Mixture of modified fatty alcohol alkoxylates

Abstract

Mixtures of modified fatty alcohol alkoxylates are described. They are preferably used as detergent for machinated dishwashing. Automated dishwashing compositions containing the mixture of modified fatty alcohol alkoxylates have a beneficial rinse aiding performance and advantageous drying capacities while reducing the amounts of fatty residues in the filter of the dishwashing machine.

Description

[0001] MIXTURE OF MODIFIED FATTY ALCOHOL ALKOXYLATES

[0002] The present invention relates to specific mixtures of modified fatty alcohol alkoxylates; to a method for their preparation; to alkoxylation products obtainable by this preparation method; to a detergent composition for machine dishwashing comprising the mixtures of modified fatty alcohol alkoxylates or the alkoxylation products; to a method of cleaning dishes in a dishwashing machine using the detergent composition according to the invention, to the use of the detergent composition according to the invention as a rinse aid during machinated dishwashing, or for improving the wettability of dishes during machinated dishwashing, or for the reduction and / or avoidance of stain and film formation, in particular fatty residue formation, on dishes, in the machine compartment and / or on the filter of the machine during machinated dishwashing, and to the use of said mixtures of modified fatty alcohol alkoxylates for improving the rinse aiding properties and / or the drying capacity of a machine dishwashing detergent composition, preferably a detergent composition according to the invention.

[0003] The requirements concerning machine-washed dishes are nowadays very high, especially when compared to manually washed dishes. Apart from residue-free cleaning, the complete washing program, typically comprising a pre-rinsing step, a main washing step, a final rinsing step and a drying step, each step often being interrupted by intermediate rinsing steps, should result in flawlessly glossy dishes free of stripes and stains. Even after proper removal of food remains from the dishes, white stains and residues derived from water hardness and other inorganic or organic salts stemming from water droplets and water films may lead to unsatisfactory dishwashing results. Therefore, rinse aids are employed in machinated dishwashing in order to improve the dishwashing performance in terms of obtaining stripe-free, stain-free and residue-free dishes. Rinse aids are typically automatically introduced from a rinse aid dispenser into the dish compartment of the dishwasher during the final rinse step. Alternatively, multifunctional detergent products often already include a rinse aid component.Typical rinse aids are liquid mixtures of weakly foaming nonionic surfactants, organic acids such as citric acid, film-inhibiting polymers, solvents such as alcohols, and other additives such as hydrotropic agents, thickeners and / or foam inhibitors. Rinse aid formulations are usually liquid at 20 °C and have an acidic pH value of 6 or less. They are often added into the dish compartment of the dishwashing machine during the final rinsing step.

[0004] The object of rinse aids is to affect the interface and surface tension of water in such a way that it can run off the rinsed surfaces as a thin film, thus that during the subsequent drying step no water droplets, limestone scales, stripes, films or other residues remain on the washed dishes.

[0005] Dishwashing in dishwashing machines, especially for domestic applications, is subject to continuous technical changes and improvements. For example, new kinds of combined products (“all in one” formulations) are developed, such as single-phase or multiphase tablets, pouches, pods and caps, or liquid formulations such as multifunctional gels. Such combined products require new rinse aid additives that are effective against stain and film formation and show beneficial rinse aid and / or drying performance, while they are present during the entire washing process.

[0006] Often, polymers are used in such detergent compositions, and are useful as water softeners and / or rinse aid additives. Different nonionic, anionic, cationic or amphoteric polymers are described in the art.

[0007] WO 2009 / 033972 A1 describes machine dishwashing detergents containing mixed hydroxy ethers, builder substances, and specific anionic copolymers, as well as the use of these machine dishwashing detergents to improve drying in machine dishwashing.

[0008] WO 94 / 22800 A1 describes mixed hydroxy ethers and machine dishwashing detergents containing these mixed hydroxy ethers.DE 3723323 A1 describes mixed hydroxy ethers, methods for producing these mixed hydroxy ethers, and the use of these hydroxy mixed ethers as foamsuppressing additives in low-foam cleaning agents.

[0009] DE 3723873 A1 describes the use of specific mixed hydroxy ethers and mixtures of such mixed hydroxy ethers in rinse aids for machine dishwashing.

[0010] EP 1229104 A2 describes dishwashing and cleaning agents containing specific mixed hydroxy ethers and the use of such mixed hydroxy ethers for washing and cleaning hard surfaces in machine dishwashers and rinse aids.

[0011] WO 99 / 13035 A1 describes surfactant mixtures containing mixed hydroxy ethers and specific other non-ionic surfactants, as well as the use of these surfactant mixtures in rinse aids.

[0012] EP 4413110 A1 describes detergent compositions for machine dishwashing comprising ethoxylated glycerol esters and modified fatty alcohol alkoxylates.

[0013] Mixed hydroxy ethers are particularly efficient non-ionic surfactants for rinsing, see e.g., WO 2008 / 095563 and WO 2021 / 089887. However, their overall performance can still be improved. Especially the use of mixed hydroxy ethers in formulations disclosed in WO 2008 / 095563 in automatic dishwashers can lead to rather high amounts of surfactant and fat residues in the filters or sieves.

[0014] In WO 2017 / 005793 a process for cleaning dishware is described, in which mixed hydroxy ethers are used in combination with polyalkoxylated polyalkylenimines to avoid significant residues of surfactant and fat in the filters or sieves of the dishwashing machine.

[0015] Although the number of effective detergent formulations known in the art is large and growing, the performance of the formulations still needs to be improved, especially in terms of rinse aid performance and drying performance of detergentsfor machinated dishwashing in combination with cleanliness in the machine, in particular low amounts of fatty residues in the filter of the dishwashing machine.

[0016] Therefore, it was an object of the present invention to provide a detergent for machinated dishwashing, which shows, upon application in a dishwashing machine, an advantageous performance, especially in terms of low amounts of fatty residues in the filter of the dishwashing machine in combination with advantageous rinse performance and drying performance.

[0017] Surprisingly, it has been found that this object can be solved by a mixture of modified fatty alcohol alkoxylates selected from the substances of the following formula (I)

[0018] Ra0-(CmH2m0)x-Y (I)

[0019] wherein

[0020] Rais a linear or branched saturated alkyl group having 6 to 30 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 6 to 30 carbon atoms, preferably 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, and more preferably is a linear or branched saturated alkyl group having 10 to 16 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 10 to 16 carbon atoms, m is 2 or 3 or combinations thereof, preferably 2,

[0021] x is an integer from 1 to 150, preferably from 1 to 100, more preferably from 2 to 75, even more preferably from 3 to 50, particularly preferably from 5 to 40, and extraordinarily preferably from 8 to 30,

[0022] Y is a group -CH2-CH(OH)-Rb, -CH2-CH(OH)-CH2-O-Rbor is a linear or branched saturated alkyl group having 1 to 32 carbon atoms, preferably -CH2-CH(OH)-Rb,

[0023] Rbis a linear or branched saturated alkyl group having 1 to 30 carbon atoms, preferably is a linear or branched saturated alkyl group having 4 to 20 carbon atoms, even more preferably is linear or branched saturated alkyl group having 8 to 12 carbon atoms, andthe average number “n” of (CmH2mO)-units of the modified fatty alcohol alkoxylates of the formula (I) in the mixture is a number from 5 to 100, preferably from 7 to 50, more preferably from 9 to 25, even more preferably from 11 to 30, and particularly preferably from 13 to 25,

[0024] characterized in that

[0025] at least 15 wt.-%, preferably at least 18 wt.-%, of the total weight of the modified fatty alcohol alkoxylates of the formula (I) in the mixture according to the invention are modified fatty alcohol alkoxylates with naunits selected from the group consisting of (C2H4O)-units, (CsHeOj-units and mixtures of (C2H4O)-units and (CsHeOj-units, where nais the integer equal to the number n in case the number n itself is an integer or nais the integer closest to the number n in case the number n itself is not an integer.

[0026] Therefore, a subject matter of the present invention is a mixture of modified fatty alcohol alkoxylates selected from the substances of the following formula (I)

[0027] Ra0-(CmH2m0)x-Y (I)

[0028] wherein

[0029] Rais a linear or branched saturated alkyl group having 6 to 30 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 6 to 30 carbon atoms, preferably 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, and more preferably is a linear or branched saturated alkyl group having 10 to 16 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 10 to 16 carbon atoms, m is 2 or 3 or combinations thereof, preferably 2,

[0030] x is a integer from 1 to 150, preferably from 1 to 100, more preferably from 2 to 75, even more preferably from 3 to 50, particularly preferably from 5 to 40, and extraordinarily preferably from 8 to 30,Y is a group -CH2-CH(OH)-Rb, -CH2-CH(OH)-CH2-O-Rbor is a linear or branched saturated alkyl group having 1 to 32 carbon atoms, preferably -CH2-CH(OH)-Rb,

[0031] Rbis a linear or branched saturated alkyl group having 1 to 30 carbon atoms, preferably is a linear or branched saturated alkyl group having 4 to 20 carbon atoms, even more preferably is linear or branched saturated alkyl group having 8 to 12 carbon atoms, and

[0032] the average number “n” of (CmH2mO)-units of the modified fatty alcohol alkoxylates of the formula (I) in the mixture is a number from 5 to 100, preferably from 7 to 50, more preferably from 9 to 25, even more preferably from 11 to 30, and particularly preferably from 13 to 25,

[0033] characterized in that

[0034] at least 15 wt.-%, preferably at least 18 wt.-%, of the total weight of the modified fatty alcohol alkoxylates of the formula (I) in the mixture according to the invention are modified fatty alcohol alkoxylates with naunits selected from the group consisting of (C2H4O)-units, (C3HeO)-units and mixtures of (C2H4O)-units and (C3HeO)-units, where nais the integer equal to the number n in case the number n itself is an integer or nais the integer closest to the number n in case the number n itself is not an integer.

[0035] The mixtures of modified fatty alcohol alkoxylates show beneficial performance as detergents for machinated dishwashing, which show, upon application in a dishwashing machine, an advantageous performance, especially in terms of low amounts of fatty residues in the filter of the dishwashing machine in combination with advantageous rinse performance and drying performance. Furthermore, not only are the fatty residues in the filter reduced, but also the cleanliness of the dishwashing machine is improved.

[0036] Preferably, the inventive mixture of modified fatty alcohol alkoxylates selected from the substances of the formula (I) is characterized in that at least 45 wt.-%, more preferably at least 55 wt.-%, of the total weight of the modified fatty alcoholalkoxylates of the formula (I) in the mixture according to the invention are modified fatty alcohol alkoxylates with (na-1 ), naor (na+1) units selected from the group consisting of (C2H4O)-units, (C3HeO)-units and mixtures of (C2H4O)-units and (C3HeO)-units, where nais the integer equal to the number n in case the number n itself is an integer or nais the integer closest to the number n in case the number n itself is not an integer.

[0037] Preferably, the inventive mixture of modified fatty alcohol alkoxylates selected from the substances of the formula (I) is characterized in that at least 70 wt.-%, more preferably at least 80 wt.-%, of the total weight of the fatty alcohol alkoxylates of the formula (I) in the mixture according to the invention are fatty alcohol alkoxylates with (na-2), (na-1 ), na, (na+1) or (na+2) units selected from the group consisting of (C2H4O)-units, (C3HeO)-units and mixtures of (C2H4O)-units and (C3HeO)-units, where nais the integer equal to the number n in case the number n itself is an integer or nais the integer closest to the number n in case the number n itself is not an integer.

[0038] Preferably, the inventive mixture of modified fatty alcohol alkoxylates selected from the substances of the formula (I) is characterized in that at least 80 wt.-%, more preferably at least 90 wt.-%, of the total weight of the fatty alcohol alkoxylates of the formula (I) in the mixture according to the invention are fatty alcohol alkoxylates with (na-3), (na-2), (na-1 ), na, (na+1), (na+2) or (na+3) units selected from the group consisting of (C2H4O)-units, (C3HeO)-units and mixtures of (C2H4O)-units and (C3HeO)-units, where nais the integer equal to the number n in case the number n itself is an integer or nais the integer closest to the number n in case the number n itself is not an integer.

[0039] The structural unit of the formula -(CmH2mO)x- in a single modified fatty alcohol alkoxylate molecule of the formula (I) may consist of one or more (C2H4O)-groups, may consist of one or more (C3HeO)-groups or may consist of a mixture of (C2H4O)- and (C3HeO)-groups. This means that “m” has the same meaning for a given group -(CmH2mO)-, but can have different meanings in different -(CmH2mO)-groups in the same single modified fatty alcohol alkoxylate molecule of the formula (I).

[0040] The groups (C2H4O), if present in the structural units of the formula -(CmH2mO)x- of the modified fatty alcohol alkoxylates of the formula (I), preferably are of the formula -CH2-CH2-O-.

[0041] The groups (CsHeO), if present in the structural units of the formula -(CmH2mO)x- of the modified fatty alcohol alkoxylates of the formula (I), preferably are of the formula -CH(CH3)-CH2-O- or -CH2-CH(CH3)-O-, i.e. of the formula:

[0042]

[0043] In the case that (C2H4O)- and (CsHeOj-groups exist in a structural unit of the formula -(CmH2mO)x-, they may be arranged blockwise, alternating, periodically and / or statistically, preferably blockwise and / or statistically. This means that in a structural unit of the formula -(CmH2mO)x-, the groups (C2H4O) and (CsHeO) may be arranged, for example, in a purely statistically or blockwise form but may also be arranged in a form which could be considered as both, statistical and blockwise, e.g. small blocks of (C2H4O) and (CsHeO) arranged in a statistical manner, or in a form wherein adjacent instances of statistical and blockwise arrangements of the groups (C2H4O) and (CsHeO) exist.

[0044] Any of the groups (C2H4O) and (CsHeO) can be linked to RaO- and -Y in a modified fatty alcohol alkoxylate molecule of the formula (I). This means, for example, that both, RaO- and -Y in a fatty alcohol alkoxylate molecule of the formula (I), may be connected to a (C2H4O)-group, they may both be connected to a (CsHeOj-group or one may be connected to a (C2H4O)-group and the other to a (CsHeOj-group.

[0045] In a preferred embodiment of the invention, the structural units -(CmH2mO)x- in the mixture of modified fatty alcohol alkoxylates of the formula (I) are (C2H4O).Modified fatty alcohol alkoxylates are already known in the prior art. Fatty alcohol ethoxylates of the prior art are e. g. described in WO 94 / 22800 A1. Modified fatty alcohol alkoxylates are also already disclosed as components for automatic dishwashing detergent compositions, e.g. in WO 2008 / 095563 A1 or EP 1741774 A1.

[0046] Modified fatty alcohol alkoxylates may be produced by the reaction of fatty alcohol with alkylene oxide e.g. using alkaline catalysts based on sodium or potassium. The catalyst may be removed or left in the fatty alcohol alkoxylate. The alkoxylated fatty alcohol is then treated with a second alkylene oxide or an alkyl- or alkenylhalide (or a different alkylating agent) in an alkaline environment.

[0047] The fatty alcohol may be produced by an alkaline hydrolysis (saponification) of a triglyceride and subsequent reduction of the fatty acid to the corresponding fatty alcohol. Common catalysts for these reactions include sodium hydroxide and potassium hydroxide.

[0048] The fatty alcohol may be obtained synthetically or, more conveniently and generally more economically, from natural sources. Triglycerides are widely distributed in nature in a variety of animal and vegetable products.

[0049] Distillation and fractionation processes may be used in the production of the fatty alcohol or carboxylic acid (before reduction) to produce the desired carbon chain distribution.

