WO2014032700A1

WO2014032700A1 - Dishwashing detergent containing alkyl ether sulphate

Info

Publication number: WO2014032700A1
Application number: PCT/EP2012/066674
Authority: WO
Inventors: Thomas Eiting; Nina Mussmann; Thorsten Bastigkeit; Konstantin Benda
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2012-08-28
Filing date: 2012-08-28
Publication date: 2014-03-06
Also published as: EP2890771A1

Abstract

The present invention relates to a dishwashing detergent, preferably a detergent for dishwashing in a machine, containing alkyl ether sulphate, and to a method for dishwashing in a machine using said dishwashing detergent. The invention further relates to the use of alkyl ether sulphate for removing soiling at low washing temperatures and for increasing the effect of a bleach system.

Description

Dishwashing detergent containing alkyl ether sulfate

The present invention describes dishwashing detergents containing alkyl ether sulfate, preferably automatic dishwashing detergents, as well as automatic dishwashing processes using these dishwashing detergents. The invention further relates to the use of

Alkyl ether sulfate to remove stains at low wash temperatures and to increase the effect of a bleach system.

Dishwashing detergents are available to the consumer in a variety of forms. In addition to the traditional liquid hand dishwashing detergents have with the spread of household dishwashers in particular the machine

Dishwashing has gained great importance. These automatic dishwashing agents are typically offered to the consumer in solid form, for example as powders or as tablets, but increasingly also in liquid form.

Low-foaming machine dishwashing formulations

For example, in EP 1 155 105 described. However, it has been found that in addition to the low foaming improved cleaning performance, especially against various difficult to eliminate soils is desirable.

Many of the conventional automatic dishwashing detergents also develop only at higher temperatures, such as from 50 ° C or even from 60 ° C a good

Cleaning performance. At these temperatures, however, of the in the

Dishwashing substances used some of the objects to be cleaned such as glasses are attacked; For example, glass corrosion occurs. Furthermore, undesirably large amounts of energy are needed to the wash liquor to such

To heat temperature or to keep at such a temperature.

The aim of this invention was to overcome the above problems.

Thus, the invention was based on the object, a dishwashing detergent with less

Foaming and improved cleaning properties against stains, such as in particular bleachable soiling caused by vegetable dyes, such as vegetables or fruits. In addition, other persistent

Stains such as egg yolk are removed.

In particular, this application was based on the object that the improved

Cleaning properties already at low-temperature cleaning cycles, eg at Rinsing bath temperatures of 40 ° C, should be achieved.

Another object of the invention was to provide a cleaning agent in which small amounts of bleaching agent as well as other components can be used to conserve resources. Thus, it is intended to provide fabrics which improve the performance of existing bleach systems, especially at low temperatures.

These objects have been achieved according to the invention by a dishwashing agent which contains an alkyl ether sulfate, a bleach catalyst and a bleach. It has been found that this combination is particularly advantageous, especially when an alkyl ether sulfate is combined with a manganese-containing bleach catalyst and an oxygen-based bleach.

Thus, an object of the present invention is a dishwashing detergent containing

(a) alkyl ether sulfate;

(b) bleach catalyst;

(c) Bleaching agent, preferably oxygen-based.

Another object of the present invention is a machine

Dishwashing process in which the dishwasher according to the invention is used.

In addition, the invention relates to the use of an alkyl ether sulfate and / or a Mn-TACN catalyst as a component of a dishwasher for removing soils at low washing temperature and the use of a

Alkyl ether sulfate for increasing the bleaching effect of a bleaching system containing a bleach catalyst (b) and a bleaching agent (c).

Dishwashing detergents, preferably automatic dishwashing detergents, in this application are compositions which can be used to clean soiled dishes in a machine dishwashing process. Thus, the dishwashing compositions according to the invention differ, for example, from so-called

Rinse aids that can be used in combination with automatic dishwashing detergents and do not develop their own cleaning effect. The dishwashing agent according to the invention is preferably a machine dishwashing detergent.

Anionic surfactants can generally be used for dishwashing.

However, their foaming behavior is a well-known problem.

Due to the foaming it usually comes in their use in the

Dishwasher to a pressure drop, which is generally associated with insufficient cleaning performance. For this reason, the use of anionic surfactants in automatic dishwashing is usually dispensed with.

According to the invention, however, it has now surprisingly been found that the

Cleaning performance of bleach-containing dishwashing detergents (especially against bleachable stains) by the addition of a special anionic surfactant, namely by the addition of alkyl ether sulfate, can be significantly increased.

In a preferred embodiment, the alkyl ether sulfate (a) is a compound of the formula (I)

Formula (I) wherein

R is an alkyl having 8 to 22 C atoms,

n is a natural number from 1 to 8 and / or

M is an alkali metal or hydrogen atom.

In a preferred embodiment, R is an alkyl having 10 to 20 C atoms, more preferably having 12 to 18 C atoms, even more preferably having 12 to 14 C atoms, in particular a linear alkyl having 12 to 14 C atoms. n is preferably a natural number from 1 to 6, more preferably from 2 to 5, and particularly preferably 2 or 3. M is preferably an alkali metal, more preferably potassium or sodium, especially sodium.

