetraacetic acid (EDTA), methylglycinediacetic acid (MGDA), and glutaminediacetic acid (GLDA). Mixtures can also be used.
Also to be mentioned as further preferred builders are polymeric aminodicarboxylic acids, their salts, or their precursor substances. Particular preference is given to using polyaspartic acids, their salts and/or their derivatives.
Particularly advantageous for the cleaning and rinse performance of dishwasher detergents of the invention is the use of citric acid and/or citrates in these compositions. Preference is therefore given to dishwasher detergents of the invention which comprise citric acid or a salt of citric acid, in which case the weight fraction of the citric acid or of the salt of citric acid is preferably from 2 to 50 wt.-%, more preferably 5 to 30 wt.-%, and especially preferably 10 to 30 wt.-%, based in each case on the total weight of the dishwasher detergent of the invention.
In another preferred embodiment of the invention, the dishwasher detergents of the invention comprise MGDA as one of their builders. Dishwasher detergents of the invention comprise preferably 0.5 to 25 wt.-% and more preferably 2 to 25 wt.-% of MGDA, based on the total weight of the dishwasher detergent of the invention.
Also suitable as organic builders are polymeric carboxylates. These are, for example, the alkali metal salts of polyacrylic acid or of polymethacrylic acid, examples being those having a relative molecular mass of 500 to 70 000 g/mol.
Suitable polymeric carboxylates are, in particular, polyacrylates, preferably having a molecular mass of 2000 to 20 000 g/mol. By virtue of their superior solubility, preference may be given in turn, from this group, to the short-chain polyacrylates having molar masses of 2000 to 10 000 g/mol and more preferably of 3000 to 5000 g/mol.
Additionally, suitable are copolymeric carboxylates. Suitable co-monomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid, and citraconic acid. Especially suitable are copolymeric carboxylates of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and/or fumaric acid. Having proved particularly suitable are copolymers of acrylic acid with maleic acid which contain 50 to 90 wt.-% of acrylic acid and 10 to 50 wt.-% of maleic acid. Their relative molecular mass, based on free acids, is preferably 2000 to 70 000 g/mol, more preferably 20 000 to 50 000 g/mol, and especially preferably 30 000 to 40 000 g/mol.
It is also possible to use copolymers of at least one monomer from the group consisting of monoethylenically unsaturated C₃-C₁₀ monocarboxylic and/or C₄-C₁₀ dicarboxylic acids or their anhydrides, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid, and citraconic acid, with at least one hydrophilically or hydrophobically modified monomer as recited below.
Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butane, pentene, hexene, and styrene, olefins having 10 or more carbon atoms or mixtures thereof, such as, for example, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene, and 1-hexacosene, C₂₂ α-olefin, a mixture of C₂₀-C₂₄ α-olefins and polyisobutene having on average 12 to 100 carbon atoms per molecule.
Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups, and also nonionic monomers with hydroxy function or alkylene oxide groups, and optionally further ionic or nonionic monomers.
Examples of the above-recited hydrophilic monomers are allyl alcohol, isoprenol, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, methoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, ethoxypolybutylene glycol (meth)acrylate, and ethoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate. Polyalkylene glycols here may contain 3 to 50, preferably 5 to 40, and more preferably 10 to 30 alkylene oxide units per molecule.
Particularly preferred monomers containing sulfonic acid groups here are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (2-acryloylamino-2-methylpropanesulfonic acid), 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide, and also salts of the stated acids, such as their sodium, potassium or ammonium salts.
Particularly preferred monomers containing phosphonate groups are vinylphosphonic acid and its salts.
Furthermore, amphoteric polymers may also be used as builders.
If the dishwasher detergents of the invention comprise one or more (co)polymeric carboxylates, the amount of these (co)polymeric carboxylates in the dishwasher detergent of the invention is preferably 0.5 to 20 wt.-% and more particularly 3 to 10 wt.-%, based on the total weight of the dishwasher detergent of the invention.
Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediaminedisuccinate, are also further preferred organic builders, which are frequently also referred to as cobuilders. In this case, ethylenediamine-N,N'-disuccinate (EDDS) is used preferably in the form of its sodium or magnesium salts. Further preferred as builder or co-builder in this context are also glyceroldisuccinates and glyceroltrisuccinates.
Dishwasher detergents of the invention may as builders preferably comprise crystalline sheet-like sodium silicates of the formula NaMSi_xO_2x+1 · yH₂O, in which M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values for x being 2, 3 or 4, and y is a number from 0 to 33, preferably 0 to 20.
The dishwasher detergents of the invention comprise preferably a weight fraction of the crystalline sheet-like silicate of the formula NaMSi_xO_2x+1 · yH₂O of 0.1 to 20 wt.-%, more preferably of 0.2 to 15 wt.-%, and especially preferably of 0.4 to 10 wt.-%, based in each case on the total weight of the dishwasher detergents of the invention.
Also employable are amorphous sodium silicates having a Na₂O:SiO₂ modulus of 1:2 to 1:3.3, preferably of 1:2 to 1:2.8, and more preferably of 1:2 to 1:2.6, which are preferably dissolution-retarded and have secondary cleaning properties. Retarded dissolution relative to conventional amorphous sodium silicates may have been brought about in a variety of ways, as for example by surface treatment, compounding, compacting, densification, or by overdrying. For the purposes of this invention, the term "amorphous" is understood to mean that in x-ray diffraction experiments, the silicates provide none of the sharp x-ray reflections of the kind typical of crystalline substances, but instead invoke at most one or more maxima in the scattered x-radiation, with a latitude of several degree units of the diffraction angle.
Alternatively, or in combination with the aforesaid amorphous sodium silicates, x-ray-amorphous silicates are used, whose silicate particles in electron diffraction experiments yield indistinct or even sharp diffraction maxima. This is to be interpreted to mean that the products have microcrystalline regions of ten to several hundred nm in size, with preference being given to values up to a maximum of 50 nm and more particularly up to a maximum of 20 nm. X-ray-amorphous silicates of this kind likewise have retarded dissolution in relation to the conventional waterglasses. Especially preferred are densified/compacted amorphous silicates, compounded amorphous silicates, and overdried x-ray-amorphous silicates.
In accordance with the present invention it is preferred for these silicates, preferably alkali metal silicates, more preferably crystalline or amorphous alkali metal disilicates, to be present in the dishwasher detergents of the invention in amounts of 3 to 60 wt.-%, preferably of 8 to 50 wt.-%, and more particularly of 20 to 40 wt.-%, based in each case on the total weight of the dishwasher detergent of the invention.