[0050] The group Rain formula (I) is selected from the group consisting of linear or branched, preferably linear, saturated alkyl groups with 6 to 30 carbon atoms, linear or branched, preferably linear, mono- or polyunsaturated alkenyl groups with 6 to 30 carbon atoms, and combinations thereof, preferably consisting of linear or branched, preferably linear, saturated alkyl groups with 8 to 20 carbon atoms, linear or branched, preferably linear, mono- or polyunsaturated alkenyl groups with 8 to 20 carbon atoms, and combinations thereof, and even more preferably consisting of linear or branched, preferably linear, saturated alkyl groups with 10 to16 carbon atoms, linear or branched, preferably linear, mono- or polyunsaturated alkenyl groups with 10 to 16 carbon atoms, and combinations thereof.

[0051] Further even more preferably the group Rain formula (I) is selected from the group consisting of linear or branched, preferably linear, saturated alkyl groups with 9 to 13, preferably 11 , carbon atoms, linear or branched, preferably linear, mono- or polyunsaturated alkenyl groups with 9 to 13, preferably 11 , carbon atoms, and combinations thereof.

[0052] Preferably, the groups Rain formula (I) are alkyl groups.

[0053] Examples of the alkyl and alkenyl groups Rain formula (I) are, e.g. the alkyl and alkenyl groups of the following alcohols Ra-OH: 1 -octanol (caprylic alcohol), 2-ethylhexanol, 1 -nonanol (pelargonic alcohol), 1 -decanol (capric 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-octadecatriene-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.

[0054] Examples of ester materials from which the groups Rain the inventive mixture of fatty alcohol alkoxylates of the formula (I) may be derived are, beeswax, carnauba wax, animal fat, e.g. tallow fat, palm oil, palm kernel oil, coconut oil, olive oil, cottonseed oil, soybean oil, peanut oil, rapeseed oil, sunflower oil, castor oil, maize oil, sesame oil, whale oil, non-edible vegetable oils, tall oil and any mixture thereof. The oil from trees is called tall oil.Used food cooking oils may also be utilised as a source of the groups Rain the inventive mixture of fatty alcohol alkoxylates of the formula (I). Triglycerides may also be obtained from algae, fungi, yeast or bacteria.

[0055] The variable x in formula (I) is an integer from 1 to 150, preferably from 5 to 100, more preferably from 5 to 50, and even more preferably from 15 to 25.

[0056] As an example of the alkyl groups Y and Rbof the compounds of the formula (I), the examples given above for the alkyl group Raof the compound of formula (I) may be mentioned. 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, iso-pentyl (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, 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.

[0057] When Y in the formula (I) represents a linear or branched alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 8 carbon atoms.

[0058] In a further preferred embodiment of the invention, Rbin formula (I) represents a linear or branched alkyl group having 8 to 22 carbon atoms.

[0059] In a further preferred embodiment of the invention, the group -(CmH2mO)x- contains one or more -C2H4O groups and one or more -CsHeO groups. In this preferred embodiment of the invention, the molar amount of the -CsHeO groups, based on the total amount of -C2H4O and CsHeO groups, is preferably less than 50%, more preferably 45% or less than 45%, even more preferably 40% or less than 40% and particularly preferably 33% or less than 33%.In a further preferred embodiment of the invention Y in formula (I) represents an alkyl group having 1 to 4 carbon atoms. In this preferred embodiment, the molar amount of the -CsHeO groups, based on the total amount of -C2H4O and -CsHeO groups, is preferably 20% or less than 20% and more preferably 10% or less than 10%.

[0060] In a further preferred embodiment of the invention, Y in formula (I) represents the group -CH2-CH(OH)-Rb, in which Rbis a linear or branched alkyl group having 1 to 30 carbon atoms. In this preferred embodiment, the molar amount of the -CsHeO groups, based on the total amount of -C2H4O and -CsHeO groups, is preferably 20% or less than 20% and more preferably 10% or less than 10%.

[0061] In a preferred embodiment of the invention, in the one or more modified fatty alcohol alkoxylates of the formula (I)

[0062] Ra0-(CmH2m0)x-Y (I)

[0063] Rais a linear or branched saturated alkyl group having 8 to 20 carbon atoms, preferably 10 to 16 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 20 carbon atoms, preferably 10 to 16 carbon atoms,

[0064] m is 2,

[0065] x is a number from 5 to 100, preferably from 15 to 25, and

[0066] Y is a group -CH2-CH(OH)-Rb, and Rbis a linear or branched alkyl group having 8 to 22 carbon atoms,

[0067] the average number “n” of (CmH2mO)-units of the modified fatty alcohol alkoxylates of the formula (I) in the mixture is a number from 7 to 50, preferably from 9 to 25, more preferably from 11 to 30, and even more preferably from 13 to 25, at least 15 wt.-%, preferably at least 18 wt.-%, of the total weight of the modified fatty alcohol alkoxylates of the formula (I) in the mixture according to the invention are modified fatty alcohol alkoxylates with naunits selected from the group consisting of (C2H4O)-units, (C3HeO)-units and mixtures of (C2H4O)-units and (C3HeO)-units, where nais the integer equal to the number n in case the number nitself is an integer or nais the integer closest to the number n in case the number n itself is not an integer,

[0068] at least 45 wt.-%, preferably at least 55 wt.-%, of the total weight of the modified fatty alcohol alkoxylates of the formula (I) in the mixture according to the invention are modified fatty alcohol alkoxylates with (na-1 ), naor (na+1) units selected from the group consisting of (C2H4O)-units, (C3HeO)-units and mixtures of (C2H4O)-units and (C3HeO)-units, where nais the integer equal to the number n in case the number n itself is an integer or nais the integer closest to the number n in case the number n itself is not an integer,

[0069] at least 70 wt.-%, preferably at least 80 wt.-%, of the total weight of the modified fatty alcohol alkoxylates of the formula (I) in the mixture according to the invention are modified fatty alcohol alkoxylates with (na-2), (na-1 ), na, (na+1) or (na+2) units selected from the group consisting of (C2H4O)-units, (C3HeO)-units and mixtures of (C2H4O)-units and (C3HeO)-units, where nais the integer equal to the number n in case the number n itself is an integer or nais the integer closest to the number n in case the number n itself is not an integer, and

[0070] at least 80 wt.-%, preferably at least 90 wt.-%, of the total weight of the modified fatty alcohol alkoxylates of the formula (I) in the mixture according to the invention are modified fatty alcohol alkoxylates with (na-3), (na-2), (na-1), na, (na+1), (na+2) or (na+3) units selected from the group consisting of (C2H4O)-units, (C3HeO)-units and mixtures of (C2H4O)-units and (C3HeO)-units, where na is the integer equal to the number n in case the number n itself is an integer or na is the integer closest to the number n in case the number n itself is not an integer.

[0071] In a more preferred embodiment of the invention, in the one or more modified fatty alcohol alkoxylates of the formula (I)

[0072] Ra0-(CmH2m0)x-Y (I)

[0073] Rais a linear or branched saturated alkyl group having 9 to 13 carbon atoms, preferably 11 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 9 to 13 carbon atoms, preferably 11 carbon atoms,m is 2,

[0074] x is a number from 10 to 40, preferably from 15 to 30, and

[0075] Y is a group -CH2-CH(OH)-Rb, and Rbis a linear or branched alkyl group having 8 to 12 and preferably 10 carbon atoms,

[0076] the average number “n” of (CmH2mO)-units of the modified fatty alcohol alkoxylates of the formula (I) in the mixture is a number from 13 to 25,

[0077] at least 15 wt.-%, preferably at least 18 wt.-%, of the total weight of the modified fatty alcohol alkoxylates of the formula (I) in the mixture according to the invention are modified fatty alcohol alkoxylates with naunits selected from the group consisting of (C2H4O)-units, (C3HeO)-units and mixtures of (C2H4O)-units and (C3HeO)-units, where nais the integer equal to the number n in case the number n itself is an integer or nais the integer closest to the number n in case the number n itself is not an integer,

[0078] at least 45 wt.-%, preferably at least 55 wt.-%, of the total weight of the modified fatty alcohol alkoxylates of the formula (I) in the mixture according to the invention are modified fatty alcohol alkoxylates with (na-1 ), naor (na+1) units selected from the group consisting of (C2H4O)-units, (C3HeO)-units and mixtures of (C2H4O)-units and (C3HeO)-units, where nais the integer equal to the number n in case the number n itself is an integer or nais the integer closest to the number n in case the number n itself is not an integer,

[0079] at least 70 wt.-%, preferably at least 80 wt.-%, of the total weight of the modified fatty alcohol alkoxylates of the formula (I) in the mixture according to the invention are modified fatty alcohol alkoxylates with (na-2), (na-1 ), na, (na+1) or (na+2) units selected from the group consisting of (C2H4O)-units, (C3HeO)-units and mixtures of (C2H4O)-units and (C3HeO)-units, where nais the integer equal to the number n in case the number n itself is an integer or nais the integer closest to the number n in case the number n itself is not an integer, and

[0080] at least 80 wt.-%, preferably at least 90 wt.-%, of the total weight of the modified fatty alcohol alkoxylates of the formula (I) in the mixture according to the invention are modified fatty alcohol alkoxylates with (na-3), (na-2), (na-1 ), na, (na+1), (na+2) or (na+3) units selected from the group consisting of (C2H4O)-units, (C3HeO)-units and mixtures of (C2H4O)-units and (C3HeO)-units, where nais the integer equal tothe number n in case the number n itself is an integer or nais the integer closest to the number n in case the number n itself is not an integer.

[0081] The inventive mixture of modified fatty alcohol alkoxylates of the formula (I) may advantageously be prepared by alkoxylation using an alkaline earth metal catalyst.

[0082] A further subject matter of the invention is a method for preparing an inventive mixture of modified fatty alcohol alkoxylates of the formula (I)

[0083] Ra0-(CmH2m0)x-Y (I)

[0084] wherein

[0085] Ra, m, x, and Y are as defined above, and the average number “n” of (CmH2mO)-units of the modified fatty alcohol alkoxylates of the formula (I) in the mixture according to the invention is as defined above,

[0086] from ethylene oxide, propylene oxide or a mixture of ethylene oxide and propylene oxide, one or more fatty alcohols of the formula (II), preferably a mixture of fatty alcohols of the formula (II)

[0087] RaO-H (II)

[0088] wherein Rain formula (II) has the same meaning as in formula (I), and one or more modifying reagents of the formula (III)

[0089] Z-Rb (III)

[0090] wherein Rbin formula (III) has the same meaning as in formula (I), and Z is a functional group selected from the group consisting of epoxide, glycidyl ether, chloride, bromide, iodide, -OTMS (TMS = trimethylsilyl), -OTES (TES = triethylsilyl), OTBS (TBS = te / Y-butyldimethylsilyl), OTIPS (TIPS = triisopropylsilyl), OTBDPS (TBDPS = tert-butyldiphenylsilyl), -O-SO2-OCH3, -O-SO2-OCH2-CH3, preferably epoxide, chloride, -O-SO2-OCH3, more preferably epoxide,characterized in that in the method a catalyst (C) based on an alkaline earth metal is used and

[0091] at least 15 wt.-%, preferably at least 18 wt.-%, of the total weight of the modified fatty alcohol alkoxylates of the formula (I) in the mixture according to the invention are modified fatty alcohol alkoxylates with naunits selected from the group consisting of (C2H4O)-units, (C3HeO)-units and mixtures of (C2H4O)-units and (C3HeO)-units, where nais the integer equal to the number n in case the number n itself is an integer or nais the integer closest to the number n in case the number n itself is not an integer.

[0092] The above mentioned functional groups epoxide and glycidyl ethers are defined as described by the formula:

[0093]

[0094] epoxide glycidyl ether

[0095] In the inventive method for preparing the mixture of modified fatty alcohol alkoxylates of the formula (I), the reaction of the one or more fatty alcohols of the formula (II) and the ethylene oxide, propylene oxide or a mixture of ethylene oxide and propylene oxide, must take place as a first step. After completion of the reaction, the modifying reagent of formula (III) is added in a second step.

[0096] In the inventive method for preparing the mixture of modified fatty alcohol alkoxylates of the formula (I), the molar ratio of the alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide to the one or more fatty alcohols of the formula (II) preferably is from 1:1 to 150:1, more preferably from 1:1 to 100:1, even more preferably from 2:1 to 75:1, particularly preferably from 3:1 to 50:1, extraordinarily preferably from 5:1 to 40:1, and particularly preferably from 8:1 to 30:1.

[0097] In the inventive method for preparing the mixture of modified fatty alcohol alkoxylates of the formula (I), the molar ratio of the modifying reagent of theformula (III) to the one or more fatty alcohols of the formula (II) preferably is from 0.5:1.0 to 2.0:1.0, more preferably from 0.6:1.0 to 1.5:1, even more preferably from 0.75:1.0 to 1.2: 1.0, particularly preferably from 0.9: 1.0 to 1.1:1, and extraordinarily preferably 1.0: 1.0.

[0098] Preferably, in the method according to the invention, the catalyst (C) is obtainable by a reaction involving

[0099] (a) an alkaline earth metal compound (A) and

[0100] (b) one or more substances selected from the group consisting of a carboxylic acid (B) preferably comprising 3 to 60, more preferably 3 to 46, carbon atoms; a polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol; a C1-C18 alkyl-capped polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol; an alcohol solvent; and mixtures including any of the foregoing, and

[0101] (c) a strong acid (AC).

[0102] Herein, all reported molecular weight values refer to the weight-average molecular weight (Mw).

[0103] The weight-average molecular weight of the polymeric products described herein, such as the polyalkylene glycol or the C1-C18 alkyl-capped polyalkylene glycol used in the preparation of the catalyst (C), is preferably determined via Gel Permeation Chromatography (GPC) according to DIN 55672-1. This method specifies the procedure and conditions for determining the molecular weight distribution of polymers using tetrahydrofuran (THF) as the eluent, from which the weight average molecular weight (Mw) can be calculated.

[0104] Preferably, in the method according to the invention the alkaline earth metal compound (A) is selected from the group consisting of magnesium hydroxide, magnesium acetate, magnesium carbonate, magnesium sulfate, magnesium phosphate, calcium hydroxide, calcium acetate, calcium carbonate, calcium sulfate, calcium phosphate, strontium hydroxide, strontium acetate, strontium carbonate, strontium sulfate, strontium phosphate, barium hydroxide, bariumacetate, barium carbonate, barium sulfate, and barium phosphate. In a more preferred embodiment of the method according to the invention, the alkaline earth metal compound (A) is selected from the group consisting of calcium hydroxide, calcium acetate, calcium carbonate, calcium sulfate, and calcium phosphate. In another more preferred embodiment of the method according to the invention, the alkaline earth metal compound (A) is selected from the group consisting of magnesium hydroxide, magnesium acetate, calcium hydroxide, calcium acetate, strontium hydroxide, strontium acetate, barium hydroxide, and barium acetate. Particularly preferably, in the method according to the invention, the alkaline earth metal compound (A) is selected from the group consisting of calcium acetate and calcium hydroxide.

[0105] The carboxylic acid (B) mentioned under component (b) above may e.g. be a carboxylic acid, wherein the carboxylic acid function -COOH is connected to a hydrocarbon group but may also e. g. be a carboxylic acid wherein the carboxylic acid function -COOH is connected to a hydrocarbon group that contains or is interrupted by ether functions.

[0106] The alcohol mentioned in component (b) is an alcohol wherein the hydroxyl function -OH is bonded to a hydrocarbyl group.

[0107] Preferably, in the method according to the invention, the alcohol solvent is an alcohol solvent having 1 to 5 carbon atoms, more preferably propan-2-ol, or a mixture thereof with water.

[0108] Preferably, in the method according to the invention, the strong acid (AC) is an acid which has a PKA value of 3 or less, preferably 2 or less, more preferably 0 or less, and often -3 or less.

[0109] Preferably, the acid (AC) is selected from the group consisting of acids of sulfur oxides and phosphorus oxides, more preferably from the group consisting of sulfuric acid, sulfurous acid, sulfonic acids (among the sulfonic acids methanesulfonic acid is preferred), phosphorus acid, phosphorous acid and phosphonic acids (among the phosphonic acids methane phosphonic acid is preferred).

