EP2788466B1 - Use of formulations for machine dishwashing - Google Patents

Description

• (a1) mindestens ein Copolymer, erhältlich durch Copolymerisation von
  • (a1.1) mindestens einem N-Vinylamid,
  • (a1.2) Vinylacetat,
  • (a1.3) mindestens einem Polyether,
  • (a1.4) gegebenenfalls mindestens einem weiteren Comonomer,
• (a2) mindestens ein Alkoxylat der allgemeinen Formel (I)
  
          R¹-(OCH₂CHR²)_mOR³     (I)
  
  wobei die Variablen wie folgt definiert sind:

  R¹

  C₈-C₂₄-Alkyl, linear oder verzweigt,

  R²

  C₁-C₁₀-Alkyl, jeweils gleich oder verschieden, linear oder verzweigt, oder Wasserstoff,

  R³

  Wasserstoff oder C₁-C₄-Alkyl, linear oder verzweigt,

  m

  eine Zahl im Bereich von 1 bis 100,

  in Formulierungen für die automatische Geschirrreinigung.

The present invention relates to the use of preparations containing

• (a1) at least one copolymer obtainable by copolymerization of
  • (a1.1) at least one N-vinylamide,
  • (a1.2) vinyl acetate,
  • (a1.3) at least one polyether,
  • (a1.4) optionally at least one further comonomer,
• (a2) at least one alkoxylate of the general formula (I)
  
  R ¹ - (OCH ₂ CHR ² ) _m OR ³ (I)
  
  where the variables are defined as follows:

  R ¹

  C ₈ -C ₂₄ -alkyl, linear or branched,

  R ²

  C ₁ -C ₁₀ -alkyl, in each case identical or different, linear or branched, or hydrogen,

  R ³

  Is hydrogen or C ₁ -C ₄ -alkyl, linear or branched,

  m

  a number in the range of 1 to 100,

  in formulations for automatic dishwashing.

Furthermore, the present invention relates to the use of certain copolymers.

Formulations for machine dishwashing demanding demands are made. In addition to the actual residue-free cleaning you want to ensure that dishes, metal objects and glasses shine flawlessly. Until about 2001, therefore, in many cases, a cleaner, a rinse aid and a so-called regenerating salt were dosed separately into the dishwasher, wherein the regenerating salt binding of calcium ions and magnesium ions zukam and the rinse aid had the task for a flat flow of water on the dishes and prevent the formation of limescale and water spots.

Since then introduced "3 in 1" dishwashing detergents combine the function of detergent, rinse aid and regenerating salt in one product. This eliminates the need for the consumer refilling rinse aid and salt in the dishwasher. The incorporation of additional functions (eg protection against glass corrosion and protection against the tarnishing of silver) led to the development of x in 1 (with eg x = 6 or 9) or "all in one" products.

WO 2008/132131 discloses the use of a combination of at least one alcohol alkoxylate, at least one short chain alcohol ethoxylate, at least one sulfonate group-containing polymer and / or at least one hydrophilically modified polycarboxylate and optionally a polycarboxylate, together with common other ingredients to improve the rinse performance in phosphate-containing and phosphate-free machine dishwashing detergents.

DE 102 33 834 A discloses as nonionic surfactants in machine dishwashing detergents alkoxylated, preferably ethoxylated primary alcohols having 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol. Preferred are alcohol ethoxylates of alcohols of native origin having 12 to 18 carbon atoms, such as coconut, palm, tallow or oleyl alcohol, with an average of 2 to 8 moles of EO per mole of alcohol.

Many "X in 1" or "all in one" dishwashing detergents do not yet achieve the good rinse results that can be achieved with the use of separate rinse aids, namely, strip-free and drip-free draining of the dishes from the dishes this is obtained shiny and without dried water droplets (spotting). It was also shown that when rinsing, especially in slightly harder water, so at 10 ° dH and more, the filming can still improve. Filming is understood to mean the formation of a flat-undesirable-coating. Accordingly, the more uniform and low deposits on the surfaces of the objects to be washed are the better the values for filming.

It was therefore the task to provide formulations that can be used in "X in 1" or "All in one" dishwashing detergent, so that you can or dosing the rinse aid, for example via tablet in the main rinse, but only in Klärspülgang a good effect is observed.

Accordingly, the use of formulations defined above were found in formulations for machine dishwashing, in short also called preparations used in the invention.

• (a1) mindestens ein Copolymer, kurz auch Copolymer (a1) genannt. Copolymer (a1) ist erhältlich durch Copolymerisation von

  (a1.1)

  mindestens einem N-Vinylamid, beispielsweise N-Vinylformamid oder N-Vinylacetamid, vorzugsweise mindestens einem N-Vinyllactam, beispielsweise N-Vinylpyrrolidon und N-Vinylcaprolactam,

  (a1.2)

  Vinylacetat,

  (a1.3)

  mindestens einem Polyether,

  (a1.4)

  gegebenenfalls mindestens einem weiteren Comonomer, beispielsweise (Meth)acrylsäure, (Meth)acrylnitril und C₁-C₄-Alkyl-(meth)acrylate.

Preparations used according to the invention contain

• (a1) at least one copolymer, also called copolymer (a1) for short. Copolymer (a1) is obtainable by copolymerization of

  (A1.1)

  at least one N-vinylamide, for example N-vinylformamide or N-vinylacetamide, preferably at least one N-vinyllactam, for example N-vinylpyrrolidone and N-vinylcaprolactam,

  (A1.2)

  vinyl acetate,

  (A1.3)

  at least one polyether,

  (A1.4)

  optionally at least one further comonomer, for example (meth) acrylic acid, (meth) acrylonitrile and C ₁ -C ₄ -alkyl (meth) acrylates.

Examples of suitable polyethers (a1.3) are polybutylene glycols obtainable by the polymerization of 2,3-dimethyloxirane or 2-ethyloxirane. Preferred polyethers (a1.3) are selected from polyethylene glycol, polypropylene glycol and polytetrahydrofuran, and from copolymers of ethylene oxide and propylene oxide and / or 2,3-dimethyloxirane or 2-ethyloxirane. The above-mentioned copolymers of ethylene oxide and propylene oxide and / or 2,3-dimethyloxirane or 2-ethyloxirane may be random copolymers or block copolymers, for example, ethylene oxide and propylene oxide may be AB type or ABA type ones.

Polyether (a1.3) may be unilaterally or both sides etherified with C ₁ -C ₂₀ alkanol or an alkylating agent, in each case identical or different, preferably with C ₁ -C ₁₈ -alkanol, for example with methanol, ethanol, n-butanol, Isopropanol, n-propanol, isobutanol, n-pentanol, n-hexanol, n-octanol, n-nonanol, n-decanol, n-dodecyl alcohol, n-tridecanol, n-hexadecanol or n-octadecanol.

In another embodiment of the present invention, polyether (a1.3) is a diol.

In one embodiment of the present invention, polyether (a1.3) has an average molecular weight M _w in the range of 1,000 to 100,000 g / mol, preferably 1,500 to 35,000 g / mol, particularly preferably 10,000 g / mol. The average molecular weights M _w are determined from the OH number measured according to DIN 53240 or by gel permeation chromatography (GPC).