The phosphates have proven to be effective builders in relation to the cleaning performance. Among the multiplicity of phosphates available commercially, the greatest significance in the detergents industry is possessed by the alkali metal phosphates, especially pentasodium and/or pentapotassium triphosphate (sodium and/or potassium tripolyphosphate).
Alkali metal phosphates here is the overarching designation for the alkali metal salts (especially sodium and potassium salts) of the various phosphoric acids, among which it is possible to differentiate metaphosphoric acids (HPO₃)_m and orthophosphoric acid H₃PO₄, as well as representatives of higher molecular mass. The phosphates here unite a number of advantages: they act as alkali metal carriers, prevent limescale deposits on machine components, and contribute to the cleaning performance.
Phosphates particularly important technically are pentasodium triphosphate Na₅P₃O₁₀ (sodium tripolyphosphate) and also the corresponding potassium salt pentapotassium triphosphate K₅P₃O₁₀ (potassium tripolyphosphate). Also used preferably in accordance with the invention are the sodium potassium tripolyphosphates.
Where phosphates are used in the dishwasher detergents of the invention, preferred compositions comprise phosphate(s), preferably alkali metal phosphate(s), more preferably pentasodium and/or pentapotassium triphosphate (sodium and/or potassium tripolyphosphate), in amounts of 2 to 50 wt.-%, preferably of 2 to 30 wt.-%, more preferably of 3 to 25 wt.-%, and especially preferably of 3 to 15 wt.-%, based in each case on the weight of the dishwasher detergent of the invention.
Further builders which the dishwasher detergents of the invention may comprise are one or more phosphonates, which are frequently also referred to as cobuilders. The weight fraction of phosphonate, based on the total weight of the dishwasher detergent of the invention, is preferably 0.5 to 20 wt.-% and more preferably 1.0 to 10 wt.-%.
The complex-forming phosphonates embrace a series of different compounds such as, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta(methylenephosphonic acid) (DTPMP). Particularly preferred are hydroxyalkane- and aminoalkanephosphonates. Among the hydroxyalkanephosphonates, particular significance, preferably as a cobuilder, is possessed by 1-hydroxyethane-1,1-diphosphonate (HEDP). It is used preferably as the sodium salt, with the disodium salt giving a neutral reaction and the tetrasodium salt an alkaline reaction (pH 9). Suitable aminoalkanephosphonates include ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and also their higher homologs. They are used preferably in the form of the neutrally reacting sodium salts (e.g., as the hexasodium salt of EDTMP and/or as the hepta- and octasodium salt of DTPMP). From the class of the phosphonates, preference is given to using HEDP.
Dishwasher detergents of the invention may comprise alkali metal hydroxides as further builders. These alkali metal carriers are preferably used only in small amounts, preferably in amounts of 10 wt.-% or less, more preferably 6 wt.-% or less, especially preferably 5 wt.-% or less, particularly preferably 0.1 to 5 wt.-%, and exceptionally preferably 0.5 to 5 wt.-%, based on the total weight of the dishwasher detergent of the invention.
In a further preferred embodiment of the invention, the dishwasher detergents of the invention comprise one or more builders from the group of the organic builders. In one particularly preferred embodiment of the invention, the dishwasher detergents of the invention comprise one or more builders from the group consisting of citrate, methylglycinediacetic acid (MGDA), and ethylenediamine-N,N'-disuccinate (EDDS). In an especially preferred embodiment of the invention the dishwasher detergents of the invention comprise MGDA.
The dishwasher detergents of the invention may comprise the aforesaid builders either individually or else in the form of mixtures of two, three, four or more builders.
In one preferred embodiment of the invention the dishwasher detergents of the invention comprise no phosphate builders and no phosphate-based builders and preferably are phosphate-free.
The dishwasher detergents of the invention comprise the one or more builders preferably in amounts of 2 to 50 wt.-%, more preferably in amounts of 10 to 30 wt.-%, and especially preferably in amounts of 10 to 25 wt.-%, based in each case on the total weight of the dishwasher detergent of the invention.
A protein and/or enzyme may be protected, particularly during storage, against forms of damage such as inactivation, denaturing or disintegration (as a result, for example, of physical influences, oxidation or proteolytic cleavage). Where the proteins and/or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, especially if the dishwasher detergents of the invention also comprise proteases. Dishwasher detergents of the invention may comprise stabilizers for this purpose. The provision of such agents in dishwasher detergents of the invention represents a preferred embodiment of the present invention.
Preference is given in particular to those dishwasher detergents which comprise 0.1 to 12 wt.-%, more preferably 0.2 to 10 wt.-%, and especially preferably 0.5 to 8 wt.-%, of enzyme preparation, based in each case on the total weight of the dishwasher detergent of the invention.
The cleaning performance of dishwasher detergents of the invention may be improved through the addition of organic solvents. In one preferred embodiment of the present invention, therefore, dishwasher detergents of the invention comprise at least one organic solvent. Preferred liquid dishwasher detergents of the invention comprise organic solvent in amounts of 0.2 to 15 wt.-%, more preferably in amounts of 0.5 to 12 wt.-%, and especially preferably in amounts of 1.0 to 10 wt.-%, based in each case on the total weight of the dishwasher detergent of the invention.
These organic solvents are, for example, monoalcohols, diols, triols, polyols, ethers, esters and/or amides. Particularly preferred here are organic solvents which are water-soluble, with "water-soluble" solvents in the sense of the present specification being solvents which at room temperature are miscible with water completely (i.e., without a miscibility gap).
The organic solvents from the group of the organic amines and/or the alkanolamines are effective in relation to the cleaning performance and especially in relation to the cleaning performance on bleachable stains, particularly on tea stains.
The dishwasher detergents of the invention may have thickeners added to them. In the dishwasher detergents of the invention it is possible to use the thickeners that are typically used in dishwasher detergents.
The respective dishwasher detergents of the invention advantageously comprise the thickener in amounts which are preferably from 0.1 to 8 wt.-%, more preferably from 0.2 to 6 wt.-%, and especially preferably from 0.4 to 4 wt.-%, based on the total weight of the dishwasher detergent of the invention.
The foam inhibitors, color particles, silver protectants, agents for preventing the tarnishing of silver, metal corrosion inhibitors, dyes, fillers, microbicides, hydrotropes, antioxidants, enzyme stabilizers, fragrances, solubilizers, carrier materials, processing assistants, pigments, and pH modifiers may be selected from the corresponding substances which are typically used in dishwasher detergents.