[0110] Sulfuric acid, sulfurous acid and methane sulfonic acid are particularly preferred.

[0111] Extraordinarily preferably, in the method according to the invention, the strong acid (AC) is sulfuric acid.

[0112] Preferably, in the method according to the invention, the molar ratio of the alkaline earth metal compound (A) to the strong acid (AC) is from 1.0:0.1 to 1.0: 1.0, more preferably from 1.0:0.2 to 1.0:0.9 and even more preferably from 1.0:0.3 to 1.0:0.8.

[0113] Preferably, in the method according to the invention, the polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol is a polyethylene glycol having a molecular weight from 100 g / mol to 1500 g / mol.

[0114] Preferably, in the method according to the invention, the C1-C18 alkyl-capped polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol is a methyl-capped polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol and more preferably is a methyl-capped polyethylene glycol having a molecular weight from 100 g / mol to 1500 g / mol.

[0115] Preferably, in the method according to the invention, volatile components are removed before the catalyst (C) is used for the preparation of the mixture of modified fatty alcohol alkoxylates of the formula (I).

[0116] In one preferred embodiment of the method according to the invention, a carboxylic acid (B) is used in the preparation of the catalyst (C).

[0117] Preferably, in the method according to the invention, the molar ratio of alkaline earth metal compound (A) to carboxylic acid (B) in the preparation of the catalyst (C) is from 1:1 to 1 :5.

[0118] Preferably, the carboxylic acid (B) is represented by formula (IV),Rc-[O]q-[CH2CH2-O]P-CH2COOH (IV)

[0119] wherein

[0120] Rcis selected from saturated or unsaturated, linear or branched Ci to C30 hydrocarbyl groups, preferably Ci to C22 hydrocarbyl groups, and more preferably Ce to Cis hydrocarbyl groups,

[0121] q is 0 or 1 , and

[0122] p is, based on molar average, a number from 0 to 11 , preferably from 1 to 11 , more preferably from 1 to 9, and even more preferably from 2 to 7.

[0123] In a more preferred embodiment of the invention, the carboxylic acid (B) is represented by formula (IV),

[0124] Rc-[O]q-[CH2CH2-O]P-CH2COOH (IV) wherein

[0125] Rcis selected from saturated or unsaturated, linear or branched Ci to C30 hydrocarbyl groups, preferably Ci to C22 hydrocarbyl groups, and more preferably Ce to Cis hydrocarbyl groups,

[0126] q is 0, and

[0127] p is 0, and

[0128] preferably is isononanoic acid or oleic acid.

[0129] In another more preferred embodiment of the invention, the carboxylic acid (B) is represented by formula (IV),

[0130] Rc-[O]q-[CH2CH2-O]P-CH2COOH (IV) wherein

[0131] Rcis selected from saturated or unsaturated, linear or branched Ci to C30 hydrocarbyl groups, preferably Ci to C22 hydrocarbyl groups, and more preferably Ce to C18 hydrocarbyl groups,

[0132] q is 1, and

[0133] p is, based on molar average, a number from 0 to 11 , preferably from 1 to 11 , more preferably from 1 to 9, and even more preferably from 2 to 7, andpreferably, R4is oleyl, q is 1 , and p is, based on molar average, 5.

[0134] In one preferred embodiment of the invention, the catalyst (C) is obtainable by a reaction involving

[0135] (a) calcium hydroxide and

[0136] (b) a carboxylic acid (B), which is represented by formula (IV),

[0137] Rc-[O]q-[CH2CH2-O]P-CH2COOH (IV)

[0138] wherein

[0139] Rcis selected from saturated or unsaturated, linear or branched Ci to C30 hydrocarbyl groups, preferably Ci to C22 hydrocarbyl groups, and more preferably Ce to Cis hydrocarbyl groups,

[0140] q is 0, and

[0141] P is 0,

[0142] and preferably is isononanoic acid, and

[0143] an alcohol solvent, preferably an alcohol solvent having 1 to 5 carbon atoms, more preferably propan-2-ol, or a mixture thereof with water, and (c) sulfuric acid.

[0144] In another preferred embodiment of the invention, the catalyst (C) is obtainable by a reaction involving

[0145] (a) calcium hydroxide and

[0146] (b) a carboxylic acid (B), which is represented by formula (IV),

[0147] Rc-[O]q-[CH2CH2-O]P-CH2COOH (IV)

[0148] wherein

[0149] Rcis selected from saturated or unsaturated, linear or branched Ci to C30 hydrocarbyl groups, preferably Ci to C22 hydrocarbyl groups, and more preferably Ce to Cis hydrocarbyl groups,

[0150] q is 1, andp is, based on molar average, a number from 0 to 11 , preferably from 1 to 11 , more preferably from 1 to 9, and even more preferably from 2 to 7, and

[0151] preferably, R4is oleyl, q is 1, and p is, based on molar average, 5, and

[0152] an alcohol solvent, preferably an alcohol solvent having 1 to 5 carbon atoms, more preferably propan-2-ol, or a mixture thereof with water, and (c) a strong acid and preferably sulfuric acid.

[0153] In another preferred embodiment of the invention, the catalyst (C) is obtainable by a reaction involving

[0154] (a) calcium acetate and

[0155] (b) a polyalkylene glycol having a molecular weight from 100 g / mol to

[0156] 1500 g / mol or mixtures of such polyalkylene glycols, and

[0157] (c) sulfuric acid.

[0158] In another preferred embodiment of the invention, the catalyst (C) is obtainable by a reaction involving

[0159] (a) calcium acetate and

[0160] (b) a carboxylic acid (B), which is represented by formula (IV),

[0161] Rc-[O]q-[CH2CH2-O]P-CH2COOH (IV)

[0162] wherein

[0163] Rcis selected from saturated or unsaturated, linear or branched Ci to C30 hydrocarbyl groups, preferably Ci to C22 hydrocarbyl groups, and more preferably Ce to Cis hydrocarbyl groups,

[0164] q is 0, and

[0165] p is 0, and

[0166] preferably, is oleic acid, and

[0167] a C1-C18 alkyl-capped polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol, preferably a methyl-capped polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol and morepreferably a methyl-capped polyethylene glycol having a molecular weight from 100 g / mol to 1500 g / mol or mixtures of such alkyl-capped polyalkylene glycols, and

[0168] (c) sulfuric acid.

[0169] In another preferred embodiment of the invention, the catalyst (C) is obtainable by a reaction involving

[0170] (a) calcium acetate and

[0171] (b) an alcohol solvent, preferably an alcohol solvent having 1 to 5 carbon atoms, more preferably propan-2-ol, or a mixture thereof with water, and (c) sulfuric acid.

[0172] The molar ratio of alkaline earth metal compound (A) to carboxylic acid (B) (molar ratio (A):(B)) in the preparation of the catalyst (C) preferably is from 1:1 to 1 :5. More preferably, the molar ratio (A):(B) is from 1:1.5 to 1:4, even more preferably from 1 : 1.8 to 1 :2.2 and particularly preferably from 1 : 1.9 to 1 :2.1. In an extraordinarily preferred embodiment of the invention, the molar ratio of (A):(B) in the preparation of the catalyst (C) is approximately 1:2.

[0173] In one preferred embodiment of the invention, the reaction for the preparation of the catalyst (C) is carried out in the presence of at least one polar solvent, more preferably a polar solvent comprising at least one hydroxyl group, even more preferably at least one alcohol having 1 to 5 carbon atoms or a mixture thereof with water. In a particularly preferred embodiment, the polar solvent is propan-2-ol or a mixture thereof with water. In another particularly preferred embodiment, the polar solvent is ethanol or a mixture thereof with water.

[0174] It is particularly advantageous to prepare the alkaline earth metal catalyst (C) by first allowing the alkaline earth metal compound (A) to react with the carboxylic acid (B), preferably in a solvent as described above, after which the reaction mixture is further treated with the acid (AC), preferably sulphuric acid.It is also particularly advantageous to prepare the alkaline earth metal catalyst (C) by first dispersing the alkaline earth metal compound (A) in a polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol or mixtures of such polyalkylene glycols, or in a C1-C18 alkyl-capped polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol, preferably a methyl-capped polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol and more preferably a methyl-capped polyethylene glycol having a molecular weight from 100 g / mol to 1500 g / mol or mixtures of such alkyl-capped polyalkylene glycols, optionally in the presence of water, after which the reaction mixture is further treated with the acid (AC). The dispersing step may be performed in the presence of a carboxylic acid (B), which is represented by formula (IV),

[0175] Rc-[O]q-[CH2CH2-O]P-CH2COOH (IV) wherein

[0176] Rcis selected from saturated or unsaturated, linear or branched Ci to C30 hydrocarbyl groups, preferably Ci to C22 hydrocarbyl groups, and more preferably Ce to C18 hydrocarbyl groups,

[0177] q is 0, and

[0178] p is 0, and

[0179] preferably is oleic acid.

[0180] It is also particularly advantageous to prepare the alkaline earth metal catalyst (C) by first dispersing the alkaline earth metal compound (A) in an alcohol solvent, preferably an alcohol solvent having 1 to 5 carbon atoms, more preferably propan-2-ol, or a mixture thereof with water, after which the reaction mixture is further treated with the acid (AC).

[0181] For the reaction by which the alkaline earth metal catalyst (C) is obtained, any common reactor may be employed, preferably a reactor with an agitating / mixing means, such as, e.g., a magnetic stirrer, a mechanical stirrer, a static mixer, a blender, a batch disperser, or a Rotor-Stator disperser.The preparation of the catalyst (C) is preferably carried out under a pressure of from 0.5 to 2 bar, more preferably from 0.8 to 1.5 bar, even more preferably from 0.9 to 1.2 bar. In a preferred embodiment of the invention, the catalyst is prepared under atmospheric pressure. Furthermore, the catalyst (C) is preferably prepared at a temperature of from -30 °C to 80 °C, preferably from -10 °C to 60 °C, more preferably from 0 °C to 50 °C. In a preferred embodiment of the invention, the catalyst is prepared at a temperature of from 20 to 40 °C, especially at room temperature.

[0182] The thus prepared alkaline earth metal catalyst (C), preferably the calcium catalyst, typically has a content of alkaline earth metal ions, preferably Ca2+ions, that is from 0.5 to 10 wt.-%, often from 1 to 7 wt.-%, often from 2.0 to 5.5 wt.-%.

[0183] Optionally, the catalyst may be purged of volatile components, such as the solvent, water and other volatile by-products by employing commonly used methods. Preferably, the volatile components are removed in vacuo, e.g. under a pressure below 0.8 bar, preferably below 0.3 bar, more preferably below 0.1 bar, and / or at elevated temperatures, e.g. 50 to 180 °C, preferably 70 to 150 °C, more preferably 80 to 140 °C.

[0184] In a particularly preferred embodiment of the invention, the volatile compounds are removed on a rotary evaporator at a pressure below 0.1 bar and a temperature of from 80 °C to 140 °C.

[0185] Preferably, the method of the invention for preparing a mixture of modified fatty alcohol alkoxylates of the formula (I) according to the invention comprises the steps of

[0186] i) introducing the catalyst (C) as defined above and one or more fatty alcohols of the formula (II) as described above into a pressure-resistant reactor; ii) optionally replacing the air in the reactor with nitrogen or other protective gas;

[0187] iii) optionally drying the reactor content at a temperature of from 50 to 200 °C and / or a pressure below 0.8 bar;iv) heating the content of the reactor to a temperature of from 80 °C to 200 °C; v) optionally pressurizing the reactor with nitrogen or other protective gas to a pressure of from 0.3 bar to 3.5 bar above atmospheric pressure;

[0188] vi) pressurizing the reactor with alkylene oxide gas selected from the group consisting of ethylene oxide gas, propylene oxide gas and mixtures of ethylene oxide gas and propylene oxide gas to a pressure of from 1.5 bar to 10 bar above atmospheric pressure with the proviso that the pressure is above the pressure prior to step vi);

[0189] vii) allowing the mixture to react until the pressure in the reactor is constant. viii) optionally adding a second alkaline catalyst to the mixture

[0190] ix) adding one or more modifying reagents of the formula (III) and continue stirring, until sufficient conversion is monitored

[0191] x) optionally adding an acid to neutralize the product mixture

[0192] In step i), the catalyst (C) may be introduced as obtained from the reaction of its preparation described above directly, or in its form that has been purged of volatile compounds, but preferably as obtained from the reaction of its preparation described above directly. The fatty alcohols of formula (II) may be introduced in their raw form or may be purified prior to use.

[0193] The catalyst (C) is preferably introduced into the reactor in an amount from 0.1 to 5 wt.-%, preferably from 0.2 to 3 wt.-%, more preferably from 0.3 to 2 wt. % based on the total weight of the mixture of fatty alcohol of formula (II) and alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide.

[0194] The pressure-resistant reactor is not particularly limited but is designed to withstand the pressures employed in the process, thus that it is not damaged during the process. Preferably, the reactor is designed to withstand pressures both above 10 bar, more preferably above 15 bar, and below 0.01 bar, more preferably below 0.001 bar. Preferably, the pressure-resistant reactor is an autoclave, more preferably an autoclave equipped with an agitating means such as a magnetic or a mechanical stirrer.Generally, the replacement of air in the reactor with nitrogen or other protective gas is not necessarily required, because the mixture of modified fatty alcohol alkoxylates of the formula (I) according to the invention would at least partially be generated in the process. However, air, particularly oxygen, in the reactor may lead to safety concerns during alkoxylation reactions in general and decomposition products due to oxidation and / or hydrolysis of the employed materials and of the generated products, especially at elevated temperatures. Therefore, it is advisable to carry out step ii) of the method of the invention after step i).

[0195] In general, the step of drying the reactor content is also not necessarily required, because the mixture of modified fatty alcohol alkoxylates of the formula (I) according to the invention would at least partially be generated in the process. However, water and other volatile impurities may facilitate undesired side reactions under the reaction conditions. Especially if in step i) the catalyst (C) is introduced into the reactor as obtained from the reaction of its preparation described above directly, it is advisable to carry out the drying step, since the directly obtained catalyst (C) typically contains residues of polar solvents or their mixtures with water. In case the catalyst (C) is purged of volatile components before introducing it into the reactor, the drying step iii) may be omitted.

[0196] Nevertheless, in this case it may be advisable to carry out step iii) since volatile components may also be present as impurities in the one or more fatty alcohols of formula (II). Therefore, in particularly preferred embodiments, step iii) is carried out.

[0197] The step iii) of drying the reactor content is typically performed at a temperature of from 50 °C to 200 °C, preferably of from 50 °C to 180 °C, more preferably of from 60 °C to 150 °C, even more preferably of from 70 °C to 130 °C, particularly preferably of from 80 °C to 120 °C, and at a pressure below 0.8 bar, preferably below 0.1 bar, more preferably below 0.05 bar. The thus generated vacuum is preferably a dynamic vacuum.

[0198] The vacuum pump for generating the vacuum is not particularly limited; it is, however, preferable to use an aspirator for generating the vacuum. Furthermore, itis advisable to reduce the pressure and increase temperature in the reactor gradually to prevent boiling retardation. In a particularly preferred embodiment, the step of drying the reactor content is carried out at a temperature of from 80 °C to 120 °C and a pressure below 0.01 bar, preferably over a period of at least

[0199] 15 minutes, more preferably over a period of at least 30 minutes, even more preferably over a period of at least 1 hour. It is particularly preferred to dry the content of the reactor to constant mass.

[0200] After the drying step iii), the fluid line between the vacuum pump and the reactor is interrupted, to ensure that the components added to the reactor after the drying remain in the reactor and are not directly withdrawn therefrom. Furthermore, it is preferable to compensate the vacuum in the reactor with nitrogen or other protective gas before carrying out the further steps, to reduce the risk of air entering the reactor.