In a preferred embodiment of the present invention, copolymer (a1) is a graft copolymer in which at least one polyether (a1.3) serves as the graft base to which N-vinylamide (a1.1), vinyl acetate (a1.2) and optionally at least one further comonomer (a1.4) are grafted on, for example by free-radical copolymerization.

In one embodiment of the present invention, in such copolymers (a1) which are graft copolymers, grafted in the side chains N-vinylamide (a1.1), vinyl acetate (a1.2) and optionally at least one further comonomer (a1.4). In another embodiment of the present invention, branches of such copolymers (a1) which are graft copolymers contain in each case only copolymerized N-vinylamide (a1.1) or only vinyl acetate (a1.2) or optionally only further comonomer (a1.4).

Examples of suitable further comonomers (a1.4) are (meth) acrylic acid, (meth) acrylonitrile and C ₁ -C ₄ -alkyl (meth) acrylates, preferably acrylic acid, methyl acrylate, ethyl acrylate and n-butyl acrylate. In one embodiment of the present invention, copolymer (a1) has an average molecular weight M _w in the range of from 90,000 to 140,000 g / mol as determined by GPC.

In one embodiment of the present invention, copolymer (a1) has a Fikentscher K value in the range of 10 to 60, preferably 15 to 40, measured in a 1 wt% ethanolic solution at room temperature.

In one embodiment of the present invention, copolymer (a1) comprises copolymerized: in total in the range from 30 to 80% by weight, preferably 40 to 70% by weight, particularly preferably 50 to 60% by weight, of N-vinylamide (a1.1 )
in total in the range from 10 to 50% by weight, preferably from 15 to 35% by weight, particularly preferably from 25 to 35% by weight, of vinyl acetate (a1.2),
in total in the range from 10 to 50% by weight, preferably up to 30% by weight, particularly preferably up to 25% by weight and very particularly preferably up to 20% by weight of polyether (a1.3),
in total in the range from zero to 10% by weight of comonomer (e) (a1.4),
in each case based on the mass of the total copolymer (a1).

• (a2) mindestens ein Alkoxylat der allgemeinen Formel (I),
  
          R¹-(OCH₂CHR²)_mOR³     (I)
  
  kurz auch Alkoxylat (a2) genannt, in dem die Variablen wie folgt definiert sind:

  R¹

  C₈-C₂₄-Alkyl, verzweigt oder vorzugsweise linear, beispielsweise n-Octyl, n-Decyl, n-Dodecyl, n-Tetradecyl, n-Hexadecyl, n-Octadecyl, n-Eicosyl,

  R²

  C₁-C₁₀-Alkyl, jeweils gleich oder verschieden, linear oder verzweigt, Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Amyl, iso-Pentyl; n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Octyl, n-Decyl, iso-Decyl, besonders bevorzugt Methyl
  oder vorzugsweise Wasserstoff,

  R³

  Wasserstoff oder C₁-C₄-Alkyl, verzweigt oder vorzugsweise linear, beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, besonders bevorzugt Methyl oder n-Butyl,

  m

  eine Zahl im Bereich von 1 bis 100. Die Zahl m bezeichnet einen Mittelwert und kann eine ganze Zahl sein, muss aber keine ganze Zahl sein.

Preparations used according to the invention also contain

• (a2) at least one alkoxylate of the general formula (I),
  
  R ¹ - (OCH ₂ CHR ² ) _m OR ³ (I)
  
  also called alkoxylate (a2) in short, in which the variables are defined as follows:

  R ¹

  C ₈ -C ₂₄ -alkyl, branched or preferably linear, for example n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl,

  R ²

  C ₁ -C ₁₀ -alkyl, in each case identical or different, linear or branched, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl iso-amyl, iso-pentyl; n-hexyl, iso-hexyl, sec-hexyl, n-octyl, n-decyl, iso-decyl, most preferably methyl
  or preferably hydrogen,

  R ³

  Is hydrogen or C ₁ -C ₄ -alkyl, branched or preferably linear, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, particularly preferably methyl or n-butyl,

  m

  a number in the range of 1 to 100. The number m denotes an average and may be an integer, but need not be an integer.

Alkoxylates of the formula (I) can, if one chooses m greater than 1 and at least two R ^{2 are} different from each other, be random copolymers or block copolymers, preferably they are block copolymers. In embodiments in which the groups R ^{2 are} different and m is greater than 3, preferably greater than 5, the various alkoxide units may be distributed statically or in blocks in alkoxylate (a2), preferably in blocks.

Preferred alkoxylates (a2) are alkoxylated, preferably ethoxylated primary alkanols having 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alkanol. Particular preference is given to alkoxylates of alcohols of natural origin having 12 to 18 C atoms, such as coconut, palm, tallow or oleyl alcohol, ethoxylated with an average of 2 to 8 moles of EO per mole of C ₈ -C ₁₈ -alkanol. C ₁₂ -C ₁₄ -alkanols, ethoxylated with on average 3 or 4 moles of EO per mole of alkanol, C ₉ -C ₁₁ -alkanols, ethoxylated with an average of 7 moles of EO per mole of alkanol, C ₁₃ -C ₁₅ -alcohols may be mentioned by way of example , ethoxylated with an average of 3, 5, 7 or 8 moles of EO per mole of alkanol, and C ₁₂ -C ₁₈ alcohols, ethoxylated with an average of 5 moles of EO per mole of alkanol.

• Gemische von C₁₃- bis C₁₅-Oxoalkoholen, alkoxyliert mit 9 mol Ethylenoxid und 2 mol Butylenoxid pro mol,
• iso-C₁₀-Alkohole, alkoxyliert mit 10 mol Ethylenoxid und im Mittel 1,5 mol 1,2-Pentenoxid,
• C₁₀- bis C₁₂-Fettalkohole, alkoxyliert mit 9 mol Ethylenoxid und 5 mol Propylenoxid,
• C₁₃- bis C₁₅-Oxoalkohole, alkoxyliert mit im Mittel 4,46 mol Ethylenoxid + 0,86 mol Butylenoxid, einfach endgruppenverschlossen mit einer Methylgruppe,
• 2-Propylheptanol, alkoxyliert mit 4,5 mol Ethylenoxid und im Mittel 0,9 mol Propylenoxid und Mischungen von mindestens zwei der vorstehend genannten Alkoxylaten (a2).

By way of example may be mentioned

• Mixtures of C ₁₃ - to C ₁₅ -oxo alcohols, alkoxylated with 9 mol of ethylene oxide and 2 mol of butylene oxide per mol,
• iso-C ₁₀ -alcohols alkoxylated with 10 mol of ethylene oxide and on average 1.5 mol of 1,2-pentenoxide,
• C ₁₀ - to C ₁₂ -fatty alcohols alkoxylated with 9 mol of ethylene oxide and 5 mol of propylene oxide,
• C ₁₃ - to C ₁₅ -oxo alcohols, alkoxylated with on average 4.46 mol of ethylene oxide + 0.86 mol of butylene oxide, simply end-capped with a methyl group,
• 2-propylheptanol, alkoxylated with 4.5 mol of ethylene oxide and on average 0.9 mol of propylene oxide and mixtures of at least two of the abovementioned alkoxylates (a2).