In the case where M is a hydrogen atom, the term alkyl ether sulfate also encompasses the free acid, ie the alkyl ether sulfuric acid.

In a particularly preferred embodiment, the inventive

Dishwashing detergent is an alkyl ether sulfate in which R is a linear alkyl having 12 C atoms and n is 2.

The constituent (a) may preferably also be mixtures of alkyl ether sulfates, in particular of alkyl ether sulfates of the formula (I).

It has unexpectedly been found that the alkyl ether sulfates described above in the dishwashing detergent according to the invention have a surprisingly good emulsifying effect even at temperatures around 40 ° C. and do not tend to form undesirable high foaming. It appears that the alkyl ether sulfates advantageously prevent rewet by wash water, especially at low temperatures.

Another advantage of the cleaning agent according to the invention is that even with the use of washing or cleaning programs, which require less water than before for the washing or cleaning process and / or lead to shorter-lasting cleaning process and therefore increasingly for the consumer of become economic and ecological importance maintaining above emulsifier effect.

Preferably, the alkyl ether sulfate in the dishwashing detergent according to the invention in an amount of 0.05 to 20 wt .-%, preferably 0, 1 to 10 wt .-%, more preferably 1, 0 to 8.0 wt .-%, in particular 2.0 to 5.0 wt .-%, based on the

Total weight of the dishwashing detergent.

The bleach catalysts (b) contained in the dishwashing detergent according to the invention are usually substances which enhance the bleaching effect of the bleaching agent (c). Preferably, these are compounds containing transition metal salts or transition metal complexes. Examples of transition metals are Mn, Fe, Co, Ru, Ti, V, Cu and Mo. Transition metal complexes such as, for example, salts and / or carbonyl complexes of Mn, Fe, Co, Ru and Mo can be used as a bleach catalyst. Furthermore, Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru amine complexes are also used as bleach catalysts usable.

The bleach catalyst particularly preferably contains manganese (Mn) as transition metal, particularly preferably complexes of manganese in the oxidation state I I, II I, IV or V.

As ligands, one or more macrocyclic ligand (s) having the donor functions N, NR, PR, O and / or S may preferably be used. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the dishwasher detergent according to the invention, which as ligand (s) compounds based on 1, 4,7-Triazacyclononan (TACN) and / or 1, 5,9-triazacyclododecane (TACD), more preferably based on 1, 4,7-triazacyclononane (TACN). Examples of these are 1, 4,7-triazacyclononane (TACN), 2-methyl-1, 4,7-triazacyclononane (2-MeTACN), 1, 4,7-trimethyl-1, 4,7-triazacyclononane (1, 4 , 7-Me ₃ TACN), 1, 2,4,7-tetramethyl-1, 4,7-triazacyclononane (1, 2,4,7-Me ₄ TACN) and 1,5,9-trimethyl-1,5 , 9-triazacyclododecane (1, 5, 9-Me ₃ TACD).

In a particularly preferred embodiment, the catalyst is Mn-TACN. By Mn-TACN is meant complexes of manganese with one or more ligands based on 1, 4,7-triazacyclononane (TACN) or derivatives of TACN. Suitable manganese complexes are, for example, [Mn ^m ₂ (-O) ₁ (-OAc) ₂ (TACN) ₂ ] (CIO ₄ ) 2, [ηη "'ηη' ^v (μ-O) ₂ (μ-OAc) ₁ (TACN ) ₂ ] (BPh ₄ ) ₂ , [Μη ' ^ν ₄ (μ-0) ₆ (ΤΑΰΝ) ₄ ] (αθ ₄ ) ₄ , [ ^{Μη ΙΜ} ₂ (μ-0) ₁ (μ-ΟΑϋ) ₂ (2 MeTACN) ₂ ] (CI0 ₄ ) ₂ , [Mn ^m Mn ^lv (-O) ₁ (-OAc) ₂ (2-MeTACN) ₂ ] (CI0 ₄ ) ₃ , [ηη ' ^v ₂ (μ-0) ₃ ( -Β-TACN) ₂ ] (PF ₆ ) ₂ and [ ^{Μη ιν} ₂ (μ- ^O ) ₃ (1, 2,4,7-Me ₄ TACN) ₂ ] (PF ₆ ) _2, wherein OAc of the OC (0 ) CH ₃ corresponds.

Very particularly preferred bleach catalysts (b) for the inventive

Dishwashing detergents are complexes of manganese with 1,4,4-trimethyl-1, 4,7-triazacyclononane (1,4,7-Me ₃ TACN) and / or 1,2,4,7-tetramethyl-1,4,7 -triazacyclononane (1, 2,4,7-Me ₄ TACN), since this can be achieved particularly advantageous by the tasks described above.

The aforementioned bleaching catalysts (b), in particular with Mn as the transition metal, are used in an amount of preferably 0.001 to 1 wt .-%, more preferably from

0.0025 wt% to 0.75 wt%, more preferably from 0.005 to 0.5 wt%, and in particular from 0.01 wt .-% to 0, 10 wt .-%, each based on the total weight of the dishwashing detergent used.