[0201] Step iv) of heating the content of the reactor is generally performed at a temperature of from 80 °C to 200 °C, preferably from 120 °C to 190 °C, more preferably from 150 °C to 180 °C. This temperature is maintained at least until step vi) is finished, preferably until step vii) is finished.

[0202] After setting the temperature in step iv), the reactor may be optionally pressurized in step v) with nitrogen or other protective gas to a pressure of from 0.3 to 3.5 bar, preferably of from 0.4 to 3.3 bar, more preferably of from 0.5 to 3.0 bar, even more preferably of from 0.7 to 2.5 bar and particularly preferably of from 0.8 to 2.2 bar above atmospheric pressure. By carrying out this step v), alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide introduced in the following step is diluted with the protective gas, thus that pressure-controlled dosage of alkylene oxide into the reactor is facilitated.

[0203] In step vi) the reactor is further pressurized with alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide to a total internal pressure of from 1.5 to 10 bar, preferablyfrom 2 to 8 bar, more preferably from 3 to 6 bar, even more preferably from 4 to 5 bar, above atmospheric pressure, with the proviso that the pressure in step vi) is above the pressure before step vi).

[0204] During step vii), after introduction of the intended amount of alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide, the alkylene oxide inlet is closed and the reaction is allowed to proceed until the pressure in the reactor is constant.

[0205] In the sense of the invention, the pressure is considered constant, if it does not change by more than 0.05 bar over a period of 15 minutes, preferably 30 minutes, more preferably 1 hour. It is particularly preferred that the pressure in the reactor does not change by more than 0.01 bar over a period of 1 hour.

[0206] In step viii), the optional alkaline catalyst is preferably introduced into the reactor in an amount from 0.1 to 5 wt.-%, preferably from 0.2 to 3 wt.-%, more preferably from 0.3 to 2 wt. % based on the total weight of the mixture of fatty alcohol of formula (II) and alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide.

[0207] In step viii), the optional alkaline catalyst is selected from the group consisting of sodium hydroxide, potassium hydroxide and sodium methylate, preferably sodium hydroxide.

[0208] During step ix), after introduction of the intended amount of one or more modifying reagents of the formula (III), the dosing inlet is closed, and the reaction is allowed to proceed until the pressure in the reactor is constant.

[0209] In step ix) the reaction progress may be monitored by hydroxyl value, cloud point or epoxide value.In step x), optionally an amount of acid is added, which is sufficient to adjust the pH to 6 to 8 (5% substance in 1:1 ethanol / water). The acid is selected from the group consisting of acetic acid, lactic acid and isononanoic acid.

[0210] After completion of step x), it is advisable to remove residual alkylene oxide from the reactor before isolating the mixture of modified fatty alcohol alkoxylates of the formula (I) according to the invention, in order to prevent any unwanted reactions with alkylene oxide from taking place after isolation of the product. Preferably, residual alkylene oxide is removed from the reactor by cooling the reactor content to a temperature of from 50 to 120 °C, more preferably from 70 to 100 °C and even more preferably from 85 to 95 °C, and employing a pressure of below 0.8 bar, preferably below 0.1 bar, more preferably below 0.05 bar. The thus generated vacuum is preferably a dynamic vacuum. The vacuum pump for generating the vacuum is not particularly limited; it is, however, preferable to use an aspirator for generating the vacuum. Removal of residual alkylene oxide under these conditions is preferably carried out for at least 10 minutes, more preferably at least 30 minutes and even more preferably at least 1 hour.

[0211] The method of isolation of the mixture of modified fatty alcohol alkoxylates of the formula (I) according to the invention is not particularly limited. However, it is preferable to isolate the product at elevated temperatures, specifically at temperatures of from 50 to 150 °C, preferably from 60 to 140 °C, more preferably from 80 to 120 °C. At these temperatures, the mixture of modified fatty alcohol alkoxylates of the formula (I) according to the invention is typically in a liquid state and has a sufficiently low viscosity, and therefore may be transferred out of the reactor more easily than in the solid state, e.g. by pouring the product out of the reactor or via a bottom valve, thereby minimizing the amount of residues in the reactor. Thus, the subsequent cleaning and maintenance of the reactor is also facilitated.

[0212] The method for preparing a mixture of modified fatty alcohol alkoxylates of the formula (I) according to the invention using the catalyst (C) described above maybe interrupted at any stage, and continued at a later point in time, without the reaction time being significantly increased.

[0213] The mixture of modified fatty alcohol alkoxylates of the formula (I) according to the invention may occur together with starting material used for its preparation, in particular fatty alcohol in case the inventive mixture is prepared by alkoxylation of fatty alcohols (in the following referred to as “composition A”). In case fatty alcohol is present in the compositions A, the fatty alcohols may be present in an amount of 0.01 wt.-% or more, or 0.05 wt.-% or more, or 0.1 wt.-% or more, or 1.0 wt.-% or more, in each case based on the total weight of the composition A. In case fatty alcohols is present in the compositions A, the fatty alcohols is present in an amount of preferably less than 15.0 wt.-%, more preferably less than 10.0 wt.-%, even more preferably less than 5.0 wt.-%, particularly preferably less than 2.0 wt.-% and extraordinarily preferably less than 1.0 wt.-%, in each case based on the total weight of the composition A.

[0214] During the preparation of the mixture according to the invention, by-products may be formed. The formation of by-products in chemical reactions is quite normal since these reactions usually do not take place with a selectivity of 100 %.

[0215] However, in case by-products are formed during the preparation of the mixture according to the invention, these by-products are formed in an amount of preferably less than 20.0 wt.-%, more preferably less than 15.0 wt.-%, even more preferably less than 10.0 wt.-%, particularly preferably less than 6.0 wt.-%, extraordinarily preferably less than 5.0 wt.-% and especially preferably less than 2.0 wt.-%, in each case based on the combined total weight of the mixture according to the invention and the by-products, and in particular in case the inventive mixture is prepared by a method according to the invention.

[0216] Starting material, and in particular fatty alcohols, occurring together with the mixture according to the invention is considered to form part of the by-products.

[0217] Furthermore, the mixture according to the invention may be purified after its preparation and prior to its use, e.g. by distilling, stripping or filtering-off by-products, but in a preferred embodiment, the mixture may be used as obtained without prior purification.

[0218] A further subject matter of the invention is an alkoxylation product obtainable by the inventive method described above for preparing a mixture according to the invention. The alkoxylation product comprises a mixture of modified fatty alcohol alkoxylates of the formula (I) according to the invention and may optionally comprise further substances such as starting materials or reactants, in particular fatty alcohols of the formula (II), and / or by-products.

[0219] The inventive mixtures of modified fatty alcohol alkoxylates of the formula (I) or the inventive alkoxylation product may also be bio-based.

[0220] Bio-based fatty alcohol alkoxylates of formula (I) can, for example, be prepared from (i) fatty alcohol and (ii) ethylene oxide, propylene oxide or mixtures of ethylene oxide and propylene oxide, wherein at least a part of one of the aforementioned alkylene oxides is bio-based.

[0221] Bio-based ethylene oxide can be obtained from bio-ethanol, which can be obtained from natural sources like corn, sugarcane, or cellulosic biomass through fermentation. Bio-ethanol is then dehydrated to produce bio-ethylene. The bioethylene is then oxidized with oxygen over a silver catalyst to produce bio-based ethylene oxide.

[0222] Bio-based propylene oxide can be obtained from

[0223] 1) bio-glycerol, which can be obtained from biodiesel production, hydrolysis of vegetable oils, or fermentation of sugars. Bio-glycerol is then converted to acrolein via dehydration. Acrolein is hydrogenated to produce bio-propanol and subsequently dehydrated to provide bio-propylene, which is epoxidized to produce propylene oxide using hydrogen peroxide; or

[0224] 2) bio-ethanol, which can be obtained from natural sources like com, sugarcane, or cellulosic biomass through fermentation. Bio-ethanol is then dehydrated to produce bio-ethylene. The bio-ethylene is then catalyticallydimerized to bio-butene. Bio-butene and bio-ethylene are then converted to bio-propylene via metathesis. The bio-propylene is then catalytically converted to propylene oxide.

[0225] Preferably, the materials used to prepare the inventive mixture of modified fatty alcohol alkoxylates of the formula (I) or the inventive alkoxylation product are biobased and derived from natural sources. More preferably, the inventive mixture of modified fatty alcohol alkoxylates of the formula (I) or the inventive alkoxylation product has at least 25 wt.-%, preferably at least 50 wt.-%, more preferably at least 75 wt.-%, even more preferably at least 90 wt.-% and particularly preferably 100 wt.-% bio-based carbon content, in each case relative to the total mass of carbon in the mixture of modified fatty alcohol alkoxylates of the formula (I) or relative to the total mass of carbon in the alkoxylation product, respectively.

[0226] The mixture of modified fatty alcohol alkoxylates of the invention may be used in substance, but may also be provided as solutions. The latter exhibit beneficial handling properties and are more easily dosed. Preferably, the solutions comprise the mixture of modified fatty alcohol alkoxylates of the invention in an amount from 50 to 90 weight-% based on the total weight of the solution or dispersion. Suitable solvents for such solutions are for example water, ethanol, propanol, butanol, ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, 1,2 butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, butyl glycol, butyl diglycol and butyl polyglycol. These solvents are preferably used in an amount from 10 to 50 wt.-% and more preferably in an amount from 10 to 25 wt.-%, in each case based on the total weight of the solution. Even more preferably, the inventive solutions comprise water.

[0227] These inventive solutions are liquid and comprise the mixture of modified fatty alcohol alkoxylates of the invention in a high concentration. They may e.g. represent high concentrated liquid handling forms of the inventive mixture of modified fatty alcohol alkoxylates and may be used for the preparation of inventive detergent compositions to be used by end-consumers. These inventive solutions comprising the mixture of modified fatty alcohol alkoxylates of the invention in a high concentration nevertheless possess an advantageous low viscosity in thesense that this viscosity causes, for example, no issues on pumpability or dosage consistency during the preparation of the inventive detergent compositions to be used by end-consumers.

[0228] A further subject matter of the invention is a detergent composition for machine dishwashing comprising Z1) the inventive mixture of modified fatty alcohol alkoxylates of formula (I) or the inventive alkoxylation product.

[0229] The mixture of modified fatty alcohol alkoxylates Z1) may be used both in conventional rinse aids and in conventional combined products, as well as any other forms of detergent formulations known in the art. The mixture of modified fatty alcohol alkoxylates Z1 ) show their beneficial effects independently of the form or preparation method of the detergent composition for machine dishwashing. Another benefit of the invention is that the detergent composition for machine dishwashing according to the invention leads to an improved drying capacity of the dishes treated with the composition of the invention.

[0230] Furthermore, the mixture of modified fatty alcohol alkoxylates Z1) do not increase the foaming rate of detergent compositions, thus that the detergent composition for machine dishwashing according to the invention is weakly foaming.

[0231] Moreover, the detergent composition for machine dishwashing according to the invention retains the beneficial rinse aiding properties even in phosphate-free compositions.

[0232] Preferably, the detergent composition for machine dishwashing according to the invention comprises the mixture of modified fatty alcohol alkoxylates Z1) in amounts of from 0.1 to 15 wt.-%, preferably from 0.5 to 10 wt.-%, more preferably from 1 to 6 wt.-%, based on the total weight of the detergent composition.

[0233] The pH value of the detergent composition for machine dishwashing according to the invention is preferably from 8 to 13, more preferably from 9 to 11.5, even morepreferably from 9.5 to 11.5 measured at 20 ° C, as a 10 wt.-% aqueous solution of the detergent composition for machine dishwashing according to the invention.

[0234] Preferably, the detergent composition for machine dishwashing according to the invention may further to the mixture of modified fatty alcohol alkoxylates Z1 ) comprise one or more components selected from:

[0235] Z2) one or more enzymes;

[0236] Z3) one or more builders;

[0237] Z4) one or more bleaching agents;

[0238] Z5) one or more surfactants;

[0239] Z6) one or more polymers;

[0240] Z7) one or more further additives, preferably selected from the group consisting of chelating agents, glass corrosion inhibitors, water, organic solvents, thickeners, foaming inhibitors, color particles, silver protecting agents, agents for preventing the tarnishing of silver, corrosion inhibitors, colorants, fillers, germicidal agents, hydrotropic agents, antioxidants, enzyme stabilizers, perfumes, solubilizers, carriers, processing aids, pigments and pH regulators.

[0241] Preferably, the one or more enzymes of component Z2), if present, are selected from the group consisting of proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases and oxidoreductases.

[0242] The enzymes are typically of natural origin. Improved variants that are based on natural molecules are obtainable for the use in detergent compositions for machine dishwashing and are accordingly preferred.

[0243] Among the proteases, those of the subtilisin type are preferred. Examples are the subtilisins BPN’ and Carlsberg, as well as their advanced forms, protease PB92, subtilisins 147 and 309, alkaline protease from Bacillus lentus, subtilisin DY and subtilases.Examples for amylases applicable according to the invention are a-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus nigerand A. oryzae as well as their derivatives improved for use in detergent compositions for machine dishwashing. Furthermore, a-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin-glucanotransferase (CGTase) FROM B. agaradherens (DSM 9948) are preferred.

[0244] Furthermore, lipases or cutinases may be used in the detergent composition of the invention, in particular due to their triglyceride-cleaving activities, but also for in situ preparing peroxy acids from appropriate precursors. Exemplary lipases are those originating from Humicola lanuginosa (Thermomyces lanuginosus) or their advanced forms, especially those with the amino acid exchange D96L. Exemplary cutinases are those originally isolable from Fusarium solani pisi and Humicola insolens.

[0245] Moreover, enzymes can be used that are pooled under the term hemicellulases. These are, for example, mannanases, xanthanlyases, pektinlyases (=pektinases), pektinesterases, pektatlyases, xyloglucanases (=xylanases), pullulanases and [3-glucanases.

[0246] For increasing the whitening effect, the detergent composition of the invention may also comprise oxidoreductases, for example oxidases, oxygenases, katalases, peroxidases, such as halo-, chloro-, bromo-, lignin-, glucose or mangan-peroxidases, dioxygenases or laccases (phenoloxidases, polyphenoloxidases). Advantageously, additional, preferably organic, more preferably aromatic compounds that interact with the enzymes, are added in order to increase the activity of the corresponding oxidoreductases (enhancers) or in order to facilitate the electron transport between the oxidizing enzymes and the contaminations if their redox potentials have a large difference (mediators).

[0247] The enzymes may be used in any form known in the art, for example as granulated, extruded or lyophilized solid preparations or, particularly in liquid or gel formulations, as solutions of the enzymes, preferably highly concentrated, with a low water content and / or mixed with stabilizers.Alternatively, the enzymes may be in an encapsulated form, both in solid and in liquid compositions. For example, an enzyme solution may be spray-dried or extruded together with a preferably natural polymer or in the form of capsules, e.g. such, where the enzymes are enclosed in a solidified gel or such of the core-shell type, where an enzyme-containing core is coated with a water-, air- and / or chemical-impermeable protective coating. In additional layers further active agents such as stabilizers, emulsifiers, pigments, Whiteners or dyes may be included. Such capsules are prepared by known methods, e.g. shaking granulation or rolling granulation or in fluidized bed processes. Advantageously, such granulates are coated with polymeric film-forming agents and therefore low on dust and storage stable.

[0248] Furthermore, it is possible to compound two or more enzymes to prepare granules with multiple enzymatic activities.

[0249] The detergent composition for machine dishwashing according to the invention comprises the one or more enzymes Z2), if present, preferably in amounts of from 1x1 O’6to 5 wt.-%, more preferably from 1x1 O’5to 3 wt.-%, even more preferably from 1x1 O’4to 2 wt.-%, based on the total weight of the detergent composition.