R¹

einem linearen C₁₆-C₁₈-Alkylrest,

R³

lineares oder verzweigtes C₁-C₆-Alkyl oder vorzugsweise Wasserstoff,

x

im Bereich von 8 bis 10, vorzugsweise 8, 9 oder 10,

bevorzugt. Besonders bevorzugte Ethoxylate der Formel (II) sind solche auf Basis von Talgfettalkoholen (C₁₆-C₁₈-Alkoholen) mit im Mittel 9 mol Ethylenoxid pro mol Talgfettalkohol.Alkoxylates of the formula (I) are ethoxylates of the formula (II)

R ¹ - (OCH ₂ CH ₂ ) _x -OR ³ (II)

With

R ¹

a linear C ₁₆ -C ₁₈ -alkyl radical,

R ³

linear or branched C ₁ -C ₆ -alkyl or preferably hydrogen,

x

in the range of 8 to 10, preferably 8, 9 or 10,

prefers. Particularly preferred ethoxylates of the formula (II) are those based on tallow fatty alcohols (C ₁₆ -C ₁₈ -alcohols) with an average of 9 mol of ethylene oxide per mole of tallow fatty alcohol.

Preferred linear C ₁₆ -C ₁₈ alkanols are n-hexadecanol and n-octadecanol. These can be obtained by hydrogenation of natural tallow fat. However, the linear C ₁₇ -alkanol is also suitable.

Mixtures of linear C ₁₆ and C ₁₈ alkanols of natural origin are also known as tallow fatty alcohol. Tallow fatty alcohols have a low proportion of unsaturated constituents, in particular fractions of mono- or polyunsaturated C ₁₆ - and C ₁₈ -alcohols. However, these are, based on the amount of alcohol, generally at most 5 wt .-%, preferably 0.1 to 2 wt .-%. In the context of the present invention, preferably tallow fatty alcohols are to be subsumed under the name of C ₁₆ -C ₁₈ -alkanols because of the only slight contamination with unsaturated alkanols.

In one embodiment of the present invention, preparations used in the invention contain from 1 to 60% by weight of copolymer (a1) and from 40 to 99% by weight of alkoxylate (a2), preferably from 1 to 50% by weight of copolymer (a1) and 50 to 99% by weight of alkoxylate (a2).

In one embodiment of the present invention, copolymer (a1) and alkoxylate (a2) are present as solid solution in preparations used according to the invention. The term "solid solution" is intended to denote a state in which copolymer (a1) is dispersed in a microdispersed or, ideally, molecularly dispersed form in a solid matrix of alkoxylate (a2), as can be demonstrated, for example, by microscopy.

In one embodiment of the present invention, preparations (a) used according to the invention are present as free-flowing and flowable water-soluble powders.

In one embodiment of the present invention, preparations (a) used according to the invention are present as powders having a mean particle diameter in the range from 100 to 1500 μm. In another embodiment of the present invention, preparations (a) used according to the invention are present as granules.

In another embodiment of the present invention, preparations (a) used according to the invention are present as compact mixtures or as a layer, for example as spheres or hemispheres for dishwasher tablets or as coatings of whole dishwasher tablets or as coatings of parts of dishwashing tablets, for example individual surfaces or sections of surfaces of dishwasher tablets.

If preparations used according to the invention are used as or for the preparation of formulations for cleaning dishes, dishes are obtained which are excellently cleaned and in particular have little limescale. Furthermore, dishes washed with the formulations described above show very good filming properties.

A further subject of the present invention is the use of formulations used according to the invention in formulations for machine dishwashing, also referred to as use according to the invention for short. Another object of the present invention is a method for machine dishwashing using at least one formulation used in the invention. Another object of the present invention are formulations for machine dishwashing, containing at least one preparation according to the invention, for example in the range of 0.1 to 20 wt .-%, based on the invention used formulation.

1. (a) insgesamt im Bereich von 0,1 bis 20 Gew.-% mindestens eine erfindungsgemäß verwendete Zubereitung, bevorzugt 0,5 bis 15 Gew.-%, besonders bevorzugt 1 bis 10 Gew.-%.
2. (b) insgesamt im Bereich von 0 bis 10 Gew.-% nichtionisches Tensid, das von Copolymer (a1) und von Alkoxylat (a2) verschieden ist, kurz auch Tensid (b) genannt,
3. (c) insgesamt im Bereich von 0 bis 20 Gew.-% ein oder mehrere Polycarboxylate, kurz auch Polycarboxylat (c) genannt,
4. (d) insgesamt im Bereich von 0 bis 50 Gew.-% Komplexbildner, die von anorganischen Phosphaten verschieden sind, kurz auch Komplexbildner (d) genannt,
5. (e) insgesamt im Bereich von 0 bis 70 Gew.-% ein oder mehrere anorganische Phosphate, kurz auch Phosphat (e) genannt,
6. (f) insgesamt im Bereich von 0 bis 60 Gew.-% weitere Builder und Cobuilder, die jeweils von Komplexbildner (d) verschieden sind, kurz auch Builder (f) bzw. Cobuilder (f) genannnt,
7. (g) insgesamt im Bereich von 0 bis 30 Gew.-% Bleichmittel, kurz auch Bleichmittel (g) genannt, und gegebenenfalls Bleichaktivatoren oder Bleichkatalysatoren,
8. (h) insgesamt im Bereich von 0 bis 8 Gew.-% Enzym(e),
9. (i) insgesamt im Bereich von 0 bis 50 Gew.-% ein oder mehrere weitere Zusatzstoffe, und gegebenenfalls Wasser.

In one embodiment of the present invention, formulations used according to the invention contain:

1. (A) in total in the range of 0.1 to 20 wt .-%, at least one preparation according to the invention, preferably 0.5 to 15 wt .-%, particularly preferably 1 to 10 wt .-%.
2. (b) in total in the range of 0 to 10% by weight of nonionic surfactant other than copolymer (a1) and of alkoxylate (a2), also referred to as surfactant (b) for short,
3. (c) in total in the range from 0 to 20% by weight of one or more polycarboxylates, also called polycarboxylate (c) for short,
4. (d) in total in the range from 0 to 50% by weight of complexing agents other than inorganic phosphates, also called complexing agents (d) for short,
5. (e) in total in the range from 0 to 70% by weight of one or more inorganic phosphates, in short also called phosphate (s),
6. (f) in total in the range from 0 to 60% by weight of further builders and cobuilders which are each different from complexing agent (d), in short also builder (f) or cobuilder (f),
7. (g) in total in the range from 0 to 30% by weight of bleach, also referred to as bleach (g) for short, and, if appropriate, bleach activators or bleach catalysts,
8. (h) in total in the range of 0 to 8% by weight of enzyme (s),
9. (i) in total in the range of 0 to 50% by weight of one or more further additives, and optionally water.