Tableting aids (Component Z7)

As used herein, a tableting aid may be understood in the broadest sense as generally understood in the art. Typically, a tableting agent supports the formation of a compact and cohesive tablet when formed from the other ingredients. In a preferred embodiment, the tableting aid is selected from one or more types of polyethylene glycol (PEG), one or more polysaccharides (e.g., cylclodextrine, starch, cellulose) and derivatives thereof (e.g., methyl cellulose, hydroxymethyl cellulose, starch derivatives). In a preferred embodiment, the tableting aid has a mean molecular weight (e.g., determined by means of size exclusion chromatography) of more than 500 Da, of more than 100 Da, or of more than 5000 Da.

Polymers others than component Z7 (Component Z8)

Suitable polymers of component Z8) include washing or cleaning-active polymers, for example rinse aid polymers and/or polymers which act as softeners. In general, the dishwasher detergent of the present invention may include, as polymers of component Z8), nonionic, cationic, anionic and/or amphoteric polymers.
Cationic polymers in the context of the present invention are polymers which 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 dialkylaminoacrylates and methacrylates, vinylpyrrolidone-methoimidazolinium chloride copolymers, quaternized polyvinyl alcohols, or polymers having the INCI names polyquaternium 2, polyquaternium 17, polyquaternium 18 and polyquaternium 27.
If cationic polymers are used in component Z8), they are preferably selected from copolymers comprising polyalkylene oxide groups and quaternary nitrogen atoms. More preferably the cationic polymers of component Z8) are copolymers comprising 0.1 to 99.9 mol-%, preferably 20.0 to 80.0 mol-%, more preferably 22.0 to 77.6 mol-% of one or more cationic structural units (D); and
0.1 to 99.9 mol-%, preferably 0.4 to 20.0 mol-%, more preferably 0.5 to 4.4 mol-% of one or more macromonomeric structural units (E),
wherein the one or more cationic structural units (D) are represented by the following general formulae (XI) and/or (XII):

wherein R¹⁹ and R²¹ are equal or different and are independently selected from hydrogen and/or a methyl group;
R²⁰, R²², R²³ and R²⁴ are equal or different and are independently selected from the group consisting of hydrogen, an aliphatic hydrocarbon residue having 1 to 20, preferably 1 to 4 carbon atoms, a cycloaliphatic hydrocarbon residue having 5 to 20, preferably 5 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms and/or polyethylene glycol (PEG), and preferably are equal or different and independently selected from the group consisting of hydrogen and/or methyl, and particularly preferably are methyl;
Y is the same or different and is selected from oxygen, NH and/or NR²²,
V is the same or different and is selected from -(CH₂)_x-,
x is the same or different and is a number from 1 to 6;
X and X₁ are equal or different and are independently selected from a halogen atom, C₁ to C₄-alkylsulfate and/or C₁ to C₄ alkylsulfonate; and
the one or more macromonomeric structural units (E) are represented by the following general formula (XIII):
wherein

R25: is the same or different and is H and/or methyl;
Z: is the same or different and is C=O and/or O(CH₂)₄, preferably O(CH₂)₄,
u: is, on molar average, a number from 0 to 7, preferably from 0 to 6; and
v: is, on molar average, a number from 1 to 150, preferably from 11 to 150, more preferably from 12 to 150.