[0250] This amount relates to active protein. The protein concentration can be determined by known methods such as the BCA-method or the biuret method.

[0251] The builders Z3) as well as other ingredients which may be used in detergent composition of the present invention are disclosed, e.g. in US 2010 / 0160204 and EP-A 1757676.

[0252] The builders Z3), if present, may be selected, e.g., from the group consisting of carbonates, bicarbonates, organic builders, preferably methylglycinediacetic acid (MGDA), silicates, phosphates, phosphonates and alkali metal hydroxides.

[0253] Preference is given to the use of carbonate(s) and / or bicarbonate(s), preferably alkali metal carbonate(s), more preferably sodium carbonate.These substances are preferably used in amounts of from 2 to 50 wt.-%, preferably from 10 to 30 wt.-% and in particular from 10 to 25 wt.-%, based on the total weight of the detergent composition according to the invention. Organic builders include polycarboxylates, polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, and dextrins. Useful organic builders are, among others, polycarboxylic acids usable in the form of the free acid and I or their sodium salts, wherein polycarboxylic acids are understood as those carboxylic acids which carry more than one acid moiety. For example these may be 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 mixtures thereof. In addition to their builder effect, the free acids typically also have the property of an acidifying agent and thus also serve to set a lower and milder pH for the detergent composition according to the invention. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, tartaric acid and any mixtures thereof are suitable.

[0254] Common aminocarboxylic acids that are preferred in the context of the present invention are, for example, ethylenediaminetetraacetic acid (EDTA), methylglycine-diacetic acid (MGDA) and glutamic diacetic acid (GLDA) or mixtures thereof.

[0255] Further preferred builders are polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to using polyaspartic acids, their salts or their derivatives.

[0256] Particularly advantageous for the cleaning and rinse aiding properties of the detergent composition of the invention is the use of citric acid and / or citrates.

[0257] Preference is given to detergent compositions which contain citric acid or a salt of citric acid, the weight fraction of citric acid or of the salt of citric acid preferably being from 2 to 50 wt.-%, more preferably from 5 to 30 wt.-% and even more preferably from 10 to 30 wt.-%, based on the total weight of the detergent composition.In another preferred embodiment of the invention, the detergent composition of the invention contain MGDA as one of their builders. The detergent composition of the invention preferably contain from 0.5 to 25 wt.-%, more preferably from 2 to 25 wt.-% of MGDA, based on the total weight of the detergent composition.

[0258] As organic builders, polymeric carboxylates are also suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 500 to 70,000 g / mol. Suitable polymeric carboxylates are in particular polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses of from 2,000 to 10,000 g / mol and more preferably from 3,000 to 5,000 g / mol are even more preferred in this group.

[0259] Also suitable are copolymeric carboxylates. Suitable comonomers are mono-ethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid. Particularly suitable are copolymeric carboxylates of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90 wt.-% of acrylic acid and 10 to 50 wt.-% of maleic acid have proven to be particularly suitable. Their molecular weight relative to free acids is preferably from 2,000 to 70,000 g / mol, more preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol. It is also possible to use copolymers of at least one monomer selected from the group consisting of monoethylenically unsaturated C3-C10 mono- or C4-C -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 hydrophilic or hydrophobic modified monomer, as listed below.

[0260] Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butane, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof, for example 1 -decene, 1 -dodecene, 1 -tetradecene, 1 -hexadecene,

[0261] 1 -octadecene, 1-eicosene, 1-docosene, 1 -tetracosene and 1 -hexacosene,C22-a-olefin, a mixture of C2o-C24-a-olefins and polyisobutene having a numberaverage of 12 to 100 carbon atoms per molecule.

[0262] Suitable hydrophilic monomers are monomers with sulfonate or phosphonate groups and nonionic monomers with hydroxyl function or alkylene oxide groups and optionally other ionogenic or nonionogenic monomers. Examples of the above listed 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 may contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.

[0263] Particularly preferred monomers containing sulfonic acid groups are

[0264] 1-acrylamido-1 -propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (2-acryloylamino-2-methylpropane-sulfonic acid), 2-methacrylamido-2-methylpropanesulfonic acid,

[0265] 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-sulfopropylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and salts of said acids, such as their sodium, potassium or ammonium salts.

[0266] Particularly preferred phosphonate group-containing monomers are vinylphosphonic acid and its salts. Moreover, amphoteric polymers can also be used as builders.

[0267] When the detergent composition according to the invention comprises one or more (co)polymeric carboxylates, the amount of these (co)polymeric carboxylates in theautomatic dishwashing agent according to the invention is preferably 0.5 to 20 wt.-% by weight and in particular 3 to 10 wt.-%, based on the total weight of the detergent composition of the invention.

[0268] Oxidisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate are further preferred organic builders, often referred to as co-builders. Among these, ethylenediamine-N,N'-disuccinate (EDDS) is preferred, especially used in the form of its sodium or magnesium salts. Furthermore as a builder or co-builder preferred in this context are glycerol disuccinates and glycerol trisuccinates.

[0269] The detergent composition according to the invention may preferably contain builders of crystalline sodium sheet silicates of the general formula NaMSixO2x+r yF , wherein M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, more preferably 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.

[0270] The detergent composition according to the invention preferably contains the crystalline sodium sheet silicates of formula NaMSixO2x+r yF in an amount of 0.1 to 20 wt.-%, more preferably from 0.2 to 15 wt.-%, even more preferably from 0.4 to 10 wt.-%, based on the total weight of the detergent composition for machine dishwashing.

[0271] It is also possible to use amorphous sodium silicates having a modulus Na2O:SiO2 of from 1 :2 to 1 :3.3, preferably from 1 :2 to 1 :2.8 and in particular from 1 :2 to 1 :2.6, which preferably show delayed dissolution and secondary wash properties. The dissolution delay compared to conventional amorphous sodium silicates can be caused in different ways, for example by surface treatment, compounding, compaction, condensing or over-drying. In the context of this invention, the term "amorphous" means that the silicates do not produce sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most cause one or more maxima of the scattered X-ray radiation, which have a width of multiple degrees of the diffraction angle.Alternatively or in combination with the aforementioned amorphous sodium silicates X-ray-amorphous silicates can be used, the silicate particles of which show blurred or even sharp diffraction maxima in Electron diffraction experiments.

[0272] This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, with values of up to a maximum of 50 nm and in particular up to a maximum of 20 nm being preferred. Such X-ray amorphous silicates also have a dissolution delay compared to the conventional water glasses. Particularly preferred are condensed / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray-amorphous silicates. In the context of the present invention, it is preferred that these silicates, preferably alkali metal silicates, particularly preferably crystalline or amorphous alkalidisilicates, are present in the detergent composition for machine dishwashing of the invention in amounts of from 3 to 60 wt.-%, preferably from 8 to 50 wt.-% and more preferably from 20 to 40 wt.-%, based on the total weight of the detergent composition.

[0273] Phosphates have proven to be effective builders in terms of cleaning performance. Among the large number of commercially available phosphates, the alkali metal phosphates have the greatest importance in the washing and cleaning industry, in particular pentasodium triphosphate or pentapotassium triphosphate (sodium or potassium tripolyphosphate).

[0274] Alkali metal phosphates is the summary term for the alkali metal salts (especially sodium and potassium salts) of the various phosphoric acids such as metaphosphoric acids (HP03)m, orthophosphoric acid H3PO4 and higher molecular weight representatives. The phosphates combine several advantages: they act as alkali metal carriers, prevent lime deposits on machine parts and contribute to the cleaning performance of the detergent composition.

[0275] Technically particularly important phosphates are the pentasodium triphosphate NasPsO (sodium tripolyphosphate) and the corresponding potassium saltpentapotassium triphosphate K5P3O10 (potassium tripolyphosphate). The sodium potassium tripolyphosphates are also preferably used according to the invention. If phosphates are used in the detergent composition according to the invention, preferred agents comprise phosphate(s), preferably alkali metal phosphate(s), more preferably pentasodium or pentapotassiumtriphosphat (sodium or potassium tripolyphosphate), in amounts of from 2 to 50 wt.-%, preferably from 2 to 30 wt.-%, more preferably from 3 to 25 wt.-% and particularly preferably from 3 to 15 wt.-%, based on the total weight of the detergent composition according to the invention.

[0276] As further builders, the detergent composition for machine dishwashing according to the invention may contain one or more phosphonates, which are often referred to as co-builders. The amount of phosphonates in the detergent composition of the invention is preferably 0.5 to 20 wt.-% and more preferably 1.0 to 10 wt.-%, based on the total weight of the detergent composition.

[0277] The chelating phosphonates include a number of different compounds such as 1 -hydroxyethane-1 , 1 -diphosphonic acid (HEDP) or diethylenetriamine penta(methylenephosphonic acid) (DTPMP). Particularly preferred are hydroxyalkane and aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1 -hydroxyethane-1, 1 -diphosphonate (HEDP) is of particular importance, preferably as a co-builder. It is preferably used as a sodium salt, of which the disodium salt reacts neutral and the tetrasodium salt reacts alkaline (pH 9). As aminoalkanphosphonates, ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylenephosphonate (DTPMP) and their higher homologues, among others, are applicable. They are preferably used in the form of neutral reacting sodium salts (e.g. as the hexasodium salt of EDTMP or as hepta- and octasodium salt of DTPMP). From the class of phosphonates, HEDP is preferably used.

[0278] Detergent compositions according to the invention can contain, as further builders, alkali metal hydroxides. These alkali carriers are preferably only used in small amounts, typically in amounts of 10 wt.-% or less, preferably 6 wt.-% or less, morepreferably 5 wt.-% or less, even more preferably 0.1 to 5 wt. % and in particular 0.5 to 5 wt.-%, based on the total weight of the detergent composition.

[0279] In a further preferred embodiment of the invention, the detergent composition according to the invention comprises one or more builders from the group of organic builders. In a particularly preferred embodiment of the invention, the detergent composition contains one or more builders from the group consisting of citrate, methylglycinediacetic acid (MGDA) and ethylenediamine-N,N'-disuccinate (EDDS). In a particularly preferred embodiment of the invention, the automatic dishwasher detergents according to the invention contain MGDA, specifically its trisodium salt.

[0280] The detergent composition according to the invention can contain said builders both individually and in the form of mixtures of two, three, four or more builders. In a preferred embodiment of the invention, the detergent composition according to the invention does not contain any phosphate builders.

[0281] The detergent composition according to the invention contains the one or more builders of component Z3), preferably in amounts of from 2 to 50 wt.-%, more preferably in amounts of from 10 to 30 wt.-% and especially preferably in amounts of from 10 to 25 wt.-%, based on the total weight of the detergent composition for machine dishwashing according to the invention.

[0282] The bleaching agent Z4) of the detergent composition for machine dishwashing according to the invention, if present, preferably contains one or more substances selected from the group consisting of bleaches, bleach activators and bleach catalysts.

[0283] As bleach, the detergent composition of the invention may contain an oxygen bleach. Among these oxygen bleaches, which yield H2O2 in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further applicable bleaches are, for example, peroxypyrophosphates, citrate perhydrates and H2O2-yielding peroxy acid salts orperoxy acids, such as peroxy benzoates, peroxy phthalates, diperoxy azelaic acid, Phthaloiminoperoxy acid or diperoxy dodecanedioic acid. Organic bleaches can also be used. Typical organic bleaches are diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaches are the peroxy acids, such as alkyl peroxy acids and aryl peroxy acids.

[0284] The detergent composition according to the invention preferably comprises one or more bleaches selected from the group consisting of oxygen bleaches, peroxy pyrophosphates, citrate perhydrates, and H2O2-delivering peroxy acid salts or peroxy acids and organic bleaches. Particularly preferably, the detergent composition contains 1.0 to 20 wt.-%, preferably 4.0 to 18 wt.-% and more preferably 8 to 15 wt.-% of an oxygen bleach, preferably sodium percarbonate, based on the total weight of the detergent composition for machine dishwashing.

[0285] To achieve an improved bleaching effect when dishwashing at temperatures of about 60 °C and below, the inventive detergent composition may additionally contain one or more bleach activators. Preferably, the one or more bleach activators are selected from the group consisting of which, under the conditions of perhydrolysis, result in aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 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 above-stated number of carbon atoms and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) being particularly suitable.

[0286] Bleach activators, in particular TAED, are preferably used in amounts of up to 10 wt.-% by weight, more preferably in amounts of from 0.1 to 8 wt.-% even more preferably in amounts of from 2 to 8 wt.-%, particularly in amounts from 2 to 6 wt.-%, based on the total weight of the detergent composition according to the invention.

[0287] In addition to, or in place of, the conventional bleach activators, so-called bleach catalysts can also be used. These substances are bleach-enhancing transitionmetal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo-salen complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands and Co, Fe, Cu and Ru amine complexes can also be used as bleach catalysts.

[0288] It is particularly preferred to use complexes of manganese in the oxidation state II, III, IV or V, which preferably contain one or more macrocyclic ligands with donor functions N, NR, PR, 0 and / or S. Preferred are ligands having nitrogen donor functions. It is particularly preferred to use bleach catalyst(s) which contain as macromolecular ligands 1 ,4,7-trimethyl-1 ,4,7-triazacyclononane (Me-TACN),

[0289] 1 ,4,7-triazacyclononane (TACN), 1 , 5, 9-trimethy 1-1 ,5,9-triazacyclododecane

[0290] (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). Suitable manganese complexes are, for example, [Mnlll2(p-O)i(p-OAc)2(TACN)2](CIO4)2, [MnIHMnlv(p-O)2(p-OAc)i (TACN)2](BPh4)2, [Mnlv4(p-O)6(TACN)4](C I O4)4, [Mnlll2(p-O)i (p-OAc)2(Me-TACN)2](CIO4)2, [MnlllMnlv(p-O)i(p-OAc)2(Me-TACN)2](CIO4)3, [Mnlv2(p-O)3(Me-TACN)2](PF6)2 and [Mnlv2(p-O)3(Me / Me-TACN)2](PF6)2(OAc=OC(O)CH3).

[0291] In a further preferred embodiment of the invention, the detergent composition according to the invention comprises one or more bleach catalysts from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of the complexes of manganese with 1 , 4, 7-trimethy I-1,4, 7-triazacyclononane (Me-TACN) and 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me4-TACN), since the cleaning result can be significantly improved by these bleach catalysts.

[0292] Preferably, the bleaching agent Z4) comprises one or more bleaches and one or more substances from the group of bleach activators and bleach catalysts. More preferably, the bleaching agent comprises one or more bleaches, one or more bleach activators, and one or more bleach catalysts.

[0293] The detergent composition according to the invention contains the bleaching agent of component Z4), if present, preferably in amounts of 1 to 40 wt.-%, more preferably inamounts of 0.5 to 30 wt.-% and even more preferably in amounts of 3 to 25 wt.-%, based on the total weight of the detergent composition.

[0294] The one or more surfactants of component Z5) of the detergent composition according to the invention, if present, are preferably selected from the group consisting of nonionic surfactants, zwitterionic surfactants, anionic surfactants, cationic surfactants and mixtures thereof.

[0295] Suitable nonionic surfactants may be any nonionic surfactants known in the art, preferably selected from the group consisting of fatty alcohol alkoxylates, endcapped fatty alcohol alkoxylates, ethylene-oxide / propylene-oxide-blockcopolymers, N-acylglucamides and epoxy-capped poly(alkoxylated) alcohols.