Data in% by weight are based on the total solids content of the formulation used according to the invention.

In one embodiment of the present invention, formulations used according to the invention have a pH in the range from 5 to 14, preferably 8 to 13.

In one embodiment of the present invention, formulations used according to the invention may have a water content in the range from 0.1 to 10% by weight, based on the total solids content, of the formulation used according to the invention.

Surfactant (b) can also be referred to below as component (b). Polycarboxylate (c) may also be referred to below as component (c). Complexing agent (d) can also be referred to below as component (d), etc. Preferably, formulations used according to the invention comprise at least one substance selected from component (b) to component (i), where component (i) is different from water.

In one embodiment of the present invention, additives (i) are selected from anionic or zwitterionic surfactants, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents, tabletting aides, disintegrating agents, thickeners and solubilizers.

The components (b) to (i) are described in more detail below by way of example.

In addition to the nonionic surfactants of component (a) contained in preparations (a) according to the invention, formulations used according to the invention may contain up to 10% by weight of surfactant (s) (b), for example low or low foaming nonionic surfactants.

Preferably, formulations used according to the invention contain in total in the range from 0.1 to 10% by weight, preferably from 0.25 to 5% by weight, of surfactant (b).

In one embodiment of the present invention, surfactant (b) is selected from di- and multiblock copolymers composed of C ₁ -C ₂₀ alkanol, ethylene oxide and propylene oxide.

In another embodiment of the present invention, surfactant (b) is selected from reaction products of sorbitan esters with ethylene oxide and / or propylene oxide. Other suitable surfactants (b) are selected from ethoxylated or propoxylated sorbitan esters. Also suitable are amine oxides or alkyl glycosides. An overview of suitable further nonionic surfactants can be found in EP-A 0 851 023 and in DE-A 198 19 187 ,

In one embodiment of the present invention, formulations used according to the invention comprise a mixture of several different surfactants (b).

In one embodiment of the present invention, the preparation used according to the invention comprises at least one polycarboxylate (c), for example alkali metal salts of (meth) acrylic acid homo- or (meth) acrylic acid copolymers. Preferably, formulations used according to the invention contain in total in the range from 0.1 to 20% by weight of polycaboxylate (e) (c).

Suitable comonomers for (meth) acrylic acid copolymers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid. A suitable acrylic acid polymer is in particular polyacrylic acid, which is preferably a average molecular weight M _w in the range of 2000 to 40,000 g / mol, preferably 2,000 to 10,000 g / mol, in particular 3,000 to 8,000 g / mol. Also suitable are copolymeric polycarboxylates (c), especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.

It is also possible to use copolymers of at least one monomer selected from the group consisting of monoethylenically unsaturated C ₃ -C ₁₀ -mono- or 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 Monomers are used as enumerated below.

Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof, for example 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-hexadecene and 1-octadecene. Eicosene, 1-docoses, 1-tetracoses and 1-hexacoses, C ₂₂ -α-olefin, a mixture of C ₂₀ -C ₂₄ -α-olefins and polyisobutene having an average of 12 to 100 carbon atoms.

Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups, as well as nonionic monomers having hydroxy function or alkylene oxide groups. Examples include: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-coethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate. The polyalkylene glycols contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units.

Particularly preferred sulfonic acid-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2 hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and salts of said acids, such as their sodium, potassium or ammonium salts.

Particularly preferred phosphonate group-containing monomers are the vinylphosphonic acid and its salts.

In one embodiment of the present invention, formulations used according to the invention contain in the range of up to 50% by weight of complexing agent (d), for example at least 0.1% by weight, preferably from 1 to 45% by weight and more preferably from 1 to 40% by weight .-%. Preferred complexing agents (d) are selected from aminocarboxylates and polyaminocarboxylates and their salts, in particular alkali metal salts, and derivatives thereof, such as, for example, methyl esters.

For the purposes of the present invention, aminocarboxylates are understood as meaning nitrilotriacetic acid and those organic compounds which have a tertiary amino group which has one or two CH ₂ -COOH groups which, as mentioned above, can be partially or completely neutralized. In the context of the present invention, polyaminocarboxylates are understood as meaning those organic compounds which have at least two tertiary amino groups which independently of one another have one or two CH ₂ -COOH groups which, as mentioned above, can be partially or completely neutralized ,

In another embodiment of the present invention is selected aminocarboxylates of such organic compounds having a secondary amino group having one or two CH (COOH) CH ₂ COOH group (s) which - as mentioned above - partially or completely neutralized can or can be. In another embodiment of the present invention, polyaminocarboxylates are selected from those organic compounds having at least two secondary amino groups each having a CH (COOH) CH ₂ -COOH group which may be partially or completely neutralized as mentioned above.

Particularly preferred aminocarboxylates and polyaminocarboxylates are selected from nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid and methylglycinediacetic acid (MGDA), glutamic acid diacid, iminodisuccinic acid, hydroxyiminodisuccinic acid, ethylenediamine disuccinic acid, aspartic acid diacetic acid and their salts, for example their alkali metal salts, in particular their potassium and sodium salts , Particularly preferred complexing agents (d) are methylglycinediacetic acid and its salts.

As component (e), the formulation used according to the invention may contain in the range of up to 70% by weight of phosphate (s), for example in the range from 5 to 60% by weight, particularly preferably in the range from 20 to 55% by weight.

Examples of phosphates (e) are in particular alkali metal phosphates and polymeric alkali metal phosphates, which may be chosen in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of such phosphates (e) are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium tripolyphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate having a degree of oligomerization of 5 to 1000, preferably 5 to 50, and the corresponding potassium salts, or mixtures of sodium hexametaphosphate and the corresponding potassium salts, or mixtures of Sodium and potassium salts. Preferred phosphates (e) are alkali metal phosphates, in particular Pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate), further sodium metaphosphate.

In a preferred embodiment of the present invention, the formulation used according to the invention contains no phosphate (s); wherein formulations having less than 100 ppm by weight of phosphate (s), based on the solids content of the relevant formulation used according to the invention, are considered to be phosphate-free in the context of the present invention.

As component (f), the formulation used according to the invention may contain up to 60% by weight of builder (f) or cobuilder (f), for example in the range from 0.1 to 60% by weight. For the purposes of the present invention, builder (f) or cobuilder (f) are water-soluble or water-insoluble substances which are different from inorganic phosphate and complexing agent (d) and whose main task consists in binding calcium and magnesium ions.

Builder (f) can be selected from low molecular weight carboxylic acids and their salts, such as citric acid and its alkali metal salts, in particular anhydrous trisodium citrate or trisodium citrate dihydrate. Further suitable builders (f) are furthermore succinic acid and its alkali metal salts, fatty acid sulfonates, α-hydroxypropionic acid, alkali metal malates, fatty acid sulfonates, C ₁ -C ₂₀ -alkyl or C ₂ -C ₂₀ -alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, oxydisuccinate, gluconic acids , Oxadiacetates, carboxymethyloxysuccinates, tartrate monosuccinate, tartrate disuccinate, tartrate monoacetate, tartrate diacetate and α-hydroxypropionic acid.