In these cationic polymers the molar amounts of the structural units (D) and (E) are based on the total weight of the cationic polymer.
The cationic polymers comprising structural units (D) and E) may preferably also comprise structural units resulting from the polymerization of further monomers such as further nonionic monomers, preferably amides and more preferably N,N-dimethyl acrylamide.
Amphoteric polymers in the context of the present invention have, alongside positively charged groups, also negatively charged groups or monomeric units in the polymer chain. These negatively charged groups or monomeric units may be derived, e.g. from carboxylic acids, sulfonic acids ot phosphonic acids.
Preferable amphoteric polymers applicable in component Z8) of the dishwasher detergent of the invention are selected from the group consisting of alkylacrylamide/acrylic acid-copolymers, alkylacrylamide/methacrylic acid copolymers, alkylacrylamide/methylmethacrylic acid copolymers, alkylacrylamide/acrylic acid/alkyl aminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/methacrylic acid/alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/methylmethacrylic acid/alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/alkylmethacrylate/alkylaminoethylmethacrylate/alkylmethacrylate copolymers, and copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or not-ionogenic monomers. Further preferably applicable amphoteric polymers are selected from the group consisting of acrylamidoalkyl-trialkylammonium chloride/acrylic acid copolymers and their alkaline metal or ammonium salts, acrylamidoalkyl-trialkylammonium chloride/methacrylic acid copolymers and their alkaline metal or ammonium salts, and methacroylethylmetaine/methacrylate copolymers.
If the dishwasher detergent of the invention contains cationic and/or amphoteric polymers in component Z8), these polymers are preferably present in amounts of from 0.01 to 10 wt.-%, based on the total weight of the dishwasher detergent of the invention. In the context of the present invention, preference is given to those dishwasher detergents, in which the weight fraction of the cationic and/or amphoteric polymers is from 0.01 to 8 wt.-%, preferably 0.01 to 4 wt.-%, more preferably from 0.01 to 2 wt.-%, especially preferably 0.01 to 1 wt.-%, based on the total weight of the dishwasher detergent of the invention.
Another group of preferably applicable polymers applicable in component Z8) of the dishwasher detergent of the invention are alkoxylated polyalkyleneimines.
Alkoxylated polyalkyleneimines have a polyalkyleneimine backbone and alkoxy chains. Preferably, the polyalkyleneimine is polyethyleneimine. More preferably, the alkoxylated polyalkyleneimine is not quaternized.
If the dishwasher detergent comprises alkoxylated polyalkyleneimines in component Z8), it preferably comprises from 1% to 10 wt.-%, more preferably from 1% to 8 wt.-% of alkoxylated polyalkyleneimines, based on the total weight of the dishwasher detergent of the invention.
Preferably, the alkoxylated polyalkyleneimine used in component Z8) comprises 0.5 to 40 wt.-%, more preferably 1 to 30 wt.-%, especially preferably 2 to 20 wt.-% of the polyalkyleneimine backbone and
60 to 99 wt.-%, more preferably 60 to 95 wt.-%, especially preferably from 60 to 90 wt.-% of the alkoxy chains.
Preferably, the alkoxy chains have an average of from about 1 to about 50, more preferably from about 2 to about 40, especially preferably from about 3 to about 30, particularly preferably from about 3 to about 20, and exceptionally preferably from about 4 to about 15 alkoxy units, which are preferably ethoxy units. In other suitable alkoxylated polyalkyleneimines for use in component Z6), the alkoxy chains have an average of from about 0 to 30, more preferably from about 1 to about 12, especially preferably from about 1 to about 10 and particularly preferably from about 1 to about 8 propoxy units. Exceptionally preferred are alkoxylated polyethyleneimines wherein the alkoxy chains comprise a combination of ethoxy and propoxy chains, in particular polyethyleneimines comprising chains of from 4 to 20 ethoxy units and from 0 to 6 propoxy units.
Preferably, the alkoxylated polyalkyleneimine is obtained from alkoxylation wherein the starting polyalkyleneimine has a weight-average molecular weight of from about 100 to about 60,000, preferably from about 200 to about 40,000, more preferably from about 300 to about 10,000 g/mol. In a preferred embodiment, a polyethyleneimine with a weight average molecular weight of 600 g/mol ethoxylated with 20 EO groups per NH group is used as the alkoxylated polyalkyleneimine.
Other suitable polyalkyleneimines for applicable in component Z8) of the dishwasher detergent of the invention include compounds having the following general structure: bis((C₂H₅O)(C₂H₄O)_n)(CH₃)-N⁺-C₂H_2x-N⁺-(CH₃)-bis((C₂H₅O)(C₂H₄₀)_n), wherein n is a number from 20 to 30, and x is a number from 3 to 8, or sulfated or sulfonated variants thereof.
In a preferred embodiment, the dishwasher detergent of the invention comprises 0.5 to 30 wt.-%, preferably 1 to 25 wt.-%, more preferably 2 to 20 wt.-%, especially preferably 3 to 15 wt.-%, and particularly preferably 5 to 10 wt.-% of component Z1), based in each case on the total weight of the dishwasher detergent of the invention. In an alternative preferred embodiment, the dishwasher detergent of the invention comprises 7 to 20 wt.-%, preferably 10 to 18 wt.-%, and more preferably 12 to 15 wt.-% of component Z1), based in each case on the total weight of the dishwasher detergent of the invention.
In a preferred embodiment, ratio of surfactant which is on magnesium carbonate to magnesium carbonate is in the range of 0.1 : 10 to 10: 0.1, or in the range of 0.5 : 5 to 5: 0.5, or in the range of 0.7 : 2 to 2: 0.7.
In a preferred embodiment, the dishwasher detergent comprises 0.1 to 20 wt.-%, preferably 0.5 to 15 wt.-%, more preferably 5 to 10 wt.-%, especially preferably 2 to 5 wt.-%, and particularly preferably 3 to 4 wt.-% of surfactant which is comprised on magnesium carbonate in component Z1), based in each case on the total weight of the dishwasher detergent of the invention.
In a preferred embodiment, the dishwasher detergent comprises 1 x 10^-6 to 5 wt.-% of component Z2), based on the total weight of the dishwasher detergent of the invention.
In a preferred embodiment, the dishwasher detergent comprises 0.01 to 10 wt.-%, preferably 0.1 to 5 wt.-%, more preferably 0.2 to 4 wt.-%, even more preferably 0.4 to 3 wt.-%, 0.5 to 2 wt.-% or 0.2 to 1 wt.-%, of component Z3), based in each case on the total weight of the dishwasher detergent of the invention,.
In a preferred embodiment, the dishwasher detergent comprises 0 to 40 wt.-%, preferably 1 to 40 wt.-%, more preferably 2 to 20 wt.-%, even more preferably 5 to 10 wt.-%, of component Z4), based in each case on the total weight of the dishwasher detergent of the invention.
In a preferred embodiment, the dishwasher detergent comprises 0 to 50 wt.-%, preferably 0 to 15 wt.-%, more preferably 0 to 10 wt.-%, even more preferably 0.5 to 7 wt.-%, and especially preferably 3 to 7 wt.-%, of component Z5), based in each case on the total weight of the dishwasher detergent of the invention.
In a preferred embodiment, the dishwasher detergent comprises 0 to 80 wt.-%, preferably 0 to 70 wt.-%, more preferably 0 to 60 wt.-%, of component Z6), based in each case on the total weight of the dishwasher detergent of the invention (e.g., including 2 to 50 wt.-% of one or more builders, based on the total weight of the dishwasher detergent).
In a preferred embodiment, the dishwasher detergent comprises 0 to 50 wt.-%, preferably 0.1 to 40 wt.-%, more preferably 0.5 to 20 wt.-%, even more preferably 1 to 10 wt.-%, of component Z7), based in each case on the total weight of the dishwasher detergent of the invention.
In a preferred embodiment, the dishwasher detergent comprises 0 to 10 wt.-%, of component Z8), based on the total weight of the dishwasher detergent of the invention.
With particular preference the dishwasher detergents of the invention comprise

Z1) 0.5 to 30 wt.-%, preferably 1 to 25 wt.-%, more preferably 2 to 20 wt.-%, especially preferably 3 to 15 wt.-%, and particularly preferably 5 to 10 wt.-% of component Z1),
Z2) 1 x 10^-6 to 5 wt.-% of component Z2), and
Z3) 0.01 to 10 wt.-%, preferably 0.1 to 5 wt.-%, preferably 0.2 to 4 wt.-%, preferably 0.4 to 3 wt.-%, preferably 0.5 to 2 wt.-% or 0.2 to 1 wt.-%, of component Z3), and optionally
Z4) 0 to 40 wt.-% of component Z4), and optionally
Z5) 0 to 50 wt.-%, preferably 0 to 15 wt.-%, preferably 0 to 10 wt.-%, more preferably 0.5 to 7 wt.-%, and especially preferably 3 to 7 wt.-% of component Z5), and optionally
Z6) 0 to 80 wt.-%, preferably 0 to 70 wt.-%, preferably 0 to 60 wt.-%, more of component Z6), and optionally
Z7) 0 to 50 wt.-%, preferably 0.1 to 40 wt.-%, preferably 0.5 to 20 wt.-%, preferably 1 to 10 wt.-%, of component Z7), and optionally
Z8) 0 to 10 wt.-% of component Z8),