In a preferred embodiment of the invention, the weight ratio of alkyl ether sulfate (a) to bleach catalyst (b) is 500: 1 to 1: 1, preferably 450: 1 to 10: 1, more preferably 400: 1 to 20: 1 and especially 375: 1 to 40: 1. It has been found that a particularly good cleaning effect, in particular at 40 ° C, can be achieved by the aforementioned ratio. The effects of the above-mentioned components on the detergency of the dishwashing detergent appear to have a mutually reinforcing effect in the above ratio.

The dishwashing detergent according to the invention also contains bleaching agent (c), preferably an oxygen-based bleaching agent. Such bleaches can be understood to mean water replenishing compounds. Exemplary of such compounds may be mentioned sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate.

Other bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ 0 ₂ - peracidic salts or peracids, such as Perbenzoeate, peroxophthalates,

Diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, e.g. Dibenzoyl. Other organic bleaches are the peroxyacids, with particular mention being made of the alkylperoxyacids and the arylperoxyacids.

In a particularly preferred embodiment, the dishwashing detergent contains

Sodium percarbonate, more preferably a coated sodium percarbonate, as

Bleaching agents based on oxygen.

The proportion by weight of the bleaching agent, based on the total weight of the

Dishwashing agent is in preferred embodiments from 0, 1 to 30 wt .-%, preferably from 5 to 20 wt .-% and in particular from 6 to 15 wt .-%.

In a preferred embodiment, the dishwashing agent according to the invention may further comprise a bleach activator (d). As bleach activators are usually understood substances which are under

Perhydrolysis aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or

optionally substituted perbenzoic acids. The aliphatic peroxycarboxylic acids and / or perbenzoic acids are bleaches, but due to a low

Storage stability should not be included directly in the dishwashing detergent. They are therefore generated only when needed.

Suitable substances are the O- and / or N-acyl groups of the mentioned

Carry carbon number and / or optionally substituted benzoyl groups.

Preference is given to polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.

Bleach activators, preferably TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1 to 10% by weight, especially 0.5 to 8% by weight and more preferably 1.0 to 6% by weight .-%, based on the total weight of the

Dishwashing detergent.

In addition to the abovementioned components (a) to (d), the dishwashing composition according to the invention may contain further constituents. Preferably, it contains nonionic surfactants (e), builders (f), alkaline agents (g), enzymes (h), anionic polymers (i), disintegrants (j) and / or other additives.

Nonionic surfactants (e), also called nonionic surfactants in the art, are surfactants which do not form ions in aqueous solution. They usually have a polar and a non-polar part, but as mentioned have no partial charge and are thus neutral.

The nonionic surfactant is preferably a nonionic surfactant or a plurality of nonionic surfactants having the general formula

R 0 [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) R ² , in which R is a linear or branched aliphatic Hydrocarbon radical having 4 to 22, in particular 6 to 18, carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof and x and z for values between 0 and 40 and y represent a value of at least 15, preferably from 15 to 120, more preferably from 20 to 80.

Alternatively preferred are in particular end-capped poly (oxyalkylated) nonionic surfactants according to the formula

R 0 [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular 6 to 16, carbon atoms or mixtures thereof, R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof and y is a value between 15 and 120, preferably 20 to 100, in particular 20 to 80 stands. The group of these nonionic surfactants include, for example, hydroxy mixed ethers of the general formula C ₆ -22-CH (OH) CH ₂ O- (EO) 2 O -i ₂ O-C2 -26, for example the C ₈ -i ₂ fatty alcohol (EO) ₂₂ - 2-hydroxydecyl ether and the C ₄ . ₂₂ fatty alcohol (EO) ₄₀ -8o-2-hydroxyalkyl ethers.

In a particularly preferred embodiment, the dishwashing detergent contains a low-foaming nonionic surfactant of the general formula

R CH (OH) CH ₂ 0- (CH 2 CH ₂ 0) 2o-i2o-R ^2, wherein R and R ² are independently a linear or branched aliphatic hydrocarbon radical having from 2 to 20, especially 4 to 16, carbon atoms.

Further preferred are nonionic surfactants of the formula

R 0 [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x represents values between 0.5 and 4, preferably 0.5 to 1.5, and y represents a value of at least 15.

Nonionic surfactants of the general formula are furthermore also according to the invention R 0 [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms or mixtures thereof , R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is a value between 1 and 40 and y is a value between 15 and 40, where the alkylene units [CH ₂ CH (CH ₃ ) O] and [CH ₂ CH ₂ O] randomized, i. in the form of a random statistical distribution.

The group of preferred end-capped poly (oxyalkylated) nonionic surfactants also includes nonionic surfactants of the formula

R 0 [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R and R ² independently of one another represent a linear or branched, saturated or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably -CH ₃ and x and y independently represent values between 1 and 32, with nonionic surfactants with R ³ = -CH ₃ and values for x of 15 to 32 and y of 0.5 and 1.5 being very particularly preferred.