[0296] Among these nonionic surfactants of component Z5), preferred surfactants have the general formula (V)

[0297] Rd0-(CmH2m0)s-H (V),

[0298] wherein

[0299] Rdis a linear or branched saturated alkyl group of 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,

[0300] m is 2 or 3 or combinations thereof,

[0301] s is an integer from 1 to 150,

[0302] and wherein the group -(CmH2mO)s- comprises one or more -C2H4O groups and additionally may comprise one or more -CsHeO groups, and, if the group -(CmH2mO)s- comprises simultaneously -C2H4O- and -CsHeO groups, the -C2H4O-and -CsHeO groups can be distributed in any manner, preferably in statistical, gradient-like or block-like manner, and more preferably in a block-like manner within the -(CmH2mO)s- group and the molar amount of -C2H4O groups in the group -(CmH2mO)s- is preferably greater than the molar amount of -CsHeO groups.

[0303] Examples for the alkyl- and alkenyl-groups of Rdof formula (V) are, e.g. the alkyl and alkenyl groups of the following alcohols Rd-OH: 1 -octanol (caprylic alcohol),2-ethylhexanol, 1 -nonanol (pelargonic alcohol), 1 -decanol (capric alcohol),

[0304] 1 -undecanol, 1 -dodecanol (lauryl alcohol), 1 -tridecanol, isotridecanol,

[0305] 1 -tetradecanol (myristyl alcohol), 1 -pentadecanol, 1 -hexadecanol (cetyl alcohol), cis-9-hexadecene-1 -ol (palmitoleyl alcohol), 1 -heptadecanol, 1 -octadecanol (stearyl alcohol), cetearyl alcohol, 16-methylheptadecan-1-ol (Isostearyl alcohol), 9E-octadecene-1-ol (elaidyl alcohol), cis-9-octadecene-1-ol (oleyl alcohol), oleyl cetyl alcohol (i.e. , a mixture of oleyl alcohol and cetyl alcohol),

[0306] 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-octadecatriene-1-ol (elaidolinolenyl alcohol), 1 -nonadecanol,

[0307] 1-eicosanol (arachidyl alcohol), 1-heneicosanol, 1 -docosanol (behenyl alcohol), cis-13-docosen-1-ol (erucyl alcohol), 1-tetracosanol (lignoceryl alcohol),

[0308] 1-hexacosanol (ceryl alcohol), 1 -octacosanol (montanyl alcohol) and 1 -triacontanol (myricyl alcohol) or mixtures thereof.

[0309] Rdin formula (V) preferably represents 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 18 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 18 carbon atoms, and particularly preferably 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.

[0310] Preferably, the groups Rdin formula (V) are alkyl groups.

[0311] Preferably, s in formula (V) is an integer from 1 to 50, more preferably from 3 to 25, and even more preferably from 5 to 20.

[0312] In a preferred embodiment of the surfactants of formula (V), the group -(CmH2mO)s-consists of one or more -C2H4O groups and contains no -CsHeO groups.In a further preferred embodiment of the surfactants of formula (V), the group -(CmH2mO)s- contains one or more -C2H4O groups and one or more -CsHeO groups. In this preferred embodiment, the molar amount of the -CsHeO groups, based on the total amount of -C2H4O and CsHeO groups, is preferably less than 50%, more preferably 45% or less than 45%, even more preferably 40% or less than 40% and particularly preferably 33% or less than 33%.

[0313] In a further preferred embodiment of the surfactants of formula (V), the molar amount of -CsHeO groups, based on the total amount of -C2H4O and -CsHeO groups, is preferably 20 to less than 50%, more preferably 33 to 45 %, and even more preferably 33 to 40%.

[0314] In a particularly preferred embodiment of the surfactants of formula (V), the one or more nonionic surfactants of component Z5) of the detergent composition according to the invention contain a molar average of 8 -C2H4O groups and 4 -CsHeO groups and Rdrepresents 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.

[0315] The one or more nonionic surfactants of component Z5) of the detergent composition according to the invention preferably has a cloud point of 30 to 600C.

[0316] The detergent composition according to the invention contains the one or more nonionic surfactants of component Z5), if present, preferably in amounts of from 0.1 to 15 wt.-%, more preferably in amounts of from 0.2 to 10 wt.-% and even more preferably in amounts of 0.2 to 5 wt.-%, in each case based on the total weight of the detergent composition according to the invention.

[0317] The variable "s" in the one or more compounds of formula (V) represents molar averages, i.e. the detergent composition according to the invention may contain several compounds of formula (V) with different degrees of alkoxylation.Preference is also given to detergent compositions according to the invention, where the one or more surfactants of component Z5) are selected from the group of N-acylglucamines, which are also known as N-1 -deoxysorbityl fatty acid amides or glucamides, of the formula (VI),

[0318]

[0319] wherein Rfis 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

[0320] R9is hydrogen or a linear or branched saturated alkyl group having 1 to 4 carbon atoms.

[0321] Preferably, in the one or more N-acylglucamines of formula (VI), R9is a methyl group.

[0322] In the one or more N-acylglucamines of the formula (VI), Rfis preferably a linear or branched saturated alkyl group having 11 to 17 carbon atoms or a linear or branched unsaturated alkenyl group with one or more double bonds and 11 to 17 carbon atoms.

[0323] More preferably, in the one or more N-acylglucamines of formula (VI) Rfis 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.

[0324] In a preferred embodiment, 50 wt.-% or more, more preferably 60 to 99 wt.-% and even more preferably 70 to 98 wt.-% of the groups Rfin the one or more N-acylglucamines of the formula (VI) are linear or branched saturated alkyl groups with 17 carbon atoms.

[0325] In a further preferred embodiment, 0.1 to 50 wt.-%, more preferably 0.5 to 40 wt.-% and even more preferably 1.0 to 30 wt.-% of the groups Rfin the one or more N-acylglucamines of the formula (VI) are linear or branched saturated alkyl groups with 15 carbon atoms.

[0326] In a further preferred embodiment, 50 wt.-% or more of the Rfgroups in the one or more N-acylglucamines of the formula (VI) are linear or branched unsaturated alkenyl groups having one or more double bonds.

[0327] In a particularly preferred embodiment 50 wt.-% or more, more preferably 80 wt.-% or more and even more preferably 90 wt.-% or more of the groups Rfin the one or more N-acylglucamines of the formula (VI) are linear or branched alkenyl groups having one or more double bonds and 17 carbon atoms.

[0328] Particularly preferably, in the one or more N-acylglucamines of formula (VI), Rfis a linear group.

[0329] In another preferred embodiment, in the one or more N-acylglucamines of formula (VI) RfCO derives from lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid or linolenic acid. In a more preferred embodiment, in the one or more N-acylglucamines of the formula (VI) RfCO derives from stearic acid, oleic acid, linoleic acid or linolenic acid. In an even more preferred embodiment, in the one or more N-acylglucamines of formula (VI), RfCO derives from oleic acid, linoleic acid or linolenic acid, and in a particularly preferred embodiment, in the one or more N-acylglucamines of formula (V) RfCO derives from oleic acid.

[0330] The detergent compositions according to the invention comprise the one or more surfactants of component Z5), if present, preferably in amounts of from 0.1 to 15 wt.-%, more preferably in amounts of from 0.2 to 10 wt.-% even more preferably in amounts of from 0.2 to 5 wt.-%, based on the total weight of the detergent composition for machine dishwashing according to the invention.Suitable cationic surfactants of component Z5), which may be used instead of or together with the other surfactants mentioned herein, are, e.g., surfactants of formulae (VII), (VIII) and / or (IX),

[0331]

[0332] q

[0333] 113

[0334] R

[0335] wherein

[0336] each R10group 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 hydroxyalkyl groups having 1 to 6 carbon atoms;

[0337] each R11group 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;

[0338] R12is the same as R10or (CH2)n-T-R11;

[0339] R13is the same as R10, R11or (CH2)n-T-R11;

[0340] T is selected from -CH2-, -O-CO- or -CO-O-;q is an integer from 0 to 5;

[0341] X is an inorganic or organic anion having the charge b-;

[0342] b is a number from 1 to 4; and

[0343] c is a number having a value of 1 / b.

[0344] Further cationic surfactants suitable as component Z5) of the detergent composition according to the present invention are compounds of formula (X),

[0345]

[0346] wherein

[0347] R14is a linear or branched, preferably linear saturated alkyl group having from 1 to 6 carbon atoms;

[0348] R15, R16and R17are 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;

[0349] R18is 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;

[0350] 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-;

[0351] b is a number from 1 to 4; and

[0352] c is a number having a value of 1 / b;

[0353] with the proviso that at least one group of R15, R16and R17is -CO-R18which forms an ester moiety with the oxygen atom of an ethoxy group;

[0354] the sum of r + s + t is a number from 1 to 70; andif one or more of r, s and / or t is 0, the corresponding group R15, R16and / or R17is a linear or branched saturated alkyl group having 1 to 18 carbon atoms or a linear or branched unsaturated alkenyl group havin 2 to 18 carbon atoms.

[0355] Preferable zwitterionic surfactants applicable as component Z5) are selected from the group consisting of Cs to Cis, preferably C12 to Cis amine oxides and sulfo-and hydroxyl betaines, such as N-alkyl-N,N-dimethylamino-1 -propanesulfonate, wherein the alkyl group may be C9 to Cis, preferably C10 to C14.

[0356] Preferable anionic surfactants applicable as component Z5) are selected from alkyl ethoxysulfates having a degree of ethoxylation of more than 3, more preferably 4 to 10 and even more preferably 6 to 8 and an alkyl chain length in the range of Cs to C16 and preferably Ci 1 to C15. In addition, branched alkyl carboxylates have been found to be useful for the purposes of the present invention when the branching occurs in the middle and the average total chain length is 10 to 18, preferably 12 to 16 with a side chain length of 2 to 4 carbon atoms. An example of this is 2-butyloctanoic acid. The anionic surfactant is usually of a type having good solubility in the presence of calcium. Furthermore, alkyl (polyethoxy) sulfates (AES), alkylbenzene sulfonates and short-chain Cs-C -alkyl sulfates and sulfonates are among such anionic surfactants. It has been revealed that straight-chain fatty acids are ineffective because of their sensitivity to calcium.

[0357] In preferred embodiments, the detergent composition for machine dishwashing according to the present invention comprises cationic and / or zwitterionic surfactants in component Z5) in amounts smaller than 6 wt.-%, preferably smaller than 4 wt.-%, more preferably smaller than 2 wt.-%, even more preferably smaller than 1 wt.-%.

[0358] Suitable polymers of component Z6) include washing or cleaning-active polymers, for example rinse aid polymers and / or polymers which act as softeners. In general, the detergent composition for machine dishwashing according to the present invention may include, as polymers of component Z6), 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.

[0359] If cationic polymers are used in component Z6), they are particularly preferably copolymers comprising polyalkylene oxide groups and quaternary nitrogen atoms. More preferably the cationic polymers of component Z6) 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

[0360] 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),

[0361] wherein the one or more cationic structural units (D) are represented by the following general formulae (XI) and / or (XII):

[0362]

[0363]

[0364] wherein R19and R21are equal or different and are independently selected from hydrogen and / or a methyl group;

[0365] R20, R22, R23and R24are 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;

[0366] Y is the same or different and is selected from oxygen, NH and / or NR22,

[0367] V is the same or different and is selected from -(CH2)w-

[0368]

[0369] w is the same or different and is a number from 1 to 6;

[0370] X and Xi are equal or different and are independently selected from a halogen atom, Ci to C4-alkylsulfate and / or Ci to C4 alkylsulfonate; and

[0371] the one or more macromonomeric structural units (E) are represented by the following general formula (XIII):

[0372]

[0373] wherein

[0374] R25is the same or different and is H and / or methyl;

[0375] Z is the same or different and is C=O and / or O(CH2)4, preferably O(CH2)4,

[0376] u is, on molar average, a number from 0 to 7, preferably from 0 to 6; and

[0377] v is, on molar average, a number from 1 to 150, preferably from 11 to 150, more preferably from 12 to 150.

[0378] 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.

[0379] Preferable amphoteric polymers applicable in component Z6) of the detergent composition 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 detergent composition for machine dishwashing according to the invention contains cationic and / or amphoteric polymers in component Z6), these polymers are preferably present in amounts of from 0.01 to 10 wt.-%, based on the total weight of the detergent composition. In the context of the present invention, preference is given to those detergent compositions, 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.-%, even more preferably 0.01 to 1 wt.-%, based on the total weight of the detergent composition.

[0380] Another group of preferably applicable polymers applicable in component Z6) of the detergent composition for machine dishwashing 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.

[0381] If the detergent composition comprises alkoxylated polyalkyleneimines in component Z6), the composition preferably comprises from 1 to 10 wt.-%, more preferably from 1 to 8 wt.-% of alkoxylated polyalkyleneimines, based on the total weight of the detergent composition.

[0382] Preferably, the alkoxylated polyalkyleneimine used in component Z6) comprises 0.5 to 40 wt.-%, more preferably 1 to 30 wt.-%, even more preferably 2 to 20 wt.-% of the polyalkyleneimine backbone and

[0383] 60 to 99 wt.-%, more preferably 60 to 95 wt.-%, even more preferably from 60 to 90 wt.-% of the alkoxy chains.

[0384] Preferably, the alkoxy chains have an average of from about 1 to about 50, more preferably from about 2 to about 40, even more preferably from about 3 to about 30 and particularly preferably from about 3 to about 20 especially 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, evenmore preferably from about 1 to about 10 and particularly preferably from about 1 to about 8 propoxy units. Especially 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.

[0385] 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.

[0386] Other suitable polyalkyleneimines for applicable in component Z6) of the detergent composition of the invention include compounds having the following general structure: bis((C2H50)(C2H40)n)(CH3)-N+-CxH2x-N+-(CH3)-bis((C2H50)(C2H4o)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.

[0387] The one or more further additives Z7) are preferably selected from the group consisting of chelating agents, glass corrosion inhibitors, water, organic solvents, thickeners, foaming inhibitors, color particles, silver protecting agents, agents for preventing the tarnishing of silver, corrosion inhibitors, colorants, fillers, germicidal agents, hydrotropic agents, antioxidants, enzyme stabilizers, perfumes, solubilizers, carriers, processing aids, pigments and pH regulators.

[0388] Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors are, among others, magnesium, cobalt and zinc salts and magnesium, cobalt and zinc complexes.Proteins and / or enzymes, such as those in Z2), may be particularly sensitive to damage such as inactivation, denaturation or degradation during storage (e.g. by physical influences, oxidation or proteolytic cleavage). In the case of microbial recovery of the proteins and / or enzymes, inhibition of the proteolysis is particularly preferred, in particular if the automatic dishwasher detergents according to the invention also contain proteases. Therefore, the detergent composition for machine dishwashing according to the invention may contain enzyme stabilizers. The provision of such agents in the detergent composition constitutes a particularly preferred embodiment of the invention.

[0389] Preferably, such detergent compositions contain 0.1 to 12 wt.-%, more preferably 0.2 to 10 wt.-%, even more preferably 0.5 to 8 wt.-%, based on the total weight of the detergent composition, of such enzyme stabilizers.

[0390] The cleaning performance of the detergent composition according to the invention can be improved by the addition of organic solvents. A preferred embodiment of the present invention is therefore a detergent composition according to the invention which contains at least one organic solvent. Preferred liquid machine dishwashing detergent compositions according to the invention contain organic solvent in amounts of from 0.2 to 15 wt.-%, more preferably in amounts of from 0.5 to 12 wt.-% and even more preferably in amounts of from 1.0 to 10 wt.-%, based on the total weight of the detergent composition.

[0391] These organic solvents are for example monoalcohols, diols, triols, polyols, ethers, esters and / or amides. Particular preference is given to organic solvents which are water-soluble, "water-soluble" solvents in the sense of the present application are solvents which are completely miscible with water at room temperature (i.e. , without miscibility gaps). The organic solvents from the group of organic amines and / or alkanolamines are effective in terms of cleaning performance and in particular with regard to the cleaning performance of bleachable soiling, especially on tea stains.In order to achieve the desired viscosity of a liquid detergent composition according to the invention, thickeners can be added to this composition. In the detergent composition for machine dishwashing according to the invention, the thickeners commonly used in detergent compositions for machine dishwashing can be used.