The dishwasher detergents of the invention may be produced in solid form and also as a combination of solid and liquid presentation forms.
Preferred dishwasher detergents of the invention are those which are solid at 20°C or in which at least one phase is solid. Suitable solid presentation forms include, in particular, powders, granules, extrudates or compacts, especially tablets, in single-phase or multiphase form. Tablets are formulated for single-dose applications. The solid compositions of the invention preferably comprise 20 wt.-% or less than 20 wt.-% of water, more preferably 0.1 to 20 wt.-% of water, and especially preferably 0.5 to 5 wt.-% of water, based in each case on the total weight of the dishwasher detergent of the invention. In another preferred embodiment of the invention, the dishwasher detergents of the invention are anhydrous.
In one especially preferred embodiment of the invention, the dishwasher detergent of the invention is solid at 20°C and is in the form of a tablet.
Preference is also given to detergent compositions for machine dishwashing according to the invention, which comprise dishwasher detergents of the invention and are enclosed in a water-soluble foil, preferably a polyvinyl alcohol containing foil.
In the context of the present invention, the term "water soluble foil" means that the foil comprises a water-soluble polymer, copolymer or mixtures thereof in a weight fraction of at least 90 wt.-%, based on the weight of the foil. Water soluble polymers in the context of the present invention are polymers which are soluble in water at 25°C to an amount of more than 2.5 wt.-%, based on the amount of water.
Preferable materials of the water soluble foil are at least partially composed of a substance selected from the group consisting of polyvinyl alcohols, acetalized polyvinyl alcohols, polyvinylpyrrolidones, gelatine, polyvinyl alcohols substituted with sulfate, carbonate and/or citrate, polyalkylene oxides such as polyethylene oxides, acrylamides, cellulose esters, cellulose ethers, celullose amides, cellulose, polyvinyl acetate, polycarboxylic acids and their salts, polyaminoacids or peptides, copolymers of acrylamides and (meth)acrylic acid, polysaccharides such as starch or guar derivatives, and compounds with the INCI names polyquaternium 2, polyquaternium 17, polyquaternium 18 and polyquaternium 27. In a particularly preferred embodiment, the material of the water-soluble foil comprises polyvinyl alcohol.
In a further preferred embodiment of the invention, the material of the water-soluble foil comprises mixtures of different substances, such as copolymers. Such mixtures enable the adjustment of the mechanical properties of the foil and the container formed thereof and may affect the degree of water solubility. Preferably, the water-soluble foil contains at least one polyvinyl alcohol and/or at least one polyvinyl alcohol copolymer.
A further subject of the invention is a method for cleaning dishware in a dishwasher, wherein soiled dishware is treated in a dishwasher with an aqueous alkaline composition comprising a dishwasher detergent of the invention.
In the method of the invention for cleaning dishware, the pH of the aqueous alkaline composition is preferably 8 or more and more preferably 9 or more.
The dishwasher detergent of the invention or surfactants on magnesium carbonate carrier Z1) of the dishwasher detergents of the invention may be advantageously suitable as rinse agent in machine dishwashing, preferably in a method of the invention for cleaning dishware in a dishwasher.
A further subject of the present invention is therefore the use of a dishwasher detergent of the invention or of one or more surfactants on magnesium carbonate carrier Z1) of the dishwasher detergents of the invention may be for use as a rinse agent in machine dishwashing, preferably in a method of the invention for cleaning dishware in a dishwasher.
The dishwasher detergents of the invention or the one or more surfactants on magnesium carbonate carrier Z1) of the dishwasher detergents of the invention are advantageously suitable for improving the wettability of dishware, for reducing the spotting and filming on dishware, for reducing, minimizing or preventing fatty residues in the machine department of an automatic dishwashing machine, for improving the rinse performance of a dishwasher detergent, preferably of a dishwasher detergent of the invention, or for improving the drying performance of a dishwasher detergent, preferably of a dishwasher detergent of the invention, more preferably in a method of the invention for cleaning dishware in a dishwasher.
A further subject of the present invention is therefore the use of a dishwasher detergent of the invention or of one or more surfactants on magnesium carbonate carrier Z1) of the dishwasher detergents of the invention for improving the wettability of dishware or for reducing spotting and filming on dishware, preferably in a method of the invention for cleaning dishware in a dishwasher.
A further subject of the present invention is the use of a dishwasher detergent of the invention or of one or more surfactants on magnesium carbonate carrier Z1) of the dishwasher detergents of the invention for reducing, minimizing or preventing fatty residues in the machine department of an automatic dishwashing machine, preferably in a method of the invention for cleaning dishware in a dishwasher.
A further subject of the present invention is the use of a dishwasher detergent of the invention or of one or more surfactants on magnesium carbonate carrier Z1) of the dishwasher detergents of the invention for improving the rinse performance of a dishwasher detergent, preferably of a dishwasher detergent of the invention, more preferably in a method of the invention for cleaning dishware in a dishwasher.
A further subject of the present invention is the use of a dishwasher detergent of the invention or of one or more surfactants on magnesium carbonate carrier Z1) of the dishwasher detergents of the invention for improving the drying performance of a dishwasher detergent, preferably of a dishwasher detergent of the invention, more preferably in a method of the invention for cleaning dishware in a dishwasher.
The preferred embodiments specified above for the dishwasher detergents of the invention are also valid correspondingly for the method of the invention for cleaning dishware in a dishwasher and also for the inventive use of the dishwasher detergents of the invention or of the one or more surfactants on magnesium carbonate carrier Z1) of the dishwasher detergents of the invention as rinse agents in machine dishwashing, for reducing, minimizing or preventing fatty residues in the machine department of an automatic dishwashing machine, for improving the wettability of dishware, for reducing the spotting and filming on dishware, for improving the rinse performance of a dishwasher detergent, preferably of a dishwasher detergent of the invention, and for improving the drying performance of a dishwasher detergent, preferably of a dishwasher detergent of the invention.
The invention is elucidated in more detail below by means of examples, without being limited to these examples. Insofar as not explicitly stated otherwise in the examples, the percentages in the examples are to be understood as percentages by weight (wt.-%).

Examples

Abbreviations used are as follows:

a.i.	active ingredient
MGDA-Na₃	methylglycinediacetic acid, trisodium salt
Polycarboxylate	commercially available as Sokalan^® PA 30 CL from BASF
TAED	Tetraacetylethylenediamine
HEDP	1-hydroxyethane-1,1-diphosphonate
Genapol^® EC50	nonionic modified fatty alcohol polyglycol ether commercially available from Clariant (surfactant according to formula (XI)) (Clariant, Switzerland)

Example 1: Drying performance and clean dishwasher interior

The drying performance of the detergent composition for machine dishwashing F1 (dishwasher detergents according to the invention) was investigated.

Testing conditions:

Dishwashing machine:	Miele G 1222 SC GSL-2
Testware dishes:	10 appetizer spoons
	10 appetizer forks
	10 appetizer knives
	10 teaspoons
	2 vegetable serving spoons
	12 drinking glasses
	10 porcelain cups
	25 porcelain plates
	3 SAN (poly-styrene-co-acrylonitrile) plates
	3 PP (polypropylene) plates
	6 PP bowls
Dishwashing program:	P4R0 without pre-rinsing
	main rinse at 50°C
	final rinse at 65°C
Water hardness:	21 °dH
Wasser softening:	none
Detergent dosage:	18 g, added into the detergent tablet tray immediately after opening of the dosing chamber
Contamination:	50 g frozen dirt, added immediately after opening of the dosing chamber
Rinse aid:	none
Cleaning cycles:	4

All items were treated once with demineralized water, Neodisher A 8, citric acid, and demineralized water.