Further examples of builders suitable (f) are silicates, in particular sodium disilicate and sodium metasilicate, zeolites, layer silicates, particularly those having the formula α-Na ₂ Si ₂ O _5, β-Na ₂ Si ₂ O _5, and δ-Na ₂ Si ₂ O ₅ .

Examples of cobuilders (f) are phosphonates, for example hydroxyalkane phosphonates and aminoalkane phosphonates. Among the hydroxyalkane phosphonates, preference is given to 1-hydroxyethane-1,1-diphosphonate (HEDP) as co-builder (f). It is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediaminetetra-methylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral reacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.

Furthermore, carbonates and bicarbonates are used, of which the alkali metal salts, in particular sodium salts, are preferred, for example sodium carbonate and sodium bicarbonate.

In one embodiment of the present invention, formulations used in the invention contain up to 30% by weight of bleach (g) and optionally one or more bleach activators or bleach catalysts.

In one embodiment of the present invention, formulations used according to the invention contain one or more oxygen bleaches or one or more chlorine-containing bleaches. Examples of suitable oxygen bleaching agents are sodium perborate, anhydrous or, for example, monohydrate or tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, monohydrate, hydrogen peroxide, persulfates, organic peracids such as peroxylauric acid, peroxystearic acid, peroxy-α-naphthoic acid, 1,12-diperoxydodecanedioic acid Perbenzoic acid, 1,9-diperoxyazelaic acid, diperoxyisophthalic acid, in each case as the free acid or as the alkali metal salt, in particular as the sodium salt, furthermore sulfonyl peroxyacids and cationic peroxyacids.

For example, formulations used in the present invention may contain in the range of 0.5 to 15 weight percent oxygen bleach.

Suitable chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.

Formulations used according to the invention may contain, for example, in the range of from 3 to 10% by weight of chlorine-containing bleach.

Formulations used in the invention may contain one or more bleach catalysts. Bleach catalysts can be selected from bleach-enhancing transition metal salts or transition metal complexes such as manganese, iron, cobalt, ruthenium or molybdenum-salene complexes or manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and cobalt, iron, copper and ruthenium-amine complexes can also be used as bleach catalysts.

Formulations used according to the invention may contain one or more bleach activators, for example N-methylmorpholinium acetonitrile salts ("MMA salts"), trimethylammonium acetonitrile salts, N-acylimides such as N-nonanoyl succinimide, 1,5-diacetyl-2,2-dioxo hexahydro-1,3,5-triazine ("DADHT") or nitrile quats, ie trimethylammonium acetonitrile salt (s).

In one embodiment of the present invention, the formulation used according to the invention contains in the range from 0.1 to 10% by weight of bleach activator, preferably from 1 to 9% by weight, particularly preferably from 1.5 to 8% by weight, based on the entire formulation used according to the invention.

For example, formulations used according to the invention may contain a total of up to 8% by weight of enzyme (h), preferably from 0.1 to 3% by weight, based in each case on the total solids content of the formulation used according to the invention. Examples of enzymes (h) are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.

In one embodiment of the present invention, formulations used according to the invention may contain in total from 0.1 to 50% by weight of one or more additives (i). Examples of additives (i) are anionic or zwitterionic surfactants, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents, tableting aids, disintegrating agents, thickeners and solubilizers.

Disintegrating agents are also called tablet disintegrants. Examples are crosslinked polyvinylpyrrolidones.

Example of tabletting aids is polyethylene glycol, for example having a molecular weight M _w of at least 1500 g / mol. Example of tableting aids is polyethylene glycol, for example having a molecular weight M _w of more than 1,500 g / mol to a maximum of 8,000 g / mol.

Examples of anionic surfactants are C ₈ -C ₂₀ -alkyl sulfates, C ₈ -C ₂₀ -alkyl sulfonates and C ₈ -C ₂₀ -alkyl ether sulfates having one to six ethylene oxide units per molecule.

Examples of zwitterionic surfactants are derivatives of quaternary aliphatic ammonium or phosphonium salts or of tertiary sulfonium salts in which the aliphatic groups can be unbranched or branched and in which one of the aliphatic substituents is a C ₆ -C ₂₀ -alkylene radical, preferably a C ₈ -C ₁₈ -alkylene having an anionic group, for example, a carboxyl group, a sulfate group, a phosphate group or a phosphonic acid group.

Specific examples of zwitterionic surfactants are betaines, for example cocamidopropyl betaine.

Formulations used according to the invention may contain one or more alkali carriers. Alkaline carriers, for example, provide the pH of at least 9 when an alkaline pH is desired. Suitable examples are alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal hydroxides and alkali metal metasilicates. Preferred alkali metal is in each case potassium, particularly preferred is sodium.

Formulations used in the invention may contain one or more corrosion inhibitors. This is to be understood in the present case, such compounds that inhibit the corrosion of metal. Examples of suitable corrosion inhibitors are triazoles, especially benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles Phenol derivatives such as hydroquinone, catechol, hydroxyhydroquinone, gallic acid, phloroglucin or pyrogallol.

In one embodiment of the present invention, formulations used in the invention contain a total of in the range of 0.1 to 1.5 wt .-% corrosion inhibitor.

In one embodiment of the present invention, formulations used according to the invention contain inhibitors of glass corrosion. Glass corrosion can be manifested by clouding, iridescence, streaks and lines on glass surfaces. Preferred inhibitors of glass corrosion are selected from the group of magnesium, zinc and bismuth salts and complex compounds of zinc, magnesium or bismuth.

Formulations used according to the invention may contain one or more defoamers selected, for example, from silicone oils and paraffin oils.

In one embodiment of the present invention, formulations used according to the invention generally contain in the range from 0.05 to 0.5% by weight defoamer.

In one embodiment of the present invention, formulations used according to the invention may contain one or more acids, for example methanesulfonic acid or its salts.

In one embodiment of the present invention, formulations used according to the invention may comprise one or more dyes. An example of a suitable dye is Patent Blue.

In one embodiment of the present invention, formulations used according to the invention may contain one or more perfumes, for example a perfume.

In one embodiment of the present invention, the formulations used in the invention may contain one or more preservatives, for example, 2-methyl-2 H- isothiazol-3-one (Kathon CG).

A suitable filler is, for example, sodium sulfate.

Examples of suitable organic solvents are ethanol, isopropanol and propylene glycol.

Cleaning formulations used according to the invention may be liquid, a gel or in solid form, single- or multiphase, in the form of tablets or in the form of other dosing units.

If one uses formulations used according to the invention for cleaning dishes, dishes are obtained which are excellently cleaned and in particular have little limescale. Furthermore, dishes washed with formulations used according to the invention show very good filming properties.

A further subject of the present invention is the use of machine-dishwashing formulations according to the invention. A further subject of the present invention is a process for the automated cleaning of dishes using at least one formulation described above (US Pat.