Other preferred nonionic surfactants are the end-capped ones

poly (oxyalkylated) nonionic surfactants of the formula

R 0 [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² , in which R and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is in between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. When the value x> 2, each R ³ in the above formula R 0 [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 may be} different. R and R ² are

preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15. As described above, each R ³ in the above formula may be different if x> 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1 such that the above formula is R 0 [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH ) CH ₂ OR ² simplified. In the latter formula, R, R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R and R ² Have 9 to 14 carbon atoms, R ^{3 is} H and x assumes a value of 6 to 15.

Further preferred nonionic surfactants are nonionic surfactants of the general formula

R 0 (AlkO) _x M (OAlk) _y OR ² , where R and R ² independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22

Carbon atoms; Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms; x and y independently represent values between 1 and 70; and M is an alkyl group from the group CH ₂ , CHR ³ , CR ³ R ⁴ , CH ₂ CHR ³ and

CHR ³ CHR ⁴ , wherein R ³ and R ^{4 are} independently a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms.

Nonionic surfactants of the general formula are particularly preferred here

R is -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y O-CH ₂ CH (OH) -R ² , wherein R, R and R ² independently of one another are an alkyl radical or alkenyl radical having 6 to 22 carbon atoms and x and y independently of one another represent values between 1 and 40.

Particular preference is given here to compounds of the general formula

R is -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y O-CH ₂ CH (OH) -R ² where R is a linear, saturated alkyl radical 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and x and y independently of one another have values of 20 to 30. Corresponding compounds can be obtained, for example, by reaction of alkyldiols HO-CHR-CH ₂ -OH with ethylene oxide, followed by reaction with an alkyle epoxide to close the free OH functions to form a dihydroxy ether.

In a further preferred embodiment, the nonionic surfactant is selected from nonionic surfactants of the general formula

R-O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which R and R ² independently represent an alkyl or alkenyl radical having 4 to 22 carbon atoms, R ³ and R ⁴ independently each represents H or an alkyl radical or alkenyl radical having 1 to 18 carbon atoms and x and y independently of one another represent values between 1 and 40.

Preference is given here in particular to compounds of the general formula R -0 (CH ₂ CH ₂ 0) _x CR ³ R ⁴ (OCH ₂ CH ₂₎ _y OR ^2, are in which R ³ and R ⁴ is H and the indices x and y independently are from each other assume values from 1 to 40, preferably from 1 to 15.

Particular preference is given in particular to compounds of the general formula

R -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which the radicals R and R ² independently of one another represent saturated alkyl radicals having 4 to 14 carbon atoms and the indices x and y independently of one another assume values of 1 to 15 and in particular of 1 to 12.

Further preferred are those compounds of the general formula

R -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which one of the radicals R and R ^{2 is} branched.

Very particularly preferred compounds of the general formula R in the accept the indices x and y are independently values 8-12 -0 (CH ₂ CH ₂ 0) _x CR ³ R ⁴ (OCH ₂ CH ₂₎ _y OR ^2,.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the methods II trade products of the formulas mentioned are usually not from an individual representative, but from mixtures, which may result in both the C chain lengths and for the degrees of ethoxylation and degrees of alkoxylation averages and resulting broken numbers.

The aforementioned nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants. Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,

Particular preference is given to those nonionic surfactants which have a melting point above room temperature. Nonionic surfactants having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, are particularly preferred. The proportion by weight of the nonionic surfactant in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is 0.1 to 20% by weight, more preferably 0.5 to 15% by weight, in particular 2.5 to 10% by weight.

In a preferred embodiment, the weight ratio of alkyl ether sulfate to nonionic surfactant is 3: 1 to 1: 3, in particular 2: 1 to 1: 2, particularly preferably 1, 5: 1 to 1: 1.5.

Builders (f) are usually substances that contribute to ensuring the cleaning performance of the dishwashing detergent by, inter alia, inhibiting the formation of limescale deposits on machine components and thus allow an efficient transfer of energy to the water.

The proportion by weight of the builders in the total weight according to the invention

Dishwashing agent is preferably 15 to 80 wt .-% and in particular 20 to

70% by weight. The builders include in particular carbonates, phosphates, citrates, and

Silicates.

Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of from 2 to 30 wt .-%, preferably from 4 to 28 wt .-% and in particular from 8 to 24 wt .-%, each based on the total weight of the dishwashing detergent.

Preference is also the use of phosphate (s). Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are the most important in the detergent and cleaner industry.

Alkali metal phosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acid (HP0 ₃ ) _n and orthophosphoric H ₃ P0 _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts or lime incrustations on the objects to be cleaned and, moreover, contribute to the cleaning performance.

Particularly preferred phosphates according to the invention are the pentasodium triphosphate, Na ₅ P ₃ Oio (sodium tripolyphosphate) and the corresponding potassium salt Pentakalium triphosphate, K5P3O-10 (potassium tripolyphosphate). The sodium potassium tripolyphosphates are also preferably used according to the invention.

If phosphates are used as builders in dishwasher detergents in the context of the present application, these contain phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of from 5 to 60 Wt .-%, preferably from 15 to 45 wt .-% and in particular from 20 to 40 wt .-%, each based on the total weight of the dishwashing detergent.

Polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals and dextrins are also used as preferred builders. This class of substances is also referred to as organic cobuilders and described below.

If a polycarboxylic acid is used as the builder, it can be used in the form of the free acid and / or its alkali metal salts, in particular sodium salts, polycarboxylic acid meaning that carboxylic acid which carries more than one acid function. By way of example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such an application is not objectionable for environmental reasons, as well as mixtures of these. In addition to their builder effect, the free acids typically also have the property of a

Acid component and thus also serve to set a lower and milder pH of detergents or cleaners.

Particularly preferred dishwashing agents according to the invention contain as builders citrate, preferably sodium citrate. The dishwashing agent according to the invention preferably contains 2 to 40 wt .-%, preferably 5 to 30 wt .-% and in particular 7 to 20 wt .-% citrate, in particular sodium citrate, based on the total weight of the dishwashing detergent.

The citrates are preferably used with carbonates and / or bicarbonates. Preferred dishwashing detergents therefore contain a builder combination of phosphate and carbonate / bicarbonate or of citrate and carbonate / bicarbonate or of phosphate, citrate and carbonate / bicarbonate.

Particularly preferred dishwashing detergents are characterized in that the

Dishwashing detergent at least two builders from the group of phosphates, carbonates and citrates, wherein the proportion by weight of these builders, based on the

Total weight of the automatic dishwashing agent, preferably 5 to 80 wt .-%, preferably 15 to 75 wt .-% and in particular 30 to 70 wt .-% is. The

Combination of two or more builders from the above-mentioned group has proven advantageous for the cleaning and rinsing performance of automatic dishwashing agents according to the invention.

As builders, polymeric polycarboxylates are also suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a weight-average molar mass of from 500 to 70,000 g / mol.

Suitable polymers are, in particular, polyacrylates, which preferably have a weight average molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have a weight-average molar mass of from 2,000 to 10,000 g / mol, and particularly preferably from 3,000 to 5,000 g / mol, may again be preferred from this group.

The weight-average molar masses can be determined by means of gel permeation chromatography.

The content of (homo) polymeric polycarboxylates in the automatic dishwashing agent is preferably 0.5 to 20 wt .-% and in particular 3 to 10 wt .-%.

Automatic dishwasher detergents according to the invention can be used as builder crystalline layered silicates of the general formula

NaMSi _x 0 _{2x +} i ^■ y H ₂ O, where M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1, 9 to 4, particularly preferably 2, 3 or 4, and y for a Number from 0 to 33, preferably from 0 to 20.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus 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 delayed release and have secondary washing properties. In preferred dishwashing detergents according to the invention, the content of silicates, based on the total weight of the dishwashing detergent, is limited to amounts of from 0 to 10% by weight, preferably from 0 to 5% by weight and in particular from 0 to 2% by weight.

Particularly preferred dishwashing agents according to the invention are free of silicates.

In addition to the aforementioned builders, the inventive

Dishwashing agents include alkaline agents (g), preferably alkali metal hydroxides, in particular sodium hydroxide. These alkaline agents are preferred in the dishwashing agents in amounts of from 0 to 10% by weight, preferably from 0 to 6% by weight, preferably from 0 to 5% by weight, more preferably between 0, 1 and 5% by weight. % and in particular between 0.5 and 5 wt .-%, each based on the total weight of

Dishwashing agent, used. Alternatively preferred dishwashing detergents are free of alkali metal hydroxides.

As a further constituent, dishwashing agents according to the invention may preferably contain enzymes (h). These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. Enzymes in the dishwashing detergents may preferably be present in amounts of from 0.0001 to 10% by weight, preferably from 0.01 to 5% by weight, preferably from 0.1 to 3% by weight, more preferably between 0.2 and 2 wt .-%, each based on the

Total weight of the dishwashing detergent, are used.

Among the proteases, those of the subtilisin type are preferable. Examples of these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase attributable to the subtilases, but no longer to the subtilisins in the strictest sense , Proteinase K and the proteases TW3 and TW7.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from β. amyloliquefaciens, from β. stearothermophilus, from Aspergillus niger and A. oryzae, as well as those improved for use in detergents and cleaners

Further developments of the aforementioned amylases. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from β. agaradherens (DSM 9948).

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to obtain suitable precursors in situ To produce peracids. These include, for example, the lipases originally obtainable or further developed from Humicola lanuginosa (Thermomyces lanuginosus), in particular those having the amino acid exchange D96L.

Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Advantageously, organic, particularly preferably aromatic, interacting with the enzymes are additionally preferably used

Compounds added to enhance the activity of the respective oxidoreductases (enhancer) or at greatly different redox potentials between the

oxidizing enzymes and soiling to ensure the flow of electrons (mediators).

A protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred. The dishwashing compositions according to the invention can be used for this purpose

Stabilizers included.

Washing or cleaning-active proteases and amylases are generally not provided in the form of the pure enzyme but rather in the form of stabilized, storable and transportable preparations. Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, preferably as concentrated as possible, sparing in water and / or added with stabilizers or further auxiliaries.

Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities. As can be seen from the previous statements, the enzyme forms only a fraction of the total weight of conventional enzyme preparations. Enzyme preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and in particular between 0.8 and 10 Wt .-% of the enzyme.

The dishwashing agents according to the invention preferably contain from 0.1 to 12% by weight, preferably from 0.2 to 10% by weight and in particular from 0.5 to 8% by weight, of the enzyme preparations, based on the total weight of the dishwashing detergent.

Dishwashing agents according to the invention may contain as further constituent in a preferred embodiment at least one anionic polymer (i). Preferred anionic polymers here are the copolymeric polycarboxylates and the copolymeric polysulfonates.

The proportion by weight of the anionic polymer in the total weight of the dishwashing agent according to the invention is preferably 0.1 to 20 wt .-%, preferably 0.5 to 18 wt .-%, particularly preferably 1, 0 to 15 wt .-% and in particular 4 to 14 wt .-%.

The dishwashing agent according to the invention is preferably a solid dishwashing detergent. A "solid dishwashing detergent" is to be understood as meaning a dishwashing detergent which is in a solid state of aggregation at 25 ° C. and a pressure of 1 bar.

The dishwashing compositions according to the invention are preferably in the form of a shaped body, in particular a compactate, especially as a tablet. The moldings may take any geometric shape such as concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylindrical, octahedral, conical, pyramidal, ellipsoidal, pentagonal, octagonal and octagonal prismatic as well as

rhombohedral forms.

The production of the shaped bodies, in particular of the tablets, is preferably carried out by compressing particulate starting substances. To prepare the tablets, a premix is preferably compressed in a so-called matrix between two punches to form a solid compactate. This process, hereinafter referred to as tableting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection. The tableting is preferably carried out on so-called rotary presses. The ingredients provided for tabletting can be added in the form of a common particulate premix at the same time or in the form of individual, separate powders or granules offset in time or at the same time in the die, wherein the

Dosing a preformed particulate premix is preferred.

It has surprisingly been found that the granules according to the invention used for the production of the moldings can be pressed particularly well. Thus, compacts having a hardness in the range from 150 to 250 N, in particular in the range from 200 to 230 N, which in addition is a particularly good one, can preferably be obtained by using a pressing force of 40 to 65 kN, more preferably 48 to 60 kN

Have trickle behavior. The granules can thus preferably be pressed with relatively low pressing force into compact materials having a relatively high hardness, which moreover preferably have a very good trickling behavior.

In a further preferred embodiment, the shaped bodies may contain disintegrating agents (j). The effect of disintegrants is usually that they are at

Water access their volume increase, on the one hand, the intrinsic volume increases (swelling), or on the other hand, but also on the release of gases, a pressure can be generated, which can disintegrate the tablet into smaller particles.

For example, cross-linked polyvinylpyrrolidone (crospovidone) can be used as disintegrant, preferably in particulate form.

The dishwashing compositions according to the invention can disintegrate, in particular

Polyvinylpyrrolidone, preferably in an amount of 0, 1 to 5 wt .-%, in particular in an amount of 0.2 to 3 wt .-%, in particular in an amount of 0.3 to 1, 8 wt .-%, contained, based on the total weight of the dishwashing detergent.

In addition or as an alternative to the polyvinylpyrrolidone particles, further

Disintegrating agents may be contained in the moldings of the invention, for example

Carbonate / citric acid systems or carbonate in combination with other organic acids, synthetic polymers or natural polymers or modified natural substances such as cellulose and starch and their derivatives as well as alginates or casein derivatives. Furthermore, gas-evolving effervescent systems can also be used as further disintegrants. Preferred effervescent systems consist of at least two constituents which react with one another to form gas, for example from alkali metal carbonate

and / or bicarbonate and an acidifying agent which is suitable from the Alkali metal salts in aqueous solution to release carbon dioxide. An acidifying agent which releases carbon dioxide from the alkali salts in aqueous solution is, for example, citric acid.

In an alternative preferred embodiment, however, the shaped bodies can also be used in combination with other forms of supply, in particular in combination with solid forms

Supply forms such as powders, granules or extrudates or in combination with liquid supply forms based on water and / or organic solvents.

The shaped body may, for example, also be a granulate which is contained in a bag or a casting mold.

The simplest realization possibility lies in two or more multilayer tablets, each layer of the molding representing a single phase. By virtue of the phase or layered structure, the various constituents which fulfill the different functions of a dishwashing detergent can preferably be kept separate from one another such that they can not undesirably interact before the washing cycle.

Therefore, particularly preferred are two- or multi-phase tablets, for example

Two-layer tablets, in particular two-layer tablets with a trough and a molded body located in the trough. Alternatively, however, it is also possible to prepare multiphase tablets in which one phase is integrated in the form of an intercalation into the other phase (s).

In this case, it has unexpectedly proven to be particularly favorable that a first phase contains a combination of alkyl ether sulfate (a), bleach catalyst (b) and bleach (c) and a second phase contains enzymes and optionally alkyl ether sulfate (a). As a result, even at low temperatures excellent cleaning performance was found.