Evaluation:

Evaluation of the testware was started 30 minutes after the dishwashing cycle was completed. During this time, the dishwasher door was closed. For each test, dishwashing cycles 2 to 4 were evaluated. The assessment was carried out in each case with an illumination of 1000 - 1500 lux.
In a fixed order and with a set time limit, the number of adherent drops of residual water was counted for each testware item. Depending on the counted number of drops, the following rating of the drying performance results for each testware item: Rating for porcelain, stainless steel and glass:

0 dry, no water drops

1 1 water drop

2 2 water drops

3 3 water drops

4 4 water drops

5 5 water drops

6 more than 5 water drops

Rating for plastics:

0 dry, no water drops

1 1 water drop

2 2 water drops

3 3 water drops

4 4 water drops

5 5 water drops

6 6 water drops

7 7 water drops

8 more than 7 water drops
In this rating scheme, there is a score of 0 for best performance and a score of 6 for worst performance for each testware dish made of porcelain, stainless steel or glass and a score of 8 for the worst performance for each testware dish made of plastic. For each dishwashing cycle 2, 3 and 4, the sum of the scores of all test dishes was formed. The overall result is categorized into performance groups:

○ = bad results

+ = good results

++ = very good results

The results are shown in the following Table A.
Furthermore, the fatty residues in the machine department of the automatic dishwashing machine and in particular on plastic parts (e.g. filter, rinse aid chamber) of the machine department of the dishwashing machine were evaluated. The overall result is categorized into performance groups:

○ = bad results

+ = good results

++ = very good results

These results are also shown in Table A.

Composition:

The composition of the formulation F1 is shown in the following Table A.

Example 2: Rinse performance of detergent compositions for machine dishwashing

The rinse performance of the formulation F1 according to the invention was investigated.

Testing conditions:

Dishwashing Machine:	Miele G 1222 SC GSL
Testware dishes:	6 drinking glasses (higher quality) (8 material groups)
	6 drinking glasses (lower quality)
	3 PP bowls
	3 melamine plates
	3 butter dishes + 4 knives (stainless steel; lower quality)
	4 knives (stainless steel; higher quality)
	3 porcelain plates (higher quality)
	3 porcelain plates (lower quality)
Dishwashing program:	program 4, R = 2 without pre-rinsing
	main rinse at 50°C
	final rinse at 65°C
Water hardness:	21 °dH
Water softening:	none
Detergent dosage:	18 g, added to the dosage chamber before starting the test
Contamination:	100 g frozen dirt, added immediately after the opening of the dosage chamber
Rinse aid:	none
Cleaning cycles:	4

All testware dishes except for the PP bowls were treated once with demineralized water, Neodisher A 8, citric acid and again demineralized water.

Evaluation:

Evaluation of the testware was begun at least 60 minutes after opening the door of the dishwashing machine after completion of the dishwashing cycle. For each test, dishwashing cycles 2 to 4 were evaluated. The assessment was carried out according to the following rating:

Rinse performance effects considered for the visual rating:

Stains	Stains of different size and intensity
Contact spots	Stains resultant from contact points between the testware dishes and parts of the dishwashing machine
Stripes	Rinse aid stripes
Film formation	continuous film spread uniformly on the testware dishes
Structured film formation	Dispersed torn film
Solid residues	Solid powder or crystalline residues
Fatty residues	Fatty drops or fatty film formation
Iridescence	Shimmering, iridescence

Visual rating marks:

10	Perfect
9	Perfect to barely visible
8	Barely visible
7	Barely visible to visible
6	Visible
5	Visible to disturbing
4	Disturbing
3	Disturbing to unacceptable
2	Unacceptable
1	Absolutely unacceptable

The combination of the above listed eight rinse performance effects leads to a rating from 1 to 10 according to the above visual rating marks, wherein a rating of 1 represents the worst performance and a rating of 10 represents the best performance. For each of the above 8 testware material groups in each dishwashing cycle, an average rating was determined, followed by calculating the sum of ratings for all material groups in each individual dishwashing cycle, followed by determining an average rating for the entirety of dishwashing cycles 2 to 4. The resultant average rating was used as the final rinse performance of the formulation F1 and is categorized into performance groups:

○ = bad results

+ = good results

++ = very good results

Composition:

The composition of the formulation F1 according to the invention is shown in the following table A. The results are also shown in Table A.

Table A: Composition, drying performance, fatty residues and rinse performance of formulation F1

Component	F1 wt.-%^*)
Trisodium citrate Dihydrate	28.5
Sodium carbonate	19.5
Sodium silicate (Britesil H20^® (PQ Corp., PA, USA))	2.0
MGDA-Na₃ (Trilon^® M Max Granules (BASF SE, Germany))	15.0
Polycarboxylate (Sokalan^® PA 30 CL (BASF SE, Germany))	10.0
Natriumpercarbonate (Oxyper SCS^® (Solvay, Belgium))	9.0
TAED (Peractive AC white^® (WeylChem, Germany))	2.0
HEDP	0.9
Protease (Blaze Evity 100T^®, Novozymes, Denmark)	0.9
Amylase (Stainzyme 120T^®, Novozymes, Denmark)	0.9
Water	6.0
Polyethyleneglycol (PEG6000)	2.0
Zinc salt (Zinc sulfate)	0.5
50 wt.-% Genapol^® EC50 on magnesium carbonate carrier (1)	3.5* (7.0)**
Sodium sulfate	Ad 100**)

Technical performance:
drying performance	+
rinse performance	++
Fatty residues	++

o = bad results
+ = good results
++ = very good results
^*) The ingredients were added according to their active component content in wt.-%.
^**) Sodium sulfate is added as a filler for a constant mass balance of the dishwasher detergent, without a function and without influence on the performance of the dishwasher detergent.
^***) Active content of the surfactant on magnesium carbonate carrier in wt.-% (i.e., mass content of surfactant (without magnesium carbonate carrier) which is on magnesium carbonate carrier)
^****) content of the surfactant on magnesium carbonate carrier in wt.-% (i.e., sum of the mass content of surfactant (which is on magnesium carbonate carrier) and magnesium carbonate carrier)