It should be understood by the term "tableware" in connection with dishwashing not only porcelain dishes and plastic dishes, but also cutlery, such as silver cutlery or plastic cutlery, pots, frying pans, kitchen utensils such as lemon or garlic presses or measuring cup, and also glasses and glassware for Cook.

Machine dishwashing is preferably dishwashing with a dishwasher (English: automatic dishwashing).

In one embodiment of the present invention, water having a hardness in the range of 1 to 30 ° dH, preferably 2 to 25 ° dH, is used for cleaning, by which is meant, in particular, the calcium hardness.

The cleaning process according to the invention gives dishes which are excellently cleaned and in particular have little limescale. Furthermore, dishes washed with formulations used according to the invention show very good filming properties.

• (a1.1) mindestens einem N-Vinylamid
• (a1.2) Vinylacetat,
• (a1.3) mindestens einem Polyether,
• (a1.4) gegebenenfalls mindestens einem weiteren Comonomer,

in Formulierungen für die maschinelle Geschirrreinigung.Another object of the present invention is the use of copolymer (a1) obtainable by copolymerization of

• (a1.1) at least one N-vinylamide
• (a1.2) vinyl acetate,
• (a1.3) at least one polyether,
• (a1.4) optionally at least one further comonomer,

in formulations for machine dishwashing.

In a preferred variant, characterized in that copolymer (a1) is obtainable by copolymerization of
in total in the range from 30 to 80% by weight of N-vinylamide (a1.1),
in total in the range from 10 to 50% by weight of vinyl acetate (a1.2),
in total in the range from 10 to 50% by weight of polyether (a1.3),
in total in the range from zero to 10% by weight of comonomer (e) (a1.4),
in each case based on the mass of the total copolymer (a1).

Further properties of copolymer (a1) are described above.

Another object of the present invention is a process for the preparation of preparations according to the invention, characterized in that at least one copolymer (a1) and at least one alkoxylate (a2) are mixed together.

In a preferred variant, the procedure is to melt at least one copolymer (a1) or at least one alkoxylate (a2), to mix it with copolymer (a1) or alkoxylate (a2) and then to allow it to cool.
In another preferred variant, the procedure is such that at least one copolymer (a1) and at least one alkoxylate (a2) are mixed together in each case in the molten state and then allowed to cool.

In one embodiment, copolymer (a1) and alkoxylate (a2) are mixed together, for example in bulk or in the presence of water, and the water is then optionally removed. Water can be removed by evaporation, for example.

In a preferred embodiment of the present invention, copolymer (a1) is melted, for example in a stirred vessel, in a heatable tube or in an extruder, and then mixed with alkoxylate (a2) in solid or molten form. Then you can cool down. In another embodiment of the present invention, alkoxylate (a2) is melted, for example in a stirred vessel, in a heatable tube or in an extruder, and then mixed with copolymer (a1) in solid or molten form. Then you can cool down.

In a preferred embodiment of the present invention, copolymer (a1) and alkoxylate (a2) are each mixed in solid form, then the resulting mixture is melted, for example in a stirred vessel, in a heatable tube or an extruder, and then allowed to cool.

In another preferred embodiment of the present invention, copolymer (a1) may be melted with solid alkoxylate (a2) to melt alkoxylate (a2). During or after this, the mixture is mixed and then allowed to cool.

In another preferred embodiment of the present invention, copolymer (a1) and alkoxylate (a2) are separately melted, mixed, and then allowed to cool.

Thus, for example, it is possible to process melt-liquid copolymer (a1), as obtained after the purification operations following its preparation, in a further step. For example, molten copolymer (a1) can be introduced into a suitable mixing device and mixed with at least one alkoxylate (a2). Suitable mixing means are, for example, a second extruder, kneaders, dynamic and static mixers, and combinations thereof.

A suitable embodiment is the melting of copolymers (a1) and mixing with alkoxylate (a2). In this case, one can proceed by metering the copolymer (a1) and alkoxylate (a2) individually or as a mixture into one or more feed openings of an extruder and melting them with mixing and then cooling and granulating again. Or else one melts only the copolymer (a1) and doses alkoxylate (a2) at one or more points via a side dosing (side screw conveyor) in the liquid melt of copolymer (a1). In this embodiment, the extruder screw should be provided with suitable mixing elements. Suitable mixing elements can be, for example, conveying and non-conveying kneading blocks, tooth mixing elements, elements with perforated webs, turbine mixing elements, hedgehogs, tooth blocks, etc.

In one embodiment, the dry copolymer (a1) is recovered in the presence of alkoxylate (a2). For this, alkoxylate (a2) may be added to a solution or dispersion of the copolymer (a1) or the molten copolymer (a1), and the resulting mixture may be fed to an extruder, or alkoxylate (a2) is separately introduced into the extruder. For example, the nonionic surfactant (a2) may be cold-fed into the extruder as a solid or liquid and the polymer solution pumped to it, and both degassed together, or the polymer solution is introduced, i. pumps them into the heated extruder and evaporates only a certain proportion of the solvent (for example, 50-95%) and then at a later stage, the nonionic surfactant (a2) or solid as a slurry and evaporates solvent together.

After cooling of the mixture of copolymer (a1) and alkoxylate (a2), it is possible to allow to cool and optionally to comminute. For comminution are in principle all the usual known techniques such as hot or cold deduction. Allow to cool and chopping can be done in any order. Thus, it is possible, for example, to cut off an extrudate of copolymer (a1) and alkoxylate (a2) with rotating knives or with an air jet and then cool with air or under protective gas. In another variant, it is possible to deposit an extrudate of copolymer (a1) and alkoxylate (a2) as a melt strand on a cooled belt (stainless steel, Teflon, chain belt) and to granulate or grind after solidification.

Other shredding methods such as sprayer staring are possible.

Compounds of the general formula (I) can be obtained by alkoxylation of the corresponding C ₈ -C ₂₄ -alcohols with alkylene oxides. In this case, an etherification, z. B. with a suitable alcohol or with another alkylating agent, in particular with dimethyl sulfate, or esterification with a carboxylic acid.

Preferably, R ^{2 is} hydrogen.

The alkoxylation can be carried out, for example, using alkaline catalysts such as alkali metal hydroxides or alkali metal alkoxides, or with acidic catalysts, for example BF ₃ .H ₃ PO ₄ , BF ₃ .2 (C ₂ H ₅ ) ₂ O, BF ₃ , SbCl ₅ , SnCl ₄ · Perform 2 H ₂ O or hydrotalcite, or with double metal cyanide catalysts.

Processes for the preparation of copolymer (a1) are known per se, see, for example WO 2007/051743 , The preparation is preferably carried out by free-radically initiated polymerization, preferably in solution, in nonaqueous organic solvents or in mixtures of water and nonaqueous organic solvents. Suitable non-aqueous organic solvents are, for example, alcohols, such as methanol, ethanol, n-propanol, and isopropanol, and also glycols, such as ethylene glycol and glycerol. Further suitable solvents are esters such as, for example, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate or butyl acetate, ethyl acetate being preferred. To carry out the free-radical copolymerization, polyethers (a1.3) are preferably added, and N-vinylamide (a1.1), vinyl acetate (a1.2) and optionally further comonomer (a1.4) are added, together or separately, simultaneously or in succession ,

The free radical copolymerization is preferably carried out at temperatures of 60 to 100 ° C. For example, suitable pressure is normal pressure, but one can also choose higher or lower pressure.