[0392] Advantageously, liquid detergent compositions according to the invention contain one or more thickeners in amounts preferably from 0.1 to 8 wt.-%, more preferably from 0.2 to 6 wt.-% and even more preferably from 0.4 to 4 wt.-%, based on the total weight of the liquid detergent composition according to the invention.

[0393] Foaming inhibitors, color particles, silver protecting agents, agents for preventing the tarnishing of silver, corrosion inhibitors, colorants, fillers, germicidal agents, hydrotropic agents, antioxidants, enzyme stabilizers, perfumes, solubilizers, carriers, processing aids, pigments and pH regulators may be selected from the corresponding substances commonly used in detergent compositions for machine dishwashing.

[0394] Preferably, the detergent composition for machine dishwashing according to the invention comprises from 0.1-15 wt.-% of the mixture of modified fatty alcohol alkoxylates of formula (I) and from 1x1 O’6to 5 wt.-% of at least one enzyme component Z2), 2 to 50 wt.-% of at least one builder Z3), 1 to 40 wt.-% of at least one bleaching agent Z4), optionally 0 to 15 wt.-% of at least one surfactant Z5), optionally 0-10 wt.-% of at least one polymer Z6) and optionally 0 to 70 wt.-% of at least one further additive Z7), based on the total weight of the detergent composition.

[0395] Particularly preferably, the detergent composition for machine dishwashing according to the invention comprises

[0396] Z1 ) 0.1 to 15 wt.-% of component Z1 ),

[0397] Z2) 1x1 O’6to 5 wt.-% of component Z2),

[0398] Z3) 2 to 50 wt.-% of component Z3),

[0399] Z4) 1 to 40 wt.-% of component Z4),Z5) 0 to 15 wt.-% of component Z5),

[0400] Z6) 0 to 10 wt.-% of component Z6), and

[0401] Z7) 0 to 70 wt.-% of component Z7),

[0402] based on the total weight of the detergent composition.

[0403] In a further preferred embodiment, the detergent composition according to the invention contains no phosphate-based builders, and more preferably the detergent compositions according to the invention contains no phosphates, i.e. they are phosphate-free.

[0404] The detergent composition for machine dishwashing according to the invention can be prepared in solid or liquid form and as a combination of solid and liquid forms.

[0405] Preference is given to detergent compositions according to the invention, which are solid at 20 °C. Powder, granules, extrudates or compactates, in particular tablets in single-phase or multiphase form are particularly suitable as solid forms. Tablets are formulated for single-dose applications. The solid compositions according to the invention preferably contain less than 20 wt.-% of water, more preferably 0.1 to 20 wt.-% of water and even more preferably 0.5 to 5 wt.-%, based on the total weight of the detergent composition according to the invention. In another preferred embodiment of the invention, the detergent composition for machine dishwashing is anhydrous.

[0406] Preferably, the detergent composition according to the invention is characterized in that it is a solid composition at 20 °C, and preferably is in the form of a tablet.

[0407] In a particularly preferred embodiment of the invention, the solid detergent composition for machine dishwashing is in the form of a tablet.

[0408] Preferably, the detergent composition according to the invention is characterized in that the composition is wrapped in a water-soluble foil, preferably based on polyvinylalcohol.Preference is also given to detergent compositions for machine dishwashing according to the invention, which comprise one or more modified fatty alcohol alkoxylates of formula (I) and are enclosed in a water-soluble foil, preferably a polyvinyl alcohol containing foil.

[0409] 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.

[0410] 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.

[0411] In a further preferred embodiment, 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.In a further preferred embodiment, the detergent composition according to the invention is liquid at 20 °C. The liquid formulation, preferably based on water and / or organic solvents, can be provided in a thickened form, as a gel. Capsules (caps) are particularly suited for liquid formulations in single-phase or multiphase form. Preferably, the liquid detergent composition for machine dishwashing according to the invention contain up to 60 wt.-% of water, more preferably from 10 to 60 wt.-% of water, even more preferably 25 to 60 wt.-% of water, based on the total weight of the liquid detergent composition for machine dishwashing according to the invention.

[0412] In a particularly preferred embodiment, the detergent composition for machine dishwashing according to the invention is provided in the form of a powder, a gel, a pod, a cap or as a liquid rinse aid.

[0413] The detergent composition for machine dishwashing according to the invention is advantageously suitable for cleaning dishes in dishwashers, dirty dishes being treated in a dishwashing machine with an aqueous alkaline composition containing the detergent composition according to the invention, or alternatively with an aqueous composition at a pH ranging from 5.5 to 8.5 comprising the detergent composition of the invention.

[0414] A further aspect of the invention is therefore a method of cleaning dishes in a dishwashing machine, in which contaminated dishes are treated in the dishwashing machine with an aqueous composition at a pH ranging from 5.5 to 8.5, preferably 6 to 8, more preferably 6.5 to 7.5, comprising a detergent composition according to the invention.

[0415] Another further aspect of the invention is a method of cleaning dishes in a dishwashing machine, wherein contaminated dishes are treated in the dishwashing machine with an aqueous alkaline composition comprising the detergent composition for machine dishwashing according to the invention.In this method of cleaning dishes, the pH of the aqueous alkaline solution is preferably 8 or above, more preferably 9 or above. In a particularly preferred embodiment, the pH of the aqueous alkaline solution is from 8 to 13. In a particularly more preferred embodiment, the pH of the aqueous alkaline solution is from 9 to 12.

[0416] The preferred embodiments described above for the detergent composition for machine dishwashing according to the invention also apply correspondingly to the process according to the invention for cleaning dishes in a dishwasher and to the use according to the invention of the detergent composition according to the invention or of the mixture of modified fatty alcohol alkoxylates of component Z1 ) of the detergent composition according to the invention as rinse aids in automatic dishwashing, for the improvement of the wettability of dishes, the reduction of stain and film formation on the dishes, the machine compartment and / or the filter of the machine during machinated dishwashing, and the use of the mixture of modified fatty alcohol alkoxylates Z1 ) for improving the rinse aiding properties and / or the drying capacity of a machine dishwashing detergent composition.

[0417] A further subject matter of the invention is a method of cleaning dishes in a dishwashing machine, in which contaminated dishes are treated in the dishwashing machine with an aqueous alkaline composition comprising a detergent composition containing the inventive mixture of modified fatty alcohol alkoxylates of the formula (I) or of the inventive alkoxylation product.

[0418] Preferably, the method of cleaning dishes in a dishwashing machine is characterized in that the pH value of the aqueous alkaline solution is from 8 to 13, preferably 9 to 12.

[0419] In a preferred embodiment the method of cleaning dishes in a dishwashing machine is characterized in that contaminated dishes are treated in the dishwashing machine with an aqueous composition at a pH ranging from 5.5-8.5 comprising an inventive detergent composition for machine dishwashing.A further subject matter of the invention is the use of the inventive detergent composition for machine dishwashing or of the inventive mixture of modified fatty alcohol alkoxylates of the formula (I) or of the inventive alkoxylation product as a rinse aid during machinated dishwashing.

[0420] A further subject matter of the invention is the use of the inventive detergent composition for machine dishwashing or of the inventive mixture of modified fatty alcohol alkoxylates of the formula (I) or of the inventive alkoxylation product for improving the wettability of dishes during machinated dishwashing.

[0421] A further subject matter of the invention is the use of the inventive detergent composition for machine dishwashing or of the inventive mixture of modified fatty alcohol alkoxylates of the formula (I) or of the inventive alkoxylation product for the reduction and / or avoidance of stain and film formation on the dishes, the machine compartment and / or the filter of the machine during machinated dishwashing.

[0422] Depending on the additives contained in the machine dishwashing product, fatty white to orange residues can form in the dishwasher in combination with fatty components from the added soil. These residues can be deposited on the outside of the dispenser door, in the rinse aid compartment, and both inside and outside the plastic sieve and metal filter. The formation of these residues can depend on various factors including product formulation, water hardness, and the types of soils being cleaned.

[0423] A further subject matter of the invention is the use of the inventive mixture of modified fatty alcohol alkoxylates of the formula (I) or the inventive alkoxylation product for improving the rinse aiding properties and / or the drying capacity of a machine dishwashing detergent composition.

[0424] Further preferred embodiments of the invention may arise from the combination of above-described preferred embodiments.The invention is explained in more detail below by the examples and the claims. Unless explicitly stated otherwise in the examples, the percentages in the examples are to be understood as percent by weight (wt.-%).

[0425] EXAMPLES

[0426] The examples below are intended to illustrate the invention in detail without, however, limiting it thereto.

[0427] Example 1

[0428] Methods of preparation of catalyst (C) with carboxylic acid of formula (IV)

[0429] a) A mixture of 1047.0 g of a carboxylic acid of formula (IV) under the trademark Emulsogen™ COL 050 marketed by C lariant, 55.8 g of calcium hydroxide and 360.6 g of propan-2-ol is agitated at ambient temperature for 5 minutes with a batch disperser (Ultra Turrax from IKA Werke GmbH & Co KG). After this, 44.2 g of concentrated sulfuric acid are added over 2 minutes and the mixture is again agitated for 5 minutes with the batch disperser, providing a catalyst with a Ca2+content of 2.00 wt.-%.

[0430] b) A mixture of 1047.0 g of a carboxylic acid of formula (IV) under the trademark Emulsogen™ COL 050 marketed by C lariant, 55.8 g of calcium hydroxide and 360.6 g of propan-2-ol is agitated at ambient temperature for 5 minutes with a batch disperser (Ultra Turrax from IKA Werke GmbH & Co KG). After this, 42.9 g of methanesulfonic acid (99 wt.-%) are added over 2 minutes and the mixture is again agitated for 5 minutes with the batch disperser, providing a catalyst with a Ca2+content of 2.00 wt.-%.

[0431] c) A mixture of 1047.0 g of a carboxylic acid of formula (IV) under the trademark Emulsogen™ COL 050 marketed by C lariant, 55.8 g of calcium hydroxide and 360.6 g of propan-2-ol is agitated at ambient temperature for5 minutes with a batch disperser (Ultra Turrax from IKA Werke GmbH & Co KG). After this, 603.7 g of sulfurous acid (6 wt.-%) are added over two minutes and the mixture is again agitated for 5 minutes with the batch disperser. The solvent mixture is removed under vacuum, providing a catalyst with a Ca2+content of approximately 2 wt.-%.

[0432] Emulsogen™ COL 050 is a commercial product carboxylic acid (B) comprising, as main component, a carboxylic acid represented by formula (IV) wherein Rcis oleyl, q is 1 , and p is, based on molar average, 5.

[0433] d) A mixture of 622.0 g iso-nonanoic acid, 1922.4 g of propan-2-ol and 147.6 g water was dispersed for 1 minute with a Rotor-Stator disperser. 148.2 g of calcium hydroxide were added within 30 minutes. After this, 60.05 g of concentrated sulfuric acid were added within 5 minutes and the mixture was again dispersed for 120 minutes, providing a catalyst with a Ca2+content of 2.75 wt.-%. This catalyst is further referred to as CC-1.

[0434] Further catalysts are prepared according to synthesis example 1 d) but with the sole difference that 72.06 g of concentrated sulfuric acid are used or that 84.07 g of concentrated sulfuric acid are used or that 96.09 g of concentrated sulfuric acid are used.

[0435] Method of preparation of catalyst (C) with a polyalkylene glycol

[0436] e) A mixture of 1500 g of polyalkylene glycol under the name Polyglykol 1000 marketed by Clariant (a polyethylene glycol with a mean molecular weight (average molecular weight) of 1000 g / mol) and 270.1 g of calcium acetate monohydrate is agitated with a lab disperser. After this, 165 g of concentrated sulfuric acid (98%) are added and the mixture is again agitated with the lab disperser to yield the final catalyst with a Ca2+content of 3.1 wt.-%.Method of preparation of catalyst (C) with a methyl-capped polyalkylene glycol and a carboxylic acid (B)

[0437] f) A mixture of 350 g of methyl-capped polyethylene glycol with an average molecular weight of 350 g / mol, 240 g of calcium acetate monohydrate, and 350 g of oleic acid is agitated with a lab disperser. After this, 60 g of concentrated sulfuric acid (98%) is added and the mixture is again agitated with the lab disperser to yield the final catalyst with a Ca2+content of 5.5 wt.-%.

[0438] Method of preparation of catalyst (C) with an alcohol solvent

[0439] g) A mixture of 525 g of isopropanol and 150 g of calcium acetate monohydrate was agitated with a lab disperser. After this, 75 g of concentrated sulfuric acid (98%) was added and the mixture was again agitated with the lab disperser to yield the final catalyst with a Ca2+content of 4.6 wt.-%. This catalyst is further referred to as CC-2.

[0440] General procedure for the preparation of mixtures of modified fatty alcohol alkoxylates of the formula (I):

[0441] The fatty alcohol of the formula (II) and the catalyst are placed into a glass autoclave, which is then flushed with nitrogen by alternatingly applying vacuum and introducing nitrogen (3 cycles). The mixture is dried under aspirator vacuum at 100 °C for 1 hour. The pressure in the autoclave is restored to ambient pressure with nitrogen and heated to 170 °C. At this temperature the autoclave is pressurized with nitrogen to a pressure of 2.0 bar above atmospheric pressure, after which pressure-controlled dosage of alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide takes place up to a maximum pressure of 4.5 bar above atmospheric pressure.The alkoxylation is carried out in a semi-batch process with automated dosage of alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide within a given temperature window and up to the specified maximum pressure. The pressure is adjusted according to the increased filling volume of the vessel. After introduction of the intended amount of alkylene oxide and closing the alkylene oxide inlet, the reaction is continued until the pressure becomes constant.

[0442] The reactor content is cooled to 90 °C and aspirator vacuum is applied for

[0443] 30 minutes in order to remove residual alkylene oxide. The temperature is reduced to 80 °C and the final product is transferred into storage vessels and analyzed. A typical batch scale is 400 g to 2000 g. The uptake of the intended amount of alkylene oxide can be assured by gravimetry and by determination of the hydroxyl value according to DIN EN ISO 4629-2.

[0444] The oxide homologue distribution of the mixture of modified fatty alcohol alkoxylates of formula (I) can be determined by gas chromatographic analysis, preferably according to the method described in EP 0133715 A1 or

[0445] WO 2010 / 121975 A1.

[0446] The measured values are area-% values and can be converted to wt.-% as known by the person skilled in the art.

[0447] Preferably, the oxide homologue distribution of the mixture of modified fatty alcohol alkoxylates of the formula (I) (measured in area-%) can be determined by gas chromatography using a packed column (ZB-5HT Inferno). The samples preferably are derivatized by reaction with BSTFA (N,O-Bis(trimethylsilyl)trifluoracetamide).

[0448] All inventive examples showed distributions where the naas described above was above 15 wt-%. All comparative examples showed distributions where the naas described above was below 10 wt-%. The distribution was measured of theintermediate before the modifying reagent was added. The distribution does not change after the modifying step.

[0449] Then, the alkoxylation product is introduced into the reaction vessel for modifying step, followed by the addition of sodium methylate (5-10 mol%). The mixture is then heated to an internal temperature of 140°C while simultaneously applying a vacuum of approximately 50 mbar. Once these conditions are achieved, the product mixture is allowed to dry for 1 hour. Subsequently, the vacuum is discontinued, and nitrogen is introduced to neutralize the pressure, followed by a moderate nitrogen flow over the mixture. The modifying reagent (1 eq.) is then added gradually over a 60-minute period. The reaction is maintained at the same temperature and allowed to continue until full conversion is observed, typically taking 2 to 4 hours. The progress of the reaction is e.g. monitored by measuring the epoxide number according to EN ISO 3001.