From the results in the above table A it is evident that the use of the dishwasher detergent F1 lead to good to very good results in the rinse and drying performance along with no significant fatty residues in the machine department of the automatic dishwashing machine and in particular on plastic parts of the machine department.
Replacing Genapol^® EC50 on magnesium carbonate carrier (3.5 wt.-% in surfactant) in F1 by Genapol^® EC50 without carrier (F1') significantly more fatty residues are observed in the machine department of the automatic dishwashing machine and in particular on plastic parts of the machine department (see Table B). Table B: Fatty residues of formulations F1, F1'

Surfactant F1 wt.-%^*) F1' wt.-%^*)

50 wt.-% Genapol^® EC50 on magnesium carbonate carrier (1) 3.5*** (7.0)**** -

Genapol^® EC50 - 3.5

Technical performance:

Fatty residues ++ ○

○ = bad results
+ = good results
++ = very good results

Claims

A dishwasher detergent comprising
Z1) one or more surfactants on magnesium carbonate carrier which are selected from the group consisting of fatty alcohol alkoxylates and end-capped fatty alcohol alkoxylates of the formula (XI)

RaO-(AO)x-Y (XI),

in which
R_a is a linear or branched saturated alkyl group having 8 to 30 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 30 carbon atoms,

A is selected from the group consisting of -C₂H₄- and -C₃H₆-,

x is a number from 1 to 150,

Y is a group -CH₂-CH(OH)-R_b, R_b is a linear or branched saturated alkyl group having 1 to 30 carbon atoms, and where the group -(AO)_x- comprises one or more -C₂H₄-O-groups and may additionally comprise one or more -C₃H₆-O- groups, and, when the group -(AO)_x- simultaneously comprises -C₂H₄-O- and -C₃H₆-O- groups, the -C₂H₄-O- and -C₃H₆-O- groups may be distributed over the -(AO)_x- group in any desired way, preferably in random, gradient-like or block-like manner and more preferably in block-like manner, and the molar amount of the -C₂H₄-O- groups in the group -(AO)_x- is preferably greater than the molar amount of the -C₃H₆-O- groups in the group -(AO)_x-;

Z2) one or more enzymes; and

Z3) one or more glass corrosion inhibitors.
The dishwasher detergent according to claim 1, characterized in that Y is -CH₂-CH(OH)-R_b, wherein R_b is a linear or branched saturated alkyl group having 8 to 22 and preferably 8 to 20 carbon atoms.
The dishwasher detergent according to claim 1 or 2, characterized in that:
the molar amount of the -C₃H₆-O- groups in the group -(AO)_x-, based on the total amount of -C₂H₄-O- and -C₃H₆-O- groups in the group -(AO)_x-, is 20% or less than 20% and preferably 10% or less than 10%; or

in formula (XI) the group -(AO)_x- comprises on molar average 8 -C₂H₄-O- groups and 4 -C₃H₆-O- groups and R_a is a linear or branched saturated alkyl group having 12 to 15 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 12 to 15 carbon atoms.
The dishwasher detergent according to one or more of claims 1 to 3, characterized in that it comprises at least one surfactant, preferably one or more surfactants on magnesium carbonate carrier of component Z1), selected from the group consisting of the end-capped fatty alcohol ethoxylates of the formula (XI) in which
R_a is a linear or branched saturated alkyl group having 8 to 20 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 20 carbon atoms,

A is -C₂H₄-,

x is a number from 15 to 25,

Y is -CH₂-CH(OH)-R_b, wherein R_b is a linear or branched saturated alkyl group having 8 to 22 and preferably 8 to 20 carbon atoms.
The dishwasher detergent according to one or more of claims 1 to 4, characterized in that the one or more glass corrosion inhibitors of component Z3) are selected from the group consisting of, preferably water-soluble, salts or complexes of one or more cations selected from the group consisting of zinc, magnesium, cobalt, bismuth, and combinations of two or more thereof.
The dishwasher detergent according to one or more of claims 1 to 5, characterized in that it further comprises at least one further surfactant which is optionally on magnesium carbonate carrier selected from the group consisting of:
(a) N-acylglucamides of the formula (XII),
in which
Rb is a linear or branched saturated alkyl group having 11 to 21 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 11 to 21 carbon atoms, and

Rc is hydrogen or a linear or branched saturated alkyl group having 1 to 4 carbon atoms and preferably a methyl or an ethyl group,
preferably wherein, in the formula (XII), Rc is a methyl group and/or RbCO derives from oleic acid;

(b) glycerol triester ethoxylates of formula (I),
wherein
R¹, R² and R³ are equal or different and are independently selected from linear or branched saturated alkyl groups having 7 to 25 carbon atoms or linear or branched unsaturated alkenyl groups having one or more double bonds and 7 to 25 carbon atoms;

m, n and o are equal or different and are each independently a number from 1 to 200, preferably from 1 to 80, more preferably from 2 to 70, with the proviso that the number-average of the sum of m + n + o is greater than 5, preferably from 20 to 70, more preferably from 30 to 60,
preferably wherein at least one glycerol triester ethoxylate of formula (I) is prepared from ethylene oxide and one or more triglycerides of formula (II)
in the presence of a calcium catalyst (C), wherein
the calcium catalyst (C) is a catalyst obtainable by a reaction involving
(A) calcium hydroxide and

(B) a carboxylic acid comprising 3 to 40 carbon atoms,
wherein the molar ratio of calcium hydroxide (A) to carboxylic acid (B) in the preparation of the catalyst (C) is from 1:1 to 1:5;

(c) compounds of formula (X),
wherein
R¹⁴ is a linear or branched, preferably linear, saturated alkyl group having from 1 to 6 carbon atoms;

R¹⁵, R¹⁶ and R¹⁷ are equal or different and are independently selected from the group consisting of hydrogen, linear or branched saturated alkyl groups having from 1 to 18 carbon atoms, linear or branched unsaturated alkenyl groups having one or more double bonds and from 2 to 18 carbon atoms, and -CO-R¹⁸;

R¹⁸ is a linear or branched saturated alkyl group having 7 to 19 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 7 to 19 carbon atoms;

r, s and t are equal or different and are independently a number from 0 to 50;

X is an inorganic or organic anion having the charge b-;

b is a number from 1 to 4; and

c is a number having a value of 1/b;
with the proviso that at least one group of R¹⁵, R¹⁶ and R¹⁷ is -CO-R¹⁸ which forms an ester moiety with the oxygen atom of an ethoxy group;
the sum of r + s + t is a number from 1 to 70; and
if one or more of r, s and/or t is 0, the corresponding group R¹⁵, R¹⁶ and/or R¹⁷ is a linear or branched saturated alkyl group having 1 to 18 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 2 to 18 carbon atoms,
preferably wherein, in formula (X),
R¹⁴ is methyl,