The invention will be explained in more detail by the following working examples.

working examples I. Substances used I.1 Preparation of Copolymers (a1) I.1.1 Preparation of copolymer (a1-1)

Feed 1: 240 g of vinyl acetate (a1.2)
Feed 2: 456 g of vinylcaprolactam (a1.1-1) dissolved in 240 g of ethyl acetate
Feed 3: 10.44 g of tert-butyl perpivalate (75% by weight in aliphatic mixture), diluted with 67.90 g of ethyl acetate

104.0 g of polyethylene glycol (M _w : 6000 g / mol) (a1.3-1), dissolved in 25 g of ethyl acetate, were initially introduced into a stirred apparatus and the mixture was heated to 77 ° C. under an N ₂ atmosphere. Once the internal temperature of 77 ° C was reached, 1 g of feed 3 was added and polymerized for 15 min. Subsequently, the metering of feed 1, feed 2 and feed 3 was started simultaneously. Feed 1 and feed 2 were metered in within 5 hours, and feed 3 was metered in within 2 hours. After all feeds had been metered in, the reaction mixture was stirred for a further 3 hours at 77.degree. Thereafter, the reaction mixture was diluted with 500 ml of water. Subsequently, volatile constituents were removed by steam distillation. The thus-obtained aqueous solution of copolymer (a1-1) was freeze-dried. Copolymer (a1-1) were obtained after grinding as a very good flowable powder. M _w : 44,000 g / mol

I.1.2 Preparation of copolymer (a1-2) Feed 1: 500 g of vinylcaprolactam (a1.1-1) and 180 g of vinyl acetate (a1.2), dissolved in 100 g of ethyl acetate Feed 2: 10.50 g of tert-butyl perethylhexanoate (98% by weight), diluted with 94.50 g of ethyl acetate

100.0 g of polyethylene glycol (M _w : 6000 g / mol) (a1.3-1) and 20 g of vinyl acetate (a1.2), dissolved in 165 g of ethyl acetate, were initially charged in a stirred apparatus and heated under an N ₂ atmosphere at 77 ° C. Once the internal temperature of 77 ° C was reached, 10.5 g of feed 2 was added and polymerized for 15 min. Subsequently, the metering of feed 1 and feed 23 was started simultaneously. Feed 1 was metered in within 5 hours, and feed 2 was metered in within 2 hours. After all feeds had been metered in, the reaction mixture was stirred for a further 3 hours at 77.degree. Thereafter, the reaction mixture was diluted with 500 ml of water. Subsequently, volatile constituents were removed by steam distillation. The thus-obtained aqueous solution of copolymer (a1-1) was freeze-dried. Copolymer (a1-2) were obtained after grinding as a very good flowable powder.

I.1.3 Preparation of Additional Copolymers (a1-3) to (a1-5)

The procedure was as described in Example I.1.2, but in each case different compositions of feed 1 and feed 2 were selected.
The following copolymers were obtained according to Table 1. Table 1: Composition of copolymers (a1-1) to (a1-5) copolymer Composition in% by weight K value (1% by weight in ethanol) (A1.3-1) (A1.1-1) (A1.2) (A1-1) 13 57 30 19.8 (A1-2) 12.5 62.5 25 18.5 (A1-3) 12.5 60 27.5 40.4 (A1-4) 14 51 35 25.2 (A1-5) 14 53.5 32.5 22.4

The alkoxylate (a2-1) used was: nC ₁₈ H ₃₇ - (OCH ₂ CH ₂ ) ₉ -OH

II. Preparation of formulations used according to the invention and of comparative formulations II.1 Preparation of basic mixtures

As the polycarboxylate (c-1) was used: random copolymer of acrylic acid / AMPS (2-acrylamido-2-methylpropanesulfonic acid), weight ratio 7: 3, partially neutralized with NaOH, Mw: 20,000 g / mol, K value: 40 , pH 5 (1% in distilled water).

For the preparation of base mixtures, the respective substances according to Table 2 were mixed dry in a food processor and divided with the aid of a sample divider. Table 2: Composition of basic mixtures BF-P free BF-P sustainably protease 1 1 amylase 0.2 0.2 Polycarboxylate (c-1) 10 6.5 sodium 10.5 14 tetraacetylethylenediamine, 4 4 sodium tripolyphosphate - 50 Na ₂ Si ₂ O ₅ 2 2 Na ₂ CO ₃ 18.8 18.8 Sodium citrate dihydrate 33 - Methylglycinediacetic acid, tri-sodium salt 15 - HEDP 0.5 0.5 HEDP: disodium salt of hydroxyethane (1,1-diphosphonic acid)
All quantities in g.

II.2 Preparation of Preparations According to the Invention and of Comparative Preparations

Preparation of inventive preparation EZ-1

10 g of alkoxylate (a2-1) were melted and mixed with 5 g of solid (copolymer (a1-1) to form an inhomogeneous mixture in the form of a turbid solution.) After cooling to room temperature and re-melting, a homogeneous mixture was obtained It was allowed to cool to room temperature and received Formulation EZ-1 EZ-1 was solid at room temperature.

II.3 Preparation of phosphate-free formulation EF-1 used according to the invention

19.95 g of BP-P free base mixture were introduced. Subsequently, EZ-1 was melted and 1.6 g of EZ-1 containing 1.05 g (a2-1) and 0.55 g (a1-1) was added dropwise to BP-P free. The thus available formulation EF-1 was allowed to solidify.

II.4 Preparation of phosphate-containing formulations used according to the invention and comparative formulations 11.4.1 Preparation of Formulation EF-1 P Used According to the Invention

20.4 g of base mixture were added to BP-P. Subsequently, 0.9 g of EZ-1 was melted and dripped onto BP-P-containing. The thus available formulation EF-1 P was allowed to solidify.

II.4.2 Preparation of Comparative Formulation V-F-2P

20.4 g of base mixture were added to BP-P. Then 0.6 g of alkoxylate (a2-1) were melted and dripped onto BP-P-containing. The thus obtainable comparative formulation V-F-2P was allowed to solidify.