Dishwashing agents according to the invention are preferably metered units

prefabricated. These dosing units preferably include those for a

Cleaning cycle necessary amount of washing- or cleaning-active substances.

Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g. The volume of the aforementioned metering units and their spatial form are with

particular preference chosen so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.

The dishwashing compositions according to the invention, in particular the prefabricated dosage units, in a preferred embodiment have a water-soluble coating.

Particularly preferred dishwashing agents according to the invention contain

From 0.05% to 20% by weight, preferably from 0.1% to 10% by weight; in particular 1, 0 to 5% by weight, alkyl ether sulfate (a);

0.001% by weight to 1% by weight, preferably 0.01% by weight to 0, 10% by weight

Bleach catalyst (b), especially Mn-TACN;

0.1 to 30% by weight, preferably 5 to 20% by weight, in particular 6 to 15% by weight of bleaching agent (c), in particular sodium percarbonate;

0 to 10 wt .-%, preferably 0.5 to 8 wt .-%, in particular 1, 0 to 6 wt .-%, bleach activator (d), preferably tetraacetylethylenediamine;

0 to 20% by weight, preferably 0.5 to 15% by weight, in particular 2.5 to 10% by weight, of nonionic surfactants (e);

0 to 80 wt .-%, preferably 15 to 80 wt .-%, in particular 20 to 70 wt .-%. Builders (f);

0 to 10 wt .-%, preferably from 0.01 to 5 wt .-%, preferably from 0, 1 to 3 wt .-%, particularly preferably between 0.2 and 2 wt .-% enzymes (h); and optionally

0 to 20 wt .-%, preferably from 0.5 to 18 wt .-%, in particular 1, 0 to

15 wt .-% of an anionic polymer, preferably a copolymeric anionic

Polymer.

In addition to the ingredients described above, the compositions according to the invention may contain further additives such as washing or cleaning-active substances, preferably from the group of glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers.

The combinations of ingredients described above are preferably suitable for cleaning dishes in dishwashing, especially in machine

Dishwashing. Another object of the present application is therefore a machine

Dishwashing process, in which a dishwashing detergent according to the invention is used. In the method for cleaning dishes in a dishwasher using a dishwashing detergent according to the invention, dishwashing detergent is preferably metered or introduced into the interior of a dishwasher during the passage of a dishwashing program, before the main wash cycle or during the main wash cycle. The dosing or the entry of the dishwashing detergent according to the invention into the interior of the dishwasher can be done manually, but preferably the dishwashing detergent is used by means of the dosing chamber

Dishwasher dosed into the interior of the dishwasher. In the course of the cleaning process preferably no additional water softener and no additional rinse aid is metered into the interior of the dishwasher.

A preferred embodiment is a machine dishwashing process using the inventive, preferably solid, dishwashing detergent, in particular in the form of a previously mentioned shaped body, in particular for removing soiling. These soiling may preferably be soils of egg yolk or more preferably bleachable soils such as vegetable dyes.

The dishwashing process is preferably carried out at a liquor temperature below 50 ° C, preferably at 35-45 ° C. In a preferred embodiment, the dishwashing process takes 5 to 90 minutes, in particular 10 to 75 minutes, particularly preferably 20 to 60 minutes. In alternatively preferred embodiments, the dishwashing process takes a maximum of 50, 40 or 30 minutes.

Another object of the present invention is a kit for a

Dishwasher comprising a) a machine dishwashing detergent according to the invention,

b) a manual that informs the consumer about the machine

Dishwashing detergent is to be used without the addition of a rinse aid and / or a softening salt.

The dishwasher detergents according to the invention show their advantageous

Cleaning properties especially in the above-mentioned low-temperature cleaning method and in the abovementioned short-term cleaning method. Thus, a further subject of the invention is the use of the dishwashing agent according to the invention in a dishwashing process for the removal of stains at a washing temperature of 20 to 50 ° C, preferably 25 to 48 °, especially 35 to 45 ° C.

Finally, the invention relates to the use of an alkyl ether sulfate (a) as a constituent of a machine dishwashing agent for removing stains at a washing temperature of 20 to 50 ° C, preferably 25 to 48 °, especially 35 to 45 ° C. In a preferred embodiment, the use of the alkyl ether sulfate is carried out in combination with a bleach catalyst (b), preferably a manganese-containing bleach catalyst, in particular Mn-TACN.

In a further aspect of the invention, it has been found that the use of a Mn-containing bleach catalyst, in particular containing a Mn-TACN

Bleaching catalyst leads to unexpectedly good results in the above low-temperature cleaning process. Therefore, a further subject of the invention is the use of a Mn-containing bleach catalyst, in particular a Mn-TACN-containing bleach catalyst, as a constituent of a dishwasher detergent for removing stains at a temperature of 20 to 50 ° C, preferably from 25 to 48 ° C, more preferably from 35 to 45 ° C and especially from 40 ° C.