R¹⁵, R¹⁶ and R¹⁷ are equal or different and are independently selected from the group consisting of hydrogen and -CO-R¹⁸; and R¹⁸ is a linear or branched saturated alkyl group having 7 to 19 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 7 to 19 carbon atoms; with the proviso that at least two of the groups R¹⁵, R¹⁶ and R¹⁷ are -CO-R¹⁸ which form an ester moiety with the oxygen atom of an ethoxy group;

r, s and t are equal or different and are independently a number from 1 to 30; the sum of r + s + t is a number from 3 to 70;

X is an inorganic or organic anion having the charge b-;

b is 1; and

c is 1; or

(d) a combination of two or more thereof, such as a combination of (a) and (b), of (a) and (c), of (b) and (c), or pf (a), (b) and (c),

preferably, wherein the dishwasher detergent is characterized in that it further comprises at least one further surfactant which is optionally on magnesium carbonate carrier selected from the group consisting of (a), (b) and a combination of (a) and (b).
The dishwasher detergent according to one or more of claims 1 to 6, characterized in that component Z1) comprises the one or more surfactants in an amount ranging from 10 to 300 wt.-%, preferably from 40 to 250 wt.-%, more preferably from 50 to 200 wt.-%, especially preferably from 60 to 170 wt.-%, and particularly preferably from 70 to 150 wt.-%, based on the total weight of the magnesium carbonate carrier.
The dishwasher detergent according to one or more of claims 1 to 7, characterized in that it comprises the one or more surfactants on magnesium carbonate carrier of component Z1) in an amount from 0.5 to 30 wt.-% and preferably in an amount from 3 to 25 wt.-%, based in each case on the total weight of the dishwasher detergent.
The dishwasher detergent according to one or more of claims 1 to 8, characterized in that the one or more enzymes of component Z2) are selected from the group consisting of proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases, oxidoreductases, and mixtures thereof.
The dishwasher detergent according to one or more of claims 1 to 9, characterized in that it comprises the one or more enzymes of component Z2) in an amount from 1 x 10^-6 to 5 wt.-%, preferably in an amount from 1 x 10^-5 to 3 wt.-%, and more preferably in an amount from 1 x 10^-4 to 2 wt.-%, based in each case on the total weight of the dishwasher detergent.
The dishwasher detergent according to one or more of claims 1 to 10, characterized in that it comprises component Z3) in an amount from 0.01 to 10 wt.-%, preferably in an amount from 0.1 to 5 wt.-%, more preferably in an amount from 0.2 to 4 wt.-%, even more preferably in an amount from 0.4 to 3 wt.-%, from 0.5 to 2 wt.-% or from 0.2 to 1 wt.-%, based in each case on the total weight of the dishwasher detergent.
The dishwasher detergent according to one or more of claims 1 to 11, characterized in that it further comprises one or more further substances selected from the components Z4), Z5), Z6), Z7), and/or Z8):
Z4) a bleaching system,

Z5) one or more surfactants other than those of component Z1), preferably wherein the one or more surfactants other than those of component Z1 are selected from the group consisting of fatty alcohol alkoxylates, end-capped fatty alcohol alkoxylates, ethyleneoxide-propylenoxide-blockcopolymers, N-acylglucamines, N-acylglucamides, gylcerol triester alkoxylates, esterquats, and mixtures thereof, and more preferably wherein the one or more surfactants of component Z5) are on the magnesium carbonate carrier,

Z6) one or more further additives, preferably selected from the group consisting of builders, complexing agents, water, organic solvents, thickeners, foam inhibitors, color particles, silver protectants, agents for preventing tarnishing of silver, metal corrosion inhibitors, dyes, fillers, microbicides, hydrotropes, antioxidants, enzyme stabilizers, fragrances, solubilizers, carrier materials, processing assistants, pigments, and pH modifiers,

Z7) one or more tableting aids, preferably selected from polyethylene glycol, polysaccharides, and derivatives thereof,

Z8) one or more polymers other that component Z7),
and the pH of the dishwasher detergent at 20°C is preferably from 8 to 14, more preferably from 9 to 11.5, and especially preferably from 9.5 to 11.5, measured as a 10 wt.-% solution of the dishwasher detergent in water,
preferably wherein the dishwasher detergent comprises:
Z1) 0.5 to 30 wt.-%, preferably 1 to 25 wt.-%, more preferably 2 to 20 wt.-%, especially preferably 3 to 15 wt.-%, and particularly preferably 5 to 10 wt.-% of component Z1),

Z2) 1 x 10^-6 to 5 wt.-% of component Z2), and

Z3) 0.01 to 10 wt.-%, preferably 0.1 to 5 wt.-%, preferably 0.2 to 4 wt.-%, preferably 0.4 to 3 wt.-%, preferably 0.5 to 2 wt.-% or 0.2 to 1 wt.-%, of component Z3), and optionally

Z4) 0 to 40 wt.-% of component Z4), and optionally

Z5) 0 to 50 wt.-%, preferably 0 to 15 wt.-%, preferably 0 to 10 wt.-%, more preferably 0.5 to 7 wt.-%, and especially preferably 3 to 7 wt.-% of component Z5), and optionally

Z6) 0 to 80 wt.-%, preferably 0 to 70 wt.-%, preferably 0 to 60 wt.-%, of component Z6), and optionally

Z7) 0 to 50 wt.-%, preferably 0.1 to 40 wt.-%, preferably 0.5 to 20 wt.-%, preferably 1 to 10 wt.-%, of component Z7), and optionally

Z8) 0 to 10 wt.-% of component Z8),
based in each case on the total weight of the dishwasher detergent.
The dishwasher detergent according to one or more of claims 1 to 12, characterized in that it comprises no phosphate builders and no phosphate-based builders and preferably is phosphate-free.
The dishwasher detergent according to one or more of claims 1 to 13, characterized in that it is solid at 20°C and is in the form of a tablet.
A method for cleaning dishware in a dishwasher, characterized in that soiled dishware is treated in a dishwasher with an aqueous alkaline composition comprising a dishwasher detergent according to one or more of claims 1 to 14.
Use of one or more surfactants on magnesium carbonate carrier of component Z1) as described in one or more of claims 1 to 4 or a dishwasher detergent according to one or more of claims 1 to 14:
(i) as a rinse agent in machine dishwashing;

(ii) for improving the wettability of dishware or for reducing spotting and filming on dishware;

(iii) for reducing, minimizing or preventing fatty residues in the machine department of an automatic dishwashing machine;

(iv) for improving the rinse performance of a dishwasher detergent; or

(v) for improving the drying performance of a dishwasher detergent, preferably in a method according to claim 15.