III. Test of formulations used according to the invention and comparative formulations

• Geschirrspüler: Miele G 1222 SCL
• Programm: 50°C mit R-time 2 (8 min) (ohne Vorspülen)
• Spülgut: 3 Messer (WMF Tafelmesser Berlin, Monoblock)
  • 3 Trinkgläser Amsterdam 0,2 I
  • 3 FRÜHSTÜCKSTELLER "OCEAN BLAU" (aus Melamin-Harz)
  • 3 Porzellanteller FAHNENTELLER FLACH 19 CM
• Anordnung: Messer in der Besteckschublade, Gläser im oberen Korb, Teller im unteren Korb
• Geschirrspülmittel: 21 g
• Schmutzzugabe: 100 g Klarspülschmutz (enthält Ei, Stärke und Fett), wurde eingefroren dosiert Klarspültemperatur: 65°C
• Wasserhärte: 21°dH (Ca/Mg):HCO₃ (3:1):1.35
• Spülzyklen:6; dazwischen jeweils 1 h Pause (10 min bei geöffneter Spülmaschinentür, 50 min bei geschlossener Spülmaschinentür)
• Auswertung: Visuell nach 6 Spülzyklen in einer abgedunkelten Kammer unter Licht hinter einer Lochblende

The following experimental conditions were selected for the tests for machine dishwashing:

• Dishwasher: Miele G 1222 SCL
• Program: 50 ° C with R-time 2 (8 min) (without prewash)
• Wash ware: 3 knives (WMF table knife Berlin, Monoblock)
  • 3 drinking glasses Amsterdam 0.2 I
  • 3 BREAKFAST "OCEAN BLUE" (made of melamine resin)
  • 3 porcelain plate FLAG TILE FLAT 19 CM
• Arrangement: knife in the cutlery drawer, glasses in the upper basket, plates in the lower basket
• Dishwashing detergent: 21 g
• Dirt addition: 100 g rinse aid dirt (contains egg, starch and fat), was frozen dosed rinse temperature: 65 ° C.
• Water hardness: 21 ° dH (Ca / Mg): HCO ₃ (3: 1): 1.35
• Purge cycles: 6; between each 1 h break (10 min with open dishwasher door, 50 min with closed dishwasher door)
• Evaluation: Visually after 6 wash cycles in a darkened chamber under light behind a pinhole

The washware was evaluated after 6 rinse cycles using a score scale from 10 (very good) to 1 (very poor). Scores were given from 1 - 10 for spotting (very many, intense spots = 1 to no spots = 10) and for filming the scores 1 - 10 (1 = very strong surface, 10 = no surface).

IV.1 Results with phosphate-free formulations

The test results are summarized in Table 3 (see next page).

IV.2 Results with Phosphate-Containing Formulations

The test results are summarized in Table 4 (see next page). Table 3: Dishwasher tests with phosphate-free formulation EF-1 spotting Filming formulation knife glasses Melaminteller porcelain plates knife glasses Melaminteller porcelain plates EF-1 10 10 8th 7 5 6 6 6 spotting Filming formulation knife glasses Melaminteller porcelain plates knife glasses Melaminteller porcelain plates EF-1P 7 7 9 8th 5 7 8th 7 VF-2P 7 2 2 3 6 7 8th 8th

Claims (14)

1. The use of preparations comprising

   (a1) at least one copolymer obtainable by copolymerization of

   (a1.1) at least one N-vinylamide,

   (a1.2) vinyl acetate,

   (a1.3) at least one polyether,

   (a1.4) optionally at least one further comonomer,

   (a2) at least one alkoxylate of the general formula (I)
   
           R¹-(OCH₂CHR²)_mOR³     (I)
   
   where the variables are defined as follows:

   R¹ is C₈-C₂₄-alkyl, linear or branched,

   R² is C₁-C₁₀-alkyl, in each case identical or different, linear or branched, or hydrogen,

   R³ is hydrogen or C₁-C₄-alkyl, linear or branched,

   m is a number in the range from 1 to 100,

   in formulations for machine dishwashing.
2. The use according to claim 1, which comprises in the range from 1 to 50% by weight of copolymer (a1) and 50 to 99% by weight of alkoxylate (a2).
3. The use according to claim 1 or 2, wherein copolymer (a1) is obtainable by copolymerization of in total in the range from 30 to 80% by weight of N-vinylamide (a1.1),
   in total in the range from 10 to 50% by weight of vinyl acetate (a1.2),
   in total in the range from 10 to 50% by weight of polyether (a1.3),
   in total in the range from zero to 10% by weight of comonomer(s) (a1.4),
   in each case based on the mass of the total copolymer (a1).
4. The use according to any one of claims 1 to 3, wherein copolymer (a1) is a graft copolymer.
5. The use according to any one of claims 1 to 4, wherein N-vinylamide (a1.1) is selected from N-vinyllactams.
6. The use according to any one of claims 1 to 4, wherein N-vinylamide (a1.1) is selected from N-vinylpyrrolidone and N-vinylcaprolactam.
7. The use according to any one of claims 1 to 6, wherein polyether (a1.3) is selected from polyethylene glycols having an average molecular weight M_w in the range from 1000 to 100 000 g/mol.
8. The use according to any one of claims 1 to 7, wherein alkoxylate (a.2) is selected from ethoxylates of linear C₁₆-C₁₈-alkanols having on average 8.5 to 9.5 mol of ethylene oxide per mole of linear C₁₆-C₁₈-alkanol.
9. The use according to any one of claims 1 to 8, wherein the alkoxylate (a2) comprises at least 80% by weight of at least one ethoxylate of linear C₁₆-C₁₈-alcohols of the formula (I) where m is selected from 8, 9 and 10.
10. The use according to any one of claims 1 to 9, wherein copolymer (a1) and alkoxylate (a2) are present as solid solution.
11. A machine dishwashing method using at least one formulation comprising

    (a) in total in the range from 0.1 to 20% by weight of at least one preparation according to any one of claims 1 to 9,

    (b)in total in the range from 0 to 10% by weight of nonionic surfactant which is different from copolymer (a1) and from alkoxylate (a2),

    (c) in total in the range from 0 to 20% by weight of one or more polycarboxylates,

    (d) in total in the range from 0 to 50% by weight of complex formers which are different from inorganic phosphates,

    (e) in total in the range from 0 to 70% by weight of one or more inorganic phosphates,

    (f) in total in the range from 0 to 60% of further in particular phosphate-free builders and cobuilders which are in each case different from complex former (d)

    (g) in total in the range from 0 to 30% by weight of bleaches and optionally bleach activators or bleach catalysts,

    (h) in total in the range from 0 to 8% by weight of enzyme (s),

    (i) in total in the range from 0 to 50% by weight of one or more further additives,
    and optionally water.
12. The method according to claim 11, wherein additives are selected from anionic or zwitterionic surfactants, alkali carriers, corrosion inhibitors, antifoams, dyes, fragrances, preservatives, fillers, organic solvents, tableting auxiliaries, disintegrants, thickeners and solubility promoters.
13. The use of copolymer (a1) obtainable by copolymerization of

    (a1.1) at least one N-vinylamide,

    (a1.2) vinyl acetate,

    (a1.3) at least one polyether,

    (a1.4) optionally at least one further comonomer,
    in formulations for machine dishwashing.
14. The process according to claim 13, wherein copolymer (a1) is obtainable by copolymerization of in total in the range from 30 to 80% by weight of N-vinylamide (a1.1),
    in total in the range from 10 to 50% by weight of vinyl acetate (a1.2),
    in total in the range from 10 to 50% by weight of polyether (a1.3),
    in total in the range from zero to 10% by weight of comonomer(s) (a1.4),
    in each case based on the mass of the total copolymer (a1).