In a further aspect of the invention it has been found that alkyl ether sulfates for

Performance enhancement of existing bleaching systems can be used. The

Alkyl ether sulfates can therefore be used to existing bleaching systems or existing

Dishwashing detergent containing bleaching systems can be added as a "booster". Another object of the invention is therefore the use of an alkyl ether sulfate to increase the bleaching action of a bleaching system comprising a bleach catalyst and a

Bleaching agent, for example at a temperature of 20 to 50 ° C, preferably from 25 to 48 ° C, more preferably from 35 to 45 ° C and in particular from 40 ° C.

The explanations given above regarding the dishwashing agent according to the invention (for example concerning the chemical structure of the alkyl ether sulfate or of the bleach catalyst) are also applicable to the uses according to the invention.

The present invention will be illustrated by the following example. Examples

Example 1 (according to the invention):

A dishwashing detergent was prepared according to the following recipe:

Alkyl ether sulfate 5.0% by weight

Bleach catalyst 0, 1% by weight

Bleach 14.6% by weight

Phosphates 41, 2% by weight

Carbonates 12.2% by weight

Enzymes 2.9% by weight

Nonionic surfactants 6.4% by weight

Additives 17.6% by weight

Example 2 (according to the invention):

A dishwashing detergent was prepared according to the following recipe:

Alkyl ether sulfate 2.5% by weight

Bleach catalyst 0, 1% by weight

Bleach 14.6% by weight

Phosphates 43.7% by weight

Carbonates 12.2% by weight

Enzymes 2.9% by weight

Nonionic surfactants 6.4% by weight

Additives 17.6% by weight

Example 3 (comparison)

A dishwashing agent was prepared analogously to Example 2, except that the amount of alkyl ether sulfate was replaced by phosphates.

Example 4: Cleaning performance in automatic dishwashing

The cleaning performance of the formulations according to the invention was tested on the following apparatus:

Bosch SMS86, program "soft 40", water with 21 ° dH

The cleaning performance was determined according to the standard in the field IKW method (cleaning performance is shown as a value of 1 to 10, the higher the value, the better the cleaning performance). In particular, the cleaning performance of vegetable stains were evaluated. The results are shown in the following table:

Recipe IKW value

Example 1 7.0

Example 2 6.8

Comparative Example 3 5.8

Claims

claims

1 . Dishwashing detergent containing

(a) alkyl ether sulfate,

(b) bleach catalyst,

(c) Bleaching agent.

2. Dishwashing detergent according to claim 1, characterized in that it is the alkyl ether sulfate (a) is a compound according to formula (I)

Formula (I) wherein

R is an alkyl having 8 to 22 C atoms,

n is a natural number from 1 to 8 and

M is a metal or hydrogen atom.

3. Dishwashing detergent according to claim 1 or 2, characterized in that the alkyl ether sulfate (a) in an amount of 0.05 to 20 wt .-%, based on the total weight of the dishwashing detergent, is included.

4. Dishwashing detergent according to one of claims 1 to 3, characterized in that the bleach catalyst (b) contains a transition element, preferably manganese.

5. Dishwashing detergent according to one of claims 1 to 4, characterized in that the bleach catalyst (b) contains Mn-TACN.

6. Dishwashing detergent according to one of claims 1 to 5, characterized in that the weight ratio of alkyl ether sulfate (a) to bleach catalyst (b) is 500: 1 to 1: 1.

7. Dishwashing detergent according to one of claims 1 to 6, characterized in that the bleaching agent (c) is sodium percarbonate.

8. Dishwashing detergent according to one of claims 1 to 7, characterized in that the bleaching agent (c) in an amount of 0, 1 to 30 wt .-%, based on the total weight of the dishwashing detergent, is included.

9. Dishwashing detergent according to one of claims 1 to 8, characterized in that it contains a bleach activator (d), preferably tetraacetylethylenediamine.

10. Dishwashing detergent according to one of claims 1 to 9, characterized in that it

0.05 to 20% by weight, alkyl ether sulfate (a);

From 0.001% to 1% by weight of bleach catalyst (b), especially Mn-TACN;

0.1 to 30% by weight, bleaching agent (c), in particular sodium percarbonate;

0 to 10% by weight, bleach activator (d),

0.5 to 20% by weight, nonionic surfactants (e),

10 to 80 wt .-% builders (f) and

0 to 10 wt .-% enzymes (h) contains.

1 1. Dishwashing detergent according to one of claims 1 to 10, characterized in that it is in the form of a shaped body, preferably in the form of a compact, in particular in the form of a tablet.

12. Dishwashing detergent according to claim 1 1, wherein it is a multi-phase tablet and wherein a first phase comprises a combination of alkyl ether sulfate (a), bleach catalyst (b) and bleach (c) and a second phase enzymes (h) and optionally alkyl ether sulfate (a) contains.

13. Machine dishwashing process, characterized in that a

Dishwashing agent according to one of the preceding claims is used.

14. Use of an alkyl ether sulfate and / or a Mn-TACN catalyst as

Component of a machine dishwashing detergent for the removal of

Stains at a washing temperature of 20 to 50 ° C.

15. Use of an alkyl ether sulfate to increase the bleaching action of a

Bleaching system containing a bleach catalyst and a bleach.