[0450] Table 1 Synthesis of inventive modified fatty alcohol alkoxylates 1-1, I-2, I-3, I- 4, I-5, I-6, I-7, and I-8

[0451]

[0452]

[0453] *) EO = ethylene oxide

[0454] Table 2 Synthesis of comparative examples C-1 , C-2 and C-3

[0455]

[0456] *) EO = ethylene oxide

[0457] Compositions:

[0458] The compositions of the formulations F1-F11 are shown in Tables 3.1 and 3.2.

[0459] Example 2

[0460] Drying capacity

[0461] The drying capacity of the detergent composition for machine dishwashing according to the invention was investigated. This refers to the ability of a machine dishwashing product to allow the residual water still adhering to the dishes to run off or evaporate during the drying step of the dishwasher cycle, so that the dishes are dry when the door is opened.

[0462] The drying capacity of the formulations F2 to F9 according to the invention was investigated. As a comparative example, the drying capacity of the comparative formulations F1, F10 and F11 was tested.Testing conditions:

[0463] Dishwashing machine: Miele G 1223 SC GSL-2

[0464] Test ware dishes: 10 appetizer spoons

[0465] 10 appetizer forks

[0466] 10 teaspoons

[0467] 10 appetizer knives

[0468] 2 serving spoons

[0469] 12 drinking glasses

[0470] 10 porcelain cups

[0471] 25 porcelain plates

[0472] 3 SAN (poly-styrene-co-acrylonitrile) plates

[0473] 3 PP (polypropylene) plates

[0474] 6 PP bowls

[0475] Dishwashing program: without pre-wash, 50 °C for 3 minutes in cleaning step,

[0476] 65 °C in rinse step

[0477] Water hardness: 21 + / - 1°dH

[0478] Water softening: none

[0479] Detergent dosage: 18 g added to the dry dosage chamber before starting the test

[0480] Contamination: 50 g ballast soil added immediately after the opening of the dosage chamber

[0481] Rinse aid: none

[0482] Cleaning cycles: 4; 1 for preconditioning and 2-4 for performance evaluation

[0483] All items were pre-treated twice with an alkaline cleaner and demineralized water, once with an acidic cleaner and demineralized water followed by final treatment only with demineralized water.Evaluation:

[0484] Evaluation of the test ware was started 30 minutes after the dishwashing cycle was completed. During this time, the dishwasher door was kept closed. For each test, dishwashing cycles 2 to 4 were evaluated. In a fixed order and with a set time limit, the number of adherent drops of residual water was counted for each test ware item. Depending on the counted number of drops, the following rating of the drying capacity results for each test ware item:

[0485] Rating:

[0486] 0 dry, no water drops

[0487] 1 1 water drop

[0488] 2 2 water drops

[0489] 3 3 water drops

[0490] 4 4 water drops

[0491] 5 5 water drops

[0492] 6 6 water drops

[0493] 7 7 water drops

[0494] 8 more than 7 water drops.

[0495] In this rating scheme, there is a score of 0 for best performance and a score of 8 for worst performance for each test ware dish. In Tables 3.1 and 3.2 the average scoring for all evaluated cycles on each material class is given.

[0496] Example 3

[0497] Rinse aiding performance of detergent compositions for machine dishwashing

[0498] The rinse aiding performance of the formulations F2 to F9 according to the invention was investigated. As comparative examples, the rinse aiding performance of the comparative formulations F1 , F10 and F11 was tested.Testing conditions:

[0499] Dishwashing machine: Miele G 1222 SC GSL

[0500] Test ware dishes: 12 drinking glasses

[0501] (8 material groups) 3 PP bowls

[0502] 3 PE (polyethylene) lids

[0503] 3 melamine plates

[0504] 2 butter dishes

[0505] 4 knives (stainless steel; lower quality)

[0506] 4 knives (stainless steel; higher quality)

[0507] 6 porcelain plates (medium quality)

[0508] Ballast dishes: 10 dinner plates

[0509] 9 soup plates

[0510] 7 dessert plates

[0511] 5 coffee cups

[0512] Dishwashing program: without pre-wash, 50 °C for 3 minutes in cleaning step,

[0513] 65 °C in rinse step

[0514] Water hardness: 21 + / - 1°dH

[0515] Water softening: none

[0516] Detergent dosage: 18 g, added to the dry dosage chamber before starting the test

[0517] Contamination: 100 g frozen dirt, added immediately after the opening of the dosage chamber

[0518] Rinse aid: none

[0519] Cleaning cycles: 4; 1 for preconditioning and 2-4 for performance evaluation

[0520] All items were pre-treated twice with an alkaline cleaner and demineralized water, once with an acidic cleaner and demineralized water followed by final treatment only with demineralized water.Evaluation:

[0521] Evaluation of the test ware was started 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:

[0522] Visual rating marks:

[0523] 10 Perfect

[0524] 9 Perfect to visible

[0525] 8 visible

[0526] 7 visible to disturbing

[0527] 6 Disturbing

[0528] 5 Disturbing to very disturbing

[0529] 4 Very disturbing

[0530] 3 Very disturbing to unacceptable

[0531] 2 Unacceptable

[0532] 1 Absolutely unacceptable

[0533] Half intermediate grades are also awarded.

[0534] These marks are used for evaluating the overall effect after each of the cycles 2 to 4. After the fourth cycle also the following different effects that can occur on the dishware are evaluated according to these rating marks.

[0535] Rinse aid effects considered for the visual rating:

[0536] Spotting or: stains in various sizes and intensities

[0537] Contact spots stains resultant from water pitches or contact points between the test ware dishes and parts of the dishwashing machine

[0538] Stripes stripes in various sizes and intensities having run off from spots or contact spots

[0539] Film formation continuous film spread uniformly on the test ware dishes

[0540] Structured film formation dispersed torn filmSolid residues solid powder or crystalline residues

[0541] Fatty residues fatty drops or fatty film formation

[0542] Iridescence shimmering, iridescence

[0543] Other other effects

[0544] The overall effect and each of the above listed eight rinse aid effects lead 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 these effects on the above material groups (glass, plastics, porcelain, stainless steel) an average rating for the dishwashing cycles 2 to 4 was determined. All mean values of the complete visual assessment are then multiplied by 10 in order to calculate an average respective performance index for each effect on each material group (10: worst performance; 100: best performance).

[0545] Results are shown in Tables 3.1 and 3.2.

[0546] Example 4

[0547] Fatty residues

[0548] The fatty residues precipitated on the filter were determined to assess the cleanliness in the machine after operating the dishwasher. The amount of fatty residues on the filter evaluated after the last cycle is given in Tables 3.1 and 3.2.

[0549] After the evaluation of all test ware dishes from the last test rinse cycle is completed, the sieve system of the dishwasher including the filter is taken out of the machine and is examined visually and gravimetrically. Particularly fatty white to orange residues that may have been deposited in various places in the dishwasher by the end of the washing cycle, depending on the machine dishwashing product used, are assessed. The fatty residues can be found outside of the plastic sieve, inside the plastic sieve, on the metal sieve, below the metalsieve and in the machine on the outside of the dosing chamber, inside the rinseaid chamber and below the sieve system on the bottom of the dishwasher. These residues are evaluated according to the following scale from 1 to 7. 1 means the worst and 7 the best result. Half intermediate grades are also awarded. The average of the sum of all six grades is taken to evaluate the fatty residues in the dishwasher.

[0550] Visual rating grades:

[0551]

[0552] Results are shown in Tables 3.1 and 3.2.Table 3.1 : Compositions, drying capacity, fatty residues and rinse aiding performance of formulations F1-F6

[0553]

[0554]

[0555] *) The ingredients were added according to their active component content in wt.-%.

[0556] **> Sodium sulfate is added as a filler for a constant mass balance of the detergent composition, without a function and without influence on the performance of the detergent composition.

[0557] All formulations F1-F6 show very good drying capacity and rinse aiding performance. The inventive formulations F2-F6 show significantly lower amounts of fatty residues in the filter as well as in the dishwasher in total.The results demonstrate an advantageous effect of the inventive mixtures of modified fatty alcohol alkoxylates.

[0558] Table 3.2: Compositions, drying capacity, fatty residues and rinse aiding performance of formulations F1 & F7-F11

[0559]

[0560]

[0561] The ingredients were added according to their active component content in wt.-%.

[0562] **> Sodium sulfate is added as a filler for a constant mass balance of the detergent composition, without a function and without influence on the performance of the detergent composition.

Claims

PATENT CLAIMS1. A mixture of modified fatty alcohol alkoxylates selected from the substances of the following formula (I)Ra0-(CmH2m0)x-Y (I)whereinRais a linear or branched saturated alkyl group having 6 to 30 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 6 to 30 carbon atoms, preferably 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, and more preferably is a linear or branched saturated alkyl group having 10 to 16 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 10 to 16 carbon atoms, m is 2 or 3 or combinations thereof, preferably 2,x is an integer from 1 to 150, preferably from 1 to 100, more preferably from 2 to 75, even more preferably from 3 to 50, particularly preferably from 5 to 40, and extraordinarily preferably from 8 to 30,Y is a group -CH2-CH(OH)-Rb, -CH2-CH(OH)-CH2-O-Rbor is a linear or branched saturated alkyl group having 1 to 32 carbon atoms, preferably - CH2-CH(OH)-Rb,Rbis a linear or branched saturated alkyl group having 1 to 30 carbon atoms, preferably is a linear or branched saturated alkyl group having 4 to 20 carbon atoms, even more preferably is linear or branched saturated alkyl group having 8 to 12 carbon atoms, andthe average number “n” of (CmH2mO)-units of the modified fatty alcohol alkoxylates of the formula (I) in the mixture is a number from 5 to 100, preferably from 7 to 50, more preferably from 9 to 25, even more preferably from 11 to 30, and particularly preferably from 13 to 25,characterized in thatat least 15 wt.-%, preferably at least 18 wt.-%, of the total weight of the modified fatty alcohol alkoxylates of the formula (I) in the mixture are modified fatty alcohol alkoxylates with naunits selected from the group consisting of (C2H4O)-units, (C3HeO)-units and mixtures of (C2H4O)-units and (C3HeO)-units, where nais the integer equal to the number n in case the number n itself is an integer or nais the integer closest to the number n in case the number n itself is not an integer.

2. The mixture of modified fatty alcohol alkoxylates according to claim 1 , characterized in that at least 45 wt.-%, preferably at least 55 wt.-%, of the total weight of the modified fatty alcohol alkoxylates of the formula (I) in the mixture are modified fatty alcohol alkoxylates with (na-1 ), naor (na+1) units selected from the group consisting of (C2H4O)-units, (C3HeO)-units and mixtures of (C2H4O)-units and (C3HeO)-units, where nais the integer equal to the number n in case the number n itself is an integer or nais the integer closest to the number n in case the number n itself is not an integer.

3. The mixture of modified fatty alcohol alkoxylates according to claim 1 or 2, characterized in that at least 70 wt.-%, preferably at least 80 wt.-%, of the total weight of the fatty alcohol alkoxylates of the formula (I) in the mixture are fatty alcohol alkoxylates with (na-2), (na-1 ), na, (na+1) or (na+2) units selected from the group consisting of (C2H4O)-units, (C3HeO)-units and mixtures of (C2H4O)-units and (C3HeO)-units, where nais the integer equal to the number n in case the number n itself is an integer or nais the integer closest to the number n in case the number n itself is not an integer.

4. A method for preparing a mixture of modified fatty alcohol alkoxylates of the formula (I) according to one or more of claims 1 to 3 from ethylene oxide, propylene oxide or a mixture of ethylene oxide and propylene oxide, one or more fatty alcohols of the formula (II), preferably a mixture of fatty alcohols of the formula (II)RaO-H (H)wherein Rain formula (II) has the same meaning as in claim 1 for formula (I), and one or more modifying reagents of the formula (III),Z-Rb (III)wherein Rbin formula (III) has the same meaning as in formula (I) in claim 1 , and Z is a functional group selected from epoxide, glycidyl ether, chloride, bromide, iodide, -OTMS, -OTES, -OTBS, -OTIPS , -OTBDPS, -O-SO2-OCH3, -O-SO2-OCH2-CH3, preferably epoxide, chloride, -O-SO2-OCH3, more preferably epoxide, characterized in that in the method a catalyst (C) based on an alkaline earth metal is used andat least 15 wt.-%, preferably at least 18 wt.-%, of the total weight of the modified fatty alcohol alkoxylates of the formula (I) in the mixture are modified fatty alcohol alkoxylates with naunits selected from the group consisting of (C2H4O)-units, (C3HeO)-units and mixtures of (C2H4O)-units and (C3HeO)-units, where nais the integer equal to the number n in case the number n itself is an integer or nais the integer closest to the number n in case the number n itself is not an integer.

5. The method according to claim 4, characterized in that the catalyst (C) is obtainable by a reaction involving(a) an alkaline earth metal compound (A) and(b) one or more substances selected from the group consisting of a carboxylic acid (B) preferably comprising 3 to 60, more preferably 3 to 46, carbon atoms; a polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol; a C1-C18 alkyl-capped polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol; an alcohol solvent; and mixtures including any of the foregoing, and(c) a strong acid (AC).

6. The method according to claim 5, characterized in that the alkaline earth metal compound (A) is selected from the group consisting of magnesium hydroxide, magnesium acetate, calcium hydroxide, calcium acetate, strontiumhydroxide, strontium acetate, barium hydroxide, and barium acetate, preferably from the group consisting of calcium acetate and calcium hydroxide.

7. The method according to claim 5 or 6, characterized in that the strong acid (AC) is sulfuric acid.

8. The method according to one or more of claims 5 to 7, characterized in that the molar ratio of the alkaline earth metal compound (A) to the strong acid (AC) is from 1.0:0.1 to 1.0: 1.0, preferably from 1.0:0.2 to 1.0:0.9 and more preferably from 1.0:0.3 to 1.0:0.8.

9. Alkoxylation product obtainable by a method according to one or more of claims 4 to 8.

10. A detergent composition for machine dishwashing comprising Z1) a mixture of modified fatty alcohol alkoxylates of formula (I) according to one or more of claims 1 to 3 or an alkoxylation product according to claim 9.

11. The detergent composition according to claim 10, which further to the mixture of modified fatty alcohol alkoxylates Z1) comprises one or more components selected from:Z2) one or more enzymes, preferably selected from the group consisting of proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases and oxidoreductases;Z3) one or more builders;Z4) one or more bleaching agents;Z5) one or more surfactants;Z6) one or more polymers;Z7) one or more further additives, preferably selected from the group consisting of chelating agents, glass corrosion inhibitors, water, organic solvents, thickeners, foaming inhibitors, color particles, silver protecting agents, agents for preventing the tarnishing of silver, corrosion inhibitors, colorants, fillers, germicidal agents, hydrotropic agents, antioxidants, enzymestabilizers, perfumes, solubilizers, carriers, processing aids, pigments and pH regulators.

12. The detergent composition according to claim 10 or 11 characterized in that it is a powder, gel, pod, cap or liquid rinse aid.

13. A method of cleaning dishes in a dishwashing machine, in which contaminated dishes are treated in the dishwashing machine with an aqueous alkaline composition comprising a detergent composition according to one or more of claims 10 to 12.

14. The use of the detergent composition according to one or more of claims 10 to 12 or of the mixture of modified fatty alcohol alkoxylates of formula (I) according to one or more of claims 1 to 3 or of the alkoxylation product according to claim 9 as a rinse aid during machinated dishwashing and / or for improving the wettability of dishes during machinated dishwashing and / or for the reduction and / or avoidance of stain and film formation on the dishes, the machine compartment and / or the filter of the machine during machinated dishwashing.

15. The use of the mixture of modified fatty alcohol alkoxylates of formula (I) according to one or more of claims 1 to 3 or of the alkoxylation product according to claim 9 for improving the rinse aiding properties and / or the drying capacity of a machine dishwashing detergent composition.

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